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American Institute of Chemical American Institute of Chemical Engineers – Delaware Valley SectionEngineers – Delaware Valley Section

An Introduction to Green Chemistry An Introduction to Green Chemistry and Engineeringand Engineering

November 18November 18thth 2011 2011

Ken Rollins CEng, FIChemEKen Rollins CEng, FIChemE

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What is green chemistry and what is green What is green chemistry and what is green engineering?engineering?

Green chemistry/green engineering is Green chemistry/green engineering is concerned with the design and use of concerned with the design and use of processes and products that are feasible and processes and products that are feasible and economical while minimizing the risk to human economical while minimizing the risk to human health and the environment, and the health and the environment, and the generation of pollution at source.generation of pollution at source.

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The Twelve Principles of Green ChemistryThe Twelve Principles of Green Chemistry1.1. Prevent WastePrevent Waste

2.2. Safer Chemicals and ProductsSafer Chemicals and Products

3.3. Less Hazardous Chemical SynthesesLess Hazardous Chemical Syntheses

4.4. Use Renewable FeedstocksUse Renewable Feedstocks

5.5. Use Catalytic ReactionsUse Catalytic Reactions

6.6. Avoid Chemical DerivativesAvoid Chemical Derivatives

7.7. Maximise Atom EconomyMaximise Atom Economy

8.8. Safer Solvents and Reaction ConditionsSafer Solvents and Reaction Conditions

9.9. Increased Energy EfficiencyIncreased Energy Efficiency

10.10. Design Chemicals to Degrade after UseDesign Chemicals to Degrade after Use

11.11. Pollution using Real Time AnalysisPollution using Real Time Analysis

12.12. Minimize Accident PotentialMinimize Accident Potential

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Principle #1 - Prevent WastePrinciple #1 - Prevent Waste

Design chemical syntheses to prevent waste. Leave no waste Design chemical syntheses to prevent waste. Leave no waste to treat or to clean upto treat or to clean up

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Principle #2 – Safer Chemicals & ProductsPrinciple #2 – Safer Chemicals & Products

Design chemicals/products to be fully effective but with little Design chemicals/products to be fully effective but with little or no toxicityor no toxicity

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Principle #3 - Less Hazardous Chemical Principle #3 - Less Hazardous Chemical SynthesesSyntheses

Design reactions to use and/or generate chemicals with Design reactions to use and/or generate chemicals with little or no toxicity to humans, and with low environmental little or no toxicity to humans, and with low environmental impactimpact

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Principle #4 - Use Renewable FeedstocksPrinciple #4 - Use Renewable Feedstocks

Use raw materials that are renewable rather than depleting. Use raw materials that are renewable rather than depleting. Bio-based materials or other processes’ waste materials, Bio-based materials or other processes’ waste materials, rather than fossil-based materials – oil, coalrather than fossil-based materials – oil, coal

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Principle #5 - Use Catalytic ReactionsPrinciple #5 - Use Catalytic Reactions

Catalysts are renewable and can be re-used many times, in Catalysts are renewable and can be re-used many times, in preference to the use of excess stoichiometric reagents preference to the use of excess stoichiometric reagents which generate wsteswhich generate wstes

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Principle # 6 - Avoid Chemical DerivativesPrinciple # 6 - Avoid Chemical Derivatives

Avoid chemical derivatives used as ‘temporary by-products’, Avoid chemical derivatives used as ‘temporary by-products’, which generate wasteswhich generate wastes

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Principle # 7 – Maximize Atom EconomyPrinciple # 7 – Maximize Atom Economy

The final product should contain the maximum number of The final product should contain the maximum number of atoms in the the starting materialsatoms in the the starting materials

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Principle # 8 – Use Safer Solvents and Principle # 8 – Use Safer Solvents and Reaction ConditionsReaction Conditions

Avoid solvents if possible. Consider using water or other Avoid solvents if possible. Consider using water or other innocuous materials. Minimize innocuous materials. Minimize

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Alternate ‘Green’ SolventsAlternate ‘Green’ Solvents

• Supercritical Carbon DioxideSupercritical Carbon Dioxide

• Supercritical WaterSupercritical Water

• Ionic LiquidsIonic Liquids

..

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BiomimicryBiomimicry

Imitate Mother Nature ?Imitate Mother Nature ?

How about a material with the strength of a Spider’s web ?How about a material with the strength of a Spider’s web ?

One of Paul Anastas’ examples. A glue that mimicked the One of Paul Anastas’ examples. A glue that mimicked the adhesive power of a limpet ?adhesive power of a limpet ?

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Principle # 9 – Increased Energy EfficiencyPrinciple # 9 – Increased Energy Efficiency

Operate at ambient temperature and atmospheric pressure Operate at ambient temperature and atmospheric pressure where possible where possible

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Principle # 10- Design Chemicals to Principle # 10- Design Chemicals to Degrade after UseDegrade after Use

Choose materials that will degrade after use rather than Choose materials that will degrade after use rather than those that will accumulate in the environment those that will accumulate in the environment

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Principle # 11- Analyze in Real TimePrinciple # 11- Analyze in Real Time

Use real time process analysis to monitor and control Use real time process analysis to monitor and control reactions rather than historical datareactions rather than historical data

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Principle # 12 - Minimize Accident Principle # 12 - Minimize Accident PotentialPotential

Minimize the potential for fires, explosions and other Minimize the potential for fires, explosions and other hazards by selection of chemicals and their forms hazards by selection of chemicals and their forms (gas/liquid ?)(gas/liquid ?)

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ACS – GCI Pharma RoundtableACS – GCI Pharma Roundtable

Much of the work in promoting green chemistry and Much of the work in promoting green chemistry and engineering is undertaken by the Green Chemistry Institute – engineering is undertaken by the Green Chemistry Institute – an arm of the American Chemistry Society. an arm of the American Chemistry Society.

Together with most of the major pharmaceutical Together with most of the major pharmaceutical manufacturers, they have established the ACS GCI Pharma manufacturers, they have established the ACS GCI Pharma Roundtable to catalyze the implementation of green Roundtable to catalyze the implementation of green chemistry and green engineering within that industrychemistry and green engineering within that industry

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Concept of Process Mass IntensityConcept of Process Mass Intensity

One of the concepts to come out of the ACS GCI Pharma One of the concepts to come out of the ACS GCI Pharma Roundtable is that of Process Mass Intensity. This is defined Roundtable is that of Process Mass Intensity. This is defined as the summation of the mass of all materials used in a as the summation of the mass of all materials used in a process, including water, catalysts, solvents and reagents, process, including water, catalysts, solvents and reagents, divided by the mass of product. The PMI index is used as an divided by the mass of product. The PMI index is used as an indication of ‘greenness’indication of ‘greenness’

In the petroleum industry this PMI has a value a little over In the petroleum industry this PMI has a value a little over unity, and increases through general chemicals and specialty unity, and increases through general chemicals and specialty chemicals industries. The pharmaceutical industry chemicals industries. The pharmaceutical industry demonstrates the highest PMIs – often over 100demonstrates the highest PMIs – often over 100

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ACS-GCI Solvent Selection GuideACS-GCI Solvent Selection Guide

The Roundtable has also published, in April 2011, a Solvent The Roundtable has also published, in April 2011, a Solvent Selection Guide. Industrial organic solvents are assessed in Selection Guide. Industrial organic solvents are assessed in terms of safety, health, environmental impact on air, water, terms of safety, health, environmental impact on air, water, and waste. These assessments are ranked on a scale of 1- and waste. These assessments are ranked on a scale of 1- 10, with 1 being the most desirable and 10 the least. This 10, with 1 being the most desirable and 10 the least. This guide is color coded with scores of 1-3 in green, 4-7 yellow guide is color coded with scores of 1-3 in green, 4-7 yellow and 8-10 in red.and 8-10 in red.

American Institute of Chemical American Institute of Chemical Engineers – Delaware Valley SectionEngineers – Delaware Valley Section

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GCN & NNFCC in the UKGCN & NNFCC in the UK

Two leading promoters of Green Chemistry and Engineering Two leading promoters of Green Chemistry and Engineering in the UKin the UK

• Green Chemistry Network – based out of the Green Chemistry Network – based out of the University University of Yorkof York

• National Non-Food Crops Centre (NNFCC)National Non-Food Crops Centre (NNFCC)

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The Twelve Principles of Green EngineeringThe Twelve Principles of Green Engineering1.1. Ensure Inherent SafetyEnsure Inherent Safety2.2. Prevent Waste rather than Treat WastePrevent Waste rather than Treat Waste3.3. Separation & Purification to Minimize Energy and Materials UseSeparation & Purification to Minimize Energy and Materials Use4.4. Maximize Mass, Space, Energy and Time EfficiencyMaximize Mass, Space, Energy and Time Efficiency5.5. Output Pulled rather than Input PushedOutput Pulled rather than Input Pushed6.6. Conserve ComplexityConserve Complexity7.7. Durability rather than ImmortalityDurability rather than Immortality8.8. Meet the Need while Minimizing ExcessMeet the Need while Minimizing Excess9.9. Minimize Material DiversityMinimize Material Diversity10.10. Integrate Material and Energy FlowsIntegrate Material and Energy Flows11.11. Design for a Commercial AfterlifeDesign for a Commercial Afterlife12.12. Renewable rather than DepletingRenewable rather than Depleting

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Principle #1 - Ensure Inherent SafetyPrinciple #1 - Ensure Inherent Safety

Strive to ensure that all materials and energy Strive to ensure that all materials and energy

inputs/outputs are as inherently non-hazardous as possibleinputs/outputs are as inherently non-hazardous as possible

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Inherent Safety as Applied to a Chemical Inherent Safety as Applied to a Chemical ProcessProcess

A chemical process is inherently safer if it reduces or A chemical process is inherently safer if it reduces or eliminates the hazards associated with materials used and eliminates the hazards associated with materials used and operations, and that this reduction or elimination is a operations, and that this reduction or elimination is a permanent and inseparable part of that processpermanent and inseparable part of that process

Per Trevor Kletz and Dennis Per Trevor Kletz and Dennis HendershotHendershot

American Institute of Chemical Engineers – American Institute of Chemical Engineers – Delaware Valley SectionDelaware Valley Section

Concepts of Inherent SafetyConcepts of Inherent SafetyIntensificationIntensification Using less of a hazardous material. Using less of a hazardous material. Smaller (intensified) equipment can reduce the Smaller (intensified) equipment can reduce the hazardous inventory and minimize the consequences hazardous inventory and minimize the consequences of accidentsof accidents

AttenuationAttenuation Using a hazardous material in a less Using a hazardous material in a less hazardous form, for example, a diluted acid rather hazardous form, for example, a diluted acid rather than a concentrated one. Larger particle size to than a concentrated one. Larger particle size to minimize a dust explosion hazard.minimize a dust explosion hazard.

SubstitutionSubstitution Using safer material. Water instead of a Using safer material. Water instead of a flammable solvent.flammable solvent.

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Principle #2 - Prevent Waste rather than Principle #2 - Prevent Waste rather than Treat WasteTreat Waste

Better to prevent waste streams occurring rather than Better to prevent waste streams occurring rather than

treating them afterwardstreating them afterwards

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Principle #3 Principle #3 - - Separation & Purification Separation & Purification Operations Selection Operations Selection

Separation & Purification Operations Designed to Minimize Separation & Purification Operations Designed to Minimize

Energy and Materials UseEnergy and Materials Use

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Principle #4 - Maximize EfficienciesPrinciple #4 - Maximize Efficiencies

Processes and products should be designed to maximize Processes and products should be designed to maximize

Mass, Space, Energy and Time EfficienciesMass, Space, Energy and Time Efficiencies

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Principle #5 - Output Pulled not Input PushedPrinciple #5 - Output Pulled not Input Pushed

Often a reaction or transformation is "driven" to completion by Often a reaction or transformation is "driven" to completion by adding more energy/materials to shift the equilibrium to adding more energy/materials to shift the equilibrium to generate the desired output. However, this same effect can be generate the desired output. However, this same effect can be achieved by designing reactions in which outputs are removed achieved by designing reactions in which outputs are removed from the system, and the reaction is instead "pulled" to from the system, and the reaction is instead "pulled" to completion without the need for excess energy/materials.completion without the need for excess energy/materials.

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Principle #6 - Conserve ComplexityPrinciple #6 - Conserve Complexity

Value-conserving recycling, where possible, or beneficial Value-conserving recycling, where possible, or beneficial disposition, when necessary, End-of-life design decisions disposition, when necessary, End-of-life design decisions for recycle, reuse, or beneficial disposal should be based for recycle, reuse, or beneficial disposal should be based on the invested material and energy and subsequent on the invested material and energy and subsequent complexitycomplexity

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Industrial Symbiosis at Kalundborg, DenmarkIndustrial Symbiosis at Kalundborg, Denmark

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Principle #7 - Durability rather than Principle #7 - Durability rather than ImmortalityImmortality

Targeted durability should be a design goalTargeted durability should be a design goal

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CFCsCFCsThese coolant chlorofluorocarbons are:These coolant chlorofluorocarbons are: Non-flammableNon-flammable Non-toxicNon-toxic EffectiveEffective InexpensiveInexpensive Stable – so stable that they migrate to the upper atmosphere, Stable – so stable that they migrate to the upper atmosphere,

where UV-induced fragmentation causes ozone depletionwhere UV-induced fragmentation causes ozone depletion

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Principle #8 - Meet the Need, Minimizing ExcessPrinciple #8 - Meet the Need, Minimizing Excess

Designing for unnecessary overcapacity or over capability is a Designing for unnecessary overcapacity or over capability is a

design flawdesign flaw

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Principle #9 - Minimize Material DiversityPrinciple #9 - Minimize Material Diversity

Material diversity in multi-component systems is to be Material diversity in multi-component systems is to be minimizedminimized

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Principle #10 - Integrate Material & Energy FlowsPrinciple #10 - Integrate Material & Energy Flows

• Water Loop ClosureWater Loop Closure

• Integrate Heat/Cool LoopsIntegrate Heat/Cool Loops

• CogenerationCogeneration

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Pinch TechnologyPinch Technology

Pinch technology, developed principally by Bodo Linnhoff at Pinch technology, developed principally by Bodo Linnhoff at the University of Manchester in the UK, is a methodology for the University of Manchester in the UK, is a methodology for the integration of heating and cooling systems for the integration of heating and cooling systems for maximizing energy efficiency. maximizing energy efficiency.

American Institute of Chemical Engineers – American Institute of Chemical Engineers – Delaware Valley SectionDelaware Valley Section

Simple Heat Exchange SystemSimple Heat Exchange System

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Hot Stream3500 lb/hr

400 deg F

70 deg F

Coolant 0.98MM Btu/hr

Cold Stream4000 lb/hr

90 deg F

400 deg F

Heating0.87MM Btu/hr

American Institute of Chemical Engineers – American Institute of Chemical Engineers – Delaware Valley SectionDelaware Valley Section

Integrated Heating and CoolingIntegrated Heating and Cooling

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Hot Stream3500 lb/hr

400 deg F

70 deg F

Coolant0.67MM Btu/hr

Cold Stream4000 lb/hr

200 deg F

90 deg F

Heating0.56MM Btu/hr

290 deg F

400 deg F

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Principle #11 - Design for a Commercial Principle #11 - Design for a Commercial AfterlifeAfterlife

Products and processes should be designed for a commercial Products and processes should be designed for a commercial afterlifeafterlife

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Principle #12 - Renewable not DepletingPrinciple #12 - Renewable not Depleting

Material and energy inputs should be from renewable Material and energy inputs should be from renewable

resources not depleting resourcesresources not depleting resources

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Green Corrosion InhibitorsGreen Corrosion Inhibitors

Traditional corrosion protection methods often rely on Traditional corrosion protection methods often rely on hazardous substances, notably carginogenic chromates. hazardous substances, notably carginogenic chromates. Research in Europe is demonstrating the use of ‘intelligent’ Research in Europe is demonstrating the use of ‘intelligent’ self healing inhibitors. The controllable delivery is based on self healing inhibitors. The controllable delivery is based on incorporating nano-containers of organic inhibitors in incorporating nano-containers of organic inhibitors in protective films of silica and zirconia – both benign and protective films of silica and zirconia – both benign and abundant. Release of material in triggered by pH.abundant. Release of material in triggered by pH.

taken from GCN Newsletter (UK) April 2007taken from GCN Newsletter (UK) April 2007

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Biocatalysis – the use of enzymes or whole Biocatalysis – the use of enzymes or whole cells in the manufacturing processcells in the manufacturing process

..

Bicatalysts can simplify or enable production of complex Bicatalysts can simplify or enable production of complex molecules. These often eliminate the requirement for molecules. These often eliminate the requirement for elaborate separation and/or purification steps. Reactions may elaborate separation and/or purification steps. Reactions may be undertaken under milder conditions of temperature, be undertaken under milder conditions of temperature, pressure and pH. Such biocatalytic reactions are by nature pressure and pH. Such biocatalytic reactions are by nature safer.safer.

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Microchannel ReactorsMicrochannel Reactors

The use of microchannel reactors for catalytic hydrogenation The use of microchannel reactors for catalytic hydrogenation reactions has the potential to improve a significant number of reactions has the potential to improve a significant number of catalytic hydrogenation reactions in both the chemical and catalytic hydrogenation reactions in both the chemical and pharmaceutical industries.pharmaceutical industries.

These reactors could significantly improve the efficiency and These reactors could significantly improve the efficiency and safety of such manufacturing processes. These reactors possess safety of such manufacturing processes. These reactors possess small transverse dimensions with high surface-to-volume ratios small transverse dimensions with high surface-to-volume ratios and consequently exhibit enhanced heat and mass-transfer rates.and consequently exhibit enhanced heat and mass-transfer rates.

Taken from a Promotional Brochure from US Dept. of Energy Taken from a Promotional Brochure from US Dept. of Energy

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Metabolic Pathway EngineeringMetabolic Pathway Engineering

Genetic modification of micro-organisms to make them Genetic modification of micro-organisms to make them produce the desired chemical.produce the desired chemical.

Many examples – ethanol, 1.3 PDO, 1,4 BDO, succinic acid Many examples – ethanol, 1.3 PDO, 1,4 BDO, succinic acid etc etc.etc etc.

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AcknowledgementsAcknowledgements

Jacobs & KBR for supporting this webinar – hopefully they Jacobs & KBR for supporting this webinar – hopefully they will continue throughout the serieswill continue throughout the series

My peer reviewers – Linda, Jasmine and BobMy peer reviewers – Linda, Jasmine and Bob

Paul Anastas & David Shonnard – for their published works Paul Anastas & David Shonnard – for their published works which have contributed so much to this materialwhich have contributed so much to this material

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Questions ?Questions ?