production of biodiesel from waste oil via catalytic
TRANSCRIPT
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Production of Biodiesel from Waste Oil via Catalytic
Distillation
Zhiwen Qi, Yuanqing Liu, Blaise Pinaud, Peter RehbeinZhiwen Qi, Yuanqing Liu, Blaise Pinaud, Peter RehbeinFlora T.T. Ng*, Garry L. Rempel
Department of Chemical Engineering, University of Waterloo200 University Avenue West, Waterloo, ON, N2L3G1
Rio, Brazil, March 8-13, 2009
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Why Biodiesel
Advantages of Biodiesel
Traditional Energy Resources�Oil Accounts for 40% of all energy usage
�By 2010, half of all oil reserves will be consumed in our planet
Advantages of Biodiesel� Renewable & Biodegradable
� Free of Sulfur and Aromatics
� No engine modification necessary
� Lower CO and Particulate Matters
� Lower life-cycle CO2 emission
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Life Cycle of Biodiesel vs
Petroleum Diesel
The CO2 Cycle is CLOSED for biodiesel
CO2 cycle CANNOT be closed for petroleum diesel
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Why Waste Oil ?Obstacles to biodiesel production :
� High cost of virgin vegetable oil as feedstock
� Impact on food demand
Alternative Feedstocks:
� Yellow grease, Animal Fat, Jatropha
� Contain free fatty acid (FFA)
� Fatty acids neutralize the basic NaOH catalyst (formation of soap)
� Use liquid acid, e.g. H2SO4 -corrosion and environmental impact
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A Novel Approach
Application of catalytic distillation for biodiesel production using a solid acid catalyst
� Eliminates the associated separation process
� More energy efficient due to the in situ utilization of heat from exothermic reactions for distillation
� Increase conversion for equilibrium limited reactions-continuous removal of products ( Le Chatelier’s Principle)
� Allows nearly stoichiometric ratio of oil to methanol
� Eliminates the associated separation process
� Prevents undesirable consecutive reactions
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Catalytic Distillation (CD)Condenser
Light Product
Reflux
Rectifying Zone
Heavy Reactant
�Catalytic Distillation combines a reactor and a distillation column into one unit
� Solid Catalyst is
� Rectifying zone on the top
Boilup
Reboiler
Heavy Product
Reaction Zone
Stripping Zone
Light Reactant
� Solid Catalyst is located into the reaction zone
� Stripping zone on the
bottom
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Kinetic Model
� TransesterificationTriolein + 3 Methanol 3 Methyl Oleate + Glycerol
� Esterification
Oleic Acid + Methanol Methyl Oleate + Water
kf
kb
kf
kb
Reactions
r = kfCTrioleinCMethanol − kbCEsterCGlycerol
kb
Literature data for Conversion of TrioleinKulkarni, M.G., Gopinath, R., Meher, L.C. & Dalai A.K. 2006. Solid acid catalyzed biodiesel production by simultaneous esterification and transesterification
� First order for each reactant and second order for overall reaction
� Transesterification was assumed to be dominant (90% Triolein)
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Kinetic Model (2)
� Using Arrhenius Equation
� Generate Arrhenius Plot to find k0 and Ea
k = k0 exp − Ea
RT
� Compare the fitted kinetics with experimental data
( ) kTR
Ek a
o ln/1ln =−
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CD Model in Aspen Plus CondenserUnreacted Methanol
Oil Feed
Oil Feed Location
Methanol to
Reflux Ratio
(3, 5, 25, Total)
Liquid Molar Holdup
(200, 300, 400, 500)
T
� Radfrac is used tomodel a reactive distillation column
� Property Method: UNIQUAC
� Parameters Tuned: Reflux Ratio, Reboiler Ratio, Pressure, Feed Ratio and Feed Stage
Reboiler
Biodiesel Products
Methanol Feed
Methanol Feed Location
Methanol to Oil Feed Ratio
(4~6)
Boilup Ratio
(1, 1.2, 3, 5)
(200, 300, 400, 500)
Total Stage
(22, 30, 42)
P1~20atm
UNIQUAC
� Binary Mixture Estimation: UNIFAC
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Optimization Results
Comparison of Two Cases:
Column Design Case 1 Case 2
Total Stage 30 30
Reactive Stage 2-26 2-28
Reflux Ratio 3 Total Reflux
Boilup Ratio 2 2
Pressure (atm) 20 20
Methanol/Triolein Feed Ratio
3.86 5.31
Liquid Holdup (mol/stage)
300 300
Conversion 95.5% 95.8%
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Column Temperature
Case 1Reflux Ratio=3Treboiler = 509.86 ̊C
Glycerol decomposes over 290 ̊C
Treaction-zone = 190~216 ̊C
Case 1 (Reflux Ratio = 3)
Case 2
Case 2(Total Refux)
Treboiler = 256.03 ̊C
Total reflux is applied
Treaction-zone = 182~200 ̊C
Major challenge is high column temperature
Case 2 (Total Reflux)
More active catalyst is required
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Composition Profile
Case 1 � Methanol concentration at
bottom is 0.044%, and top product 99.994%
� Methanol can be recycled back to the column directly.to the column directly.
Case 2
�Methanol Concentration at
bottom is 38.565%
�Further methanol
purification is necessary.
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Current Research
�Development of more active solid acid catalyst
� Our own kinetic parameters will be
� Experiments will be performed in a pilot-
scaled CD column
parameters will be applied to the CD model
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Acknowledgement
The financial support for this project from Natural Science and Engineering Research Council of Canada (NSERC), Strategic Projects Program, is gratefully acknowledged.gratefully acknowledged.
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