conversion of jatropha curcas oil into biodiesel

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


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.“


0

50

100

150

200

250

300

350

400

2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

Publications on JatrophaSource: SciFinder


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


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.


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


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


-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


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


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


Novel Class of Cyclobutan Mojety

W.Haas, H.Sterk, M.Mittelbach: J. Nat. Prod. 2002


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


HPLC:

Toxic variety

Non toxicvariety

Phorbol esters


min0 2 4 6 8 10

mAU

0

1

2

3

4

5

6

7


HPLC:

Oil:

Toxic variety

Methyl Ester:

After trans-esterification

Phorbol esters

min0 2 4 6 8 10

mAU

-10

-8

-6

-4

-2


M.Mittelbach, Eco Asia Conference October 28, 2008, Hong Kong

Source: www.jatropha.de

M.Mittelbach, Bogor 2008


Jatropha curcas Plantation, Tierra Caliente, Mexico, 2/2010Age: 3 years, with Irrigation


Jatropha curcas Plantation, Tierra Caliente, Mexico, 2/2010Age: 3 years, without Irrigation


T+

T+-

T+,T-

T-T-

T+-

T++

21 Jatropha Curcas Oil Samples from MexicoBIOTOP-Project, Student Exchange, July 2010


Oils &

Fats

FAME

FattyAcids

Glycerine

FattyAlcohols

Sulpho-FAME

FA-EthoxylatesFA-Sulfates

APGTechnical EstersAlkyl chlorides

SoapsDimer acidsFA esters

Chemicals

FAEE Biodiesel

Oleochemicals Specialities

Fuels


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


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


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


Most Promising Technologies

R.Altman, www.caafi.org, 2009


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)


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


Hydrotreated vegetable oils (HVO)

n H2 3 R - CH3 + 6 H2O + H3C - CH2 - CH3

Hydroisomerization

Branched hydrocarbons


FAME as Renewable Resources, 1

R = fatty acid chainR-COOCH3

CH2OCORC

CH2OCOR

CH2OCOR

CH3CH2

CH2OHC

CH2OH

CH2OH

CH3CH2

Trimethylolpropan

LubricantsHydraulic fluids



R-COOCH3

HO

RCOO

2-Ethylhexanol

R = fatty acid chain

LubricantsCutting fluids

Fatty acid-2-ethylhexanoate



R-COOCH3

O

R - COO - (CH2 - CH2 - O) - CH3


n

n

FAME-ethoxylates Nonionic Dete rgents


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


saccharose

Octaacylsaccharose "Olestra"

KOH/MeOHFAME

glucoseX = COR


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


Epoxidation of Olefins

HC CH

O+ HX

HC CH

OH X

HX End productH2 AlcoholH2O DiolROH Ether alcoholRCOOH HydroxyesterR2NH AminoalcoholHCl Chlorhydrin


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


Co Metathesis with Ethene

(CH2)n COOR

n=7: Ölsäureestern=11: Erucasäureester

(CH2)n COOR

CH2 CH2


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


WG NAWARO


Thank You for Your Kind Attention!

conversion of jatropha curcas oil into biodiesel

Design

mittelbach lublijana

jatropha curcas groningen

oil of jatropha curcas

evaluation of jatropha

jatropha curcas plantation

biodiesel analysis

lignocellulosic biodiesel

cfpp c