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Industrial Scale Production of Palm Super Olein Using Modified and Innovative Dry Fractionation Technique

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Industrial Scale Production of Palm Super Olein using Modified and Innovative
Dry Fractionation Technique

Article · January 2018


DOI: 10.21608/ejchem.2018.2293.1186

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1 Egypt.J.Chem. Vol. 61, No.1, pp. 1 - 11 (2018)

Industrial Scale Production of Palm Super Olein Using Modified


and Innovative Dry Fractionation Technique
Hanafy A. Hashem1, Nasser E.Abd- Ellh1, Ghareeb A. Abd-Eltawab2 and Adel
G. Abdel-Razek*3
1
Department of Food Science and Technology, Faculty of Agric., Al-Azhar University, Cairo, Egypt.
2
Ajwa for Food Industries Company -Attaka- Suez- Egypt.
3
Department of Fats and Oils, National Research Centre, Dokki 12622, Cairo, Egypt.

P ALM oil is vastly utilized in food processing, principally attributed to the physical and
chemical characteristics that make it especially suitable for many food applications. The
present work aimed to make attempts at finding a method for producing a novel palm super
olein (PSO) through a new modified industrial application process. Pure and modified palm
olein (palm olein + 5% palm oil) with an iodine value of 56.5 and 56.4 respectively were
crystallized with a controlled cooling system and convenient stirring process. The slurry was
then fractionated by dry fractionation either by conventional method at 17⁰C or by innovative
method at 16.6°C. By varying the fractionation conditions used, a range of super olein and palm-
mid fractions with different chemical and physical properties could be obtained. The Rancimat
method was utilized to determine the oxidative stability of various palm oil fractions. Also, the
physical and the chemical parameters of the different fractions were evaluated, whereas fatty
acid composition was determined by GLC. The obtained PSO by fractionation using modified
olein at 16.6 ⁰C gave PSO with MP 9⁰C and also enhanced the cloud point, melting point and
iodine value. It is recommended that the modified and innovative dry fractionation process,
performed in large-scale, can be taken as a model for improving palm oil fractionation.

Keywords: Palm olein, palm super olein, Innovative dry fractionation, Palm-mid fractions,
Oxidative stability.

Introduction with high melting point free from trans fatty


acids[5].
The fractionation of vegetable oils is one of the
main modification procedures used by the industry Fractionation on the production level can be
to give it the necessary elasticity for the proper use categorized into three classes, dry, detergent, and
of palm oil and its fractions in the numerous fatty- solvent fractionation, based on the proceeding
foods[1]. The fractionation technique is the major and crystallization methods. These techniques
modern modification method utilized especially have been utilized in manufacturing cooking and
for palm oil separation[2, 3]. It is worthy to frying oils from palm oil, namely olein and super
mention that, palm oil production is still increasing olein were evaluated by many authors[6,7]. Dry
rapidly in recent years and turn into the world’s fractionation is a simple physical separation method
most-produced and consumed oil[4]. In edible which fulfils recent growing environmental and
oil manufacturing, fractionation method depends health interests. Dry fractionation technology has
on cooling of palm oil under control system, shown good progress due to modern improvements
thereby induces a fractional crystallization. The in melt crystallization and application of
liquid form (olein) is subsequently isolated from membrane filter press[8]. At the same time, the dry
the solid form (stearin) using a filtration system. fractionation is an economical and safe technology.
Palm stearin, rich in solid fat content, is suitable The cloud formation in palm olein products during
as a component of the specialty fats important in transportation as well as storage in cold weather
a bakery, confectionery, and pastries products. is an important issue. So, the turbidity is formed
Fractionation is thus set to fit the predominant due to crystallization of palm olein during winter
modification method to produce saturated fats weather[9].

*Corresponding author e-mail: [email protected]


DOI: 10.21608/EJCHEM.2018.2293.1186
©2017 National Information and Documentation Center (NIDOC)
2
HANAFY A. HASHEM et al.

Actually, there is nothing improper regarding of dry fractionation by using two new modified
the oil quality, but it is important to prohibit methods different from the conventional one.
crystallization because consumers consider that Also, it was planned to try achieving extraordinary
turbidity of an oil is a kind of adulteration. The physical and chemical characteristics of PSO.
crystals appear in palm olein at lower temperatures Furthermore, it was a target to prevent cloud
are mainly due to diglycerides content. The forming as far as possible to ameliorate PSO and
clouding problem in palm olein has been solved its mixtures to make it more appropriate for cold
to a certain extent by blending it with soft oils or weather.
adding additives or using a double fractionation
method [9]. Thus, it was necessary to search for Materials and Methods
methods to improve palm olein fractionation Materials
to achieve sufficient removal of high-melting- All samples, refined, bleached and deodorized
point components. The functionality of palm (RBD) palm olein (POL), MP 23ºC and IV 56, as
super olein to achieve specialty oils reveal a well as RBD palm oil (PO) with MP 37ºC and IV
market for new high-quality productivity like 52, used in the present study were kindly obtained
fractionated products. Recently, the industrial from Ajwaa Factory for Food Industries, Attaka,
edible oil sector has turned into a significant Suez, Egypt. Also, all experiments and processing
field for a technological R&D. Furthermore, trials were carried out in a plant of 176 ton capacity,
optimization of the crystallization situations for in the same factory. This factory is interested in
an utmost retention of natural characteristics edible oil processing and palm oil fractionation.
without affecting the quality of the palm oil is a All solvents of HPLC grade, from Sigma–Aldrich
serious challenge. Therefore, the topic which will (St. Louis, MO, USA). FAME standards was
be discussed in this study is strongly related and purchased from Supelco (Bellefonte, PA, USA).
useful to the edible fats and oils production sector.
It is well known that the fractionation conditions Methods
can be modified for the production of a demand Experimental treatments
specific fraction for a special application[10, 11]. The industrial-scale experiments in
It was objective to carry out the industrial scale crystallization process were carried out in four
trials as shown in Fig. 1.

Fig. 1. Flow chart of palm olein fractionation of LF (SPO) and SF (PMF) produced by modified and conventional
fractionation methods.
Egypt.J.Chem. 61, No.1 (2018)
3
INDUSTRIAL SCALE PRODUCTION OF PALM SUPER OLEIN USING

P S O: palm super olein P M F: palm mid fraction temperature at 16.6°C (Exp. II). In addition,
LF: Liquid fraction SF: Solid fraction in Exp. III and Exp. IV, 5% PO was added to
POL as trials to enhance the seeding during the
Dry fractionation of palm olein
crystallization process. The products, namely,
A fractionation plant (Tirtiaux unit, Belgium) PSOs (PSO1, 2, 3 & 4 liquid fractions) and palm–
include 4 crystallizers with a capacity of 44 mid fractions (PMF1, 2, 3 & 4 solid fractions)
ton each in which the RBD POL was charged, were obtained (Fig. 1).
stirred and kept at the required temperature. The
crystallizers were provided with agitators, cooling Conventional method (heating at 55°C) while
modified method (heating at 45°C and with
serpentines and double cooling wall.
addition of 5% palm oil) were adopted. In both
Dry fractionation (without any solvent), methods the heating was carried out for one hour.
applied to PO, involving the fractional After that the oil was cooled to 17°C and 16.6°C
crystallization of a solid phase and its separation under controlled conditions with cold water for
from the liquid phase. Thus POL was fractionated about 24 hours for conventional and modified
methods respectively. The filtration was followed
by conventional method at 17⁰C (Exp. I). This dry
after 4 h using a batch belt filter. The cooling
fractionation method was compared to modified
process of oil was controlled by a circulating unit
method (adopted in this work) using fractionation and general control unit as illustrated in Fig.2.

Fig. 2. Modified and traditional cooling curve of palm olein.

Egypt.J.Chem. 61 , No.1 (2018)


4
HANAFY A. HASHEM et al.

Analytical methods of PO under control system, thereby induce a


Determination of physical properties fractional crystallization. The liquid part (olein) is
Color (C), density (D), refractive index (RI), thereafter separated from the solid part (stearin)
melting point (MP) via slip point method, cloud by the filtration system. In the present work,
point (CP) and cold test (CT) of the investigated the innovative developed method (on industrial
oil samples were determined according to AOCS large-scale) was done, as a trial, to improve the
(2000) [12]. technology of crystallization and dry fractionation
of POL.
Determination of chemical properties of palm
olein and its fractions Physical properties of POL and its fractions
Free fatty acids % (FFA %) as oleic acid, The major physical properties of original POL
peroxide value (PV meq O2/kg oil) and iodine and its fractions obtained at 17°C (PSO1& PMF1)
value (IV) of the studied oil samples were and modified fraction at 16.6°C; (PSO2, PMF2).
determined according to the methods described Another new modified was blend between POL +
by AOCS (2000) [12]. 5% PO and its fractions at 17°C (PSO3, PMF3)
and at 16.6°C (PSO4, PMF4) were shown in
Oxidative stability Table 1. Concerning the yields ratio of PSO:
The induction period (IP) measurements were PMF, the values 71.08: 28.92 in (fractionation 1),
carried out on the investigated oil samples. IP 65.81: 34.19 in (fractionation 2), 69.90: 30.10 in
indicates the oil resistance to oxidative rancidity, (fractionation 3) and 60.73: 39.27 in fractionation
and then the shelf life of the oil can be estimated. 4 were obtained (Table 1).
The IP, as oxidative stability index, of the tested
oils were measured by an automated Rancimat From the results in Table 1 it could be
(MetrohmUd. CH- 9100 Herisau, Switzerland, noticed that the yields of PSO as liquid fractions
model 679) at 100°C, comprises of the control (LF) were higher than that of PMF as a solid
unit and the wet section containing six reaction fraction (SF). This might be attributed to the
vessels, according to the method described by major unsaturated fatty acid components in
AOCS, 1997 [13]. POL. Meanwhile, the fractionation at high
temperature leads to formation of fewer crystals,
Gas chromatographic analysis of the fatty hence reducing the amount of PMF. However, by
acids decreasing the fractionation temperatures from
Fatty acids methyl esters  (FAME) were 17 to 16.6 °C and in presence of 5% PO, the
prepared according to AOCS official method yields of PSO were decreased while PMF yields
and assessed by GC [14]. Diluted FAME were were increased. These results agree with that
separated on a HP 5890 series II (Hewlett recorded by Calliauw et al., and Ablatip et al.,
Packard, Palo Alto, USA) equipped with an [15,16] they found that the SF yield is strongly
innowax capillary column (30 m_0.20 mm_0.20 dependent on crystallization temperature, as
mm) and FID (FID). Hydrogen was used as the crystallization temperature increased, the SF
carrier gas at flow rate of 1.5 ml min–1. The yield decreased and vice versa.
column temperature was isotherm (210°C).
Detector and injector temperatures were set at Similar to pure POL (3.7R /Y) (Table 1). The
240°C. Fatty acids were identified by comparison color value of PSO samples obtained by different
of the retention times with authentic standards dry fractionation methods showed a small
and the results were calculated as percentage of variation, amounting to 3.8 in PSO1, PSO3; 4.1
total fatty acids. and 4.4 in PSO2 and PSO4, respectively. Also,
it was found that a relatively small variation in
Statistical analysis color of PMF1, PMF2, PMF3 and PMF4 (3.1,
The results were expressed as the mean±SE. 3.2, 3.1 and 3.4 respectively). These results are in
Results were analyzed statistically using the one- harmony with those of Kellens et al., [17] as they
way analysis of variance ANOVA followed by reported that the pigment concentrated in LF.
Duncan’s test. In all cases p<0.05 was used as the
criterion of statistical significance. The density results of the modified and
traditional samples were recorded in Table 1. It
Results and Discussion was found that the density of pure POL compared
A fractionation method depends on cooling to the modified one (with 5% PO) were 0.9098
and 0.9064 respectively. The densities of modified
Egypt.J.Chem. 61, No.1 (2018)
5
INDUSTRIAL SCALE PRODUCTION OF PALM SUPER OLEIN USING

treated sample amounted to 0.9133 and 0.8998 treatment, it decreased to 4°C (PSO4). These
which are higher than that of the conventional results are in agreement with those found by Zaliha
treatment (0.9121 and 0.8996) in LF and SF et al., [19], who reported that lower crystallization
respectively. Concerning the modified blends, temperatures, lead to lower cloud points of the
it was noticed that the densities of modified fractions. Also, Deffense[20] reported that the
treatment PSO4 and PMF4 were slightly higher main objective of fractionation is to obtain POL
than that of the conventional treatment. Generally with low cloud point to be suitable as a cooking oil.
it was noticed that the densities of LF`s were Concerning the cold test, it gave positive results in
higher than that of SF`s amounted to 0.9121, both conventional and modified treatments.
0.9133, 0.9125 and 0.9151 in PSO1, PSO2 PSO3
and PSO4, respectively, in comparison to 0.8996, The results of FFA, PV, IV& IP of modified
0.8998, 0.8997 and 0.9031 for PMF1, PMF2, and conventional POL fractionation methods
PMF3 and PMF4, respectively. were shown in Table 2.

Concerning refractive index, no clear The results of FFA %, show nearly no


difference was observed in the investigated oil significant variations in original, conventional
samples. It was ranged from 1.4554 to 1.4598 and modified samples. Concerning, the PV of the
(Table 1). It was noticed that the MP of PSO2 & original, conventional and modified samples (LF
PMF2 (11 & 32) lower than that in PSO1 & PMF1 & SF), it ranged from 3.33 to 3.80 meq O2/kg.
(13°C & 36°C). From Table 1 it can be observed From the results recorded in Table 2, it
that the melting point of different fractions (PSO was found that the increase in the amount of
and PMF) was dependent on crystallization unsaturation character (expressed as IV) at
temperatures. While the addition of PO to POL modified temperature was noticed and amounted
without decrease of crystallization temperatures to 61.6 for PSO2 and 45.2 for PMF2 than that of
has no significant effect on melting point of PSO3 the original (56.5) and PSO1 60.8 & PMF1, 43.9.
comparing to PSO1 as well as PMF3 comparing In another case of modified treatment, the addition
to PMF1 fraction. The addition of PO to POL at of 5% PO at crystallization temp. (16.6⁰C) leads
modified of crystallization temperature (16.6⁰C) to increase in IV reached to 61.0 for PSO3 and
improved separation efficiency and lead to a 64.8 for PSO4 at 16.6⁰C and 17⁰C respectively.
decrease of PSO and PMF melting points. This In modified SF (PMF4), IV amounted to 47.0 in
may be due to the presence of high melting point comparison to 44.1 in conventional PMF3. The
saturated triglycerides (present in the added PO), increase in IV of PSO fractions due to the increase
which helps nucleation and crystallization rates. of MUFA and PUFA groups. These results are
Whereas lowering the crystallization temperature in agreement with those found by Zaliha et al.,
to 16.6⁰C helps crystals to grow. These results [19] as they reported that, the iodine values
are in harmony with the finding of Omar et al., of liquid fractions increased as crystallization
[8] who reported that the addition of specific temperatures decreased. Dang et al., [21] reported
fatty materials to palm oil at different ratios that the crystallization temperature has a great
improved the nucleation and crystallization rates. function in the operation of oil crystallization.
While Arnaud Collignan[18] studied the effect of The crystallization process under various cooling
temperature on the characteristics of animal fat conditions lead to increase in cooling rate and
fractionation. decrease in particle size, which display that
Cloud point is a test to determine the temperature the cooling rate plays an influential role in the
at which the oil begins to cloud resulting from efficiency of nucleation.
crystallization under controlled cooling condition. It is worthy to mention that the addition of palm
It was found that there was a significant variation oil to palm olein (modified palm olein) at 17°C
in the value of cloud point of PSO fractions (without decrease of crystallization temperature)
obtained by dry fractionation methods (Table 1). has no significant effect on the CP, MP and IV of
The modified crystallization temperature leads PSO fraction. Also, a clear good relation between
to decrease in cloud point of both PSO fractions IV and CP of the oil fraction at the different
from 6.5 °C (PSO1) to 5.5°C (PSO2), in LF. The crystallization temperatures appeared. Thus,
addition of 5% PO to POL in classical fractionation super palm olein samples with high IV had low
temperature, the PSO3 fraction (LF) had the high cloud points, in comparison to SPO samples with
cloud point (6.5°C) comparing to the modified low IV had high CP. In addition, fractionation of
Egypt.J.Chem. 61 , No.1 (2018)
6
HANAFY A. HASHEM et al.

POL is closely associated with its chemical and samples showed high oxidative stability but
physical properties. almost similar for LF (38.3 inPSO1, PSO2, PSO3
and 38.1 in PSO4).These results are in accordance
Oxidative stability of investigated palm olein and with that reported by many authors [6,7,22] they
its fractions reported that the long induction period of POL
The induction period (IP) measured at 100°C is comparable with that of other vegetable oils
was carried out on the oil fractions in order to (sunflower-soybean and rapeseed), owing to
provide a quick indication of the trends of the their inherent composition and to the presence of
heated samples towards resistance to oxidation. vitamin E (tocopherols and tocotrienols) in PO
From the data recorded in Table 2, it was noticed which have a natural antioxidants efficiency. In
that the IP in the Rancimat test of super olein

TABLE 1. Physical properties of LF`s (SPO) and SF`s (PMF) produced by modified and conventional fractionation
methods.

Original Modified Blend


Original POL
POL (POL+5% PO) Modified
Characteristics
(Zero 1 2 3 4 Blend
time) (17⁰C) (16.6⁰C) (17⁰C) (16.6⁰C) (Zero time)
71.08a 65.81d 69.90b 60.73c
PSO
±0.34 ±0.48 ±0.52 ±0.14
Yield (%) - -
28.92d 34.19b 30.10c 39.27a
PMF
±0.32 ±0.51 ±0.49 ±0.17
3.8c 4.1b 3.8c 4.4a
PSO
3.7c ±0.055 ±0.11 ±0.071 ±0.084 3.7a
Color (R/Y)
±0.055 3.1 c
3.2 c
3.1 c
3.4 b ±0.055
PMF
±0.11 ±0.55 ±0.55 ±0.11
0.9121ab 0.9133a 0.9125a 0.9151a
PSO
0.9098 b ±0.0002 ±0.0002 ±0.0012 ±0.006 0.9064a
Density (g/ml)
±0.0003 0.8996 c
0.8998 c
0.8997 c
0.9031 b ±0.0003
PMF
±0.0002 ±0.0002 ±0.0001 ±0.0001
1.4591c 1.4595c 1.4593c 1.4598b
PSO
Refractive 1.4585 a ±0.0001 ±0.0002 ±0.0002 ±0.0002 1.4581a
index ±0.0002 1.4554 c
1.4556 c
1.4554 c
1.4559 b ±0.0002
PMF
±0.0002 ±0.0002 ±0.0002 ±0.0002
13b 11c 13b 9.0d
PSO
Melting point 23 a ±0.33 ±0.13 ±0.32 ±0.36 24a
(°C) ±0.26 36 b
32 c
37 d
29 e ±0.26
PMF
±0.32 ±0.41 ±0.5 ±0.15
6.5b 5.5c 6.5b 4.0d
PSO
Cloud point 11.5a ±0.071 ±0.011 ±0.005 ±0.004 12 a
(°C) ±0.16 ±0.16
PMF - - - -

PSO +ve +ve +ve +ve


Cold test +ve +ve
PMF +ve +ve +ve +ve

The values are represented as means ±SD


The values with the same letters are non-significant at p≤5
1: Conventional fractionation of pure palm olein
2: Enhanced fractionation of pure palm olein
3: Conventional fractionation of modified palm olein
4: Innovative fractionation of modified palm olein
POL: palm olein PO: palm oil P S O: palm super olein P M F: palm mid fraction
LF: Liquid fraction SF: Solid fraction +ve: positive

Egypt.J.Chem. 61, No.1 (2018)


7
INDUSTRIAL SCALE PRODUCTION OF PALM SUPER OLEIN USING

TABLE 2. Chemical properties of LF (SPO) and SF (PMF) produced by modified and conventional fractionation
methods.

Modified Blend
Original Original POL
(POL+5% PO)
Characteristics POL 1 2 3 4 Modified
(Zero time) (17⁰C) (16.6⁰C) (17⁰C) (16.6⁰C) Blend
0.17ab 0.17b 0.17b 0.18a
PSO
Free fatty acid 0.15 c ±0.0071 ±0.011 ±0.0055 ±0.0044 0.15a
(%) ±0.0071 0.13 b
0.13 b
0.13 b
0.13 b ±0.007
PMF
±0.011 ±0.011 ±0.007 ±0.007
3.6d 3.62c 3.61b 3.80a
PSO
Peroxide value 3.4 c ±0.019 ±0.017 ±0.023 ±0.016 3.51a
(meqo2/kg) ±0.029 3.33 c
3.36 ab
3.34 bc
3.39 a ±0.03
PMF
±0.02 ±0.05 ±0.015 ±0.015
60.8d 61.6b 61.0c 64.8a
PSO
56.5 e ±0.055 ±0.055 ±0.033 ±0.055 56.4a
Iodine value
±0.054 43.9e 45.2c 44.1d 47e ±0.055
PMF
±0.084 ±0.18 ±0.15 ±0.1
38.3b 38.3b 38.3ab 38.1c
Induction period PSO 38.5a 38.6d
±0.044 ±0.084 ±0.11 ±0.055
at 100°C by ±0.089 ±0.089
Rancimat (h) PMF - - - -
The values are represented as means ±SD
The values with the same letters are non-significant at p≤5
1: Conventional fractionation of pure palm olein
2: Enhanced fractionation of pure palm olein
3: Conventional fractionation of modified palm olein
4: Innovative fractionation of modified palm olein
POL: palm olein PO: palm oil P S O: palm super olein P M F: palm mid fraction
LF: Liquid fraction SF: Solid fraction

addition, the ratio between unsaturated: saturated it was found that significant decreasein all
fatty acids was (1:1) as mentioned by Teah[23]. solid fractions namely PMF1, PMF2, PMF3
and PMF4(modified and conventional method).
Fatty acid profiles of palm olein and its fractions Whereas, when the addition of 5% PO to POL,
Fatty acid compositions of original and no significant change in the linolenic (18:3)
modified POL fractions compared to conventional content.
method are shown in Table 3. The most predominate
FA`s in original POL were oleic (42.24) and The proportions of SFA, USFA, and PUFA for
palmitic (39.6). In modified fractionation (temp. PSO show variations in their amounts. It was also
16.6⁰C), it was found that palmiticacid is 41.29 found that in solid fraction (PMF1, PMF2, PMF3
PMF2compared to 41.24 PMF1 whereas, it and PMF4), showed increasing in the SFA and
decreased in LF; POS1 and PSO2.Concerning decreasing in MUSFA in both samples prepared
oleic acid it was increased in modified fractionation by conventional and modified methods (Table 3).
(16.6⁰C) amounted to 47.63 in PSO2 compared to Whereas SFA decreased and MUSFA increased
the 47.2 in PSO1 (conventional method). In another in liquid fractions, namely PSO1, PSO2, PSO3 &
way of modification applied with an addition of 5% PSO4.
PO , lead to decreasing in palmitic acid in LF from The Proportion of PUFA increased in modified
39.62 (modified POL) to 33.11 & 32.64 in PSO3 temperature treated samples in comparison
& PSO4 and increasing in oleic acid from 42.21 to to those prepared by conventional method in
47.27 & 48.19 respectively. LF, whereas no significant changes in case of
In the solid fraction, palmitic acid increased solid fractions. When adding 5% PO, the PUFA
and oleic acid decreased in PMF3 & PMF4. increase in PSO3 & PSO4, whereas a decrease in
Concerning the amount of linoleic acid (18:2), PMF3 & PMF4 is obtained.

Egypt.J.Chem. 61 , No.1 (2018)


8
HANAFY A. HASHEM et al.

TABLE 3. Fatty acids composition of LF (SPO) and SF (PMF) produced by modified and conventional
fractionation methods.

Modified Blend Modified


Original Original POL
(POL+5% PO) Blend
Characteristics POL
1 2 3 4 (Zero
(Zero time)
(17⁰C) (16.6⁰C) (17⁰C) (16.6⁰C) time)
0.41c 0.38d 0.40b 0.30e
PSO
Lauric acid 0.44a ±0.0071 ±0.011 ±0.009 ±0.014 0.44b
C 12:0 ±0.0071 0.46a 0.46a 0.46a 0.45ab ±0.007
PMF
±0.009 ±0.011 ±0.008 ±0.005
1.30b 1.24d 1.28c 1.05e
PSO
Myristic acid 1.33a ±0.011 ±0.013 ±0.002 ±0.013 1.34ab
C 14:0 ±0.011 1.33a 1.33ab 1.32b 1.32b ±0.011
PMF
±0.008 ±0.004 ±0.004 ±0.007
33.20b 32.95d 33.11c 32.64e
PSO
palmitic acid 39.60a ±0.011 ±0.013 ±0.009 ±0.071 39.62e
C 16:0 ±0.011 41.42a 41.29c 41.39b 41.21d ±0.011
PMF
±0.008 ±0.013 ±0.005 ±0.013
3.42b 3.24d 3.40c 2.95e
PSO
Stearic acid 4.47a ±0.012 ±0.018 ±0.002 ±0.009 4.49e
C 18:0 ±0.011 5.66a 5.54c 5.64b 5.41d ±0.011
PMF
±0.004 ±0.005 ±0.016 ±0.005
47.20d 47.63b 47.27c 48.19a
PSO
Oleic acid 42.24e ±0.04 ±0.016 ±0.013 ±0.021 42.21a
C 18:1 ±0.011 39.55e 39.76c 39.59d 39.84b ±0.011
PMF
±0.004 ±0.004 ±0.011 ±0.008
13.80d 14.15b 13.87c 14.54a
PSO
Linoleic acid 11.22e ±0.023 ±0.009 ±0.009 ±0.014 11.20a
C 18:2 ±0.011 10.90a 10.95c 10.92d 11.10b ±0.011
PMF
±0.015 ±0.011 ±0.008 ±0.011
0.21b 0.23b 0.21b 0.25a
PSO
Linolenic acid 0.22b ±0.008 ±0.011 ±0.008 ±0.015 0.22a
C 18:3 ±0.011 0.20a 0.20a 0.20a 0.20a ±0.01
PMF
±0.008 ±0.008 ±0.005 ±0.005
0.46b 0.18c 0.46b 0.08d
PSO
Arachidic acid 0.48a ±0.005 ±0.008 ±0.009 ±0.008 0.48a
C 20:0 ±0.008 0.48a 0.47a 0.48a 0.47a ±0.008
PMF
±0.005 ±0.004 ±0.005 ±0.004
PSO 38.79 37.99 38.65 37.02
Saturated fatty acids 46.32 46.37
PMF 49.35 49.09 49.29 48.86
Unsaturated fatty PSO 61.21 62.01 61.35 62.98
53.68 53.63
acids PMF 50.65 50.91 50.71 51.14
PSO 47.20 47.63 47.27 48.19
MUSFA 42.24 42.21
PMF 39.55 39.76 39.59 39.84
PSO 14.01 14.38 14.08 14.79
PUSFA 11.44 11.42
PMF 11.10 11.15 11.12 11.30
PSO 0.63 0.61 0.63 0.59
SFA/USFA 0.86 0.86
PMF 0.97 0.96 0.97 0.96
PSO 3.37 3.31 3.36 3.26
MUSFA/PUSFA 3.69 3.70
PMF 3.56 3.57 3.56 3.53
PSO 0.36 0.38 0.36 0.40
PUSFA/SFA 0.25 0.25
PMF 0.22 0.23 0.23 0.23

Egypt.J.Chem. 61, No.1 (2018)


9
INDUSTRIAL SCALE PRODUCTION OF PALM SUPER OLEIN USING

Table 3 shows the GLC analysis of fatty Fractionation by the traditional method at
acids of palm olein, palm super olein and palm 17°C resulted in the highest super palm olein
mid fractions obtained by dry fractionation yield but with low oleic acid content. While DF
technique. From Table 3, it was noticed that the at relatively lower crystallization temperature
fatty acid composition of the modified POL and (16.6°C) showed a considerable effect on the fatty
pure POL samples were found to be nearly the acid composition of liquid fractions as well as
same. Regarding to the liquid fractions (PSO), IV, MP and CT in comparison with that at higher
the major constituent unsaturated fatty acid crystallization temperature (17°C).
(USFA) was oleic followed by linoleic acids.
Whereas, linolenic acid was present in minor Conclusion
quantities in the four liquid fractions (Table 3). Contributing to the sustainable development
Concerning the SFA in the LF`s, palmitic acid was of palm oil industry via identifying and
the major constituent followed by stearic acid, addressing some hot spots. The dry fractionation
whereas, lauric, myristic and arachidic acids are technology (simplest and cheapest process) starts
the minor constituents. new possibilities of applications by reducing
On the other hand, SFA of PMF(PMF1, PMF2, crystallization temperature (modified treatment
PMF3 and PMF4 obtained by dry fractionation 16.6°C) and innovative method by adding 5% PO
of palm olein) were calculated (Table 3). Thus, for improving the seeding process (16.6°C).These
Lauric and myristic acids were present in similar industrial modifications revealed that the physical
minor quantities in both PMF1 and PMF2 and chemical properties of the palm olein fractions
(0.46%, 1.33%) whereas they were 0.46%, 1.32 have positive effects. So, the production of PSO
% in PMF3 and 0.45, 1.32% in PMF4. While with IV of more than 62 with good oxidative
palmitic and stearic acids were detected in PMF1 stability, cold stability and low cloud point
amounted to 41.42 %, 5.66%; in PMF2 41.29 %, would require a proper cooling profile and good
5.54% and 41.39 %, 5.64 % 41.21%, 5.41% in separation. The obtained PSO by fractionation
PMF3 and PMF4 respectively. From Table 3 it using modified olein (95% palm olein & 5%
can be seen that no variation in levels of arachidic palm oil) at 16.6 °C gave PSO with MP 9°C and
acid (C20:0) in the four samples. also enhanced the cloud point; melting point and
iodine value.
Regarding unsaturated fatty acids (USFA),
namely, oleic, linoleic and linolenic acids, it It is recommended that the modified and
is clear that oleic acid was the most prevalent innovative dry fractionation process performed in
unsaturated fatty acid in all samples. Linoleic large-scale, can be taken as a model for improving
acid was the second major unsaturated fatty palm oil fractionation.
acid which presents in all PMF in similar Acknowledgment
amounts. Whereas, linolenic acid was detected
in similar minute amounts in all PMF samples The authors would like to thank Ajwaa
(0.2 %). These results are in harmony with Company for Food Industries, Attaka, Suez,
those of JiePeng et al., [24], as they reported Egypt for their kind cooperation.
that low temperature brings the directional References
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the separating efficiency and purity of the 1. Dijkstra A. J., Chapter 12; Fractionation, in Book:
products and mixed the crystals with a large Edible Oil Processing from a Patent Perspective.
number of low melting compositions. As shown Springer New York Heidelberg Dordrecht
in Table 3 the amounts of SFA and USFA in olein London. Library of Congress Control Number:
samples were nearly similar (46.32%, 53.68% 2012936065 (2013).
in pure POL and 46.37%, 53.63% in modified
2. Timms R.E., Principles of Fat Fractionation
PO). In addition, the amounts of USFA were
(Society of Chemical Industry lecture Paper
much higher than that in all fractions (PMF`s).
Series, Paper No. 0039), Society of Chemical
It was also found that PSO fractionated at lower
Industry, London, UK (1994).
temperatures contained less SFA, more USFA
than PSO fractionated at a higher temperature. 3. Calliauw G., Fredrick F., Gibon V., De Greyt W.,
These results are in agreement with that reported Wouters J., Foubert I. and Dewettinck K., On
by Hasmadi et al., [25]. the fractional crystallization of palm olein: Solid
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10
HANAFY A. HASHEM et al.

solutions and eutectic solidification.  Food Res. and oils. Methods And Recommended Practices
Int., 43, 972-981 (2010). Of The American Oil Chemists’ Society, 4th ed.,
American Oil Chemists’ Society, USA (1997).
4. Hamm W., Trends in edible oil fractionation.
Trends in Food Science & Technology. 6(4), 121- 14. AOCS American Oil Chemists’ Society. Official
126 (1995). Method Ce 1k‐07. Direct methylation of lipids
for the determination of total fat, saturated, cis‐
5. Timms, R. E., Fractional crystallization the fat
monounsaturated, cis‐polyunsaturated, and trans
modification process for the 21st century. Eur. J.
fatty acids by chromatography. Official Methods
Lipid Sci. Technol., 107(1), 48- 57 (2005).
and Recommended Practices of the American Oil
6. Abdel-Razek A.G., Hassanein M.M.M., Rudzińska Chemists’ Society, 5thed., USA (2007).
M. and El-Mallah M.H., Role of minor constituents
15. Calliauw G., Gibon V., Greyt W. De., Plees L.,
and balanced fatty acids in upgrading the
Foubert I. and Wettinck K. D., Phase composition
low stability of cooking oils blended with
during palm olein fractionation and its effect on
palm super olein.  Asian Journal of Scientific
soft PMF and super olein quality. J. Am. Oil
Research, 10, 150–159 (2017).
Chem. Soc. 84, 885-891 (2007).
7. Rudzińska M., Hassanein M.M.M., Abdel-Razek
16. Ablatip R., Yee-Ying Lee , Teck-Kim Tang , Eng-
A. G., Kmiecik D., Siger A. and Ratusz K.,
Tong Phuah , Choon-Min Lee , Chin-Ping Tan and
Influence of composition on degradation during
Oi-Ming Lai, Palm-based diacylglycerol fat dry
repeated fat-frying of binary and ternary blends
fractionation: effect of crystallisation temperature,
of palm, sunflower and soybean oils with health
cooling rate and agitation speed on physical and
optimised saturated to unsaturated fatty acid
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ratios. International Journal of Food Science and
(2013); DOI 10.7717/peerj.72.
Technology (2017). Version of Record online: 10
NOV 2017, DOI: 10.1111/ijfs.13678. 17. Kellens marc, Gibon Veronique Hendrix marc and
De greytwim, Palm oil fractionation. Eur. J. Lipid
8. Omar Z., Hishamuddin E., Sahri M. M., Fauzi S.
Sci. Technol. 109, 336- 349 (2007).
H. M., Dian N. L. H. M., Ramli M. R. and Abd-
Rashid N., Palm oil crystallization: A review. 18. Arnaud E, Collignan A. Chicken fat dry
Journal of Oil Palm Research. 27(2), 97-106 fractionation: effect of temperature and time on
(2015). crystallization, filtration and fraction properties.
European Journal Of Lipids Science And
9. Idris N. A., Jamaludin R. and Hassan H., Process
Technology 110, 239-244 (2008).
to prevent and delay clouding in palm olein. US
Patent No. 20030068426 A1 (2003) 19. Zaliha O., Chong C.L., Cheow C. S., Norizzah
A.R. and Kellens M.J., Crystallization properties
10. Hashimoto S., Nezu T., Arakawa H., Ito T. and
of palm oil by dry fractionation. Food Chemistry
Maruzeni S., Preparation of sharp-melting hard
86, 245–250 (2004).
palm midfraction and its use as hard butter in
chocolate. J. Am. Oil Chem. Soc., 78, 455-460 20. Deffense, E., Fractionation of palm oil. J. Amer.
(2001). Oil Chem. Soc. 62 (2), 376-385 (1985).

11. Krishnamurthy R. and Kellens M.Fractionation 21. Dang L., Li S., Zhang H., Si Y., Wang Z.
and winterization. In: Bailey’s Industrial Oil Crystallization behavior of palm kernel oil
and Fat Products, Volume 4, Edible Oil and Fat monitored by in-situ Focused Beam Reflectance
Products: Processing Technology, pp. 301-337 Measurement (FBRM) and Particles Video
(Y.H. Hui (ed.), John Wiley, Champaign, USA)
Microscope (PVM) during suspension
(1996).
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12. AOCS Official methods and recommended Chemistry 5, 31-38 (2015).
practices of the american oil chemists’ society.
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Egypt.J.Chem. 61, No.1 (2018)


‫‪11‬‬
‫‪INDUSTRIAL SCALE PRODUCTION OF PALM SUPER OLEIN USING‬‬

‫‪23. Teah, Y. K., Improvements in the frying quality‬‬ ‫‪25. Hasmadi M., Aini I. N., Mamot S. and Yusef M.‬‬
‫‪of vegetable oils by blending with palm olein.‬‬ ‫‪S. A., The effect of different types of stirrer and‬‬
‫‪Second Arab Conference, A. R. E., Cairo (1993).‬‬ ‫‪fractionation temperatures during fractionation‬‬
‫‪on the yield characteristics and quality of oleins.‬‬
‫‪24. Jie Peng, Xue Bai, Yunzhu Zhang, Xingpeng Bai,‬‬
‫‪Journal of Food Lipids, 9 (4), 295- 307 (2002).‬‬
‫‪Directional crystallization kinetics of coconut‬‬
‫‪oil under temperature gradient. Global journal‬‬ ‫;‪(Received 12/ 12 /2017‬‬
‫‪of science frontier research chemistry. 12 (4) 1.0‬‬ ‫)‪accepted 30 / 1 /2018‬‬
‫‪(2012).‬‬

‫إنتاج زيت سوبر أوليين النخيل على المستوى الصناعى بإستخدام طريقة معدلة ومبتكرة‬
‫لتقنية التجزئة الجافة‬
‫‪3‬‬
‫حنفى هاشم‪ ،1‬ناصر عبدالاله‪ ،1‬غريب عبد التواب‪ 2‬و عادل جبر عبد الرازق‬
‫‪1‬قسم علوم و تكنولوجيا األغذية ‪ -‬كلية الزراعة ‪ -‬جامعة األزهر‪ -‬القاهرة‪ ،‬مصر‪.‬‬
‫‪2‬شركة أجواء للصناعات الغذائية ‪ -‬عتاقة ‪ -‬السويس ‪ -‬مصر‪.‬‬
‫* ‪3‬قسم الزيوت والدهون ‪ -‬المركز القومى للبحوث‪ ،‬الدقي ‪ ،12622‬القاهرة ‪ -‬مصر‪.‬‬

‫يستخدم زيت النخيل على نطاق واسع في تجهيز األغذية‪ ،‬ويرجع ذلك أساسا إلى خصائصه الطبيعية والكيميائية‬
‫التي تجعله مناسبا ً للعديد من التطبيقات الغذائية‪ .‬وفى نفس الوقت فإن بعض التطبيقات الغذائية تحتاج إلى مشتقات‬
‫اوليين نخيل له خصائص مميزة‪ .‬ومن خالل تغيير ظروف التجزئة المستخدمة‪ ،‬يمكن أن ينتج زيت سوبر أوليين‬
‫متميز فى الخصائص الكيميائية والفيزيائية المختلفة‪ .‬لذا فإن هذه الدراسة تهدف إلى إجراء محاوالت إليجاد‬
‫طريقة مبتكرة وذات كفاءة أفضل إلنتاج زيت سوبر أوليين نخيل له خصائص طبيعية وكيميائية مميزة تناسب‬
‫عدة إستخدامات فى مجال الصناعات الغذائية‪ ،‬وذلك من خالل تجارب تطبيقية عملية على نطاق صناعى‪ .‬حيث‬
‫تم تبريد وبلورة زيت أوليين النخيل التقليدى وكذلك المعدل (زيت أوليين النخيل ‪ ٪5 +‬زيت النخيل)‪ .‬وتمت‬
‫التجزئة الجافة بإتباع برنامج تبريد حرارى خاص وذلك بإستخدام الطريقة التقليدية عند ‪ 17‬م‪ °‬أو بطريقة مبتكرة‬
‫عند ‪ 16.6‬م‪ .°‬تم استخدام طريقة الرانسيمات لتقديرالثبات ضد األكسدة لمختلف مشتقات زيت النخيل‪ .‬أيضا‪ ،‬تم‬
‫تقييم الخصائصالطبيعية والكيميائية لنواتج البلورة المختلفة وتم دراسة تراكيب األحماض الدهنية بواسطة جهاز‬
‫الكروماتوجرافى الغازى السائل‪ .‬وقد تميززيت سوبر أوليين النخيل الذى تم الحصول عليه عن طريق التجزئة‬
‫باستخدام زيت األوليين المعدل (المضاف إليه ‪ %5‬زيت نخيل) عند ‪ 16.6‬م‪ °‬حيث حقق تحسن أدى إلى إنخفاض‬
‫فىنقطة اإلنصهار لتصل إلىدرجة حرارة ‪ 9‬م‪ °‬وكذلك قد حسنت هذه المعاماالت من قيم الرقم اليودى ودرجة‬
‫تعكير الزيت عند درجات الحرارة المنخفضة‪ ،‬مما يجعل الزيت المنتج بهذه الطريقة يناسب عديد من التطبيقات‪.‬‬
‫وعلى النطاق الصناعى فإن إستخدام عملية التجزئة الجافة المبتكرة والمعدلة المتبعة فى هذه الدراسة‪ ،‬يمكن أن‬
‫تؤخذ كنموذج لتحسين تجزئة زيت النخيل‪.‬‬

‫)‪Egypt.J.Chem. 61 , No.1 (2018‬‬

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