Lipase catalyzed transesterification of plant oils with dialkyl carbonates [Elektronische Ressource] / vorgelegt von Tjahjono Herawan

Lipidforschung

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2004
• Nombre de lectures: 10
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

LIPASE-CATALYZED TRANSESTERIFICATION OF
PLANT OILS WITH DIALKYL CARBONATES




Von der Fakultät für Mathematik, Informatik und Naturwissenschaften
der Rheinisch-Westfälischen Technischen Hochschule Aachen
zur Erlangung des akademischen Grades eines Doktors
der Naturwissenschaften genehmigte Dissertation



vorgelegt von


Master of Science
Tjahjono Herawan


aus Surakarta - Indonesia



Berichter : Prof. Dr.rer.nat. Siegfried Warwel
Universitäts-Prof. Dr.rer.nat. Walter Leitner




Tag der mündlichen Prüfung : 29 November 2004




Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.







The whole research work of this thesis was carried out at the Institute for Lipid
Research, Federal Research Centre for Nutrition and Food (BFEL) in Münster
– Germany, formerly known as Institute for Biochemistry and Technology of
Lipid (H.P. Kaufmann-Institute) Federal Centre for Cereal, Potato and Lipid
Research (BAGKF) in Münster – Germany, between June 2001 and June
2004.

Acknowledgments
I wish to express my sincere appreciation and gratitude to Prof. Dr. S. Warwel,
(The former Head of the Institute for Lipid Research, Federal Centre for
Cereal, Potato and Lipid Research (BAGKF) in Münster - Germany, for
supervising this work and for the attention he paid to me during my studies,
Deeply gratitude is due to Prof. Dr. M. Rüsch gen. Klaas, Professor of
Department of Technology, Neubrandenburg University of Applied Sciences,
Neubrandenburg - Germany, for his guidance, sincere assistance and for his
excellent supervision,
Deeply gratitude is also due to Prof. Dr. W. Leitner, the Head of Institute of
Technical Chemistry and Macromolecular Chemistry at RWTH Aachen
Germany, for his acceptance to be my examiner,
I would like to thank Dr. N. Weber, Professor and Director of Institute for Lipid
Research, Federal Research Centre for Nutrition and Food (BFEL) in Münster
- Germany, for giving me opportunity to complete my work in his institute,
I am deeply grateful for overwhelming guidance, support and excellent
supervision I have received from Dr. F. Brüse,
I would like to thank some of colleagues in Institute for Lipid Research in
Münster such as Dr. E. Fehling and Frau E. Klein, who guide me how to use
Gas Chromatography and always help me when I have problem with this
instrument, Dr. L. Brühl and Frau. B. Bielefeld, who help me to analyze some
sample with HPLC, Dr. K. Vosmann, who help me to analyze some sample
with GC-MS, Frau C. Essman who help me to analyze water content by Karl-
Fischer, and also to Frau P. Weitkamp and Frau U. Ender for technical
assistance, I would like to thank Mr. Dipl-ing. B. Kleinsteuber, TÜV-Rheinland Germany,
for his help and giving me the opportunity to come to Germany,
I would like to thank Dr. K.D. Mukherjee, Dr. B. Wiege, Frau B. Ache, and all
of colleagues in Institute for Lipid Research in Münster for hospitality and
personal help,
I also would like to thank Prof. Dr. M. Liauw, Professor of Technical Chemistry
and Reaction Engineering at RWTH Aachen Germany for some suggestion
and his acceptance to be my examiner,
Gratitude is due to Dr. Z. Poeloengan, Director of Indonesian Oil Palm
Research Institute (IOPRI), for giving me the opportunity and scholarship to
pursue this study,
Gratitude is also due to Dr. P. Guritno, Dr. Darnoko, Drs. B.H. Sulistyo, Dr. Tri
Haryati, Dr L. Buana, Dr. J. Elisabeth, Drs E. Nuryanto MSc, and all
colleagues in Post Harvest Group of Indonesian Oil Palm Research Institute
(IOPRI) for their support,
No words are sufficient to thank my wonderful wife “Ami”. The patience, love,
sacrifice, encouragement, care and support freely given by her during my
study and my live were invaluable. The youthful spirit of our daughter ‘Fildzati’
and son ‘Fadhlan’ gave me the energy and perspective to finish this work.
Last but not least, I would like to thank my parents and all my families for their
never-ending support.












Abbreviations and Trade Name

ANL Aspergillus niger lipase
CB Silica Candida antarctica lipase supported on silica
CCL Candida cilyndracea lipase
CL-5 Chirazyme L-5 lipase
CPL Carica papaya lipase
CRL Candida rugosa lipase
DEC Diethyl carbonate
DG Diglyceride
DMC Dimethyl carbonate
EDTA-Na Ethylene diamine tetra acetic acid, disodium salt 2
EE Ethyl Ester
®Esterase Hog-liver esterase immobilized on eupergit C
EtOH Ethanol
HPL Hog Pancreas lipase
Hvtox Toxic Hazard Value ( 0.0 – 5.0 )
IM PS-30 Pseudomonas cepacia immobilized within phylosilicate sol-gel
matrix
Lipozyme® Immobilized Mucor miehei lipase
ME Methyl Ester
MeOH Methanol
MG Monoglyceride
MJL Mucor javanicus lipase
MML Mucor miehei lipase
®N 435 Novozym 435 (Candida antarctica lipase immobilized within
acrylic resin)
Na HPO .12H O Sodium hydrogen phosphate 2 4 2
Na HPO .2H O 2 4 2
Na SO Sodium sulphate 2 4
Na PO .12H O Sodium phosphate 3 4 2PFL Pseudomonas fluorescens lipase
PMF Palm oil mild fraction
ScCO Super critical carbon dioxide 2
SP 435 Candida antarctica lipase supported on a macroporous acrylic
resin
TG Triglyceride
3TLV Threshold Limit Value (mg/m or ppm)












































Content
Acknowledgments
Abbreviations and Trade Names
Content
1. Introduction ....................................................................................……….1
2. Literature Review .................................................................................…..2
2.1 Introduction …………………………………………………………...……3
2.2 Recent Development in the Production of Alkyl Esters ……………….5
2.2.1 Preparation of Alkyl Esters Using Chemical Catalyst ……………6
2.2.2 Preparation of Alkyl Esters Using Enzyme Catalyst ….…….......8
2.2.2.1 Lipase ……………………………………………………...…...8
2.2.2.2 Enzymatic Alcoholysis with or without Organic Solvent ….10
2.2.2.3 Lipase-Catalyzed Transesterification of Vegetable Oils
with Others Alkyl Sources………………………………...…..20
2.3 Recent Development in (Oilseed) Solvent Extraction Process ......….24
2.4 Reactive Extraction of Acylglycerides ………………………………... 26
2.5 Dialkyl Carbonate as Alternative Solvent for Oilseed Extraction and
Alkyl Ester Synthesis ………………………………………………...…. 29
2.6 Palm Kernel Oil and Others Potential Tropical Oil as Alkyl Esters Raw
Material …………………………………………………………………... 33
2.6.1 Palm (Elais guineensis) Kernel Oil …………..…….……….…... 34
2.6.2 Rubber (Hevea brasiliensis) Seed Oil …….….……………….....37
2.6.3 Others Potential Tropical Oil ……….… …………………….…..39
2.6.3.1 Candle Nut (Aleurites moluccana) Oil ….……………......39
2.6.3.2 Fenugreek (Trigonella foenum-graecum L.) Oil......…...…41
2.6.3.3 Saga Seed (Adenanthera pavonine) Oil …………....…....43

3. Results and Discussion ......................................................................….45
3.1 Introduction .....................................................................................…45
3.2 Screening of Commercially Available Lipases for Their Abilities to
Transesterify the Triglyceride of Palm Kernel Oil with Dimethyl or
Diethyl Carbonate ...........................................................................…46 3.2.1 Lipase Transesterification of Palm Kernel Oil with Dialkyl
Carbonates or Alcohol in the Presence of Isohexane …........…46
3.2.2 Lipase Transesterification of Palm Kernel Oil with Dimethyl
Carbonate as Substrate and Solvent ..…...................................54
3.2.3 Summary ...................................................................................56
3.3 Transesterification of Palm Kernel Oil with Dimethyl and Diethyl Car-
bonate Catalyzed by Novozym 435 ................................................…57
3.3.1 Effect of Alkyl Sources on the Esters Formation .......................57
3.3.2 Effect of Substrate Molar Ratio on the Esters Formation ......…61
3.3.3 Effect of Amount of Novozym 435 on the Esters Formation ..…65
3.3.4 Effect of Reaction Temperature on the Esters Formation .....…69
3.3.5 Effect of Water on the Esters Formation................................…74
3.3.6 Effect of Repeated Used of Enzyme on the Ester Formation …81
3.3.7 Effect of Quality of Dialkyl Carbonates on the Ester Formation.83
3.3.8 Effect of Type of Solvent on the Ester Formation ..................…85
3.3.9 Effect of Amount of Solvent on the Ester Formation ...........…..88
3.3.10 Summary ................................................................................93
3.4 Transesterification of Rubber Seed Oil