ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Process Intensification for SustainableIndustrial Activities
Sunil S. BhagwatDepartment of Chemical Engineering, ICT-Mumbai
Green Process, IGCW-2017, Mumbai
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Outline
1 Process Intensification
2 NanoStructured Reaction Media
3 Kinetics
4 Selectivity
5 Summary
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Principles of Intensification
Chemical and other processes - need for intensificationPrinciples of intensification:
TimeSpace/ steps/ equipmentMaterials/ yieldUtilities
Means: Ulrasound, novel media, novel processesIntensification of chemical reactions throughnano-structured aqueous mediaIntensification of processes through utilisation of wasteheat
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Center of Excellence in Process Intensification
World bank supported program for three yearsMultiple aspects of Chemical and Allied Industrycovered by over fifteen projectsSolar energy assisted synthesis of zinc oxidenanoflowers. Indian Patent Application:1624/MUM/2015, 2015Microwave Assisted Halogenation Reactions usingFlow ReactorMicrowave assisted synthesis of bioactive colorantsindigoid / azulene / C-C bond formation
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Center of Excellence in Process Intensification
Sorption Enhanced Hydrogen ProductionProcess intensification using Cavitational reactorsExtraction of Turmeric and Pepper Oleoresin byEnzyme-Assisted Supercritical Carbon DioxideMicrowave assisted bifunctional catalysis for tandemreactionsExtraction Of Natural Ingredients Using NovelExtraction Techniques : Glycyrrhizic acid fromGlycyrrhiza glabra, Marmelosin from Aegle Marmelosand Corosolic acid from Lagerstroemia Speciosa -ultrasound assisted extractionWater Disinfection by Hydrodynamic Cavitation in IndiaMark II Hand Pump
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Comparison of Useful Temperature Range
TrackingMethod
Collector Type AbsorbtionMethod
TempRangeoC
Stationary Flat Plate Flat 30–80Evacuated Tube Flat 50–200
Compound Parabolic Tubular 60–240Singleaxis
tracking
Linear FrenselReflector
Tubular 60–300
Parabolic Trough Tubular 60–250Cylindrical Trough Tubular 60–300
Twoaxes
tracking
Parabolic DishReflector
Point 150-200
Heliostat field Point 100-500
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Concept of Energy Ladder
Electricity Most usefulFuel
Hot oil40 bar steam10 bar steam3 bar steam1 bar steam
Hot water/gas Least useful
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Mixing Fluids & Exergy Loss
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Solar based absorption refrigeration system
COOLING
WATER
Flue Gas
PLANT
(10 TR)
REFRIGERATION
TOWER
Oils CE Computational Lab
CHILLED WATER RETURN
COOLING
WATER
SUPPLY
15 TR
COOLING
10 m3/h
CWP− 1
CHILLED WATER SUPPLY
2 m3
CHILLED
WATER
TANK
II
9 C
2 m3
CHILLED
WATER
TANK
I
12 C
ABSORPTION
SOLAR COLLECTOR
31 kg/hr
PIPE NATURAL GAS
7 kg/h
6.5 m3/hr
SUNLIGHT
( 60 kW)
CWP−2
10 m3/h
HOT
WATER
TANK
II
90 C
2 m3
HWP 1
6.5 m3/h
HWP2
2 m3
HOT
WATER
TANK
I
83 C
Steam generation
RETURN
35 C
25 m3/h
32 C
2 TR Indoor Unit (5 NOs)
HOT WATER GENERATOR
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Refrigeration System Comparison
The input of energy should be corrected to its value for truecomparison of the coefficient of performance.
System Sink Duty Source Conventional
COP
Corrected
COP
Mechanical 40oC 0oC Electricity 2.2 2.2
Thermal 40oC 0oC 110oC Heat 0.62 3.4
Mechanical 40oC 15oC Electricity 4.1 4.1
Thermal 40oC 15oC 110oC Heat 0.76 4.1
Thermal 40oC 15oC 70oC Heat 0.45 5.1
Heat based refrigeration is a lucrative option, especially for largeinstallations
Two lakh lit/day milk chilling center saving 3/4th of electricityconsumption implemented
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
NanoStructured Reaction Media: Adsorptionand Self Assembly
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SCHEMATIC OF A NORMAL MICELLE
The first choice amphiphilic molecules have is to go to the’wall’ or the interface. Second choice makes themaggregate in different shapes.
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Relative Thickness of Interfacial area
Diameter Interphase Volume(nm) (nm) (%)
Macroemulsions ~ > 1000 2.5 1.5Microemulsions 10-100 2.5 15-85
Micelles ~ 2.5 2.5 ~ 100
Interfacial area(cm2/cm3)
L/L dispersions (5 mm size) ~ 1Emulsion (50 µm size) ~ 10
Microemulsions (10 nm size) ~ 106
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Applications of surfactants and microemulsions
Formulations where there is a need for mixing hydrophobicand hydrophillic substrates
Paints Food additivesPharmaceuticals Pesticides
Dyeing SeparationsFuel additives Reactions
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Advantages of Surfactant media for reactions
Enhancement in overall reaction rateFavorable orientation of moleculesManipulation of Regio- and Stereo selectivityLocalised concentration of reagentChange in locale of reactionMicellar solubilization of phenols is greatly affected byposition of the substituent group in aromatic ringDifference in solubilities can be explained in terms ofthe orientation of molecule adsorbed on the micelleThe solubilization with specific orientation is useful inmicellar regioselective synthesis
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Alkaline Hydrolysis
2,4-dinitrochlorobenzene – by cationic micelles – sp.rate increase 10-100 foldp-nitrophenyl diphenyl phosphate – hexadecane inwater microemulsion stabilized by CTAB & 1-butanol.p-nitrophenylbenzoate – CTAB & sodium dodecylsulphate microemulsions.2,4 dichlorophenyl benzoate – sp. rate increases by 45fold
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Oxidation
Half mustard oxidation by tert-butyl hydroperoxide &hypochlorite
OHHO
R S2
HO OH
OCl
R SO2
HOCl
water
cyclo−
hexane
ClCH CH −S−CH CH Cl2 2 2 2
CH CH −S−CH CH Cl23 2 2
MUSTARD
Half MUSTARD
Destruction is very rapid in microemulsion
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Oxidation - prevention
Oxidation of fats - rancidity. Most antioxidants - oil insolubleProcess
Intensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Oximation of cyclododecanone
ONOH
(NH OH)2 2
+ 2H O2+ H SO
2 4
42 H SO
600 fold enhancement in the specific rate of the reaction inmicroemulsions of SLS/n-butanol
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Phenol Chlorination
Excess chlorination –> Trichlorophenol
O HCl
O H
Cl
O HCl Cl
O H
Cl
Cl
O HCl Cl
Cl
O H
455 K 492 K
483 K493 K
448 K
30%
70%
Close boiling points –> Isolation difficult
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Phenol Chlorination
HCl-H2O2 as chlorinating agentenvironmentally safeCompatible with surfactant additivesH2O is the only byproductReaction is well controlled by manipulating the molarratio of HCl and H2O2
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Selectivity with substituted phenols
o-/p- ratioCompound Conventional Our work SurfactantO-Cresol ∼ 0.5 5-10 10mM BKC3,5-Xylenol < 0.3 10-20 10mM LAOAcetanilide ∼ 0.35 2.6 10mM SDSo-chlorophenol 0.22 1.0 10mM SDSBenzoic acid (o-/p-)< 0.1 2-4 10mM SDSChlorobenzene ∼ 0.5 ∼ 3 25mM CTABChlorobenzene ∼ 0.5 ∼ 7 25mM SDSIodobenzene ∼ 0.5 ∼ 5 25mM SDS
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Location and orientation of phenol
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Reduction
Regioselective reduction of isophorone in micelles µemulsions
O
CH3
CH3
C3
H
H
O
CH3
CH3
C3
H
O
CH3
CH3
C3
H
H
O
CH3
CH3
C3
H
+
NaBH4
1,2 reduction
1,4 reduction
Cis + Trans
1,2-/1,4- product ratio 58/42→ 75/25
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Non micellar effects
Micelles are short livedEmulsion droplets and solid dispersions: more“permanent” surfactant layerOther reaction successfully catalysed by micellization :Reimer Tiemann reaction (o-/p- decrease from 70/30 to40/60) and Halogenation of substituted phenol(selectivity and rate improvement)Surfactant catalysis of solid catalysed reactions
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Heck reaction
Generation of new carbon-carbon bondHomogenous solutions: palladiun catalyst, phosphineligands and an inorganic baseRate ~ 0.003 min−1
Drawbacks: Product contamination with catalyst,Phosphine ligand and catalyst air sensitivity, Catalystrecycling, Usage of polar aprotic solvents
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Heck reaction: Pd/C with Cationic
Surfactant loading less than 20% of earlier
Anionic surfactants are not so effective
Reactivity:K2CO3 > Na2CO3 TEA � NaOH� CH3COONa0.17M BKC, k = 0.063min−1
K2CO3 catalysed heck reaction of iodobenzene/styrene at800C
Catalyst loading: 0.01mol/mol
Similar observation for most cationic surfactants as BKC,CTAB and CPC
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Possible mechanism
P
Catalyst Surface
Micelle
emulsified droplet
P P
Catalyst Surface
Micelle
emulsified droplet
PP
Micelle
R R
emulsified droplet
Catalyst Surface
Micelle
Catalyst Surface
emulsified droplet
R R
step2= reaction of reactants on the catalyst surface to form products
step3=transfer of products from catalyst surface to emulsion droplet/micelle
step1=transfer of reactants from emulsion droplet/micelle to catyst surface
R=reactants P=products
step3
step1
Micelle
step2
Adsorbed surfactant layer provides a preferred location
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Growth of ultrafine particles in microemulsions
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+
+
+
+
Step 1
Step 2
Reactants A
Reactants B
Step 1 Step 2Step 3
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Droplet exchange
0 20 40 60 80 100 120
Time (ms)
0
0.1
0.2
0.3
0.4
0.5
Abso
rban
ce
experimental values
model fitting
kex
= 5.6 x 104 (lit/mol.s)
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Fuels
Gasoline, diesel, fuel oils microemulsionsReduced peak temperature leading to lower NOxemissionHigher flash pointcontrolled pool burningSafety in storage and transport without affectingatomised burning in engineCan water help fuel burn? Yes! Better fuel atomization
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
Summary
Process Intensification leads to greener processesType of energy equally important as amountSurfactant based media are greener aqueous solventsNano-structured solvents can alter kinetics andselectivity of reactionsSolubilization leads to enhanced rates of reaction - timeintensificationOrientation of molecules is responsible for theselectivity - material intensification
ProcessIntensification
ICT/CE/SSB
ProcessIntensification
NanoStructuredReactionMedia
Kinetics
Selectivity
Summary
THANK YOU ([email protected])
Non-micellar
effects
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