Poster Presentations – Education and Training€¦ · Mrs Mara Kefalopoulou, IChemE . ......

ChemEngDayUK2017 Better Life, Better World

27–28 March 2017, University of Birmingham

ChemEngDayUK 2017 Book of Abstracts

Editors: Bingyu Zhuo, Joe Wood and Zhibing Zhang

ChemEngDayUK 2017

Better Life, Better World

27-28 March 2017 University of Birmingham Chair: Professor Zhibing Zhang, University of Birmingham Vice Chair: Professor Joe Wood, University of Birmingham Organising Committee: Professor Mostafa Barigou, University of Birmingham Professor Jarka Glassey, Newcastle University Professor Liam Grover, University of Birmingham Professor Peter Fryer, FREng, University of Birmingham Professor Alexei Lapkin, University of Cambridge Professor Paula Mendes, University of Birmingham Professor Ian Norton, University of Birmingham Professor Raffaella Ocone, FREng, Heriot-Watt University Professor Mark Simmons, University of Birmingham Professor Robert Steinberger-Wilckens, University of Birmingham Professor Hugh Stitt, FREng, Johnson Matthey Professor Owen Thomas, University of Birmingham Ms Sarah Fleming, University of Birmingham Mr Matt Stalker, IChemE Ms Rae Arnold, HCEUK & IChemE Mrs Mara Kefalopoulou, IChemE

Table of Contents

Table of Contents Plenary Lectures 11

Mooney D., Building Immunity with Biomaterials ............................................................................................................. 11

Gladden L., Magnetic Resonance Imaging: Opportunities in Chemical Engineering Research and Practice ..................... 11

Noble I., Meeting the Challenges for the Future of Our Food - Engineering a More Sustainable Global Food System .... 12

Keynote Lectures 13

York D., The Engineering of Formulated Products ............................................................................................................. 13

Brandon N., Electrochemical Engineering for Energy Applications .................................................................................... 13

Matar O., A Fundamental Approach to Modelling Multiphase Flows: Correlations No More .......................................... 14

Hardacre C., Non Thermal Activated Catalysis ................................................................................................................... 14

Howdle S. M., Green Polymers: Chemistry and Processing ............................................................................................... 15

Titchener-Hooker N.,The Bioprocessing Challenges of Targeted Healthcare Manufacture .............................................. 15

Research Talks 16

Product Engineering .............................................................................................................................................. 16

Seville J and Leeke G., Effective Nanoparticulate Pharmaceutical Products by Supercritical Fluid Routes ...................... 17

Povey M., Characterisation of Powder by Acoustic Means ............................................................................................... 18

Early Career Industrial Research ............................................................................................................................ 19

Watson A., The Collaboration between Chemical Engineers and Chemists to Produce Medicines Sustainably .............. 20

Wilikinson S.K., Turnbull S.A., Yan E. and Marigo M., Understanding the Parameters behind Powder Flow Modelling .. 21

Catro J., Martin C., Ahmad R., Coyle T., Bartkowiak S., Sebastine I., Fields S., Water M. and Magee E., Practical

Experiments and Experience on the Ajax Twin Screw Mixer from Coating to Agglomeration .......................................... 22

Energy Generation, Storage and Utilisation ............................................................................................................ 23

Song Q., Functional Microporous Membranes for Energy and Environmental Applications ............................................ 24

Mirzaeian M., Investigating the Root-Cause of Unsatisfactory Performance of the Li/Air Battery: The Electrochemical

Performance Analysis of the Battery under Different Operation Conditions .................................................................... 25

Chemical Engineering Fundamentals...................................................................................................................... 26

Bannerman M. C., SimCem: A Thermodynamic Toolkit for Python/C++ ........................................................................... 27

Vigolo D., Riccomi M., Alberini F., Brunazzi E., Ault J.T. and Stone H. A., Flow Visualization of the Trapping Induced by

Vortex Breakdown at a Junction ........................................................................................................................................ 28

Chemical Engineering at Interface.......................................................................................................................... 29

D'Agostino C., NMR Studies of Gelatin Structure Alteration Induced by Swelling and Solid Particle Permeation ............ 30

Aleem H., Incorporating Sustainability Considerations in the Lifecycle of Medical Devices ............................................. 31

Sans V., 3D Printing Advanced Reactors for the Synthesis of Silver Nanoparticles ........................................................... 32

Ladewig B., Enantiomeric Molecular Separation via Selective Adsorption on Metal Organic Frameworks ...................... 33

Biological Engineering ........................................................................................................................................... 34

Thomas O., Mixed Polyelectrolyte Brush Surfaces Display ‘Chameleon-Like’ Protein Binding and Elution Properties .... 35

Klymenko O., Designing an Artificial Golgi Reactor to Improve the Efficacy of Therapeutic Proteins .............................. 36

3-Minute Research Highlight Talks 37

Product Engineering .............................................................................................................................................. 37

Vaclav S., Continuous Co-Crystallization of Benzoic Acid and Isonicotinamide by Mixing-Induced Supersaturation:

Exploring Opportunities Between Reactive and Antisolvent Crystallisation Concepts ..................................................... 38

El Hebieshy J., An Experimental Investigation of Size Induced Segregation during Die Filling .......................................... 39

Zhang J. and Wu C., The Effect of Water Content on Mechanical Properties of Microcrystalline Cellulose and Mannitol

Powders .............................................................................................................................................................................. 40

DiPaolo T., The Formulation of a Suspending Vehicle ....................................................................................................... 41

Zhang X., Hu J. F., Zhang Z., Preparation and Characterisation of Antifouling and Antiseptic Microcapsules .................. 42

Matos R. L., Supercritical Precipitation and Coating of Curcumin on Lactos Surface for Pulmonary Delivery .................. 43

Ebrahim W., Single Droplet Drying at High Temperatures ................................................................................................. 44

Karampalis D., Dissolution Phenomena of Spray Dried Powders by Single Particle Approach ......................................... 45

Chong J. Y., Wang B. and Li K., Ceramic/ Stainless Steel Composite Hollow Fibre Membranes for Water Treatment ..... 46

Almena A., Modelling, Simulation and Economical Evaluation of Dry Food Manufacture at Different Production Scales

............................................................................................................................................................................................ 47

Energy Generation, Storage and Utilisation ............................................................................................................ 48

Johnson E., Greening Britain’s Gas: The Potential for Supplying Biomethane and Hydrogen via the Gas Grid to People’s

Homes ................................................................................................................................................................................ 49

Al Jamri M., Integration of Renewable Energy Sources into Petroleum Refining for Sustainable Production of

Transportation Fuels .......................................................................................................................................................... 50

Zhang D., Lattice Boltzmann Simulation of Liquid-Gas Two-Phase Flow and Oxygen Diffusion in Polymer-Electrolyte

Membrane .......................................................................................................................................................................... 51

Mushtag O. and Tokay B., Metal Organic Framework Membranes for Natural Gas Purification ...................................... 52

Kalargaris I., An Experimental Investigation of the Effects of Fueling a Di Diesel Engine with Plastic Pyrolysis Oil .......... 53

Jager N., Apfelbacher A., Daschner R. and Hornung A., Storable Energy Carriers beyond the Electricity Marked:

Thermo-Catalytic Reforming (TCR®) to Contribute to the Present Energy Challenges ...................................................... 54

Yu Q., Thermo-Mechanical Analysis of Microcapsule Containing Phase Change Material (PCM) for Cold Storage ......... 55

Cho J., Nature-Inspired Fractal Flow Field for PEM Fuel Cells ............................................................................................ 56

Paulilo A., Life Cycle Assessment of Reprocessing of Spent Nuclear Fuel in the UK .......................................................... 57

Caro M. A., Optimization of Dilute Sulfuric Acid Saccharification of Steam Exploded Pineapple Peels for Bioethanol

Production .......................................................................................................................................................................... 58

Chemical Engineering Fundamentals...................................................................................................................... 59

Romano M. G., Brunazzi E., Simmons M. and Alberini F., Toward Online Rheology Measurements in Stirred Vessels ... 60

McDonough J., A Study of the Flow Structures Generated by Oscillating Flows in a Helically Baffled Tube .................... 61

Ejim L. N., Yerdelen S., McGlone T., Florence A., Rielly C. D. and Reis N. M., Characterizing Liquid-Solid Plug Flows in

Meso-Scale Oscillatory Flow Tubes .................................................................................................................................... 62

Badve M., Barigou M.,Flow of Gas-Liquid Foams through Narrow Complex Passages ..................................................... 63

Turchi M., In Silico Modelling of Complex Drug Formulations ........................................................................................... 64

Bandulasena M. V., Vladisavljevic G. T., Willcock H. and Benyahia B., Production of Biocompatible Gold Nanoparticles

for Drug Delivery Using Droplet Based Glass Capillary Microfluidic .................................................................................. 65

Wu K., Pattern Formation in Pulsed Gas-Solid Fluidized Beds: Insights from Experiments and Computations ................ 66

Kontziampasis D., Manga M. S., Castro J. and York D., Coating Particles Using High Viscous Fluids and Foams with Non-

Ideal Mixers 67

Nguyen T., Modelling the Drying Behaviour of Polymeric Droplets at High Temperature ................................................ 68

Ding P., Castro J., Bakalis S. and Zhang Z., Foaming Non-Newtonian Viscous Liquid for Particle Coating ........................ 69

Catalysis and Sustainable Green Chemistry ............................................................................................................ 70

Serrano R. C., Predicting the Cradle-to-Gate Environmental Impact of Chemicals from Molecular Descriptors and

Thermodynamic Properties via Mixed-Integer Programming ........................................................................................... 71

Li C., Flow Synthesis of Zn/Cr-Oxide Based Catalysts Allowing Hydrogen Sulphide Insensitive Methanol Synthesis ....... 72

Qu X., Garforth A. A. and Fan X., Optimization of Fe-ZSM-5 Coatings on SiC Cellular Foams for Phenol Wastewater

Treatment ........................................................................................................................................................................... 73

Darby M., Towards the Development of Single Atom Alloy Catalysts as a Means of Escaping Linear Scaling Relations .. 74

Guharoy U., DFT Study of Dry (CO2) Reforming of Methane over Tin-Doped Ni (111) Surface ......................................... 75

Waldron C., Multistep Synthesis of Benzylacetone in Micropacked Bed Reactors ........................................................... 76

Manning J., The Application of Green Chemistry to Enable Sustainable Manufacture of Bioinspired Nanosilica ............ 77

Turganaly R., Pt/Cu Single Atom Alloy Catalyst for Coke Free Methane Activation .......................................................... 78

Omojola T., Effect of Si/Al Ratios and Mass Transfer during the Adsorption, Desorption and Activity of Methanol and

DME Over ZSM-5 Catalysts ................................................................................................................................................. 79

Chekasov N., Increased Deactivation Stability of ZSM-5 Zeolite in a Methanol to Gasoline Conversion via Desilication

and Ca Ion Exchange .......................................................................................................................................................... 80

Biological Engineering ........................................................................................................................................... 81

Mulakhudair A., Fermentation Integrated with in situ Separation of Bio-Products Using Microbubble Technology ....... 82

Fernandez-Castane A., Bioprocessing Biologically Synthesised Magnetic Nanoparticles: Production, Recovery and

Purification of Magnetosomes ........................................................................................................................................... 83

Wang H., Rational Encapsulation of Needle-Shaped Nanocrystals into Zein@Au Hybrids for Controlled Release and

Active Targeting.................................................................................................................................................................. 84

Kelly C. M., Automated Micro-Volume Capillary Circular Dichroism and Fluorescence Spectroscopy for Rapid Analysis of

Protein Conformation ........................................................................................................................................................ 85

Rasheed A., Prediction of the Steady State Performance of Sequencing Batch Reactors from Batch Kinetic Tests ......... 86

Wu A., Application of Robust Model Identification Techniques in the Activated Sludge Process..................................... 87

Chin M., A Biomaterial-Based Platform for the Optimisation of Therapeutic Immune Cell Culture ................................. 88

Wan Mahmood W. M. A. Theodoropoulos C and Gonzalez-Miquel M., Lipid Extraction from Microalgal Biomass Using

Bio-Based Solvents ............................................................................................................................................................. 89

Nazki A. A., From Basic Enzymatic Building Blocks to Bacterial Signalling Pathways: A Systematic Elucidation of Spatial

Regulation and Compartmentalization of Biochemical Pathways ..................................................................................... 90

Chemical Engineering at Interface.......................................................................................................................... 91

Airey J., The Tribological Performance of Gas Turbine Lubricants ..................................................................................... 92

Principe I., Development of Nitrogen Doped Resorcinol-Formaldehyde Gels for Carbon Capture................................... 93

de Oliveira Filho P., On Ultrasonic Aerosol Generation and Transport under Uncertainty ............................................... 94

Esteban J., Simons T., Moxon T., Bakalis S. and Fryer P. J., Uptake of A Non-Ionic Surfactant by a Tableted Compacted

Powder Preparation ........................................................................................................................................................... 95

Nirmalkar N. and Barigou M., Generation of Bulk Nanobubbles in The Presence of Salts or Surfactants ........................ 96

Ozcan A. and Yazaydin O., Realistic Membrane Simulations for Nanoporous Materials .................................................. 97

Sebastia-Saez D., CFD Study of the Liquid-Gas Interface in Structured Packings .............................................................. 98

Evans A., Investigation of the Dynamic Adsorption of CO Using Metal-Organic Frameworks .......................................... 99

Abidin M. I. I. Z., Park K. H. and Angeli P., Studies on Two-Phase Flow Past Bluff Body in a Pipe ................................... 100

Petsagkourakis P., IQC Analysis of Constrained Model Predictive Control of Large-Scale Systems ................................ 101

Poster Presentations 102

Product Engineering ............................................................................................................................................ 102

Gray A., The Influence of Structural and Physico-Chemical Characteristics of Perfume Capsules on Their Burst

Properties ......................................................................................................................................................................... 102

Cai J., Wu C. and Zhao X., A Numerical Study of Number Concentration Distribution of Gas-Cylindrical Particles Flow

Based on CFD-DEM ........................................................................................................................................................... 103

Lomeli M., Process Simulation and Multiobjective Optimisation of the Production of Biomass-Derived Renewable

Polyesters ......................................................................................................................................................................... 104

Silvarrey L. D., Non-Thermal Plasma Assisted Pyrolysis of Waste High Density Polyethylene for Monomer Recovery .. 105

Iosson C., Characterising Chocolate Paste and the Impact on Downstream Processes .................................................. 106

Garay A. G., Economic and Environmental Assessment in the Production of Propylene Glycol from Biodiesel Glycerol

Under Uncertainty ............................................................................................................................................................ 107

Su X., Electrodeposition of Cu from Deep Eutectic Solvents by Using Pulse Current ...................................................... 108

Okeyo C., Mallet F., Rahmanian N. and Schafer F., Simple Lab Set-Up for Agitated Filter Drying of Active Pharmaceutical

Ingredients ....................................................................................................................................................................... 109

Vollans A., The Bradford Process: A New Novel Titanium Production Method - Development and Optimization ......... 110

Gouseti O., Freeze-Drying of Concentrated Sucrose Solutions ........................................................................................ 111

Green M., Moving Plastics into the Circular Economy by Chemical Engineering ............................................................ 112

Hussain M., Cayre O. J. and Bayly A. E., Engineering Washing Powder from Ternary Anionic Surfactant/Polycarboxylate

Based Polymer/Water Systems ........................................................................................................................................ 113

Li Y., Engineering Nano-Assemblies of Inorganic Particles ............................................................................................... 114

Maxfield L., Prediction of Self-Heating in Spray Dryer Wall Build-Up of Detergent Powder ........................................... 115

Green M., Griffiths A., Seville J., Thorpe R. and Leeke G., Fuel from Waste Plastic - Towards a Circular Economy for

Plastics .............................................................................................................................................................................. 116

Peletiri S. P., Rahmanian N. and Muitaba I. M., Effect of Impurities on Rich CO2 Fluids in Pipelines .............................. 117

Sebastine I., Ahmad R., Jackson T., White A. and Smith D.,Optimisation of Particulates Processing, Packaging and Filling

in a Pilot Scale Facility ...................................................................................................................................................... 118

Farshchi A., Hassanpour A., Caragay J and Bayly A.,Characterization of Spray-Dried Detergent Powders ..................... 119

Simons T., Esteban J, Bakalis S., Zhang Z., Duckitt C.and Tantawy H., Micromanipulation Experiments to Study Adhesive

Forces between Model Detergent Particles ..................................................................................................................... 120

Soori U., Yuen P. W. T., Selvagumar S, Zahidi U, James D and Richard M ,Chemical Sensing of Washing Powder by

Multispectral Imaging ...................................................................................................................................................... 121

Cao H., Kinetics of Gas Behaviour in Detergent Slurry under Pressurisation-Depressurisation Process ......................... 122

He L., Xing L., Zhuo B., Castro J., Bakalis S. and Zhang Z., Soft Particle Coating with Salt in a Fluidised Bed Coater ....... 123

Zhuo B., Xing L, He L., Zhang Z., Bakalis S. and Castro J., Improvement in Flowability of Soft Particles with Coating .... 124

Meng Z. and Coppens M., Preparation and Characterizations of Hybrid Mesoporous Silica Membrane on Polymer

Substrates ......................................................................................................................................................................... 125

Roettger K., Smith A., Taylor M. and Carrol J., Prospect Liquid Scale up Facility for Process Development and

Metrological Studies......................................................................................................................................................... 126

Energy Generation, Storage and Utilisation .......................................................................................................... 127

Aboelazayem O., Gadalla M. and Saha B., Optimising Biodiesel Production from Waste Cooking Oil Using Supercritical

Methanol .......................................................................................................................................................................... 127

Ker J. H., Bieber N., Wang X. and Shah N., Sustainable Planning of Energy-Water-Food Nexus Using Decision Making

Tools ................................................................................................................................................................................. 128

Wright A., The Development of a DBD Plasma, Microbubble Enhanced Waste Treatment Reactor 129

Aldawasari Y., Systems Analysis of Road Transportation Decarbonisation Options........................................................ 130

Hu G., Fernandez J., Doluda V. and Rebrov E. V., Design of a Microstructured Reactor/Heat-Exchanger for a Single Step

Methanol-to-Hydrocarbon Process over a ZSM-5 Zeolite ............................................................................................... 131

Ajisegiri G., Design and Simulation of Eco-Industrial Parks Using Agent-Based Modeling Approach ............................. 132

Bidokhti N. and Yazaydin O., Application of Carbonized Metal Organic Frameworks in Electrochemical Energy Storage

Devices ............................................................................................................................................................................. 133

Hart A., Thai-CAPRI Heavy Oil Recovery Process: Past, Present and Future .................................................................... 134

Karatrantos A. and Cai Q.,Understanding the Electrode-Electrolyte Interactions in Energy Storage Batteries Using

Molecular Simulations ...................................................................................................................................................... 135

Abbas Q., Electrochemical Performance of Resorcinol-Formaldehyde Based Carbons /Activated Carbons as

Electroactive Materials for Supercapacitor Applications ................................................................................................. 136

Zweig S., Controlling Process Parameters during the Wood Pellet Production Process to Minimise Pellet Breakage and

the Risk of Dust Explosions ............................................................................................................................................... 137

Nair P. K. and Rahmanian N., Impact of Impurities on Formation of Carbon-Dioxide Hydrates ..................................... 138

Mardle P. and Du S., Study in the Scalable Fabrication of NiPt Nanowires for PEMFC Application ................................ 139

Chemical Engineering Fundamentals.................................................................................................................... 140

Hallaca F., Fragkopoulosa I. S., Conellb S. D. and Mullera F. L., Micro-Mechanical Properties of Organic Crystals ........ 140

McDonough J., Applications of 3D Printed Fluidic Oscillators to Process Intensification ................................................ 141

Al-Janabi N., Carbon Capture Processes: From Chemistry to Application ....................................................................... 142

Fuentes J. L., Fouling Modelling in Crude Oil Preheat Systems........................................................................................ 143

Simionesie D., Model Asphaltene Aggregation ................................................................................................................ 144

Pineda M., Statistical Mechanics Modelling and Coarse-Grained Description of NO Oxidation on Pt(111) ................... 145

Ledezma-Martinez M., Jobson M. and Smith R., A New Design Approach for Crude Oil Distillation Systems with Pre-

Separation Units ............................................................................................................................................................... 146

Migliozzi S., Experimental and Computational Fluid Dynamic Studies of Continuous Mixing of Highly-Viscous non-

Newtonian Mixtures ......................................................................................................................................................... 147

Tsochataridou S., Understanding the Mechanism of CO2 Transport through Dual-Phase Membranes .......................... 148

Macri D., Titania Powders in the SLS Process ................................................................................................................... 149

Hoghton A., Non-Ambient Powder X-Ray Diffraction of Metal-Organic Framework Crystals ......................................... 150

Al-Sharify Z. T., Al-Najjar S. Z. and Barigou M., Impeller Drawdown and Dispersion of Floating Particles in non-

Newtonian Fluids .............................................................................................................................................................. 151

Mahdi F., Effect of Operational Parameters of Colloid Mill on Calcium Carbonate and Cellulose Suspensions ............. 152

Ejeh J. O., Liu S. and Papageorgiou L. G., An Optimisation-Based Approach for Process Plant Layout ........................... 153

Mavrou P., Predicting Moisture Migration in Composite Food Systems during Storage ................................................ 154

Ahmed T., Optimisation of Three-Phase Separator Design: A Mathematical .................................................................. 155

Alizadeh M., Hassanpour A., Asachi M., Ghadiri M. and Bayly A., Numerical Investigation of the Effect of Adhesion on

the Vibration-Induced Segregation of Powder Mixtures ................................................................................................. 156

Bracconi M., Maestri M., Groppi G., Tronconi E., de la Fonte C. P. and Fan X., Analysis of Multiphase Flow in Open-Cell

Foams by CFD Simulations on Virtually Reconstructed Geometries................................................................................ 157

Alfutimie A., Arafeh A. and Aleem H., An Investigation into the Influence of Process Variables on the Product Size

Distribution in a Semibatch Reaction Crystallization Process .......................................................................................... 158

Sun L. and Jia Z.,Simulation of Industrial Scale Super Open Rack Vaporizer ................................................................... 159

Catalysis and Sustainable Green Chemistry .......................................................................................................... 160

Onyenkeadi V. N., Greener Synthesis of Styrene Carbonate from CO2 Using Heterogeneous Catalyst .......................... 160

Wongsirichot P., Rapeseed Meal Pretreatment for Improved Biopolymer Production .................................................. 161

Ozturk B., Deterpenation of Folded Citrus Essential Oils Using Bio-Solvents .................................................................. 162

Gadkari S., Microwave Assisted Thermocatalytic Decomposition of Methane: Numerical Analysis .............................. 163

Gollakota A. R. K., CFD Approach for Developing Next Generation Bio Fuels through Catalytic Upgrading Procedure . 164

Xiang H., Siperstein F., Gorgojo R. and Fan X., Metal-Organic Frameworks (MOFS) for Alkene/Alkane Separation ...... 165

Routoula E. and Patwardhan S. V., Peroxidase Immobilisation on Bio-Inspired Silicas for Dye Degradation ................. 166

Abdulridha S., Garforth A. and Fan X., Preparation of Mesoporous Y Zeolite Using Hard Templates for Catalytic Cracking

of Heavy Oil ...................................................................................................................................................................... 167

Vakili R., Gorgojo-Alonso P., Holmes S. M. and Fan X., Microwave Assisted Synthesis of Zirconium-Based Metal Organic

Frameworks: Optimisation and Gas Adsorption .............................................................................................................. 168

Stamatious I., Determination of Mass Transfer Resistances of Fast Reactions in Three-Phase Mechanically Agitated

Reactors ............................................................................................................................................................................ 169

Limleamthong P., Multi-Criteria Screening of Chemicals Considering Thermodynamic and Life Cycle Assessment

Metrics via Data Envelopment Analysis: Application to CO2 Capture .............................................................................. 170

Collett C., Insights into the Origin of the Catalytic Activity of Biomass-Derived Carbon ................................................. 171

Armas P. V., Effect of Water on Cu Electrodeposition from Ethaline Based Deep Eutectic Solvent ............................... 172

Choolaei M., A Single Step Synthesis Approach for Preparing Nanocrystalline Powder of Gadolinium-Doped Ceria (GDC)

for Solid-Oxide Fuel Cells .................................................................................................................................................. 173

Garcia M., Representation of Vapour-Liquid-Equilibria and Densities of Unloaded and Loaded Deea Solutions: Enrtl

Model ............................................................................................................................................................................... 174

Alkailani A., Al-Duri B. and Wood J., Hydrogenation Conversion of Furfural into 2-Methylfuran (2-MF) Using Platinum

with Different Supported Catalysts .................................................................................................................................. 175

Kapil N., Nigra M. M. and Coppens M., Gold-Based Catalyst with Locally Controlled Chemical and Geometric

Environments to Tune Catalytic Performance ................................................................................................................. 176

Onoja O., The Oxidative Coupling of Methane: Application of Membrane Reactor to Enhance the Yield of Higher

Hydrocarbons ................................................................................................................................................................... 177

Venezia B., Constantinou A., Wu G. and Gavriilidis A., Aerobic Oxidation of Benzyl Alcohol in a Catalytic Membrane

Reactor: Experiments and Modelling ............................................................................................................................... 178

Crake A., Christoforidis K. C. and Petit C., Multifunctional Porous Materials for Combined CO2 Capture and Conversion

.......................................................................................................................................................................................... 179

Biological Engineering ......................................................................................................................................... 180

Joseph S., Manufacture and Characterisation of Protein Nanoparticles as Surrogate Virus Mimics for the Optimisation

of Chromatography Media ............................................................................................................................................... 180

Alves I. P. and Reis N. M., A New Microfluidic Test for Rapid Detection of E.Coli Infections .......................................... 181

Gu L. and Mavituna F., Exploitation of Interspecies Interactions for Pharmaceutical Production .................................. 182

Liamas E., Black R., Mulheran P., Thomas O. and Zhang Z. J., A Multiscale Study on the Effect of Surface Chemistry on

Protein Adsorption ........................................................................................................................................................... 183

Chemical Engineering at Interface........................................................................................................................ 184

Svensson M., The Effect of Novel Binders on the Performance of Capacitive Deionization for Water Purification 184

Ajentifuia A. and Jobson M., Novel Hybrid Adsorption-Distillation Flowsheets for the Separation of Close-Boiling

Mixtures ......................................................................................................................................................................... 1845

Zympeloudi D., Investigating Soil Removal Mechanisms, To Minimize Water Usage during Domestic Wash Processes186

Simou K., Nanomechanics of Articular Cartilage And Synovial Fluid ............................................................................... 187

Derkani M., Understanding the Colloidal Interactions at Oil/Rock Interfaces ................................................................. 188

Ibrahim D., Jobson M., Li J. and Guillen-Gosalbez G., Design of Flexible Heat-Integrated Crude Oil Distillation Units .. 189

Dong X., Light-Responsive IRMOF 5: Improved Ligand Synthesis and MOF Stability Study ............................................ 190

Tam B. and Yazavdin O., Design of Electric Field Controlled Molecular Gates Hosted in Metal-Organic Frameworks ... 191

Zhao K., Three-Dimensional Modelling of Thin Liquid Films over Spinning Disks ............................................................ 192

Park K. H., Voulgaropoulos V., Chinaud M. and Angeli P., Laser Imaging in Liquid-Liquid Flows .................................... 193

Rakovitis N., Li J. and Zhang N., A Novel Approach for Scheduling of Operations in a Large-Scale Scientific Services

Facility .............................................................................................................................................................................. 194

Lynch M., Chaperonin-Inspired Enzyme Immobilisation on Mesoporous Silica SBA-15.................................................. 195

Garcia-Trinanes P., Berry R. J. and Bradley M., Virtual Formulation Laboratory for Prediction and Optimisation of

Manufacturability of Advanced Solids Based Formulations ............................................................................................ 196

Education/Training ............................................................................................................................................. 197

Heslop M., Dimension in Presenting Assignments - Making Clear the Compiler's Perspective ...................................... 197

Pollock M. and Sorensen E., Effectively Conveying the Importance and Relevance of Safety to Undergraduates While

Educating Them in Good Practices ................................................................................................................................... 198

Rogers T., A Complimentary CPD Program for Involving PhD Students as Partners for UG Learning ............................. 199

Zweig S., Enhancing the Student Learning Experience in Chemical Engineering by Employing a Virtual Laboratory ..... 200

Garcia-Trinanes Pablo, Zigan S., Coutroubis A. and Brow D., Chemical Engineering in the UK – A New Paradigm ........ 201

Glassey J and Ostrowski B., Mixed Polyelectrolyte Brush Surfaces Display ‘Chameleon-Like’ Protein Binding and Elution

Properties ......................................................................................................................................................................... 202

List of Abstracts not Included 203

Plenary Lectures

Plen ary Lectures

Monday 27th March 2017 Monday

Professor David Mooney, Harvard University, USA

Building Immunity with Biomaterials

Dysfunction of the immune system underlies many diseases. However, strategies to effectively program

an immune response, and reprogram undesired responses, by manipulating a patient’s immune cells are

at an early stage. We are creating biomaterials capable of concentrating, interrogating, and

manipulating immune cells ex vivo and in the body by controlling, in space and time, the interaction of

the immune cells with immunomodulatory agents. The utility of this concept in the development of

therapeutic cancer vaccines will be highlighted.

David is the Pinkas Family Professor at Harvard University and the Wyss Institute. He earned his PhD at

MIT and BS in Chemical Engineering at the University of Wisconsin. He is a member of the National

Academy of Engineering and the National Academy of Medicine.

Tuesday 28th March 2017 Monday

09:00-09:45

Plenary Session (Elgar Concert Hall, Bramall Music Building)

Speaker: Professor Lynn Gladden CBE, FRS, FREng, University of Cambridge Magnetic resonance imaging: opportunities in chemical engineering research and practice

Chair: Professor Jonathan Seville, FREng, University of Surrey

Professor Lynn F Gladden FRS FREng, University of Cambridge, UK

Magnetic Resonance Imaging: Opportunities in Chemical Engineering Research and

Practice

This presentation will discuss the many ways in which imaging and tomographic methods, and magnetic

resonance imaging (MRI) in particular, can contribute to chemical engineering research and practice.

Many of the examples will be taken from the world of reaction engineering but examples of how these

MRI methods can be transferred to other sectors such as EOR R&D will also be shown. The

presentation will be based around 3 themes:

How can imaging aid the development and validation of simulation codes?

What’s happening inside the ‘black box’? – examples of how imaging can help identify the correct

physical mechanism upon which we can base models better able to describe chemical engineering

processes

Examples of where magnetic resonance can provide information which has, as yet, been unobtainable;

for example, phase behaviour inside catalyst pellets, and direct measurements of mass transfer.

Lynn is the Shell Professor of Chemical Engineering at the University of Cambridge. Alongside her

research interests, she is a member of Shell Science Council and the Science and Technology Advisory

Council to NPL. She is also a member of the US National Academy of Engineering.

12:10-12:55 Plenary Session (The Elgar Concert Hall, Bramall Music Building)

Speaker: Professor David Mooney, Harvard University, USA Building immunity with biomaterials

Chair: Professor Liam Grover, University of Birmingham

Plenary Lectures

Tuesday 28th March 2017

13:30-14:15

Plenary session (Elgar Concert Hall, Bramall Music Building)

Speaker: Professor Ian Noble, Senior R&D Director, Mondelez, UK Designing for our future food system

Chair: Professor Peter Fryer, FREng, University of Birmingham

Monday

Professor Ian Noble, Mondelez R&D, UK

Meeting the Challenges for the Future of our Food - engineering a more sustainable Global

Food System

Our 20th Century Industrial Food System succeeded in preparing low cost, convenient foods, where

preference and cost were key drivers. The new challenges ahead of us are far more complex. Now

we must address sustainable uses of raw materials and energy, together with new targets for

consumer needs, which include long term health as well as short term pleasure. Success will depend

on meeting the aspiration of consumers to be both delighted and well nourished, whilst re-assuring

them of their future well-being – posing new questions and challenges.

I lead the Global Category Product Platforms Group for Chocolate focused on delivering the strategic

innovation and renovation agenda for brands including Cadbury’s Dairy Milk and Milka around the

world. I am also fortunate to be the site leader for the Bournville R&D Centre in Birmingham.

Prior to joining Mondelez, I led the Global Emerging Snacks Technology group for PepsiCo R&D based

across R&D Centres in Shanghai, Leicester, Plano (Texas) and Monterrey (Mexico) creating and

delivering new technologies for non-Core products. Previous roles included the Global Snacks R&D

strategy lead and Europe Foods Innovation R&D group.

I joined PepsiCo in 2007, from Unilever where I was latterly the Global FoodService Beverages R&D

Director having joined the Colworth House research laboratory completing my PhD in Biochemical

Engineering in 1994 and worked in Sri Lanka, Japan, China, France, the Netherlands and the UK, from

background research to commercial market leadership, and introduced Open Innovation into Foods

R&D.

13

Keynote Lectures

Keynote Lectures

Monday 27th March 2017

14:00-14:30

Keynote session on Product Engineering (WG5, Aston Webb A Block)

Speaker: Professor David York, FREng, University of Leeds

The engineering of formulated products

Chair: Professor Ian Norton, University of Birmingham

Professor David York FREng, University of Leeds, UK

The Engineering of Formulated Products

The traditional role of the chemical engineer is someone who designs and develops the processes that

make a diverse range of chemicals at full scale based on their expertise in unit operations, chemical

reaction equilibrium and kinetics and scale up. In doing so they have to take into consideration health

and safety and cost issues.

Formulated products, however are purchased by customers for their functionality rather than their

chemistry. This functionality can be achieved by a variety of different chemical components. In addition

a key property that influences functionality is the physical structure of the product. This structure is

heavily dependent on the process conditions as much as the material properties of the components.

Indeed engineering such structures by physical processes are not only cheaper but also allow

structures that cannot be achieved by chemistry manipulation alone.

The skills to do this are part of the chemical engineer’s toolbox with their knowledge of heat and mass

transfer, chemistry, scale up and the ability to create mathematical models. Thus this talk will discuss the

importance of the chemical engineer being involved in the design of formulated products at the very

start, and even in understanding the usage process to develop cost effective and customer preferred

products.

David holds the chair of Structured Particulate Materials at Leeds after 35 years as a research engineer at Procter and Gamble.

There he developed processes for the synthesis of novel formulated products from bench to plant start up and led a team of

engineers looking into novel technologies to radically change the market, one of which led to the multi billion business involving

water soluble unit dose products.


14:00-14:30

Keynote session on Energy Generation, Storage and Utilisation (Main

Lecture Theatre, Aston Webb C Block)

Speaker: Professor Nigel Brandon, FREng, Imperial College Electrochemical engineering for energy applications

Chair: Professor Robert Steinberger-Wilckens, University of Birmingham

Professor Nigel Brandon OBE FREng, Imperial College London, UK

Electrochemical Engineering for Energy Applications

The presentation will discuss the need for innovation in the way we produce and use energy, and the

role that electrochemical technologies can play in enabling the transition to a lower carbon energy

system. The presentation will draw on the authors own experience of developing fuel cell, hydrogen

and energy storage technologies to show the increasing opportunity for electrochemical technologies

in the energy sector, and in turn the growing need for electrochemical/chemical engineers able to

address this.

Nigel is an electrochemical engineer whose research interests are focussed on electrochemical devices

for energy applications. He heads the Sustainable Gas Institute at Imperial College London, is Director

of the Hydrogen and Fuel Cell Hub, Co-Director of the Energy SuperStore Hub, and founder of the UK

fuel cell company Ceres Power.

14

Keynote Lectures


14:00-14:30

Keynote session on Chemical Engineering Fundamentals (G33, Aston Webb B Block)

Speaker: Professor Omar Matar, Imperial College A fundamental approach to modelling multiphase flows: Correlations no more

Chair: Professor Mostafa Barigou, University of Birmingham

Professor Omar Matar, Imperial College London, UK

A Fundamental Approach to Modelling Multiphase Flows: Correlations No More

The ability to predict the behaviour of multiphase flows accurately, reliably, and efficiently addresses a

major challenge of global economic, scientific, and societal importance. These flows are central to

micro-fluidics, virtually every processing and manufacturing technology, oil-and- gas, nuclear, and

biomedical applications. Significant advances have been made in the numerical

procedures to simulate these flows; examples of these include the use of Large Eddy Simulations to

simulate turbulence, and interface-capturing or tracking techniques to deal with the free surface.

These codes have made progress in simulating the interaction of a turbulent flow field with an

interface, however, there remains a large gap between what is achievable computationally and

‘real-life’ systems; the latter are beyond what can be addressed with current methods. As a result, the

use of empirical correlations to bridge this gap remains the norm. We will present the latest on the

modelling framework that we are currently developing as part of the Multi-scale Examination of

MultiPHase physIcs in flowS (MEMPHIS) programme in order to minimise the use of correlations and

shift towards the use of numerical simulations as a truly predictive tool that can be used as a sound

basis for design. The framework features massively-parallelisable interface-capturing and front-

tracking methods, 3D, adaptive, unstructured meshes, and sophisticated multi-scale, multiphysics

models. Support from the Engineering & Physical Sciences Research Council, UK (grant no.

EP/K003976/1) is gratefully acknowledged.

Omar is a Professor in Fluid Mechanics in the Department of Chemical Engineering at Imperial College

London. He is a Petronas/Royal Academy of Engineering Research Chair in Multiphase Fluid

Dynamics, and a Fellow of the American Physical Society. He has co-authored over 200 refereed

papers, 5000 citations, h-index of 42, and over 55 invited talks. He is the Editor-in-Chief of J. Eng.

Math., and has received over £20m in funding from EPSRC and industry, including the £5m EPSRC

Programme Grant ‘Multi-scale examination of multiphase physics in flows (MEMPHIS)’. He is also the

Director of the Transient Multiphase Flow 18-company oil-and-gas consortium, and the Deputy

Director of an EPSRC Centre for Doctoral Training in Fluid Dynamics across Scales.

Tuesday 28th March 2017 Monday

09:55-10:25

Keynote session on Catalysis and Sustainable Green Chemistry (Main

Lecture Theatre, Aston Webb C Block)

Speaker: Professor Chris Hardacre, University of Manchester Non thermal activated catalysis

Chair: Professor Joe Wood, University of Birmingham

Professor Chris Hardacre, University of Manchester, UK

Non Thermal Activated Catalysis

This presentation will examine the use of non-thermal plasma activation of heterogeneous catalysts

for gas phase reactions. Specifically, the use hybrid plasma-catalysis for deNOx, CH4 oxidation and

low temperature water gas shift reactions will be shown using in-situ infra-red and x-ray absorption

spectroscopy to understand the effect of the plasma on the catalyst structure, surface species and

reaction mechanism.

Chris obtained his PhD from Cambridge University in 1994 and moved to Queen’s University, Belfast

in 1995. In 2016 he moved to the University of Manchester where he is Head of the School of

Chemical Engineering and Analytical Science. He is a Co-PI for the UK Catalysis Hub and has

published over 370 papers, 9 patents and 6 book chapters.

15

Keynote Lectures

Tuesday 28th March 2017 M

09:55 -10:25

Keynote session on Chemical Engineering at Interface (WG5, Aston Webb A Block)

Speaker: Professor Steven M Howdle, University of Nottingham Green polymers: chemistry and processing

Chair: Professor Paula Mendes, University of Birmingham

Professor Steven Howdle, University of Nottingham, UK

Green Polymers: Chemistry and Processing

The lecture will describe our development of new polymers from renewable resources and also the

use of scCO2 to create new polymers and new polymeric materials, via sustainable routes, for

applications from drug delivery through to paints and coatings.

Steve’s research focuses on sustainable chemistry and in particular on the utilisation of supercritical

carbon dioxide for synthesising new polymers and for innovative polymer processing. He has

published ~ 320 papers in this field and has commercialised his research through spin out company

Critical Pharmaceuticals focussed upon using scCO2 to prepare polymeric drug delivery devices.

Tuesday 28th March 2017 Mo

09:55-10:25

Keynote session on Biological Engineering (G33, Aston Webb B Block)

Speaker: Professor Nigel Titchener-Hooker, FREng, University College London The bioprocessing challenges of targeted healthcare manufacture

Chair: Professor Owen Thomas, University of Birmingham

Professor Nigel Titchener-Hooker FREng, University College London, UK

The Bioprocessing Challenges of Targeted Healthcare Manufacture

The past decades have seen biopharmaceuticals begin to dominate the drug development pathway and

already we can see potent biologics bringing benefits to populations on a truly impressive scale. There

remains much to do before we can claim however that the benefits of our burgeoning capabilities in the

life sciences are fully translated into treatments, delivered globally. That challenge, of enabling the

exquisite power of biologically-derived drugs and treatments to benefit world-wide populations, will

require significant engineering innovation. This talk will look at some of these development and

illustrate potential solutions driven by work from the Department of Biochemical Engineering at

University College London (UCL); a pioneer in the field.

Challenges will be used to illustrate the nature of the advances made and of the path ahead. The first is

the need to move rapidly from promising drug candidate to a robust and efficient process. Here UCL

created the concept of ultra scale-down (USD) which can enable process insights to be gained with a

few 10’s of mL of material.

Second is the need to make best decisions, be that at the level of technology choice or on a portfolio of

drugs for development. So called Decisional Tools have been deployed to address such questions and

to provide critical direction to research efforts as drugs move toward manufacture.

The talk will be supported with relevant industrial examples to demonstrate how our capacity to

engineer global biological solutions continues to advance the translation of exciting life science into

commercial outcomes.

Nigel is Dean of UCL Engineering and was for the past 7 years head of the Department of Biochemical

Engineering. He directs the EPSRC Centre for Innovative Manufacturing of Emerging Macromolecular

Therapies. This involves collaboration with an international consortium of 30 companies and is valued at

over £45M. As the first director of the Engineering Doctorate Centre for Bioprocess Leadership he

managed a portfolio of over 60 doctorate programmes with companies spanning the whole breadth of

the biotech industry.

16 16

Research Talks


14:40-15:20 Session on Product Engineering - Research Talks (WG12, Aston Webb A Block)

Chair: Professor Michael Adams, FREng, University of Birmingham

14:40-15:00 Professor Jonathan Seville, University of Surrey Effective nanoparticulate pharmaceutical products by supercritical fluid routes

15:00-15:20 Professor Malcolm Povey, University of Leeds Characterisation of powder by acoustic means

Research Talks

Product Engineering

17

Research Talks

Effective Nanoparticulate Pharmaceutical Products by Supercritical Fluid Routes

Jonathan Seville1* and Gray Leeke2

1 University of Surrey 2 University of Canfield

Email: [email protected]

A supercritical fluid (SCF) is a fluid above its critical temperature and pressure. SCFs possess low viscosity and

high diffusivity, and their density and solvent power are readily tunable by changing the temperature or pressure.

The most commonly used SCF is carbon dioxide (scCO2), because of its low critical conditions and high availability.

The use of this fluid is also carbon-neutral as the CO2 is captured from other industrial processes and can be

recycled in use. The interesting properties of SCFs have led to their exploitation in many different fields such as

extraction and chromatography.

Of relevance to this project is their use in particle engineering. Several techniques have been developed in which

nano and microparticles are produced using SCFs (particularly scCO2). These methods can be more attractive

than many conventional particle production techniques because:

1. Micro and nano particles with a narrow size distribution can be produced in one step;

2. The use of organic solvents can be eliminated or greatly reduced;

3. The processes can be less damaging to active substances;

4. The processes may produce products that are not obtainable by other means.

However, it is difficult to capture these small particles and preserve their properties during subsequent

processing. This work has therefore focussed on developing methods for collecting such particles directly from

SCF precipitation processes and incorporating them into a readily processable form. We have successfully

processed both real pharmaceutically active materials in this way and demonstrated that the resulting products

are more available as a result. Specifically, small, precipitated drug particles have been collected/coated onto the

surfaces of pharmaceutical excipients (the non-active components of pharmaceuticals) to form products that can

be readily converted into dosage forms such as tablets. This work has resulted in the development of a process

which we hope will remove one of the major blocks in the acceptance of SCF particle production in industry - the

difficulty of integrating the particle formation step into conventional downstream processes.

18

Research Talks

Characterisation of Powder by Acoustic Means

Malcolm Povey

University of Leeds


Ultrasound is a promising technique for the characterization of powders since ultrasound velocity is strongly

controlled by the effective frame modulus of the powder. Experimental data is presented on the propagation of

ultrasound through detergent powders in a variety of states between free flowing and a solid cake and the

dramatic changes observed are explained in terms of acoustic propagation theory. This provides a fully

quantitative approach to the characterization of powders in a variety of conditions.

The technique involves robust and economic transducers which are capable of transmitting sound through a

cardboard detergent pack. The technique also works under flow as well as in beds which need not necessarily be

compacted.

19

Research Talks


Early Career Industrial Research

16:00-17:30 Session on Early Career Industrial Research (Main Lecture Theatre, Aston Webb C Block)

Session Chairs: Professor Hugh Stitt, FREng, Johnson Matthey and Professor Raffaella Ocone, FREng, Heriot-Watt University

16.00-16:20 Anna Watson, AstraZeneca, UK The collaboration between chemical engineers and chemists to produce medicines sustainably

16.20-16:40 Sam Wilkinson, Johnson Matthey Technology Centre, UK Understanding the parameters behind powder flow modelling

16.40-17:00 Jerome Castro, Procter & Gamble Technical Centres Limited, UK Practical experiments and experience on the ajax twin screw mixer from coating to agglomeration

17.00-17:30 Raffaella Ocone, FREng, Chair of IChemE’s Research Committee, Heriot-Watt University Early Career Researchers’ Forum – Introduction and Launch

20

Research Talks

The Collaboration between Chemical Engineers and Chemists to Produce Medicines

Sustainably

Anna Watson

AstraZeneca


AstraZeneca's purpose is to push the boundaries of science to deliver life changing medicines. In delivering that

purpose successfully, we must consider the impact of our medicines on the planet in terms of their natural resource

use and the environmental safety of the medicines themselves.

One of the simplest definitions of sustainability is “Being in business for the long term and deservedly so”. This

definition captures two key elements: the long-term delivery of a particular enterprise's purpose, and delivering in

such a way that society and all its stakeholders deem us worthy to continue.

Chemical engineers and chemists are at the heart of delivering a sustainable future for AstraZeneca. This article

discusses the procedures, targets and tools used to ensure sustainability. Firstly, green chemistry is adopted during

route design to ensure our active pharmaceutical ingredients (APIs) are constructed in an efficient manner with due

consideration of the burden of the route. We have observed many occasions where close chemist-engineer

relationships have been the pivotal contribution to success.

Various tools and guides are used during process development. For example, the solvent selection guide allows

chemists to specify required characteristics for a solvent (chemical functionality, physical properties, environmental,

regulatory) and provides an appropriate shortlist from a collection of 272 solvents. The shortlist generated can be

refined further based on simulation and experimentation. The other tools are discussed in the article.

The article discusses a recent case study which demonstrates all embodiments of sustainability across the

development portfolio: good process chemistry, use of green chemistry tools and metrics, elimination of hazardous

substances and review using lifecycle analysis (LCA).

Finally, the article looks to the future, to the new chemistry and chemical engineering challenges of continuous

processing and non-classical therapeutic agents such as oligonucleotides and antibodies.

21

Research Talks

Understanding the Parameters behind Powder Flow Modelling S. K. Wilkinson, S. A. Turnbull, Z. Yan, E. H. Stitt and M. Marigo

Johnson Matthey Technology Centre, PO Box 1, Belasis Avenue, Billingham, Cleveland, TS23 1LB, UK


In engineering modelling, numerous parameters sit behind both empirical (correlation) and fundamental models.

Depending on the case, a given parameter (value) could have a significant impact on the predictive capability of the

model and therefore its value (as an input) should be confidently understood. Statistical and sensitivity analysis

methods have been commonly applied in areas such as chemical reaction kinetics, where uncertainties in

underpinning kinetic rate constants can have a huge impact on factors such as reactor sizing and safety (e.g.

prediction of thermal runaway scenarios). In this paper we turn our attention to a very different field, prediction and

understanding of powder flow behaviour, where improved modelling confidence can in turn lead to better design of

processes such as powder transportation, tabletting and milling.

Discrete element method (DEM) based on the description of the microscopic contacts between a number of discrete

particles is widely used to predict bulk powder behaviour from single particles. However, input particle parameter

calibration is still a challenging concern for a precise DEM modelling [1]. In previous work it has been demonstrated

that a statistical methodology can be used to understand the impact of DEM input parameters where the link

between these parameters and output responses were considered at 3 levels, i.e., empirical, semi-empirical and

mechanistic [2]. In the present study, we apply a similar statistical methodology by simulating a Freeman FT4 powder

rheometer (Freeman Tech., Malvern, UK).

In a Freeman FT4 rheometer the flowability of a powder is reflected by the force and torque necessary to drive the

impeller upwards and downwards during standard test cycles [3]. The objective of the current work is: (1) to

understand the influence of input single particle properties on bulk powder responses; and (2) to explore the

possibility of using the FT4 for DEM model calibration purposes in real powder processes.

In this work [4], the flow energy tests with FT4 were modelled using LIGGGHTS Open source DEM code [5]. A Hertz-

Mindlin model was employed to model inter-particle contacts, and the Johnson-Kendall-Roberts model was

incorporated to account for the particle cohesion. A parametric study on the impact of the input particle properties

(namely: Young’s modulus E, restitution coefficient ε, cohesion energy density k and inter-particle static /rolling

friction coefficients µs/µr) on the flowability of monosized spherical particles (d = 2 mm) was carried out first using a

Design of Experiments (DoE) approach. In this approach a full, half and quarter factorial DoE was used, to ascertain

the extent of simulations that need be carried out to gain a good understanding of key system parameters. These

designs contained 35, 18 and 10 simulations respectively, and the merits of each are evaluated in this paper.

It is shown that both force and torque responses are highly sensitive to variation in inter-particle static friction

coefficient, and to a lesser extent, rolling friction coefficient. The restitution coefficient is insignificant. When the

Young’s modulus is at a high value the cohesion energy density is insignificant; when it has a lower value the cohesion

energy density can have a very significant effect, showing an interaction between the two parameters.

References:

[1]M. Marigo and E.H. Stitt, Discrete Element Method (DEM) for Industrial Applications:Comments on Calibration and Validation for the

modelling of Cylindrical Pellets, KONA Powder & Particle Journal, 32 (2015) 236-252

[2] Z. Yan, S.K. Wilkinson, E.H. Stitt, M. Marigo, Discrete Element Modelling (DEM) input parameters: understanding their impact on model

predictions using statistical analysis, Computational Particle Mechanics (2015), 2, 3, 283-299

[3] R. Freeman, Measuring the flow properties of consolidated, conditioned and aerated powders—a comparative study using a powder

rheometer and a rotational shear cell, Powder Technology 174(1) (2007) 25-33

[4] Wilkinson S.K., Turnbull S., Yan Z., Stitt E.H., Marigo M., A parametric evaluation of powder flowability using a Freeman rheometer through

statistical and senstivity analysis: A discrete element method (DEM) study, Comp. and Chem. Eng., 97, (2017), 161-174

[5] Kloss, C. Goniva, A. Hager, S. Amberger, and S. Pirker, Models, algorithms and validation for opensource DEM and CFD–DEM. Progress in

Computational Fluid Dynamics, an International Journal, 12(2) (2012) 140-152

22

Research Talks

Practical Experiments and Experience on the Ajax Twin Screw Mixer from Coating to

Agglomeration

Jerome Castro1*, Clare Martin1, Ruksanna Ahmad2, Thomas Coyle2, Sylviane Bartkowiak2, Immanuel Sebastine2, Simon

Fields3, Mark Water3 and Eddie Magee3 1Procter & Gamble Technical Centres Limited, Newcastle Innovation Centre, NE12 9BZ UK

2Centre for Process Innovation, National Formulation Centre, Sedgefield TS21 3FD 3Ajax Equipment, Bolton, BL2 2AR


Funded through the Chariot Consortium, a continuous particle/ powder granulation pilot plant capability at CPI has

been set-up, featuring two scales of Twin Screw Continuous Mixer from Ajax Equipment and several powder and

liquid feeders, including different analytical tools such repour density, particle size measures, ERH and FT4 Powder

Rheometer. The mixers in CPI have been designed with enough capabilities and flexibilities to allow a good range of

R&D development. This includes variable blades and angles, variable mixer tilt, multiple feeding ports, and multiple

top and bottom liquid ports, different configurations thereof.

The following study, reports a collection of basic practical experiments, observation and experiences that have been

learned on the Ajax Mixers through the CPI pilot plant facility, with applications ranging from simple dry mixing, to

coating to granulation of model particles and liquids. The report will include observed effects when playing with blade

angles from forward angles to back mixing, it will share experiences on top spraying vs. bottom addition of liquids,

basic liquid to powder integration and how fundamental concepts such as K. Hapgood’s Spray Flux model can help

overcome oversize growth. It will also report observations on effects of fill level and tip speeds and share basic pulsed

RTD techniques that our university partners have used to enable a more detailed study of the mixing phenomena.

The aim overall is to excite on what’s possible.

23

Research Talks

Monday 27th March 2017 M

Energy Generation and Utilisation

16:00-16:40 Session on Energy Generation, Storage and Utilisation- Research Talks (WG5, Aston Webb A Block)

Chair: Professor Robert Steinberger-Wilckens, University of Birmingham

16:00-16:20 Qilei Song, Imperial College London Functional microporous membranes for energy and environmental applications

16:20-16:40 Mojtaba Mirzaeian, University of the West of Scotland Investigating the root-cause of unsatisfactory performance of the Li/air battery: The electrochemical

performance analysis of the battery under different operation conditions

24

Research Talks

Functional Microporous Membranes for Energy and Environmental Applications

Qilei Song

Imperial College London


Sustainable energy and clean environment are key global challenges in the 21st century. Breakthrough technologies

and step-change materials are desirable for energy and environmental processes, such as natural gas production and

conversion, renewable energy production and storage, CO2 capture, catalytic production of renewable fuels, and

water purification and desalination. Novel functional nanomaterials hold great promises for solving these global

challenges.

I will introduce our recent work on novel microporous materials, such as metal-organic frameworks (MOFs), polymers

of intrinsic microporosity (PIMs), and porous organic cages (POCs), which are promising for a wide range of

applications in separations, catalysis, and energy storage. I will present our work on synthesis and fabrication of these

materials into membranes and understandings of their structures and properties, particularly selective molecular

transport for gas separation, water desalination, nanofiltration, and selective ion transport for battery applications.

We developed a range of techniques to design microporous membranes, such as polymer/MOF nanocomposites,

photochemical modified and crosslinked PIM polymers, and solution-processed porous organic cage membranes, and

polymer nanofilm membranes by in situ polymerisation. Molecular sieve membranes derived from PIMs polymer

show ground-breaking separation performance gas separation and molecualr separation in organic solvents. I will

also highlight the broad potential of microporous materials and polymer membranes for energy conversion and

storage applications, such as ion-selective membranes for redox flow batteries, fuel cells, and advanced batteries.

References:

[1] M.F. Jimenez Solomon, Q. Song, K.E. Jelfs, M. Munoz-Ibanez, A.G. Livingston. Polymer nanofilms with enhanced

microporosity by interfacial polymerization. Nature Materials, 2016, 15 (7), 760-767.

[2] Q. Song, et al. Porous Organic Cage Thin films and Molecular Sieve Membranes. Advanced Materials, 2016, 28 (13),

2629–2637.

[3] Q. Song, et al. Nature Communications, 2014, 5, 4813.

[4] Q. Song, et al. Nature Communications, 2013, 4, 1918.

[5] Q. Song, et al, Energy & Environmental Science, 2012, 5, 8359-8369.

25

Research Talks

Investigating the Root-Cause of Unsatisfactory Performance of the Li/Air Battery: The

Electrochemical Performance Analysis of the Battery under Different Operation Conditions

Mojtaba Mirzaeian

University of the West of Scotland


Because of their inherent simplicity in concept batteries are at the forefront of the electrical energy storage systems. Lithium based batteries possess the highest energy density, highest specific energy and highest operating voltage among the existing battery technologies, and are expected to play an increasingly important role in meeting the power requirements of upcoming systems. Commercial rechargeable lithium batteries use lithium transition metal oxides, typically LiCoO2, as cathode and graphite as anode. Their specific capacity is limited by the cathode and does

not exceed 200 mA h g-1

.

The capacity and level of energy storage of a lithium battery can be enhanced remarkably by using a completely different approach in which Li as anode is directly combined with oxygen as cathode active material in a Li/air cell assembly. The cell's air electrode is a composite electrode made of porous carbon, catalyst and binder in which several electrochemical and transport processes occur simultaneously. Oxygen accessed from environment is reduced catalytically on the electrode surface and the catalytically formed oxygen anions react with lithium cations supplied by the anode and delivered by the electrolyte to form Li2O2 within the porous structure of air electrode

during discharge process.

Despite a significant increase in its specific capacity and energy density, major challenges yet will have to be solved if a Li/air battery is to succeed. This study is aimed to identify root-cause of these major issues toward fixing the existing, unsatisfactory state of Li based cells and also understand their performance under different conditions to improve the battery's safety in practical applications where safety and reliability of the device is crucial.

The electrochemical performance of the Li/air battery under different operation conditions was investigated to elucidate the effects of discharge rate, discharge depth and charge taper voltage on the performance, state of charge and abuse tolerance of the battery.

Galvanostatic discharge profiles at various discharge rates showed that the effective capacity of the cell drops with increase in the discharge rate. However the cell's cycleability improved with increase in the discharge rate due to the ease of stripping the Li2O2

film formed on the electrode surface reversibly at higher rates, compared with the

incomplete removal of discharge products deeply formed within the pores at low discharge rates.

The performance of the cell discharged at different cut off voltages showed that decreasing the depth of discharge decreases the rate of capacity fade and improves the cell cycleability. Study of the cell performance at different charge taper voltages showed that the cell capacity increases with charge taper voltage for charge potentials up to 4.45 V. For charge potentials above 4.45 V, the cell performance deteriorates with increasing charge taper voltage significantly, probably due to the decomposition of the electrolyte at higher charge potentials. It is believed that a potential of 4.45 V is the edge of breakdown potential of propylene carbonate based electrolytes used in the battery and a discharge potential above this will result in the overcharge abuse of the cell.

26

Research Talks

Monday 27th March 2017 Mo

Chemical Engineering Fundamental 16:40-17:20 Session on Chemical Engineering Fundamentals - Research Talks (WG5, Aston Webb A Block)

Chair: Dr John Chew, University of Bath

16:40-17:00 Marcus Campbell Bannerman, University of Aberdeen SimCem: A thermodynamic toolkit for Python/C++

17:00-17:20 Daniele Vigolo, University of Birmingham Flow visualization of the trapping induced by vortex breakdown at a junction

27

Research Talks

SimCem: A Thermodynamic Toolkit for Python/C++

Marcus Campbell Bannerman

University of Aberdeen


Modern chemical engineering has thermodynamics at the core of every process model. Every calculation requires a

database of physical properties that are inserted into a "fluid package" to describe the phase behaviour and

energetics of the process. Both of these are readily available in process simulators such as HYSYS but are often

expensive. In addition, their programming interfaces are difficult to extend due to the use of outdated programming

approaches or cryptic interfaces. Free software for thermodynamic modelling is available but is often highly

specialised for one particular thermodynamic model/application or limited to ideal models.

Here, a new free thermodynamic package called SimCem is presented. SimCem is implemented in modern C++ and

has a Python interface to allow easy and natural access to standard models (currently ideal gas, incompressible

solids/liquids and cubic EOS). A basic database of thermodynamic properties is also included that allows the

immediate modelling of ideal gas and hydrocarbon systems and can be easily extended to other systems thanks to its

simple human-readable format (XML). Although only a limited number of fluid packages are currently available in

SimCem, the underlying framework uses a general approach to facilitate the development and implementation of

new thermodynamic models. Symbolic algebra is used within the code to generate all thermodynamic properties

from a single Helmholtz or Gibbs energy generating function for each model. Thus the thermodynamic equilibrium

solver does not need to be specialised for a particular model and extension is straightforward.

SimCem has already found application in cement chemistry research; however, this package can also be used to

enhance the delivery of programming courses within chemical engineering as it allows students to quickly and easily

incorporate fluid packages into their exercises. A range of web tools for teaching and research purposes are also

being developed and released on SimCem.com using the software. Currently available are combustion calculators and

cement thermodynamics tools, but fundamental teaching models (i.e. McCabe-Thiele distillation, pipeline simulation)

are also in development.

28

Research Talks

Flow Visualization of the Trapping Induced by Vortex Breakdown at a Junction

D. Vigolo1, M. Riccomi2, F. Alberini1, E. Brunazzi2, J. T. Ault3 and H. A. Stone3 1School of Chemical Engineering, University of Birmingham, B15 2TT, UK 2Department of Civil and Industrial Engineering, Università di Pisa, Italy

3Department of Mechanical and Aerospace Engineering, Princeton University, USA


Micro/milli-fluidic devices are becoming an important reference for several disciplines and are quickly increasing their

applications in scientific, as well as industrial, environment. Here we present experimental investigations of the

vortex breakdown happening at a T-, Y- or “arrow” shaped junction responsible for the trapping of light material

suspended in solution. Considering the ubiquitous nature of T-junctions and bifurcation in general, in industrial as

well as biological environments, it is extremely interesting to better understand how this trapping phenomenon

happens.

Once the dispersion of particles get trapped at the bifurcation, it remains for an indefinitely long time. This

phenomenon will induce an accumulation of low density material at the bifurcation. As a result, unwanted separation

may occur leading to a lower degree of mixing in the final product. Moreover, air bubbles accumulation (and

coalescence) will lead to the development of potentially dangerous air pockets within the flow. In particular, we

observed the flow profiles at different sections in order to perform a three-dimensional study of complex structures,

such as vortices and recirculation zones, that develop at a bifurcation. We explored Reynolds number ranging from 50

to about 500 for different milli-fluidic devices. Thus, we compared standard micro-PIV and a novel optical technique,

the Ghost Particle Velocimetry (GPV), that was recently introduced, to investigate the onset of vortex breakdown. A

performance comparison has been designed to underline the strengths and weaknesses of the two experimental

techniques. Moreover, the experimental results were compared with single-phase OpenFoam numerical simulations

performed in the same flow conditions.

29

Research Talks

27Monday 27th March 2017 Monday 27 March 2017

E

ngineering Interface

16:00-17:20 Session on Chemical Engineering at Interface - Research Talks (WG12, Aston Webb A Block)

Chair: Dr Frankie Rawson, University of Nottingham

16:00-16:20 Carmine D’Agostino, University of Cambridge NMR studies of gelatin structure alteration induced by swelling and solid particle permeation

16:20-16:40 Hosam Aleem, University of Manchester Incorporating sustainability considerations in the lifecycle of medical devices

16:40-17:00 Victor Sans, University of Nottingham 3D printing advanced reactors for the synthesis of silver nanoparticles

17:00-17:20 Bradley Ladewig/Jenny Wang, Imperial College Enantiomeric molecular separation via selective adsorption on metal organic frameworks

30

Research Talks

NMR Studies of Gelatin Structure Alteration Induced by Swelling and Solid Particle

Permeation

Carmine D'Agostino

University of Cambridge


Gelatin gels are increasingly involved in many industrial applications, such as scaffold for tissue engineering and drug

delivery, due to several advantages including cost efficiency and bio-compatibility. Generally, their treatment requires

the use of aqueous solvents, which cause a significant swelling, due to the ability of solvent molecules to penetrate

through gel macromolecules, affecting polymer structure, in particular by increasing its total volume. Nevertheless,

swelling mechanisms and their effect on gel structure are not totally understood. In this work, NMR diffusion and

relaxation techniques are used in order to probe molecular transport and dynamics within the gelatin structure. From

such measurements it is possible to infer new insights into micro-structural changes induced by swelling and

permeation of solid particles, hence relating this with changes at a more macroscopic level.

31

Research Talks

Incorporating Sustainability Considerations in the Lifecycle of Medical Devices

Hosam Aleem

The University of Manchester


The continuing rise in the global population and in particular the ageing of this population in the west is increasing the demand on healthcare provision. With the advancement in technology, healthcare is increasingly relying on medical devices including for diagnostic purposes (e.g. x-ray, Ultrasound, MRI), therapeutic (e.g. dialysis, pacemakers) or support (e.g. blood warmer, heart-lung machine). From a regulatory viewpoint medical device classification is primarily based on risk to the patient, but also risk to the medical practitioner. However, risk to the environment is not taken into consideration. The higher the risk to the patient, the more stringent the regulatory requirements are on the quality assurance of medical devices including in design, manufacture, testing and use. Consequently, sustainability considerations are viewed as by medical device manufacturers as yet another design constraint. However, with the current awareness of the limitation of natural resources and the impact of human activity on the environment, we cannot afford to ignore such issues anymore. Furthermore, improving the sustainability of medical devices, may in the long term render them more economically beneficial, by including the whole lifecycle of the device into consideration rather than just its medical use. This should ultimately widen their availability, helping to meet the aforementioned global rise in demand for healthcare.

In this work we investigate the impact of incorporating sustainability considerations into medical device design and usage. The approach taken is that of Life Cycle Assessment (LCA) of the device to identify hotspots in the life cycle, allowing changes to be made to areas with a higher impact on sustainability. In doing so carbon footprint is used as a low level indicator of sustainability, calculated using the widely used software CCalc. The lifecycle covers the device from extraction of raw materials to decommissioning. Carbon footprint was calculated before and after suggesting changes to device design and utilisation.

Two medical devices of varying complexity were analysed. Firstly a scalpel was used as a simple example to test the concepts. The change suggested in the usage was to deploy reusable blades, which would require sterilisation prior to each reuse. This demonstrates the trade-off in cost and environmental impact between the savings in raw material and the energy required for sterilisation. The use of recycled material was also studied.

Secondly a blood warmer was then studied where, in addition, more complex changes were investigated to improve its sustainability. Those included the use of bioplastics for tubing, disposable versus rechargeable batteries (including material savings and energy expending as above) and heating element options..

The findings of this study show that sustainability considerations can indeed be incorporated into medical devices while at the same time reducing cost in the long term, however, some changes may increase risk to the patient. Hence, very careful analysis and close collaboration with medical professionals is necessary when dealing with more complex devices, to ensure that no additional risk to the patient is unwittingly introduced. Whilst cost and sustainability can be improved these factors must never come before patient safety.

32

Research Talks

3D Printing Advanced Reactors for the Synthesis of Silver Nanoparticles

Victor Sans

University of Nottingham


In this contribution, our recent efforts to develop advanced reactor engineering concepts employing 3D printing will

be presented. Additive manufacturing, commonly known as 3D printing is becoming an increasingly popular

manufacturing technique due to the possibility to generate tailored and complex geometries in a rapid and cost

efficient manner. The application to of this technique to develop simple fluidic devices has been recently

demonstrated. Nevertheless, the potential for developing mesoscale chemical reactors with advanced mixing

features is hugely underexplored. As a case study, the development of mesoscale continuous-flow oscillatory baffle

reactors (mCOBR) employing stereolithography (SLA) will be presented. The high resolution of the printer allows

printing complex features, such as baffles and threads in a very precise fashion, thus enabling the development of

reactors which would be extremely hard by any other manufacturing technique. The efficient mixing at the macro

and microscale is demonstrated by synthesising silver nanoparticles with very narrow particle size distribution in a

mCOBR in a highly controlled and stable fashion.

33

Research Talks

Enantiomeric Molecular Separation via Selective Adsorption on Metal Organic

Frameworks

Bradley Ladewig



Separation of racemic drugs is of great significance in producing effective and safer pharmaceuticals since most of

enantiomers have different pharmacological and toxicological properties, but at present it is a significant challenge to

achieve the resolution of raceme economically and efficiently. The last two decades have seen a growing trend

towards metal organic frameworks possessing high porosity and large specific surface areas, and within this field,

synthesis of chiral metal organic frameworks is an increasingly important area in separating racemic pharmaceutical

drugs. Because the diversity coordination of the central metal ions and carboxylic acid, these self-assembled

crystalline materials have shown great potential to achieve the diversity of structures and multifunction. While some

research has been carried out on chiral metal organic frameworks, only a small number of them have proven to be

both excellent adsorbents for one enantiomer of a racemic mixture, and also strong enough to be applied in industry.

This study therefore sets out to synthesise a wide range of robust and more porous homochiral metal organic

frameworks to selectively adsorb enantiomers. The influence of different conditions such as temperature, pH and

different solvents will be investigated and the separation conditions will be optimised in order to achieve the highest

possible separation factor. Single Crystal X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Fourier

Transform Infrared Spectroscopy (FTIR) will be used to test the microstructure of the metal organic framework

materials and the heat stability of the samples will be measured by Thermogravimetric Analyzer (TGA). A pair of

chiral metal organic framework materials based upon zinc nitrate hexahydrate and L-lactic acid (L-lac) ligands, and an

organic connector terephthalic acid, have been prepared by the solvothermal reaction. The performance of

[Zn2(bdc)(L-lac)(dmf)] separating racemic mixtures of 2-Butanol and 1-phenylethanol were studied via optimizing

different desorption solvents, adsorption time, and the molar ratio of L-lactate acid. Enantioselective excess (ee)

toward 2-Butanol and 1-phenylethanol were determined by GC with ee values of up to 32%. For sorption experiment,

longer adsorption time leads to a better ee. Also, the molar ratio of L-lactic acid can be optimal within a certain small

range. Although the current study is based on a small sample of experiments, the findings suggest the metal organic

frameworks of [Zn2(bdc)(L-lac)(dmf)] have promising capability for the separation of alcohol enantiomers. One of the

more significant findings to emerge from this study is that the crystal materials of [Zn2(bdc)(L-lac)(dmf)] have the

potential to achieve a good separation of pharmaceutical enantiomers. Future research should therefore concentrate

on the investigation of the separation of racemic drugs and how to apply this technique in industry.

Keywords: Racemic drugs, metal organic frameworks, L-lactic acid

34

Research Talks

Tuesday 28th March 2017

Biologi

cal Engineering

11:40-12:20 Session on Biological Engineering – Research Talks (G33, Aston Webb B Block)

Chair: Dr Robert Falconer, University of Sheffield

11:40-12:00 Owen Thomas, University of Birmingham Mixed polyelectrolyte brush surfaces display ‘chameleon-like’ protein binding and elution properties

12:00-12:20 Oleksiy Klymenko, University of Surrey Designing an artificial golgi reactor to improve the efficacy of therapeutic proteins

35

Research Talks

Mixed Polyelectrolyte Brush Surfaces Display ‘Chameleon-Like’ Protein Binding and

Elution Properties

Owen Thomas

University of Birmingham


By tethering two oppositely charged smart polymer chains, poly(2-vinyl pyridine) and poly(methacrylic acid), adjacent

to one another on a support at high grafting density, we have succeeded in generating high capacity adsorbents,

which in response to discrete changes in environmental pH have the 'Chameleon-like' ability to reversibly transform

between anion exchange, hydrophobic mixed mode and cation exchange functionalities. Here we: (i) introduce the

mixed polyelectrolyte (PEL) brush concept and what is known about pH induced changes that occur in mixed PEL

layers; (ii) describe manufacturing approaches we have used to create well-characterized mixed PEL brush modified

adsorbents; (iii) illustrate the effects of pH, brush composition, polymer chain length and inter-graft spacing on the

selectivity of binding of anionic, neutral and basic proteins out of a four protein mix (ovalbumin, beta-lactoglobulin,

carbonic anhydrase, lysozyme); and finally (iv) show the effectiveness of `pH shift only' and salt-mediated elution of

bound protein species from mixed PEL adsorbents.

36

Research Talks

Designing an Artificial Golgi Reactor to Improve the Efficacy of Therapeutic Proteins

Oleksiy Klymenko

University of Surrey


The use of mammalian expression systems for the production of biopharmaceuticals has enjoyed substantial growth in recent years in comparison with their microbial counterparts. This trend has been driven by the higher safety and efficacy of human or humanised glycoproteins compared with those derived from non-mammalian systems. Mammalian systems, however, have a number of drawbacks including slow growth rates, low productivity, sensitivity to shear stress, and complex growth medium requirements. Moreover, the distribution of glycoforms (i.e., sugar chains (glycans) covalently attached to the protein backbone) resulting from these systems is typically highly heterogeneous so that a significant fraction of glycoproteins may be less effective than the target glycoform.

In contrast, non-mammalian cell-based systems exhibit much faster cell growth and product expression rates while being less sensitive to mechanical stress and requiring much simpler medium formulations. However, despite significant progress in engineering prokaryotic and lower eukaryotic cell factories, it is extremely difficult to ensure optimal expression of the relevant enzymes to achieve homogeneous product with target human-like glycoform. It has been proposed, however, that posttranslational modification of glycans can be performed after the expression by employing the relevant enzymes in an in vitro environment. Therefore, combining the benefits of glycoprotein expression from robust and efficient non-mammalian hosts with glycosylation in an Artificial Golgi reactor (AGR) may offer significant enhancement both in product quality and quantity through better control and reproducibility of the glycosylation process in vitro in line with the Quality by Design paradigm.

Using chemical engineering principles, we propose here an approach to the design and optimisation of such artificial reactors based on detailed mathematical models of mass transport and enzymatic reactions therein focusing on monoclonal antibody (mAb) therapeutics. Three potential configurations of an AGR have been considered for in vitro glycosylation of mAbs based on the expected relative rates of mass transport and enzymatic reactions: (i) a microcapillary film reactor, (ii) packed bed reactor with non-porous pellets, and (iii) packed bed reactor with porous pellets. All three designs are based on a sequential application of immobilised enzymes catalysing the different stages of glycosylation to achieve their complete spatial segregation thus reducing the number of possible glycan structures. Geometrical and operational parameters of the reactors have been optimised using the developed mathematical models to ensure sufficiently high conversion levels in each reactor compartment and thus eliminate alternative pathways leading to undesired terminal species to direct the whole process towards the desired glycan structure. The three AGR designs have been thoroughly characterised theoretically and shown to achieve target glycoform at a

predefined conversion level although the particular choice may depend on additional process or economic

constraints. The modular design concept and principles underlying the models and reactor optimisation approach can

be easily extended to cover any number of individual enzymatic steps and may find applications to enzymatic

reaction design in other areas of biochemical engineering

37 37

3-Minute Research Highlight Talks


3 Minutes Research Highlight Talks

Product Engineering

14:30-15:20 Session on Product Engineering: 3-Minute Research Highlight Talks (WG5, Aston Webb A Block)

Chair: Dr Tom Mills, University of Birmingham

14:30-14:35 Vaclav Svoboda, University of Strathclyde Continuous co-crystallization of benzoic acid and isonicotinamide by mixing-induced supersaturation:

Exploring opportunities between reactive and antisolvent crystallization concepts

14:35-14:40 Joesry El Hebieshy, University of Surrey An experimental investigation of size induced segregation during die filling

14:40-14:45 Jianyi Zhang, University of Surrey The effect of water content on mechanical properties of microcrystalline cellulose and mannitol

powders

14:45-14:50 Toni-Bianca DiPaolo, University of Birmingham The formulation of a suspending vehicle

14:50-14:55 Xiaotong Zhang, University of Birmingham Preparation and characterisation of antifouling and antiseptic microcapsules

14:55-15:00 Ravenna Lessa Matos, University of Birmingham Supercritical precipitation and coating of curcumin on lactose surface for pulmonary delivery

15:00-15:05 Wael Ebrahim, University of Leeds Single droplet drying at high temperatures

15:05-15:10 Dimitris Karampalis, University of Birmingham Dissolution phenomena of spray dried powders by single particle approach

15:10-15:15 Jeng Yi Chong, Imperial College London Ceramic/ stainless steel composite hollow fibre membranes for water treatment

15:15-15:20 Alberto Almena Ruiz, University of Birmingham Modelling, simulation and economical evaluation of dry food manufacture at different production

scales

38


Continuous Co-Crystallization of Benzoic Acid and Isonicotinamide by Mixing-Induced

Supersaturation: Exploring Opportunities Between Reactive and Antisolvent

Crystallisation Concepts

Svoboda Vaclav

CMAC, Univeristy of Strathclyde


Multicomponent crystalline materials are composed of more than one molecule in its crystal lattice. This

includes co-crystals, solid solutions, solvates, and salts. The interest in multicomponent systems is a growing

trend within the pharmaceutical industry. Co-crystals are of benefit due to their ability to tailor physical and

pharmaceutical properties of active pharmaceutical ingredients (APIs) such as solubility, bioavailability,

stability, and the processability of the solid powder within industrial manufacturing processes [1]. They can

also be utilized to expand IP portfolios. However, co-crystallization is inherently more complex than single

component crystallization as it involves an additional component with new potential solid phases. Having

additional components and related process variables makes navigating the phase diagram and crystallization

process more challenging.

This study combines reactive and antisolvent crystallization concepts to demonstrate a wider range of options

for solvent system selection in multicomponent crystallization. This approach was applied to investigate

continuous crystallization of 1:1 and 1:2 co-crystals of benzoic acid and isonicotinamide [2]. Design of

Experiments approach was used to identify conditions where pure co-crystal phases are obtained. Based on

this the continuous mixing-induced co-crystallization process was implemented to selectively produce either

1:1 or 2:1 co-crystals.

References: [1] Domingos S, André V, Quaresma S, Martins ICB, Minas da Piedade MF, Duarte MT. New forms of old drugs: improving without changing: New forms of old drugs. J Pharm Pharmacol. 2015 Jun;67(6):830 -46. [2] Seaton CC, Parkin A, Wilson CC, Blagden N. Controlling the formation of benzoic acid: isonicotinamide molecular complexes. Cryst Growth Des. 2008;9(1):47 -56.

39


An Experimental Investigation of Size Induced Segregation during Die Filling

Joesry El Hebieshy



Segregation of powder mixtures during manufacturing can have a detrimental effect on the product quality.

Die filling is a widely used manufacturing step in many industries, including metallurgy, the pharmaceutical

industry and the ceramics industry. There is an increasing demand in industry in understanding and predicting

segregation behaviour during die filling, in order to ensure the quality of end products that are generally

manufactured with powder mixtures. In the present study, we developed a segmented die and experimentally

investigated the segregation tendency of three binary mixtures of two monodisperse spherical particle

powders during die filling. The components of the mixtures had a mean particle size of 150 µm and 500µm but

with a similar true density. Various composition ratios between the two powders, namely, 1:3, 1:1 and 3:1

w/w, were considered. The results revealed that a fluidization segregation mechanism dominates die filling

processes, where the smaller particles are forced to the top of the die due to the entrainment of the air

escaping from the die. It was also shown that the speed of the shoe had a substantial effect on the segregation

tendency, especially in the upper half of the die where an increase in shoe speed caused an increase in the

abundance of coarse particles. The initial composition ratio of the mixtures, on the other hand, had only a

minor effect on the segregation tendency.

40


The Effect of Water Content on Mechanical Properties of Microcrystalline Cellulose

and Mannitol Powders

Jianyi Zhang and Chuan-Yu Wu

Department of Chemical and Process Engineering, University of Surrey, Guildford, GU27XH, UK


Moisture exists at most of stages during the tablet manufacturing process, and water molecules interact with

pharmaceutical powder all the time. The water-powder interaction was reported as one of the main factors

affecting the powder properties and the compressed tablet quality. Hence a good understanding of the impact

of water content on powder behaviours during compression and tablet relaxation behaviours is vital to

optimize the quality of the final products. In this study, two common pharmaceutical excipients,

microcrystalline cellulose (MCC PH 102) and mannitol SD 100 powders were selected to demonstrate the

influence of water content on material properties of plastic and brittle powders, respectively. The powders

were stored in an environmental chamber for more than 24 hours to achieve different water contents before

the compression. Heckel and Kawakita equations were used to analyse particle rearrangements,

compressibility and in-die material recovery. The material relaxation in storage and the tablet tensile strength

obtained from diametrical compression were also examined. The results reveal that

(1) Comparing with mannitol SD 100 powder, MCC PH 102 powder had better ability to absorb water from

surroundings. Its water content increased from 4.2 % to 10.9 % when the relative humidity was raised from 10 %

to 85 %. On the contrary, the water content of mannitol SD 100 powder remained stable at about 0.8 % at

different relative humidity.

(2) For MCC PH 102 powder, the water absorbed in the powder softened the powder bed, which increased the

material compressibility, particle breakage possibility and in-die material recovery. In storage, tablet with low

water content (e.g. 4.2 %) showed material expansions but tablets with high water content (e.g. 10.9 %)

exhibited material shrinkage behaviours instead. The tensile strength of tablets also significantly decreased as

the water content increased.

(3) For mannitol SD 100 powder, although the apparent water content in mannitol powder was independent if

the storage humidity, but the powder stored at higher relative humidity showed better compressibility and

particle breakage in the compression. The tablet also exhibited more intensive volume shrinkage than that

made of dry powders.

41


The Formulation of a Suspending Vehicle

Toni-Bianca DiPaolo



Pharmaceutical specials are commonly used as an alternative dosage form for those who cannot or are unable

to swallow solid dosage forms, such as tablets. They are prepared by dispersing the Active Pharmaceutical

Ingredient (API) or a compounded unit dose into an appropriate liquid, the suspending vehicle, producing an

oral liquid dosage form. In a hospital setting, up to 67 % of children are given a specials prescription [1-3] with

this figure rising to 90 % in paediatric and neonatal intensive care units [1,3,4].

However, the stability of pharmaceutical specials is a major concern. Due to their poor stability and short

shelf-life, specials are currently prepared as soon as an order is placed, or a prescription received.

Consequently, this is time consuming, inefficient and not cost-effective. Therefore, it is desirable to produce a

novel, stable suspending vehicle which allows for specials to be prepared in advance, left on the shelf, and

used when required.

In order to formulate a desirable suspending vehicle, an AR2000 cone and plate rheometer (TA Instruments)

was used to determine the rheological behaviour of current commercial suspending vehicles. In addition, the

ingredients of popular suspending vehicles were researched in order to ascertain the fundamental categories

of ingredients, as well as the areas in which novel, alternative ingredients were required. From this initial

research, the criteria for the novel formulation was obtained; a shear thinning fluid containing certain

categories of ingredients with a defined viscosity range, similar to that of the commercial vehicles. Following

this, a method for the formulation of a novel vehicle was developed at lab scale with a variety and

combination of different ingredients being used.

A potentially unique, novel vehicle has been formulated at lab scale. It has comparable results to the

commercial vehicles in terms of rheology, viscosity and aesthetics, with some additional benefits. The method

is now being replicated at larger scales using 2 L and 5 L mixing vessels of standard configuration and geometry.

Mixing rule studies looking at the effect of mixing parameters such as impeller speed, mixing time and

temperature have been carried out and the optimal parameters for mixing decided upon. Once the final

formulation is confirmed, stability, suspendability and compatibility tests involving both the suspending vehicle

on its own and with the API suspended in it will be carried out.

References:

[1] S. Conroy et al., Survey of Unlicensed and Off Label Drug Use in Paediatric Wards in European Countries, BMJ 320, pp.79 -82, 2000. [2] J. McIntyre et al., Unlicensed and Off Label Prescribing of Drugs in General Practice, Archives of Disease in Childhood 83, 498-501, 2000. [3] B. Horen et al., Adverse Drug Reactions and Off-Label Drug Use in Paediatric Outpatients, Journal of Clinical Pharmacology 54, pp. 665-670, 2002. [4] A.J. Nunn, Making Medicines that Children can Take, Archives of Disease in Childhood 88, 369-371, 2003.

42


Preparation and Characterisation of Antifouling and Antiseptic Microcapsules

Xiaotong Zhang, J. F. Hu and Z. Zhang



Wind power is a type of sustainable energy, which can be generated using wind farms constructed offshore.

However, equipment for such power generation tend to suffer from corrosion and surface fouling by marine

microbes. Capsaicin has been found to repel microbes. The objective of this study is to achieve sustained

release of capsaicin from microcapsules, which can be incorporated in coating for protection of surfaces of

equipment for wind power generation. Microcapsules consisting of a core of capsaicin and shell of cellulose

acetate butyrate (CAB) were prepared using a solvent evaporation method, which was based on emulsification

of oil in aqueous phase in a stirred vessel with a Rushton turbine and a Silverson high shear mixer respectively.

The effects of formulation and processing conditions of the microcapsules on their surface morphology,

structure, size, encapsulation efficiency, payload of the active ingredient, mechanical properties and its release

rate in aqueous environment have been investigated using a range of experimental techniques, including

scanning electron microscopy (SEM), transmission electron microscopy (TEM), Malvern particle sizing, UV/VIS

spectrophotometry and micromanipulation respectively. It has been found that the microcapsules prepared by

both the mixing devices were spherical and had smooth surface. Microcapsules with varying mean size in a

range of tens of microns and size distributions were obtained, and using the Silverson high shear mixer overall

generated microcapsules with narrower size distributions than the stirred vessel with a Rushton turbine. The

typical encapsulation efficiency and payload were 86 % and 17 % respectively. The micromanipulation

measurements show that the microcapsules were strong and did not show clear rupture under compression

for applied forces up to 547 mN, which is equivalent to nominal stress of 35.5 MPa. The release experiments

indicate that sustainable release of capsaicin over 6-12 months was achievable because of its low solubility in

water and a good barrier property of the microcapsule shell. The details of the experimental results and their

significance will be presented.

43


Supercritical Precipitation and Coating of Curcumin on Lactos Surface for Pulmonary

Delivery

Ravenna Lessa Matos



The Supercritical Antisolvent (SAS) process was integrated with a fluidized bed under pressure to develop dry

powder formulations suitable for pulmonary delivery. The single-step process allows for the simultaneous

precipitation and coating of active pharmaceutical ingredients on the surface of excipients. In this work,

curcumin was used as model drug and lactose as model excipient. The following process parameters were

investigated: pressure, varying from 80-130 bar; temperature, with values from 35-50 °C; drug/lactose mass

ratio, from 1 % to 6 %. Ethanol was used as solvent. Curcumin-lactose composites were analysed in terms of

surface morphology, drug content uniformity and coating yield. Due to the high degree of mixing, a uniform

coating of drug onto lactose surface was achieved with coating yield between 82-95 %. The process yield was

higher than 93 % in all cases.

44


Single Droplet Drying at High Temperatures

Wael Ebrahim

University of Leeds


Spray drying is not solely a process for removing water; it is a particle formation process, the product of which

will have certain property and performance requirements. Control and manipulation of the created

particle/film structure during spray drying is critical for the successful development of products with enhanced

properties. For this reason, the study of particle structure during drying has attracted significant interest along

the years, focusing on predicting dried particle structure, properties and drying rate based on droplet drying

history. In the case of drying above boiling temperature, the estimation of final size, structure/morphology and

density of the dried particle becomes even more challenging. This is because when the particle’s temperature

rises above the boiling point, bubble nucleation, growth and collapse within the droplet can have a significant

effect on the final structure and the drying rates of the droplets. For these systems, only limited studies were

reported and a deeper understanding of behavior across a wide drying history, drop size, initial slurry

concentration and material property space is still lacking. This is due to the very complex nature and

limitations of the experimental methods which slows down experimentation and doesn’t allow for drying small

droplet sizes or materials with high viscosity.

This project aims to develop experimental and modelling methods that enable dried particle structure,

properties and drying rate to be predicted based on droplet drying history, particularly focusing on effects

driven by boiling. A characteristic drying curve model (CDC) and a diffusion based model were used to

determine when boiling occurs. The models include four main variables namely air temperature, initial

moisture content, critical moisture content and droplet size. The conditions at which the droplet reaches

boiling has been determined, specifically focusing on the moisture content at the boiling temperature as

function of air temperature. The results demonstrate that the moisture content at the boiling increases with

increasing temperature. It was also shown that the initial moisture content have little to no effect on the

moisture content at which the droplet boils. The modelling results obtained will be used as a basis for future

drying experiments which are to be carried out on a single droplet drying rig currently being constructed. This

rig will be used for the assessment of morphologies, transformations and drying behavior under simple

isothermal drying to gain initial understanding and experience with the systems before conducting a more

complete mapping across a wide range of process conditions, initial water content and initial drop size.

45


Dissolution Phenomena of Spray Dried Powders by Single Particle Approach

Dimitris Karampalis



Particle dissolution is a commonly occurring process in powder industry. The aim of the presented work was to

develop a novel analytical method based on optical microscopy to understand spray-dried powder dissolution

experiments from a single particle approach. Dissolution process of individual particle was observed using an

inverted light microscope with Peltier stage to control solvent temperature. Recorded images were analyzed

using Image Processing to extract dissolution profiles based on surface area changes as a function of time. SEM

and XRT results show that particles with the same ingredients but produced with different slurry mix moisture

during spray drying process form different morphology and microstructure across the size range. Distinguished

dissolution phenomena including wetting, disintegration, diffusion have been detected and significantly

magnified from the microscale scope providing a deeper understanding of porous particle dissolution.

Significant differences on disintegration phenomena and dissolution behaviors has been observed, which

probably can link slurry mix process to dissolution mechanism from the chemical point of view. The release

rates calculated by Noyes-Whitney equation were used to predict bulk particles dissolution profiles. The

comparison between these profiles and those measured by conductivity meter further proved the feasibility of

our approach. Results show that image analysis of single particle dissolution can be used as an accurate tool

for the prediction of bulk particle dissolution profiles.

46


Ceramic/ Stainless Steel Composite Hollow Fibre Membranes for Water Treatment

Jeng Yi Chong, Bo Wang and Kang Li

Barrer Centre, Department of Chemical Engineering, Imperial College London, UK


Stainless steel is an attractive material for membrane applications due to its excellent mechanical strength and

chemical resistance. Compared to inorganic materials such as ceramic, stainless steel is highly ductile and is

easy to handle at industrial scale. Porous stainless steel hollow fibres have been successfully fabricated by

phase inversion methods [1]. While some work has been done to study the sintering conditions [2-3], the

improvement in achieving smaller pore size of stainless steel hollow fibres is still limited, constraining their

practical applications especially in water treatment. In our study, a phase-inversion assisted co-extrusion

technique has been used to fabricate dual-layer ceramic-stainless steel hollow fibres in one step. The inner

layer consists of stainless steel, provides a strong mechanical strength to the hollow fibres. The outer layer is a

mixture of stainless steel and yttria-stabilized zirconia, creating a separating layer for the hollow fibres. The

mean pore size of the hollow fibre membranes prepared by this method can be reduced to approximately 300

nm. This is much smaller than what reported in previous studies where the pore size is generally larger than 1

µm [4]. The pure water flux of the dual-layer stainless steel hollow fibre membranes can reach as high as 3000

LMH bar-1 making it attractive for water treatment applications.

Keywords: Hollow Fibre, Stainless Steel, Water Treatment

References:

[1] M. Luiten-Olieman, et al., Porous stainless steel hollow fiber membranes via dry - wet spinning, Journal of Membrane Science, 2011. 370: 124-130. [2] D. Schmeda-Lopeza, et al., Stainless steel hollow fibres - Sintering, morphology and mechanical properties, Separation and Purification Technology, 2015. 147: 379-387. [3] W. Rui, et al., Effects of sintering atmospheres on properties of stainless steel porous hollow fiber membranes, Journal of Membrane Science, 2015. 489: 90-97. [4] M. Wang, et al. Fabrication, characterization and separation properties of three-channel stainless steel hollow fiber membrane, Journal of Membrane Science, 2016. 515: 144-153.

47


Modelling, Simulation and Economical Evaluation of Dry Food Manufacture at

Different Production Scales

Alberto Almena



We belong to the era of globalization. Over the past century, the tendency of the industry evolved from small

manufacturers spread over cities or villages, to centralized production processes, taking advantage of the

economy of scale by lowing the production costs down in the manufacturing process of a good. However, a

contrasting method is under study, defined as a comeback to small artisan production well distributed that

could bring advantages in terms of society benefits, quality improve, environmental impact and, why not,

economical as well. This is call distributed manufacturing and its success has been proved recently in several

industries, such as automotive industry or brewery sector, with promising results.

In this work, as a case study of dry food manufacture, a model for the design, simulation and optimization of

an entire plant for dry baby porridge production is developed. Starting from the composition of the recipe and

the targeting the maximum moisture content, a flowsheet is built comprised by all the stages needed for the

dry porridge production. These processing steps are the milling of raw materials, dry mixing of cereals, water

addition for a later gelatinization, drying process and steam generation, cooling, additional ingredients mixing

and packing. The model is used to analyse profitability, energy consumption and CO2 emissions across a range

of production rates, i.e. 0.5 kg/h to 6300 kg/h. Three scales of production have been set: homemade, catering

manufacturing and plant production. Catering scale has been thought as multiple scattered homemade

kitchens. Thus, the manufacturing process for the two first groups differs from the industrial one, choosing an

artisan-making way for baby food.

Depending on the throughput required, an optimal manufacturing scenario is found, i.e. homemade

production is advised from 0.5 kg/h to 15 kg/h, catering is the most profitable from 15 kg/h to 200 kg/h and

above that, plant production has the highest net profit. However, the range of application for the catering

scale can be extent to a wider range, up to 500 kg/h, as its production cost remains at the same slightly higher

than plant production one, while keeping extremely lower initial investment. In addition, the introduction of

transport cost in future work will support to widen the range of profitability for the catering scale even more.

With regard to plant scale evaluation, the major energy consumption of the process corresponds to the drying

step, reaching a 75 % of the total energy supply at higher production capacities. Thus, choosing the proper

dryer model and operation conditions is essential for an optimized design. Usually, main energy in food

processing is needed for water phase changes, so a sensitivity analysis of the variation in the economics due to

water concentration is carried out at plant scale. An important increase of the investment required is obtained

when water content in gelatinization step increase from 80 w% to 90 w%, especially at production capacities

over 2000 kg/h. In addition, the model is able to compare multi-plant production and address the efficiency

loses due to multi-product manufacturing.

48



Energy Generation, Storage and Utilisation

14:30-15:20 Session on Energy Generation, Storage and Utilisation: 3-Minute Research Highlight Talks

(Main Lecture Theatre, Aston Webb C Block)

Chair: Professor Shanwen Tao, University of Warwick

14:30-14:35 Erin Johnson, Imperial College London Greening Britain’s gas: supplying homes with biomethane and hydrogen via the gas grid

14:35-14:40 Mohamed Al Jamri, University of Manchester Integration of renewable energy sources into petroleum refining for sustainable production of

transportation fuels

14:40-14:45 Duo Zhang, University of Surrey Lattice Boltzmann simulation of liquid-gas two-phase flow and oxygen diffusion in polymer-electrolyte

membrane fuel cell

14:45-14:50 Qasim Mushtag, University of Nottingham Metal organic framework membranes for natural gas purification

14:50-14:55 Ioannis Kalargaris, University of Surrey An experimental investigation of the effects of fueling a DI diesel engine with plastic pyrolysis oil

14:55-15:00 Jäger Nils, Institute Branch Sulzbach-Rosenberg, Germany Storable energy carriers beyond the electricity marked: Thermo-catalytic reforming (TCR®) to

contribute to the present energy challenges

15:00-15:05 Qinghua Yu, University of Birmingham Thermo-mechanical analysis of microcapsule containing phase change material (PCM) for cold

storage

15:05-15:10 Jason Cho, University College London Nature-inspired fractal flow field for PEM Fuel Cells

15:10-15:15 Andrea Paulillo, University College London Life cycle assessment of reprocessing of spent nuclear fuel in the UK

15:15-15:20 Mark Anthony Caro, University of the Philippines Los Baños, Philippines Optimization of dilute sulfuric acid saccharification of steam exploded pineapple peels for bioethanol

production

49


Greening Britain’s Gas: The Potential for Supplying Biomethane and Hydrogen via the

Gas Grid to People’s Homes

Erin Johnson



How do you heat your home now? How will you heat your home in the future? Can you do it in a way that doesn't cost the earth or change your way of life?

Greenhouse gas emissions from residential heating must be slashed to near zero to meet 2050 targets. This will be a major challenge since 30% of UK energy is for residential heating [1]. 12% of the UK's emissions come from gas-fired residential heating alone [1,2,4]. It was thought that all this should be powered by renewable electricity, but it is now becoming clear that it might be impractical, expensive and take too long [2,4]. The electricity grid supplies only 20% of UK energy [1] and peak winter heat demands are several times what the electricity grid can provide. Homes would need new heat pump systems, streets would be dug up to install larger cables, and vast amounts of additional storage and low carbon generation would be required just for winter. Britain relies heavily on natural gas with one of the most comprehensive gas networks in the world, a valuable asset for 23million homes. Instead of switching entirely from gas to electricity, can we switch from natural gas to low-carbon green gas?

Biomethane from anaerobic digestion is established in Britain but limited by resource availability. However, manufactured bio-synthetic natural gas has considerable potential due to a wider resource base. Surplus renewable electricity could be converted to hydrogen through water electrolysis. Hydrogen manufactured from natural gas has the most potential for large-scale low-cost rollout if carbon capture and storage (CCS) was rolled out. Ultimately, hydrogen could be carbon negative if made from biomass with CCS.

To maximise benefits, gas network operators must adapt to changing compositions and distributed producers within an increasingly integrated supply chain. If green gas is pursued, a range of whole system benefits can be realised. Less peak electricity generation, storage and system upgrades would be needed and a financially sustainable level of gas network utilisation ensured, ultimately providing good value to the consumer. Perhaps the greatest benefit is that consumers get to keep boilers in their home, which will maximise uptake and allow emissions to be reduced quickly.

This presentation outlines the main technology options for revolutionising gas supplies and looks at the challenges and opportunities for a green gas system. It will be argued that green gas transported via the existing public gas network must be pursued to provide low-carbon, affordable and reliable heat with minimal consumer disruption. It challenges the perceived wisdom of fully electrifying domestic heat and offers solutions which make the most of our country's existing assets and resources. Green gas systems can help build a better life and a better world - providing clean, affordable and familiar energy.

Reference: [1] BEIS, Energy Consumption in the UK, 2016 [2] CCC, Next Steps for UK Heat Policy, 2016

[3] DECC, UK Greenhouse Gas Emissions, 2016

[4] KPMG, 2050 Energy Scenarios, 2016

50


Integration of Renewable Energy Sources into Petroleum Refining for Sustainable

Production of Transportation Fuels

Mohamed Al Jamri

University of Manchester


The integration of renewable resources in the transportation fuel system requires the investigation of resource

compatibility with existing infrastructure and the exploitation of potential integration points within the

transportation fuel system. Recent work has been focusing on the exploitation of second generation biomass

feedstock in the production of liquid fuels via gasification and pyrolysis processes.

Gasification destroys the biomass chemical building blocks to form carbon monoxide and hydrogen, while

pyrolysis focuses on the conversion of biomass polymers (cellulose, hemicellulose and lignin) into simpler

materials in the form of dense viscous oil (bio-oil). This research is concerned with the second processing

option, since it allows the assessment of several integration options within conventional petroleum refineries,

in particular hydroprocessing upgrade processes. The research focuses on developing a systematic

methodology for the modelling of bio-oil hydrotreating and hydrocracking processes on molecular scale using

Molecular Type and Homologous Series matrix (MTHS) approach. This approach is based on the

characterisation of the various types of molecular attributes found in bio-oil using an optimisation/regression-

based approach to capture the largest possible number of molecules present. The capability of this

characterisation approach is illustrated using several case studies. Reactor models are then constructed based

on large scale and complex reaction networks synthesised using the MTHS matrix framework. The outcome of

this project is expected to help in better characterisation of the various molecular structures present in bio-oil

and better understanding of its hydroprocessing kinetics, leading to a detailed, molecular-level models that

can allow effective optimisation of biomass processing and can be linked to conventional refinery hydrogen

network models.

Keywords: Hydrotreating, Hydrocracking, bio-oil, biomass, refinery, MTHS matrix

51


Lattice Boltzmann Simulation of Liquid-Gas Two-Phase Flow and Oxygen Diffusion in

Polymer-Electrolyte Membrane

Duo Zhang



Polymer electrolyte membrane fuel cell (PEMFC) has higher efficiency and energy density and is capable of

rapidly adjusting to power demands. Effective water management is one of the key issues for increasing the

efficiency of PEMFC. In the current study, a lattice Boltzmann model is developed to simulate the water

intrusion and oxygen diffusion in polymer-electrolyte membrane fuel cell with electrochemical reaction on the

catalyst layer taken into account. The carbon paper gas diffusion layer is reconstructed using the stochastic

method. Coupling two-phase flow field with concentration field enables this model with the capability to

achieve the accurate information of concentration of oxygen and current density distribution when water

penetrate into the gas diffusion layer. In this paper, this model is used to investigate the effect of microporous

layer on the cell performance. The results clearly show that the liquid water content can be reduced with the

existence of microporous layer and thus the current density can be increased. The developed lattice

Boltzmann model is useful for studying chemical engineering systems that have multi-phase flows and reaction.

52


Metal Organic Framework Membranes for Natural Gas Purification

Qasim Mushtaq and Begum Tokay

Chemical & Environmental Engineering Department, Advanced Materials Research Group, Faculty of

Engineering, University of Nottingham, NG7 2RD, University Park Campus, Nottingham, UK


Carbon dioxide is a contaminant in natural gas that lowers the calorific value of the gas and causes acidity

leading to corrosion of pipelines and in the presence of water. Polymeric membranes are the first

commercialised examples because of their ease of manufacture. However, of the hundreds polymeric

membranes developed only a small number have reached commercial scale as there is a trade-off between gas

permeability and selectivity, described by the Robeson's upper bound [1]. Moreover, gases like CO2 plasticize

the polymer chains; weaken the structure mechanically that impedes gas selectivity [2].

Metal organic frameworks (MOFs) are self-assembling hybrid structures that contain inorganic and organic

units that can be tailored for specific application [3]. They possess ultra high porosity, surface area, and gas

uptakes [4 - 7]. A subclass of MOFs is zeolitic imidazole frameworks (ZIFs) with similar topology to zeolites with

high thermal and chemical stabilities. There is a huge potential of growth in the area of MOF membranes for

CO2 capture because of the limitless combination of its constituents providing allowance for pore size to be

tuned.

Although MOF synthesis is relatively straightforward, MOF membrane manufacturing has many challenges.

Without any additional substrate modification, heterogeneous nucleation density is low that leading to weak

bonding between the organic subunit and substrate surface [4, 8-12]. Surface modification has adopted to

promote heterogeneous nucleation. One of the methods of surface modification is seeding in order to induce

nucleation and crystallisation of MOFs on the substrate surface [13] and increase the interaction between

MOF layer/substrate.

In this study, we investigated the effect of metal salts used during ZIF-8/ceramic membrane synthesis on the

performance of CO2 separation from methane. We also explored the effect of metal salt/linker concentration

on membrane microstructure. Activation conditions after membrane synthesis was also investigated.

Reactivity of the metal salt affects both particle size and crystal morphology of the ZIF-8 crystals and rate of

nucleation affecting the heterogeneous nucleation [14].

53


An Experimental Investigation of the Effects of Fueling a Di Diesel Engine with Plastic

Pyrolysis Oil

Ioannis Kalargaris



The explosive growth in plastic production has given rise to environmental issues that require urgent attention,

such as the depletion of crude oil and the disposal of plastic waste. Plastic waste which is a major component

of the municipal solid waste can be treated effectively and produce high quality oil. Besides addressing the

issue of plastic disposal, the production of high quality oil could also reduce global dependence on fossil fuels

at a time of ever-increasing energy demands. In the present work, a high quality oil was manufactured from

plastics through the pyrolysis process. The properties of the plastic pyrolysis oil were analysed, and found to

be comparable to those of diesel fuel. The oil was then used to fuel a four cylinder diesel engine, in different

blends with diesel and at various loads. The engine's performance, combustion characteristics and exhaust

emissions were measured in order to determine the optimal operating conditions. The experimental

investigation revealed that the engine was able to run on 100% plastic pyrolysis oil at high loads, although the

engine's ignition delay period was longer, the cylinder peak pressure and heat release rate were higher, and

the brake thermal efficiency was lower in comparison to diesel operation. Moreover, the plastic pyrolysis oil

produced greater quantities of all the measured exhaust emissions (NOx, UHC, CO and CO2). However, the

addition of diesel to the plastic pyrolysis oil was found to significantly improve all the engine characteristics.

These results suggest that under certain operating conditions, plastic pyrolysis oil is a viable alternative fuel for

diesel engines.

54


Storable Energy Carriers beyond the Electricity Marked: Thermo-Catalytic Reforming

(TCR®) to Contribute to the Present Energy Challenges

N. Jäger, A. Apfelbacher, R. Daschner and A. Hornung

Fraunhofer UMSICHT, Institute Branch Sulzbach-Rosenberg, Germany


The contribution of renewable energy sources to the United Kingdom and German energy requirements is

steadily increasing. In the last 15 years there was a significant growth in the contribution of renewable energy

production due to massive federal subsidies in Germany. However, the promotion of renewable energy is

focused on the electricity sector. The share of renewables in the heating and transport sectors have largely

stagnated. Fossil energy sources remain the dominant source of energy supply in these sectors and thus the

dependence on imported fossil fuels remains. To achieve the national and international climate objectives,

existing and new potentials have to be further developed.

The expansion of the renewable electricity generation is based on the extensive expansion and market

integration of fluctuating resources such as solar and wind. The rapid increase of these volatile power

generation capacities opens new potentials for storage solutions beyond the electricity market. Thermal and

chemical and storage technologies are going to be two significant building blocks in the successful

implementation of volatile power generation.

Against this background, Fraunhofer UMSICHT is carrying out research on a new procedure to convert biogenic

residues into valuable storable products. The Thermo-Catalytic Reforming (TCR®) technology is an

intermediate pyrolysis process combined with catalytic reforming as a second step. This novel staged-pyrolysis

reforming unit is converting residual biomass into storable carbon/climate neutral liquids fuels, gases, as well

as solid energy carriers for energetic or material purposes. Fraunhofer UMSICHT focuses on the integration of

this platform technology to contribute present energy, environmental and resource challenges.

The presentation will highlight the potentials and chances of the Thermo-Catalytic Reforming to contribute

present energy challenges beyond the electricity sector, by showing some of the most recent achieved

accomplishments. Developments to date of the Germany Energiewende will be pointed out in context of the

UK energy market. Within the scope of the conference, the focus will be on developed value chains and

product streams.

55


Thermo-Mechanical Analysis of Microcapsule Containing Phase Change Material

(PCM) for Cold Storage

Qinghua Yu



Cryogenic-temperature cold storage is one of the keys to improve the overall performance of the liquid air

energy storage (LAES) and pumped thermal electricity storage (PTES) systems. Microencapsulated phase

change materials in slurries (MPCMSs) have great potential application for cryogenic-temperature cold storage

as they combine the advantages of phase change materials (PCM) and liquid sensible storage materials.

However, most of the previous efforts are on moderate or high temperature MPCMSs with a melting point

above -20 ˚C. Little research activities on cryogenic MPCMSs can be found nationally and internationally.

Technically the cryogenic MPCMSs are more challenging than that of moderate temperature due to

deformation or fragility of the shell layer of microcapsules and poor heat transfer under cryogenic conditions.

A key to the success of MPCMSs in cryogenic temperature cold storage is the stability of microcapsules under

repeatable pumping and cyclic heating and cooling. The heat transfer behaviours of microcapsules directly

influence charging/discharging properties of cold energy into/from MPCMSs. In the present paper, a thermo-

mechanical model, based on energy conservation equations, pressure-dependent solid-liquid equilibriums,

Lamé’s equations and buckling theory, was established to describe the behaviour of a spherical microcapsule

containing PCM for cryogenic-temperature cold storage. The influences of shell thickness, initial inside

pressure and cooling rate on the solidification process of PCM is therefore studied for this specific geometrical

case, including the complicated interactions with freezing point of PCM. The pressure variation and shell

deformation (buckling) due to volume change during the solidification process are examined. The buckling

occurs only when the shell is thin enough and the buckling mode is dependent on the shell thickness. The

buckling mode predicted by the thermos-mechanical model agrees well with that observed by experiment.

56


Nature-Inspired Fractal Flow Field for PEM Fuel Cells

Jason Cho

University College London


One of the ongoing challenges faced by polymer electrolyte membrane (PEM) fuel cells for broader commercialization is the accomplishment of uniform gas distribution across the catalyst layer. Ensuring reactant homogeneity is essential to improve fuel cell efficiency and to forestall adverse side reactions that are detrimental to fuel cell longevity. Within the confines of the conventional flow fields, such as serpentine channels, this is an unavoidable consequence, due to reactant depletion across the channel and over the active area as a whole.

This work aims to address the issue by implementing a novel 3D flow field inspired by the fractal geometry of the upper respiratory tract of the human lung. The human lung has been shown to have an optimal architecture that uniformly distributes oxygen from the trachea to the alveoli. Furthermore, the human lung transitions between two flow regimes: 14-16 upper generations of branches dominated by convection, and 7-9 lower generations of space-filling acini dominated by diffusion. The upper generations of branches are designed to slow gas flow to a rate compatible with the rate in the diffusional regime (Pe ≈ 1) and the entropy production was shown to be uniformly distributed in both regimes.

Furthermore, the scalability of fractal networks helps to bridge multiple length scales by the addition of further generations. These characteristics that make the lung an optimal transport structure are all desirable for a PEM fuel cell. However, rather than uniformly distributing oxygen in a given volume, we wish to distribute the gases uniformly over a plane to ultimately deliver a uniform concentration of reactant throughout the catalyst layer.

The fractal pattern consists of repeating “H” shapes. The three-dimensional branching structure allows only the outlets of the fractal inlet channel to be exposed to the MEA, eliminating the reactant depletion along the channel, and thus providing uniform local conditions on the surface of the catalyst layer.

In this study, the reactant flow and cell performance were modeled for different numbers of fractal branching generation. Optimal performance was reached for branching levels N = 5. Based on the simulation results, three fractal flow field prototypes were produced via selective laser sintering (SLS), a «3D printing» method, each representing a branching generation level of N = 3, 4 and 5, and validated against a standard serpentine flow field.

The results suggest improved mass transport for the fractal flow fields at high current density, due to the homogeneous gas distribution. The fractal prototype with N = 4 generations demonstrated improved performance over the serpentine at all operating conditions investigated and a good correlation with the results predicted by the model. The worse-than-expected performance of for N = 5 generations at higher humidity level reveals insufficient convective liquid water removal due to the slow air velocity from each fractal outlet hampering effective diffusion within the porous medium.

The findings elucidate the need for implementation of active water management systems to alleviate flooding for the fractal flow fields, especially at higher generation levels where flooding is projected to be more pronounced.

57


Life Cycle Assessment of Reprocessing of Spent Nuclear Fuel in the UK

Andrea Paulillo



One of the biggest challenges facing the expansion of the Nuclear Energy is the lack of a sustainable - and

internationally agreed - approach for the management of Nuclear Waste. Life Cycle Assessment (LCA)

technique may help tackling this issue by evaluating and comparing alternative strategic options from a

sustainable perspective. The LCA, in fact, allows understanding and assessing the relations between

environment and human activities, by quantifying the potential impact of products over their complete life

cycle (from raw materials to final disposal). The life cycle - or “cradle to grave” - perspective represents LCA

main feature and also its main advantage over other environmental tools. The application of the LCA

technique to the nuclear field may support the decision-making process as well as contribute to improving

public attitudes towards the Nuclear Industry. Nonetheless, in the nuclear industry, LCA is either applied

poorly or not at all. The main reason may be found in the lack of a consistent and standardised approach for

assessing the impact of radioactive particles or materials released into the environment.

With this in mind, we have first developed a novel framework for assessing the impact of radioactive emissions,

both in terms of direct aerial and liquid releases and from solid waste stored in a Geological Disposal Facility.

This framework envisages four steps and assesses the impact of ionising radiation in terms of the risk of

detrimental effect to human beings. From this general framework, two alternative methodologies have been

derived and operationalised; they differ solely in the way transport of radionuclides from the release source to

the receptor is modelled. The general approach and the two alternative methodologies will be discussed at the

conference.

Furthermore, with the aim of validating the proposed framework, the UK current approach for Nuclear Spent

Fuel management is adopted as a case study. According to the approach proposed by Clift et al. [1], the system

is divided into two subsystems: Foreground and Background. The Foreground system includes all the

operations carried out at Sellafield site; for those, only `real' data collected on site are used. Besides the

radiological impacts, several other impact categories, including Global Warming Potential, are analysed.

Results of the study will show the overall environmental performance of the reprocessing procedure of spent

nuclear fuel in the UK, and will also allow identification of the stages that have the most environmental impact.

Particular emphasis will be given to the difference in terms of impact between direct radioactive releases and

solid nuclear waste as a means of comparison between reprocessing and direct disposal of nuclear waste. This

study represents a preliminary step towards a better understanding of the environmental impacts of different

options for nuclear waste management. Preliminary results of the LCA study will be presented at the

conference.

References: [1] R. Clift, A. Doig, and G. Finnveden, “The Application of Life Cycle Assessment to Integrated Solid Waste

Management,” Process Saf. Environ. Prot., vol. 78, no. 4, pp. 279 -287, 2000.

58


Optimization of Dilute Sulfuric Acid Saccharification of Steam Exploded Pineapple

Peels for Bioethanol Production

Mark Anthony Caro

University of the Philippines Los Baños


Energy production from renewable sources and waste reduction are two of the most pressing issues the world

faces. However, renewable energy production, while reducing waste, is either competing with food production,

or is too costly. In the present study, renewable energy generation was coupled to waste reduction. An

optimization study on the dilute acid saccharification of steam - exploded pineapple peelings for bioethanol

production was conducted using Central Composite Design (CCD). Three factors were considered in the study,

namely: solids loading, acid concentration, and reaction time. Factor screening was not employed, as the

factors and their corresponding ranges were chosen based on literature values. Reducing sugar yield (RSY) was

chosen as the response since it is directly related to saccharification efficiency, hence ethanol yield. Solids

loading was found to have negative effect on the response; whereas acid concentration has a positive effect

on the reducing sugar yield but up to a certain extent only. Reaction time has no effect on the reducing sugar

yield. A statistical model was developed using Response Surface Methodology (RSM) and the calculated

optimum conditions were: solids loading of 23.82 % (w/v), acid concentration of 1.86 % (v/v) and reaction time

of 80 minutes. Using the optimum conditions, the predicted reducing sugar yield of 57.52 % was obtained. This

was in good agreement with the experimental verification results of 57.24 % reducing sugar yield. The

theoretical ethanol concentration from this yield is 8.35 % (v/v).

59



Chemical Engineering Fundamentals

14:30-15:20 Session on Chemical Engineering Fundamentals: 3-Minute Research Highlight Talks

(G33, Aston Webb B Block)

Chair: Dr Bushra Al-Duri, University of Birmingham

14:30-14:35 Manuele Giovanni Romano, University of Birmingham Toward online rheology measurements in stirred vessels

14:35-14:40 Jonathan McDonough, Newcastle University A study of the flow structures generated by oscillating flows in a helically baffled tube

14:40-14:45 Louisa Ejim, Loughborough University Characterizing liquid-solid plug flows in meso-scale oscillatory flow tubes

14:45-14:50 Mandar Badvar, University of Birmingham Flow of gas-liquid foams through narrow complex passages

14:50-14:55 Mattia Turchi, University of Surrey/Unilever In silico modeling of complex drug formulations

14:55-15:00 Monalie Bandulasena, Loughborough University Production of biocompatible gold nanoparticles for drug delivery using droplet based glass capillary

microfluidic

15:00-15:05 Kaiqiao Wu, University College London Pattern formation in pulsed gas-solid fluidized beds: Insights from experiments and computations

15:05-15:10 Dimitrios Kontziampasis, University of Leeds

Coating particles using high viscous fluids and foams with non-ideal mixers

15:10-15:15 Tien Nguyen, University of Leeds Modelling the drying behaviour of polymeric droplets at high temperature

15:15-15:20 Ping Ding, University of Birmingham Foaming non-newtonian viscous liquid for particle coating

60


Toward Online Rheology Measurements in Stirred Vessels

Manuele Giovanni Romano1,2, E. Brunazzi1, M. Simmons1 and F. Alberini2 1Depeartment of Civil and Industrial Engineering, Universita di Pisa, I-56126 Pisa, Italy

2School of Chemical Engineering, University of Birmingham, B15 2TT, UK


The viscosity is an important parameter which is often used for quality control in the manufacture formulated liquid products. The blending of formulated fluids is a critical step, where changes in viscosity can drastically affect the overall performance of a process. Generally, formulated fluids are viscous fluids with complex rheological properties. When they are handled in stirred vessels, laminar or transitional regimes occur in the system. In laminar mixing conditions, large D/T impellers (~1) have been shown to be particularly effective for mixing of viscous fluids in stirred vessels. In the literature, there has been a lot of research investigating flow properties and performance of different impellers, such as Peters and Smith (1969), Murthy Shekhar and Jayanty (2003), Foucault, Ascanio and Tanguy (2005). Reynolds number is the standard non-dimensional number which is used to define the flow conditions of the system. For Newtonian fluids, it is calculated from a characteristic velocity, a characteristic length (diameter of the impeller), the density and the viscosity of the processed fluid. With non-Newtonian fluids, the approximation of an average viscosity in the system is not easy, since it is function of the shear rate which varies a lot inside the vessel. Authors often use the “effective viscosity” given by Metzner and Otto's model (1957), even if it refers to the region near the impeller only. In this work a new technique to characterize an average viscosity in a stirred vessel is proposed. The model takes in account the power input, the rheology of the fluid and the pressure oscillations at the wall of the vessel. Power input gives information about the regions near the impeller, the pressure oscillations give information about the regions near the wall and the fluid rheology model gives information about what happens in the bulk. The velocity field is computed using angle-resolved particle image velocimetry (PIV). Different fluids have been used; Newtonian fluids have been used as base case to validate the combined measurements of the torque and pressure at the wall, then fluids with more complex rheological behaviour (high elasticity, shear thinning and yield stress) have been investigated. All experiments have been conducted with an anchor impeller in laminar regime at comparable Reynolds numbers. The obtained flow measurements have been used to derive shear rates at the edge of the impeller and in the rest of the volume of the vessel. Torque measurements are used to calculate shear stress in the region near the impeller. Pressure measurements are used to calculate shear stress at the wall. Finally, a distribution of local viscosity is determined from the shear rate field and the shear stress field. The average viscosity (bulk viscosity) of the system then can be calculated from Kp, Po and Re. It is well established that Kp depends only on the geometry of the impeller and not on the fluid. Knowing Kp and the Po (from the Torque measurements) a reference global Reynolds number is calculated. The average viscosity is then compared to the viscosity distribution obtained from the PIV, torque and pressure at the wall measurements. The final aim is to develop statistical models which will allow the evaluation of a bulk viscosity at different impeller speeds by measuring torque and pressure at the wall and knowing the rheological flow curves of the fluid. This is a contribution towards online rheology in stirred vessels.

References:

[1] Irving H.F. and Saxton R.L., 1967, Mixing of high viscosity materials, in Mixing: Theory and Practice, Vol. II, V. W. Uhl and J. B. Gray,

eds., Academic Press, New York.

[2] Peters D.C. and John Smith M., 1969, Mixing in anchor agitated vessels. Can J Chem Eng, 47: 268 -271.

[3] Metzner A.B. and Otto R.E., 1957, Agitation of non-Newtonian fluids. AIChE J, 3: 3 -10.

[4] Murthy Shekhar S. and Jayanti S., 2003, Mixing of Power Law fluids using anchors: Metzner-Otto concept revisited. AIChE J, 49: 30-

40.

[5] Foucault S., Ascanio G. Tanguy P.A., 2005, Power characteristics in coaxial mixing: Newtonian and Non-Newtonian Fluids, Ind Eng

Chem Res 44: 5036-5043.

61


A Study of the Flow Structures Generated by Oscillating Flows in a Helically Baffled

Tube

Jonathan McDonough

Newcastle University


Oscillatory baffled reactors (OBRs) operate through the superposition of an oscillatory motion on to a net flow

in a tube fitted with baffles. The baffles disrupt the boundary layer at the tube wall, whilst oscillation results in

improved mixing through the formation of vortices. OBRs are therefore intensified reactors capable of

achieving plug flow at low flow rates (laminar regime) because they behave as many well-mixed tanks-in-series.

By exploiting this plug flow behaviour, mesoscale OBRs (characteristic 5 mm diameter) have subsequently

been applied as flow chemistry screening platforms using the time-to-distance transformation that plug flow

facilitates.

The selection of baffle type has implications regarding the “operating window” size for achieving plug flow.

This operating window has been described with the velocity ratio, ψ, which is the ratio of oscillatory velocity to

net flow velocity. For instance, smooth constrictions and axial discs are able to provide good quality plug flow

(defined as being equivalent to 10 or more tanks-in-series) when the velocity ratio is selected in the range of: 5

< ψ < 10. Helical coils on the other hand exhibit much wider operating windows for plug flow: 5 < ψ < 250. In

the OBR, radial motion as a consequence of vortex formation is responsible for minimising the amount of axial

dispersion that can take place. It has been hypothesised that when using helical coils, an additional swirling

element to the flow provides another mechanism to limit axial dispersion.

These swirling flows have previously been qualitatively identified, but in this study these flows were

investigated both numerically and experimentally using CFD and PIV for the first time. Comparison between

the numerical and experimental results was achieved by comparing the vortex areas and positions (using the

Q-criterion fields), and by comparing wall shear stress profiles (indicating flow reattachment points). In

summary, the laminar solver results were able to match the bulk flow features observed from the PIV

experiments.

The 3D flow structures obtained via simulation were subsequently visualised using isosurfaces of the Q-

criterion and streamlines. The characteristic feature is a helically shaped vortex that forms behind the baffle,

which is intrinsically linked with the swirling behaviour. Here, streamlines move both radially (wrapping

around the vortex structure) and tangentially. Using the swirl number and an analogous `radial' number, a

transition point between vortex-dominated and swirl-dominated mixing was observed providing evidence that

the working hypothesis is valid. Here, it was found that when the oscillation intensity is increased, the

tangential motion of the flow increases at a faster rate than the increase in radial flow because the sizes of the

vortices are limited by the column diameter. Thus, whereas the radial flow enhancement is limited in other

baffle designs (e.g. smooth constrictions and axial discs), the helical coil can still minimise axial dispersion

through swirl at high oscillation intensities.

62


Characterizing Liquid-Solid Plug Flows in Meso-Scale Oscillatory Flow Tubes Louisa N. Ejim1, Stephanie Yerdelen2, Thomas McGlone2, Alastair Florence2, C.D Rielly1 and Nuno M. Reis1, 3

1 Loughborough University 2 University of Strathclyde

3 University of Bath


Oscillatory flow reactors (OFRs) are a new generation of tubular mixing and reaction equipment uniquely

capable of combining continuous near plug flow with homogeneous particle suspension [1], yet the design of

OFRs for liquid-solid and multi-phase flow processes relies on rules established during the past 2-3 decades

from single, liquid-phase studies. A Design of Experiment (DoE) approach was herein implemented for

establishing the relationship between four key geometrical parameters of the inner tube baffles and both the

suspension of particles and the axial dispersion for liquid-solid continuous flows in a 10 mm internal diameter

(d) meso-scale tube. The parameters evaluated were the orifice open diameter (d0 = 0.35d - 0.50d); the open

cross section area (α = 0.12d -0.25d), constriction spacing (l = 1.5d - 3.0d) and baffle shape (sharp vs smooth

edged). A total of ten tubes were tested, five consisting of smooth periodic constrictions (SPC) and the other

five of sharp edged periodic constrictions (SEPC) according to a full factorial approach. Each tube was

experimentally evaluated via optical imaging of suspended mono-dispersed polyvinyl chloride (PVC) particles

that nicely mimic the flow properties of crystals. Both SPC and SEPC meso-tubes were capable of delivering a

near plug behavior, and the values of axial dispersion coefficient (Dc) estimated for the solids varied in the

range of 1.0-2.2×10-4 m2 s-1. In contrast, the minimum (critical) fluid oscillation conditions required for full

suspension of particles varied significantly, in general with the SPC tubes requiring up to 50 % lower amplitude

for effective particles suspension. Overall, the inner tube geometry requiring the lowest energy input for

homogeneous particle suspension and minimum Dc (i.e. sharpest residence time distribution) presented a l/d

= 3, d0 = 0.35d, α = 12 % and SPC design [2]. This study is believed to support the future design of optimized

meso-scale OFR systems for continuous screening and manufacturing of value-added liquid-solid and multi-

phase systems, such as catalytic and crystallization processes.

References:

[1] N. Reis, A.A. Vicente, J.A. Teixeira, M.R. Mackley, Chem. Eng. Sci., 59:4967 -4974 (2004). [2] L.N. Ejim, S. Yerdelen, T. Mcglone, I. Onyemelukwe, B. Johnston, A.J. Florence, N.M. Reis, Chem. Eng. J. 308:669-68 2(2016).

63


Flow of Gas-Liquid Foams through Narrow Complex Passages

Mandar Badve and M. Barigou



The flow of gas-liquid foams through gradually/suddenly contracting/expanding narrow channels, where both

bulk and interfacial properties are important, is challenging and technically important. These complex

geometries can have significant effects on foam structure and the flow regime, and may destabilise foam

structure, giving morphological transformations. For example, the industrial process of foam extrusion, or

discharge from a pressure vessel, can change foam texture by changes in gas volume fraction and/or bubble

growth, flow induced bubble coalescence/aggregation, and changes in liquid phase bulk and surface rheology.

These phenomena are not fully understood but are crucial in food processing, e.g. for ice cream flowing

through a nozzle. They are also important for flow in or filling of narrow vessels or channels with complex

cross sections. Thus a foam with inadequate rheological properties may not readily flow through narrow

passages and constrictions, giving poor `fill'. Relevant applications include foam-sclerotherapy for varicose

veins, flow of aerated confectionary in narrow channels and complex moulds, filling of cavities with insulation

foam, flow of foamed cement slurries in narrow oil-well annuli, filling of hollow aerofoil sections with

polyurethane foam to make aerodynamic tethers for communication and geoengineering applications, and

production of pre-insulated pipes for district heating. In this work, we study the phenomena associated with

2D and 3D aqueous gas-liquid foams flowing through 2D narrow channels containing sudden as well as gradual

contractions and expansions. Thus, foam behaviour is examined as a function of foam flowrate, initial bubble

size and flow constriction geometry and size. The effects on the entire flow field including foam liquid holdup,

foam pressure drop, foam velocity profile, and foam morphology and structure are reported.

64


In Silico Modelling of Complex Drug Formulations

Mattia Turchi

University of Surrey / Unilever


Emulsions are widely used personal care and drug formulation for enhancing the solubility and delivery of

functional ingredients. . Many experiments have been reported to evaluate how functional chemical

compound of interest can partition between phases. A great challenge is to predict the thermodynamic

properties of chemical solubility and partition in multiphase emulsions. Two methods widely used for the

prediction of the partition coefficient of solute in standard mixtures are UNIFAC and COSMO-RS. For complex

formulations of emulsions the structure of the aggregates formed after mixing is complex. The prediction of

the partition coefficient could be carried out by the determination of the Gibbs free energy profile through the

aggregate (micelle or micro-emulsion). Outlined here is an approach that could reliably predict both the

aggregate structures and the Gibbs free energy profile. Here the in-silico prediction of the partition coefficient

is achieved in two steps:

1) At first a molecular dynamic simulation (MD's) is performed to determine the micelle and emulsion

structure of the simulated system.

2) In the second stage the output coordinate file of the formed aggregate is processed in COSMOtherm to

determine the Gibbs free energy profile and so the partition coefficient through the whole structure of the

aggregate.

We report initial progress in predicting the partition of wide chemical space in a model SDS micelle system.

The predicted partition coefficient is then compared to published experimental data in order to evaluate the

accuracy and reliability of the methodology. Further work will be carried for real-world emulsion systems to

achieve a good agreement between calculated and experimental data. The overall aim is to establish an in-

silico methodology that could be used to speed up the design, screening and optimisation of emulsion based

formulations for enhanced delivery of personal care and pharmacokinetic benefits.

65


Production of Biocompatible Gold Nanoparticles for Drug Delivery Using Droplet

Based Glass Capillary Microfluidic

M.V.Bandulasena, G.T. Vladisavljević, H. Willcock and B. Benyahia

Loughborough University


Gold nanoparticles (AuNPs) are increasingly investigated in academia and industry alike because of their

unique properties amongst which biocompatibility, versatility and relatively easier synthesis and easier

detection. The biocompatibility feature makes AuNPs an excellent candidate for drug and gene delivery

applications while surface plasmon resonance makes them a good candidate for imaging and diagnostic

applications. Currently, the most common method to synthesise AuNPs is via batch-wise reduction reaction

between a gold salt and a reducing agent. The method suffers from several limitations particularly poor

control of both particle size and polydispersity due to poor control of mixing and batch-to-batch variation. The

objective of this research is to develop a reliable method for a continuous production of well controlled AuNPs.

As such, a chemical reduction of tetrachloroaurate trihydrate (gold salt) by ascorbic acid was carried out, at

room temperature, using a 2 phase reaction droplet based glass capillary microfluidic device. This method

showed enhanced control of the size and polydispersity index (PDI) compared to the results we obtained

previously using a single phase co-flow glass capillary microfluidic device (Bandulasena et al., 2017 –

submission stage for publication). The investigation showed that particle size strongly depends on the droplet

size as smaller particles were obtained with smaller droplets. One effective way to fine tune the droplet size

was achieved by manipulating the outer phase flowrate. In addition, smaller droplets can be obtained using

smaller collection capillary orifice diameter. Both methods were successfully used to synthesize AuNPs with

controlled size. As a future development, the method will be extended to the simultaneous synthesis and

functionalization of AuNPs (continuous integrated approach).

66


Pattern Formation in Pulsed Gas-Solid Fluidized Beds: Insights from Experiments and

Computations

Kaiqiao Wu



Bubbling gas-solid fluidized bed reactors have been widely used in various industrial applications, where fast heat and

mass transfer between gas and solids are desired. However, the mixing and transport properties, and the resulting

reactor performance, are intertwined with the complex bubble dynamics, which bring significant challenges in the

operation, design and scale-up of fluidized bed reactors [1].

By introducing additional degrees of freedom, the chaotic bed hydrodynamics could be manipulated to become more

ordered and controlled [2,3]. It has been demonstrated experimentally that pulsating the gas flow can lead to a

periodically ordered flow of bubbles [4]. In a quasi-2D bed, bubbles rise in a staggered fashion, forming hexagonal arrays

with a characteristic wavelength independent of the system dimensions. This striking phenomenon not only provides

great potential to controlled operation and scale-up of fluidized beds, but its occurrence also excels as a rigorous

validation tool for computational fluid dynamics (CFD) codes and the physics at the basis of these codes [5].

Since its first discovery, little progress has been achieved, and the fundamentals of pattern formation in fluidized beds still

remain largely unexplored. Missing the first principles that govern pure granular media, applying theoretical and

mathematical analysis becomes extremely challenging. Over the last two decades, computational codes have been

increasingly implemented to provide fundamental insights into granular flow. Nevertheless, it is remarkable that such

simulations were unable to convincingly reproduce the experimental observations for pulsed gas-solid fluidized beds until

now [5,6].

In this contribution, we discuss our latest insights on pattern formation in pulsed fluidized beds, obtained from both

experimental and computational studies. Our numerical results agree quantitatively with the experimentally witnessed

patterns, serving as reliable tools to analyse the pattern dynamics and to shed light on the underlying physics.

References:

[1] D. Kunii and O. Levenspiel. In Fluidization Engineering (Second Edition), Butterworth-Heinemann, Boston, 1991. [2] M.-O. Coppens and J.R. van Ommen. Structuring chaotic fluidized beds. Chem. Eng. J., 96: 117-124, 2003 [3] J.R. van Ommen, J. Nijenhuis, C.M. van den Bleek and M.-O. Coppens. Four ways to introduce structure in fluidized bed reactors, Ind. Eng. Chem. Res., 46: 4236-4244, 2007. [4] Y. Cheng, S. Kaart, C. M. van den Bleek, and M.-O. Coppens. Control of chaotic dynamics in a 2D fluidized bed by periodic gas injection, in: L. Glicksman (Ed.), Proc. of AIChE Annual Meeting 31: 312, 1999. [5] K. Wu, L. de Martín, L. Mazzei, M.-O. Coppens. Pattern formation in fluidized beds as a tool for model validation: a two-fluid model based study, Powder Technol., 295: 35-42, 2016. [6] X.S. Wang, M.J. Rhodes, Pulsed fluidization -- a DEM study of a fascinating phenomenon, Powder Technol., 159:142-149, 2005.

67


Coating Particles Using High Viscous Fluids and Foams with Non-Ideal Mixers

Dimitrios Kontziampasis1, Mohammed Soyeb Manga1, Jerome Castro2 and David York1 1School of Chemical and Process Engineering University of Leeds, LS2 9JT, UK

2P&G Technical Centres Limited, Newcastle Innovation Centre UK, NE12 9BZ, UK


One of the most important challenges in modern product engineering is to identify processes and methods

which lead to the efficient coating of particles using high viscous fluids in conventional non-ideal mixers

running in a continuous manner. Coating of high viscous liquids on particles has applications in several fields

which range from industry to science. Applications include controlled and targeted release, product stability

during storage and transportation, aesthetics, control of surface mechanical properties and several others.

In order to achieve coating of particles with viscous fluids, one needs to identify the mechanisms of coating as

opposed to agglomeration, segregation, and caking when liquids of different mechanical and chemical

properties are used. This study proposes the utilisation of foam systems which are based on high viscous

liquids, in order to coat model particles. Air is introduced as a component, thus lowering the liquid content and

subsequently allowing for better spreading of the liquid.

In order to understand the mechanics of coating particles with the use of foam systems, two different mixer

setups are used (paddle and twin screw) in a static batch operation. This is advantageous due to the fact that

the shear forces, as well as the mixer dimension of the two systems during mixing are completely different. A

comparative study between the mixers is performed in terms of coating quality as a function of various

engineering process parameters. The correlation of the two systems is investigated to indicate if particle

coating using foam systems can be predicted using a smaller lab-scale mixer. The final product’s coating quality

is analysed with the help of a home-made image analysis software. This software calculates the intensity of

coating on a large area of the sample, by doing a statistical analysis of the intensity of colour and colour

distribution.

Time, particle fill level, liquid/foam content, mixing speed are investigated towards the effect they have on the

coating process. The results show a good correlation between the two types of mixers in batch operation,

allowing for a scale up prediction of the process. The use of foam systems demonstrate more effective coating

compared to the liquid counterpart, if the mechanical properties of the foam system decrease its structural

strength.

In the latter stages the performance of a twin screw mixer continuous system is evaluated by comparing the

coating efficiency. Several different viscosities of initial liquids are used and compared to their equivalent foam

systems. This leads to a validation of the role of the mechanical properties of the foam system. The final

outcome is the confirmation of the hypothesis that the use of foam systems improve the coating efficiency of

particles comparing to that of the equivalent liquids in continuous systems. As in batch mode this applies to all

foam systems that have the appropriate desirable mechanical properties.

68


Modelling the Drying Behaviour of Polymeric Droplets at High Temperature

Tien Nguyen

University of Leeds


Spray drying is a widely used industrial operation in numerous manufacturing sector such as biochemical,

pharmaceutical, dairy and food products. The product's specifications, which depend mainly on final particle

morphology, vary across sectors hence demanding different optimization strategies. Methods for quick and

effective prediction of particle morphologies are required rather than the current time-consuming and high

cost experimental approaches. Currently, spray dryer models are based on simplified assumptions of single

droplet drying, where a system of billion drops is simplified down to one creating a quick and convenient

method to provide valuable information in terms of mass, moisture and temperature changes through the

spray drying process. However, the complicated morphological changes occurring during drying of single

droplet/particles are not typically captured. Consequently, the final particle morphology is not fully predictable.

This can only be achieved if a structural model is integrated into droplet drying kinetic models.

A model for polymeric droplet drying at high temperature is developed in the present work. The model

captures the advection of suspended solids and describes the viscoelastic properties of shell formed at boiling

temperature. It looks to understand how different behaviours of the polymeric shell during drying result in

different final morphologies, taking into account bubble nucleation, growth and collapse effects at high

temperatures. The plan for developing this model can be seen as a three-step approach. Firstly, the heat and

mass transfer within a droplet is studied theoretically since the temperature and concentration gradient are

critical for assessment of shell formation process. The shell properties are studied under high temperature.

The rheology of viscoelastic skin and how it reacts to internal and external stress are examined in detail in

order to anticipate whether it can form a shell or `puff'. Thermo-mechanics will be integrated into the kinetic

model to fully predict the morphological formation routes of polymeric particles. The model predicts

temperature and composition gradient, shell's behaviour and shape during drying and final particle's

morphologies.

The modelling approach will be presented along with initial modelling results.

69


Foaming Non-Newtonian Viscous Liquid for Particle Coating

Ping Ding1, Jerome Castro2, Serafim Bakalis1 and Zhibing Zhang1 1School of Chemical Engineering, University of Birmingham, Birmingham B15 2TT UK

2P&G Technical Centre Limited, Newcastle Innovation Centre, NE12 9BZ, UK


Coating of particles can often be achieved using a shell material dissolved in aqueous phase, which are

generated into tiny liquid droplets and sprayed onto the surface of the core particles in a fluidised bed coater.

However spraying, can very difficult when the application requires for highly viscous liquid with very low water

content. It is proposed to create foams from these viscous liquids for use as coating material. This work aims to

investigate the foam preparation from non-Newtonian viscous liquid in different mixing devices and processing

conditions.

A co-polymer solution was used together with a surfactant in this study. Experiments were carried out at

250 °C in a jacketed stirred vessel without baffles (T = 90mm). A Rushton turbine impeller (D = 50mm) and a

high shear mixer (Silverson L5M-A, Rotor D = 30mm) were used repectively. Viscosity were measured using

Hybrid Rheometer (Discovery HR-1, TA Instrument) and Bholin rheometer (Malvern Instruments, UK) with the

geometeries of 60mm cone and plate, and 40 mm parallel plates dependig on the materials to be measured.

The structure were measured using a optical microscopy

Results show that the model copolymer solution is Newtonian viscous liquid of 4.7 Pa.s whilst the surfactant

used is a two phase system with shear thinning viscosity. The mixtures of the two in different concentration

ranges were of two phase system with shear thinning viscosity. The foam prepared in different processing

conditions also show shear thinning viscosity. It is however interesting to notice that the viscosity of the

generated foam were usually higher than the initial liquid mixture.

By using the Rushton turbine impeller and high shear mixer, the foams generated showed similar bubble size

distribution, viscosity and gas hold up but the energy dispassion rate required by the Rushton turbine impeller

was approximately 10 times lower than the high shear mixer. This might be explained by that in non-

Newtonian viscous liquid, agitation tends to cause cavern formation and in general, bigger impellers generate

bigger caverns at the same power input.

At the Surfactant concentration in the range from 10 wt. % to 20 wt. % and air flow rate 0.2 L/min – 1.0 L/min,

the gas hold up of the foam was approximately 0.42. When the mixture was diluted with 25 wt. % to 50 wt. %

water, the gas hold up can be higher than 0.67. Bubble size was generally in the range of 10 - 300 µm and

reduced with the increase of impeller speed. Gas hold up increased with the air flow rate initially but maintain

nearly constant when the flow rate further increased.

The research proved methodology of foaming viscous liquid with controlled structure and suitable rig for

process scale up.

70


Tuesday 28 March 2017

Catalysis and Sustainable Green Chemistry

11:30-12:20 Session on Catalysis and Sustainable Green Chemistry: 3-Minute Research Highlight Talks

(Main Lecture Theatre, Aston Webb C Block)

Chair: Professor Alexei Lapkin, University of Cambridge

11:30-11:35 Raul Calvo-Serrano, Imperial College London Predicting the cradle-to-gate environmental impact of chemicals from molecular descriptors and

thermodynamic properties via mixed-integer programming

11:35-11:40 Changdong Li, University of Warwick Flow synthesis of Zn/Cr-oxide based catalysts allowing hydrogen sulfide insensitive methanol

synthesis

11:40-11:45 Xiaoxia Ou, University of Manchester Optimization of Fe-ZSM-5 coatings on SiC cellular foams for phenol wastewater treatment

11:45-11:50 Matthew Darby, University College London Towards the development of single atom alloy catalysts as a means of escaping linear scaling

relations

11:50-11:55 Utsab Guharoy, University of Surrey DFT Study of dry (CO2) reforming of methane over tin-doped Ni(111) surf

11:55-12:00 Conor Waldron, University College London Multistep synthesis of benzylacetone in micropacked bed reactors

12:00-12:05 Joseph Manning, University of Sheffield The application of green chemistry to enable sustainable manufacture of bioinspired nanosilica

12:05-12:10 Rustam Turganaly, University College London Pt/Cu single atom alloy catalyst for coke free methane activation

12:10-12:15 Toyin Omojola, University of Bath Effect of Si/Al ratios and mass transfer during the adsorption, desorption and activity of methanol and

DME over ZSM-5 catalysts

12:15-12:20 Nikolay Chekasov, University of Warwick Increased deactivation stability of ZSM-5 zeolite in a methanol to gasoline conversion via desilication

and Ca ion exchange

71


Predicting the Cradle-to-Gate Environmental Impact of Chemicals from Molecular

Descriptors and Thermodynamic Properties via Mixed-Integer Programming

Raul Calvo Serrano



Life Cycle Assessment (LCA) has gained wider acceptance in green chemistry as an effective tool for quantifying

the environmental impact of chemicals considering all the stages in their life cycle. Unfortunately, LCA studies

require large amounts of data that are hard to gather in practice, a limitation that is particularly critical in the

complex processes and value chains of chemical industry.

In this work we show that the life cycle impact associated with the cradle-to-gate production of a wide range

of organic chemicals can be predicted from attributes based on their molecular structure and thermodynamic

properties via multi-linear regression. A mixed-integer programming (MIP) optimisation framework is

introduced that streamlines the LCA calculations by systematically constructing short-cut predictive models of

cradle-to-gate life cycle impact containing key molecular and thermodynamic attributes identified using binary

variables.

On applying our method to an LCA data set containing 88 chemicals, 17 molecular descriptors and 15

thermodynamic properties, we produced estimates for widely used metrics such as cumulative energy

demand (CED), global warming potential (GWP) and Eco-indicator 99 (EI99) with relative errors of enough

quality for the purposes of an LCA study. Our optimisation framework leads to simple linear models that are

amenable for implementation in computer aided molecular design software, thereby opening new avenues for

the inclusion of sustainability principles in the early stages of the development of new chemicals.

72


Flow Synthesis of Zn/Cr-Oxide Based Catalysts Allowing Hydrogen Sulphide

Insensitive Methanol Synthesis

Changdong Li

University of Warwick


Zn/Cr oxide catalysts are confirmed as poison-tolerant in methanol synthesis being in particular insensitive to hydrogen

sulphide (H2S). Parent materials suffer however of lower activity compared to Cu/ZnO-Al2O3 catalysts. We succeeded

improving substantially catalyst activity by e.g. Nickel(II) and Iron(III) addition to Zn/Cr oxides while preserving poison

resistance. Catalysts are hydrotalcite-derived using a novel flow synthesis method which amalgamates numerous reaction

steps into one continuous operation. Compared to conventional co-precipitation, flow synthesis produces high yields of

mixed oxides with superior properties such as high specific surface area. Those materials exhibit more potential reaction

sites leading to better catalytic performance. Preparation of hydrotalcite precursors with largest surface areas requires

however fine control of the pH and temperature as well as longer residence times in staged aging coils. Active oxide

catalysts were obtained by calcination at 320 °C.

The impact of poisoning was explored by precise controlled admission of H2S to a syngas (H2/CO) feed and monitoring of

the methanol formation at 50 bar. Multiple pulse-wise introduction of a H2S/Argon mixture to the pressurized syngas feed

allowed a quasi-uninterrupted catalytic reaction. A mass spectrometer (MS) following the Argon tracer indicated the

presence of H2S for about 4 hours at quasi-constant concentration of about 500 ppm. Catalyst performance was

established by an online gas chromatograph (GC) enabling quantitative detection of syngas and methanol. Poison

insensitivity of prepared Zn/Cr-based oxide catalyst was shown at 300 °C and a commercial Cu-based catalyst was tested

as reference catalyst at 240 °C under the same poison conditions. Among Zn/Cr oxide catalysts the Fe-doped material

shows the highest CO conversion and methanol space-time yield (STY) but the lowest methanol selectivity of only 87 %.

The latter is related to a competitive production of methane and higher alcohols. The Ni-doped catalyst shows a slightly

lower performance than the Fe-doped material but higher methanol selectivity. The non-doped Zn/Cr oxide catalyst has

the lowest catalytic performance but higher methanol selectivity than the Fe-doped catalyst. Before the injection of H2S,

all tested catalysts were run overnight to evaluate their performance stability in clean syngas. Productivities to methanol

with pure synthesis gas feed are compared for all tested catalysts. Zn/Cr-based oxides catalysts are proven to perform

very stable reaching at 300 °C nearly half that productivity observed for the Cu-based commercial catalyst at 240 °C. It is

noteworthy that the Cu-based commercial catalyst showed slight initial deactivation with a decline of less than 5 % before

stabilising methanol productivity. The impact of hydrogen sulphide was assessed recorded performance data over 80

hours subsequent to injection. The productivity to methanol over the Cu-based commercial catalyst shows a subtle but

overall tremendous deactivation dropping performance in the 80 hours test to 5 % of the initial methanol productivity. On

the contrary, Zn/Cr-based catalysts show stable performance after H2S admission and the methanol productivity

decreased only over the Fe-doped catalyst by less than 2 %. Therefore, the Zn/Cr-based oxides catalysts confirmed their

superior poison resistance and suitable dopants added to Zn/Cr oxide catalysts allow a striking improvement in methanol

productivity.

Acknowledgement

We acknowledge financial support from the European Commission 7th Framework program: BIOGO project (grant no:

604296) www.biogo.eu

73


Optimization of Fe-ZSM-5 Coatings on SiC Cellular Foams for Phenol Wastewater

Treatment

Xiaoxia Ou, Arthur A. Garforth and Xiaolei Fan



Recently, macrocelluar foams stimulated ideas of designing multiscale porous structured materials for

catalytic/chemical applications. β-SiC open-cell foams, are better supports for developing structured catalytic

reactors for process intensification than conventional periodical monoliths, due to their high porosities (ca.

90 %, light weight and low pressure drop), stochastic structures (enhanced transport phenomena), high

mechanical strength and high oxidation and chemical resistance [1-3]. Hydrothermal syntheses of Fe-ZSM-5

coatings on SiC sponges were explored for the first time. XRD, SEM, FT-IR, Raman, UV-vis and BET tests were

carried out to comprehensively study the structures of Fe-ZSM-5 coatings. The catalytic performances of the

composite materials were tested by phenol wastewater treatment. Both batch reactor and fixed-bed reactor

were applied during the reaction and operating conditions were optimized.

The results showed different status of Fe in the structure of Fe-ZSM-5/SiC and the efficiency of the catalyst in

phenol wastewater treatment, as well as no secondary pollution during the treatment

Reference:

[1] X. Fan, X. Ou, F. Xing, G. A. Turley, P. Denissenko, M. A. Williams, N. Batail, C. Pham, A. A. Lapkin, Catal.

Today, 2016, DOI: 10.1016/j.cattod.2015.12.012.

[2] M. Lacroix, P. Nguyen, D. Schweich, C. Pham Huu, S. Savin-Poncet, D. Edouard, Chem. Eng. Sci., 2007, 62,

3259-3267.

[3] F.C. Buciuman, B. Kraushaar-Czarnetzki, Catal. Today, 2001, 69, 337-342.

74


Towards the Development of Single Atom Alloy Catalysts as a Means of Escaping

Linear Scaling Relations

Matthew Darby



The rational design of heterogeneous catalysts remains a formidable task, though if successful will pave the

way to more efficient and effective catalysts. Linear scaling relations have provided important steps in

advancing rational design, significantly facilitating the task faced. For example, the Brønsted-Evans-Polanyi

(BEP) relationship correlates the binding energy of a species with its activation energy for a given chemical

reaction, allowing for deductions to be made about a variety of catalytic surfaces based on fundamental

surface adsorption properties. The Sabatier principle connects the BEP relation to catalytic activity yielding

Volcano plots which demonstrate that the most active catalysts must bind substrates strongly enough to

dissociate reactants but weakly enough to allow for desorption.

Ab initio calculations, using for instance density functional theory (DFT), allow for the simulated study of

important catalytic materials. Many such studies on metal surfaces have demonstrated the validity of BEP

relationships for numerous simple chemical reactions, allowing for extrapolations and inferences to be made

about more complicated, yet related systems. The apparent universality of the BEP relation could, on one hand,

be extremely useful in predicting the activity of a catalytic surface, though on the other hand will inevitably

limit the prospects of catalyst due to the linearity between activation energy and binding strength.

Many of the catalysts that adhere to BEP type linear models often exhibit spatial homogeneity. Moving away

from such surfaces, stepped or kinked surfaces as well as metal alloys have much greater spatial heterogeneity

and in many instances still show BEP type trends, for example in the cases of pseudomorphic-monolayers and

near-surface-alloys. In this study, we focus on alloys consisting of single, isolated metal dopant atoms

dispersed in the surface layer of a host metal; these materials are referred to as single atom alloys (SAAs). High

single atom dispersity in the surface of a SAA leads to unique strain and ligand effects unseen in pure metal

and other alloy structures, giving rise to some counterintuitive surface binding properties. In addition, the high

degree of spatial heterogeneity in the surface of a SAA may limit the description of its behaviour by simple BEP

relations. It has been shown in several systems that SAAs can adsorb and dissociate reactants at one site

before facile spillover to the host metal allows for further reaction to occur.

We present a DFT-based study of nine SAAs formed from coinage metal hosts doped with individual surface

atoms of Pt group metals. We investigate the chemistries of catalytically relevant bond dissociation reactions

such as the scission of C-H, N-H, H-H and O-H bonds. Our results illustrate how strain and ligand effects

contribute to the reactivity of the dopant atom, showing that different host metals can result in reduced or

increased reactivity compared to the pure dopant metal surfaces. We demonstrate that isolated single atoms

are sufficient for such chemistries, modifying the activity and selectivity. Moreover, we rigorously evaluate the

validity of the BEP relationship on each SAA, determining the cause of deviations from a linear correlation.

75


DFT Study of Dry (CO2) Reforming of Methane over Tin-Doped Ni (111) Surface

Utsab Guharoy



The CO2 dry reforming of methane (DRM) is an industrially important reaction for combining two undesirable

greenhouse gases CH4 and CO2 to produce syngas (CO+H2) with desirable H2/CO ratios for conversion of long

chain hydrocarbon via Fischer-Tropsch synthesis. Nickel (Ni) is the most widely used catalyst for DRM due to its

high activity and low cost. However, Ni undergoes sever coke deposition at typical reaction conditions, which

essentially deactivates the catalyst. One of the strategies to prevent carbon deposition in DRM is by

developing bimetallic catalysts. Liu et al.[1] experimentally investigated the surface alloying over mono-

metallic Ni surface with Sn and found that the bimetallic properties of the catalysts improves the resistance to

carbon deposition considerably during DRM. However, the underlining reaction mechanisms remain unclear.

In this paper, we report our efforts in unraveling the fundamental mechanisms of the improved resistance to

carbon deposition by bimetallic catalysts. The DRM reaction mechanisms CH4 + CO2 = 2CO + 2H2 on both Sn-

doped Ni (111) surface and Ni (111) mono-metallic surface have been studied using density functional theory

(DFT) simulations. The DFT simulations are performed using the plane wave CASTEP package. From the DFT

simulations we firstly demonstrate the carbon deactivation chemistry over both surfaces and secondly develop

a micro-kinetic model to explore the influence of reaction temperatures and H2/CO ratio on the reaction rate.

References:

[1] Liu, J., Peng, H., Liu, W., Xu, X., Wang, X., Li, C., Zhou, W., Yuan, P., Chen, X., Zhang, W. and Zhan, H. (2014),

Tin Modification on Ni/Al2O3: Designing Potent Coke-Resistant Catalysts for the Dry Reforming of Methane.

ChemCatChem, 6: 2095–2104. doi:10.1002/cctc.201402091

76


Multistep Synthesis of Benzylacetone in Micropacked Bed Reactors

Conor Waldron



The three reaction steps in the synthesis of benzylacetone were studied in isolation using micropacked bed

reactors to identify the best operating conditions for a combined microreactor system. The three steps are

benzyl alcohol oxidation to benzaldehyde over a AuPd/TiO2 catalyst, benzaldehyde carbon-carbon coupling

with acetone over a TiO2 catalyst to produce benzalacetone and finally benzalacetone hydrogenation with a

Pd/TiO2 catalyst to produce benzylacetone. This reaction sequence was chosen because it represents a wide

range of industrially relevant chemistries (oxidation, coupling, reduction) with catalysts and mass transfer

effects, it requires separation between reaction stages and there are safety concerns (oxygen and hydrogen

gas are both required). The microreactor system can address the above challenges, and it can also be used for

system wide optimisation studies.

A Model Based Design of Experiments (MBDoE) approach was used to study each reaction to maximise the

amount of information gained from the minimum number of experiments with the ultimate aim of obtaining

kinetic parameters and identifying the optimum operating conditions. The first reaction, benzyl alcohol

oxidation has already been well studied [1]. The second reaction, benzaldehyde acetone carbon-carbon

coupling over TiO2 was found to be affected by external mass transfer and exhibited product inhibition. The

catalyst was also found to deactivate and this was accounted for in the kinetic study through suitable

deactivation kinetics.. The third reaction, benzalacetone hydrogenation with a Pd/TiO2 catalyst, was shown to

be a fast reaction with selectivity concerns due to over reduction of the final product.

References:

[1] Noor Al-Rifai, F.G., Moataz Morad, Enhong Cao, Stefano Cattaneo, Meenakshisundaram Sankar, Vivek Dua,

Graham Hutchings, Asterios Gavriilidis, Hydrodynamic Effects on Three Phase Micro-Packed Bed Reactor

Performance - Gold-Palladium Nanoalloy Catalysed Benzyl Alcohol Oxidation. 2016.

77


The Application of Green Chemistry to Enable Sustainable Manufacture of

Bioinspired Nanosilica

Joseph Manning

University of Sheffield


Porous silica is a technologically important material with applications in the polymers, catalysis, drug delivery

and separations sectors, worth an estimated $3.6 billion per annum (World Specialty Silicas, The Freedonia

Group, 2010). Bioinspired silica, synthesised using biologically inspired organic “additives”, are greener

alternatives to many existing silicas (Chem. Commun., 2011, 47, 7567). However, bioinspired (and other

templated) silicas require high energy purification e.g. high-temperature calcination, leading to material and

energy wastefulness and preventing their industrial implementation. Although alternatives to calcination have

been reported, e.g. solvent extraction, they are energy intensive so are unsustainable on a larger scale (Chem.

Soc. Rev., 2013, 42, 4217).

Using recently developed molecular dynamics forcefields of amorphous silica surfaces (Chem. Mater., 2014, 26,

2647), we have investigated the extraction of additives from silica surfaces for the first time. We discovered

that pH can be used to controllably extract additives from silica hybrids without the need for any further

energetic driving force, unlike the traditional mesoporous silicas (Chem. Mater., 1996, 8, 2068). Unlike other

purification methods, modification of silica surface chemistry through partial extraction was possible creating a

wide range of tailored silicas directly. Furthermore, with the ability to directly modify silica surface chemistry

rather than using separate purification and functionalisation steps, we have been able to eliminate a synthesis

step from the production of silica entirely.

Once extracted additives can be directly reused for further silica synthesis, creating new bioinspired silica from

old reaction media. We have therefore been able to scale-up to produce hundreds of grams per day without

the need for specialist equipment, demonstrating the improved scalability of the new technique. Process

calculations indicate that extraction and additive reuse can reduce the energy requirements of purification by

over 90% compared to conventional purification methods, while the room temperature reaction can reduce

the energy requirement by >90% (Chem. Eng. J., 2014, 244, 483), thus significantly reducing both the cost and

wastefulness.

Therefore, by applying green chemistry principles to the synthesis and purification of bioinspired silica we have

developed a cleaner, cheaper, and readily scalable method for silica production, a significant technological

advance. We show that this method provides an effective “lab to market” route in applications ranging from

environmental remediation (Environ. Sci. Technol., 2012, 46, 13354) to drug delivery (J. Mater. Chem. B, 2014,

2, 5028).

78


Pt/Cu Single Atom Alloy Catalyst for Coke Free Methane Activation

Rustam Turganaly



The availability of shale gas has led to an increased interest in the activation of C-H bonds due to the potential

for new synthetic routes to fine chemicals. Traditionally Ni or Pt catalysts are capable of performing these

chemistries due to high activity in C-H bond breaking, however both surfaces are highly susceptible to coke

formation and subsequent deactivation. Conversely, Cu based catalysts are relatively inactive for such

chemistries, though offer high resilience to coking. Utilising Pt/Cu single atom alloys (SAAs) we have shown a

theoretically and experimentally the activation of C-H bonds in methane and butane. Moreover we find that

using this SAA catalyst, we dramatically reduce the risk of coking and see negligible deactivation under

operating conditions. In this work, we present a kinetic study for methane C-H activation over a Pt/Cu (111)

SAA catalyst. Our simulations are parameterised using first principles density functional theory calculations,

where we compute the potential energy surface for CH4 dehydrogenation through CH3, CH2 and CH to atomic C.

Using kinetic Monte Carlo we reproduce experimental observations giving validation to our model system,

allowing us to analyse key reaction statistics and evaluate the catalytic performance under a variety of

operating conditions. Moreover we demonstrate the key differences between pure Pt, Cu and Pt/Cu (111) SAA

catalysts paying particular attention to relative activities and selectivities. In addition, we extrapolate from our

data using linear scaling relations to make predictions about new SAA catalysts which we identify as having

favourable reaction energetics that suggest there is potential for C-H activation and C-C coupling in conjuction

with a low coking risk.

79


Effect of Si/Al Ratios and Mass Transfer during the Adsorption, Desorption and

Activity of Methanol and DME Over ZSM-5 Catalysts

Toyin Omojola

University of Bath


There exist fundamental challenges in describing the early stages of the conversion of methanol to

hydrocarbons (MTH). Initially present oxygenates (methanol and its anhydrous equilibrium product, dimethyl

ether (DME)) compete for active sites. This suggests a need to verify the primary reactant, the mechanistic

pathway leading to the primary product and the primary product. Prominent direct mechanisms for primary

olefin formation involving intermediates such as surface carbenes, tri-methyloxonium ion, methane-

formaldehyde, methyl ethyl ether and CO have been proposed. Alternatively, impurities such as acetone or

ethanol in the feed or incomplete combustion of organics in the zeolite have been shown to lead to a

hydrocarbon pool that propagates steady state hydrocarbon formation during later stages. The origin of this

hydrocarbon pool either directly or indirectly is still, however, debated. Through a combined experimental and

kinetic modelling methodology, we have studied the adsorption, desorption and activity of methanol and DME

over fresh and activated ZSM-5 catalysts of different Si/Al ratios using transient methods (TPD, TPSR and step

response) under ultrahigh vacuum conditions in a TAP reactor and under atmospheric pressure conditions in a

steady state fixed bed reactor. Under steady state conditions, experiments used ZSM-5 catalysts (Si/Al=36) in

powder form. Low concentrations of DME (99.99 vol%) and methanol (99.93 wt%) in nitrogen were used as

inlet reactants. H-forms were obtained by subjecting the received ammonium forms to 30% O2/N2 and

ramping up to 723 K at 10 K min-1, holding for 30 mins before being subsequently cooled to reaction

temperature at 25 K/min. Process conditions were chosen to probe early stages of the reaction when

methanol/DME transformation is tuned towards olefin formation (723 K) or gasoline formation (643 K). The off

gases were kept insulated and sampled through an online gas chromatography-flame ionization detector (GC-

FID) equipped with an Equity 1 fused silica capillary column and a mass spectrometer (MS). Transient

experiments used ZSM-5 zeolites of different Si/Al ratios. It was observed that desorption is affected by re-

adsorption and activity is affected by pore diffusion under chosen process conditions. Desorption of

oxygenates were dependent on Si/Al ratios and propene, the primary product formed, was controlled by mass

transfer limitations under low inlet methanol or DME partial pressures. Kinetic parameters for desorption and

activity were obtained using FORTRAN. Further experiments would be carried out over ZSM-5 monoliths to

investigate the influence of catalyst loading, temperature and weight hourly space velocity on primary olefin

formation; taking into account internal and external mass transfer effects. Also, using a spatially resolved

analysis technique, further research would be carried out to obtain a spatio-temporal map of species along the

axial length of the fixed bed reactor during conditioning and steady state conditions of MTH conversion.

80


Increased Deactivation Stability of ZSM-5 Zeolite in a Methanol to Gasoline

Conversion via Desilication and Ca Ion Exchange

Nikolay Chekasov

University of Warwick


Hydrocarbon fuels are crucial for transportation, but sustainability and continued supply problems are yet to

be solved. In this respect, the conversion of biomass into hydrocarbons could be economically viable and the

individual steps of biomass pyrolysis, conversion to syngas, methanol synthesis and its conversion into

hydrocarbons have already been demonstrated at the industrial scale. The latter reaction of conversion of

methanol to hydrocarbons (MTH), however, suffers from relatively short H-ZSM-5 catalyst lifetime, which

makes the process less attractive due to large energy costs required for catalyst regeneration. Hence, the aim

of the current work was to study the methods to improve the catalyst lifetime in the MTH reaction.

We have shown that the strong acid sites which lead to aromatisation products and formation of coke, could

be suppressed in Ca-exchanged ZSM-5 catalysts. The ion-exchange was performed with a NH4-ZSM-5 zeolite

using a solution of NH4NO3 (1 M) and Ca(NO3)2 (0.005 -1.0 M) for 3 h under stirring. The obtained zeolites

were dried, calcined at 550 °C and pelletized for a particle size fraction of 250 -500 μm. The mesoporosity was

introduced with a treatment of the calcined Ca-ZSM-5 zeolite with a 0.2 M NaOH solution in the temperature

range from 45 to 60 °C for 30 min. Afterwards, the solids were filtered, washed with water and exchanged with

an excess of a 1 M NH4NO3 solution, dried and calcined at 550 °C. The MTH reaction was performed in a

tubular fixed-bed reactor with 100 mg of the catalyst at a methanol flow rate of 10 μL min-1, a nitrogen flow

rate of 10 mL min-1 (STP) and a pressure of 5 bar. The products were analysed with an on-line GC equipped

with a FID detector.

The microporosity and particle size distribution remained the same after the Ca-exchange step however the

total methanol conversion in the MTH reaction was increased by 10 %. The catalyst lifetime was also increased

for all Ca-ZSM-5 catalysts studied. It appears that the Ca2+ ions block only superacid sites that have very minor

contribution to the MTH reaction. The alkali treatment introduced mesopores with a diameter of 3.4 – 4.0 nm

that were absent in the initial ZSM-5 catalyst. Interestingly, the total volume of mesopores increased at a

higher desilication temperature, however the pore diameter remained virtually the same. This observation

indicates that the alkali treatment resulted in a precisely-targeted dissolution of material along preferential

crystal directions.

The catalytic results in the MTH reaction showed that the introduced mesoporosity lead to a 4.2-fold increase

in methanol conversion. Thus, a combination of the Ca-exchange step and the alkali treatment was shown to

increase the H-ZSM-5 catalyst lifetime by an order of magnitude.

Acknoledgement

The research has received funding from the European Community’s FP7 Programme, grant agreement no.

604296.

81



Biological Engineering

11:30-12:20 Session on Biological Engineering: 3-Minute Research Highlight Talks (WG12, Aston Webb A Block)

Chair: Prof. Daniel Bracewell, University College London

11:30-11:35 Ali Mulakhudair, University of Sheffield Fermentation integrated with in situ separation of bio-products using microbubble technology

11:35-11:40 Alfred Fernández-Castané, University of Birmingham Bioprocessing biologically synthesised magnetic nanoparticles: Production, recovery and purification

of magnetosomes

11:40-11:45 Hongdi Wang, University of Birmingham Rational encapsulation of needle-shaped nanocrystals into zein@Au hybrids for controlled release and

active targeting delivery

11:45-11:50 Charles Moore-Kelly, University of Birmingham Automated micro-volume capillary circular dichroism and fluorescence spectroscopy for rapid analysis

of protein conformation

11:50-11:55 Adamu Rasheed, University of Aberdeen Prediction of the steady state performance of sequencing batch reactors from batch kinetic tests

11:55-12:00 Anthony Wu, University of Surrey Application of robust model identification techniques in the activated sludge process

12:00-12:05 Matthew Chin, University College London A biomaterial-based platform for the optimisation of therapeutic immune cell culture

12:05-12:10 Wan Mohd Asyraf Wan Mahmood, University of Manchester Lipid extraction from microalgal biomass using bio-based solvents

12:10-12:15 Stella Totti, University of Surrey A promising highly porous 3D scaffolding system for in vitro pancreatic tumour development and

drug screening

12:15-12:20 Aiman Alam, Imperial College London From basic enzymatic building blocks to bacterial signalling pathways: a systematic elucidation of

spatial regulation and compartmentalization of biochemical pathways

82


Fermentation Integrated with in situ Separation of Bio-Products Using Microbubble

Technology

Ali Mulakhudair

The University of Sheffield


Zymomonas mobilis has long been known as the best microbial producer of ethanol, and it is widely used to

produce a large quantity of ethanol in anaerobic conditions, offering many advantages over other ethanol

producers such as Saccharomyces cerevisiae. Under aerobic condition, however, this bacterium produces a

reasonable amount of acetaldehyde and carbon dioxide with lower quantity of ethanol. Acetaldehyde and

carbon dioxide accumulation in the fermentation broth can cause severe inhibition for Zymomonas growth.

Removing the accumulated acetaldehyde and carbon dioxide, however, reduces the chemical activity of the

gaseous products with a negative value change in Gibbs free energy; hence the biological reactions become

thermodynamically favourable and provides momentum for the formation of more products. Microbubbles

generated by fluidic oscillation were used to remove both acetaldehyde and carbon dioxide from the

fermentation broth. The results show that the Zymomonas growth is inhibited by acetaldehyde at

concentration as low as 0.1% with several morphological changes seen of the bacterial cells by SEM. This

inhibition can be avoided by stripping with microbubbles, which removes acetaldehyde from the fermentation

broth with 99% efficiency, leading to relatively high microbial growth. Using the microbubble technology,

however, gives 45% yield of ethanol and 1% yield of acetaldehyde with 110% yield of microbial biomass in

comparison with 70%, 0.5% and 90% yield for ethanol, acetaldehyde and biomass respectively in the control

group. Also, the microbubble-sparged group produces 900% more carbon dioxide than the control group.

Additionally, the oxygenation concurrent with the stripping process by microbubbles efficiently maintained the

oxygen concentration in the fermentation broth above the critical oxygen concentration, leading to stable

aerobic conditions. This approach has potentially high ramifications particularly for fermentation-based

industries and it promises to offset many of traditional aerobic fermentation deficiencies.

83


Bioprocessing Biologically Synthesised Magnetic Nanoparticles: Production, Recovery

and Purification of Magnetosomes

Alfred Fernandez-Castane



Biologically synthesized magnetic nanoparticles, namely magnetosomes are an attractive alternative to

existing commercial magnetic particles because of their ferrimagnetic properties, narrow size distribution and

high specific absorption rate. Numerous efforts have been made over the last few years to improve

magnetosome yields using genetic modifications or improvement of culture conditions of magnetotactic

bacteria (MTB). However, large-scale cultures delivering high-cell densities in combination with efficient

magnetosome recovery remains a challenging step toward industrial application. Moreover, magnetosome-

membrane proteins can be used as an anchor for the fusion of proteins for a wide range of biotechnological

and healthcare applications. Therefore, membrane integrity needs to be taken into account upon cell

disruption. Here, we present a robust platform for the production of magnetosomes in relatively high-cell

density cultures of Magnetospirillum gryphiswaldense MSR-1 in 5 L bioreactors. We have used a simple

fermentation strategy employing a pH-stat approach and minimal control of bioprocess parameters. A range of

methods for cell disruption followed by magnetic separation using a newly-designed ‘rotor-stator’ type High

Gradient Magnetic Fishing (HGMF) for the downstream processing and separation of magnetosomes was

tested.

84


Rational Encapsulation of Needle-Shaped Nanocrystals into Zein@Au Hybrids for

Controlled Release and Active Targeting Delivery

Hongdi Wang



Fabrication of a versatile nanocarrier based on self-assembled structures of gold nanoparticles encapsulated

by zein is reported. It has been found that efficient loading capacities were displayed for needle-shaped

hydroxycamptothecin (HCPT) nanocrystals as a model drug. The surface modification with folate-conjugated

polydopamine (FCP) rendered them stable in the bloodstream and also facilitated their selective cellular

internalization and enhancement of endocytosis. The release of the model drug from nanocomplexes (NCs)

was shown to be limited (around 20%) at physiological pH but significantly elevated (over 65%) at

endosomal/lysosomal pH and (over 90%) at enzymatic environment. Compared to free HCPT and its non-

targeting equivalent (i.e. the NCs without FCP), HCPT@AuNPs-Zein-FCP exerted a prolonged blood circulation

and superior tumour suppression capacity as well as low side effects due to their active and passive targeting

delivery in vivo. These results suggest that the NCs with well-defined core (AuNPs) @shell (zein-FCP)

nanostructures with HCPT nanocrystals embedded hold great promise to serve as a safe and effective

therapeutic formulation, which might be capable of delivering drugs in a predictable and controllable manner.

85


Automated Micro-Volume Capillary Circular Dichroism and Fluorescence

Spectroscopy for Rapid Analysis of Protein Conformation

Charles Moore Kelly



The propensity for proteins to unfold and self-associate presents a major concern to the biopharmaceutical

industry. Not only do unfolded proteins exhibit reduced therapeutic efficacy, they also display an enhanced

propensity to aggregate and invoke immune responses in patients. This, combined with the realization that the

biomanufacturing process itself can strongly influence product quality, drives the biopharmaceutical

manufacturing sector's yearning for better ways to accurately determine the quality of its recombinant protein

products at all stages during and post manufacture. Improved understanding of the impact of processing

environment on biotherapeutic degradation requires the development of generic and robust high-throughput

Process Analytical Technologies (PAT) that can effectively monitor a given target protein's structural state so

that high quality can be designed into the product.

In our laboratories, we have developed high-throughput 96-well plate PAT instrumentation that allows circular

dichroism and intrinsic protein fluorescence spectroscopic measurement to be performed on the same protein

sample. By robotically injecting said samples into a micro-volume capillary flow cell, complementary

information about the tertiary and secondary structural state of protein sample can be collected in an

unattended manner, and with much reduced sample requirements compared to conventional spectroscopic

procedures.

We have applied the system to investigate the impact of various processing buffers on the structural state of

monoclonal antibodies (mAbs), demonstrating how this technique may be used to optimise processing

conditions to maintain the structural integrity of a protein product. Additionally, we have sought to further

adapt the system to carry out on-line structural analysis of protein eluting from chromatographic columns,

with the aim to introduce this technology directly onto product processing lines.

86


Prediction of the Steady State Performance of Sequencing Batch Reactors from Batch

Kinetic Tests

Adamu Rasheed



This study aims to investigate the possibility of calculating the periodic steady state of sequencing batch

reactors (SBRs) using kinetic parameters obtained from batch tests. Two industrial wastewaters were treated

in SBRs with measurement of the substrate removal and biomass production. Three batch tests at different

initial substrate to biomass ratios (high, moderate and low) were carried out on each of the two wastewaters,

with measurement of the oxygen uptake rate (OUR). The OUR profiles were used for the estimation of the

kinetic parameters using a mathematical model consisting of substrate hydrolysis, biomass growth and

endogenous metabolism. The estimated kinetic parameters were then used to calculate the substrate and

biomass concentration at the periodic steady state of the SBRs and the obtained values were compared with

the experimental data from the SBR runs. The parameter fitting showed that it was not possible for one set of

kinetic parameters to describe different tests even for the same wastewater. However, when fitted

individually, the model gave good description of the experimental data for each tests, even though with

different set of parameters. When used to calculate the periodic steady state of the SBR, the estimated

parameter values gave in all cases a complete removal of the biodegradable COD, in agreement with the

experimental data. In terms of biomass concentration, the batch tests gave good predictions with the tests

carried out at low initial substrate to biomass ratio. The prediction of the model was strongly influenced by the

parameter values of endogenous metabolism constants (b), and biomass growth yield (Yx/s) and much less

affected by the value of maximum growth rate (µmax).

87


Application of Robust Model Identification Techniques in the Activated Sludge

Process

Anthony Wu



Increasing awareness of climate change and regulatory changes has motivated efforts to reduce energy

consumption in the wastewater treatment process (WWTP). Aeration needed for the activated sludge process

(ASP) is one of the largest energy demands in the WWTP. Model predictive control (MPC) can improve the

process operation by reducing aeration when the influent ammonium load is lower, whilst ensuring the

effluent does not breach consent. In a case study of a wastewater treatment process in Lancaster, MPC

reduced the energy consumed in the activated sludge process by over 25 %. MPCs make process changes

based on predictions from dynamic models describing the process. But model identification of an ASP unit

faced with a number of challenges. Typically, historically sampled data is information-poor; it does not

describe how changes in the manipulated variables affect the control variables and are not suitable for model

identification. The process itself is very slow, highly non-linear and very noisy. Additionally, there are

limitations on how much time and resources are allocated for data collection.

This ongoing research project investigates the application of robust hybrid modelling techniques to enhance

data-driven modelling. Two avenues are explored: constrained model identification and the design of

experiment using the persistence of excitation. Model identification is an optimisation problem where model

parameters are estimated based on the best model fit to training data. If the amount of information-rich

training data is limited, data-driven modelling techniques often overfit the model to the training dataset or

identify correlations which are physically incorrect (e.g. steady-state gain being of the opposite sign). In

constrained model identification, `a priori' information is added as constraints to the optimisation problem to

ensure that the identified model remain physically reasonable. These constraints make the model

identification more robust, especially when information-rich data is sparse, so more accurate models can then

be used for MPC. The second avenue considers the design of step tests to sufficiently excite the process, which

generates more information-rich data, whilst ensuring that the effluent remains within consent. The

persistence of excitation is reviewed at the end of each sampling trial to assess the information captured and

the steps to implement in the next trial. Additionally, it can assess if sufficient information has been collected

already, allowing the data collection to end earlier and save on project resources.

At the time of writing, simulated examples are used to analyse the conditions where constrained model

identification estimated better models compared to the unconstrained approach. Observations have been

noted relating to the size of the training dataset, model structure, system dynamics and the amount of

background noise. Disturbance inputs and missing data will be considered to better reflect the challenges in an

actual ASP unit. Ultimately, this research will be demonstrated on an operating ASP unit. The comparison using

simulated examples also help identify other applications where this research output can be used. This research

is a collaboration between the University of Surrey and Perceptive Engineering Limited and funded by the

Engineering and Physical Sciences Research Council.

88


A Biomaterial-Based Platform for the Optimisation of Therapeutic Immune Cell

Culture

Matthew Chin



Adoptive T cell therapy is emerging as a major cancer treatment modality due to its recent successes in

treating leukaemia patients. Crucial to the efficacy of the therapy is the capacity to implement large-scale in

vitro expansion and activation of clinical-grade T cells, before infusion into the patient. Yet, there is currently a

limited repertoire of in vitro T cell culture platforms. Moreover, existing platforms often overlook the

importance of physical parameters, such as culture substrate stiffness, in T cell activation. To address this, we

propose a stiffness-tunable hydrogel culture platform for in vitro T cell culture. The potential impact of such a

platform lies in its ability to synergistically harness biomechanical and biochemical parameters to fine-tune T

cell behaviour. This approach could therefore lead to faster expansion, enhanced activation and greater

control over the therapeutic potency of the cellular product. In this work, T cell-stimulating substrates were

constructed in a range of stiffness using antibody-coated polyacrylamide hydrogels. Successful antibody

attachment was confirmed by immunofluorescence. Confocal microscopy also showed that antibodies were

consistently confined to a thin layer on the surface of all hydrogel samples. Furthermore, we were able to

optimise gel compositions such that no difference in surface ligand density was observed across gels of

different stiffness. This indicates independent control of substrate stiffness and surface ligand density (both

important regulators of T cell behaviour) can be achieved using the hydrogel platform. Moreover, T cells

cultured on hydrogels of different stiffness exhibited differential activation levels, as indicated by their

secretion of Interleukin-2. In summary, preliminary findings suggest that the hydrogels can be made into T

cell-stimulating culture substrates. This raises the potential of using them as an alternative technology to

optimise T cell behaviour in immunotherapy. Future studies will focus on finding the optimal ranges of

stiffness and ligand density needed for enhanced in vivo efficacy of T cells.

89


Lipid Extraction from Microalgal Biomass Using Bio-Based Solvents

Wan Mahmood W. M. A, Theodoropoulos C and Gonzalez-Miquel M



Microalgae are classified as the third generation of biofuel based on its high lipid accumulation. Currently,

highly toxic volatile organic compounds (VOCs), such as hexane, are used as the main conventional solvents for

lipid extraction from microalgae for biofuel production. The goal of this work is to assess the feasibility of using

bio-based solvents to replace VOCs as extraction solvents in developing environmentally friendly processes for

biofuel production from microalgal biomass. Preliminary lipid extraction studies on two dried microalgae

strains, Chlorella vulgaris and Nannochloropsis sp., were performed via Soxhlet extraction method using bio-

based solvents (i.e. ethyl acetate, ethyl lactate, cyclopentyl methyl ether (CPME) and 2-methyltetrahydrofuran

(2-MeTHF)) and were compared against hexane as benchmark VOC solvent for lipid extraction. Overall results

indicate that all the bio-based solvents tested in this work are able to extract lipids from microalgae biomass,

with no significant variation on the fatty acid composition for all extracts. Moreover, the highest gravimetric

yields for both Chlorella vulgaris and Nannochloropsis sp. were obtained when using 2-MeTHF as extraction

solvent. Therefore, it can be concluded that bio-based solvents have the potential to extract lipids from

microalgae outperforming conventional solvents such as hexane. This will help in developing eco-efficient

processes for biofuel production towards building a more sustainable economy based on biomass.

90


From Basic Enzymatic Building Blocks to Bacterial Signalling Pathways: A Systematic

Elucidation of Spatial Regulation and Compartmentalization of Biochemical Pathways

Aiman Alam Nazki



Complex and highly interconnected networks of proteins govern essential cellular processes. Sophisticated

intracellular architecture is a vital organiser of protein networks and function. Compartmentalisation is an

example of a spatial organisation mechanism; seen in a wide range of organisms, from bacteria to eukaryotes,

it serves as an integral part of cellular function. Compartments are an evolutionary hallmark and there is a

growing experimental effort to understand natural systems and build synthetic compartments. For example,

artificial compartments are designed to function as “chemical microreactors” with spatially segregated

reaction pathways.

In mathematical modelling studies, the role of compartments either goes unacknowledged, or is subsumed in

model kinetics. Typically purely kinetic or ODE models, with a few exceptions, are used to study naturally

compartmentalised systems. This work was motivated by the widespread presence and the important role of

compartmentalisation in natural systems. Our aim was to understand the role compartments play in

controlling enzymatic reaction pathways. These modification pathways drive cellular processes and are basic

building blocks of larger signalling networks.

We present two studies, in the first; we considered a wide array of typical enzymatic modification pathways.

We built explicit spatial models to mimic compartmentalisation as well as transport of reaction components

between compartments- a common theme in biological systems. The first study allowed us to gain insights

into the capabilities and constraints conferred by compartmentalising an array of enzymatic pathways. Our

work shows that compartmentalisation can significantly affect pathway characteristics and ignoring it may

result in misleading model predictions.

In the second study, we built on the above investigation of building blocks and their extensions, and applied it

in the context of studying compartmentalisation in a real system- the bacteria, Caulobacter.

Compartmentalisation is seamlessly integrated into the spatiotemporally choreographed phases of the cell

cycle in Caulobacter. By building a bridge from building blocks to real bacterial enzymatic pathways, we sought

to understand the logic of control of key enzymatic pathways by compartmentalisation. This part of the work

has implications in understanding spatial organisation of pathways in other bacterial organisms, as well.

Our work acts as a scaffold to build on exploring more complex enzymatic modification pathways, as well as a

potential design framework to build synthetic compartments.

91



Chemical Engineering at Interface

11:30-12:20 Session on Chemical Engineering at Interface: 3-Minute Research Highlight Talks

(WG5, Aston Webb A Block)

Chair: Professor Paula Mendes, University of Birmingham

11:30-11:35 Jake Airey, Rolls-Royce plc The tribological performance of gas turbine lubricants

11:35-11:40 Ivan Principe, Strathclyde University Development of nitrogen doped resorcinol-formaldehyde gels for carbon capture

11:40-11:45 Pedro Ivo de Oliveira Filho, University College London On ultrasonic aerosol generation and transport under uncertainty

11:45-11:50 Jesús Esteban, University of Birmingham Uptake of a non-ionic surfactant by a tableted compacted powder preparation

11:50-11:55 Neelkanth Nirmalkar, University of Birmingham Generation of bulk nanobubbles in the presence of salts or surfactants

11:55-12:00 Aydin Ozcan, University College London Realistic membrane simulations for nanoporous materials

12:00-12:05 Daniel Sebastia-Saez, University of Surrey CFD study of the liquid-gas interface in structured packings

12:05-12:10 Arwyn Evans, Imperial College London Investigation of the dynamic adsorption of CO using metal-organic frameworks

12:10-12:15 Mohd Izzudin Izzat Zainal Abidin, University College London Studies on two-phase flow past bluff body in a pipe

12:15-12:20 Panagiotis Petsagkourakis, University of Manchester IQC analysis of constrained Model Predictive Control of large- scale system

92


The Tribological Performance of Gas Turbine Lubricants

Jake Airey

University of Birmingham/ Rolls-Royce


Tribology is the science and technology of interacting surfaces in relative motion and involves contact mechanics, friction, wear and lubrication.

The purpose of this project is to evaluate the performance of a number of novel and commercial lubricant candidates over the range of conditions seen within the oil system of Rolls-Royce gas turbines. This project will focus especially on Rolls-Royce's future concept gas turbine design called the UltraFanTM, which presents a new tribological challenge for the lubricant and therefore the effect of different lubricant formulations needs to be investigated. This design features a Power GearBox (PGB) that allows optimisation of the speed of the fan system and the intermediate pressure (IP) turbine. The PGB allows the fan to rotate slower than the IP turbine to which it is connected. Therefore, the IP turbine can rotate faster and hotter and this allows it to be made smaller, which gives rise to a huge efficiency benefit. Slowing the fan speed also results in a reduction in both noise and turbulence. It is the first of its kind in the large civil engine market. Therefore, the lubrication system needs to be able to support the new PGB environment as well its other locations such as various bearing chambers and other gearboxes.

The general formulation of an aviation lubricant consists mostly a long chain ester base stock (usually around 95% of the overall composition) and then a variety of additives to enhance there performance further. These additives include anti-oxidants, anti-wear additives, corrosion inhibitors and anti-foamants.

In order to evaluate the performance of different lubricant formulations, two different tribology rigs are be used called the Mini-Traction Machine (MTM) which has a Spacer Layer IMaging (SLIM) capability and also a Micro-Pitting Rig (MPR).

The MTM measures measure and friction between a ball and disc under lubrication under a variety of sliding and rolling conditions. Parameters such as the lubricant temperature, the load, the speed at which the specimens are rotating and the slide-roll ratio (SRR) can be controlled to create a contact condition similar to what is experienced within the oil system of a gas turbine.

The SLIM uses optical interferometry to measure the thickness of the anti-wear additive films on that are chemisorbed onto the surface of the specimens.

The MPR is similar to the MTM in that it measures friction and wear over a range of sliding and rolling conditions under lubrication except this has a slightly different geometry in that a central roller is contacted by three rings which all contact it with the same load. But this rig is more used to assess lubricant performance by simulating lifetime wear and by observing the progression of a wear mechanism known as micropitting.

The work presented will provide some background information on the area as well as the purpose of the project, will describe the initial research conducted using the MTM and MPR and also briefly discuss the direction of future work.

93


Development of Nitrogen Doped Resorcinol-Formaldehyde Gels for Carbon Capture

Ivan Principe

Strathclyde University


Resorcinol-Formaldehyde (RF) xerogels are organic materials that have been widely studied due to their industrially relevant characteristics, such as high surface areas, suitable pore size and pore volume on which target species can be adsorbed; additionally, RF gels have significant potential to be tailored to specific applications [1], including catalysis, thermal insulation, filtration, energy storage, and gas treatment, especially CO2 capture.

This research focuses on controlling the chemical and physical properties, on both the macroscopic and microscopic scale, with an investigation into the effect these changes have on their application as carbon capture materials. Xerogel properties have been tailored, within this study, by altering the synthesis procedure with focus on monomer concentrations and catalyst to monomer ratio.

Nitrogen has been incorporated into the gel structure in order to enhance the favourable Lewis acid-base interaction with CO2 [2]. Melamine (M) is used in order to incorporate Nitrogen (N) into the gel structure; and partially replace the Resorcinol (R) typically used, resulting in a Melamine-Resorcinol-Formaldehyde (MRF) gel. Repeatability is crucial to method development and validation was achieved by the preparation of a number of gels using a variety of synthetic condition and process routes.

There are a number of parameters that can be altered when synthetizing a gel, namely, R/C (catalyst) and R/F molar ratios, concentration of M, solid content, solution pH, catalyst, solvent, temperature, time, and agitation. This research aims to tailor the gel structure (pore size and volume, surface area, etc.) to enhance the CO2 adsorption capacity and kinetic performance. It will also be important to obtain a better understanding of the N- CO2 interaction. Among all the parameters mentioned above, there are two main aspects influencing the sol-gel chemistry of xerogels synthesised by base catalysed routes, which are the concentration of monomers and catalyst and the initial pH of the sol. Hence, R/C and R/F molar ratios, and M concentration, were chosen for in depth analysis. These factors were varied and their effect on gel properties characterised, allowing a better understanding of how gel properties can be tailored and their impact on gel performance. The remaining parameters were held constant throughout the experiments. RF gels produced were subsequently characterized using volumetric and gravimetric analysis to determine porous structure and quantify CO2 capture capacities and kinetics.

Observations indicate that, texturally, increasing M concentration produces a similar effect as increasing R/C values, which increases pore size, while decreasing surface area. There is also a tendency to increase pore volume when R/C or M increase individually but pore volume and surface area decrease drastically when both variables increase simultaneously. Microporosity also tends to be greater for lower R/C (50-100) than for higher R/C (200-400) and, at the same time, both parameters decrease as concentration of M is increased.

References: [1] Tamon, H.I., H.; Mikami, M.; Okazaki, M., Porous structure of organic and carbon aerogels synthesized by sol-gel polycondensation of resorcinol with formaldehyde. Carbon, 1997. 35(6): p. 791-796. [2] Liu, X., et al., From melamine-resorcinol-formaldehyde to nitrogen-doped carbon xerogels with micro- and meso-pores for lithium batteries. Journal of Materials Chemistry A, 2014. 2(35): p. 14429-14438.

94


On Ultrasonic Aerosol Generation and Transport under Uncertainty

Pedro Ivo de Oliveira Filho



This work presents models for ultrasonic aerosol generation and its transport. It is suitable for applications

that depend on fluid atomisation and transport, for example, spray drying or cooling, ink-jet printing,

agricultural sprays and film coating. In particular, this work has been done in the context of the scale-up of an

aerosol-assisted chemical vapour deposition process, which is often used in the synthesis of films, coatings,

nanotubes and composites. Models for fluid atomisation and transport are presented, which are important

elements for the process transition from the lab to the industrial scale. The aerosol generation is modelled

through an ultrasound atomiser, whereas the aerosol transport system is modelled through straight pipes,

possibly inclined, and bends. Aerosol deposition during transport occurs mainly due to drop gravitational

settling, turbulent diffusion, Brownian diffusion and impaction in elbows, which are modelled. The main

contribution of this work is the proposition of a method to predict the droplet size distribution and fraction

delivered to the deposition site, according to the geometry of the piping system and the properties of the

aerosol and carrier gas.

The formation of the aerosol through ultrasonic vibration has been modelled aiming to predict the median

diameter of the generated droplets, assuming a log-normal distribution, as a function of the fluid and atomiser

properties. Such distribution is the input of the transport model, which incorporates the deposition

mechanisms mentioned above. Different scenarios are studied for the transport system, including horizontal,

inclined or vertical pipes and their combinations using bends. To exemplify the results, small particles have

been found to be transported more effectively. They are mainly deposited in the walls of the transport system

due to Brownian diffusion, which is not considerably affected by the pipe orientation or diameter. On the

other hand, large particles are greatly affected by turbulent deposition and gravitational settling, which made

them more likely to be deposited than the small ones. For a particular log-normal distribution of droplet sizes

entering the transport system, the output prediction is a skewed distribution, which includes sufficient

information to predict the amount and sizing of the aerosol. An extreme case of a coiled pipe has been studied

and further used to test the model fully. Then, it has been validated experimentally for coiled pipes ranging

from 2 m to 8 m of length, including droplet sizing by laser diffraction.

The models and methods presented in this work have been used to reach conclusions and make conjectures

regarding aerosol generation and transport. Different types of losses are taken into consideration, suitable for

transport distances on the scale of industrial processes. The stochastic nature of both aerosol generation and

the factors that cause deposition during transport are incorporated by the model, through the use of

probability distribution functions. The representation and impacts of the uncertainties, especially the ones

verified during the experiments, form the basis for further research.

95


Uptake of A Non-Ionic Surfactant by a Tableted Compacted Powder Preparation

Jesús Esteban, Tom A.H. Simons, Thomas E. Moxon, Serafim Bakalis and Peter J. Fryer



Penetration and imbibition of liquids into porous media is a phenomenon of significance in several applications

both in nature and industry. The latter includes events of relevance in multiphase catalytic reactions, flotation

in the mining industry, ink-jet printing, fabric dying or coating of porous materials. In these and other activities,

the effectiveness of the process or the final quality of the product is in many cases directly related to the rate

and extent of the penetration of the liquid into the porous medium [1].

The imbibition of liquids into different porous materials has been widely reported in literature, although in

most occasions such works refer to the penetration of droplets in non-compacted substrates [2, 3].

To understand penetration and the kinetics of the process into compacted porous preparations, a study has

been made making use of solid materials that are relevant in the formulation of powder detergents and a non-

ionic liquid surfactant.

This work presents the following items:

(a) A methodology to prepare and analyse compacted porous media of controlled inner structure, including

porosity and its distribution. For this, a microtester was used to compress the powders under different loads

and velocities and analysis of the internal structure was realised using micro-computed tomography, a non-

invasive technique.

(b) Gravimetric quantification of the liquid uptake process following a modified Wilhelmy plate technique [4].

For this purpose, the tableted samples were mounted on a tensiometer replacing an ordinary Wilhelmy plate;

then, mass uptake was measured performing a multicycle impregnation experiment infusing and withdrawing

the non-ionic surfactant.

(c) Visualization of the extent of liquid penetration using a fluorescent microscope mounting and fixing the

optically active tablets on an Epoxy resin.

(d) Finally, the liquid uptake by the porous tablets is described following a model based on capillary action.

References:

[1] Gambaryan-Roisman, T., Liquids on porous layers: wetting, imbibition and transport processes. Current

Opinion in Colloid & Interface Science, 2014. 19(4): p. 320-335.

[2] Hapgood, K.P., et al., Drop penetration into porous powder beds. Journal of Colloid and Interface Science,

2002. 253(2): p. 353-366.

[3] Nguyen, T., W. Shen, and K. Hapgood, Drop penetration time in heterogeneous powder beds. Chemical

Engineering Science, 2009. 64(24): p. 5210-5221.

[4] Moghaddam, M.S., et al., Multicycle Wilhelmy Plate Method for Wetting Properties, Swelling and Liquid

Sorption of Wood. Langmuir, 2013. 29(39): p. 12145-12153.

Acknowledgement

The authors would like to thank the Advanced Manufacturing Supply Chain Initiative (AMSCI) for funding the CHARIOT Consortium.

AMSCI is a government supply chain fund which is helping to rebuild British manufacturing prowess.

96


Generation of Bulk Nanobubbles in The Presence of Salts or Surfactants

Neelkanth Nirmalkar and M. Barigou



Bulk nanobubbles are a novel class of bubbles which pose many challenges to our understanding of bubble

physics and behaviour. Based on classical theory, the lifetime of bulk nanobubbles should be of the order of

microseconds, however, these nanobubbles display long term stability. Whilst our understanding of bulk

nanobubble properties and longevity is limited, a wide range of industrial applications have already been

suggested including surface cleaning, drug delivery, ultrasound imaging, tissue preservation and food flavour

retention. The scarce literature reports available suggest that there is immense scope for these nano-entities

to impact and perhaps revolutionise many current industrial processes.

In this work, we investigate the characteristics of bulk nanobubbles generated in the presence of salts

(monovalent, multivalent) and surfactants (anionic, cationic, nonionic). A technique which indirectly tracks

nanoparticles and analyses their Brownian motion in real time is used to visualise the nanobubbles and

measure their size distribution and number concentration. Nanobubbles produced in pure water possess a

negative surface charge. The presence of a non-ionic surfactant does not affect this charge, but anionic

surfactants lead to a stronger negative surface charge whilst cationic surfactants produce positively charged

nanobubbles. At the same time, for all types of surfactant, the number concentration of bulk nanobubbles

decreases with increasing surfactant concentration. Similarly, the population of nanobubbles produced in the

presence of salt reduces as the concentration of salt increases, and this effect is more pronounced for

multivalent salts. This seems to suggest that the electric double layer of the nanobubbles deteriorates with

ionic strength and, therefore, nanobubble nucleation is reduced in the presence of excess co-ions and counter

ions. Interestingly, generation in an alkaline medium leads to the formation of much larger populations of

nanobubbles compared to an acidic medium where the surface charge on the nanobubbles tends to be

neutralised by the positive protons. This finding further strengthens the belief that it is the surface charge

which is responsible for the promotion of bulk nanobubble nucleation and stability. However, whilst in a

similar way to salts all types of surfactant are detrimental to nanobubble nucleation, the underlying

mechanism seems not to be related to the surface charge and could not be attributed to variations in surface

tension since the effect was observed both below and above the surfactant critical micelle concentration.

97


Realistic Membrane Simulations for Nanoporous Materials

Aydin Ozcan and Ozgur Yazaydin

University College of London


Membranes have huge importance for various application areas such pharmaceutical, petro-chemical,

materials purification and biomedical industries. For example, the market share of dialysis applications of

membranes alone exceeds one billion dollar annually. Therefore, designing target-specific membranes have a

great importance and computer simulations open a window to that purpose by describing the interaction

between molecules and membranes. In our study, we introduced a new non-equilibrium molecular dynamics

simulation method to perform “realistic” permeation simulations for molecules across a membrane. The

methodology is based on taking the concentration of species at the inlet and outlet of the membrane as

“collective variables” and controlling them by self-adaptive bias forces. We demonstrate the new method for

methane, ethane, ethylene permeation and ethane/ethylene separation through a flexible ZIF-8 membrane.

The results show that the new method successfully maintains a concentration gradient between the inlet and

outlet of the membrane facilitating the diffusion of molecules. The main novelty of the methodology

introduced in this study is that it allows continuous steady state simulations of mixture permeation through a

membrane while maintaining the concentration of the species at the inlet and outlet of membrane.

98


CFD Study of the Liquid-Gas Interface in Structured Packings

Daniel Sebastia-Saez



This work focuses on the development of the gas-liquid interface over the walls of structured packings by

means of Computational Fluid Dynamics (CFD) simulations. CFD is needed so as to gain insight on the flow

within intricated geometries used in chemical absorbers for Carbon Capture and Storage (CCS). Although

computationally expensive, interface tracking techniques such as the Volume of Fluid (VoF) method allows one

to study the formation of the liquid patterns and irregularities (liquid maldistribution) on the packing walls

instead of the desirable gravity-driven liquid film, as well as the reactive absorption of gas components into

the liquid phase. A simplified computational domain consisting in a small inclined plate is used because of

computational economy reasons. Special focus has been placed on the verification of the simulations, since

systematic assessment of the grid convergence and the grid discretization errors on multiphase CFD

applications are particularly scarce in the literature. The generalized Richardson extrapolation is applied in the

present simulations with this purpose, showing that the selected range of values of the grid spacing gives way

to results which lie within the asymptotic range of convergence. Once the verification of the simulations is

accomplished, the results are compared against experimental data available in the literature for validation

purposes. The simulations are utilized thereafter to carry out an assessment of the influence of the plate

inclination and the liquid inlet velocity on the patterns formed by the gravity-driven liquid film, aiming at

maximizing the gas-liquid interface, since the latter is a critical parameter to the mass transfer performance of

the column. The Froude number is therefore proposed so as to describe the effect of the above mentioned

design parameters on the liquid spreading. The effect of other parameters (viscosity, surface tension, etc.) on

the liquid flow is also assessed. Particular attention is given to the static contact angle, since it has been

indicated in previous studies that it has the greatest effect on the liquid spreading over the packing.

Measurements of the static contact angle on commercial packing surfaces have been taken and introduced

thereafter as boundary conditions in the simulations so as to predict the shape of the rivulets formed on the

inclined surface and the residence time of the solvents. The reactive mass transfer has also been assessed by

using subroutines written in C language and attached to the main ANSYS Fluent code. The concentration

profiles of the species involved in the process are thus obtained, showing the depletion of the carbon dioxide

by virtue of the fast kinetics of the reaction as soon as it crosses the interface.

This work provides thus a CFD tool which can be applied to the selection of packings for a particular

application or to the design process of new products.

99


Investigation of the Dynamic Adsorption of CO Using Metal-Organic Frameworks

Arwyn Evans



Carbon Monoxide (CO) is an important industrial gas. Its uses range from being a reducing agent in the

smelting metals to being a vital component of synthesis gas (syngas), used during the synthesis of methanol

and synthetic oils. Production of CO is accomplished through various processes typically involving partial

combustion of hydrocarbon. These processes result in impurities in the gas stream, including nitrogen (N2),

carbon dioxide (CO2) and water (H2O). Due to similar size, molecular weight and boiling points, it is particularly

challenging to separate CO and N2. Presently, the most common large scale method for this separation is

through cryogenic distillation. This approach is not only costly, but also ineffective in purifying CO with high

concentrations of N2.

This study investigates the use of a class of adsorbents, namely metal-organic frameworks (MOFs), for

purification and separation of CO from gas streams containing high levels of N2. MOFs exhibit favourable gas

storage and separation characteristics due to the tunable properties from the hybrid organic-inorganic

framework. Particularly, several MOFs were synthesized, characterized and then tested for CO adsorption

under dynamic conditions. Different sub-categories of MOFs containing coordinatively unsaturated metal sites

were investigated to compare the effect of metal impregnation against intra-framework open metal sites. The

mechanisms of adsorption were studied so as to identify the features controlling the uptake, selectivity and

heat of adsorption. From the mechanistic and structural information obtained, a best-performing sorbent to

date for dynamic CO uptake was synthesized.

100


Studies on Two-Phase Flow Past Bluff Body in a Pipe

M. I. I. Zainal Abidin, Kyeong H. Park and Panagiota Angeli



Flow past a bluff body above a critical Reynolds number gives rise to a time-periodic regime characterized by

an alternate shedding of vortices behind the bluff body and a von Kármán vortex street. In this work, the

generation of instabilities behind a cylindrical bluff body bounded by a pipe wall and its effects on flow pattern

transitions in oil-water flows from separated to dispersed are studied. Numerical analysis was also carried out

with a commercial code (FLUENT) to assist the design of the bluff body. The work is conducted in a horizontal

37 mm ID acrylic pipe at various oil and water flowrates. The bluff body is a cylinder with diameters 2mm,

5mm and 8mm and is located in the water phase, transverse to the flow direction. Investigations are

conducted for flow rates that result in stratified flow in the absence of the bluff body with a Y-inlet used to

bring in contact the two fluid with minimum mixing. High speed imaging is used to record the flow patterns

and the characteristics of the interface in the wake of the cylinder. The results show that the transition

boundary from stratified to dispersed flows varied as the size of the cylinder is modified. The effect of the

cylinder size on the characteristics of the waves (frequency, amplitude) downstream the cylinder is also

analysed.

101


IQC Analysis of Constrained Model Predictive Control of Large-Scale Systems

Panagiotis Petsagkourakis



Technological advances have led to the widespread use of more complex systems in both industry and

everyday life. Model predictive control (MPC) has been applied to wide range of applications [1]. The MPC

solves an optimization problem in order to minimize/maximize an objective function using the process model

and any other additive constraints. However, many physical systems consist of Partial Differential Equations

(PDEs) [3] and, as a result, many computational problems may arise. This work exploits the dissipative nature

of the underlying phenomena for model order reduction (MOR). Successive linearization is employed off-line

in order to reduce the computational time, constructing a model pool of reduced linear models. These

problems contain many uncertainties that affect the system's stability. The stability and robustness of

predictive control can be analyzed using the theory of integral quadratic constraints (IQCs) [4]. A dissipation

inequality is used [5] to compute an upper bound for the input/output gain when MPC is employed, exploiting

the IQCs in order to consider uncertainties of the closed loop system. The effectiveness of the proposed

method is demonstrated on a chemical engineering application.

References: [1] Camacho, Bordons (2007) Model Predictive Control. Aging (Albany NY).

[2] Edgar TF, Campbell WJ, Bode C (1999) Model-based control in microelectronics manufacturing. Proc 38th

IEEE Conf Decis Control (Cat No99CH36304) 4:85 -91.

[3] Xie W, Bonis I, Theodoropoulos C (2015) Data-driven model reduction-based nonlinear MPC for large-scale

distributed parameter systems. J Process Control 35:50 -58.

[4] Heath W, Li G, Wills A, Lennox B (2005) IQC analysis of linear constrained MPC. IEEE Spons.

[5] Bin Hu MJL, Seiler P (2008) Robustness Analysis of Uncertain Discrete-Time Systems with Dissipation

Inequalities and Integral Quadratic Constraints. Int J Robust Nonlinear Control 18:557 -569

102 102

Poster Presentations – Product Engineering

Poster Presentations

Product Engineering

The Influence of Structural and Physico-Chemical Characteristics of Perfume

Capsules on Their Burst Properties

Andrew Gray

School of Chemical Engineering, University of Birmingham, Birmingham B15 2TT


Capsules on a microscopic scale with a core of perfume have found applications in many products as a means

of targeted fragrance delivery. The impermeable capsules should ideally survive harsh processing conditions,

storage in a product formulation, and initial deposition on the target, rupturing upon application of mechanical

force by the consumer. This delayed release promotes the longevity of the fragrance and acts to improve the

consumer perception of product performance.

It is necessary to have a good understanding of the mechanical strength of the capsules to identify under what

magnitude of force the capsules are likely to burst. A novel micromanipulation technique, developed in

Birmingham by Professor Zhibing Zhang, was used to measure mechanical response of single capsules under a

compressive force1, 2.

A landscape analysis of capsules was carried out, whereby the structural and phyisco-chemical properties of

the capsules were individually controlled with respect to a reference to understand the influence of each

parameter on the mechanical properties of capsules, and what this consequently translates to in the structure.

The construction of a model, based on the results, will allow prediction of the response of capsules under

compression depending on their synthesis variations. Overall the information enables a more refined approach

to the formulation of capsules to maximize performance as fragrance delivery vehicles in the laundry process.

References:

[1] Zhang et al., (1991) A novel micromanipulation technique for measuring the bursting strength of single

mammalian cells, Appl. Microbiol. Biotechnol. 36, 208

[2] Zhang et al., (1999) Mechanical strength of single microcapsules determined by a novel micromanipulation

technique, J. Microencap, 16, 117

103


A Numerical Study of Number Concentration Distribution of Gas-Cylindrical Particles

Flow Based on CFD-DEM

Jie Cai1, 2, Chuan-yu Wu1 and Xiaobao Zhao2 1University of Surrey, Guildford GU2 7XH, Surrey, UK

2School of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing 210042, China


Circulating fluidized beds (CFB) involving cylindrical particles are often encountered in industrial and agricultural

processes such as direct combustion of biomass straws, molding and drying of cylindrical pills, and molding and machining

of composite materials of short fibres. Number concentration of particles in a circulating fluidized bed is one of the most

important fluidized behaviors of circulating fluidized bed because it directly reflects the quality of fluidization. And one of

the research emphases on circulating fluidized bed is to improve the number concentration of particles in the circulating

fluidized bed. Number concentration of cylindrical particles in these processes is of utmost importance as it directly

determines the number concentration distribution of cylindrical particles and hence the hydrodynamics of the gas-

cylindrical particle flow which in turn dictates the overall performance of the system. However, a good understanding of

the theory underlying the gas-cylindrical particle flow is largely lacking due to the complex geometry of cylindrical

particles, in particular in the presence of turbulence.

Experimental study of the gas-cylindrical particle flow behavior has been proven difficult due to technological limitations

regarding collection of data associated with the orientation of individual particles. These limitations have greater impact

in situations where the turbulence is present and significantly affects the flow of cylindrical particles. As yet, no method of

reliable measurement of the orientation of cylindrical particles has been published. Thus, development of accurate and

efficient theoretical models to predict the cylindrical particle orientation under turbulence conditions becomes critical.

Therefore it is valuable to establish an efficient gas-cylindrical particle flow and study the gas-cylindrical particle flow

using the model. In this study a three-dimensional multi-way coupling model was developed for predicting the number

concentration of cylindrical particles in a circulating fluidized bed based on CFD-DEM. In this model, the force and

movement of cylindrical particles in a fluid field was solved by rigid body dynamics and gas-solid flow theory. The coupling

algorithm between motorial cylindrical particles and the turbulence was established by incorporating the correlation

between Lagrangian time scales and the RNG model. Collisions among cylindrical particles were solved by combining

rigid body impact dynamics with the hard sphere model. The model was verified by a cold state experiment of gas-

cylindrical particle flow in a riser, and the simulated results are in good agreement with the experimental results,

including overall orientation and overall number concentration of cylindrical particles in a riser. In addition, some number

concentration behaviors of cylindrical particles during the fluidization were investigated by simulation. The results

showed that in radial direction, the number concentration of cylindrical particles increases from the central region to the

region next door to near-wall region and then declines in the near-wall region, which is different from that of spherical

particles. The number concentration of cylindrical particles in the region next door to near-wall region becomes higher

with the incremental slenderness ratio of cylindrical particles and yet that in near-wall region declines. The number

concentration of cylindrical particles becomes lower with the increasing height position of the riser. The effect of inlet

wind velocity on the number concentration of cylindrical particles was found to be marginal.

Keywords: orientation, cylindrical particle, gas-solid flow, multi-way coupling, collisions among cylindrical particles

104


Process Simulation and Multiobjective Optimisation of the Production of Biomass-

Derived Renewable Polyesters

Monica Lomeli

University of Liverpool


For the first time, we present the process simulation and multiobjective optimisation of the polyesterification

of a library of biomass-derived renewable polyesters: poly(1,5-pentylene succinate) (PTS), poly(1,5-pentylene

2,5-furandicarboxylate -co-1,5-pentylene succinate) (PTFTS) and poly(1,5-pentylene 2,5-furandicarboxylate)

(PTF). Three different industrial reactor configurations were considered: Batch, plug flow reactor (PFR) and

reactive distillation as a process intensification method. The simulation environment was implemented in

Aspen Plus™ and the e-constraint method was followed for the multiobjective optimisation problem,

considering two objective functions that maximise the number molecular weight (Mn) and minimise the heat

duty Q of the reactor. The efficient operation points are reported for each case through the construction of

Pareto frontiers and the performance of the polymers was compared to that of petroderived polyethylene

teraphthalate (PET) in terms of sustainability indicators: Specific energy intensity (RSEI), global warming

potential (GWP) and mass intensity (MI) as well as final polymer attributes, such as segments' concentration

and Mn profiles. The kinetic rate expressions were defined following the functional group approach for step-

growth kinetics whereas the calculation of thermodynamic properties was performed using the Poly(NRTL)

activity coefficient method coupled with the Van Krevelen group contribution method. The kinetic parameters

were estimated by fitting a polyesterification model found in the literature to the experimental data in

Matlab™. The results suggested that the optimum process temperatures were in the range of 190 °C to 215 °C

whereas for PET was 269 °C. The number molecular weight Mn was in the range of 4.2 and 4.7 kDa, which is

suitable for the intended application, coil coatings. The simulated Mn for PET was lower, 3.6 kDa. The

polymerisation is not sensible to the batch reactor or PFR, which allows a flexible and cost-effective operation.

Reactive distillation was the most energy-effective configuration, proving the concept of process

intensification. The results suggest that the production of biomass-derived polyesters release less CO2, as their

GWP represents a reduction of 60 % in respect to PET, as well as lower RSEI (0.78 kBTU·kg-1). The synthesis of

PET presented the highest energy consumption and CO2 release among all the polymers studied, suggesting

that our polyesters would be a sustainable and efficient alternative to conventional PET. The present work

provides comprehensive fundamentals towards a feasible reactor process simulation, and industrial scale up of

the polyesterification of biomass-derived products.

105


Non-Thermal Plasma Assisted Pyrolysis of Waste High Density Polyethylene for

Monomer Recovery

Laura Diaz Silvarrey



Plastic products use has widely spread due to their convenience, versatility, low price and durability. Hence,

plastic waste generation has also increased in the last decade. The amount and composition of plastic waste

varies depending on several factors such as living conditions, economical structure, season and culture;

however, they usually comprise of a mixture of high and low density polyethylene (HDPE and LDPE),

polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and polyethylene terephthalate (PET). Although

environmental waste policies try to maximise the efficient use of resources following the Waste Hierarchy (i.e.

prevention, re-use and recycling, followed by material or energy recovery and finally landfill disposal) in order

to move towards a zero waste society; the reality in most countries is different. For example, in the European

Union, only 26 % (mainly HDPE and PET) of the total plastic waste generated in 2013 were recycled whilst 29 %

were incinerated and 43 % disposed in landfills.

Plastic waste is formed mainly by carbon (80 %) and hydrogen and they present high volatile matter content

(90 %) and calorific value (40 MJ/kg) which are characteristics comparable to fossil fuels. These properties

point them as ideal feedstock for thermo-chemical recycling (pyrolysis) where the plastic structure is altered to

form liquid, gas and solid products of chemical value. Previous results carried out in this research showed that

HDPE pyrolysis yielded around 80wt% of liquid product, formed by a mixture of C5-C20+ alkanes; and around

20wt% gas comprised mainly of methane.

Current research trends suggest the use of advantage technologies, like plasma, to enhance the thermal

decomposition of low thermal conductivity materials like plastics. Thermal plasma assisted pyrolysis (T =

10,000 K) has been studied for plastic waste treatment showing potential for monomer recovery. However,

thermal plasma generation is very energy intensive making plastic waste management less profitable and

environmentally sustainable. However, non-thermal plasma (T = 100-400 K) operates at lower temperatures

reducing the costs and increasing the sustainability of the process.

Preliminary results of HDPE non-thermal plasma assisted pyrolysis showed a considerable increase of the gas

yield (40 wt%) at the expense of the liquid yield (60 wt%). The gas was found to be formed mainly by ethylene

which is the monomer used to manufacture polyethylene as well as a main chemical block for several chemical

processes. The liquid composition was also affected by the use of non-thermal plasma.

The detailed description of the experimental set up and the effect of temperature, heating rate and plasma

power in liquid/gas yield and composition will be given in the presentation, as well as preliminary results

comparing conventional and non-thermal plasma assisted pyrolysis of HDPE.

106


Characterising Chocolate Paste and the Impact on Downstream Processes

Charlotte Iosson



Combining cocoa butter, cocoa liquor, milk solids and sugar produces a chocolate paste which is then refined and mixed with additional fat to produce molten chocolate. Due to the high solids fraction and broad particle size distribution, this paste is a complex material and its texture is difficult to measure: instead we rely on experienced operators to visually assess the texture and adjust refiner settings to cope accordingly.

We have therefore identified a need to measure paste texture/rheology and to this end we have adapted a back extrusion technique in which the forces required to push a probe into a pot of paste can be used to generate fundamental rheological properties of the paste. The ability to quantify the paste texture will be used to collect data on how texture is influenced by processing parameters and how downstream operating conditions can be optimised for a given paste texture or composition. Simple power-law (CMC solution) and Herschel-Bulkley (Xantham Gum) fluids have been used to validate the method before the technique can be adapted to measure chocolate paste, a dense suspensions of solids which must be tested at 40 °C.

This method should enable us to quantify the evolution of paste rheology as a measure of mixing progress during a batch and for comparison of batches produced under different conditions. It is expected that this technique can be adapted for use alongside production lines to improve monitoring and control of the process and drive product quality and consistence.

107


Economic and Environmental Assessment in the Production of Propylene Glycol from

Biodiesel Glycerol Under Uncertainty

Andres Gonzalez Garay



The global policies introduced to develop a bio-based economy have promoted the increase of biodiesel

production, generating large amounts of waste glycerol which is available as a low-cost feedstock. This work

presents the production of propylene glycol as an alternative route to valorise biodiesel glycerol under

economic and environmental criteria. By means of modelling and optimisation tools, three different routes

based on waste glycerol were assessed and compared against the conventional industrial process, which relies

on the use of oil-based propylene oxide. To determine the environmental impact attached to each route, Life

Cycle Assessment (LCA) principles were applied accounting for uncertainties commonly neglected in similar

studies. The performance of the different cases shows that the oil-based technology can be surpassed

simultaneously in economic and environmental aspects (190 % increment in profit and 74 % reduction in

environmental impact). Altogether, this work exhibits the viability to develop sustainable schemes based on

waste glycerol towards the production of high value chemicals, such as propylene glycol, while promoting

holistic bioeconomy frameworks.

108


Electrodeposition of Cu from Deep Eutectic Solvents by Using Pulse Current

Xiaomeng Su

University of Strathclyde


Cu electrodeposition is of great significance in various industries, such as electronics, sensors and aerospace.

Electroplating is the main production process for the deposition of metallic Cu films. Traditionally the process

was performed using aqueous solutions due to their convenience and low cost. However, such electrolytes

suffer a number of drawbacks including poor deposit quality for some metals and pose serious environmental

concerns, for example, when cyanide or chromium (VI) electrolytes are used. In addition, other metals with

very negative reduction potentials, like aluminium and magnesium, cannot be plated from the aqueous

solutions. Deep eutectic solvents, which are a type of room temperature molten salts, serve as the alternative

and can overcome many of the limitations of aqueous solution.

The nature of the applied deposition current is another important factor. The application of direct current (DC)

is the conventional method for plating metals. However, the deposit quality and metal properties are

inadequate in many cases. One way of improving the deposits is by using additives, but these need to be

monitored carefully to maintain performance. However, these issues can often be solved by applying pulse

current (PC) without the use of additives. This research investigates the combined effects of using deep

eutectic solvents and pulsed current deposition. The aim is to explore how they affect the morphology and

microstructure of the metal deposit, with comparisons of the results to those obtained using aqueous

solutions and direct current plating.

109


Simple Lab Set-Up for Agitated Filter Drying of Active Pharmaceutical Ingredients

C. Okeyo1, F. Mallet2, N. Rahmanian1 and F. Schäfer2 1School of Engineering, Faculty of Engineering and Informatics, University of Bradford, Bradford, BD7 1DP, UK

2Particle Engineering Team, Novartis Pharma AG, Novartis Campus, Basel, CH-4002, Switzerland


One of the critical process steps in the manufacture of Active Pharmaceutical Ingredients (APIs) is the drying

step. Agitated drying is the preferred method of drying as it increases the rate of production by enhancing

heat & mass transfer but it exposes the API to attrition and agglomeration. In this work, attrition is defined as

the surface wear and fragmentation of particles whereas agglomeration is the natural phenomenon of

particles sticking to each other or to solid surfaces because of binding mechanisms.

In the lab, the smallest scale testing of Active Pharmaceutical Ingredients (APIs) is an agitated dryer of 100 mL

scale. Hence, we developed a lab scale of 50 mL. With this new set-up, the engineers & scientists are able to

use the proposed workflow & new equipment to have a good grasp of what kind of phenomena they can

expect when drying at a larger scale. To develop the process, the following model compounds are used:

Paracetamol, Caffeine, D-Mannitol (here: Mannitol), and Vanillin.

In conclusion, the new Miniature Agitated Filter Dryer that has been built shows promise in being able to be

used for better understanding of agitated drying of APIs by obtaining data at a smaller scale of 50 ml. The key

parameters to control during investigative studies, as confirmed in literature and empirically, are as follows:

particle properties, agitation protocol, solubility and moisture content (% Loss on Drying).

Keywords: Drying, Agitated Drying, Agitated Filter Drying, API, Lab-Scale

110


The Bradford Process: A New Novel Titanium Production Method - Development and

Optimization

Adam Vollans

The University of Bradford


Titanium, often regarded as a wonder metal is currently an underused material due to its high cost; related to

the expensive production methods needed to manufacture it (The Kroll Process) and lack of any scaled-up

alternative processes (e.g. The FFC Cambridge Process).

This report focuses on the development and optimisation at the laboratory scale of “The Bradford Process” a

new novel method for Titanium Production by reduction of titanium dioxide via calcium metal; developed by

Dr. Raj. Patel and Dr. Jeya K. Ephraim which is simple, green, rapid and cheap compared to existing methods.

This research was carried out using laboratory grade titanium dioxide (anatase; 99.7%) and calcium metal

(98.8%) mixed under wetting conditions and reacted in a vacuum furnace followed by washing, acid leeching

and drying. Sample analysis was performed via: wet chemical analysis, powdered X-Ray diffraction (P-XRD),

scanning electron microscopy with energy dispersive X-Ray spectroscopy (SEM-EDX) and particle size analysis.

This work details the determination of the solid-solid phase reaction kinetics of the process along with

optimised operating conditions, in conjunction with characterisation of the produced titanium via:

composition, purity, phase and mechanical testing analysis of an injection moulded test piece. On-going scale-

up studies are also discussed.

111


Freeze-Drying of Concentrated Sucrose Solutions

Ourania Gouseti



Freeze-drying is typically associated with high quality dried food products (e.g. freeze-dried instant coffee)

compared to other drying techniques (e.g. spray drying). Due to its high-energy demand, energy efficient

processes are continuously being sought. One way to reduce energy consumption during freeze-drying is by

processing highly concentrated (i.e. low in water content) systems. Understanding the link between processing

conditions and product quality is necessary in order to design processes that produce foods with the desired

characteristics. Factors that determine the drying efficiency and properties of the final freeze-dried products

include the concentration of the initial system as well as the drying conditions.

In this work freeze-drying of aqueous sucrose solutions was studied. The effect of primary drying temperature

(-20 °C and -40 °C), temperature transition between primary and secondary drying (fast, slow) and initial

sucrose concentration (10 - 60 % by weight) on the properties (moisture content, volume expansion) of the

final product were studied.

At the lowest investigated concentrations (10 and 20% by weight) the dried systems had generally low

moisture contents (< 5 % moisture) and maintained constant volumes throughout the freeze-drying process.

When the initial sucrose concentration increased, the final dried systems showed higher moisture contents (up

to 8 % moisture) and increased volumes (by up to 8-fold increase compared to the initial volume for the 60 %

initial sucrose system), indicating structure expansion of the system during drying. Gradual temperature

transition between primary and secondary drying resulted in volume retention during drying of the 30 % initial

sucrose concentration system and had little effect on the remaining systems.

Overall this work provides an insight of freeze-drying of highly concentrated systems and presents structure

expansion during freeze-drying, with the potential to produce highly porous solid food matrices.

112


Moving Plastics into the Circular Economy by Chemical Engineering

Matt Green

Recycling Technologies Ltd


Plastic has a significant role to play in the quest for a sustainable future given its unique properties. Global

production has topped 300 Mt pa, and this is expected to double in the next 20 years. However, the systems

for dealing with plastic waste lag significantly behind other materials. The Ellen MacArthur Foundation with

McKinsey at the World Economic Forum reported in the Global Plastic Packaging Roadmap (GPPR) in January

2016 that only 14% of plastic packaging is collected for recycling with just 10 % actually recycled. The rest,

residual plastic waste [RPW] goes to landfill (40 %), incineration (14 %), or shockingly, leaks into the

environment (32 %). This report predicts that, with no change, by 2050 there will be more plastic than fish in

the world's oceans! Our objective is to bring chemical engineering techniques to ensure change and prevent

this from happening.

Mechanical recycling has inherent limitations in producing polymer grades at a price and quality to compete

with virgin polymers. Our aims were to create a process with a high return on investment, with scalability and

with the capability to produce a quality comparable to virgin material.

Recycling Technologies' [RT] innovative sustainably-focused design for the chemical recycling of plastic was

initiated at Warwick University. RT developed and industrialised this technology with a collaboration of

partners from the waste industry, academia and professional practitioners. RT have developed a simple

process, with transportable, modular, mass-producible units (RT 7000) to each recycle 7000 tonnes of RPW per

year on existing waste management sites, turning the RPW into a material called “Plaxx®”. Plaxx® is a clean

hydrocarbon with properties similar to, but cleaner than, crude oil from which polymer manufacturers can

derive feedstock to replace LPG and Naphtha

The original research on the cracking process was conducted on a laboratory scale testing rig (Mark II). A

Knowledge Transfer Partnership with the University of the West of England (UWE) was able to prove that the

hydrocarbon product generated by the Mark II, PlaxxTM, is a viable ultra-low-sulphur Heavy Fuel Oil (HFO)

through chemical analysis and engine trials. Ricardo and Lloyds Register are collaborating with RT in land-

based and sea-based large engine trials.

The success of the Mark II provided the momentum for a one-tenth scale prototype of the final process,

capable of processing 700 tonnes of RPW a year: the RT700.

The RT700 has been commissioned to the point of producing the Plaxx® from RPW, which is being used for

various testing and trials.

With the full collaboration of the local council, the RT700 is being installed at Swindon's recycling centre to

demonstrate its capability to process several feedstock streams as well as its ability to operate on a 24/7 basis.

113


Engineering Washing Powder from Ternary Anionic Surfactant/Polycarboxylate

Based Polymer/Water Systems

M.Hussain, O.J.Cayre and A.E.Bayly

University Of Leeds


Washing powder is usually produced by a process route in which a surfactant slurry is mixed, pumped,

atomized and dried in a spray dryer. The structure of the material changes as it passes through each of these

processes. The slurry structure directly influences the structure of the final product, which needs to be closely

controlled to maximise the product performance in terms of cake strength, flowability and dissolution

properties.

This work explores the structure of a lyotropic surfactant, linear alkylbenzene sulphonate, before any

processing has taken place and intuitively, the initial structure of the slurry prior to any processing will directly

influence the power properties. To understand this, various phase diagrams are presented showing the

influence of polycarboxylate based polymers on the self-assembling structure of the anionic surfactant. It is

clear that different lamellar phases can be induced by increasing the surfactant and polymer concentration;

the lamellar phases present all consist of the same basic bilayer structure, yet they have different physical and

optical properties, which can be related to differences in the physical properties of the slurry, and this work

will attempt to depict this. This understanding can ultimately be exploited to optimize the functional

properties of the washing powder.

Furthermore, the phase rule is explored. Theoretically one should be able to easily predict the number of

phases present in a system when defining the components and conditions present. However as there is a

distribution of positional isomers present in the surfactants used more phases than might be expected may be

seen, as shown by the systems studied.

114


Engineering Nano-Assemblies of Inorganic Particles

Yefeng Li

University of Leeds


Nano-particles, with particle size less than 1 µm, tend to be difficult for users to handle. Therefore they are

often assembled into larger granules for ease of handling and to allow controlled delivery in their desired

function. Engineers who manufacture granules want to be able to control and predict the structures formed

and ultimately predict the functional performance of the granular products.

This project studies the spray drying of Titanium Dioxide (TiO2) slurries. The first stage of the study focuses on

the creation of various morphologies via spray drying approaches. The techniques for controlling product

morphologies are explored via manipulation of the particle-particle interactions in the slurry before they are

dried in order to develop an understanding of how the slurry characteristics and the spray dry processing

conditions effect the drying transformation.

Models will also be used for the prediction of the structural evolution of the droplets. The controlled the

morphologies are then expected to correlate with the required structural properties to fit end applications,

such as mechanical breakage and milling properties. Finally, the relationship between the slurry characteristics,

operation aspects of the spray drier and the nature of the morphology produced will be developed.

In the present work, characterisations were performed on both alumina coated and non-coated TiO2 slurries

in order to develop an overall understanding of the slurry materials provided. SEM results demonstrated the

morphology of the uncoated particle was elliptic with diameter of 300nm, and the coated particles were found

to be highly aggregated. The presence of alumina coating on the surface of titanium dioxide particles was

identified with the EDX analysis. Slurries characterisation work (via sizing, sedimentation, rheology and Cryo-

SEM studies) concluded: in non-coated TiO2 slurry, particles start to flocculate at the iso-electric point. Alumina

coated TiO2 slurry had a highly aggregated structure regardless of its pH.

The subsequent spray drying study investigates how the type of slurry, the structure (stability) of slurries, and

the solid content of the slurry affect the resulting morphology. The obtained dry TiO2 granule products were

smaller in size and more spherical in shape when compared against industry products. This is possibly caused

by the lowered solid content of slurry and drying temperature. In addition, the obtained granules had a solid

structure, which was consistent with theoretical predictions (via Péclet number calculation).

115


Prediction of Self-Heating in Spray Dryer Wall Build-Up of Detergent Powder

Lewis Maxfield

University of Leeds


In the spray drying of detergent powders, it is common for layers of powder to accumulate on the inner walls

of the spray drying tower. At the high operating temperatures of the spray drying tower, the detergent

powders in question are known to undergo the process of self-heating, whereby exothermic reactions

occurring in the powder layer can cause the core temperatures of these layers to increase significantly. If

sufficient self-heating occurs then the powder begins to char, with these charred particles compromising the

quality of the final product, while in extreme cases thermal runaway can occur. Being able to predict this

behaviour through the characterisation of these powders and modelling of these systems will not only help to

limit these problems, but will allow the optimisation of the process for current and new detergent powder

formulations.

Characterising the detergent powder involves measuring the self-heating reactions kinetics and other heat and

mass transfer properties that influence this behaviour. Different methods such as the cross-point temperature

method, steady-state basket method, and thermogravimetric analysis have been used to explore different self-

heating reaction models for the powder. This work compares these methods and aims to establish the best

means of determining these kinetics and the reaction model most representative of the observed behaviour.

Other experimental methods have been applied to measure kinetics for a reaction engineering approach

drying model, thermal conductivity of the powder, and the effective heat transfer coefficient of the convective

oven used.

By building on existing models of similar systems, and by applying the measured reaction kinetics and heat and

mass transfer properties, this work aims to model the self-heating behaviour of baskets of detergent powder

using a 2D transient model with coupled conduction and reaction behaviour, built using gPROMS ModelBuilder

and MATLAB. This model measures the transient evolution of temperature, liquid moisture content in the

particles, vapour concentration in the voids between the particles, and the concentration of reactive

component along a discretised domain in the radial and axial directions as these baskets are heated under

oven conditions. Having validated the model against temperature profiles measured during the basket heating

experiments for both detergent powder and skimmed milk powder, whose properties are better documented

in literature, it has been successfully used to predict the critical external temperature of a number of different

sized baskets of detergent powder. This model can then be adapted to predict the self-heating behaviour in

spray drying tower wall build-up and explore the effects of build-up properties and tower temperature on this

behaviour. This model will also allow optimum tower temperatures and process conditions for current and

new detergent powder formulations to be determined.

116


Fuel from Waste Plastic - Towards a Circular Economy for Plastics

M. Green1, A. Griffiths1, Jonathan Seville2, R. Thorpe2 and G. Leeke3 1Recycling Technologies Ltd

2CMAC, Univeristy of Strathclyde 3University of Cranfield


Plastic has a significant role to play in the quest for a sustainable future given its unique properties. Global

production has topped 300 Mt pa, and this is expected to double in the next 20 years. However, the systems

for dealing with waste plastic lag significantly behind those for other materials. The Ellen MacArthur

Foundation with McKinsey at the World Economic Forum reported in the Global Plastic Packaging Roadmap in

January 2016 that only 14 % of plastic packaging is collected for recycling with just 10 % actually recycled. The

rest, residual plastic waste [RPW], goes to landfill (40 %), incineration (14 %), or shockingly, leaks into the

environment (32 %). Their report predicts that, with no change, by 2050 there will be more plastic than fish in

the world's oceans! Engineering methods for recycling waste plastics are urgently required. The challenge is to

turn a standard waste plastic feedstream into a hydrocarbon product comparable to virgin material, and to do

this in a process of appropriate scale and with attractive return on investment.

Recycling Technologies' [RT] innovative pyrolysis-based design for the chemical recycling of plastic has been

developed in conjunction with a series of academic and industrial partners, starting from an initial concept

from the University of Warwick. RT has developed and industrialised the technology with partners from the

waste industry and professional practitioners. The innovative equipment design consists of transportable,

modular, mass-producible units, each designed to recycle 7000 tonnes of RPW per year on existing waste

management sites, turning mixed plastic waste into a clean hydrocarbon with properties similar to, but cleaner

than, crude oil, from which polymer manufacturers can derive feedstock to replace LPG and Naphtha. The

process can also be used to make a viable ultra-low-sulphur Heavy Fuel Oil (HFO); Ricardo and Lloyds Register

are collaborating with RT in land-based and sea-based large engine trials using this fuel.

In the current state of development of the concept, a scaled prototype of the final process, capable of

processing 700 tonnes of RPW per year, has been commissioned to the point of producing tonnage quantities

of product, which is being used for extensive testing and trials. In the spring of 2017, this unit will move to the

Swindon Borough Council recycling centre with the aim of demonstrating its capability to process several

different feedstock streams as well as its ability to operate on a 24/7 basis.

The paper describes the essential elements of the process and summarises the results to date.

117


Effect of Impurities on Rich CO2 Fluids in Pipelines

S. P. Peletiri, N. Rahmanian1 and I. M. Mujtaba

School of Engineering, Faculty of Engineering and Informatics, University of Bradford, Bradford, BD7 1DP, UK


The carbon dioxide (CO2) captured from power plants or oil and gas processing facilities which are used either

for storage in saline aquifers/depleted oil reservoirs or enhanced oil recovery are rarely pure and may contain

several impurities. These impurities have effects on the phase behaviour of transported CO2 in pipelines which

in turn can have adverse effect on the economy of the transportation process by increasing the number of

booster stations installed in the pipeline, the diameter and strength of the pipeline material. It is therefore

crucial to understand the effect of these impurities on the flowing fluid for an efficient operation of CO2

pipelines.

The effect of 10 % of each impurity; nitrogen (N2), methane (CH4), hydrogen sulphide (H2S), oxygen (O2),

sulphur dioxide (SO2), nitrogen oxide (NO) and carbon monoxide(CO); in 90 % CO2 is considered in this study.

Aspen HYSYS (ver.8.8) is used to simulate the properties of the binary fluids (CO2 and one impurity). Most

impurities cause an increase in pressure drop. SO2 has the highest reduction of pressure drop while H2 causes

the highest increase in pressure losses. All impurities cause an increase in critical pressure with H2 resulting in

the highest critical pressure and SO2 the least. The lowest critical temperature was with CH4 while the highest

critical temperature was with SO2. All impurities cause a two-phase region of the rich CO2 fluid. H2S make a

narrow phase envelope (i.e. closeness of the bubble and dew point curves) while CO causes a very wide two

phase region at CO2 pipeline operational temperatures and pressures. The change in temperature is least

pronounced with H2 and most pronounced with SO2.This study identifies the impurities which have the most

adverse and favourable effects on CO2 transportation in terms of operation and design which finally influence

the capital and operational costs of CO2 pipelines.

Keywords: CO2 pipeline, impurities, critical pressure, critical temperature, phase envelope, bubble point, dew

point.

118


Optimisation of Particulates Processing, Packaging and Filling in a Pilot Scale Facility

Immanuel Sebastine1, Dr Ruksanna Ahmad1, Dr Tony Jackson1, Andrew White1 and Mr David Smith2

1Centre for Process Innovation 2DJS Process Consulting Ltd


The abstract outlines a pilot scale research facility for particulates mixing, processing, packaging and filling at

Centre for Process Innovation (CPI). The success of any formulated product is not only dependent upon its

formulation but also the packaging within which it is sold. Handling and processing of powders and particles

pose many challenges in manufacturing. The performance of a packing line process is a function of the

equipment, process design, the physical properties of the product and the process control strategy employed.

The industry is heavily reliant on packaging as both the means to present the product to the consumer and as

the method of providing protection to the product between manufacture and end use. Currently a major

industrial capability gap in the behaviour of new formulations and it is not known until a new product moves

to full scale production trials. A research facility with a very broad application based upon common powder

handling and dosing equipment would enable to understand the behaviour of new powder and complex

particle formulations. CPI is creating a package filling research capability for formulations of particulates based

around a highly instrumented pilot line. The state of the art instrumentation will enable a seamless integration

with particle modelling activities such as model validation and real life technical insights guiding model

development. The facility could be used by clients to make test runs with new products and packages creating

representative packed samples for consumer testing or other technical tests. Whilst at top level, problems in

the powder industry related to the packing of dry materials are not dissimilar to other packaged dry consumer

goods, the study outlines six specific focus areas that will be of particular interest and relevance in the food

industry: pack to pack content variability, reduction of product “give away”, quick changeovers without

contamination, process reliability losses (down times), training and demonstration of process improvements &

scale up. It is common, even in multinationals, for in depth technical training on equipment operating

principles to be weak. Whilst operators and plant level engineers will be able to operate equipment safely

under normal conditions, they will not have adequate knowledge to troubleshoot problems or to make

meaningful continuous improvement. The pilot scale facility would be ideal for technical training courses in the

operating principles, best operating practices & trouble shooting of powder packaging and filling.

119


Characterization of Spray-Dried Detergent Powders

Amin Farshchi, Ali Hassanpour, Joel Caragay and Andrew Bayly

University of Leeds, Leeds, LS2 9JT, UK


Detergent powders were produced by spray drying of slurries containing linear alkylbenzene sulphonate (LAS),

hydrophobically modified carboxylate polymer, sodium sulphate, and sodium silicate. In this study the

morphological and surface properties, internal structure and self-assembled nano-structures in resulting spray-

dried detergent powders were investigated. Microscopic observations, using Scanning Electron Microscopy

(SEM) and Morphology G3, detergent powders produced from high-water content (60 wt%) were more

irregular in shape with rougher edges, while low-water content (30 wt%) slurries have a tendency to produce

particles with more spherical and smooth characteristics. 3D reconstructed volumes obtained from x-ray

microtomography techniques showed the presence of large volume fraction of (22.7 %), i.e., the ratio of

volume of undissolved sodium sulphate to that of all constituents) in detergent powders produced from low-

water content slurries. However, as the water content increased the aforementioned volume fraction

decreased to 0.7 %. A combination of SEM and Microtome techniques also was used to probe the

microstructure of powder shells. These results suggested that in spray-dried powders produced from low-

water content slurries, the texture of the wall appears noticeably compact, while detergent slurries with lower

solids content led to the formation of irregular open pores with some degree of interconnection. Wide-angle

x-ray diffraction measurements revealed that in the absence of binders, i.e., sodium silicate and polymers, and

low water concentration, thenardite only exists as the most stable polymoph of sodium sulphate. However,

with increasing the concentration of water or addition of binders to the formulation a metastable phase of

sodium sulphate can also be detected. Diffraction peaks of small-angle x-ray diffraction measurements

corresponded to lamellar domains. The addition of sodium silicate resulted in the disappearance of lamellar

phases with large d-spacing values.

Keywords: Detergent powder, spray drying, morphology, x-ray microtomography

120


Micromanipulation Experiments to Study Adhesive Forces between Model Detergent

Particles

Tom A.H. Simons1, Jesús Esteban1, Serafim Bakalis1, Zhibing Zhang1, Claire Duckitt2 and Hossam Tantawy2 1School of Chemical Engineering, University of Birmingham, Birmingham, B15 2TT, UK

2Procter & Gamble Newcastle Innovation Centre, Whitley Road, Longbenton, Newcastle, NE12 9TS,


Powder caking is an undesired effect of particles bonding and clumping, commonly encountered in chemical,

pharmaceutical, food and detergent industries in production and storage. Caking studies have focused

primarily on bulk materials, as presented in an overview by Calvert et al. [1]. A more fundamental

understanding and prediction of caking may be obtained by investigating both bulk materials and individual

particles [2]. Interactions between model particles representative for detergents, studied in

micromanipulation experiments, will be presented here.

Model particles were first prepared by coating microcrystalline cellulose spheres with a layer of one of the

detergent chemicals in a fluidized bed. Adhesive forces between a pair of particles of the same composition

were then measured for different coating chemistries using a micromanipulation setup very similar to the one

presented by Zhang et al. [3]. In these experiments particles were lightly compressed and subsequently

retracted to measure the maximum pull off force with a μN-range force transducer. Coating chemicals thought

to cause the highest adhesive forces at usual lab conditions were ranked quantitatively. These results may be

used for product design and formulation regarding caking prevention. Future research will focus on precise

control of relative humidity and temperature during measurements to study how these two environmental

parameters affect the resulting adhesive forces, as well as on the effect of liquid bridges between two particles.

Acknowledgement:

This study being part of the 'CHARIOT'-project, we are grateful for AMSCI funding.

References:

[1] G. Calvert, N. Curcic, C. Redhead, H. Ahmadian, C. Owen, D. Beckett, M. Ghadiri, Powder Technology, 249

(2013), 323 - 329.

[2] M. Wahl, U. Bröckel, L. Brendel, H.J. Feise, B. Weigl, M. Röck, J. Schwedes, Powder Technology, 188 (2008),

147 - 152.

[3] Z. Zhang, M.L. Sisk, H. Mashmoushy, C.R. Thomas, Particle & Particle Systems Characterisation, 16 (1999),

278 - 283.

121


Chemical Sensing of Washing Powder by Multispectral Imaging

Soori U, Yuen PWT, Selvagumar S, Zahidi U, James D and Richard M

Centre for Electronic Warfare, Information & Cyber (EWIC), Cranfield University, Defence Academy of UK,

Shrivenham SN6 8LA


Domestic washing powder consists on a unique washing formula which contains more than 20 different

chemicals in a mixture. For washing powder manufacturer, it is very crucial to enumerate these chemicals

mixture from mixing to packaging cycle for quality assurance. However, it is extremely difficult to quantify the

quantity of each constituent by conventional broadband RGB images, as most of them appear in the same

shape, size and white colour in the visible spectrum. On the other hand, spectrometer based measurements

also have other weaknesses namely, limited sample size and computational cost. This imposes a technical

challenge for the powder manufacturing industry to seek for an effective quality control system during powder

production and packaging.

Hyperspectral imaging (HSI) and Multispectral imaging (MSI) is well-known for chemical discrimination through

spectral analysis. However, it creates another problem to quantify subpixel small powder chemicals in the

mixture due to the limited spatial resolution in the HSI/MSI system. This research formulates part of the AMSCI

funded CHARIOT project to develop a low cost near real-time system for at-line quantification of powder

mixture during production. This work compares the capabilities of subpixel powder classification using

Adaptive Cosine Estimator (ACE) algorithm, Support Vector Machine (SVM) and spectral Unmixing under the

Nonnegative Constrained Least Squares (NCLS) within Linear Mixing Model (LMM) using both reflectance and

1st and 2nd order derivatives.

The performance of the powder discrimination is assessed by 1) ground truth map for colour powder mixture

extracted from high-resolution DSLR images, 2) the pre-mix volume of individual powder constituents for

white samples. It is observed that the Unmixing under NCLS method has provided a better means to quantify

the mixtures of 3, 5 and 7 different chemical powders for at least 20mm x 20mm sample size. Moreover, in

order to facilitate at-line classification of powder mixture active MSI system have been developed, which is

capable to perform in near real-time. The demonstration of Multispectral Chemical Analysis and Mapping

(MCAM) for Powder Production will be organised in ChemEngDayUK conference.

122


Kinetics of Gas Behaviour in Detergent Slurry under Pressurisation-Depressurisation

Process

Hui Cao



In the presented research, three gases – air, argon and carbon dioxide have been used to investigate the gas

effect on slurry volume expansion during pressurisation and depressurisation process. The concept behind this

research is to assess the effect of additional gas in high pressure pipe (between 60 to 80 bar) with the

potential benefit to increase particle porosity after spray drying process.

The slurry was first mixed at 60 °C with 250 and 400 rpm mixing rate which created two air bubble size

distribution within the slurry (characterised by X-ray Microtomography (XRT)). A small amount of slurry

(around 0.1 g) was then loaded to a 0.5 mL micro centrifuge tube with a safe-lock lid and sealed before

pressurisation. The tube was then opened on the top and put in a high pressure rig. The three investigated gas

was pumped into the rig to generate pressures at 30, 60 and 90 bar for air and argon, and 72 and 75 bar for

carbon dioxide. After depressurisation, optical camera was first used to characterise the volume change of the

slurry. Later on, XRT was used to reveal internal structure changes of the slurry. Results indicate that among

the three gases, carbon dioxide has the best permeability in the slurry which significantly increases the slurry

volume after depressurisation.

123


Soft Particle Coating with Salt in a Fluidised Bed Coater

Ling He1*, Lei Xing1, Bingyu Zhuo1, Jerome Castro2, Serafim Bakalis1 and Zhibing Zhang1 1School of Chemical Engineering, University of Birmingham, Birmingham B15 2TT

2P&G Technical Centres Limited, Newcastle Innovation Centre, NE12 9BZ


Undesirable caking of particles as a result of water uptake, consolidation and deformation is a common

phenomenon observed in many different powder systems on storage. Caking renders these particles unusable,

often leading to loss in original function.

In this study, hygroscopic and hardness properties of a model soft particle were improved by coating it using

different salt coating materials in a fluidised bed coater (Mini-Glatt, Glatt, Germany) with a spraying nozzle of

0.5 mm in diameter. The inlet air flow rate and coating liquid injection rate were controlled at 0.8 μL/min and

200 μL/min respectively.

Sodium chloride solution, Sodium Chloride solution with 3 % (w/v) Ethylene Glycol or 2 % (w/v) glycerol and

Silicon Dioxide (silica) and Silicon Dioxide (silica) were used as coating materials. The size of the core particles

was measured using Sympatec high speed image analysis sensor QICPIC with dry gravity disperser GRADIS. The

coating coverage and shell thickness were investigated via scanning electron microscopy (SEM) combined with

a microtome technique. The hardness, flowability and hygroscopicity of the particles before and after the

coating were characterised Uni-axial compressor test with Instron Micro Test 5848, Ring Shear Tester RST-XS

by Dietmar Schulze, and Dynamic vapour sorption respectively.

It was found that the extent of surface coverage on the core particles by sodium chloride depended on its

concentration, but sodium chloride with a concentration higher than 5 % precipitated from aqueous solution

during the fluidised bed coating, resulting in blockage of the nozzle during liquid spraying. The precipitation

issue was resolved using sodium chloride solution with 3 % (w/v) ethylene glycol or 2 % (w/v) glycerol to

reduce the vapour pressure of the salt. Full surface coverage of the core particles was achieved at a shell to

Core ratio of 15 % (w/w), with a mean shell thickness of approximately 8 μm.

The hardness of NaCl coated soft particles was improved by around 80 times but the hygroscopicity of the

coated particles was increased due to the salt’s high absorbance of water. In order to reduce the

hygroscopicity, water insoluble and non-hygroscopic silicon dioxide (silica) was applied onto NaCl coated soft

particles at a ratio of silica to NaCl coated soft particles of 2 % (w/w). The details of the results and their

significance will be presented.

124


Improvement in Flowability of Soft Particles with Coating

Bingyu Zhuo1, Lei Xing1, Ling He1, Zhibing Zhang1, Serafim Bakalis1 and Jerome Castro2 1School of Chemical Engineering, University of Birmingham, Birmingham B15 2TT UK

2P&G Technical Centres Limited, Newcastle Innovation Centre, NE12 9BZ, UK


Undesirable consolidation of particles is a common phenomenon observed in many different powder systems

on storage. Caking renders these particles unusable, often leading to loss in original function. The aim of the

study is to investigate how storage stability of these particles can be improved through coating.

Model soft particles were used as the core material which was coated with different amount and types of salts

using a Mini Glatt Fluidised Bed Coater. A commonly used water soluble polymer was also used in this

experiment as alternative coating material. The coated and uncoated particles were characterised by their

sizes, shape, surface roughness, particle density, hardness, hygroscopicity and the surface composition. The

degree of coating and coating thickness were also measured using a Scanning Electron Microscope (S.E.M)

coupled with Energy-dispersive X-ray (EDX). Confined compression test on the bulk samples were done to

determine the hardness of the material based on the compression behaviour model by Heckle and flowability

was analysed using a Dietmar-Schulze ring shear cell tester after conditioning the samples in a 30 °C/ 30%

Humidity oven. Hygroscopicity of the coated and uncoated particles was also investigated using a Dynamic

Vapour Sorption (DVS).

Results showed that an increase in hardness generally resulted in better flowability using salt coating materials.

It was also found that this could be achieved by coating the soft particles with more than 80 % coverage on the

surface of the core. Interestingly however, the same level flowability could not be achieved with the

alternative water soluble polymer despite demonstrating similar hardness and percent coverage suggesting a

different failure mode e.g. hygroscopic nature of the polymer. Hygroscopicity of the coating materials thus also

plays a role in flowability beyond hardness and coverage even with the use of salt coating materials.

125


Preparation and Characterizations of Hybrid Mesoporous Silica Membrane on

Polymer Substrates

Zheyi Meng and Marc-Olivier Coppens

University College London, Department of Chemical Engineering and Centre for Nature Inspired Engineering,

Torrington Place, WC1E 7JE, London, UK


Surfactant-templated mesoporous silica materials possess a uniform distribution of pores with a constant size,

ranging from 2 to 10 nm [1]. Due to their size-exclusion for larger molecules, stability and chemical

modifiability, they show excellent potential for applications in separation, sensing and drug release. Thus,

numerous studies have focused on the fabrication of hybrid mesoporous silica membranes (HMSM) with

porous anodic alumina substrates (AAM), which help silica to form a hierarchical structure [2, 3] in their

aligned nanochannels. However, AAM-templated HMSM is fragile, which seriously limits their potential

applications. The fabrication of a robust HMSM is still challenging.

Superior to AAM substrates, polymeric materials display good robustness as supporting materials in the

fabrication of HMSM via track-etch membranes [4] and hollow fibers [5,6]. Here, in order to find a relatively

low-cost and easy way to scale up the preparation of HMSM, we explored two methods with commercial

polymeric filtration membranes as substrates. Both methods have no special demands for a complex

apparatus, and differ in gelation and aging conditions.

By comparing SEM images, silicon content and filtration properties of HMSM samples fabricated via the two

methods, we found that the tetraethoxysilane vapor atmosphere plays an important role in increasing the

silica covering rate and improving the rejection rate of model ions (fluorescein ions, FL2-). Also, we found that

silica growing on the matrix of polymer substrates affects their mechanical strength; in particular,

polyethersulfone maintains better mechanical strength after silica growth, than nylon does.

References:

[1] Platschek, B.; Keilbach, A.; Bein, T., Advanced Materials 2011, 23 (21), 2395-2412.

[2] Yamaguchi, A.; Uejo, F.; Yoda, T.; Uchida, T.; Tanamura, Y.; Yamashita, T.; Teramae, N., Nat Mater 2004, 3

(5), 337-341.

[3] Meoto, S.; Coppens, M.-O., Journal of Materials Chemistry A 2014, 2 (16), 5640-5654.

[4] Wang, M.; Yang, G.; Jin, P.; Tang, H.; Wang, H.; Chen, Y., Scientific Reports 2016, 6, 19148.

[5] Jang, K. S.; Kim, H. J.; Johnson, J. R.; Kim, W. G.; Koros, W. J.; Jones, C. W.; Nair, S., Chemistry of Materials

2011, 23 (12), 3025-3028.

[6] Kim, H. J.; Chaikittisilp, W.; Jang, K. S.; Didas, S. A.; Johnson, J. R.; Koros, W. J.; Nair, S.; Jones, C. W.,

Industrial & Engineering Chemistry Research 2015, 54 (16), 4407-4413.

126


Prospect Liquid Scale up Facility for Process Development and Metrological Studies

Katharina Roettger, A. Smith, M. Taylor and J. Carrol

Centre for Process Innovation


The abstract outlines a pilot scale research facility for liquid scale up established by Centre for Process

Innovation (CPI) and the School of Chemical Engineering, University of Birmingham. The state of the art

facilities enable our clients to develop, prove, prototype and scale up the next generation of products and

processes. CPI’s liquid rig platform is designed to assist companies of all sizes to create innovative solutions to

traditional chemical processing techniques in order to create more efficient and sustainable manufacturing

processes. Using state of-the-art facilities and analytical tools as well as new ways of performing chemistry and

producing molecules, CPI are able to accelerate and de-risk the translation of innovations into new and

improved processes.

The new facility will have two major functions:

1. Understanding the dynamics of manufacturing formulations at different scales and enabling predictive

scale-up of batch formulation processes.

2. Developing, validating and utilising new sensor technologies and process analytics capabilities.

The initial instrumentation that will produce the data for understanding and predicating processes include

focused-beam reflectance measurements (FBRM), laser diffraction particle sizing, an in-line rheometer and

various sensors for temperature, pH and density, which will be controlled by state-of-the-art software and

provide a wealth of information about any formulation process. Together with experts from the Universities of

Birmingham, Leeds and Edinburgh, CPI will use this data to gain an understanding of the universal principles of

formulation processes.

127 127


Energy Generation, Storage and Uti lisation

Optimising Biodiesel Production from Waste Cooking Oil Using Supercritical Methanol

Omar Aboelazayem1,2, Mamdouh Gadalla2 and Basu Saha1 1School of Engineering, London South Bank University, 103 Borough Road, London, SE1 0AA, UK.

2Department of Chemical Engineering, The British University in Egypt, Misr-Ismailia Road, El-Sherouk City 11837, Cairo,

Egypt.


Petroleum based fuels are considered as main sources of world’s energy including coal, natural gas and petroleum oil

fractions. However, due to oil reserves limitation, unstable oil price and extensive emissions of greenhouse gases,

which are the main cause of global warming, make the petroleum-based energy unreliable. Consequently, it is

essential to find an alternative renewable, green and sustainable source of energy for fossil fuels replacement.

Biodiesel has been considered as an important renewable fuel in the worldwide markets, due its economic and

environmental benefits. In spite of its lower heating value, biodiesel has its advantages over petroleum based diesel

fuel: it is biodegradable and nontoxic, it provides free sulphur and aromatics combustion and it is a greener fuel as it

emits lower carbon monoxide and hydrocarbon. Waste cooking oil (WCO) has been recognised as a significant

feedstock for biodiesel production. It provides more sustainability for the product since it includes the transformation

of waste to a valuable source of energy. However, free fatty acid (FFA) content is usually high in most of the WCOs,

and hence they require pre-treatment before biodiesel processing. Biodiesel production under supercritical

conditions of methanol tolerates feedstock with high FFA content. In addition, it is a noncatalytic process which

optimise the catalyst preparation and separation costs, it operates the reaction with high conversion for both FFA

and triglycerides within short period in comparison with the conventional catalytic reactions.

In an attempt to overcome the high FFA content in WCO, this work illustrates the applicability of biodiesel production

using supercritical methanol in transesterification reaction. Response surface methodology (RSM) via Box Behnken

Design (BBD) was employed to study the significance and interactive effect of methanol to oil (M : O) molar ratio,

reaction temperature, pressure and time on biodiesel yield. A quadratic model equation has been obtained

describing the interrelationships between dependent and independent variables to maximise the response variable

(biodiesel yield). In addition, validity of the predicted model has been confirmed using Analysis of Variance (ANOVA)

method. Using numerical optimisation technique, optimum conditions for maximum biodiesel yield (96 %) has been

concluded at a methanol to oil molar ratio of 36.8 : 1, reaction temperature, pressure and time of 267 °C, 226 bar and

22 minutes, respectively. Kinetic and thermodynamic data for overall transesterification reaction have been studied

at a temperature range of 240-270 °C and the resulting reaction rate constant and activation energy are 0.0006 s-1

and 50.5 kJ/mol, respectively.

128

Poster Presentations – Energy Generation, Storage and

Utilisation

Sustainable Planning of Energy-Water-Food Nexus Using Decision Making Tools

Jen Ho Ker,Niclas Bieber, Xiaonan Wang and Nilay Shah



The United Nation’s Sustainable Development Goals (UN SDGs) condense the major challenges facing human society

into 17 categories, many of which are interlinked and related to the energy-water-food (EWF) and climate change

nexus. Integrated system analysis is more and more important for sustainable development by addressing challenges

in natural resources, economic sectors, and human behaviors in a systematic manner. However, the main

infrastructure and service of energy, water and food sectors are delivered in an isolated manner, causing investment

and operational strategies limited to a single system and neglecting potential synergies across sectors.

To address the urgent challenges society is facing in urbanization and its associated energy demand and supply, we

developed a holistic methodology and platform to support the resilient and sustainable planning at city-region level

for multiple sectors, combining agent-based modelling to simulate and forecast resource demands on spatial and

temporal scales, with resource network optimization incorporating capital expenditures, operational costs, and

environmental impacts to find optimal allocations of resources and technologies given these demands [1]. In addition

to a comprehensive study of water and sanitation sector study in a developing country context [2], we will also

demonstrate how this framework can be applied to urban energy systems and the energy-water-food nexus.

The results suggest environmentally friendly and cost effective plans for sustainable city development by 2030. Both

energy demand side simulation and supply side optimization are used to test innovative energy deployment policies

especially to address the provision of clean energy for every citizen. A set of scenarios consisting of technological

evolvement, effects of climate change and related policies are created to illustrate the application of the model

especially in energy sector development. The cost of greenhouse gas emissions and the opportunity cost of land use

based on the feasible food production are evaluated and optimized in various scenarios. Some typical scenarios are

discussed in details such as how the capacity factor reduction for large-scale hydropower or agricultural

intensification with yield increasing change the optimal power generation mix in future. Specific to the studied region

(e.g., Ghana), it is found that the reduced power generation by large-scale hydropower is compensated for by the

introduction of additional natural gas, solar thermal and photovoltaic capacity. Agricultural intensification is observed

to promote the use of both solar thermal and solar photovoltaic power with a preference for solar photovoltaic

power. Not only specific case and scenario analysis, the major contributions of this work also include the creation of a

generalized algorithm with a uniform cost function and constraints that can effectively handle and dispatch different

types of technology in a variety of essential sectors.

129


Utilisation

The Development of a DBD Plasma, Microbubble Enhanced Waste Treatment Reactor

Alexander Wright

Loughborough Univeristy


In 90 % of developing countries, sewage discharged into water courses is untreated [1]. This can not only dramatically

affect the health of inhabitants nearby who use the same water course for their drinking water supply but can also

affect the balance of the surrounding wildlife and environment. Even in developed countries there is strong evidence

showing that waste water treatment plants are not completely effective at removing pathogenic bacteria.

It is now widely known within and outside of the scientific community there is a shortage of renewable energy

options to replace the diminishing supply of fossil fuels. In recent years biomass has been seen as a sustainable

alternative to provide a transport fuel for the growing number of vehicles on the roads. Here a cellulose rich product

is fermented to form ethanol via an intermediary of glucose. However the existing methods for the breakdown of

cellulose are either energy intensive or have a high consumption of chemicals.

A novel pre-treatment reactor has been developed to address both of these global issues at the same time by

processing human faeces in waste water to not only sterilise the waste but to also produce ethanol. At the core of

the reactor is a dielectric barrier discharge plasma module which with compressed air as a process gas generates a

host of reactive oxygen and nitrogen species including ozone and hydroxyl radicals. These species have a high

oxidation potential making them highly reactive to organic molecules that are present in human faeces and target

the carbon-carbon bonds that are present in cellulose allowing for the production of glucose. To ensure efficient

delivery of these reactive species to the water, the plasma discharge is brought to the gas-liquid interface by utilising

a nickel microporous membrane as the ground electrode of the system. The membranes in combination with a fluidic

oscillator allow for the production of microbubbles which with their large surface area to volume ratio allow for the

maximised mass transfer from the plasma gas to the liquid phase.

Three operating regimes were identified by changing the modulation of the plasma. This enabled close control of the

plasma chemistry (O3, OH, etc.) and the pH of the liquid. Operating at 45 % modulation, the reactor consumes 13W of

power and is able to reduce the concentration of E. coli, a bacterium commonly found in waste water, by 4.5 logs in

20 min. A human faeces simulant was used and over a period of 30 minutes the doubled the available glucose [2].

References:

[1] Esrey, S.A. (2000). Towards a recycling society. Ecological sanitation - closing the loop to food security. In

proceedings of the international symposium, 30 -31 October, 2000. Bonn, Germany. GTZ, GmbH. 2001.

[2] Wignarajah, K., Litwiller, E., Fisher, J., Hogan, J. (2006). Simulated human feces for testing human waste

processing technologies in space systems. 36th International Conference on Environmental Systems, SAE paper no.

2006-01-2180. Norfolk, VA. 2006.

130


Utilisation

Systems Analysis of Road Transportation Decarbonisation Options

Yasmeen Aldawsari



Following the establishment of the 2008 Climate Change Act, the United Kingdom committed to reducing greenhouse gas emissions by at least 80 % below the 1990 baseline by the year 2050. To reach this goal all emissions producing sectors such as energy supply, transportation, industrial processes, and others must commit to reduce their emissions. The road transportation sector accounts for nearly 17 % of carbon dioxide emissions worldwide and 14 % of carbon dioxide emissions in the United Kingdom.

The aim of this study is to model the optimal mix of low carbon road transportation technologies and fuel pathways to reach the year 2050 carbon dioxide emissions goal and investigate how different scenarios can change the model's output. Mixed-integer linear programming is used to build the optimization model on the Advanced Interactive Multidimensional Modelling System (AIMMS). The model is built of multiple sets of data such as the types of fuels, vehicles, trips, and fuel production pathways. The model includes constraints and parameters associated with both the drivetrains and fuel pathways such as well-to-wheel carbon dioxide emissions, energy requirements, cost, and fleet travel data.

Different scenarios are generated by changing the model's inputs, such as fuel prices and number of trips taken, to

study the effect of different constraints and driving styles on the model's output. These scenarios are later compared

to the current emissions and costs to check which scenario had the biggest impact on both carbon dioxide emissions

and average cost per km. The car pooling scenario, where passengers shared trips together and the number of trips

decreased 5 % annually, is determined to be the best option due to producing the lowest carbon dioxide and lowest

average cost per km throughout the years (83 % and 17 % reduction from the current case respectively).

131


Utilisation

Design of a Microstructured Reactor/Heat-Exchanger for a Single Step Methanol-to-

Hydrocarbon Process over a ZSM-5 Zeolite

Guannan Hu1, Javier Fernández1, V. Doluda2 and Evgeny V. Rebrov 1, 2 1School of Engineering, University of Warwick, Coventry CV4 7AL, UK

2Department of Biotechnology and Chemistry, Tver State Technical University, Tver 170026, Russia


Introduction

The conversion of methanol to hydrocarbon processes (MTH) over ZSM-5 catalysts has enabled an alternative path for high-

octane gasoline based products obtained from non-oil resources [1]. The MTH reaction is strongly exothermic and has a

theoretical adiabatic temperature rise around 600 K. The heat produced mainly in the first part of the catalytic bed can result in

hot spots of considerable magnitude. An ideal reactor design should avoid excessive coke build-up in the areas of relatively low

temperature and excessive hot-spots which would decrease stability and lifetime of ZSM-5 coatings. With magnitude higher

surface to volume ratio compared to that in a conventional reactor, microstructured reactors allow to control reaction conditions

to reduce or even eliminate hot spot. By injecting cold feed between reactors or in reversal flow direction, heat transfer can be

considerably enhanced in a microstructured reactor/ heat-exchanger (MRHE).

Results and discussion

The thickness of the reactor plates, the cooling channel diameter, the length of the first reactor and the coolant flow rate have

been optimised in COMSOL Multiphysics using a 2D convection and conduction model with coupled reaction kinetics on the

catalyst surface in the reaction channel. A single periodic unit consisting of one reaction channel and one cooling channel was

modelled. The MTH reaction takes place on a catalytic coating in the reaction channel.

A single reactor/heat-exchanger made in AISI-304 stainless steel is not enough to keep the temperature gradient below the

target of 10 K. Even the optimised geometry still results in high temperature non-uniformity with a thermal gradient of 45 K in

the reaction channels. To reduce the axial temperature gradient, the reactor should be split in two parts with an additional

coolant feeding between them. The length of the first section has an optimum value at 30.0 mm with a cooling channel diameter

of 0.50 mm providing a temperature gradient of about 14 K along the reactor length. A higher length of the first reactor would

result in a higher temperature gradient: for example a length of 40.0 mm gives a temperature gradient of 22 K. The length of the

second reactor does not influence the temperature gradient in the whole range of parameters studied. The temperature non

uniformity can always be efficiently handled with adjustment of coolant flow rate in the second reactor. Therefore, the length of

two reactors was fixed at 30 mm and 170 mm to keep the total reactor length of 200 mm. This corresponds to a methanol

conversion of 55 % in the first section and 99 % at the exit from the second section. The thickness of metal plate helps to

increase the axial heat transfer more efficiently which in turns helps to reduce thermal gradients in the catalytic coating and in

the reaction channel. However too thick material would result in low space utilisation and therefore there is an optimum in the

plate thickness at a distance of 1.0 mm.

Acknowledgement

We acknowledge financial support from the European Commission 7th Framework program: BIOGO project (grant no: 604296)

www.biogo.eu

References:

[1] M. Stöcker, “Methanol-to-hydrocarbons: catalytic materials and their behavior,” Microporous Mesoporous Mater., vol. 29, no.

1 -2, pp. 3 -48, 1999.

132


Utilisation

Design and Simulation of Eco-Industrial Parks Using Agent-Based Modeling Approach

Ganiyu Ajisegiri

University of Leeds


Industrial ecosystems (IE) a subset of industrial ecology emerged as a self-organizing economic strategy. It has

offered the most attractive solution methods to several problems (i.e. energy, material resources utilization) facing

the industrial sectors that are willing to interact and share resources with each other in other to improve their

economic and environmental performance indicators. However, one of the many challenges of implementing IE

concept is the inability to find an optimal configuration for the design of a new Eco-industrial park (EIP). In this work,

a bottom-up approach (agent-based model) method is applied to the design of EIP to gain insight into their response

to any changes in internal and external decision criteria. Agent-based modelling (ABM) represents autonomous

entities, each with dynamic behaviour and heterogeneous characteristics. In this study, the process can be either

source or sink agents. Based on the autonomy of each of the process plants and their individual objectives, agent-

based model and simulation are used to analyse how the industrial park evolve over time. The agents interact with

each other within the park and their environment, resulting in emergent outcomes at the macroscale that can be

used to quantitatively analyse complex systems. The approach was demonstrated on a made-up eco-industrial park

deploying a set of energy resources within a developing-economy context as the main output stock type from the

source agents and input stock type to a sink agent. This was used as a case study to illustrate the effectiveness of the

agent-based modelling.

Keywords: Industrial ecosystems; Eco-industrial Parks, Agent-based modelling; simulation

133


Utilisation

Application of Carbonized Metal Organic Frameworks in Electrochemical Energy Storage

Devices

Naghmeh Saeidi Bidokhti and Ozgur Yazaydin



This project aims to evaluate the application of carbonised MOFs with different pore sizes in electrochemical energy

storage devices.

MOFs are highly porous materials formed from metal ions linked by different organic linkers. Carbonisation of MOFs

(CMOF) results carbons with similar pore structure of the precursor MOFs. In this study ZIF-8 and MOF-5 with pore-

sizes of 11 Å and 15 Å respectively, have been carbonized under nitrogen atmosphere. The synthesised MOFs and

CMOF were all characterized with PXRD, N2 BET analysis, TGA and EDS to assess structural and morphological

properties of the prepared samples. The pore size distribution of the CZIF-8 calculated from nitrogen adsorption

isotherm revealed a carbon with complete microporosity with the BET surface area of 1528 m2/g, whereas for the

CMOF-5 with the BET surface area 2209 m2/g, both micro and mesoporosity were observed in the pore structure of the

carbons.

Subsequently the electrochemical behaviour of the carbonized MOFs was evaluated in Li-ion batteries and

supercapacitors and the results were compared with the commercial carbons. The results will be presented from our

experiments.

134


Utilisation

Thai-CAPRI Heavy Oil Recovery Process: Past, Present and Future

Abarasi Hart



Heavy oil and bitumen reserves outweigh that of easy-to-drill, high quality conventional light crude oil, that has

approached its peak. However, are complex and hard to produce, transport and refine, due to their high viscosity,

low API gravity, high asphaltenes, heavy metals (eg., V, Ni), and heteroatom (eg., N, S) content. The high price of

crude oil in the past decades has favoured the profitability of the Steam Assisted Gravity Drainage (SAGD) technology,

for heavy oil production. SAGD uses large amounts of water and energy for steam generation, leading to high capital

and operating costs. The current low oil price has led companies to seek alternative, lower cost, oil recovery

technologies. Toe-to-Heel Air Injection (THAI) in combination with its adjunct in situ catalytic upgrading process

(CAPRI), could potentially be a solution. The THAI-CAPRI process utilises the heat from in-situ combustion for thermal

cracking and then in-situ catalytic cracking achieves substantial further upgrading of the produced oil, essentially

using the oil reservoir as a `free reactor'. An optimisation of the CAPRI section involving placing of pelletized catalysts

(Co-Mo/Al2O3, Ni-Mo/Al2O3) along the horizontal well of the THAI was carried out using a laboratory microreactor to

replicate the in-well conditions of 350-425 °C, 9-28 h-1 WHSV, and 20 bar. It was found that at 425 °C and 9 h-1 an API

gravity of ~3-7 ° points increase, 81.9% viscosity decrease, 12.4 % demetallisation and 6.6 % desulphurisation was

observed against feedstock [14 °API, 1091 mPa.s, S (3.52 wt%), Ni+V (149ppm)] compared to experiment at 350-

400 °C for 25 h time-on-stream operation. Despite this further upgrading in the produced oil at 425 °C, high coke

rejection of 51 wt% was observed. The addition of hydrogen and steam inhibited coke formation by 25.8 % and 38.6 %

relative to that observed under nitrogen atmosphere (51 wt%). The high rejection of coke on the CAPRI section

causes rapid deactivation, leading to possible plugging of the pelletized fixed-bed catalyst. In view of this, the use of

nanoparticles was studied in a stirred batch reactor under the optimised THAI-CAPRI conditions in the pelletized

catalyst bed. Catalyst particles of Pd/biomass, Pd/C, Pd/Al2O3, Al2O3, and Co-Mo/Al2O3 size 2.6 μm were studied at

425 °C, catalyst-to-oil ratio 0.02, 500 rpm, 20 bar initial pressure and 10 min reaction time. It was found that with

dispersed particles an API increase of 8-12° points and 92 % viscosity decrease was achieved while Pd supported on

biomass and alumina particles yielded less coke 5wt% and 6.6wt% compared to 12.4 wt% (Co-Mo/Al2O3) and 13.7 wt%

(Al2O3). The improved upgrading and reduced coke formation observed with particles over pelletized fixed-bed

catalyst, showed improve performance, activity and survivability of the nanosized catalyst. However, maintaining the

reaction temperature at the optimised conditions to support in-situ catalysis in the field is quite challenging. This can

be achieved by either ohmic or microwave heating, which provide direction for further investigation.

135


Utilisation

Understanding the Electrode-Electrolyte Interactions in Energy Storage Batteries Using

Molecular Simulations

Argyrios Karatrantos and Qiong Cai*

Department of Chemical & Process Engineering, University of Surrey, UK


Electrochemical energy storage batteries play an important role in the transition towards a low carbon, sustainable energy

landscape. The electrode-electrolyte interactions in energy storage batteries are one of the key factors determining the battery

performance. In this paper, we demonstrate the application of molecular dynamics (MD) simulations for studying the

interactions between nanoporous carbons and electrolyte (organic solvents containing NaPF6 salt) solutions in sodium ion

batteries (SIBs). SIBs have attracted worldwide interest as a promising next-generation energy storage technology, because of

the natural abundance, wide availability and low cost of Na resources [1]. These batteries could potentially approach the

performance of Li-ion batteries if optimal electrode and electrolyte materials are identified. Nanoporous carbons are the largest

group of the negative electrode materials for SIBs and therefore are chosen for this study. A number of organic solvents including

ethylene carbonate (EC), propylene carbonate (PC) and ethyl methyl carbonate (EMC) are chosen as they have been used for

experimental study of SIBs [2].

Using molecular simulations, the density profiles of Na+ ions, PF6

– ions and organic molecules inside carbon nanopores are

investigated for the first time. The carbon nanopores are simulated with both non-charged and charged surfaces, to mimic the

battery operation effect. Our simulations show that by increasing the carbon nanopore surface charge density and nanopore size,

the Na+ concentration inside the nanopores increases. The Na

+ ion concentration profile, inside the nanopores, depends not only

on the surface charge and the nanopore size, but also on the interactions of Na+ ions with organic solvent molecules. We also

reveal that the organic solvent molecules can form different molecular structures within the pores, depending on pore sizes and

surface charge, indicating that the reactions of these organic molecules may be different at different electrode materials sites

during battery operations [3]. The detailed description presented is important for achieving a better understanding of Na ion

batteries which could not be attained using simulations or theoretical models that overlook the presence of solvent molecules.

Molecular simulations have proved to be useful tools in revealing the fundamental understandings of the electrode-electrolyte

interactions which are often difficult to probe using experimental techniques. Using such a molecular simulation methodology,

we can easily tune to electrodes of different physical and chemical properties or different organic solvents to extrapolate battery

storage capacity under charge and discharge cycles and under operating conditions. The methodology can also be applied to

other battery systems with different electrode materials and different solvents.

References:

[1] M. D. Slater, D. Kim , E. Lee and C. S. Johnson, Adv. Funct. Mater. 2013, 23, 947.

[2] K. Vignarooban, R. Kushagra, A. Elango, P. Badami, B.-E. Mellander, X. Xu, T.G. Tucker, C. Nam, A.M. Kannan, Int. J. of

Hydrogen Energy, 2016, 41, 2829.

[3] A. Karatrantos and Q. Cai, Phys.Chem.Chem.Phys., 2016, 18, 30761.

136


Utilisation

Electrochemical Performance of Resorcinol-Formaldehyde Based Carbons /Activated

Carbons as Electroactive Materials for Supercapacitor Applications

Qaisar Abbas

University of the West of Scotland


Resorcinol (R)/formaldehyde (F) aerogels were synthesized by sol-gel polycondensation reaction using sodium carbonate as catalyst (C) followed by solvent exchange and vacuum drying. Porous structure of polymeric gels was tuned by controlling the R/C ratio. RF carbon aerogels were prepared by the pyrolysis of the RF gels at 800 °C under Argon (Ar). RF based activated carbons were produced by the activation of the resultant carbons under CO2 at different temperatures.

The Effect of variation of R/C ratio, carbonization and activation temperatures on the porous structure of resultant gels, carbons and activated carbons was investigated by characterizing the porous structure of the materials using nitrogen adsorption-desorption measurements by Tri-start (micrometrics) at 77 K.

It was shown that porous structure of the gels can be controlled by controlling the R/C ratio in the range of 100 to 500. The porous structure of the resultant carbons was further controlled by controlling the carbonization temperature. Activated carbons with pore size in the range of 2.44 to 12.47 nm and BET surface area in the range of 133 to 1398 m2/g and pore volume of 0.4148 to 1.0508 cm3/g were obtained under different activation conditions.

Circular disk electrodes with the diameter of 1.3 cm and the wet film thickness of 250µm were cast from a slurry of the carbon or/ activated carbon fine powders (80 wt%) as electroactive material mixed with XC72 Cabot carbon black as conductivity enhancer (10 wt%) and Kynar 2801 as binder (10 wt% ) in acetone using a doctor blade.

Contact angle measurements were performed to study the wettability of the electrodes prepared from carbons/activated carbons using a KSV CAM 200 goniometer with 6M KOH as the probing liquid. It was observed that the contact angle between the surfaces of the activated carbon based electrodes and the probing liquid decreases indicating that the wettability of the electrode increases with activation process mainly due to the introduction of oxygen functional groups on the surface. This was further confirmed with decrease in the contact angle between the surfaces of activated carbon based electrodes by increasing the activation temperature.

XRD patters of the carbon electrodes shows two typical broad peaks at 2θ of about 23 and 43 degrees indicating a disordered structure corresponding to the amorphous nature of the materials.

The electrodes were used in a sandwich type symmetric capacitor cell with 6 M KOH as the electrolyte. The results of cyclic voltammetry measurements indicated that the specific capacitance of the electrodes increases from 5 to 136 F/g with decrease in pore size from 4.62 to 1.80 nm for a scan rate of 20 to 5 mV/s making the synthesized activated carbons as potential electrode materials for supercapacitor applications.

137


Utilisation

Controlling Process Parameters during the Wood Pellet Production Process to Minimise

Pellet Breakage and the Risk of Dust Explosions

Stefan Zweig

University of Greenwich


The breakage of wood pellets is a major cause for the creation of fines (particles smaller than 100 microns) during the

pellet production and the handling process. The fines become airborne and can cause severe health and safety

problems in production plants. A major concern of plant operators is the creation of dust clouds which can

potentially fuel a dust explosion. The production of wood pellets is a complex process where process parameters

such as temperatures, pressure and moisture content in the pellet mill influence the strength of the wood pellets. A

comprehensive study was conducted to better understand the relationship between these process parameters and

the breakage behaviour of particles.

Pellets were produced in a large scale Buhler pellet mill. The feedstock Alder and Pine contained different moisture

levels. The variation of the steam conditioning temperature created pellets with different strengths. To evaluate the

strength of the particles the pellets were subjected to impacts on a straight metal plate in a rotary impact tester. One

finding of the study shows that the strength of pellets increased whit increasing steam moisture content. It can be

concluded that better understanding and controlling the process parameters during the pellet production process

can help to minimise the breakage of pellets. This knowledge will help industries to produce stronger wood pellets

and minimise the creation of fines to reduce risks such as dust explosions in their production and handling facilities.

138


Utilisation

Impact of Impurities on Formation of Carbon-Dioxide Hydrates

P.K.Nair and N.Rahmanian

School of Engineering, Faculty of Engineering and Informatics, Universtoy of Bradford, BD7 1DP


The continued rise in CO2 emissions threatens the life of human beings by warming the planet. Carbon Capture and

Storage (CCS) is an effective method in reducing CO2 emissions, thus over time, will inhibit the effect of global

warming. One of the major challenges that face the transportation process, an intermediate operation between

capture and storage, is potential flow assurance issues especially hydrate formation, due to the presence of

impurities such as N2 and H2O. If the conditions within the pipeline are at a high pressure and low temperature,

hydrates could form. Hydrate formation, which is the physical combination between a gas molecule and water

molecules, could cause pipe blockage and so, could stop the high-CO2 mixture being transported to its storage

location.

This study is aimed to investigate the impact of impurities on the formation of CO2 hydrates. The present study

consisted of utilizing three softwares, Aspen HYSYS V9, HydraFLASH V3.3 and Minitab V17, where a sensitivity

analysis on four scenarios was conducted. For the binary system, the results showed that H2S was the impurity which

caused the most negative effect (quicker hydrate formation). An observation into the impurities impact on the

bubble point pressure was also conducted, where, for the worst-case scenarios, it showed a significant change when

being compared to pure CO2. Further investigation will include research into tertiary component systems and case

studies to find the minimum required water vapour for hydrate formation.

Keywords: Hydrates, CCS, Carbon Dioxide, CO2 transportation

139


Utilisation

Study in the Scalable Fabrication of NiPt Nanowires for PEMFC Application Peter Mardle, Shangfeng Du

Centre for Hydrogen and Fuel Cell Research, School of Chemical Engineering, University of Birmingham, Birmingham

B15 2TT


Some of the key challenges that PEMFC development face such as low durability and high cost, stem from the

cathode catalyst in fuel cells. The conventional Pt/C catalyst does not meet the mass activity and durability required

for the extensive commercialisation of PEMFCs. As such, there is a wealth of research being conducted in

synthesising highly active, highly durable and low cost electrocatalysts for fuel cell reactions.

One way to minimise the amount of precious metal required in the PEMFC cathode is to alloy Pt with transition

metals such as cobalt or nickel. Such alloys exhibit higher activities due to a combination of structural and electronic

effects. Coupled with a much reduced amount of precious metal, the mass activity is greatly increased. Significant

improvements in the stability of Pt can also be made by using 1D structure such as single crystal nanowires (NWs),

where the preferential exposure of active crystallographic planes can improve the area specific activity to

compensate for the reduced ECSA [1]. Some work has also been conducted on combining these two areas of research

in synthesising highly active Pt-alloy nanowires [2-4].

Recently, our group adapted the formic acid reduction method of making ultra-thin single crystal PtNWs for growth

directly on a carbon paper gas diffusion layer [5, 6]. The extremely thin catalyst layer with oriented nanowires arrays

significantly reduces the mass transfer resistance and an improved power performance was achieved at high current

densities. With the aim of establishing an equally adaptable synthesis methodology, in this work, we study the

preparation of PtNi NWs by the impregnation and annealing of Ni into PtNWs supported on carbon. Experimental

results show a different annealing mechanism as compared with PtNi nanoparticles. A relatively lower temperature

can partially alloy Ni into the PtNW structure and improve the catalyst activity but similar annealing temperature as

for PtNi nanoparticles results in irreversible coarsening of the nanowires.

References:

1. Sun, S., F. Jaouen, and J. –P. Dodelet, Controlled Growth of Pt Nanowires on Carbon Nanoshpheres and Their

Enhanced Performance as Electrocatalysts in PEM Fuel Calls. Advanced Materials, 2008. 20(20) : p. 3900-3904

2. Yu, X. et al., Pt-M (M = Cu, Co, Ni, Fe) nanocrystals: from small nanoparticles to wormlike nanowires by oriented

attachment. Chemistry, 2013. 19(1): p. 233-9

3. Bu, L. et al., A General Method for Multimetallic Platinum Alloy Nanowires as Highly Active and Stable Oxygen

Reduction Catalysts. Adv Mater, 2015. 27(44): p. 7204-12

4. Lai, J., et al., Facile Synthesis of Porous PtM (M = Cu, Ni) Nanowires and Their Application as Efficient

Electrocatalysts for Methanol Electrooxidation. ChemCatChem, 2014. 6(8): p. 2253-2257

5. Lu, Y., S. Du, and R. Steinberger-Wilckens, Temperature-controlled growth of single-crystal Pt nanowire arrays for

high performance catalyst electrodes in polymer electrolyte fuel cells. Applied Catalysis B: Environmental, 2015. 164:

p. 389-395

140 140

Poster Presentations – Chemical Engineering

Fundamentals

Chemical Engineering Fundament als

Micro-Mechanical Properties of Organic Crystals François Hallaca1, Ioannis S. Fragkopoulosa1*, Simon D. Conellb2 and Frans L. Mullera1

1School of Chemical and Process Engineering, University of Leeds, Leeds, LS2 9JT, UK. 2School of Physics and Astronomy, University of Leeds, Leeds, LS2 9JT, UK.


Crystal breakage during the isolation of active pharmaceutical ingredients (API) is an issue of great concern to

the pharmaceutical industry. Conservation of the desired particle size distribution throughout downstream

processing is extremely important as changes are known to affect properties such as bioavailability and

flowability. APIs are commonly produced by batch crystallisation as crystals with high elongation, usually

needle-shaped crystals, and they are separated from the mother liquor through pressure filtration. At

industrial scale, isolation of the material is prone to significant changes in the particle size distribution. This is

typically attributed to agitation during drying. In contrast, MacLeod and Muller [1] showed that the filtration

process itself can have a profound impact on the particle size distribution of needle-shaped crystals. Thus,

particle breakage may occur both during the filtration and the subsequent agitated drying processes.

The main objective of this work is to elucidate the phenomenon of crystal fracture under pressure filtration. To

achieve this, mechanical properties, such as yield stress and hardness, need to be determined at the single

crystal level. Previously, Namazu et al. [2] conducted bending test experiments using an inorganic single crystal

(Si) fixed beam in order to evaluate the size effect on the mechanical properties of crystals in the range from

the milli- to the nanometer scale. It was interestingly found that reduction of the crystal size leads to an

increase in bending strength. Our group has developed a single crystal bending test by fixing single microscopic

crystals and applying force using Atomic Force Microscopy [3]. We applied this test to determine the

mechanical properties of beta glutamic acid, an organic needle-shaped crystal. Preliminary experiments

demonstrated that the yield stress is a strong function of the crystal shape and size. The focus of the current

study is the optimisation of the experimental set-up and procedure as well as the expansion of the bending

test to the conduction of a representative high number of experiments.

A validated solid mechanics model will be used to analyse the yield stress profile at the process scale. A

combination of in-house produced high fidelity experimental data with computer-aided stress analysis

simulations, will demonstrate the propensity for particle breakage during API isolation at scale, and it will be

used towards the improvement of the process design and operating conditions.

References:

[1] MacLeod, C.S. and F.L. Muller, On the fracture of pharmaceutical needle-shaped crystals during pressure filtration: Case studies and mechanistic understanding. Organic Process Research and Development, 2012. 16(3): p. 425-434. [2] Namazu, T., Y. Isono and T. Tanaka, Evaluation of size effect on mechanical properties of single crystal silicon by nanoscale bending test using AFM. Journal of Microelectromechanical Systems, 2000. 9(4): p. 450-459. [3] Sohi, S.S., S.D. Conell, D. Harbottle and F.L. Muller, A method for the determination of mechanical properties of needle shaped crystals using Atomic Force Microscopy. Master's Report, University of Leeds, 2016.

141

Poster Presentations - Chemical Engineering

Fundamentals

Applications of 3D Printed Fluidic Oscillators to Process Intensification

Jonathan McDonough



Fluidic oscillators of the bistable amplifier type are one example of fluidics that has found new interest in a

wide range of applications. Fluidic oscillators use internal feedback to induce periodic oscillations. By operating

these devices with multiple outlet channels, periodic flow switching between the channels leading to dual

stream pulsations can be achieved. In a previous study, the switching frequencies obtained in single feedback

loop oscillators containing two outlet channels were investigated. Here, a parametric study bolstered by the

use of 3D printing investigated the effects of seven geometrical parameters on the flow switching response for

a variety of glycerol-water mixtures. Overall, frequencies of 2-22 Hz were produced for kinematic viscosities of

1.00-4.37 mm2/s, in the range of Re = 600 -12,000. Current focus of the research is testing the use of these 3D

printed oscillators in applications relevant to process intensification. The areas of interest are: achieving lower-

flow rate pulsations, plug flow generation, enhanced heat transfer, enhanced mass transfer, improved mixing

and flow distribution. Preliminary experiments have been performed to assess the plug flow generating

capability of these devices. Here, a KCl tracer was injected at the inlet of various 3D printed reactor geometries

(straight channel, straight channel + helical coil, and helix channel) and the conductivity measured at the outlet.

The preliminary results suggest that the pulsatile flows generated by these oscillators can indeed improve the

plug flow performance of the three reactor geometries. It is intended in due course to perform a more robust

analysis of the plug flow response by using a visual dye tracer to improve the time resolution of the

measurements. Experiments are also being designed to assess the potential heat transfer and mixing

improvements. Finally, further characterisation work regarding the design of these oscillators is being

completed.

142


Fundamentals

Carbon Capture Processes: From Chemistry to Application

Nadeen Al-Janabi



Carbon dioxide capture from existing sources, such as natural or flue gases, is an attractive alternative for

controlling CO2 emission, stabilising the global warming and meeting industrial specifications. Porous

adsorbents are promising materials for CO2 removal from gas mixtures due to their ease of regeneration,

porosity and tuneable surface chemistry.

Herein, we report a study to evaluate CuBTC as a solid adsorbent for CO2 capture starting from synthesising of

the material till the final application.

An improved synthesis method was developed that resulted in high purity of CuBTC with achieving the highest

reported yield in the literature so far (89.4 %). Detailed characterisation techniques were carried out to assess

the samples’ structural properties, CO2, N2 and water vapour adsorption. Detailed analysis of hydrothermal

stability of sample was carried out which showed CuBTC as an instable structure. Further work was done to

give insight into the underlying decomposition mechanism. Therefore, modification of CuBTC MOF to enhance

its structure stability was carried out. The new modified structure, denoted as Gly-CuBTC, was fully

characterised to assess its properties, which showed in addition to the improved stability, high selectivity to

capture CO2 over N2. Furthermore, the applicability of CuBTC to be used in industry was also tested, in

comparison to that of commercial activated carbon, for CO2 capture based on a fixed-bed adsorption

configuration.

143


Fundamentals

Fouling Modelling in Crude Oil Preheat Systems

Jose Loyola Fuentes



Fouling is defined as the undesirable accumulation of solid material on heat transfer surfaces. The main

problems resulting from fouling deposition include operational, economic and environmental issues on any

operation unit within a chemical manufacturing process plant. In the case of crude oil refineries, significant

fouling occurs in the heat exchanger network used for preheating the crude oil before the distillation column,

also known as the pre-heat train. The objective of this pre-heat train is to maximise the energy recovery for

the refining process. Within the network, different fouling mechanisms can take place, since the thermal levels

on the heat exchangers change through the pre-heat train, along with the type of fluid that flows on each side

of the heat exchangers. Because of these changes, it is of great importance to assess and predict the fouling

behaviour through the entire network. Previous approaches have considered the use of laboratory

experimental measurements and modelling the fouling deposition process for specific types of crude oil. These

previous approaches have tended to concentrate on the contribution of the tube side, leaving aside the shell

side and the fouling mechanism carried out by this stream. If it can be achieved, the successful separation of

both contributions, tube and shell side, can lead to reliable fouling modelling and predictions can be made to

optimise the use of each heat exchanger within the network. To accomplish these goals, the proposed

methodology develops a direct calculation of fouling models using reconciled on-line data, splitting the fouling

contributions of shell and tube side in a crude oil preheat train. The data reconciliation problem is solved by

using a nonlinear programming optimisation procedure, where mass and energy balances are used as

constraints. The reconciliation covers the mitigation of random and gross error (bias) within the data and its

main objective is to achieve reliable measurements, in order to improve the accuracy of the predictions. The

fouling models are obtained by parametric regression, considering the observed fouling resistances and fitting

them to a specific fouling rate model for both, shell and tube side. The methodology was tested in a single

heat exchanger with different fouling mechanisms on each side. The raw data was simulated using a heat

transfer model and measurement error was added to assess the data reconciliation. Outlet temperatures were

calculated using the regressed model and these results were compared with the simulated data. The results

show good agreement with the data, presenting a relative error around 2% and the sources of error related to

the data are correctly identified. The fouling behaviour of the heat exchanger is successfully split into both

sides of the equipment and the methodology can be extended to a network for operational optimisation,

retrofit studies and optimisation of cleaning schedules.

144


Fundamentals

Model Asphaltene Aggregation

Dorin Simionesie



Asphaltenes, a class of aromatic compounds within crude oil, pose significant industrial challenges such as

reservoir impairment, inefficient separation of water from oil, and obstruction of pipelines. Because natural

asphaltenes possess an undefined molecular structure which results in a complex aggregation mechanism,

model compounds with increasing levels of structural complexity are studied in toluene and heptane, in order

to understand the behaviour of natural asphaltenes.

The kinetics of the colloidal system is examined as a function of time and concentration by dynamic light

scattering (DLS), while the molecular interactions were investigated by molecular dynamic simulations.

The hydrodynamic diameters are measured with DLS, over 168 hours, at 3 different concentrations (1, 10, 20

mg ml-1), so that the aggregation kinetics of the polyaromatic compounds is established. The relation between

molecular structure, aggregation and stability in both toluene and heptane is investigated as the addition of

longer tails, heteroatoms and acid group changes the size and structure of the nano-aggregates formed.

Molecular dynamic simulations show a bottom-up view of the interactions between the model asphaltenes as

well as the quantification of the stacking configurations when aggregation does occur. The results display the

formation of nano-aggregates with a variety of molecular configurations ranging from π-π stacking to cross

linking due to heteroatoms and acid groups.

The work aims to establish an operational envelope to investigate how specific structural features in the

asphaltene molecules` design affect their stability, interactions and aggregation in both toluene and heptane.

Future work will focus on the systematic addition of more complex chemical groups such as acids and

heteroatoms in the model`s structure as well as a deeper investigation into the conformational possibilities of

the nano-aggregates.

145


Fundamentals

Statistical Mechanics Modelling and Coarse-Grained Description of NO Oxidation on

Pt(111)

Miguel Pineda



Heterogeneous catalysis is at the heart of the chemical industry, with solid catalysts being involved in the

production of a vast majority of important chemical products. Traditional spatially uniform microkinetic mean-

field (MKM) models of chemical kinetics as well as the so-called kinetic Monte Carlo (KMC) simulation

formalisms have proved very useful in elucidating catalytic processes occurring on surface reactions. However,

it is well recognised that although MKM models and the corresponding deterministic reaction-diffusion

equations are highly efficient computationally, they suffer from the crucial problem of inaccuracy as they

neglect stochasticity, ignore detail spatial correlations due adlayer inhomogeneity, and treat the coverage

dependence of the activation energy in an approximated mean-field way. The KMC simulation on the other

hand, explicitly treats all the aforementioned sources of complexity but is computationally expensive. That is

the reason way new methodologies that can capture kinetics of surface catalysed reactions in a

computationally efficient way without sacrificing accuracy are needed. In this work, we present a methodology

based on the so-called cluster approximation that allow us to calculate in an accurate and efficient way

catalytic rates of reactions at solid surface that take into account adlayer inhomogeneity due to adsorbed

lateral interactions together with the coverage dependence of the activation barrier of reactions events. We

developed a hierarchy of approximations and applied this methodology to the NO oxidation on Pt(111).

146


Fundamentals

A New Design Approach for Crude Oil Distillation Systems with Pre-Separation Units

Minerva Ledezma-Martínez, Megan Jobson and Robin Smith

Centre for Process Integration, School of Chemical Engineering and Analytical Science, The University of

Manchester, Manchester M13 9PL, UK


Crude oil distillation is a core process in a petroleum refinery and it is also a major energy consumer. A crude

oil distillation system comprises an atmospheric distillation unit, a vacuum distillation unit, a preflash or

prefractionation unit and a preheat train.

The high operating and equipment cost, together with the complexity of the system, motivate the

development of systematic approaches for optimal system design. Pre-separation units (a preflash or

prefractionator) in a crude oil distillation system provide opportunities to reduce energy consumption,

specifically in the furnace meeting fired heating demand, considering the interactions between the separation

units and the heat recovery system.

This project focuses on the design of crude oil distillation systems with pre-separation units (preflash or

prefractionator) considering the interactions between the distillation system and the heat recovery network

(HEN). The grand composite curve (GCC) is used to explore opportunities for improving energy demand of the

crude oil distillation system.

The first part of the study starts with rigorous simulations of a crude oil distillation column in Aspen HYSYS v8.6,

accounting for product quality. In the second part, a preflash/prefractionator unit is added to the crude oil

distillation system in order to demonstrate their benefits in terms of energy savings while maintaining product

quality specifications.

Stochastic optimisation of nine operational variables of the column is performed using a MATLAB-HYSYS

interface. A simulated annealing algorithm is chosen to find optimal values for structural and operational

variables. Lower and upper bounds of the optimisation variables were selected based on results of sensitivity

analysis. Product specifications (T5 % and T95 %) are included in a penalty function as constraints.

Achieve a reduction in hot utility demand and meet product quality specifications at the same time is not a

simple task, because of the strong interactions between columns and their associated heat recovery network.

Applying the proposed design methodology to a case study shows the potential benefits of adding a pre-

separation unit (preflash/prefractionator) in a crude oil distillation system in terms of energy consumption and

product quality.

147


Fundamentals

Experimental and Computational Fluid Dynamic Studies of Continuous Mixing of

Highly-Viscous non-Newtonian Mixtures

Simona Migliozzi



Mixing processes involving non-Newtonian fluids are widely employed in several industrial applications. The

increased level of sophistication, along with the complex rheological behaviour of these mixtures, poses many

process development challenges. In this research, we focus on the manufacturing of novel non-aqueous-based

oral care products introduced in recent years to satisfy consumers with hypersensitivity conditions.

Typically, toothpaste manufacture is based on a batch approach. However, the large volumes and the non-

uniform flow fields that characterize these operations can lead to concentration and temperature gradients

within the vessels and to the establishment of dead mixing zones for more viscous fluids. New continuous

processes can prevent these problems and achieve better performance at lower cost. In particular, static

mixers are a promising alternative, especially for blending highly-viscous fluids that can be processed

exclusively in laminar flow conditions. Indeed, in this flow regime, static mixers can perform radial mixing

thanks to a periodic sequence of splitting and recombining of the fluid streams that reduces progressively the

thickness of each fluid layer, eventually promoting diffusive mass transfer between the two phases [1, 2].

Hence, our main objective was to assess the mixing efficiency of two different static mixers for the blending of

two distinct liquid phases, namely glycerol and a polymeric gel, made of polyethylene glycol and carbomer. We

employed computational fluid dynamics (CFD) to design the experimental setup and to preliminary investigate

the mixing efficiency in the two devices, i.e., the Kenics helical static mixer and the SMX [3, 4]. To validate the

CFD results and the rheological model used for the mixture, we compared the pressure drop measured

experimentally with that predicted by the fluid dynamic model. Mixing quality was investigated by means of

laser induced fluorescence (LIF), which measures the distribution of a dye at the outlet of the mixer [5].

References: [1] Ghanem, A., Lemenand, T., Della Valle, D., Peerhossaini, H., Static mixers: Mechanisms, applications, and characterization methods - A review. Chem. Eng. Res. Des. 92 (2014), 205 - 228. [2] Thakur, R.K., Vial, Ch., Nigam, K.D.P., Nauman, E.B., Djelveh, G., Static mixers in the process industries - A review. Trans. IChemE 81 Part A (2003). [3] Liu, S., Hrymak, A.N., Wood, P.E., Laminar mixing of shear thinning fluids in a SMX static mixer. Chem. Eng. Sci. 61 (2006), 1753 - 1759. [4] Rahmani, R.K., Ayasoufi, A., Keith, T.G., A numerical study of the global performance of two static mixers. J. Fluid. Eng.-T. ASME (March 2007), 338 - 349. [5] Alberini, F., Simmons, M.J.H., Ingram, A., Stitt, E.H., Assessment of different methods of analysis to characterise the mixing of shear-thinning fluids in a Kenics KM static mixer using PLIF. Chem. Eng. Sci., 112 (2014), 152 - 169.

148


Fundamentals

Understanding the Mechanism of CO2 Transport through Dual-Phase Membranes

Sotiria Tsochataridou



CO2 separation from different process streams, such as flue gases or water gas shift reaction, is a topic that has

been discussed a lot over the past few years. The importance of finding new ways of CO2 separation or

improving the existing ones, has increased significantly in recent years, because carbon dioxide emission has

become one of the most serious global environmental problems. Ceramic dual-phase membranes can operate

continuously at high temperatures and can be an efficient mean of CO2 separation due to their high selectivity

and their low energetic and economic penalties [1]. Moreover, the two phases can be separately adapted

according to the requirements of a given application [2].

This research is based on the importance of understanding the fundamentals of CO2 transport through dual-

phase membranes. Due to the membrane complexity, there is a lack of knowledge on the CO2 permeation

mechanism. Membranes with different pore structures were studied and the CO2 fluxes through the

membranes were normalised for different parameters. The complexity of the membranes was also the

motivation to develop a simpler physical system whose size, number and geometry of the pores can be

tailored with great precision. In this research, the dual-phase membranes consist of an oxygen-ionic

conducting phase (yttria-stabilized zirconia, YSZ, 8 mol% Y2O3) with a molten salt phase (eutectic mixture of

Li2CO3, Na2CO3 and K2CO3). The pores were created by drilling dense ceramic YSZ supports with laser, and the

effects of the controlling parameters were studied.

References:

[1] J.D. Figueroa et al., Advances in CO2 capture technology, International Journal of Greenhouse Gas Control.

2 (2008) 9-20

[2] X. Zhu et al., Novel dual-phase membranes for CO2 capture via an oxyfuel route, Chemical Communications.

48 (2012) 251-253

149


Fundamentals

Titania Powders in the SLS Process

Domenico Macri



In selective laser sintering (SLS) a laser beam is used to partially melt particles in a layer of powder. With

subsequent increments of powder layers it is possible to create three dimensional structures. This technique

can be used in prototyping applications able to produce customized objects with different shapes and

materials, e.g. polymer, metals and ceramics. In SLS technique the strength of the final structures increases

with the energy transferred by laser. However, it also produces a volume contraction of the sintered material

reducing the precision and the porosity of the final object. Since the energy required for sintering depends on

the particle size, sintering energies can be reduced using smaller particles, which also allow the production of

more complex and precise structures due to reduced melting.

In this work, mixtures of titania powders with different particle size distributions were employed. They were

obtained by mixing a coarser grained powder (particles in the range 10 - 100 microns) with a finer grained

powder (particles in the submicron range). The powder composition and the powder laying procedure were

studied and optimized in order to obtain specimens with desired mechanical properties and porosity. The

equipment used is a three dimensional laser sintering equipment using a 40 W CO2 laser beam purposely built.

The density and the mechanical resistance of the specimens are studied as a function of the fines content and

of the amount of energy released by the laser beam on the unit surface of the lighted area. A theoretical

modelling approach, based on the proposal of Pokluda et al. [1], is also used to estimate the strength of the

single sintered contact.

References:

[1] O. Pokluda, C.T. Bellehumeur, J. Machopoulos, Modification of Frenkel ' s Model for Sintering, AIChE J. 43

(1997) 3253 -3256. doi:10.1002/aic.690431213.

150


Fundamentals

Non-Ambient Powder X-Ray Diffraction of Metal-Organic Framework Crystals

Anthony Houghton



Metal-organic frameworks (MOF's) are a relatively new class of highly porous crystalline materials that have

various structures and functionalities and are made of metal ions coordinated by organic linkers. They are

being studied extensively due to special properties they possess, such as tunable pore size, thermal stability,

ease of synthesis and large surface areas. MOF's have a wide range of important applications such as gas

storage, separations, catalysis and sensing.

The aim of this project is to synthesize MOF's by hydro and solvo-thermal methods and study any changes in

structural properties by the combined effects of temperature, pressure and present atmosphere using non-

ambient powder X-ray diffraction (PXRD). PXRD is a fast and powerful tool to study and characterise crystalline

materials, generating spectra that contains information such as quality, purity, crystal structure and unit cell

dimensions. The temperature range studied is between 25 to 600 degrees Celsius, and a pressure range

between a partial vacuum to 10 bar. This includes measurements such as in-situ MOF activation, vacuum and

atmospheric swings to investigate any structural changes.

Results are compared with MOF's that are already synthesized, which include Cu-BTC, Fe-BTC, MIL-53, ZIF-8

and magnesium formate MOF. Refinement of data is also produced to compare measured diffraction patterns

with advanced simulated spectra, and calculate lattice parameters. It is very important to understand any

changes in structure at different conditions before being used in practical applications. Results can also help

optimise process conditions and to help predict structural transitions.

151


Fundamentals

Impeller Drawdown and Dispersion of Floating Particles in non-Newtonian Fluids

Z. T. Al-Sharify, S. Z. Al-Najjar and M. Barigou

School of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT


Previous studies on mixing of floating particles in mechanically agitated vessels focused mainly on power

saving by achieving lower just-drawdown impeller speeds and on the performance of different impeller and

baffle configurations. The internal flow field and spatial dispersion of floating particles have been little studied

experimentally. Owing to the opaque nature of such suspensions, work has been restricted to flow

visualisation through the wall and measurement of cloud depth. In particular, no work has been reported on

the drawdown of floating particles in non-Newtonian fluids. In this work, the technique of positron emission

particle tracking (PEPT) was used to investigate at the just-drawdown speed the two-phase flow field inside a

stirred vessel of polypropylene particles of 3 mm diameter and 900 kgm-3 density in fluids of Newtonian, shear-

thinning (SN) and shear-thickening (ST) rheology. Mechanical agitation was achieved by a six-blade down-

pumping pitched blade turbine (PBTD). For the first time, the effects of the fluid rheology on the two-phase

flow pattern and 3D phase velocity and concentration fields were determined for different impeller

submergence levels (S = T/4, T/3, T/2 and 2T/3) in a fully baffled vessel.

Comparison between impeller submergence levels in all fluids, revealed that lowering the impeller to S ≥ T/2

significantly enhanced the drawdown of floating particles and invariably produced a more homogenous

suspension. In the ST fluid, two circulation loops formed when the PBTD was positioned at S < T/2, while at

lower submergences (S ≥ T/2) a more complex flow pattern was established consisting of four circulation loops.

In the SN and Newtonian fluids, however, only two circulation loops were observed.

The liquid and solid phase velocity distributions allowed estimations of the spatial distribution of particle-fluid

slip velocities in the vessel. These data were used to assess, for the first time, the magnitude of the likely error

involved in local mass transfer predictions using Frössling-type correlations which are based on the particle

settling/rising velocity. Results showed that, in all fluids, such an error varied widely throughout the vessel

exceeding 150 % in some regions.

152


Fundamentals

Effect of Operational Parameters of Colloid Mill on Calcium Carbonate and Cellulose

Suspensions

Faiz Mahdi

University of Leeds


Wet grinding generally produces finer products compared to dry grinding for the same particle size distribution

with low material losses, less possibility of oxidation of the material, elimination of dust explosion, and better

heat transfer (Loh, et al., 2015; Toyokazu, 2010). A colloid mill (IKA Magic lab mixer MK Module) was used in

this work to investigate the effect of operational parameters on two materials with different particulate

characteristics. Both materials (Durcal 65 and Avicel-PH101) were milled under the same conditions to

determine the effect of the mill on particle size reduction. Number of parameters include concentration (1, 5

and 10 %wt), speed (16000 and 24000 rpm), process time (0, 0.5, 1, 2, 4, 8 and 16 min) and the rotor-stator

motor of the mill (1/4, 1/2 and full) were checked and investigated.

The results showed that, in general increasing the concentration leads to increase the milling rate. The size of

microcrystalline cellulose particles was reduced by more than twice for 1 and 5 wt% and around 9 times for 10

wt% in the first 30 s of milling after that it reached the steady states. On the other hands, calcium carbonate

showed agglomeration of particle by increasing the concentration from 5 to 10 wt% in the first 30 s. This was

clear evidence of good milling of lower concentrations of 1wt% than the higher concentrations. This means

that lower concentration is at better milling at the start. However, for higher concentrations, it showed that

the particle-particle interaction brings about size reduction, in the end, as well as from the high shear effect of

the mill. Morphological changes on the particles included increase in particle circularity at the end of the

milling duration. The energy surface area relationship as well as the milling rate was also deduced in this

research.

References:

[1] Toyokazu, Y. a. I. Y., 2010. Selection of Fine Grinding Mills. Handbook of Powder of Technology, 12(10), pp.

487-508.

[2] Loh, Z. H., Samanta, A. K. & Heng, P. W. S., 2015. Overview of Milling Techniques for Improving the

Solubility of Poorly Water-soluble drugs. Asian Journal of Pharmaceutical Sciences, Volume 10, pp. 255-274

Acknowledgment

This project has received funding from the European Union's Horizon 2020 research and innovation

programme under grant agreement No 637232.

153


Fundamentals

An Optimisation-Based Approach for Process Plant Layout

Jude O. Ejeh1, Songsong Liu2 and Lazaros G. Papageorgiou1 1Centre for Process Systems Engineering, Department of Chemical Engineering, UCL(University College London),

London WC1E 7JE, UK 2School of Management, Swansea University, Swansea, SA1 8EN, UK


This paper presents an optimisation-based framework to the multi-floor process plant layout problem. Plant

layout is an important part of the design/retrofit of a chemical plant as it involves decisions concerning the

spatial allocation of equipment items and the required connections among them by considering a number of

cost and management/engineering drivers (e.g. connectivity, operational, land area, safety, construction,

retrofit, maintenance, production organisation, etc.). Significant attention has been received over the last two

decades on the plant layout problem since chemical companies started looking for potential savings at every

stage of the design process.

This work constitutes an extension of previous work presented by Patsiatzis and Papageorgiou (2002). The

number of floors, land area, allocation of each equipment item to a floor and the overall layout of each floor

were determined by the optimisation model whilst preventing overlapping of equipment. The connection

costs, horizontal and vertical, as well the construction costs were accounted for with an overall objective to

minimize the total cost. The new key features introduced in this work include a 3D orientation for each

equipment, allowance for stacking of equipment and multi-point connections between equipment. The overall

problem is formulated as a mixed-integer linear programming (MILP) model based on a continuous domain

representation and its applicability is demonstrated by a number of illustrative examples.

References:

[1] D.I. Patsiatzis and L.G. Papageorgiou, “Optimal Multi-floor Process Plant Layout”, Comput. Chem. Eng., 26,

575-583 (2002).

154


Fundamentals

Predicting Moisture Migration in Composite Food Systems during Storage

Paschalia Mavrou



Moisture migration in manufactured foods during storage can significantly affect their quality, nutrition,

sensory attributes and shelf life. It can occur between foods and the surrounding atmosphere or between

different compartments of manufactured foods. A variety of studies can be found in published literature on

moisture migration in food materials with most of them focusing on moisture migration coupled with a heat

transfer process (e.g. baking, freezing). Most published studies adopt a phenomenological approach using

effective diffusion equation to describe moisture migration. The effective diffusion equation is limited to

homogenous materials and, in most cases, cannot be directly applied to heterogeneous materials where

moisture migration from low moisture content to high moisture content can occur

The aim of this research is to develop governing equations describing moisture transfer in heterogeneous

composite foods. A computational method has been developed to predict moisture migration in

heterogeneous composite foods. The generic moisture migration equation is applied to a manufactured ice

cream cone as an example. Minimising moisture migration from ice cream to the wrapping wafer during

storage is important for delivering superior product quality and sensory attributes such as crispiness. As a

starting point, the moisture sorption isotherm and effective diffusivity of both the wafer and chocolate coating

have been investigated experimentally and theoretically. Sorption kinetics data obtained from isotherms have

been used to obtain the effective diffusivities as a function of water activity. Separate permeability

experiments have also been conducted. Primary results confirm that the chocolate coating is the main

moisture barrier for protecting the wafer from moisture uptake. A main challenge to further progress is that all

currently available experimental data has been obtained at room temperature while many manufactured

composite foods are stored chilled or frozen. Further experimental and theoretical works will be undertaken to

investigate moisture sorption and transfer properties of composite foods at near- and sub-zero temperatures.

155


Fundamentals

Optimisation of Three-Phase Separator Design: A Mathematical Design

Tariq Ahmed

Teesside University


Separation of oil, water and gas produced from the well - stream is very important in the oil and gas industry.

Transmission of crude oil from the wellhead to the refinery requires stabilisation of the crude by removing the

unwanted gaseous and liquid phases from the crude oil in a phase separator.

Many models exist for preliminary design and sizing of the phase separators. Most of these models are based

upon either droplet settling and / or retention time theory. More recent models have been developed using

the laws of conservation (mass, momentum and energy) to achieve more accurate results and physically

visualise results through colourful presentations, graphs and contours. These models however, do not provide

adequate information of the separator such as the various liquid level heights, rely on arbitrary table look ups

for constants that are not clearly defined and more importantly do not consider the economics of the

separator.

In this paper, a new model based on droplet settling is described that aims to link the design of the separator

to the economic costs associated with its construction and operation. The model is based on minimisation of

an objective function describing economic cost using Generalised Reduced Gradient (GRG) Non-linear

optimisation. It was aimed to provide accurate separator dimensions with transparent calculations.

The paper also presents a comparison between results obtained from this model and four extant models. The

newly developed model gave results that were similar to models based on retention time theory without the

need for laboratory test data.

156


Fundamentals

Numerical Investigation of the Effect of Adhesion on the Vibration-Induced

Segregation of Powder Mixtures

Mohammadreza Alizadeh, Ali Hassanpour, Maryam Asachi, Mojtaba Ghadiri and Andrew Bayly

University of Leeds


Segregation of particles in powder mixtures is an unwanted phenomenon in which particles separate from one

another due to the differences in their physical and chemical properties. It is highly important to understand

the underlying mechanisms of segregation to control this undesired phenomenon. In this study, the effect of

coating minor components on reducing the segregation during the vertical vibration of the mixture is studied

using Discrete Element Method (DEM). An experiment is carried out for validation of the numerical simulations

in which a ternary mixture of particles including spray dried detergent powders, tetraacetylethylenediamine,

and enzyme placebo (as the minor ingredient) is introduced into a test box to make a heap and exposed to

vertical vibration. Particle shapes are obtained using their X-ray tomograms after which the clumped-spheres

technique is used to capture the effect of particles shape. Experimentally, particles adhesion is generated by

coating the minor ingredient (enzyme placebo) with Polyethylene Glycol 400 (PEG 400). For the numerical part,

the JKR theory is used for modelling the effect of adhesion/cohesion. It is observed that coating the minor

component reduces its segregation significantly; while the flowability of the whole mixture is conserved. A

good agreement between experiment and DEM modelling is observed and the results are demonstrated

qualitatively and quantitatively.

157


Fundamentals

Analysis of Multiphase Flow in Open-Cell Foams by CFD Simulations on Virtually

Reconstructed Geometries

Mauro Bracconi1, Matteo Maestri2, Gianpiero Groppi2, Enrico Tronconi2, Claudio Pereira de la Fonte1 and

Xialoei Fan1 1School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road,

Manchester, United Kingdom 2Dipartimento di Energia, Laboratory of Catalysis and Catalytic Processes, Politecnico di Milano, Milano, Italy


Open cell foams are cellular materials made of interconnected solid struts which enclose void regions communicating through open pores. High specific surface area, low density and high permeability to the fluid flow are the main characteristics of foams. Such features make these structures very attractive as enhanced catalyst carriers. Several applications have already been proposed in the context of processes limited by the external transport limitations. Moreover, these structures can be exploited even in the context of gas-liquid-solid systems. In this respect, catalytic active open foam packings are promising to enhance the performance of tubular reactors due to their low pressure drop and high specific surface area. The gas–liquid two-phase flow across the structure is extremely complex and characterized by liquid films and occurrence of the partial wetted surface depending on the gas and liquid interactions. The interfacial area between the phases is a crucial parameter since it directly affects the gas-to-liquid mass transfer rates, which are often the bottle neck of the entire process.

Computational Fluid Dynamics (CFD) is a valuable tool to enable accurate analysis of open-cell foams, being able to consider their random tridimensional geometry and to grant insight in the complex flow field. The generation of a proper computational domain is crucial to accurately carry out such analysis. A general procedure for the reconstruction of realistic foam structures starting from a few pieces of readily available geometrical information has been developed [1]. The reconstruction procedure exploits the Voronoi tessellation to generate the foam skeleton, starting from an initial set of seed points. Moreover, the characteristic clusters of solid material at the nodes are considered. The so-generated foams fully retain all the geometrical and topological properties, i.e. specific surface area, pore size distribution, of real ones as assess by the good agreement between the values evaluate on the reconstructed geometry and experimental data. Moreover, the capability of the reconstructed foams to reproduce the fluid dynamic behavior of the real foam has been assessed, in the context of single phase flows, by comparing pressure drop evaluated with numerical simulations and experimental measurements [1].

In this work, we exploit the reconstruction procedure to generate foam samples which can be investigated in the context of multiphase flows by means of CFD simulations. We considered a simple system constituted by air and water to investigate the pressure drop across these structures and to assess the capability of the reconstructed structure in properly reproducing the interactions between solid matrix and the multiphase flow. The effect of different superficial velocity of gas and liquid has been considered along with the effect of different pore sizes. Then, an analysis of the wetted area inside such structures has been carried out to assess the capability of open-cell foams in spreading the liquid along the solid surface. A parametrical analysis of the effect of the hydrodynamic properties has been carried out to elucidate their effect on the foam behavior.

References:

[1] M. Bracconi, M. Ambrosetti, M. Maestri, G. Groppi, E. Tronconi, A systematic procedure for the virtual reconstruction

of open-cell foams, CEJ (2017), doi: http://dx.doi.org/10.1016/j.cej.2017.01.069

158


Fundamentals

An Investigation into the Influence of Process Variables on the Product Size

Distribution in a Semibatch Reaction Crystallization Process

Abdullatif Alfutimie, Ali Arafeh and Hosam Aleem

School of Chemical Engineering and Analytical Science, the University of Manchester, Oxford Road, Manchester,

M13 9PL


A pilot scale experimental study of benzoic acid crystallization using a 20 litre semi-batch reactor is presented.

Hydrochloric acid was fed using a prestaltic pump into a sodium benzoate solution in the batch reactor to

produce the desired crystals.

Operational process variables can significantly influence the crystal size distribution in a semi batch reaction

crystallization of a low-soluble substance. The process variables investigated in this study were stirring rate

(agitator speed), po¬sition of the hydrochloric acid feed point along the height of the reactor, the hydrochloric

acid feed rate, and reactants concentrations. Their impact on the mean size of the benzoic acid crystals was

assessed using a Malvern Mastersizer.

In particular the mean size of the product crystals was found to decrease with decreasing stirring rate.

However, smaller crystals could still be obtained if the hydrochloric acid feed point into the reactor is located

closer to the height of the impeller blades inside the reactor. Increasing reactant concentrations or

hydrochloric acid feed rate decreased the crystal size significantly. Furthermore, this paper presents the

importance of carefully designing a process, optimizing it and being aware of the trade-offs that need to be

made between product quality and total reaction time.

159


Fundamentals

Simulation of Industrial Scale Super Open Rack Vaporizer Li Sun1 and Zhigang Jia2

1School of Chemical Engineering and Analytical Science, University of Manchester, Manchester, M13 9PL, UK 2Beijing University of Chemical Technology, Beijing, 100029, China


Super open rack vaporizer (SuperORV) uses seawater to vaporize liquefied natural gas (LNG). There have been

many works on the modeling of a SuperORV. Some models were conducted ignoring the effects of tube side

pressure drop and radial thermal resistance through the LNG. Another models assumed that the heat transfer

coefficient of the seawater was constant, which did not properly detail the conditions a real ORV perform.

Some empirical formulas were obtained without thermodynamic analysis of icing, which is a major hindrance

in the heat transfer efficiency of the superORV. Most models had been developed for small scale ORV. The

parameters used for simulating the models were not applicable to an industrial process.

In this work, we develop numerical simulation of both fluid flow and heat transfer in an industrial scale

SuperORV, considering :

fluid flow of the sea water on the heat transfer in the SuperORV;

the effects of the icing distribution on the necessary length of the vaporizing and heating sections of the

tube;

the physical properties of LNG affecting the heat transfer performance;

and configurations of the enhancement devices to improve heat transfer, including external/internal fins,

twisted tape inserts, and the draft tube in the vaporizing section.

The developed models have been verified and applied in the construction of a 200 t/h SuperORV in Jiangsu

China

160 160

Poster Presentations – Catalysis and Sustainable Green

Chemistry

Catalysis and Sustainable Green Chemistry

Greener Synthesis of Styrene Carbonate from CO2 Using Heterogeneous Catalyst

Victor Nnamdi Onyenkeadi

London South Bank


Carbon dioxide (CO2) is the most important anthropogenic greenhouse gas and therefore, it is considered as

the main contributor to global warming. However, CO2 is recognised as an abundant, cheap, recyclable and

non-toxic carbon source and thus, its utilisation for the production of value-added chemicals is extremely

beneficial for the chemical industry.

Styrene carbonate is a non-toxic, biodegradable and a valuable chemical of great commercial interest. Styrene

carbonate is an excellent precursor material for the production of polycarbonates. Styrene carbonate can be

used as a solvent for lithium battery because of its high polarity property.

Several reaction routes have been attempted for styrene carbonate production, which was phosgene,

oxidative carboxylation, direct synthesis using homogeneous catalyst and direct synthesis using a

heterogeneous catalyst. The latter being the most attractive route due to the inexpensive of raw material,

ease of catalyst recovery and the avoidance of corrosive reagents, such as phosgene and dimethyl formamide.

The research study is aimed at catalytic conversion of carbon dioxide (CO2) to value added chemicals as to

reduce the emission of greenhouse gases in order to prevent global warming. The utilisation of carbon dioxide

will not only offer one of the means to prevent global warming but also offer a mean of value-added chemicals

such as fuel additives, substitute for various chemical reagents, organic solvent and green reagents.

The synthesis of organic carbonate through cycloaddition of carbon dioxide to epoxide in the present of the

heterogeneous catalyst using high-pressure reactor is known to be a ‘Green Processes’.

Heterogeneous catalyst of metal oxides such as magnesium oxide, cerium oxide, zirconium oxide, lanthanum

oxide, lanthana doped zirconia, magnesium oxide and cerium doped zirconium oxide ceria lanthana doped

zirconia was used to synthesised styrene carbonate through cycloaddition of carbon dioxide to styrene oxide in

a batch high-pressure reactor under different reaction conditions.

Among other catalysts ceria lanthana doped zirconia catalyst showed good catalytic activity and selectivity for

styrene carbonate without any use of organic solvents. The optimum reaction conditions for the synthesis of

styrene carbonate in the presence of ceria lanthana doped zirconia catalyst system was at 408 K, 75 bar, 20 h

and 300 rpm with the corresponding yield of 52 % and conversion of 84 %.

161


Chemistry

Rapeseed Meal Pretreatment for Improved Biopolymer Production

Phavit Wongsirichot



The UK produces nearly 3 million tons of rapeseed annually, to meet both vegetable oil consumption and

biodiesel demands. The 1.5 million tons of rapeseed meal byproduct resulting from rapeseed oil production

presents a potentially valuable feedstock for the biochemical industry, due to the abundance of proteins,

lignocellulose, and antioxidants such as vitamin E and phenolics (Krautgartner et al. 2016; Lomascolo et al.

2012). While proteins and antioxidants have inherent value as food supplements for both human and livestock,

the lignocellulosic fraction could also provide a low cost substrate for fermentation and the production of

biochemicals.

This project involves the compositional characterisation of rapeseed meal and, development of fractionation

and pretreatment techniques to isolate the aforementioned fractions. Subsequently, the lignocellulosic

fraction will be hydrolysed to yield fermentable sugars including glucose, arabinose, xylose, mannose, and

galactose. Finally, fermentation using the sugars produced as a carbon source will be conducted using

Pseudomonas putida, to produce bioplastics in the Polyhydroxyalkanoates (PHAs) family.

This research aims to optimise both quantity of each isolated fraction and the suitability of rapeseed meal

hydrolysate for fermentation, through the use of acids, alkali, ionic liquids, and novel green solvents. Suitability

of hydrolysate is dictated by both the quantity of fermentable sugar produced, as well as the concentration of

inhibitory compounds inherent to the biomass or resulting from pretreatment. Synergistically, effective

extraction of phenolic compounds would greatly contribute to hydrolysate suitability, as besides from their

potential economic value as antioxidants, phenolic compounds such as sinapic acid are important

fermentation inhibitors, due to their significant antibacterial properties (Nowak et al. 1992). The findings

resulting from this project can provide useful insight in the development of an integrated biorefinery utilising

rapeseed as a feedstock.

References:

[1] Krautgartner, Roswitha, Lucile Lefebvre, Leif Erik Rehder, Mila Boshnakova, Monica Dobrescu, Bob Flach,

Jennifer Wilson, Dimosthenis Faniadis, Marta Guerrero, and Barrie Williams. 2016. "EU Oilseeds and Products

Annual 2016." In.: USDA foreign agricultural service.

[2] Lomascolo, Anne, Eva Uzan-Boukhris, Jean-Claude Sigoillot, and Frédéric Fine. 2012. 'Rapeseed and

sunflower meal: a review on biotechnology status and challenges', Applied Microbiology and Biotechnology,

95: 1105-14.

[3] Nowak, H., K. Kujawa, R. Zadernowski, B. Roczniak, and Halina KozŁowska. 1992. 'Antioxidative and

Bactericidal Properties of Phenolic Compounds in Rapeseeds', Lipid / Fett, 94: 149-52.

162


Chemistry

Deterpenation of Folded Citrus Essential Oils Using Bio-Solvents

Baranse Ozturk



Citrus essentials oils, complex mixtures of aromatic hydrocarbons obtained as by-products, present inherent antioxidant,

antibacterial, insecticidal and organoleptic properties broadly exploited for pharmaceutical, cosmetics and food

applications. [1] In essential oil industries, different concentrations of oils (i.e. folded oils) are produced by re-distilling the

oils at a low pressure to isolate a number of chemical components, mainly terpenes. These folded oils can get further

fractionated (i.e. deterpenation) to separate out the oxygenated terpenoids and remaining terpenes for commercial

purposes.

To fractionate oxygenated terpenoids from citrus essential oils, liquid-liquid extraction (LLE) is usually preferred as it can

be carried out under mild conditions to maintain the quality of the oils. However, conventional processes rely on toxic,

fossil-derived solvents for essential oil deterpenation. Currently, there is an increasing consumer pressure towards natural

products and processes that drives the need to develop sustainable techniques for essential oils purification. Therefore,

the goal of this work is to evaluate the feasibility of using bio-solvents, such as ethanol and glycerol, in the deterpenation

process of citrus essential oils.

Ethanol is a hydro soluble, polar compound that can be easily incorporated to topical fine chemical formulations,

beverages and foodstuff, enhancing the stability of the oil and the shelf life of the final products. Moreover, it can be

produced from bio-renewable sources helping in the transition from petrochemical to bio-based solvents. [2] On the

other hand, glycerol is one of the most versatile building blocks in the bio-based chemical market, with increasing surplus

due to the substantial development of the biodiesel industry [3]. Glycerol is soluble in water and alcohols due to its

polarity, and is considered a green stable compound that can also be used in formulations, beverages, food applications

and cosmetics.

In this work, deterpenation was performed using various citrus essential oils with different concentrations (5 fold orange

oil, 10 fold orange oil, 4 fold lime oil and 5 fold lime expressed oil). The liquid-liquid extraction process was performed at

298.5 K using (ethanol + water) and (ethanol+glycerol) mixtures, both at (70:30 v/v) and (80:20 v/v). The analysis was

carried out using GC/MS with 5MS capillary column. The phase equilibrium data for the different essential oil/solvent

systems is evaluated, and the selectivity and distribution coefficient values are calculated accordingly. Overall, the

obtained results indicate that the aforementioned solvents efficiently fractionate citrus essential oils, with glycerol

enhancing the extraction performance of the deterpenation process .

References:

[1] S.C. Sell. "The Chemistry of Fragrances: From Perfumer to Consumer". RSC Publishing, Cambridge, 2006.

[2] J. H. Clark et al. "Opportunities for Bio-Based Solvents Created as Petrochemical and Fuel Products Transition towards

Renewable Resources". Int. J. Mol. Sci. 2015, 16, 17101-17159.

[3] M. Pagliaro and M. Rossi. "The future of glycerol: New uses for a versatile new material". RSC Publishing, Cambridge,

2008.

163


Chemistry

Microwave Assisted Thermocatalytic Decomposition of Methane: Numerical Analysis

Siddharth Gadkari



A comprehensive 3D mathematical model is proposed for the microwave-assisted thermocatalytic

decomposition of methane, based on the unsteady heat and mass transfer equations coupled with reaction

kinetics and quasi-steady formulation of the electromagnetic field. Activated carbon, which is a good

microwave absorber is used as a catalyst. A simple kinetic model, including the catalyst deactivation by carbon

deposition is also developed from previously published experimental data and used in the analysis.

Temperature and concentration distribution profiles in the reactor are presented. A non-uniform temperature

distribution with hot-spots at the top and bottom of the catalyst bed is predicted. CH4 and H2 concentration

profiles predict a linear change along the length of the reactor. The influence of volumetric hourly space

velocity (VHSV) on the methane decomposition is also investigated. Simulation predictions of CH4 conversion

are compared with previously reported experimental results.

164


Chemistry

CFD Approach for Developing Next Generation Bio Fuels through Catalytic Upgrading

Procedure

Anjani Ravi Kiran Gollakota



The incitement for decreasing the global dependency on fossil fuel and energy is environmentally driven.

Commercialization of biofuel as an alternate to fossil fuel is still a question due to the complexities in the bio-

oil. Hence, a two-dimensional CFD (Computational fluid dynamics) steady-state model was established to

simulate the upgrading process of bio-oil obtained from the pyrolysis process in a tubular reactor. The kinetics

of the homogeneous and heterogeneous reactions were studied and integrated with the equations of

continuity, motion and energy to describe the effects of the catalytic load in terms of WHSV (weight hourly

space velocity/residence time) ranging between (1 h-1 - 2 h-1), catalyst load (60 g - 100 g), temperatures (623 K

- 673 K), and for pressures (10 bar - 14 bar) respectively. Multi-fluid Eulerian approach was used to model the

complex multiphase flows in the reactor. The kinetic reaction scheme is designed by lumping the various

classifications of bio-oil compounds into heavy non-volatiles, light non-volatiles, phenols and alkanes and

aromatics. The results from the reaction schema are found to be in good agreement with the experimental

values of the literature. With the confidence, a parametric study was carried out to analyse the hydrodynamics

of phases, composition and yield of the upgraded product species especially alkane and aromatic

hydrocarbons with the pertinent operating conditions and for a specific catalyst Pt/Al2O3. In summary, the

analysis concludes that maximum yield of alkanes and aromatic hydrocarbons are obtained for a catalytic load

of 60 g, at higher residence time i.e. 1 h-1 at 13 bar, 673 K respectively.

Keywords: catalyst load, reaction schema, residence time, tubular reactor, upgrading process.

165


Chemistry

Metal-Organic Frameworks (MOFS) for Alkene/Alkane Separation

Huan Xiang, Flor Siperstein, Patricia Gorgojo and Xiaolei Fan



Separation of alkene/alkane is an energy-intensive process in petrochemical industry. High efficient and cost-

effective adsorption process for alkene/alkane separation is considered as an important alternative to

traditional cryogenic distillation. Metal-organic frameworks (MOFs), constructed by metal-containing nodes

connected by organic ligands, are versatile and promising adsorbents for hydrocarbons separation due to their

tremendous specific surface areas, adjustable pore sizes and tunable structures. Ag+ has been demonstrated

to form π-complex with the carbon-carbon double bonds of alkene molecules to enhance their interactions

with alkene, leading to much higher selectivities towards alkene from alkane. Ag+ can also form non-covalent

with aromatic N-donor ligands. Based on these principles, Cu2(pzdc)2(bpy) (pzdc=2,3-pyrazinedicarboxylate,

bpy=4,4'-bipyridine) with N-rich channels will be synthesized, and various amount of Ag+ will be deposited to

the pores of Cu2(pzdc)2(bpy) by incipient wetness impregnation. These compounds will be characterized by X-

ray diffraction, N2 adsorption-desorption, scanning electron microscope and thermogravimetric analysis. The

adsorption and separation performance of synthesized MOFs with and without Ag+ will be investigated using a

combined experimental and simulation approach. The single-component adsorption isotherms of ethylene,

ethane, propylene and propane will be determined at 293 K, 313 K and 333 K over a pressure range of 0-20 bar

to probe the intrinsic properties of materials. The ideal adsorbed solution theory (IAST) will be used to

calculate the selectivities of ethylene/ethane and propylene/propane.

166


Chemistry

Peroxidase Immobilisation on Bio-Inspired Silicas for Dye Degradation

Eleni Routoula and Siddharth V. Patwardhana

Department of Chemical and Biological Engineering, The University of Sheffield, Sheffield S1 3JD


aWebpage: www.svplab.com

This project is about Peroxidase immobilised on novel bio-inspired silicas (BIS), applied in the degradation of

sturdy anthraquinone dyes from polluted water. Up to 84,000 tons of dyes can be lost in water and 1,200 m3

of water is consumed during textile dyeing annually, making dyestuff industry responsible for up to 20 % of the

industrial water pollution [1-5]. Peroxidases constitute a family of enzymes highly applicable in water

decontamination6, but enzymes' industrial application can be hampered by their low stability, absence of

reusability and difficulty in production and scale-up [7, 8]. Enzyme immobilisation is an established way to

improve enzymes' operational stability and reusability and it can be achieved via various techniques. However

it still faces difficulties such as partial deactivation of enzyme, enzyme leaching and overall high costs [9, 10].

Novel approaches on solid supports include bio-inspired materials synthesised fast and economically, under

mild conditions, avoiding the environmentally un-friendly methods (high temperature, toxic reagents) used in

immobilisation [11]. Supporting enzymes on novel bio-inspired silicas is a one-step process and allows tailoring

properties of the biocatalyst [12]. This presentation will cover the results from a systematic investigation of the

effects of BIS synthesis and immobilisation conditions (pH of addition, order of addition) on the immobilisation

efficiency and decolourisation performance. The physical properties, enzyme immobilisation and the enzyme

performance were correlated in order to extract design rules. From the results it will be made clear that BIS

forms a versatile platform for enzyme immobilisation and BIS-Peroxidase can be successfully applied in water

treatment.

References:

[1] Nat. Sci. 2012, 4, 22-26.

[2] Env. Int. 2004, 30, 953-971.

[3] Turk. J. Biochem. 2013, 38, 200-206

[4] Pereira, L.; Alves, M., in Environmental Protection Strategies for Sustainable Development, Malik, A. ;

Elisabeth, G., Springer Netherlands: 2012; pp 111-162.

[5] Water Res. 1997, 31, 1187-1193.

[6] Scientific World J. 2013, 9. Article ID: 714639.

[7] Chem. Soc. Rev. 2013, 42, 6262-6276.

[8] J. Chem. Biol. 2013, 6, 185-205.

[9] Chem. Soc. Rev. 2009, 38, 453-468.

[10] Curr. Opin. Chem. Biol. 2005, 9, 217-226.

[11] J. Mat. Chem. 2005, 15, 4629-4638.

[12] J. Mat. Chem. B 2013, 1, 1164-1174.

167


Chemistry

Preparation of Mesoporous Y Zeolite Using Hard Templates for Catalytic Cracking of

Heavy Oil

Samer Abdulridha, Arthur Garforth and Xiaolei Fan

School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road, Manchester,

M13 9PL


Zeolite Y is the common catalyst used in the hydrocracking processes of heavy oil due to its abundant

distribution of active sites across both internal pores and external surface. The microporous nature of zeolite Y

is causing intracrystalline diffuse problems and limits its further catalytic applications. Many efforts have been

devoted to solve the problems by controlling the size, shape and porosity. Various strategies such as

templating, post-treating and controlling synthesis parameters have been reported to produce

mesostructured zeolite Y. [1]

The hard templating route involves the use of solid materials such carbonaceous material with relatively rigid

structure serving as mesopore templates during zeolite crystallization. Carbon nanotubes are exhibiting

superior characteristics such as chemical inertness, structural diversity and ease to remove by combustion [2].

In this research, Mesoporous of NaY zeolite is synthesised using carbon nanotubes as hard template. The use

of carbon nanotubes is expected to introduce a large number of mesopores in the resulting zeolites due to its

structural diversity. The prepared catalysts are characterised by XRD, SEM and N2 adsorption. Hydrocracking

tests of the developed catalysts are implemented in a pressurised batch reactor using 1,3,5-triisopopylbenzene

(TIPB) as the model compound [3]. The developed synthetic approach is expected to enhance the availability

of mesopores in the NaY zeolite, hence benefiting the transport of reactants and products through its porous

structure leading to high catalytic activity and low yield of coke.

References:

[1] Wei, Y.; Parmentier, T. E.; de Jong, K. P.; Zecevic, J., Tailoring and visualizing the pore architecture of

hierarchical zeolites. Chem Soc Rev 2015, 44, (20), 7234-61.

[2] Iver Schmidt, A. B., Ester Gustavsson, Kenny Ståhl, Søren Pehrson, Søren Dahl, Anna Carlsson, Claus J. H.

Jacobsen,, Carbon Nanotube Templated Growth of Mesoporous Zeolite Single Crystals. Chem. Mater. 2001, 13,

4416-4418

[3] AI-Baghli, N.; AI-Khattaf, S., Catalytic cracking of a mixture of dodecane and 1,3,5 tri- isopropyl-benzene

over USY and ZSM-5 zeolites based catalysts. Studies in Surface Science and Catalysis 2005, 158, 1661-1668.

168


Chemistry

Microwave Assisted Synthesis of Zirconium-Based Metal Organic Frameworks:

Optimisation and Gas Adsorption

Reza Vakili, Patricia Gorgojo-Alonso, Stuart M. Holmes and Xiaolei Fan

School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road, Manchester,

M13 9PL, UK


Metal Organic Frameworks (MOFs) are defined as a new class of porous materials with high surface areas and

pore volumes, composed of metal clusters and organic linkers. Zr-based MOFs (for instance UiO-67) are among

the most promising MOFs for practical applications in gas adsorption and catalysis due to their exceptional

thermal and chemical stabilities. These materials are currently synthesized solvothermally; however,

introducing new synthesis methods to reduce the reaction time and improve the quality of products is usually

desirable.

In this work, UiO-67 was synthesised for the first time by a microwave-assisted method, leading to a significant

reduction in the reaction time from 24 h to less than 3 h. A systematic approach was employed to optimise the

synthesis conditions such as the reaction time, reaction temperature and the modulator concentration. The

results showed that 120 °C, 2.5 h and 40 eq of benzoic acid were the optimum conditions in which the highest

mass product and surface area of the materials, measuring 75 g and 2300 m2 g-1 respectively, were obtained.

The materials were fully characterised and their properties were compared with those synthesised by the

conventional method, confirming the similarity of surface area (2300 m2 g-1) and pore volume (0.95 cm-3 g-1)

between the materials synthesised by both methods. The gas (CO2 and CH4) adsorption capacities of the

resulting materials were measured by an intelligent gravimetric analyser, showing their high adsorption

capacity. Finally, it was concluded that the microwave method can be a good alternative for the synthesis of

UiO MOFs.

169


Chemistry

Determination of Mass Transfer Resistances of Fast Reactions in Three-Phase

Mechanically Agitated Reactors

Ilias Stamatiou

University of Leeds


A methodology for the determination of mass transfer resistances of fast reactions in three-phase

mechanically agitated slurry reactors under the reaction conditions is presented. The mass transfer resistances

affect significantly the overall mass transfer rate, the design equation and consequently the scale up of the

reactor. There is not established methodology to separate the mass transfer resistances under reaction

conditions by changing catalyst loading and manipulating the process variables, pressure and agitation speed.

This allows to avoid the use of different catalyst particles and give the chance to calculate the mass transfer

resistances without caring about the type of catalyst. We calculate each mass transfer resistance under

conditions which do not allow to neglect any of the resistances. It is shown that the level off of mass transfer

rate which is developed in the plot of mass transfer rate against agitation speed plots is not enough to

determine the limiting regime. The hydrogenation of styrene over Pd/C (5 % catalyst content) is used as case

study to demonstrate the methodology.

170


Chemistry

Multi-Criteria Screening of Chemicals Considering Thermodynamic and Life Cycle

Assessment Metrics via Data Envelopment Analysis: Application to CO2 Capture

Phantisa Limleamthong



The growing trend towards more sustainable products and processes calls for advanced decision-making tools

for the assessment and optimisation of the economic, environmental and social impact of chemicals and

chemical processes. The pressure for more sustainable processes is particularly strong in the chemical industry,

in which thousands of products are developed and launched at a very fast pace, raising the question (before

scaling them up) of whether they are more sustainable than the existing ones or not.

Particularly, in green chemistry applications, engineers and scientists are confronted with the task of screening

chemicals (e.g. mainly solvents, additives, etc.) according to sustainability principles. In practice, it is quite hard

to find a single chemical/process performing best in the whole range of sustainability metrics, as inherent

trade-offs typically arise between conflictive thermodynamic, environmental and safety metrics.

In this work we propose a new methodology to screen and select chemicals according to the extent to which

they adhere to sustainability principles that is based on Data Envelopment Analysis (DEA), a technique

developed in economics for efficiency assessment. The benefits of our method is that it does not require any

articulation of subjective weight preferences of the assessed criteria, which could bring about the variation of

assessment outcomes as nornally in the case in other traditional multi-criteria decision analysis tools.

Furthermore, our approach identifies the most efficient chemicals (according to some sustainability criteria)

and for the ones found to be inefficient it establishes in turn improvement targets that can be used to guide

research efforts in green chemistry.

The capabilities of the DEA-based approach in the context of green chemistry are demonstrated through the

screening of 125 conventional amine-based solvents for CO2 capture according to 10 performance indicators,

considering technical (economic), environmental and social aspects simultaneously. Our approach eliminates

36% of the solvents for being inefficient, establishing quantitative targets and clear guidelines on how to

improve them. The DEA models are capable of identifying the practical downsides of amines as main sources

of inefficiency through the calculation of clear improvement targets for properties such as vapour pressure,

acute toxicity and several life cycle impacts. The final aim of the DEA-based analysis is to facilitate the selection

of more sustainable chemicals in the transition towards a more sustainable chemical industry.

171


Chemistry

Insights into the Origin of the Catalytic Activity of Biomass-Derived Carbon

Catherine Collett



Introduction

The threat of climate change and ever-depleting natural resources are driving a move towards reduced use of fossil

reserves and rare metals. The aims of the present work are to demonstrate that biochar, a by-product of biomass

pyrolysis, can act as heterogeneous catalyst and to gain insights into the origins of this activity. The reactions investigated

are important in a future, sustainable, chemical industry; namely (1) the reaction of glycerol and CO2 to form to form

glycerol carbonate (GlyC), a useful precursor for the formation of polymers and plastics; and (2) the synthesis of

dimethoxymethane (DMM) from methanol (MeOH), as a precursor to dimethylcarbonate, a green solvent.

Three biochars from different source materials have been extensively characterized by a variety of methods with several

physiochemical aspects of the biochars being investigated, i.e. structural, surface chemistry and compositional factors. In

addition to being of interest in their own right as catalysts, insights into the origin of their catalytic activity can lead to a

greater understanding of beneficial carbon deposition on other heterogeneous catalysts and open up new classes of

catalytic material.

Results

The performances of the biochars in the two reactions varied; for instance whilst oil seed rape biochar (OSB) and rice

husks biochar (RHB) showed no activity for the formation of DMM from MeOH, they were the most effective catalysts for

the conversion of glycerol to GlyC. Similarly, soft wood biochar (SWB) and commercial activated charcoal (AC) were the

most effective catalysts for DMM formation, but SWB was the least effective catalyst in the formation of GlyC.

Extensive characterisation work has shown that the catalytic activity of the biochars is not simply correlated by BET

surface area or CO2 adsorption capacity. Thermogravimetric analysis (TGA) and XPS analysis have shown differences in

composition between the biochars; SWB contains almost no ash, whilst OSB and RHB have a much higher ash content. It

is therefore possible that mineral content in the ash may be contributing to catalytic activity in the glycerol upgrading

reaction - this will be tested by producing demineralised biochars from the same feedstocks and testing their subsequent

catalytic activity. XPS analysis shows that SWB is composed of 90 % C and 10 % O, with no metals detected within the

detection limit of the instrument. Comparison with AC suggests that the active sites for the conversion of methanol may

therefore be carbonaceous in character.

Significance

This work has demonstrated that carbonaceous materials derived from biomass, including waste sources, can act as

effective heterogeneous catalysts. A comparison of different biochars shows that different factors can impart activity for

different processes. This presents a new class of catalytic material to open up new reaction routes, with both catalyst and

reaction leading to improved sustainability in chemical processing. The insights gained are also applicable to the

understanding of carbon deposits formed in situ on the surface of catalysts during reactions, and can hence be applied to

broad range of catalytic systems.

172


Chemistry

Effect of Water on Cu Electrodeposition from Ethaline Based Deep Eutectic Solvent

Priscila Valverde Armas

Strathclyde University


Ionic liquids have been utilized to fabricate metals, alloys and semiconductor materials by the electrochemical

scientific community. ILs offer desirable characteristics that make them attractive for electroplating

procedures. Examples of such properties are large electrochemical windows, reasonable conductivities, low-

volatility, and environmental compatibility.

A novel class of ILs are Deep Eutectic Solvents (DESs) that show similar properties of ILs. In addition, DESs

formulated from ammonium salts as choline chloride (ChCl) and hydrogen bond donors (HBD) are one of the

most promising electrolytes since they are readily available at a reasonable cost. This work focuses on

'ethaline' which is a DES prepared by mixing choline chloride and ethylene glycol in a 1:2 molar ratio. The main

reason for selecting ethaline among other DESs is its availability as bulk reagent, ease of preparation and

handling.

Numerous metals are produced by the industry of which copper is essential for the manufacturing electronic

industry. Although DESs have been used to fabricate Cu deposits, earlier studies have concentrated on low

water-containing DESs (< 0.5 wt% H2O). This is in line with previous experiences using ILs because the

electrochemical windows of the solvents were reduced drastically (~ 2 V) with the incursion of water. Despite

the academic contributions to understand Cu electrodeposition utilizing DESs, these electrolytes are

hygroscopic and absorb water from the atmosphere unless special provisions are taken. Information in the

literature about the influence of water in Cu electrodeposition from DESs is scarce. Hence, the objective of this

study is to understand the influence of water on the morphology of Cu deposits obtained from water-

containing DESs.

We first examined the effect of adding various concentrations of water (3 - 15 wt%) on the stability of the

solution; in particular this was obtained from the polarisation behaviour of metal deposition. It was noted that

water addition affected both the limiting current for copper deposition and the deposition potential. A second

series of experiments were carried out to assess how much water is absorbed by the DES depending on the

storage conditions. The water content in these experiments was determined using Karl Fischer titration. The

effect of increasing water content on copper coordination in the solvent was explored using UV-Vis

spectroscopy.

Subsequently, Cu films were electroplated on a steel rotating disc substrate from electrolytes containing

different weight percentages of water. The deposits were characterised using Scanning Electron Microscopy

(SEM) and Energy Dispersive X-ray Spectroscopy (EDS). SEM images showed that the morphology of Cu

deposits was also dependent on the water content of the DES. The relationship between the observed changes

in electrochemical characteristics and deposit properties with increasing water content will be discussed.

173


Chemistry

A Single Step Synthesis Approach for Preparing Nanocrystalline Powder of

Gadolinium-Doped Ceria (GDC) for Solid-Oxide Fuel Cells

Mohammadmehdi Choolaei



Solid oxide fuel cells (SOFCs) have proven to be promising power generation devices because of their higher conversion efficiency, environmental friendlier operation, and fuel flexibility [1]. Among all the oxygen ion conductors, yttria stabilized zirconia (YSZ) is the most commonly used solid electrolyte material for the SOFCs [2]. However, this material requires a high operation temperature, leading to several technological problems [3]. As an alternative, electrolytes based on ceria have received much attention for intermediate temperature (IT-) SOFC, due to their considerable ionic conductivity at lower temperatures (500-700 °C) [1]. However, Bevan and Summerville [4] indicated that the introduction of the Gd

+3 ions into the CeO2 lattice results in a considerable increase in its

ionic conducting, through lowering the unit cell expansion or contraction [1]. So far, various methods have been used to prepare nano-sized doped ceria, such as the sol-gel [5], microwave-combustion, microemulsion, hydrothermal and mechanochemical [3].

In this work, gadolinium-doped ceria nano sized particles were synthesized by a modified homogeneous precipitation method consisting in the use of a cheap, novel, and environmental friendly precursor, potassium sorbate, through a simple and straightforward synthesis method.

Cerium (III) nitrate (Ce(NO3)3·6H2O, Sigma-Aldrich), gadolinium (III) nitrate (Gd(NO3)3 · 6H2O, Sigma-Aldrich) and potassium sorbate (C6H7KO2 Sigma-Aldrich) were used as starting materials without further purification. A mixed solution of cerium nitrate (0.061 mol L

−1)

and gadolinium nitrate (0.12 mol L−1

) was prepared by dissolving the starting materials in distilled water. The mixture was added dropwise to an aqueous potassium sorbate solution (0.53 mol L

−1) under vigorous stirring, at room temperature. The stirring was

continued for 5 h and then the precipitate was washed once with distilled water and centrifuged, followed by overnight drying in a vacuum oven at 60 °C. The gadolinium-doped ceria (GDC) nanocrystalline powders were prepared by calcination of the resulting dried powder at 400-600 °C (2-6 h).

The yield of the precipitation process was calculated to be min 75%. The thermal behavior of the precipitate before calcination was studied by differential scanning calorimetry (DSC) from room temperature up to 900 °C in flowing air (50 mL min

−1), indicating 340 °C as

the end of the thermal decomposition process. Structural characterization was carried out by X-ray diffraction and the crystallite size values were calculated to be lower than 50 nm, using the Scherrer equation. This result was in good agreement with the microstructure observations carried by scanning electron microscopy (SEM), also indicating a uniform size distribution of the produced nano particles.

To conclude, we have proposed an alternative simple, efficient, and environmentally-friendly method for synthesising nanocrystalline powder of GDC. The results of this study could be helpful to understand better the influence of the basic processing variables on the particle size and the other physiochemical properties of GDC nanocomposite powders produced by the modified homogeneous precipitation method.

References:

[1] Chourashiya, M. G., and L. D. Jadhav. "Synthesis and characterization of 10% Gd doped ceria (GDC) deposited on NiO-GDC anode-

grade-ceramic substrate as half cell for IT-SOFC." international journal of hydrogen energy 36, no. 22 (2011): 14984-14995.

[2] Horri, Bahman Amini, Cordelia Selomulya, and Huanting Wang. "Electrochemical characteristics and performance of anode-

supported SOFCs fabricated using carbon microspheres as a pore-former." international journal of hydrogen energy 37, no. 24 (2012):

19045-19054.

[3] Liu, Ai Zhu, Jian Xin Wang, Chang Rong He, He Miao, Yi Zhang, and Wei Guo Wang. "Synthesis and characterization of Gd 0.1 Ce 0.9

O 1.95 nanopowder via an acetic -acrylicmethod." Ceramics International 39, no. 6 (2013): 6229-6235.

[4] Bevan DJM, Summerville E. In: Gschneider KA, Eyring L, editors. Handbook on the physics, chemistry of rare-earths. Amsterdam:

North Holland; 1979. p. 4.

[5] Choo, Cheng Keong, Bahman Amini Horri, and Babak Salamatinia. "Synthesis and Characterization of Nickel (II) Oxide/Gadolinium-

Doped Ceria (NiO/GDC) Nanocomposites As a Potential Material for Anode Supported LT-SOFCs." In Proceedings of the World Congress

on Engineering and Computer Science, vol. 2. 2016.

174


Chemistry

Representation of Vapour-Liquid-Equilibria and Densities of Unloaded and Loaded

Deea Solutions: Enrtl Model

Monica Garcia

[email protected]


Carbon Capture has been recognised as the only feasible path to reach the world-wide compromise related to

Climate Change, up to 2 °C over the Earth´s temperature registered in 1990. Chemical absorption, one of the

most advanced technologies for CO2 Capture, has been proved at industrial scale and 30 % MEA is recognized

as the most feasible solvent due to its availability, performance and price. However, this technology still needs

to be techno-economically optimized. Currently, stakeholders consider that the use of new solvents and

process improvements are the key to get a more mature technology. DEEA is a renewable tertiary amine with

higher CO2 absorption capacity and lower energy consumption for its regeneration than 30 % MEA. However,

the absorption rate is low and the use of promoters is desirable.

In this work, a thermodynamic model based on the electrolyte non-random two-liquid theory (eNRTL) was

created in ASPEN PLUS and fitted to correlate and predict the partial and total pressures of the unloaded and

loaded aqueous DEEA solution. Furthermore, the model represents the density in a good agreement with

experimental results.

175


Chemistry

Hydrogenation Conversion of Furfural into 2-Methylfuran (2-MF) Using Platinum

with Different Supported Catalysts

Ahmed Alkailani, Bushra Al-Duri and Joseph Wood

School of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK.


The production of chemicals and fuels from renewables is currently the most promising route for the

replacement of their fossil derived counterparts, with a view to sustainability and reduction of greenhouse gas

emissions [1]. Furfural can be derived from lignocellulosic biomass, and is a key precursor for manufacture of

derivatives with applications in the fuel, chemical and polymer industries. 2-methylfuran (2-MF) is an

important derivative with application as a gasoline alternative, which has favourable combustion performance

in engines. MF has a higher octane number than gasoline (103 vs 96.8 RON) and their energy densities are

comparable (28.5 MJ L-1 vs 31.9 MJ L-1), such that the same volume of MF contains 34 % more energy than

ethanol as a biofuel. For the hydrogenation of furfural to MF, hydrogen needs to selectively react with the

formyl group without opening or hydrogenating the furan rings. Despite developments of this reaction,

product selectivity remains a challenge, which is investigated here.

The selective hydrogenation of furfural (FFR) to 2-methylfuran (2-MF) was investigated under mild conditions.

The use of 2-propanol as a solvent for the hydrogenation of furfural (FFR) in the liquid phase was investigated

over platinum catalyst with different supports namely, 3 wt% Pt/C, 3 wt% Pt/ZSM-5, 3 wt% Pt/HY, 5 wt%

Pt/SiO2, and 5 wt% Pt/G. catalysts screening showed that 3 wt% Pt/ZSM-5 catalyst gave the highest yield (74 %)

and selectivity (90 %) towards 2-MF. Optimum conditions for the reaction over this catalyst were identified as

2 hours reaction time at 220 °C and 30 bar hydrogen pressure at which, a FFR conversion of almost 100 % was

achieved, with a yield of 74 % towards 2-MF. Furthermore, the present system compared favourably with

other works that found the yield to be 51.1 % at the high pressure of 90 bar, long reaction time of 14 hr and

temperature around 220 °C. The conversion and yield of FFR and 2-MF respectively, were enhanced with

increasing reaction temperature and reaction time. Moreover, the Pt and zeolite supports in 3 wt% Pt/ZSM-5

heterogeneous metal catalysts has a large surface area, which enhances its catalytic activity and enables it to

almost completely convert FFR leading to a significant increase in 2-MF yield.

References:

[1] L. Grazia, A. Lolli, F. Folco. Y. Zhang, S. Albonetti, F. Cavani, Catal. Sci. Technol 6 (2016) 4418.

176


Chemistry

Gold-Based Catalyst with Locally Controlled Chemical and Geometric Environments

to Tune Catalytic Performance

Nidhi Kapil1, Michael M. Nigra2 and Marc-Olivier Coppens1 1Department of Chemical Engineering and Centre for Nature Inspired Engineering, University College London,

London, United Kingdom

2Department of Chemical Engineering, University of Utah, Salt Lake City, UT 84112, USA


Gold is widely known to exhibit magnificent properties, and once the size of the particle is below 10 nm, it acts

as a suitable catalyst in many types of chemical reactions. As the size of the particle decreases, a larger

proportion of the atoms is available on the surface to speed up the reaction. Generally, the main factors that

affect the catalysis are particle size of the metal clusters, nature of the support employed and area of contact.

[1]

Enzymes are known as nature's best catalysts, yet their performance immensely depends on their

environmental surroundings. Taking inspiration from nature, the activity and the nature of the active site of

gold metal clusters can be largely affected by their respective environment, which mainly consists of organic

bound ligands [2]. Moreover, these organic bound ligands not only affect the activity, but also impart extra

stability to the clusters [3]. It would be really exciting if the environment around the metal centre could be

modified to control the catalysis.

In this study, various sizes of gold metal clusters were synthesised, using a variety of organic ligands. It was

concluded that the steric properties of the precursor during the synthesis greatly affect the final size of the

clusters. An interesting relationship between steric hindrance of the precursor and particle size, along with

stability, will be demonstrated. These factors will help us to understand how the particles behave in different

chemical and geometric environment, which is an important aspect to control catalysis.

References:

[1] Haruta, M.; Chem. Rec., 2003, 3, 75.

[2] Trogadas, P.; Nigra, M. M.; Coppens, M.-O.; New J. Chem. 2016, 40, 4016.

[3] Nigra, M. M.; Yeh, A. J.; Okrut, A., DiPasquale, A. G.; Yeh, S. W.; Solovyov, A. Katz, A.; Dalton Trans. 2013, 42,

12762.

177


Chemistry

The Oxidative Coupling of Methane: Application of Membrane Reactor to Enhance

the Yield of Higher Hydrocarbons

Ojotule Onoja



It is widely recognized that crude oil resources will deplete within the next few decades, hence accessing alternatives, abundant, and sustainable sources for petrochemicals would be of utmost interest. Ethylene is the most widely produced organic commodity in chemical industry with an annual global demand of over 140x106 tons and a growth rate of 3.5 % per year. Currently serves as precursor for polyethylene, ethylene could also potentially serve to make high octane number fuels via oligomerization in the near future provided a cost-efficient access is retained. However, it is at present mainly produced via steam cracking of naphtha, so its availability is directly dependent on that of crude oil resources.

Methane a major constituent of natural gas which has also be increasingly obtainable from biogas, landfill, and shale gas, has been identified as an auspicious alternative raw material for ethylene production. Moreover, methane has 25 times higher global warming potential to that of CO2, pinpointing the need for its efficient utilization. Indirect methane upgrade routes typically involve the production of synthesis gas via either steam reforming or partial oxidation, the former requiring extensive heat input and the later costly pure oxygen as feedstock.

In contrast, a direct conversion route of methane to ethylene avoids the expensive syn-gas production step. As such, the Oxidative Coupling of Methane (OCM) has been conceptualized as a very promising and more economically favourable pathway than indirect routes. Since the pioneering work of Keller and Bhasin in the early 80s, numerous catalyst formulations have been studied and proven to be effective for OCM. However, none has reached the stage of commercialization, since performance in terms of C2 yield still remains relatively low. It has been recognized that commercial application of the OCM reaction will only be possible if its inherent yield limitations are overcome. As such, a need for novel concepts is imperative.

Optimal C2 selectivity, but low CH4 conversion, can be achieved at large CH4/O2 ratios that avoids unselective deep oxidation routes. Membrane reactors, combining reaction with separation, have great potential to enhance the performance of OCM. They can ensure a controlled O2 dosing along the reactor axis so that C2 production is promoted, overcoming at the same time the expensive O2 separation step from air.

In this study a preliminary investigation of OCM in both a Packed Bed Reactor (PBR) and a Membrane Reactor (MR) is conducted. The study focuses on improvements achieved by the MR in terms of CH4 conversion and C2 products selectivity. The work specifically addresses the influence of the homogeneous gas-phase reactions on performance. These radical reactions have a reduced effect in atmospheric micro-reactors, typically applied at research studies, but can have critical effects to C2 selectivity at industrial conditions. An elaborate gas phase microkinetic network is coupled to the reactor scale simulations to specifically address this. The identification of important reaction paths in this process is an effective step towards the design of an optimal OCM reactor.

178


Chemistry

Aerobic Oxidation of Benzyl Alcohol in a Catalytic Membrane Reactor: Experiments

and Modelling

Baldassarre Venezia1, Achilleas Constantinou2, Gaowei Wu1 and Asterios Gavriilidis 1a 1Department of Chemical Engineering, University College London, Torrington Place, London, WC1E 7JE, UK

2Division of Chemical and Petroleum Engineering, School of Engineering, London South Bank University, London,

SEW10AA, UK

Email: [email protected] aCorresponding author. Email address: [email protected]

This paper presents results from theoretical and experimental research concerning the aerobic oxidation of

benzyl alcohol performed in a continuous catalytic membrane reactor. The tubular membrane consisted of

three layers made of alpha-alumina and a titania top layer. Deposition of the bimetallic Au-Pd catalyst was

achieved by impregnation of a precursor solution inside the inner part of the membrane followed by drying

and calcination. Liquid benzyl alcohol was fed in the annulus between the membrane inner wall and a

concentric thermo-well, while on the external side of the membrane pure oxygen was present. This

configuration ensured a controlled contact of the two phases and a safe oxidation of benzyl alcohol in the

catalyst coated area inside the membrane. The catalyst showed excellent stability. A high selectivity to

benzaldehyde was obtained, attributed to an increased oxygen mass transfer to the catalyst region.

Conversion was found to increase with gas pressure, liquid residence time and benzyl alcohol dilution in o-

xylene, while selectivity to benzaldehyde remained nearly unchanged. A two-dimensional axisymmetric model

of the catalytic membrane was developed and results from the simulation were compared with the

experimental outcomes.

179


Chemistry

Multifunctional Porous Materials for Combined CO2 Capture and Conversion

Angus Crake, Konstantinos C. Christoforidis and Camille Petit



Rising levels of Greenhouse Gases (GHGs) in the atmosphere, such as CO2, has stimulated significant research

to find ways mitigate the impact of GHGs on the climate. Fossil-fueled power generation represents a major

source of CO2 emissions, therefore various end-of-the pipe technologies are currently proposed as carbon

management media. Solid adsorbents are a low energy intensive alternative than amine-based solvents as

these are capable of CO2 capture at low temperatures.

Metal-organic frameworks (MOFs) represent a class of solid adsorbents with chemical and structural tunability,

large porosity as well as high thermal and chemical stability. Owing to this, MOFs are promising materials for

CO2 capture. In addition, recent research efforts demonstrate the potential use of MOFs as photocatalysts,

especially in the context of CO2 reduction into useful products (e.g. CO and CH4). Considering these two

features, we are investigating the application of MOFs as bifunctional absorbent-photocatalyst materials for

the combined capture and conversion of CO2. This approach could potentially enable process intensification

and improvement of the overall Carbon Capture Utilisation and Storage process sustainability. This is because

the energy required to regenerate the adsorbent is also used to convert CO2. As part of this study, various

MOF-based materials were synthesised and characterised, and preliminary photocatalytic tests were

performed and will be presented.

Keywords: metal-organic framework, adsorption, photocatalyst, CO2 capture and conversion, multifunctional

materials

180 180

Poster Presentations – •Biological Engineering

Biological Engineering

Manufacture and Characterisation of Protein Nanoparticles as Surrogate Virus

Mimics for the Optimisation of Chromatography Media

Stephan Joseph



The acquisition of representative virus feedstock sufficient in quantity and particle concentration, as well as

the methods for monitoring these species during chromatography, pose several practical issues in the realm of

virus particle purification. We have developed a method for the reproducible manufacture of protein

nanoparticles (NPs). The NPs act as surrogate mimics for virus and virus-like particles (VLPs) in the context of

characterising viral chromatographic media performance.

In lieu of the similar size, density and surface characteristics of the protein NPs with respect to crude viral and

VLP feedstocks, as well as the ease of availability and ability to be accurately assayed, the production of

modified NPs poses a cost-effective and useful alternative method for analysing separation performance.

Specific modifications, such as conjugation with fluorophores, allow for the NPs to be tracked in both the

mobile and porous stationary phases of chromatographic media to facilitate an in-depth study of protein

species/matrix interactions.

The modified NPs are characterised using dynamic light scattering, isoelectric focusing, nanoparticle tracking

analysis, gel-electrophoresis, size-exclusion chromatography, UV and circular dichroism spectroscopy, atomic

force microscopy and transmission electron microscopy. In this way, it is possible to determine NP sizes ranges,

surface morphology, particle stability and optimum storage conditions. Cation exchange chromatography is

also utilised to determine degree of labelling and surface characteristic modification of the protein monomer

and modified protein NPs.

To optimise chromatography performance and assess binding kinetics, the use of CD spectroscopy, scanning

electron microscopy and confocal laser scanning microscopy have been employed. Varying degrees of binding

are achievable, depending on the size of the NPs and the loading buffer employed. This information can be

used to inform scale-up of viral purification columns in a cost-effective and efficient manner, as it is possible to

optimise column loading of the protein species by screening multiple loading buffer conditions at small scale.

This work details the manufacture of reproducible batches of protein NPs within a defined size range between

50 to 250 nm, using varying ratios of ethanol and methanol as desolvation agents. These sophisticated NPs,

functioning as surrogate viral mimics, serve to broaden the scope of virus chromatography and enable the

collection of effective and novel data to improve recovery and purification of viruses and VLPs for future work.

It is envisioned that the manufacture of reproducible, well characterised and multi-functional NPs will provide

a platform for assessment of established and novel viral purification media as well as informing the design of

future separation materials.

181


A New Microfluidic Test for Rapid Detection of E.Coli Infections

Isabel P. Alves1 and Nuno M. Reis1, 2 1Department of Chemical Engineering, Loughborough University, Loughborough LE11 3TU

2Department of Chemical Engineering, University of Bath, Bath BA2 7AY


Urinary Tract Infections (UTIs) are among the most common bacterial infections representing a significant

healthcare burden. Over 80 % of UTIs are caused by the same pathogenic bacteria, Escherichia coli, yet current

diagnosis of UTIs is entirely dependent on microbiological sample culture in centralised labs, which takes 2-3

days, delaying diagnosis and treatment of infections. Rapid identification of bacteria at point-of-care (POC) has

proved very challenging, with no tests currently available for identification and quantitation of pathogens near

the patient [1]. We developed a simple 'chemical engineering' solution consisting of a miniaturized test for

specific, timely and sensitive identification and quantitation of E. coli in biological samples, to help managing

prescription of antibiotics and strop the spread of antibiotic resistant strains. The microfluidic test is mass

manufactured from a 10 bore, melt-extruded microcapillary film (MCF) fabricated from Teflon-FEP. Each

capillary having an internal diameter around 200 µm is internally coated with a specific antibody allowing to

rapidly capture bacteria cells on the wall of the microcapillaries. A conventional sandwich immunoassay is then

performed which uses enzymatic amplification for colourimetric or fluorescence detection of E. coli. MCFs

strips have been recently applied to rapid detection of a range of protein biomarkers, benefiting from the

excellent transparency clarity of the material (resulting from matching of refractive index) optical interrogation

of the microcapillaries can be easily done with a portable, inexpensive optoelectronic instrument such as a

smartphone camera [2]. A full response (standard) curve carried out with 3 % w/v bovine serum albumin

spiked with E.coli on a range of 100 to 108 CFU/ml (i.e. colony forming units per mililiter) showed a limit of

detection of 102.7 CFU/ml per strip, which is equivalent to 51 CFUs per capillary, meeting the clinical threshold

required for detection of E. coli in UTI infections. The total assay time was less than < 25 minutes, and there is

potential to further speed up the bacteria detection using a combination of shorter diffusion distances and

novel engineering strategies for speeding up bacteria bounding to the microcapillary walls. We are currently

validating the test with clinical urine samples. This new E.coli microfluidic test has the potential of helping

clinicians to manage the current over prescription of antibiotics in UTIs and monitoring patients with

reoccurring disease, but the same engineering approach can be used for detecting a range of pathogens.

References:

[1] Cho, S., et al., Biosensors and Bioelectronics, 2015, 74, 601-611.

[2] Barbosa, A., et al., Biosensors and Bioelectronics, 2015, 70, 5-14.

182


Exploitation of Interspecies Interactions for Pharmaceutical Production

Lixing Gu and Ferda Mavituna



There is a hypothesis that the production of secondary metabolites, especially antibiotics, will increase in the

presence of another microbial species as this will create competition. Streptomyces coelicolor A3(2) can

produce many compounds with bioactivities including four known antibiotics, undecylprodigiosin,

actinorhodin, methylenomycin and calcium-dependent antibiotic (CDA). Now undecylprodigiosin become a hot

research topic because of its immunosuppressive and anti-cancer activities. However, Streptomyces coelicolor

produce low level undecylprodigiosin in pure culture.

The main aim of this research is to investigate the effects of interspecies interactions through signaling

molecules or other elicitors on the growth and antibiotics production by Streptomyces coelicolor in defined

medium.

References:

[1] Kieser, T., Bibb, M., Buttner, M., Chater, K. and Hopwood, D. (2000). Practical Streptomyces Genetics.

International Microbiology, 3(4), pp.260-261.

[2] Pettit, R. (2009). Mixed fermentation for natural product drug discovery. Applied Microbiology and

Biotechnology, 83(1), pp.19-25.

[3] Williamson, N., Fineran, P., Leeper, F. and Salmond, G. (2006). The biosynthesis and regulation of bacterial

prodiginines. Nat Rev Micro, 4(12), pp.887-899.

183


A Multiscale Study on the Effect of Surface Chemistry on Protein Adsorption

Evangelos Liamas1, Richard Black2, Paul Mulheran3, Owen Thomas1 and Zhenyu J. Zhang1 1School of Chemical Engineering, University of Birmingham

2Department of Biomedical Engineering, University of Strathclyde 3Department of Chemical and Process Engineering, University of Strathclyde


To enhance the biocompatibility of advanced biomaterials where protein adsorption plays a major role, it is

vital to investigate the interaction of a given biomaterial with its biological substrate/environment. In this work

we have use a combination of experimental and computational techniques to systematically examine the

adsorption of fibronectin, a major protein involved in the promotion of adsorption of cells on biomaterials, to

four chemically defined model surfaces (i.e. hydroxyl, methyl, carboxylic acid and amino-terminated self-

assembled monolayers).

Fibronectin adsorption kinetics were followed using a Quartz Crystal Microbalance, and it was found that

although both charged surfaces (-vely charged carboxyl- and +vely charged amine- terminated SAMs)

promoted larger amount of fibronectin adsorption than their neutral counterparts (methyl and hydroxyl

terminated), the time to reach equilibrium at the solid/liquid interface was considerably longer (i.e. 6000 and

4200 s for positively and negatively charged SAMs respectively cf. 3600 s for the methyl and hydroxyl capped

SAMs), in keeping with the extended time required by the polyampholytic fibronectin to rearrange its

configuration post the initial rapid adsorption phase.

Molecular Dynamics (MD) simulations were subsequently performed on ARCHER and ARCHIE-WeSt

supercomputers with the express purpose of identifying the main functional groups driving the adsorption

process. The models use explicit solvent and have between 100,000 - 150,000 atoms which require high

processing power. Owing to limitations in computing power simulations were conducted with the 8-10FNIII

fragment of fibronectin in place of the full length 440 kDa molecule. Importantly, this fragment contains the

cell-binding and synergy sites that mediate the protein-cell interaction through integrins on the surface of cells.

MD simulation results reveal that the `specific subset' of hydrophilic residues on the surface of the protein

promote the initial anchoring of the protein, followed by various other residues these vary depending on the

charge and hydrophilicity of the substrate. The unique combination of experimental and computational

approaches demonstrated here for the model protein fibronectin has provided an in depth understanding of

the influence of surface chemistry on the protein adsorption process. This approach will likely find broad

application elsewhere in the near future.

184 184

Poster Presentations – Chemical Engineering at Interface

Chemical Engineering at Interface

The Effect of Novel Binders on the Performance of Capacitive Deionization for Water

Purification

Maggie Svensson



Capacitive deionization (CDI) is a promising new technique for cost-effective and energy efficient desalination.

The CDI technology is based on ion sorption and storage of ions in an electrical double layer. The technique is

most advantageous for desalination of water with low or moderate salt concentration (brackish water) [1]. The

advantages of the CDI technique is related to its mild operational conditions with low voltage, low pressure

and low temperature. CDI is also suitable for employment as a portable fresh water resource devices, mobile

desalination stations for disaster response and community desalination plants. Most current CDI research

focuses on improving salt adsorption capabilities [2]. We know of no studies focused on investigations of

different binder's effect on performance of CDI devices. In this study two novel binders were developed and

the effect of replacing them with conventional binders such as Nafion™ was investigated.

References:

[1] Anderson, M. A.; Cudero, A. L.; Palma, J. Capacitive deionization as an electrochemical means of saving

energy and delivering clean water. Comparison to present desalination practices: Will it compete? Electrochim.

Acta 2010, 55 (12), 3845−3856.

[2] Porada, S.; Zhao, R.; van der Wal, A.; Presser, V.; Biesheuvel, P. M. Review on the science and technology of

water desalination by capacitive deionization. Prog. Mater. Sci. 2013, 58 (8), 1388−1442.

185


Novel Hybrid Adsorption-Distillation Flowsheets for the Separation of Close-Boiling

Mixtures

Ajenifuja A. and Jobson M.

Centre for Process Integration, School of Chemical Engineering and Analytical Science, The University of

Manchester, Sackville Street, Manchester, M13 9PL, UK


The drive to reduce costs and maximise profits as well as increased awareness of the environmental impacts of

the traditional technologies for energy generation has led industry to seek cheaper feedstocks and more

energy-efficient technologies for production. This drive to improve energy efficiency is even more pronounced

in industries such as crude oil refining, and air separation, where extreme temperatures for process heating

and cooling are required respectively, and greater energy efficiency could lead to significant reductions in

operating costs.

Efforts to improve the energy efficiency of these types of processes have primarily focused on improving or

optimising existing technologies, leading to highly heat integrated and complex flowsheets. This approach,

although leading to improvements in process performance, is inherently limited in its potential to bring about

energy savings, as the core technology is the same. Novel technologies are required to truly revolutionise the

performance of such processes.

This project aims to identify novel technology alternatives to cryogenic distillation-based separation processes

for the separation of highly volatile components which do not condense at ambient conditions. The focus is on

separation of fluid mixtures the constituents of which have similar physical properties and similar vapour-

liquid equilibrium behaviour. Separation by distillation of such mixtures is inherently difficult and energy

intensive, as distillation relies on volatility differences between components to be separated. Hybrid

flowsheets, incorporating cryogenic distillation, and adsorption or membrane separation processes are

explored as potential alternatives to cryogenic distillation-based flowsheets which are traditionally used for

such separations.

The separation of CO - a major feedstock in the production of acetic acid - from syngas containing N2 is the

case study in this work. This separation is conventionally carried out by cryogenic distillation. However,

conventional processes are restricted to low N2 feeds as energy costs are prohibitive for high N2 feeds: it is

difficult to separate CO and N2 as they have very similar physical properties. Hybrid flowsheets could

potentially bypass this bottleneck, thus reducing energy costs for traditional feedstock, as well as potentially

allowing the use of cheaper feedstock with higher N2 content for the production of CO.

Preliminary results from the simulation studies of adsorption-distillation hybrid flowsheet configurations for

the separation of CO from N2-rich syngas feeds will be presented. The effect of the selected hybrid flowsheet

configuration, choice of adsorbent material, and operating conditions on the energy demand of the hybrid

flowsheet will be compared to that using conventional technology.

Key words: Cryogenic distillation, Hybrid flowsheets, Adsorption-distillation flowsheets, Syngas, CO separation,

Close-boiling mixtures

186


Investigating Soil Removal Mechanisms, To Minimize Water Usage during Domestic

Wash Processes

Despoina Zympeloudi



The laundry process is a major part of household operations throughout the world, which improves people's

quality of life, but also has a significant environmental impact. By 2030 the demand of water will outstrip the

supply by 40 %, and a major contributor to the water used for domestic purposes, is the water used in laundry

and domestic cleaning. Although the popularity of washing machines continues to rise, hand wash processes

are still used by the vast majority of populations throughout the world. There are not accurate measurements

for water used in washing operations; however an order of magnitude of the water usage is 9x1011 lt/p.a. The

object of this research is to reduce the amount of water used for cleaning in domestic hand wash processes,

without compromising product performance by using engineering principles to understand the underlying

phenomena.

Hand wash process, as with every manual operation, it is very consumer dependent. After analyzing consumer

videos from different countries, provided by P&G, the hand wash process has been broken down into 4

distinct stages: (a) detergent dissolution, (b) pre treatment of fabrics, where mass transfer of the formulation's

active ingredients to the fabric and soil, (c) application of force via mechanical actions like scrubbing and (d)

rinsing.

Understanding the key parameters behind each stage, is crucial for achieving soil removal with less water. The

first step for towards this direction would be to investigate the distribution of various soils in cotton fabrics

and how the hand wash process affects it. The effect of surfactant LAS (Linear Alkylbenzene Sulfonate) was

analyzed under different temperatures with no external mechanical force. An experimental set up was

developed, where single yarns were isolated from plain cotton, were stained with olive oil and lard and were

soaked into aqueous LAS solutions. The process that simulates the pre-treatment stage, was visualized by a

fluorescent microscope.

A method was developed using the fluorescent microscope to observe the distribution of different soils on

cotton fabrics, and study their interaction with aqueous surfactant solutions. Results have shown that, a

temperature rise, increased removal for both olive oil and lard. However, elevated surfactant concentration

results in a decreasing lard removal, which is not the case for olive oil. Olive oil is removed by the rolling up

mechanism, where droplets are formed while the contact angle between oil and fabric increases as the surface

tension drops. Lard cannot be removed without the addition of external mechanical forces, except at

temperatures more than 60 °C, where it is in a liquid state.

187


Nanomechanics of Articular Cartilage and Synovial Fluid

Konstantina Simou



The degeneration of articular cartilage is suffered by millions worldwide leading to untreatable diseases such

as Osteoarthritis. Thus, it is of vital importance to understand the mechanical and lubrication function of

articular cartilage and synovial fluid, respectively, so that non-invasive diagnostic tools can be developed at the

onset of such arthritic diseases.

The aim of this project is to establish the relationship between the nanomechanical properties of

cartilage/synovial fluid against osteoarthritis patient groups (e.g. inflammatory vs. less inflammatory, stages 1-

4). In order to do achieve this a combination of Scanning Probe Microscopy, Nanotribometry, and Rheology

will enable the tribological characteristics of such system at different length scales (from nanometer to

millimetre) to be probed at a range of pressure found in the synovial joint. To date preliminary measurements

have been carried out in both synovial fluid and formulated artificial synovial fluid that exhibits similar

viscoelastic properties. A significant difference in surface adhesion was observed in the presence of synovial

fluid versus artificial fluid samples.

The results demonstrate the critical role of individual components of synovial fluid such as aggrecan and

lubricin in controlling surface mechanical properties of cartilage. As an ongoing project, we plan to

characterise the composition of synovial fluid collected from two contrast patient groups and identify the key

components that control the tribological performance of synovial joint.

188


Understanding the Colloidal Interactions at Oil/Rock Interfaces

Maryam Derkani

University of Strathclyde


Waterflooding is commonly used during conventional oil recovery to provide pressure support and to sweep any extra crude oil by way of viscose forces [1]. Low salinity waterflooding (LSW) is an Enhanced Oil Recovery (EOR) technique, including injection of brine with low ionic strength and composition. LSW has been demonstrated as a promising approach to improve the oil recovery factor; however, the principal mechanism involved in this method is not fully understood, which is a significant challenge to optimisation of the salinity and ionic composition of the injected brine. The main suspected mechanism for EOR by LSW is 'wettability alteration'. Understanding the wettability mechanism involved in LSW and the colloidal interactions at oil/rock/brine interfaces are essential to improving the efficiency of LSW.

Carbonate rock reservoirs comprise more than half of the world's oil and gas reserves [2]. Limited understanding of carbonate reservoir properties is a big challenge that the oil production industry is facing to maximise oil recovery. Complex flow mechanisms and strong adsorption between carbonate rock surface and crude oil particles can reduce hydrocarbon recovery to as low as 10 %. It is generally believed that the injection of low salinity brine dissolves rock minerals, modifies the wetting state towards a more desirable state for oil to recover [3]. The main aim of this study is to understand the fundamental physicochemical mechanisms that govern such wettability alteration by directly measuring the colloidal interactions at rock/oil interfaces and to develop a computational model, which suitably represents realistic reservoir conditions.

During this project, zeta potentials of carbonate formations in two-phase (rock/brine) and three-phase (rock/oil/brine) colloidal suspensions have been measured as a function of individual aqueous electrolyte concentration, using electrophoresis measurements. Two dominant mechanisms for surface charge modification of carbonates, in the presence of different ions and model oils, could be specific adsorption of ions at the surfaces and preferential dissolution of ions from the crystal lattice. Debye and DLVO (Derjaguin, Landau, Verwey and Overbeek) theories were implemented to calculate surface potentials on the colloidal systems. The zeta potential results were used to approximate surface charge density for symmetrical and non-symmetrical electrolytes, hence, allowing calculation of surface potential and DLVO forces. Such values will help in defining properties (stability) of the colloidal system, allowing comparison of theoretical calculations and future experimental results from atomic force microscopy.

In future work, contact angle measurements will be used to measure the degree of wettability of carbonate rock crystals at oil/brine interfaces and to further support evidence of surface charge alteration leading to wettability alteration with increasing temperature. Atomic force microscopy will be used to examine the interfaces between two solid surfaces or a liquid droplet and homogeneous or heterogeneous planar substrates. This will help to quantify colloidal interactions (van der Waals, electrostatic and hydrophobic forces) between rock surfaces in a liquid environment. In the last stage of this work, molecular-scale computational models will be used for reservoir fluid and interfacial systems to suitably represent properties of oil/rock interfaces at realistic reservoir conditions such as high temperature and pressure.

References: [1] Kazankapov, N., Enhanced Oil Recovery in Caspian Carbonates with "Smart Water" Society of Petroleum Engineers. DOI: 10.2118/171258-MS. [2] Marathe, R.; Turner, M. L.; Fogden, A., Pore-Scale Distribution of Crude Oil Wettability in Carbonate Rocks. Energy & Fuels 2012, 26 (10), 6268-6281. DOI: 10.1021/ef301088j. [3] Hiorth, A.; Cathles, L. M.; Madland, M. V., The Impact of Pore Water Chemistry on Carbonate Surface Charge and Oil

Wettability. Transport in Porous Media 2010, 85 (1), 1-21. DOI: 10.1007/s11242-010-9543-6.

189


Design of Flexible Heat-Integrated Crude Oil Distillation Units

Dauda Ibrahim1, Megan Jobson1, Jie Li1 and Gonzalo Guillén-Gosálbez2 1Centre for Process Integration, School of Chemical Engineering and Analytical Science, University of

Manchester, Manchester M13 9PL, UK 2Department of Chemical Engineering, Centre for Process Systems Engineering, Imperial College, South

Kensington Campus, London SW7 2AZ, UK


Continued global demand for petroleum products and the ongoing need to process different crude oil

feedstocks provide incentives for greater flexibility in refineries. Petroleum refineries typically process various

crude oil feedstocks in order to cope with changes in market demand for products and to stay competitive in

the refining business.

Crude oil refining starts with distillation, in which the raw crude oil is separated according to boiling points into

different products. The complex nature of crude oil distillation units, including their interactions with the

associated heat recovery network and the large number of degrees of freedom, makes their design a very

challenging task, especially when considering the need to process a variety of feedstocks.

This research develops a systematic methodology for optimisation-based design of flexible crude oil distillation

units that can process multiple varieties of crude oil feedstocks. The approach applies surrogate column

models (regressed against data generated by multiple rigorous simulations) together with stochastic

optimization. The design problem is formulated to consider both structural variables (the number of trays in

each column section) and operational variables (feed inlet temperature, pump-around duties and temperature

drops, stripping steam flow rates and reflux ratio). An efficient approach to solving the optimization problem is

developed, to search for the best design that is capable of processing multiple crudes, where heat recovery

opportunities are accounted for using pinch analysis.

The approach is illustrated by a case study; the results demonstrate that the new approach is capable of

identifying attractive design options while accounting for industrially relevant constraints.

Keywords: Genetic algorithm, surrogate models, optimization-based design, rigorous simulation, pinch

analysis

190


Light-Responsive IRMOF 5: Improved Ligand Synthesis and MOF Stability Study

Xin Dong



Metal-organic framework (MOF), as its name indicates is a coordinate complex comprising of inorganic metal

and organic ligands. MOFs started gaining attention due to its excellent surface area, which can be used as

potential CO2 adsorption application in the post combustion process. Although having high adsorption

capacity, how to develop release triggers for desorption of MOFs that do not require extra energy becomes

widely discussed. Recently, more and more functional MOFs can occur structure or property change under

certain conditions and these certain conditions are called stimuli. Among diverse stimulus, pressure and

temperature are by far most common, but these cost a large amount of energy. In contrast, light as less

investigated stimuli, is much less energy consuming and much more widely available. Comparing with the

current adsorption technology applied in the industry like pressure, temperature swing adsorption, which

consumes 40 % of production capacity of a power plant, the successful commercialized light responsive MOFs

can be the light-induced swing adsorption technology to achieve low energy consumption goal. Therefore,

how to synthesize light responsive MOFs has attracted intensive attraction.

Among the various MOFs, there are three main well known inorganic secondary building units: MOF-5, UIO-66

and paddle wheel. MOF-5, as their simple structures, can be rendered with light responsive property.

Azobenzene derivative-2-phenyldiazenyl terephthalic acid, as one of the most studied photo chromic ligand

that can take place, clean and efficient reversible photo-isomerization from the thermally stable trans isomer

to the metastable cis isomer, can be incorporated directly inside the organic linkers of framework to modify it

to be light responsive. The previous experiment data has already shown different CO2 uptake when at ambient

condition and when it was exposed to UV light irradiation.

However, there are various factors that need to be taken into consideration before applying light responsive

MOF-5 into industrial practice such as reproducibility, ligand purity and MOF stability. After following the

previous published procedure for synthesizing ligand precursor (dimethyl phenyldiazenyl terephthalate), we

found it was impractical to be scaled up. In this paper, we mainly focus on how to improve efficiency of ligand

synthesis procedure. In addition to this, the stability of light responsive MOF-5 is also investigated. Because

structures of many MOFs are easy to collapse after exposing to moisture environment which make reversible

uptake function unavailable. However, in many industrial processes like combustion, the stream containing

moisture cannot be avoided. Herein, the stability of light responsive MOF-5 structure can be investigated after

analysing X ray spectrums of activated sample at ambient for three days and freshly activated sample. Besides

inducing instability of structure, moisture in stream also competes with CO2 to be adsorbed on light responsive

MOF-5, which may have side effect on CO2 adsorption capacity.

In this paper, we mainly focus on two aspects: investigating optimum synthesis process of ligand and stability

characterization of light-responsive azo-IRMOF-5.

191


Design of Electric Field Controlled Molecular Gates Hosted in Metal-Organic

Frameworks

Benjamin Tam and Ozgur Yazaydin.

Chemical Engineering Department, University College London, Torrington Place, London WC1E 7JE, United

Kingdom


Molecular Machines and Metal Organic Frameworks (MOFs) have received much attention in recent years.

They are promising for a wide range of potential applications, from gas adsorption to catalysis and from drug

delivery to manipulation of chemical structure in nanoscales. Here we describe the concept of hosting a

molecular turnstile on hybrid organic - inorganic crystalline porous structures controlled by an electric field in

order to perform tasks, such as storage and release of methane molecules. We selected Mg-MOF-74 to host a

turnstile type molecular machine. The machine contains a negative charged tri-fluoromethyl groups and

positive charge methyl groups that response to electric field. The simulations are based on the universal force

field (UFF) and charges are taken through planewave Density Functional Theory (DFT) optimized structure.

Proposed molecular turnstiles were stable thanks to strong binding between the bicarboxyl groups and open

metal sites (OMS). No methane incursion through the molecular turnstile at the closed position and methane

were discharged by rotation of the turnstile due to switch on of the electric field.

192


Three-Dimensional Modelling of Thin Liquid Films over Spinning Disks

Kun Zhao



In this research the dynamics of a thin film flowing over a rapidly spinning, horizontal disk is considered. A set

of non-axisymmetric evolution equations for the film thickness, radial and azimuthal flow rates are derived

using a boundary-layer approximation in conjunction with the Karman-Polhausen approximation for the

velocity distribution in the film. These highly nonlinear partial differential equations are then solved

numerically in order to reveal the formation of large-amplitude waves that travel from the disk inlet to its

periphery. The spatial-temporal profile of film thickness provides us with visualization of flow structures over

the entire disk and by varying system parameters(volumetric flow rate of fluid and rotational speed of disk)

different wave patterns can be observed, including spiral, concentric, smooth waves and wave break-up in

exceptional conditions. Similar types of waves can be found by experimentalists in literature and CFD

simulation and our results show good agreement with both experimental and CFD results. Furthermore, the

semi-parabolic velocity profile assumed in our model under the waves is directly compared with CFD data in

various flow regimes by utilization of radial and azimuthal flow rates in order to validate our model.

193


Laser Imaging in Liquid-Liquid Flows

Kyeong H. Park, Victor Voulgaropoulos, Maxime Chinaud and Panagiota Angeli

Department of Chemical Engineering, University College London, Torrington Place, London WC1E 7JE, UK


In this work, two-phase oil-water flows are studied in a horizontal pipe with laser based imaging techniques.

The flow characteristics are investigated with a combination of particle image velocimetry (PIV) and laser

induced fluorescence (LIF). The work was conducted in a pilot scale facility that has an acrylic test pipe with 26

mm ID and length 4 m length. The test fluids are a silicone oil (5cSt) and a mixture of water/glycerol with

matching refractive index; this was necessary to avoid any reflections at the interfaces during the laser based

experiments. Double pulsed Nd:YAG laser was employed (532 mm) equipped with appropriate optics to

generate a laser sheet in the middle of the pipe. The aqueous phase was dyed with Rhodamine 6G to

distinguish the two phases. Experiments were carried out for mixture velocities ranging from 0.15 to 2 m/s.

Different inlet designs were used to actuate flow patterns in the test section inlet in a controlled way. A static

mixer produced dispersed flow at the inlet which settled downstream to separate layers. On the other hand, a

cylindrical bluff body located immediately downstream the Y-shaped inlet of the test section generated

interfacial waves in stratified flows that were unstable and led to drop detachment and transition to dispersed

flow. The development of the flow patterns along the pipe was investigated and parameters such as wave

length and amplitude, thickness of formed layers and drop size were measured. In addition velocity profiles

were obtained.

194


A Novel Approach for Scheduling of Operations in a Large-Scale Scientific Services

Facility

Nikolaos Rakovitis, Jie Li and Nan Zhang

School of Chemical Engineering and Analytical Science, the University of Manchester, Oxford Road, Manchester,

M13 9PL


Scientific services industry examines the properties of a number of material samples. Various analytical techniques are used to examine a number of physical and chemical properties for a large number of samples. Scientific services industry seeks ways to minimize the use of resources and raw materials and the cost of the processes, in order to increase its profit. Therefore, it is imperative to improve its planning and scheduling decisions. The most important feature in scheduling scientific services facility is that multiple tasks are performed in the same machines at the same time, which is not addressed by the existing approaches in the literature for scheduling of batch processes [1-3], refinery operations [4-6], and steel plants [3,7]. Furthermore, scheduling such facility involves a great number of samples from different clients using different processing routes, increasing the combinatorial complexity of the scheduling problem. The only work related with large-scale scientific services is from Patil et al. [8] and Lagzi et al. [9]. Patil et al. [8] developed a discrete-time model to optimize the scheduling of large-scale scientific services facility via multi-commodity flow. They used the rolling horizon technique to deal with samples that were not able to be processed during the scheduling horizon. Lagzi et al. [9] addressed the same problem with that of Patil et al. [8] and developed global event-based mathematical formulation. Their results demonstrate that their proposed multitasking formulation generated considerably better solution than its single-tasking counterpart while requiring similar solution times. However, it is found that their proposed formulation still needs large CPU time for some examples especially large-scale cases. In this presentation, we develop a novel mathematical formulation using unit-specific event-based time approach to investigate the same problem presented by Patil et al. [8] and Lagzi et al. [9]. All operational features are the same as those of Patil et al. [8] and Lagzi et al. [9]. We compare our proposed model with those of Patil et al. [8] and Lagzi et al. [9] by solving the same examples using the same optimization software and computing facility. The computational results demonstrate that our proposed unit-specific event-based formulation has much fewer discrete variables and generate the same or better solutions with less computational CPU time than those of discrete-time and global event-based formulations, resulting in a significant improvement. References: [1] Floudas C. A., Lin X. Mixed Integer Linear Programming in Process Scheduling Modeling, Algorithms, and Applications, Annals of operation research, 2005;139(1);131-162 [2] Méndez C. A., Cerdá J., Grossmann I. E., Harjunkoski I., Fahl M. State-of-the-art review of optimization methods for short-term scheduling of batch processes, Computers & Chemical Engineering, 2006;30(6);913-946 [3] Harjunkoski I., Maravelias C. T., Bongers P., Castro P. M., Engell S., Grossmann I. E., Hooker J., Méndez C., Sand G., Wassick J. Scope for industrial applications of production scheduling models and solution methods, Computers & Chemical Engineering, 2014;62;161-193 [4] Khor C. S., Varvarezos D., Petroleum refinery optimization, Optimization and engineering, 2016;1-47 [5] Li J., Misener R., Floudas C. A. Continuous-time modelling and global optimization approach for scheduling crude oil operations, American Institute for Chemical Engineers, 2012;58(1);205-226 [6] Li J., Xiao X., Floudas C. A. Integrated gasoline blending and order delivery operations: Part I. Short-term scheduling and global optimization for single and multi-period operations, AlChE journal, 2016;62(6);2043-2070 [7] Li J., Xiao X., Tang Q., Floudas C. A. Production Scheduling of a Large-Scale Steelmaking Continuous Casting Process via Unit-Specific Event-Based Continuous-Time Models: Short-Term and Medium-Term Scheduling, Industrial & Engineering Chemistry Research 2012;51(21);7300-7319 [8] Patil B. P., Fukasawa R., Ricardez-Sandoval L. A. Scheduling of operations in a large-scale Scientific services facility via multicommodity flow and an optimization-based algorithm, Industrial & Engineering Chemistry, 2015;54(5);1628-1639. [9] Lagzi1 S., Fukasawa1 R., Ricardez-Sandoval L. A. A New Multitasking Continuous Time Formulation for Short-Term Scheduling of

Operations in Multipurpose Plants, Presented in the AlChE Annual Meeting, San Francisco, CA, 2016

195


Chaperonin-Inspired Enzyme Immobilisation on Mesoporous Silica SBA-15

Michele Lynch



Enzymes catalyse biotransformations in a rapid, selective, and environmentally-friendly manner. They have

many applications, particularly in fine chemical and pharmaceutical manufacturing. However, most enzymes

have evolved to operate in neutral, aqueous solutions and at moderate temperatures. Therefore, they tend to

have poor stability in industrial chemical reactors. Immobilising enzymes onto nanostructured materials can

increase their operational stability.

In vivo, enzymes are stabilised from high temperature or unfavourable solution conditions by chaperonins.

Chaperonins, such as the GroEl/ES complex, help refold partially unfolded proteins within a narrow, cylindrical

pore that becomes negatively charged. This pore gives the substrate protein a favourable local

microenvironment for folding. While chaperonins' complete mechanisms are complex, we are inspired by

some of their fundamental properties when developing materials for enzyme immobilisation.

In this study, mesoporous silica SBA-15 is used as a synthetic chaperonin analogue because of its controlled

mesopore diameter and its negatively charged interior surface. Enzymes are immobilised on SBA-15 of

different pore diameters, and their stabilities and biocatalytic activities are tested. SBA-15 is shown to be a

valuable candidate for enzyme immobilisation, because it can protect enzymes from denaturing conditions

such as acid and the presence of protease. More fundamentally, SBA-15 is a useful material for the systematic

investigation of enzyme immobilisation parameters because of its highly tuneable pore diameter and its easily

functionalised surface. The relative importance of hydropathy, electrostatic attraction, and steric confinement

are studied in order to improve the future design of enzyme immobilisation materials.

196


Virtual Formulation Laboratory for Prediction and Optimisation of Manufacturability

of Advanced Solids Based Formulations

Pablo Garcia-Trinanes , Rob J. Berry and Mike S.A. Bradley

The Wolfson Centre for Bulk Solids Handling Technology, Faculty of Engineering and Science, University of

Greenwich, United Kingdom


The Virtual Formulation Laboratory (VFL) proposes a practical tool of simulating interactions between

components, resulting in information on the flow behaviour of particulate materials. Product desired

performance within certain formulation specifications requires developing products that present right particle

properties during the manufacturing processes and also when consumers use them. The manufacturing

processes for these products present challenges that lead to delays in the path to productivity and increased

development costs (Merrow, 1981). Building a knowledge database from existing components and fine-tuning

the relationships based on physical properties (related to morphology and/or intrinsic properties) should allow

prediction of behaviour in manufacturing scenarios and guide technology choice at an early stage. Mechanisms

such as flow, caking, wetting, segregation, dissolution, particle breakage and adhesion are important from the

manufacturing stage to the end use (DEFRA). This approach proposes to develop a tool for prediction and

optimisation of manufacturability and stability of advanced solids-based formulations and will be used by

industries allowing to quickly and accurately measure the flow properties of their materials for a range of

purposes, from bench marking and quality control to assisting reformulation (EPSRC). REFERENCES - Merrow,

E.W., Phillips, K.E., Myers, C.W. (1981) Understand Cost Growth and Performance Shortfalls in Pioneer Process

Plants (RAND/R-2569-DOE) - Development of an economic yet useful powder flowability measuring device.

DEFRA (Ref. AFM 206) - Virtual Formulation Laboratory for prediction and optimisation of manufacturability of

advanced solids based formulations. EPSRC (Ref. EP/N025261/1).

197 197

Poster Presentations – Education/Training

Education and Trai ning

Education/Training

Dimension in Presenting Assignments - Making Clear the Compiler's Perspective

Mark Heslop



Assessment and feedback (A&F) are aspects of increasing importance in contemporary HE, not least because

of the many internal evaluations, league tables and external surveys - including the NSS. For league tables in

particular, A&F are often the criteria for which there is the greatest variation - and so which determine the

ranking position of departments. This issue is partly due to the increase in student numbers and also because

students are nowadays more concerned about how the feedback can be used to feed forward to their next

submissions - it is not just the number. The major challenge is then how to deliver meaningful feedback within

a reasonable time frame: at times, A&F can sometimes feel like A&E. There have been a number of initiatives

for dealing with this issue including peer marking and the greater use of educational technology for automatic

marking. It could be argued that the "A" part of A&F does not always get the attention it deserves. The

starting point might be: what is an ideal assignment? Assignments and tutorial questions, as opposed to exams,

are important in HE because they allow subjects to be considered in greater depth. The pedagogic literature

and experience would suggest that there are many indicators of good practice. Certainly, the ideal assignment

should have clear assessment criteria - and it should be clear what is required to achieved the pass mark and

the higher grades. This is an area where there is much good practice in further education, where the

assessment of HNCs and HNDs are based on three levels: pass, merit and distinction. An ideal assignment

should be based on a typical scenario or application. Perhaps also, the ideal assignment should be

developmental - it should form part of the learning process - as well as be a tool for assessment. In this work,

it is now suggested that there is another important dimension in good assignment practice - that is, the

decision making and choices that have taken place in producing an assignment. Consider the example of a set

of tutorial questions on a particular topic. There are two types of commentary: vertical (the development

from Q1 to Q2 and Q3) and horizontal (for example, how Q1 might be modified from year to year). A vertical

commentary might explain why the questions are arranged as they are, typically in order of increasing

difficulty. A horizontal commentary might then explain how such a question has been developed from the

previous year - and how it might be improved for the next year. These such commentaries, as well as giving a

unique insight to students, also help the compiler to reflect on the choice of questions. For the case of this

author, this approach has helped to avoid duplication, change the order and improve the balance of questions.

The evidence from a small case study for a Y1 UG class would also suggest that students also appreciate the

decision making behind how course material is converted into assignments.

198 198


Effectively Conveying the Importance and Relevance of Safety to Undergraduates

While Educating Them in Good Practices

Michaela Pollock and Eva Sorensen



Safety is a key concern for all chemical engineers irrespective of their industrial sector, engineering role or

seniority. As is often quoted, everyone has the right to return home at the end of the day in the same state as

when they arrived. The challenge for educators is how to effectively convey to undergraduates, who have not

yet completed their full degree courses and have little if any practical experience, a strong safety culture and

awareness of their role in developing and maintaining safety of processes. This challenge is augmented by the

fact that safety in industry is often imparted to recent graduates by working together with experienced

engineers who have participated in numerous hazard evaluation studies and who have witnessed plant

operations at first hand.

At UCL we are developing a variety of complementary approaches to continually develop undergraduates'

hazard awareness and best practice approaches to safety with the ultimate aim of yielding responsible, aware

and proactive engineers with a strong safety culture. This has been achieved by embedding safety throughout

the undergraduate programme. Concepts of risk, hazards and inherently safe design are introduced

immediately to first year undergraduates in a non-engineering context followed by examining these principles

again in a process engineering context in the second year. Case study videos prepared by the IChemE Safety

Centre have been used in lectures to demonstrate real-life industrial incidents, the decisions and

circumstances leading to these safety incidents and illustrate principles discussed in class. Undergraduates are

given many opportunities to apply the hazard evaluation techniques they are learning in lecture case studies

and assessed workshops. Furthermore, an ongoing safety theme is incorporated into 6 week-long design

projects carried out in the first two years (called Scenarios), with each project deliverable requiring teams to

perform different hazard evaluation studies. Processes introduced in these week-long projects are used in

subsequent safety lectures to enable students to learn about hazard evaluation techniques and safety on

processes with which they are familiar.

The culmination of this is in the third year capstone design project and a separate lecture module on Safety

and Loss Prevention. In the design project, three hazard evaluation studies have been carefully designed to

convey to undergraduates how the objectives, scope and outcomes of hazard evaluations evolve throughout

the process design cycle. As undergraduates consider the knowledge they have about their process and

engineering documentation available, they can begin to understand the objectives of the hazard evaluation

techniques and the insights into the process that can be gained from the outcomes of the safety studies.

Student feedback has indicated that the challenge of identifying causes and consequences of hazards and

corresponding mitigating actions is an area for further development in teaching.

Our approach to safety teaching has been enabled through the contributions of staff with a wide variety of

academic, industrial and lab experience, replicating the wide variety of experienced engineers that graduates

will work with in their future graduate engineering roles, and within the framework of UCL's Integrated

Engineering Programme (IEP).

199 199


A Complimentary CPD Program for Involving PhD Students as Partners for UG

Learning

Thomas Rogers



PhD students play a vital role as Graduate Teaching Assistants (GTAs), delivering teaching & learning to

undergraduate students; this interaction means PhD students have a significant impact on the undergraduate

experience. Historic feedback from undergraduates shows that the GTAs are under prepared for the role:

“the worst thing about labs is the demonstrator”

First Year Undergraduate Chemist, November 2015

Enhancing training with a modular course will lead to quality learning environments and enhance student

satisfaction. A Science and Engineering Faculty Graduate Teaching Assistant training course has been created,

with modules which are generic enough to be useful across the schools but targeted to the needs of GTAs

working within the Faculty. Modules are delivered by those who work with GTAs on a daily basis, drawn from

across the Faculty.

The modules are benchmarked against the UK professional standards framework (UKPSF) of the Higher

Education Academy (HEA) and the Research Development Framework (RDF). This will allow GTAs to evidence

their training and give them the opportunity to apply for Associate Fellow of the HEA, enhancing their

employability.

A trial is currently being run jointly between the schools of Chemical Engineering and Chemistry to provide

three modules; on GTA expectations, assessment and feedback, and online marking. This is to meet the

current most vital needs of these two schools. These sessions will then be repeated in January 2017 for GTAs

starting teaching in semester 2. These same three sessions will form part of the full training programme in

September 2017.

Feedback has been collected for the results of these three sessions and used to develop the taught material.

The new material has been tested in the January sessions with more feedback collected and analysed.

200 200


Enhancing the Student Learning Experience in Chemical Engineering by Employing a

Virtual Laboratory

Stefan Zweig

University of Greenwich


The teaching strategies for Chemical Engineering include more and more research informed teaching methods

which combine cutting edge research with well-established fundamental principles. A broad range of

engineering subjects have to be incorporated into the teaching of a Chemical Engineering degree. One

example of a complex topic is the heat transfer in heat exchangers. With the aid of a virtual laboratory this

complex subject can be studied by the student at his own pace. The virtual laboratory could include the

simulation of a heat exchanger and the optimization of process parameters influencing the heat transfer

process. For example, the output temperatures could be computed for a given set of input temperatures and

flow conditions in the heat exchanger. Then efficiency curves can be computed for different flow rates.

Different student activities can be designed to challenge the students and to foster their knowledge on heat

exchanger design and operation. The students using the virtual lab environment are encouraged to ask

questions about the process and find answers by running simulations in the virtual lab. Obtained data can be

then compared with measurements from the heat exchanger in the laboratory.

An automatic assessment function could be built into the virtual lab which would ensure that tutors can record

the progress of students and help students to achieve the learning outcome of the course. The use of a virtual

and a physical systems is supporting the learning and understanding of students as well as increasing the

student learning experience in this course.

201 201


Chemical Engineering in the UK – A New Paradigm

Pablo Garcia-Trinanes1, Stefan Zigan1, Alec Coutroubis1 and David Brown2 1 Wolfson Centre for Bulk Solids Handling Technology, Faculty of Engineering and Science, University of

Greenwich, UK 2 IChemE, UK


This work looks at the implications for chemical engineering education of the current situation of the chemical

manufacturing industry, the game-changing technologies that are emerging and future demands on the sector

and the relevance of these demands for chemical engineering education and training. A recent tendency

seems to be broadening of the field by fusion of engineering with the chemical sciences in conjunction with

biological, biotechnology & food sciences and advanced materials.

The response of the education system over the years and a number of strategies to incorporate the

development and production of a diverse range of products into courses are described. Chemical engineering

has to be about an increasing range of products as well as processes. The process affects the properties of the

product but we are now focused on the way the product is used or the way it interacts with the consumer. The

important role of the chemical and process engineer’s solutions is emphasized but this also suggests that a

new way of thinking about the discipline is required.

Indeed, this presentation argues the next paradigm shift in the discipline which has been predicted for some

time addressing the recent research & development activities in various aspects of the chemical engineering

discipline. Examples of the nature of this shift are the small scale manufacture supremacy, the structured

nature of products compared with homogeneous, the domination of specialty and more flexible products and

quality over costs or the incorporation of a variety of nanotechnology to be used in product development.

202 202


Mixed Polyelectrolyte Brush Surfaces Display ‘Chameleon-Like’ Protein Binding and

Elution Properties

Glassey J1 and Ostrowski B2 1 School of Chemical Engineering and Adv. Materials, Merz Court, Newcastle University, UK.

2 INTO Newcastle University, Percy Street, Newcastle-upon-Tyne, UK.


Increasing cohort numbers of chemical engineering students over the past few years raise a number of significant

challenges in the effective delivery of core materials, and the development of essential professional skills. One particular

challenge is effective ‘small’ group teaching, where group sizes keep rising and thus potentially limiting the ability of all

students to engage proportionately in the planned educational activities. Whilst a number of technological solutions can

alleviate this issue to some extent, by enabling on-line voting in response to posed questions, or by completing electronic

tutorial problems on-line for example, these do not adequately address the need for effective cooperation in peer groups

which is essential to reinforce understanding of core materials delivered in large groups, and to develop problem solving,

team working and independent learning skills which are important for future professional life.

Diamond ranking, also called Diamond Nines, is a critical thinking tool employing visual methods, and has been employed

in primary and secondary school research (Woolner et al., 2007; Woolner et al., 2010; Clark, 2012), and in teacher training

(LSIS, n.d.). More recently, its potential for use in Higher Education (HE) has been explored with classes of international

students to improve speaking skills, to promote collaborative learning in intercultural groups (Rajendran and Ostrowski,

2011), as a potential vehicle for fostering understanding and intercultural communication across the curriculum

(Ostrowski, 2013), and in promoting reflective learning on the sustainability of chemical engineering processes (Glassey

and Haile, 2013).

Diamond ranking extends opportunities for tutors to work more closely with students by encouraging them to be active

partners in their learning through collaborative exploration of their views on, and understanding of, course materials and

tasks. The current mode of making diamond ranking available to students electronically reflects one of the strategic

objectives of the Learning, Teaching and Student Experience agenda at Newcastle University in facilitating and supporting

student learning and achievement through the application of digital technologies. This ensures that students are at the

centre of the learning experience, allowing greater control of their collaboratively negotiated understanding, and

providing feedback, which can directly inform future teaching.

This method has previously been applied as a ‘paper-based’ exercise to support the revision of core biochemistry and

microbiology material in Year 1 of the Chemical Engineering curriculum at Newcastle University (Glassey, 2010) with

somewhat limited success. An electronic version has now been developed and was tested in a Chemical Engineering Year

3 module: Process and Product Development. This contribution will: assess the student experience of using this approach

to support their revision; indicate the benefits and challenges encountered in applying this approach with core chemical

engineering curriculum modules and student skills development; and inform further development of diamond ranking as

an investigative tool when delivered electronically.

203 203

List of Abstracts not Included

Author(s) Title Poster Board Number

Espinoza C. Emulsification of Non-Newtonian Mixtures in a High Shear Mixer

19

Asachi M. Evaluation of Segregation of Formulated Powder Mixtures Using Near-Infrared Spectroscopy

29

Ariane M., Alexiadis A. and Barigou M.

Discrete Multi-Physics Approach for Modelling Flexible Biological Valves and Solid Aggregation

79

Shier A. Breakage of Needle-Like Crystals under Pressure Filtration

88

Vangala S. P. K. Computational Insights into Structure-Property Relations in Co-Doped TiO2 Using DFT

118

Totti S. A Promising Highly Porous 3D Scaffolding System for in vitro Pancreatic Tumour Development and Drug Screening

133

Nimmakayla N. S. Electronic Study of TB Causing Bacterial DNA Making Nucleotide Synthesis

138

Akpinar I. and Yazaydin O.

Adsorptive Removal of Atrazine from Water with Porous Materials

158

Arkoumanis P. Rotating Membrane Emulsification for Manufacture of Stable Pickering Emulsions

162

List of Abstracts not Included

Poster Presentations – Education and Training€¦ · Mrs Mara Kefalopoulou, IChemE . ......

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