Conversion of Jatropha Curcas Oil into BioDiesel

1. Conversion of
Jatropha Curcas Oil
Martin Mittelbach
martin.mittelbach@uni-graz.at
Institute of Chemistry (IFC)
Department of Renewable Resources
University of Graz
A-8010 Graz
Austria
International Conference on Jatropha curcas
Groningen, the Netherlands, November 1-2
M.Mittelbach, AGQM-HEC-Meeting
M.Mittelbach, ICJC 2010
M.Mittelbach, BIOTOP Workshop
September 25, 2009, 2010, Brussels
November 1-2, 2010, Groningen,Chile
September 27-28, Valparaíso, NL

2. Biofuels Activities of IFC, Uni Graz
Department of Renewable Resources
• Development of biodiesel process technologies
• Alternative feedstocks for biodiesel production
• Alternative uses for biodiesel and side products
• Research on analysis and characterization of fats and oil
derivatives
• Development of specifications
• Training and seminars on biodiesel analysis and quality
management
• Research on second generation biofuels: BTL,
biomethanol, lignocellulosic biodiesel

3. 1986: Mittelbach, Junek, Andreae: AT 386.222
M.Mittelbach; Lublijana, May 20, 2008 3

4. IFC: Over 20 Years Experience in Biodiesel
1987: 1st pilot plant worldwide for
Biodiesel Plant Amsterdam, 100.000 t/a
Biodiesel: Silberberg, Styria, Austria
BDI, Austria
Feedstocks: Trap grease, UCO, PFAD
Put into operation: 2010

5. Symposium on Biofuel
and Industrial Products
from Jatropha curcas
and other Tropical Oil Seed
Plants
Managua / Nicaragua
23 - 27 February 1997
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

6. Biomass Project within an Austrian
Development Help Project in Nicaragua
1990 – 2000
Evaluation of Jatropha curcas L. as
energy plant
Cultivation of 1.000 ha
„The biofuel part, however, suffers from the
development of fossil fuel prices, which
makes the production of diesel from physic
nut uneconomical at the moment.“
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

7. Publications on Jatropha
Source: SciFinder
400
350
300
250
200
150
100
50
0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

8. 10
/0
0
200
400
600
800
1000
1200
1400
1600
1800
2
2/
03
6/
0
10 3
/0
3
2/
04
6/
0
10 4
/0
4
2/
05
6/
0
10 5
/0
02 5
/0
06 6
/0
Gas Oil
Palm Oil
10 6
/0
02 6
/0
Soybean Oil
04 7
Rapeseed Oil
/0
06 7
/0
08 7
/0
10 7
/0
12 7
/0
02 7
/0
M.Mittelbach, ICJC 2010
04 8
/0
06 8
/0
November 1-2, 2010, Groningen, NL
08 8
/0
10 8
/0
12 8
/0
02 8
/0
04 9
/0
06 9
/0
08 9
/0
10 9
/0
12 9
/0
02 9
/1
04 0
/1
06 0
/1
0
Price Development of Vegetable Oils and Gasoil in US $/t

9. Oil Characteristics of Jatropha Curcas L.
Free Fatty Acids [%m/m] 2-15
Solvent extracted: 6.9
Cold pressed: 5.3
Iodine Number 95 - 107
Linoleic Acid [%m/m] 19 – 41
Phosphorus [mg/kg]
Solvent extracted: 88
Cold pressed: 36
Phorbol Ester Content [mg/kg] 100 - 3800
Source: Makkar et al., Mittelbach et al.
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

10. Fatty Acid Distribution of Non Edible Oils
C-16:0 C-18:0 C-18:1 C-18:2 C-18:3 Others Iodine
Nr
Rape seed 3-5 1-2 55-65 20-26 8-10 96-117
Jatropha 12-17 5-10 37-63 19-41 1-2 93-107
curcas
Pongamia 3-8 2-9 44-71 10-18 15-20 80-96
pinnata
Rubber seed 7-8 9-10 28-30 33-35 20-21 121-
145
Sal 5-9 34-48 34-45 2-3 6-12 33-45
Castor 1-2 1-2 3-4 5-6 0.5-1 87-88 82-90
Tobacco seed 11 3.5 14.5 69.5 136-
146
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

11. Biodiesel from Oil of Jatropha Curcas L.
FAME from
Fuel Parameter Rape Seed Jatropha curcas
Cetane Number 49 - 62 51 – 59
CFPP [°
C] -19 - -8 -3
Iodine Number 104 - 120 95 - 107
Oxidation Stability [h] 7 3
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

12. CFPP of B100 vs. Saturated Fatty Acids
15
Jatropha
C]
CFPP [°
10
5
typical range of
0 BioDiesel derived from
Animal Fat
-5
typical range of
BioDiesel derived from
-10 Used Cooking Oil
typical range of
-15 BioDiesel derived from
Rapeseed Oil
-20
0 5 10 15 20 25 30 35 40 45 50
Content of Saturated Fatty Acid Chains [wt.%]
Source: BDI M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

13. Toxic Principles of Jatropha Curcas L.
Phorbol esters:
mainly in the oil; esters of tigliane diterpenes
tumor promotion, cell proliferation, activation of blood
platelets, lymphocyte mitogenesis, inflammation
Curcin:
mainly in the oil cake; Ribosome-inactivating protein
Non-toxic varieties found in Mexico
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

14. DHPB: Hirota et al. 1998
15'
14' 13'
23' 21' 19' 17' 6' 12'
5'
24' 22' 20' 16' 4'
18'
1'
2' 3'
8'
O 7'
9'
10'
18 O
12
HO 11 13 17
1 H 14 15
O 11' O
19 9 16
2 10 8 H
3 4 H
7
O HO 5 6
20 OH
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

15. Novel Class of Cyclobutan Mojety
W.Haas, H.Sterk, M.Mittelbach: J. Nat. Prod. 2002
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

16. VWD1 A, Wavelength=280 nm (A060508081-0101.D)
mAU
7 HPLC:
6 Phorbol esters
5
4
Toxic variety
3
2
1
0
0 2 4 6 8 10 min
VWD1 A, Wavelength=280 nm (A060508082-0201.D)
mAU
4
3.5
3
2.5 Non toxic
1.5
2
variety
1
0.5
0
0 2 4 6 8 10 min
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

17. VWD1 A, Wavelength=280 nm (A060508081-0101.D)
mAU
7 HPLC:
6 Phorbol esters
5
4 Oil:
3
2
1
Toxic variety
0
0 2 4 6 8 10 min
VWD1 A, Wavelength=280 nm (A050608072-0101.D)
mAU
-2
-4
Methyl Ester:
-6
-8
After trans-
esterification
-10
0 2 4 6 8 10 min
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

18. Source: www.jatropha.de
M.Mittelbach, Bogor 2008
M.Mittelbach, Eco Asia Conference
October 28, 2008, Hong Kong

19. Jatropha curcas Plantation,
Tierra Caliente, Mexico, 2/2010
Age: 3 years, with Irrigation
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

20. Jatropha curcas Plantation,
Tierra Caliente, Mexico, 2/2010
Age: 3 years, without Irrigation
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

21. 21 Jatropha Curcas Oil Samples from Mexico
BIOTOP-Project, Student Exchange, July 2010
T+-
T-
T-
T+
T++
T+-
T+,T- M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

22. FAEE Biodiesel Fuels
Oleochemicals Specialities
Sulpho-FAME
FAME
FA-Ethoxylates
FA-Sulfates
Fatty
APG
Oils Alcohols
Technical Esters
& Fatty Alkyl chlorides
Acids
Fats Soaps
Dimer acids
FA esters
Glycerine Chemicals
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

23. Alcoholysis of Triglycerides
CH 2 O COR 1 CH 2 O COR 1
CH 3 OH CH 3 OH
CH O COR 2 CH O COR 2 + R3 COOCH 3
CH 2 O COR 3 CH 2 OH
Triglyceride Diglyceride
CH 2 O COR 1 CH 2 OH
CH 3 OH
CH OH + R2 COOCH 3 CH OH + R1 COOCH 3
CH 2 OH CH 2 OH
Monoglyceride Glycerol
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

24. Transesterification with Alkylacetate
3 CH 3COOR 1
3
Triglyceride Methyl-(ethyl-)acetate Triacetine FAME
Catalysts: KOH, lipases: M.Mittelbach et al., 1995, 2000, unpublished
supercritical conditions: Saka et al., 2009
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

25. Transesterification with Dimethylcarbonate
CH3OH + CO +O2
Cu
1) CH3O-
3
2) supercritical
Triglyceride Dimethylcarbonate Glycerolcarbonate FAME
1) Fabbri et al., 2007
2) S.Saka et al., 2009
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

26. Most Promising Technologies
R.Altman, www.caafi.org, 2009
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

27. New Biofuels as Diesel Fuel
BTL (Biomass to Liquid):
Gasification and FT-synthesis
Hydrotreated vegetable oils (HVO):
Direct hydrotreating of fats and oils in refineries;
integrated or stand alone
Thermochemical liquefaction of biomass:
pyrolysis, hydrothermal upgrading (HTU)
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

28. Hydrotreated vegetable oils (HVO)
Make-up
Hydrogen
Source:
Acid Gas CO2
Reactor Removal
T.L.Marker et al., UOP, 2007
Propane
& Light
Ends
Separator
Naphtha
or Jet Similar Technologies:
Water
Neste Oil: NExBTL
Axens
Diesel
Product
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

29. Hydrotreated vegetable oils (HVO)
n H2 3 R - CH3 + 6 H2O + H3C - CH2 - CH3
Hydroisomerization
Branched hydrocarbons
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

30. FAME as Renewable Resources, 1
R-COOCH 3 R = fatty acid chain
CH 2OH
CH 3CH 2 C CH 2OH
CH 2OH
Trimethylolpropan
CH 2OCOR
Lubricants
CH 3CH 2 C CH 2OCOR Hydraulic fluids
CH 2OCOR
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

31. FAME as Renewable Resources, 2
R-COOCH3 R = fatty acid chain
HO
2-Ethylhexanol
Lubricants
RCOO Cutting fluids
Fatty acid-2-ethylhexanoate
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

32. FAME as Renewable Resources, 3
R-COOCH 3 R = fatty acid chain
O
n
R - COO - (CH 2 - CH 2 - O) n- CH 3
FAME-ethoxylates Nonionic Detergents
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

33. FAME as Renewable Resources 4: Liposaccharides
R-COOCH3 R = fatty acid chain
HOCH2
O saccharose
HOCH2
O
HO
HO HO
OH O CH2OH
HO
XO
O
XOCH2
O
XO KOH/MeOH
XO XO
OX O CH2OX FAME
X = COR XO glucose
Octaacylsaccharose "Olestra"
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

34. Ozonolysis of Oleic Acid
(CH 2)n COOH
n=7: Oleic acid
Ölsäure
1) O3 2) H2O2 n=11: Erucasäure
COOH HOOC (CH 2)n COOH
Pelargonsäure
Pelargonic acid n=7: Azelainsäure
Azelaic acid
n=11: Tridecandisäure
Tridecanediacid
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

35. Epoxidation of Olefins
HC CH HC CH
+ HX
O OH X
HX End product
H2 Alcohol
H2O Diol
ROH Ether alcohol
RCOOH Hydroxyester
R2NH Aminoalcohol
HCl Chlorhydrin
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

36. Self Metathesis of Fatty Acid Esters
(CH 2)n COOR
WCl6-SnMe4
(CH2)n COOR
n=7: Ölsäureester
n = 7: Oleic acid
n=11: Erucasäureester
(CH 2)n COOR
(CH 2)n COOR
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

37. Co Metathesis with Ethene
(CH2)n COOR
n=7: Ölsäureester
n=11: Erucasäureester
CH2 CH2
(CH2)n COOR
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

38. Conclusions
• Jatropha curcas oil has similar chemical composition as
major vegetable oils
• So Jatropha oil is an ideal substitute for food oils in all
oleochemical routes
• However, the content of toxic phorbol esters could limit the
technical applications and utilizations
• The price range for the oil will be between palm oil and
rape seed oil
• The utilization of phorbol esters could give an added value
• Still the most important use for Jatropha oil will be the
biofuel market
• Full LCA for Jatropha oil has to be carried out in order to
evaluate the potential in the biofuel market
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

39. WG NAWARO
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL

40. Thank You for Your Kind Attention!
M.Mittelbach, ICJC 2010
November 1-2, 2010, Groningen, NL