Can. Inst. Food Sel. Teehnol. J. VD!. 22, No. 3, pp.
243-248, 1989
RESEARCH
Chemical and Physical Properties of Palm Oil and
Palm Olein as Affected by Hydrogenation
P,H, Yap, J.M. deMan and L. deMan 1
Department of Food Science
University of Guelph
Guelph, Ontario NIG 2WI
Abstract
Palm oil and palm olein were hydrogenated with a commercial
nickel catalyst at 175°C and 103 kPa hydrogen pressure. The
hydrogenation rate was higher with palm olein. With palm oil the
maximum level of frons isomers, 19070, was obtained at iodine value
27. With palm olein the maximum frans level was 24070 at iodine
value 31. Dropping points, solid fat content and thermal analysis
data for the hydrogenated products are presented and interpreted.
Resume
De I'huile de palme et de I'oleine de palme furent hydrogenees iI
I'aide d'un catalyseur au nickel du commerce il175°C et 103 KPa de
pression d'hydrogene. Le taux d'hydrogenation fut plus eleve avec
I'oleine de palme.Dans le cas de l'huile de palme le niveau maximum
d'isomeres trans, 19070, fut obtenu iI un indice d'iode de 27. Dans le
cas de I'oleine de palme le niveau maximum de trans fut 24070 iI un
indice d'iode de 31. Les points de liquefaction, la teneur en solides
et les donnees d'analysethermique pour les produits hydrogenes sont
presentes et interpretes.
Introduction
Palm oil is a versatile raw material for the fats and
oils industry. It is easily fractionated into a liquid and
a solid fraction, named olein and stearin as well as a
palm mid-fraction (Deffense, 1985). It is also possible
to modify both palm oil and palm olein by hydrogena-
tion to obtain hard fats with different properties. Be-
cause of the high palmitic acid content of palm oil and
its various products, it has interesting polymorphic
properties, which may be used to advantage in blend-
ing with different oils and fats used in the production
of margarines and shortenings. One particular ex-
ample is the prevention of undesirable beta polymorph
formation in margarine blends based on hydrogenated
IdeMan Food Technology Services Inc. Guelph, Ontario NIH 6B5.
Copyright 11 t 989 Canadian Institute of Food Science and Technology
243
canola oil (Weinberg, 1972; Ward, 1988; Yap, 1988).
Podmore (1987) states that palm stearin and palm olein
can both be hydrogenated to give melting curves that
can be used to produce low and high melting puff
pastry margarine when blended with liquid oils. The
use of palm oil products in the fats and oils industry
has been reviewed by Berger (1986).
The present study was undertaken to characterize
the physical properties and chemical composition of
hydrogenated palm oil and palm olein for subsequent
use in margarine blend formulations.
Materials and Methods
Refined, bleached and deodorized palm oil and
palm olein were obtained from Palmco, Inc. Portland,
OR. Hydrogenation was carried out in a Parr pressure
reaction apparatus with a 2 L vessel and a charge of 1
kg of oil. Nickel catalyst, Calsicat E472F, was used at
a level of 0.2010 by weight of the oil. The catalyst
contained 25% nickel. The temperature was 175°C,
hydrogen pressure 103 kPa (15 psi) and agitation was
850 rpm.
Iodine values were determined by the Wijs Method
(AOCS Cd 1-25). Fatty acid composition was deter-
mined by trans-esterification and analysis of the
methyl esters by gas-liquid chromatography (Shehata
and deMan, 1970), using a Varian model 1400 gas
chromatograph equipped with a flame ionization
detector. The lrans isomer content was determined by
infra-red spectrophotometry (AOCS Cd 14-61) using
a Beckman model 4300 infra-red spectrophotometer.
Dropping point of the hydrogenated fat was deter-
mined with a Mettler FP 3 automatic dropping point
apparatus (Mertens and deMan, 1972). Solid fat con-
tent was measured at 10, 20, 30 and 35°C using wide-
line nuclear magnetic resonance (AOCS-Recom-
 Table 1. Fatty acid composition of palm oil and palm olein. Table 2. Iodine value (IV) and rate of hydrogenation of palm oil
Palm oil Palm olein and palm olein.
Fatty acid 070 % Palm oil Palm olein
Hydrogenation
12:0 0.1 0.1 time (min) IV .6IV/min IV .6IV/min
14:0 1.0 1.0
16:0 44.7 39.6 o 52.5 57.0
16:1 0.1 0.1 15 41.4 0.71 40.7 1.09
18:0 4.0 4.0 30 36.6 0.51 31.0 0.87
18:1 40.1 44.0 45 32.0 0.44 21.6 0.79
18.2 9.5 10.7 60 27.0 0.42 12.5 0.74
18:3 .2 .5 75 23.5 0.38 6.0 0.68
20:0 .2 .1

mended Practice Cd 16-81). A Newport Quantity
Analyzer Mark III and a sample temperature control-
ler WR2 MK were used. Tempering of the samples was
done with a Praxis Model TU-900 tempering unit. The
melting profile of the hydrogenated fat samples was
visualized using a model DuPont 900 Thermal
Analyzer. The samples were heated at 70°C for 5 min
followed by rapid cooling at a rate of 20°C per min to
- 30°C. Heating curves were then recorded over the
temperature range of -30°C to 70°C at a heating rate
of 5°C per min. The latent heat of fusion (~ H) was
calculated from the integral surface under the peak of
the DSC thermogram. The instrument was calibrated
with indium.
Results and Discussion
The composition of the palm oil and palm olein
used in this study is listed in Table 1. Although there is
not much difference in fatty acid composition between
palm oil and palm olein, there is a considerable dif-
ference in their dropping points, which are 38.5° and
20.4°C, respectively. When palm olein is not cooled
below room temperature it will remain clear. Iodine
values were 52.0 for palm oil and 57.0 for palm olein.
The progress of hydrogenation of palm oil and palm
olein is indicated by the data in Table 2. The change in
iodine value as a function of hydrogenation time was
used to measure the hydrogenation reaction rate. The
reaction rate decreased as hydrogenation time in-
creased for both palm and palm olein. Palm olein
hydrogenated at a faster rate than palm oil, probably
because it was more unsaturated and, in addition, may
have contained less impurities that can poison the
catalyst.
Two types of isomers are formed during hydrogena-
tion of oil, i.e., trans isomers and positional isomers.
The latter are formed by migration of double bonds
along the carbon chain. Trans isomers also affect the
hardening of the oil.
The formation of trans isomers is illustrated in
Figures 1and 2 for palm oil and palm olein, respective-
ly. Higher levels of trans isomers were obtained with
palm olein. At an iodine value of 31, the trans isomer
content in hydrogenated palm olein reached a maxi-
mum of 24070. This was followed by a decline as more
of the trans isomers became saturated. The formation
of trans isomers in the hydrogenation of palm oil

GO 60

50 50

16:0 18:1 - - E J
~~ 18:1 40 16:0_
H ....X
~
-0
'uG
30
-0
30

........
>- 0
G
.f20 ~20
trGrnl
100000r,
....
G
u..
10 10

Iodine value Iodine value

Fig. I. Change in fatty acid composition and trans isomer level Fig. 2. Change in fatty acid composition and trans isomer level
during hydrogenation of palm oil. during hydrogenation of palm olein.

244 / Yap et al. J. Inst. Can. Sci. Technol. Aliment. Vol. 22. No. 3, 1989
 100
75
90
&5 80 23.5
X

...., 70 27.0
~ii c
.360
c0
~ u 50- 32.0
'0 ~ .,
.>
0-
0> "- ~O 36.6
c "0
'0. ~
0-
0
'030
V1
<-
Cl 20 41.4
25 8
10

15 7
O+--,--,--,--,----,r---r---r---y---r----j
Iodine value TemperatUl"'e i cc:
Fig. 3. Change in dropping point during hydrogenation of palm oil Fig. 4. Change in solid fat content during hydrogenation of palm oil
(A) and palm olein (B). (numbers on curves indicate iodine values).

followed a similar pattern as in the hydrogenation of
palm olein but the maximum trans isomer of 19070
occurred at an iodine value of 27.
Changes in C16 and C18 fatty acids during the
hydrogenation of palm oil and palm olein are shown
graphically in Figures 1 and 2. For both oils, 18:2 was
reduced to zero at an iodine value of about 40-42.
There was a slight increase in the level of 18: I up to this
iodine value in the palm oil but not in the palm olein.
The dropping points of palm oil and palm olein at
various iodine values are shown in Figure 3. The drop-
ping point of hydrogenated palm olein increased at a
much faster rate than that of palm oil during the first
15 min. The subsequent increase was comparable to
that of palm oil. The solid fat content of palm oil
(Figure 4) increased progressively as hydrogenation
time increased. In hydrogenated palm olein, there was
;:~ ~~1~95
a sudden increase in solid fat content during the first
45 min of the hydrogenation (Figure 5).
The performance of a fat product depends very
much on its melting profile. This can be followed by
differential scanning calorimetry (DSC). The tempera-
ture of the major melting peak indicates where the
major phase transformation of solid to liquid takes
place and this temperature is a useful indicator of the
changes in physical properties of hydrogenated fats.
Figures 6 and 7 show the DSC thermograms of
hydrogenated palm oil and palm olein at various stages
of hydrogenation. The DSC curves indicate the
progressive formation of higher melting triglycerides
during the hydrogenation which complements the data
on fatty acid composition of the hydrogenated oils as
shown in Figures 1 and 2. The thermogram of un-
hydrogenated palm oil shows two broad melting zones.
The fat first melted at 8°C to 11°C and then showed
another peak at about 30°e. The broad melting peaks
show that the oil has a wide melting range. As the
degree of hydrogenation increased, the two peaks be-
came narrower and the maximum melting tempera-
tures gradually increased (Figures 3 and 6).

?-C
~ ~21.6 The melting behaviour of hydrogenated palm olein
shows melting profiles (Figure 7) similar to those of
31.0
l-{
hydrogenated palm oil. The unhydrogenated palm
...., 70 olein shows melting peaks at 9.0°C and 13 .O°e. At low
c
,360 iodine values, a sharp peak was formed at a much
c0
50 higher temperature, around 60°C (Figure 7 and Table
...,.,u 4) indicating the formation of triglycerides with a nar-
"-40
'tJ
40.7 row melting range.
::30 57.0
The olein was hydrogenated to lower iodine values
Jl than palm oil. Hydrogenation to low iodine values is
20
difficult because of the high crystallization tempera-
10 tures of the fat which clogs the tubing in the
hydrogenation apparatus. At an iodine value of 6, the
melting range of olein was very narrow (Figure 7). All
Temperature/QC DSC thermograms exhibited an exothermic peak that
Fig. 5. Change in solid fat content during hydrogenation of palm olein appeared above the baseline (Figures 6 and 7, Tables 3
(numbers on curves indicate iodine values). and 4). Since the fat was rapidly cooled to -30°C,

Can. Insl. Food Sci. Technol. J. Vo!. 22, No. J, 1989 Yap et al. / 245
 D.:..-
57.0
ISO
52.5
33.:1
40.7
A
A I
I 41.4 I
I I
I I
I 40.0 31.0
200 0
0
le X
f:iI 36.6 fz1

:c<l :t
<l
21.6

32,0
0 0

"c
f:iI
'tl
r::
fzl 12.5
I
27.0
,
I
I
I
I
I
v I
v
~ 6.9
23.5

Q
Fig. 6. DSC heating curves (5 C/min) of palm oil at various stages Fig. 7. DSC heating curves (5°C/min) of palm olein at various stages
of hydrogenation. of hydrogenation.

crystallization most likely took place in the Cl! polymor-
phic form. Upon heating, phase transformation to the
{3' form resulted in an exothermic peak. The tempera-
tures of the last melting peak of the DSC thermogram
were, on the average, 4°C higher than those of the
dropping points (Figure 3) which also confirms earlier
findings (deMan et ai, 1989). The difference is caused
by the different heating rates in the determinations:
l°C/min in the dropping point determination and
5°C/min in the DSC analysis.
Linear regression analysis of the solid fat content at
lOoC and the .:iH of the melting peak that followed the
exothermic peaks (Tables 3 and 4) resulted in correla-
tion coefficients of 0.971 in the case of the palm oils
and 0.958 in the case of the palm oleins confirming that
.:iH is also a measure of solid fat content. The .:iH of

Table 3. DSC peak temperatures (QC) and 6H of hydrogenated palm oil at different iodine values (IV).
Endo Exo
Product
IV Peak 6H Peak 6H Peak 6H Peak 6H
Jig temp. Jig temp. Jig temp. Jig temp. Jig
QC QC QC QC
52.5 8.0 42.3 11.0 6.7 33.5 35.7 18.0 4.8
41.4 13.0 45.4 40.0 60.6 21.5 6.8
36.6 12.5 25.5 47.8 80.0 20.0 7.8
32.0 15.5 18.3 55.0 89.7 24.0 8.8
27.0 19.0 11.6 59.5 96.3 25.5 8.2
23.5 22.6 8.8 59.5 115.1 25.5 8.9

246 / Yap et al. J. InSI. Can. Sei. Teelino!. Alimenl. Vol. 22. No. 3, 1989
Table 4. DSC peak temperatures (0C) and L,H of hydrogenated References
palm olein at different iodine values (IV).
Berger, K. 1986. Palm oil products - Why and how to use them. Food
Endo Exo Technol. 40(9):72.
Product Deffense, E. 1985. Fractionation of palm oil. J. Am. Oil Chem. Soc.
IV Peak L,H Peak L,H Peak L,H
62:376.
temp. Jig temp. Jig temp. Jig DeMan, L., deMan, J .M. and Blackman, B. 1989. Physical and
°C °C °C
textural evaluation of some shortenings and margarines.
57.0 9.0 37.9 13.0 33.2 J. Am. Oil Chem. Soc. 66:128.
40.7 12.5 12.5 44.0 80.3 20.5 10.6 Mertens, W,G, and deMan, J .M. 1972. Automatic melting point
31.0 18.5 6.9 57.0 111.9 27.0 9.5 determination of fat. J. Am. Oil Chem. Soc. 49:365.
21.6 22.5 1.5 60.0 156.7 32.0 6.2 Official and Tentative Methods of the American Oil Chemists'
12.5 48.5 6.1 61.5 166.1 50.5 4.1 Society. R.O. Walker. Am. Oil Chem. Soc., Champaign
6.9 52.0 8.7 63.0 172.7 54.0 8.3 IL 61821-0489.
Podmore, J. 1987. In: Recent Advances in Chemistry and Technol-
ogy of Fats and Oils. Elsevier Applied Science, R.J.
Hamilton and A. Bhati (Eds.).
Shehata, A.A.Y. and DeMan, J.M. 1970. A simple and rapid
method for the preparation of methyl esters of fats in
milligram amounts for gas chromatography. Can. Inst.
the original palm olein was excluded as the melting Food Sci. Technol. J. 3:85.
Ward, 1. 1988. Processing Canola oil products. J. Am. Oil Chem.
temperature of this peak (l3.0°C) was too low to be Soc. 65:1731.
compared with the solid fat content at 10°C. Compar- Weinberg, B. 1972. Processing of low erucic rapeseed and canbra
ing the thermograms of palm oil with those of palm oil. Can.lnst. Food Sci. Technol. J. 5:A57.
olein of approximately the same iodine values shows Yap, P.H, 1988. Polymorphism of palm oil and the effect of addi-
tion of palm oil on the polymorphic properties of
similar melting behaviour but peak temperatures are hydrogenated canola oil. M.Sc. Thesis. University of
higher with palm olein. The reason is that palm olein Guelph.
contains more 18 carbon fatty acids which have higher
melting points (Table 1).
Thermograms are useful indictors of phase transi-
tion, melting temperatures and melting ranges.
The data presented in this paper may be useful as a
guide in the preparation of margarine and shortening
Submitted August 30, 1988
where palm oil products are used to increase polymor- Revised January 16, 1989
phic stability. Accepted January 17,1989

Can. Inst. Food Sci. Technol. J. Vol. 22, No. 3, 1989 Yap et al. / 247