M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NLM.Mittelbach, AGQM-HEC-MeetingSeptember 27-28, 2010, BrusselsM.Mittelbach, BIOTOP Workshop
September 25, 2009, Valparaíso, Chile
Martin [email protected]
Institute of Chemistry (IFC)
Department of Renewable ResourcesUniversity of Graz
A-8010 GrazAustria
International Conference on Jatropha curcasGroningen, the Netherlands, November 1-2
Conversion of Jatropha Curcas Oil
• 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
Biofuels Activities of IFC, Uni GrazDepartment of Renewable Resources
M.Mittelbach; Lublijana, May 20, 2008 31986: Mittelbach, Junek, Andreae: AT 386.222
1987: 1st pilot plant worldwide forBiodiesel: Silberberg, Styria, Austria
IFC: Over 20 Years Experience in Biodiesel
Biodiesel Plant Amsterdam, 100.000 t/a BDI, AustriaFeedstocks: Trap grease, UCO, PFADPut into operation: 2010
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Symposium on Biofuel and Industrial Products from Jatropha curcasand other Tropical Oil Seed Plants
Managua / Nicaragua23 - 27 February 1997
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Biomass Project within an AustrianDevelopment Help Project in Nicaragua1990 – 2000Evaluation of Jatropha curcas L. as
energy plantCultivation 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 2010November 1-2, 2010, Groningen, NL
0
50
100
150
200
250
300
350
400
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009
Publications on JatrophaSource: SciFinder
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Price Development of Vegetable Oils and Gasoil in U S $/t
0
200
400
600
800
1000
1200
1400
1600
1800
10/0
22/
036/
0310
/03
2/04
6/04
10/0
42/
056/
0510
/05
02/0
606
/06
10/0
602
/07
04/0
706
/07
08/0
710
/07
12/0
702
/08
04/0
806
/08
08/0
810
/08
12/0
802
/09
04/0
906
/09
08/0
910
/09
12/0
902
/10
04/1
006
/10
Rapeseed Oil
Palm Oil
Gas Oil
Soybean Oil
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Oil Characteristics of Jatropha Curcas L.
Free Fatty Acids [%m/m] 2-15Solvent 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 2010November 1-2, 2010, Groningen, NL
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 curcas
12-17 5-10 37-63 19-41 1-2 93-107
Pongamia pinnata
3-8 2-9 44-71 10-18 15-20 80-96
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 2010November 1-2, 2010, Groningen, NL
Biodiesel from Oil of Jatropha Curcas L.
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
FAME from
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
-20
-15
-10
-5
0
5
10
15
0 5 10 15 20 25 30 35 40 45 50
Content of Saturated Fatty Acid Chains [wt.%]
CF
PP
[°C
]
typical range of BioDiesel derived from Rapeseed Oil
typical range of BioDiesel derived from Used Cooking Oil
typical range of BioDiesel derived from Animal Fat
CFPP of B100 vs. Saturated Fatty Acids
Source: BDI
Jatropha
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Toxic Principles of Jatropha Curcas L.
Phorbol esters:mainly in the oil; esters of tigliane diterpenestumor 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 2010November 1-2, 2010, Groningen, NL
O HO
OH
HO
HH
O
O O
O
H1
23 4
5 6
7
89
10
1112
13
14 1516
17
18
19
20
1'
2' 3'
4'
5'6'
7'
8'
9'10'
11'
12'
13'14'
15'
16'
17'
18'
19'
20'
21'
22'
23'
24'
DHPB: Hirota et al. 1998
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Novel Class of Cyclobutan Mojety
W.Haas, H.Sterk, M.Mittelbach: J. Nat. Prod. 2002
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
min0 2 4 6 8 10
mAU
0
1
2
3
4
5
6
7
VWD1 A, Wavelength=280 nm (A060508\081-0101.D)
min0 2 4 6 8 10
mAU
0
0.5
1
1.5
2
2.5
3
3.5
4
VWD1 A, Wavelength=280 nm (A060508\082-0201.D)
HPLC:
Toxic variety
Non toxicvariety
Phorbol esters
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
min0 2 4 6 8 10
mAU
0
1
2
3
4
5
6
7
VWD1 A, Wavelength=280 nm (A060508\081-0101.D)
HPLC:
Oil:
Toxic variety
Methyl Ester:
After trans-esterification
Phorbol esters
min0 2 4 6 8 10
mAU
-10
-8
-6
-4
-2
VWD1 A, Wavelength=280 nm (A050608\072-0101.D)
M.Mittelbach, Eco Asia Conference October 28, 2008, Hong Kong
Source: www.jatropha.de
M.Mittelbach, Bogor 2008
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Jatropha curcas Plantation, Tierra Caliente, Mexico, 2/2010Age: 3 years, with Irrigation
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Jatropha curcas Plantation, Tierra Caliente, Mexico, 2/2010Age: 3 years, without Irrigation
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
T+
T+-
T+,T-
T-T-
T+-
T++
21 Jatropha Curcas Oil Samples from MexicoBIOTOP-Project, Student Exchange, July 2010
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Oils &
Fats
FAME
FattyAcids
Glycerine
FattyAlcohols
Sulpho-FAME
FA-EthoxylatesFA-Sulfates
APGTechnical EstersAlkyl chlorides
SoapsDimer acidsFA esters
Chemicals
FAEE Biodiesel
Oleochemicals Specialities
Fuels
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Alcoholysis 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+
Triglyceride Diglyceride
Monoglyceride Glycerol
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Transesterification with Alkylacetate
Triglyceride Methyl-(ethyl-)acetate Triacetine FAME
3 CH3COOR13
Catalysts: KOH, lipases: M.Mittelbach et al., 1995, 2000, unpublishedsupercritical conditions: Saka et al., 2009
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
3
Triglyceride Dimethylcarbonate Glycerolcarbonate FAME
Transesterification with Dimethylcarbonate
1) Fabbri et al., 20072) S.Saka et al., 2009
CH3OH + CO +O2
Cu
1) CH3O-
2) supercritical
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Most Promising Technologies
R.Altman, www.caafi.org, 2009
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
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 2010November 1-2, 2010, Groningen, NL
Hydrotreated vegetable oils (HVO)
ReactorReactor
WaterWater
COCO22
Propane Propane & Light & Light EndsEnds
Diesel Diesel ProductProduct
MakeMake--up up HydrogenHydrogen
SeparatorSeparator
Acid Gas Removal
NaphthaNaphthaor Jetor Jet
Source:
T.L.Marker et al., UOP, 2007
Similar Technologies:
Neste Oil: NExBTLAxens
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Hydrotreated vegetable oils (HVO)
n H2 3 R - CH3 + 6 H2O + H3C - CH2 - CH3
Hydroisomerization
Branched hydrocarbons
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
FAME as Renewable Resources, 1
R = fatty acid chainR-COOCH3
CH2OCORC
CH2OCOR
CH2OCOR
CH3CH2
CH2OHC
CH2OH
CH2OH
CH3CH2
Trimethylolpropan
LubricantsHydraulic fluids
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
FAME as Renewable Resources, 2
R-COOCH3
HO
RCOO
2-Ethylhexanol
R = fatty acid chain
LubricantsCutting fluids
Fatty acid-2-ethylhexanoate
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
FAME as Renewable Resources, 3
R-COOCH3
O
R - COO - (CH2 - CH2 - O) - CH3
R = fatty acid chain
n
n
FAME-ethoxylates Nonionic Dete rgents
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
FAME as Renewable Resources 4: Liposaccharides
R-COOCH3
O
OH
HOCH2
OH OH
O
CH2OH
OH
OH
HOCH2
O
O
XOXO OX
O
CH2OX
XO
XO
XOCH2
O
XO
R = fatty acid chain
saccharose
Octaacylsaccharose "Olestra"
KOH/MeOHFAME
glucoseX = COR
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Ozonolysis of Oleic Acid
(CH2)n COOH
1) O3 2) H2O2n=7: Ölsäuren=11: Erucasäure
COOH
Pelargonsäure
(CH2)n COOHHOOC
n=7: Azelainsäuren=11: Tridecandisäure
Oleic acid
Azelaic acidTridecanediacid
Pelargonic acid
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Epoxidation of Olefins
HC CH
O+ HX
HC CH
OH X
HX End productH2 AlcoholH2O DiolROH Ether alcoholRCOOH HydroxyesterR2NH AminoalcoholHCl Chlorhydrin
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Self Metathesis of Fatty Acid Esters
(CH2)n COOR
n=7: Ölsäureestern=11: Erucasäureester
(CH2)n COOR
WCl6-SnMe4
(CH2)n
(CH2)n
COOR
COOR
n = 7: Oleic acid
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Co Metathesis with Ethene
(CH2)n COOR
n=7: Ölsäureestern=11: Erucasäureester
(CH2)n COOR
CH2 CH2
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
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 thetechnical 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 2010November 1-2, 2010, Groningen, NL
WG NAWARO
M.Mittelbach, ICJC 2010November 1-2, 2010, Groningen, NL
Thank You for Your Kind Attention!