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Ghent, September 19, 2005
Biodiesel:Production Technologies and Perspectives
Martin Mittelbach
Institute for Chemistry (IFC)
Working Group Renewable ResourcesKarl-Franzens-University Graz
A-8010 GrazAustria
Renewable Resources and Biorefineries, 19.09.2005, Ghent
Ghent, September 19, 2005
Agenda:
• Chemical principles of BD-production• Current technologies
single feedstock, multi feedstock• New Trends
heterogenous catalysts, enzymesethyl esters, supercritical conditions
• Future perspectives: synthetic fuels• Summary
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Newsweek:
August 8, 2005
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TriacylglyceridesVegetable oils, animal fat, microbial oils
Transesterification
Biodiesel:Fatty Acid (M)ethyl Esters
from natural origin
Esterification
Fatty AcidsHydrolysis, veg. oil raffination, soap stock
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„Biodiesel“: Publications and Patents
Source: Sci-Finder, CAS-Service
0
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100
150
200
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350
400
1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005
Patents
Publications
Source: Sci-Finder, CAS-Service
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Transesterification of Triglycerides
CH2
CH
CH2
O
O
O
COR1
COR2
COR3
CH3OHCH2
CH
CH2
O
O
OH
COR1
COR2 R3 COOCH3+CH3OH
CH3OH+ R2 COOCH3
CH2
CH
CH2
O
OH
OH
COR1 CH2
CH
CH2
OH
OH
OH
R1 COOCH3+
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Catalysts for Current Technologies
Sodium methylate: Na+OCH3-
preparation: solution of Na in methanol+ commercially available, no additional step
almost water free, no saponification- high price, only fully refined oils
Sodium hydroxide, potassium hydroxide: Na+OH- , K+OH-
preparation: exothermic dissolution of solid in methanol+ lower price, oils with up to 2,5 % free fatty acids- additional step necessary, water content: saponification??
KOH vs. NaOH
faster reaction, better glycerol separation, utilization as fertilzer
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Main Chemical Reactions
Formation of methoxide:
Main side reactions: hydrolysis and saponification
R1 – COOR2 + Na+OH- R1-COO-Na+ + R2OH
R – COOH + Na+OH- R-COO-Na+ + H2O
+ CH3OH Na (K)+ OCH3-Na (K)+ OH - + H2O
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Equilibrium Hydroxide - Alkoxide
Formation of methoxide:
+ R-OH Na (K)+ RO -Na (K)+ OH - + H2O
% Water in Alcohol [OH-] [CH3O-] [C2H5O-]
0 3.7 96.31 6.8 93.230 92.0 48.0
E.F.Caldin, C.Long, 1954M.L.Bender, W.A.Glasson, 1958
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History of Alcoholysis of Triacylglycerols1852 P.Duffy: Alcoholysis of fats: J.Chem.Soc.
1944 G.B.Bradshaw: US 2,360,844preparation of pure glycerol: 2-step reaction
1950 ff Fatty alcohol production for nonionic detergentshigh temperature and pressure process240°C; 100 bar; NaOCH3; distillation
1986 Mittelbach et al. AT 386.222low temperature and pressure process forbiodiesel production: KOH; purification with IER
1990 ff over 200 patents on biodiesel production
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Biodiesel Production Technologies1) Single Feedstock Technologies
Feedstock Fully refined vegetable oils, FFA < 1 %
Catalyst NaOCH3, NaOH, KOH
Reaction conditions 40-100°C, batch or continous
Purification ME-Ester water washing, drying, no distillation
Glycerol treatment removal H2O+MeOH, opt.: distillation
Capacity 500 t – 250.000 t/a
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Biodiesel Production Technologies2) Multi Feedstock Technologies
Feedstock Crude vegetable oils, animal fat, waste oils
Catalyst Preesterif.: H+; Transesterif.: KOH
Reaction conditions 40-60°C, batch or continous
Purification ME-Ester water washing, drying, distillation
Glycerol treatment acidification, salt separation: crude glycerol
Capacity 5.000 t – 50.000 t/a
FFA: up to 100 %
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1985: 1st pilot plant worldwide for RMESilberberg, Styria, Austria
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1986: Mittelbach, Junek, Andreae: AT 386.222
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MultiMulti--FeedstockFeedstock ProductionProduction SchemeScheme ((simplifiedsimplified))
© BDI Anlagenbau Ges.m.b.H.
CatalystPreparation
Methanol
KOH
Fully automatic
TransesterificationOil Pre-
treatmentOil / Fat
MethylesterMethanol-Recovery
MethylesterPurification – Distillation
Quality Control
Glycerine phaseAfter- treatment
FertilizerSeparation
Free Fatty AcidRecovery
Crude GlycerineMethanol-Recovery
PharmaceuticalGlycerine Production
Fertilizer
Pharmaglycerine
BioDiesel
Acid
Crude Glycerine
Distillation side-product
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Biggest Multifeedstock Biodiesel Plant in AustriaArnoldstein, 25.000 t
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First Biodiesel Plant in a European Capital Ground-breaking, Vienna, 15.09.05
Capacity: 95.000 t/a; First production: 09/06
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Biggest Biodiesel Plant in Germany ADM, Hamburg, 200.000 t
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New Trends: Heterogenous Catalysts
Metal oxides (Mg, Ca, Al, Fe)Carbonates: CaCO3Ion exchange resins (acidic, alkaline)EnzymesSilicates
+ easy separation, reusablepure glycerol, no side products (salts)first industrial application 2006 ?
- high temperature and pressure, high investment costsincomplete conversion, distillation necessary
Ghent, September 19, 2005
New Trends: Enzymes as CatalystsLipases (Triacylglycerolhydrolases)
main task: lipid hydrolysisin organic solvents:
esterification, transesterificationAlcoholysis of sunflower oil with MeOH, EtOH
Mittelbach et al., 19901990 ff: 88 publications on enzymatic alcoholysis
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Immobilization of Lipases on Corn Cob GranulateFabrik der Zukunft, BMVIT
Aim: Biodiesel production process with lipases
Immobilization: 93 % physical adsorption at pH = 4.7Enzymes: Thermomyces lanuginosus, Pseudomomas sp.
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Immobilization of Lipases on Corn Cob Granulate
0
20
40
60
80
100
% A
lkyl
este
r
Methanol Ethanol, 96%
iso-Propanol 1-Butanol
1 3 6 12 24 48 h
Batch: mol.ratio triglyceride:alcohol= 1:4.5; 50°C, no solvent, 10 % lipase
R.Uitz, S.Schober, M.Müller, M.Mittelbach; 2005, submitted
Ghent, September 19, 2005
Enzymes as Catalysts: Summary
+ High catalytic activity, no solvents necessaryTransesteriifcation and esterification in 1 stepHigh conversion also with ethanolEasy separation and purification of productsSaving of chemicals
- Slow reaction ratesHigh price of enzymesDeactivation with glycerol: washing step
Economic evaluation
Enzyme: 10 €/kg and 1.700 h lifetime
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New Trends: Fatty Acid Ethyl Esters
Today‘s biodiesel production worldwide: approx. 2 mill. t/a
Almost 100 % fatty acid methyl esters
why ?
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0
100
200
300
400
500
600
700
2002 2003 2004 2005
[€/t]
E thanol
Methanol
Prices for Methanol and Ethanol
Rape seed oil520 €/t
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Fatty Acid Ethyl Esters
+ 100 % biofuelbioethanol production increasing worldwidehigher Cetane Number
- price of ethanolanhydrous ethanol necessary: via zeolitesslower transesterification; lower conversionsno separation of glycerol with common technologieshigher viscosityno EN specificationsno additional tax benefits
Ghent, September 19, 2005
New Trends: Supercritical Solvents
Definition: no differentiation between gas and liquidno liquid phase over Tc
Conditions:
Methanol Ethanol WaterTc 512.6 K 513.9 K 647.1KPc 80.9 bar 61.4 bar 220.6 bar
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Vapor Pressure Methanol
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300 350 400
Temperature [°C]
Pres
sure
[bar
]
Tc = 239.5°C
Pc = 80.9 bar
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Alcoholysis with Supercritical Methanol
Typical reaction conditions:
reaction temperature: 350°Coptimum molar ratio: oil : methanol = 1 : 40reaction time: 2 minconversion: > 95 %
+ no catalyst, no purification- high excess of methanol, high energy input
investment costs, equipment
D.Kusdiana, S.Saka, Fuels 2001
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Future Perspectives of Biodiesel
• Biodiesel production capacities are exploding worldwide
• New process technology: low production costs
• New challenge for developing countries: agriculture, labour
• Full acceptance of engine manufacturers for 5 % blend of biodiesel in mineral fuel
• Well established, harmonized specifications
Drawback: limited quantity of feedstocks
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Future Perspectives of BiodieselNew Feedstocks
• Vegetable food oils: palm, soybean, sunflower„New“ seed oils: cuphea, crambe.....
• Single cell oils: yeast, funghi, algae• Genetically modified seed oils• Non-edible seed oils
Jatropha curcas, Castor oil, Pongamia pinnataused frying oil
• Animal fat: tallow, grease, SRM-material• Waste oils and fat, soap stock, trap grease
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Future Perspectives of BiodieselNew Feedstocks
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New Trends: Synthetic BiodieselPyrolysis Fuels: any carbon source: plastic, sewage sludge
pyrolysis with/without catalystsmixture of alkanes, alkenes, aromatesgas, gasoline, diesel, residue
GTL – Fuels: Gas to liquid fuelssources: natural gas, biogassynthesis gas, synthesis with catalystsproducts: methanol, gasoline, diesel
BTL – Fuels: Biomass to liquid fuels; Sun Fuelsgasification, Fischer-Tropsch synthesissources: cellulose, wood, strawtailor made Diesel fuels
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Fischer-Tropsch Synthesis
Inventors: F.Fischer, H.Tropsch, 1925, MülheimMain goal: coal liquefaction
CO + 2 H2 -(CH2)- + H2O ∆H = -165 kJ/M
200 – 250°C, 25 bar, Fe, Co catalyst
Reaction products: straight chain hydrocarbons: ideal diesel fuels
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Biomass to Liquid Fuels
Advantages:almost unlimited sourcesdesigner fuel, chemical composition variablelow engine emissions
Disadvantages:high production costsonly industrial scale possible
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Conclusions, 1
• Biodiesel production technologies today use homogenous, alkaline catalysis like alkali alkoxides or hydroxides
• For low quality feedstocks with higher content of FFA an additional esterification step is necessary: strong acids
• Purification of biodiesel includes water washing and distillation,if necessary (waste oils etc.)
• New trends in biodiesel production includes heterogenouscatalysis, enzymes, supercritical alcohols
• Fatty acid ethyl esters will be produced in the future due to theavailability of cheap ethanol
Ghent, September 19, 2005
Conclusions, 2
• Biodiesel (FAME and FAEE) is a well established fuel and will represent the most important market share of biofuels inthe next decadesLimiting factor: availability of feedstock
• Synthetic biofuels (GTL, BTL) are taylor made products withexcellent Diesel properties. There is almost unlimited availability. However, due to thehigh production costs the time of market penetrationdepends on mineral oil price
Ghent, September 19, 2005
Bianca Bergler Mag. Bernd Nebel Mag. Firoozeh Alavian Mag. Bernd PokitsMag. Adina Fodor Florian RederSigrid Lagarde Mag. Sigurd SchoberMag. Tobias Madl Ingrid SeidlMag. Mario Müller Mag. Renate Uitz
Ghent, September 19, 2005
Publication date: 11/04
340 pages
Publisher: Martin Mittelbach