The document discusses current and emerging technologies for biodiesel production, including homogeneous and heterogeneous catalysis methods as well as new processes using enzymes, supercritical alcohols, and synthetic fuels produced from biomass; it also outlines the growth of the biodiesel industry and future perspectives including new feedstock sources and fuel standards.

1. Ghent, September 19, 2005
Biodiesel:
Production Technologies and Perspectives
Martin Mittelbach
Institute for Chemistry (IFC)
Working Group Renewable Resources
Karl-Franzens-University Graz
A-8010 Graz
Austria
Renewable Resources and Biorefineries, 19.09.2005, Ghent

2. Ghent, September 19, 2005
Agenda:
• Chemical principles of BD-production
• Current technologies
single feedstock, multi feedstock
• New Trends
heterogenous catalysts, enzymes
ethyl esters, supercritical conditions
• Future perspectives: synthetic fuels
• Summary

3. Ghent, September 19, 2005
Newsweek:
August 8, 2005

4. Ghent, September 19, 2005
Triacylglycerides
Vegetable oils, animal fat, microbial oils
Transesterification
Biodiesel:
Fatty Acid (M)ethyl Esters
from natural origin
Esterification
Fatty Acids
Hydrolysis, veg. oil raffination, soap stock

5. Ghent, September 19, 2005
„Biodiesel“: Publications and Patents
Source: Sci-Finder, CAS-Service
0
50
100
150
200
250
300
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

6. Ghent, September 19, 2005
Transesterification of Triglycerides
CH2
CH
CH2
O
O
O
COR1
COR2
COR3
CH3OH
CH2
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+

7. Ghent, September 19, 2005
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

8. Ghent, September 19, 2005
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

9. Ghent, September 19, 2005
Equilibrium Hydroxide - Alkoxide
Formation of methoxide:
+ R-OH Na (K)+ RO -
Na (K)+ OH -
+ H2O
% Water in Alcohol [OH-] [CH3O-] [C2H5O-]
0 3.7 96.3
1 6.8 93.2
30 92.0 48.0
E.F.Caldin, C.Long, 1954
M.L.Bender, W.A.Glasson, 1958

10. Ghent, September 19, 2005
History of Alcoholysis of Triacylglycerols
1852 P.Duffy: Alcoholysis of fats: J.Chem.Soc.
1944 G.B.Bradshaw: US 2,360,844
preparation of pure glycerol: 2-step reaction
1950 ff Fatty alcohol production for nonionic detergents
high temperature and pressure process
240°C; 100 bar; NaOCH3; distillation
1986 Mittelbach et al. AT 386.222
low temperature and pressure process for
biodiesel production: KOH; purification with IER
1990 ff over 200 patents on biodiesel production

11. Ghent, September 19, 2005
Biodiesel Production Technologies
1) 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

12. Ghent, September 19, 2005
Biodiesel Production Technologies
2) 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 %

13. Ghent, September 19, 2005
1985: 1st pilot plant worldwide for RME
Silberberg, Styria, Austria

14. Ghent, September 19, 2005
1986: Mittelbach, Junek, Andreae: AT 386.222

15. Ghent, September 19, 2005
MultiMulti--FeedstockFeedstock ProductionProduction SchemeScheme ((simplifiedsimplified))
© BDI Anlagenbau Ges.m.b.H.
Catalyst
Preparation
Methanol
KOH
Fully automatic
Transesterification
Oil Pre-
treatment
Oil / Fat
Methylester
Methanol-Recovery
Methylester
Purification – Distillation
Quality Control
Glycerine phase
After- treatment
Fertilizer
Separation
Free Fatty Acid
Recovery
Crude Glycerine
Methanol-Recovery
Pharmaceutical
Glycerine Production
Fertilizer
Pharmaglycerine
BioDiesel
Acid
Crude Glycerine
Distillation side-product

16. Ghent, September 19, 2005
Biggest Multifeedstock Biodiesel Plant in Austria
Arnoldstein, 25.000 t

17. Ghent, September 19, 2005
First Biodiesel Plant in a European Capital
Ground-breaking, Vienna, 15.09.05
Capacity: 95.000 t/a; First production: 09/06

18. Ghent, September 19, 2005
Biggest Biodiesel Plant in Germany
ADM, Hamburg, 200.000 t

19. Ghent, September 19, 2005
© J.Connemann

20. Ghent, September 19, 2005
New Trends: Heterogenous Catalysts
Metal oxides (Mg, Ca, Al, Fe)
Carbonates: CaCO3
Ion exchange resins (acidic, alkaline)
Enzymes
Silicates
+ easy separation, reusable
pure glycerol, no side products (salts)
first industrial application 2006 ?
- high temperature and pressure, high investment costs
incomplete conversion, distillation necessary

21. Ghent, September 19, 2005
New Trends: Enzymes as Catalysts
Lipases (Triacylglycerolhydrolases)
main task: lipid hydrolysis
in organic solvents:
esterification, transesterification
Alcoholysis of sunflower oil with MeOH, EtOH
Mittelbach et al., 1990
1990 ff: 88 publications on enzymatic alcoholysis

22. Ghent, September 19, 2005
Immobilization of Lipases on Corn Cob Granulate
Fabrik der Zukunft, BMVIT
Aim: Biodiesel production process with lipases
Immobilization: 93 % physical adsorption at pH = 4.7
Enzymes: Thermomyces lanuginosus, Pseudomomas sp.

23. Ghent, September 19, 2005
Immobilization of Lipases on Corn Cob Granulate
0
20
40
60
80
100
%Alkylester
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

24. Ghent, September 19, 2005
Enzymes as Catalysts: Summary
+ High catalytic activity, no solvents necessary
Transesteriifcation and esterification in 1 step
High conversion also with ethanol
Easy separation and purification of products
Saving of chemicals
- Slow reaction rates
High price of enzymes
Deactivation with glycerol: washing step
Economic evaluation
Enzyme: 10 €/kg and 1.700 h lifetime

25. Ghent, September 19, 2005
New Trends: Fatty Acid Ethyl Esters
Today‘s biodiesel production worldwide: approx. 2 mill. t/a
Almost 100 % fatty acid methyl esters
why ?

26. Ghent, September 19, 2005
0
100
200
300
400
500
600
700
2002 2003 2004 2005
[€/t]
Ethanol
Methanol
Prices for Methanol and Ethanol
Rape seed oil
520 €/t

27. Ghent, September 19, 2005
Fatty Acid Ethyl Esters
+ 100 % biofuel
bioethanol production increasing worldwide
higher Cetane Number
- price of ethanol
anhydrous ethanol necessary: via zeolites
slower transesterification; lower conversions
no separation of glycerol with common technologies
higher viscosity
no EN specifications
no additional tax benefits

28. Ghent, September 19, 2005
New Trends: Supercritical Solvents
Definition:
no differentiation between gas and liquid
no liquid phase over Tc
Conditions:
Methanol Ethanol Water
Tc 512.6 K 513.9 K 647.1K
Pc 80.9 bar 61.4 bar 220.6 bar

29. Ghent, September 19, 2005
Vapor Pressure Methanol
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300 350 400
Temperature [°C]
Pressure[bar]
Tc = 239.5°C
Pc = 80.9 bar

30. Ghent, September 19, 2005
Alcoholysis with Supercritical Methanol
Typical reaction conditions:
reaction temperature: 350°C
optimum molar ratio: oil : methanol = 1 : 40
reaction time: 2 min
conversion: > 95 %
+ no catalyst, no purification
- high excess of methanol, high energy input
investment costs, equipment
D.Kusdiana, S.Saka, Fuels 2001

31. Ghent, September 19, 2005
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

32. Ghent, September 19, 2005
Future Perspectives of Biodiesel
New 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 pinnata
used frying oil
• Animal fat: tallow, grease, SRM-material
• Waste oils and fat, soap stock, trap grease

33. Ghent, September 19, 2005
Future Perspectives of Biodiesel
New Feedstocks

34. Ghent, September 19, 2005
New Trends: Synthetic Biodiesel
Pyrolysis Fuels: any carbon source: plastic, sewage sludge
pyrolysis with/without catalysts
mixture of alkanes, alkenes, aromates
gas, gasoline, diesel, residue
GTL – Fuels: Gas to liquid fuels
sources: natural gas, biogas
synthesis gas, synthesis with catalysts
products: methanol, gasoline, diesel
BTL – Fuels: Biomass to liquid fuels; Sun Fuels
gasification, Fischer-Tropsch synthesis
sources: cellulose, wood, straw
tailor made Diesel fuels

35. Ghent, September 19, 2005
Fischer-Tropsch Synthesis
Inventors: F.Fischer, H.Tropsch, 1925, Mülheim
Main 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

36. Ghent, September 19, 2005
Biomass to Liquid Fuels
Advantages:
almost unlimited sources
designer fuel, chemical composition variable
low engine emissions
Disadvantages:
high production costs
only industrial scale possible

37. Ghent, September 19, 2005
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 heterogenous
catalysis, enzymes, supercritical alcohols
• Fatty acid ethyl esters will be produced in the future due to the
availability of cheap ethanol

38. 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 in
the next decades
Limiting factor: availability of feedstock
• Synthetic biofuels (GTL, BTL) are taylor made products with
excellent Diesel properties.
There is almost unlimited availability. However, due to the
high production costs the time of market penetration
depends on mineral oil price

39. Ghent, September 19, 2005
Bianca Bergler Mag. Bernd Nebel
Mag. Firoozeh Alavian Mag. Bernd Pokits
Mag. Adina Fodor Florian Reder
Sigrid Lagarde Mag. Sigurd Schober
Mag. Tobias Madl Ingrid Seidl
Mag. Mario Müller Mag. Renate Uitz

40. Ghent, September 19, 2005
Publication date: 11/04
340 pages
Publisher: Martin Mittelbach