Hamirin Abdul Kifli PhD Thesis

233 Pages·2011·5.86 MB·English

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STUDIES ON PALM OIL
WITH SPECIAL REFERENCE TO INTERESTERIFICATION
being a Thesis
presented by
HAlv1IRIN ABDUL KIFLI, M.Sc.
to the
UNIVERSITY OF ST. ANDREWS
in application for
THE DEGREE OF DOCTOR OF.PHILOSOPHY
February 1981
SUMMARY
Interesterification which can be considered as the removal of
fatty acids at random from glyceride molecules, the shuffli.ng
of these acids and their replacement of the glyceride m.olecules,
has been investigated for palrn oil, palrn oil fractions and palm
oil mixed with other vegetable o11s. The reaction 'has been
0
effected at 90 C in the presence o£ sodium. methoxide as a
catalyst. Pancreatic lipolysis has been ernployed to check the
completene s s of the reacti.on. On cOluplete :candornisation,
the fatty acid composition. of the 2-position is the sarne as that
of the whole fat either before 014 after interestel'ification.
The changes in the glyceride cO:tYlposition resulting fron'1
interesterification have been exarnined by various standard
technique s. Silver ion thin layer chron'1atography which
separates glycerides according to their degree of unsaturation
has been used extensively. Using luethyl heptadecanoate as
an internal standard various com.ponent glyc,erides have been
",
" ~
··;.{Y'
quantified. . GLG of glycerides has als~,l1!s~nused to study the
.
''''?;'~
changes in glyceride composition of fats cont£'tning a wide
".
range of fatty acid cOluposHion.
The application of thin layer chromatography, usi.ng methy_l
heptadecanoate as an interncll standard, ha.s aiso been extended
to deterrnine the esters for.r-ned during interesterification when
sodiur:n. methoxide is used as a catalyst.
The changes in physical properti.es which resuE from
interestel'ification have been determined by NMR (solids .fat
content) and DSC (thermal behaviour).
Attempts to prepare a mixture of fats and oils containing
palm oil and / or palm oil fraction s which simulate s vanaspati
have been made. Many rnixtul'es have been subjected to
interesterification and the physical properties of the products
have been investigated using NMR for all the mixtures and
DSC of selected mixtures. The SFC curve of each rnixture
has been compared with that of vana spati. Some potentially
useful mixtures are recognised.
Stereospecific glyceride analysis of various types of palm
oils has also been carried out using Brockerhoff1 s method.
This involves partial deacylation of the triacylglyce!'ols,
i.solation of the a,l3-diacylglycerols, conversion of these
diacylglycerols to phospholipid derivatives and finally
stereospecific hydrolysis by Phospholipase A from fmake
Z
venom, The possible component glycerides have then been
z-
computed as suming a i-random, random, 3.:. random
distribution of the fatty acids found in each of these positions.
The results have been discussed in tenus of double bond
nUluber and of carbon nunlber: The latter has been compared
with results obtained by gas chromatography of the whole oil.
To
Atasha and Siti Anabaena
DEC LARA TICYN
I hereby declare that this thesi-s is a record of the results
of my own experirnentG, that it is my own composi.tion, and
that it has not previously been presented ill application for a
higher degree.
The research was carried out in the Chemistry Research
Department of the University of St. Andrews under the direction
of Professor F.D. Gunstone, D.Sc. ,F.R.I.C.
C ERTIFIC P.T.E
I hereby certify that Mr. Hamil'in Abdul Kifli has spent
twelve terms at reseaJ:ch work under my supervision, has
fulfilled the conditions of the Resolution of the University
Court No.1 (1967) and that he is qualified to subm.it the
accompanying thesis in application for the degree of Doctor
of Philo s oph y.
Re search Supervi sor
LECTURE
"The Compo sition and Physical Behaviour of Fats Before and
After Interesterificz"Ltion With Special Reference to Palm Oilll
B.A. Kifli and F.D. Gunstone, presented to the ISF/AOCS
Congress, New York,April 28th, 1980.
ACKNOWLEDGEMENTS
I wish to express xny sincere grc(titude to Professor
F.D. Gunstone for his continued supervisi.on, guidance and
assistance throughout this research and writing of this thesis.
I wish also to record my sincere thanks and appreciation to
Dr. Charlie Scrimgeour for much practical advice and discussion
atthebencli., toMr. OhChuanHo and Mr. K.G. Berger of
Pall"n Oil Research Institute of Malaysia and also to Dr. F.B. Padley
of Unilever Research, Colworth House, Bedford, England; for
their assistance in NMR and DSC analyses.
Thanks must also be expressed to Pepe (E. Ba(3cetta) for
his help and good company, to Andrew Watson for his help in
photographic work and to Mr s. VV ilma Pogorzelec for typing
this thesis.
I must also express my deepest thanks and appreciation
to rny wife, Atasha, for hel' artistic talent and for sacrificing
many long hours in drawing all graphs and histograms of this
the si s.
Finally, I must convey my gratitude to the Director General
of the Palm Oil Research lnst,i.tute of Malaysia for the study
grant and full pay study leave.
CONTENTS
A bbreviations and Footnote 8 i
Sumrnary ii
CHAPTER ONE - General Introduction of Palm Oil 1
CHAPTER TWO - Interesterification Studies 8
General Introduction 8
Interesterification 8
Directed Interesterification 10
Randorn Intere sterification 12
Application of Random Interesterification 14
Nutriti.onal Evaluation of Interesterified Fats and Oils 16
Results and Discussion
Method s of Follo\ving the Proce S8 and Examining the
Products 17
Mechanism of Intere8terification U sing Sodium
Methoxide as a Catalyst 23
Changes in Glyceride Composition DuX'ing
Interesterification 25
+
Ag TLC 25
Lipolysis 34
GLC of Triglycerides 37
Formation of Methyl Esters During Interesterification 46
Physical Properties of Int,eresteri£i.ed Fats and Oils 49
Thermal Properties by DSC Analysis 55
CHAPTER THREE - Atternpts to Prepare a Mixture of Fats
and Oils Containing Palm Oil and/or
Palm Oil-Derived Fraction which
Simulates Vanaspati. 63
Introduction 63