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Characterization of Palm Fatty Acid Distillate of Different Oil Processing

Industries of Pakistan

Article  in  Journal of Oleo Science · October 2016

DOI: 10.5650/jos.ess16073

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Journal of Oleo Science
Copyright ©2016 by Japan Oil Chemists’ Society
doi : 10.5650/jos.ess16073
J. Oleo Sci. 65, (11) 897-901 (2016)

Characterization of Palm Fatty Acid Distillate of

Different Oil Processing Industries of Pakistan
Abdul Sattar Chang1, 2, Syed Tufail Hussain Sherazi1, Aftab Ahmed Kandhro2,
Sarfaraz Ahmed Mahesar1＊ , Fouzia Chang1, Syed Nasrullah Shah1,
Zahid Hussain Laghari1 and Tarique Panhwar1
1
National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro -76080, PAKISTAN
2
Dr. M. A. Kazi Institute of Chemistry, University of Sindh, Jamshoro -76080, PAKISTAN

Abstract: Palm fatty acid distillate (PFAD) is cheap and valuable byproduct of edible oil processing
industries. This study was designed to characterize PFAD collected from different local oil industries. AOCS
methods were used for the determination of physicochemical parameters such as free fatty acid (FFA),
saponification value (SV), iodine value (IV), peroxide value (PV) and moisture content. Fatty acid
composition was analyzed using GC-MS. Moisture content of samples was found to be in the range between
0.06-7.50%, while FFA, SV, IV and PV were found to be 65.70-94.68%, 195.23-219.64 mg KOH/g, 38.49-
63.10 g I2/100 g, 1.09-16.50 meq/kg, respectively. Mean value of fatty acids in PFAD was found as 0.04%
lauric, 0.42% myristic, 41.25% palmitic, 7.29% stearic, 41.58% oleic, 8.95 % linoleic, 0.04% eicosenoic,
0.27% arachidic, 0.07% docosanoic, and 0.05% tetracosanoic acid, respectively. Palmitic acid was found as
dominant saturated fatty acid 38.63-45.30%, whereas oleic acid C18:1 n9 was major unsaturated fatty acid
33.54-44.05 % in PFAD.

Key words: palm oil, deodorizer distillate, chemical characterization, fatty acid composition

1 Introduction chemical neutralization（ alkali neutralization）. Refining

Palm oil is obtained from fruits of oil palm tree （Elaeis
guineensis） . There are two different types of oils extract-
ed from palm fruit. One type of oil is obtained from meso-
carp part of palm fruit known as crude palm oil（CPO） and
other obtained from the kernel of the fruit palm and known
as palm kernel oil （PKO） 1, 2）
. Both CPO and PKO have their
own importance, characteristics and commercial value 3）.
Due to distinct fatty acid composition（FAC）and triacylg-
lycerol（TAG）profile CPO has many food applications. Gen-
erally palm oil contains about 1％ phytochemicals such as
vitamin E（600-1000 ppm） （500-700 ppm）
, carotenoid , phy-
tosterols（300-620 ppm）, squalene（250-540 ppm）, phos-
pholipids（20-100 ppm）, co-enzyme Q10（10-80 ppm）and
polyphenolics （40-70 ppm） 4）
. found to be 96.1％ of FFAs and glycerides and other minor
Crude palm oil is not directly used for edible applications
but it is refined in order to remove undesirable components
such as free fatty acids（ FFAs）, partial acylglycerides,
metals, colored compounds, odorous substances5）. Refining
of crude oil is carried out by either physical refining or
chemical process. In physical refining FFAs are removed by
distillation, while in chemical refining FFAs are removed by
process involves degumming, neutralization, bleaching and
deodorization. Last step of refining is deodorization which
is carried out through vacuum distillation. This is very im-
portant step in which odorous components and also FFAs
are removed. As a result, deodorizer distillate（DD）is pro-
duced which contains FFAs and some minor components
such as tocopherols, squalene, and phytosterols. DD is the
most important byproduct obtained and considered as the
cheap source of FFAs and other minor valuable compo-
nents such as squalene, hydrocarbons, phytosterols to-
copherols, tocotrienols, mono and di-glycerides6）. Quantity
of palm oil DD is usually about 4-5％ depending on the
level of FFAs in CPO7, 8）. In one reported study, PFAD was
components squalene（0.76％）, tocopherols and tocotri-
enols（0.48％）, phytosterols（0.37％）, and hydrocarbons
（0.71％）9）. PFAD and DD obtained from deodorization of
other vegetable oils have been used for production of bio-
diesel due to presence of high concentration of FFA10−12）.
Due to presence of tocopherols and phytosterols, PFAD
has also many other applications in foods and cosmetics in-

＊
Correspondence to: Sarfaraz Ahmed Mahesar, National Centre of Excellence in Analytical Chemistry, University of Sindh,
Jamshoro -76080, PAKISTAN
E-mail: mahesar_sarfaraz@yahoo.com
Accepted June 13, 2016 (received for review March 27, 2016)
Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online
http://www.jstage.jst.go.jp/browse/jos/  http://mc.manusriptcentral.com/jjocs

897
 A. S. Chang, S. T. H. Sherazi and A. A. Kandhro et al.
dustries13）. PFAD has been widely used in non food indus-
tries such as oleochemical industries as well as in prepara-
tion of feed and soap10, 14）.
There is growing trend to utilize cheap byproducts of in-
dustries to prepare valuable products for commercial
purpose and value addition. Focus of today’ s scientists is
on the natural materials in place of synthetic materials to
fulfill the health and environmental obligations. DD is
readily available source of bioactive components for the
production of biodiesel, polyols and other valuable prod-
ucts of industry. To find proper use of PFAD, it is essential
to characterize its composition. Therefore, aim of present
study is to characterize PFAD obtained from different
edible oil industries for their fatty acid composition and
other physicochemical parameters.
2 Materials and methods
2.1 Reagents and sample collection
All chemicals, reagents and solvents used were from E.
Merck（Darmstadt, Germany）. Fatty acids methyl esters
（FAME）standards（GLC 481-B）were purchased from Nu-
Check- Prep, Inc.（Elysian, MN）. Two PFAD samples were
collected on different dates from two batches of five differ-
ent palm oil processing industries located at Hyderabad
and Karachi, Pakistan. All the samples were stored in the
refrigerator at 4℃ till further analysis.
2.2 Physicochemical Parameters
All the physicochemical parameters such as moisture
content, FFA, IV, PV and SV of the PFAD samples were de-
termined by official AOCS methods.
2.3 Moisture content
The moisture content of PFAD was determined using
（5 g）
AOCS official method Aa 3-3815）. Sample of PFAD was
heated in an oven（ Memmert, Schwabach, Germany）at
105℃ for 3 hours.
2.4 Free fatty acid value
Amount of FFA in PFAD was determined using AOCS of-
ficial method Aa 6-3815）. Titration of sample was performed
against the standardized aqueous solution of sodium hy-
droxide. About 1 g PFAD sample was placed in a 250 mL
conical flask which contained 20 mL of neutral ethanol.
The mixture was heated, shaken and titrated against 0.1 N
sodium hydroxide in the presence of phenolphthalein indi-
cator.
2.5 Iodine value
The IV of PFAD was determined using AOCS official
method Cd 1-2515）. Iodine value indicates the presence of
unsaturation in oil or fat. PFAD was put in conical flask
898
J. Oleo Sci. 65, (11) 897-901 (2016)
（15 mL）, Wij’
containing carbon tetrachloride s reagent（25
mL）and solution of potassium iodide（5％）. Solution was
kept in dark for 30 min and liberated iodine was titrated
against 0.1 N standard sodium thiosulfate solutions using
starch as indicator.
2.6 Saponification value
AOCS official method Cd 3-2515） was used for the deter-
mination of SV. About 2 g of PFAD was taken in round
bottom flask and refluxed for 60 min in the presence of 25
mL of 95％ ethanolic potassium hydroxide. In the end titra-
tion was carried out against standardized solution of 0.5 N
hydrocholoric acid using phenolphthalein as indicator.
2.7 Peroxide value
PV was determined using AOCS official method C d
8-5315）. About 2 g of PFAD was dissolved in 15 mL mixture
of glacial acetic acid and chloroform（3:2 v/v％） . Resulting
solution was titrated against standardized solution of
sodium thiosulphate（0.1 N） using starch（1％）as indicator.
2.8 Determination of fatty acid composition
Before the determination of fatty acid composition, fatty
acids methyl esters（FAMEs） were prepared using standard
IUPAC method 2.30116）. Agilent 6890 N gas chromatograph
instrument coupled with an Agilent MS-5975 inert XL mass
selective detector and an Agilent auto sampler 7683-B
injector（Agilent Technologies, Little Fall, NY, USA）was
used in this study. The ChemStation 6890 Scale Mode soft-
ware was used for peak analysis. A capillary column
HP-5MS（5％ phenyl methyl siloxane）with column length
30 m, i.d 250 μm, film thicknes 0.25 mm was used for the
analytical separation of fatty acids. Initial Oven tempera-
ture was 150℃ maintained for 2 min then raised to 220℃
at ramp rate of 4℃/min. Helium was used as carrier gas
with flow rate of 0.8 mL/min. Injector and detector temper-
ature was set at 240 and 270℃, respectively. 1 μL quantity
of each sample was injected into the column in split mode.
Mass detector was operated with an electron impact （EI）
ion source mode at 70 eV with scan range of 50-550 m/z.
Two libraries（NIST and Wily）were used for the identifica-
tion of fatty acids in PFAD samples.
2.9 Statistical Analysis
Identification of fatty acids in PFAD samples were per-
formed by retention time and comparison of mass spectra
of known FAME standards （palmitic, oleic, stearic and lin-
oleic acid）with GC-MS libraries. Two batches of each five
PFAD samples at different processing dates were collected
and analyzed three times and data was reported as mean
with the standard deviation（SD） （n＝2×5×3）.
 Characterization of palm fatty acid distillate

3 Results and discussion which is often applied in soap and cosmetic industries22）.
3.1 Physicochemical parameters
Table 1 represents the physicochemical parameters of 3.2 Fatty acid Composition
PFAD samples obtained from different edible oil industries Fatty acid composition of PFAD assesses its possible use
such as moisture content, FFA, IV, PV and SV. All samples in industrial sector such as energy, cosmetic and soap
were reddish brown semisolid at room temperature. Mois- manufacturing industries 23）. Fatty acid composition of
ture content of PFAD samples were found to be in the PFAD samples was determined using GC-MS after prepar-
range between 0.06-7.50％. Maximum moisture found to ing methyl esters. Table 2 shows the fatty acids composi-
be 7.5％ which was higher than previous findings17）. FFA tion as a mean values with their standard deviations. Fatty
content ranged between 65.70-94.68％ with mean value of （C12:0）,
acids profile of PFAD samples includes lauric acid
80.19％, which was lower than reported FFA values17, 18）. myristic acid（C14:0）, palmitic acid（C16:0）, stearic acid
Higher mean FFA value （94.68％） was observed for PFAD-2 （C18:0）, two isomers of oleic acid（C18:1 n9 and C18:1
and lower for PFAD-1（65.70％） . FFA content of PFAD-1 in n11）, linoleic acid（C18:2 n9,12）, eicosenoic acid（C20:1
current study was found to be lowest from earlier reported n11）, eicosanoic acid（C20:0）, docosanoic acid （C22:0）and
values. tetracosanoic acid（C24:0）. Palmitic acid（C16:0）was found
IV is another parameter which indicates the unsaturation to be dominant saturated fatty acid in all PFAD samples
in oil and fat19）. In this study, IV was found in the range of ranging from 38.63-45.30％. Among the unsaturated fatty
38.49-63.10 g I2/100 g with mean value of 51.24 g I2/100 g. acids oleic acid（C18:1 n9）was found to be main fatty acid
IV found in this study was lower than reported studies17, 20）. ranged between 33.54-44.05％. Oleic acid（ C18:1 n9）in
PV indicates about the oxidation level of oil and fat with present PFAD samples was found higher than earlier
the formation of peroxides and hydroxides. PV values for reports17, 18）.
PFAD-1（16.50 meq/kg）and PFAD-5（10.16 meq/kg）were Table 3 represents the important groups and ratios of
found to be higher than earlier study21）, while PV values for fatty acids in PFAD. Saturated fatty acids（SFA）and unsatu-
PFAD-2, PFAD-3, and PFAD-4 were found to be compara- rated fatty acids（USFA）content of samples were found in
ble to previous reported values. Range of SV in this study the range of 46.28-55.82％ and 44.12-53.57％, respectively.
was found to be 195.23-219.64 mg KOH/g with mean value Among the USFA, monounsaturated fatty acids （MUFA） and
of 205.71 mg KOH/g which was slightly lower than one poly unsaturated fatty acids（ PUFA）were in the range
published data17） and similar to other study reported by between 33.94-44.35％ and 7.57-10.18％, respectively. Lin-
Moh et al.18）. SV of PFAD samples is important parameter oleic acid（C18:2 n9, 12）was the only PUFA found in

Table 1　Physiochemical characteristics of PFAD.

PFAD-1 PFAD-2 PFAD-3 PFAD-4 PFAD-5
Parameters
Range Mean Range Mean Range Mean Range Mean Range Mean
Physical Appearance Reddish brown semisolid Reddish brown semisolid Reddish brown Semisolid Reddish brown semisolid Reddish brown semisolid
Moisture Content (%) 7.90- 7.30 7.50±0.20 0.80- 0.86 0.83±0.02 1.54- 1.59 1.57±0.02 0.04- 0.08 0.06±0.00 2.32- 2.38 2.35±0.08
FFA (%) 65.50- 65.90 65.70±1.10 93.22- 95.55 94.68±2.50 84.35- 86.50 85.42±3.20 89.18- 90.85 90.21±1.99 77.31- 79.11 78.23±1.68

IV (gI2/100 g) 62.42- 64.12 63.10±1.40 37.79- 39.28 38.49±1.30 49.29- 51.24 50.33±2.01 45.21- 47.12 46.16±1.50 57.17- 59.11 58.11±1.25
PV (meq/kg) 15.89- 17.19 16.50±0.20 1.02- 1.16 1.09±0.02 3.05- 3.51 3.25±0.06 6.54- 6.85 6.68±0.08 9.87- 10.43 10.16±0.39

SV (mgKOH/g) 207.80-212.10 209.70±2.50 205.10-206.30 203.60±8.66 198.26-202.56 200.39±6.68 193.12-197.32 195.23±5.68 215.02-222.63 219.64±6.44

Table 2　Fatty acid composition of PFAD.

PFAD-1 PFAD-2 PFAD-3 PFAD-4 PFAD-5
Fatty Acid (%)
Range Mean Range Mean Range Mean Range Mean Range Mean
Lauric acid C12:0 0.001- 0.03 0.01±0.00 0.002- 0.09 0.04±0.00 0.012- 0.15 0.08±0.00 0.001- 0.08 0.02±0.00 ND ND

myristic acid C14:0 0.02 - 0.50 0.26±0.00 0.01 - 0.95 0.28±0.00 0.15 - 1.50 0.75±0.00 0.1 - 0.99 0.46±0.00 0.01 - 0.85 0.37±0.00
Palmitic; C16:0 36.99 -39.97 38.63±1.5 43.91 -46.87 45.30±1.30 39.94 -41.68 40.76±1.60 38.35 -39.68 39.09±1.20 41.65 -43.94 42.45±1.22

Stearic; C18:0 8.02 - 8.17 8.07±0.24 9.38 -10.5 9.87±0.22 5.12 - 6.97 5.93±0.24 6.17 - 6.93 6.45±0.09 5.45 - 6.72 6.12±0.07

Oleic; C18:1 n9 43.02 -45.65 44.05±1.20 33.12 -34.82 33.54±1.30 41.21 -42.46 41.54±1.29 42.45 -44.32 43.48±1.22 41.25 -42.78 42.14±1.62
Oleic; C18:1 n11 0.12 - 0.35 0.25±0.00 0.21 - 0.56 0.37±0.01 0.31 - 1.54 0.93±0.01 0.54 - 1.12 0.87±0.02 0.45 - 0.98 0.74±0.01

Linoleic; C18:2 n9,12 7.78 - 8.95 8.46±0.22 9.55 -10.83 10.18±0.34 8.70 - 9.87 9.3 ±0.24 8.31 - 9.87 9.22±0.12 7.12 - 8.04 7.57±0.16
Eicosenoic; C20:1 n11 ND ND 0.01 - 0.06 0.03±0.00 0.10 - 0.18 0.13±0.00 ND ND 0.039- 0.07 0.05±0.00

Arachidic acid C20:0 0.014- 0.21 0.11±0.00 0.11 - 0.45 0.21±0.00 0.31 - 0.56 0.44±0.00 0.11 - 0.34 0.22±0.01 0.29 - 0.52 0.36±0.01

Docosanoic acid (C22:0) 0.07 - 0.10 0.09±0.00 0.047- 0.16 0.12±0.00 0.04 - 0.09 0.07±0.00 ND ND 0.05 - 0.09 0.07±0.00

Tetracosanoic acid (C24:0) 0.05 - 0.09 0.07±0.00 ND ND 0.05 - 0.08 0.07±0.00 0.03 - 0.054 0.04±0.00 0.06 - 0.096 0.08±0.00
ND, not detected

899
J. Oleo Sci. 65, (11) 897-901 (2016)
 A. S. Chang, S. T. H. Sherazi and A. A. Kandhro et al.

Table 3　Groups and ratio between different PFAD.

Groups PFAD-1 PFAD-2 PFAD-3 PFAD-4 PFAD-5
SFA 47.24 55.82 48.10 46.28 49.45
USFA 52.76 44.12 51.90 53.57 50.50
MUFA 44.30 33.94 42.60 44.35 42.93
PUFA 8.46 10.18 9.30 9.22 7.57
SFA/UFA 0.90 1.27 0.93 0.86 0.98

samples of PFAD. Ratio of saturated to unsaturated fatty from palm fatty acid distillate by lipase-catalysed hy-
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