A Comparative Study of Chemical Analysis of Palm Kernel Oil

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Article title: A COMPARATIVE STUDY OF CHEMICAL ANALYSIS OF LOCALLY MADE AND REFINED PALM KERNEL OIL

Elaeis guineensis )
Authors: Anthony Okpe[1]
Affiliations: Department of Chemistry, College of Sciences, University of Agriculture, Makurdi-Nigeria[1]
Orcid ids: 0000-0002-9496-3291[1]
Contact e-mail: anthonyokpe@gmail.com
License information: This work has been published open access under Creative Commons Attribution License
http://creativecommons.org/licenses/by/4.0/, which permits unrestricted use, distribution, and reproduction in any
medium, provided the original work is properly cited. Conditions, terms of use and publishing policy can be found at
https://www.scienceopen.com/.
Preprint statement: This article is a preprint and has not been peer-reviewed, under consideration and submitted to
ScienceOpen Preprints for open peer review.
DOI: 10.14293/S2199-1006.1.SOR-.PP8VWDQ.v1
Preprint first posted online: 09 December 2022
Keywords: Palm Kernel Oil, Physicochemical Analysis, Saponification Value, Moisture Content Value, Peroxide Value,
Iodine Value, Free Fatty Acid Value, Chemical Analysis, Characterization, Vegetable Oil
A COMPARATIVE STUDY OF CHEMICAL ANALYSIS OF LOCALLY
MADE AND REFINED PALM KERNEL OIL (Elaeis guineensis)

Okpe, A.O.
Department of Chemistry, College of Sciences, University of Agriculture,
Makurdi-Nigeria

Correspondent mail: anthonyokpe@gmail.com

ABSTRACT
Chemical analysis of crude and refined palm kernel oil (PKO) was carried out using
AOCS and AOAC methods and the following results were obtained: for crude PKO,
saponification value; 206 mgKOH/g, iodine value; 14.86 g/100, peroxide value;
14.20 mEq/kg, free fatty acid (FFA); 5.20 mgKOH/g, moisture content; 0.28%,
specific gravity; 0.903g/cm3 density; 0.903. The corresponding values for refined
PKO using the same methods include saponification value; 249 mgKOH/g, iodine
value; 17.60g/100, peroxide value; 10.00mEq/kg, free fatty acid (FFA); 3.30
mgKOH/g, moisture content; 1.45%, specific gravity; 0.900g/cm3, density; 0.89.
The result of the characterization shows that the crude palm kernel oil is not easily
perishable since it contains a low moisture content of 0.28%, and the low FFA value
of the refined palm kernel oil is an indication that the oils will be most suitable for
biodiesel as an alternative to the conventional diesel.

KEYWORDS: Palm Kernel Oil, Physicochemical Analysis, Saponification Value,


Moisture Content Value, Peroxide Value, Iodine Value, Free Fatty Acid Value,
Characterization, Vegetable Oil.

1
CHAPTER ONE

1.0 INTRODUCTION

1.1 BACKGROUND OF STUDY


Oil palm (Elaeis guineensis) is believed to have originated from the tropical
rainforest of West Africa. It is a perennial plant that belongs to the family palm
distinctive group of monocotyledons (Tang and Teoh, 1995). The main belt runs
through the Southern Latitude of Cameroon, Ivory Coast, Ghana, Nigeria, Sierra-
Leon, and Congo (Tang and Teoh, 1995). Palm kernel oil is extracted from the seed
of the palm. The monocarp of the fruit can be extracted for palm oil. This palm oil
contains natural antioxidants (Tocopherol) and carotene which are pro-vitamin A
(Faessler et al, 2007).

Palm kernel oil has a great preponderance of saturated fatty acids than palm oil (80
% compared to 60 % for palm oil) with the major fatty acid being oil (Ihekeronye
and Ngoddy, 1995). It also contains low molecular weight fatty acids, caprylic, and
capric acid. In line with the high proportion of saturated acid, saturated triglycerides
constitute over 60 % and mono-oleic di-saturated triglycerides more than 25 % of
the total glycerides. The Iodine value is about 17 and the melting point is 25-30 °C
(Ihekeronye and Ngoddy, 1985).

Palm kernel oil, coconut oil, and palm oil are three of the few highly saturated
vegetable fats. Palm kernel oil which is semi-solid at room temperature is more
saturated than palm oil and comparable to coconut oil. All vegetable oils including
these three palm–derived oils do not contain cholesterol (found in unrefined animal
fats), although saturated fat intake increase both LDL and HDL cholesterol (Mansink
and Katan, 1992).

2
Oil nut palms are commonly planted in four tropical regions; Africa, South East
Asia, Latin America, and South Pacific. The main objective of these palm industries
is to generate oil. Palm kernel cake from the nuts of palm fruits is generated as a by-
product, along with oil as the main product. Palm Kernel Meal (PKM) is found in
large quantities in a number of tropical countries and is available at competitive
prices. Four million Mt of palm kernel cake were produced in the world in 2002 with
annual growth of 15 % of PKM within the last two decades (FAO, 2002). PKM has
been widely used in ruminant feed (Broderick et al., 1988; Moss and Givens, 1994;
Umunna et al., 1994; Chandrasekariah et al, 2001), Pig diets (Thorne et al., 1989;
Agunbiade et al., 1999; Kim et al., 2001) and rabbit diets (Aduku et al., 1988;
Aganga et al., 1991). The palm Kernel is a good source of potassium (Ekpa, 1995).
This oil palm contains organic food substances and inorganic elements, upon which
life and industries depend. The fruit yields two oils, palm oil and kernel oil, each
exhibiting differences in composition, properties, and applications. Palm kernel oil
is similar to coconut oil in composition and both are the only source of lauric oil
available in the world market (Berger et al., 1991). The cake residue obtained after
extracting oil is used in livestock feeds, while the palm and kernel oil is used in soap
production, vegetable oil, and margarine (Ekpa, 1995). Besides industrial
applications, these oils are used locally as body creams, cooking oils, and
medicinally, as antidotes for poisoning and as surface protectants for minor wounds.
Palm oils from the dura and tenera varieties of the oil palm differ in their percentage
fatty acid composition (Ekpa, 1995) and their interaction with lauric acids oils. Both
species exhibit markedly different characteristics in their melting point and free fatty
acid formation on exposure to light.

3
1.2 Statement of the Problem
There is an increasing demand for vegetable oils and thus the need to ascertain the
chemical composition of these oils (particularly palm kernel oil) to serve as
alternatives for industrial and domestic use.

1.3 Aim and objectives

The study is aimed at evaluating the chemical properties of palm kernel oil.
Other objectives include;

▪ To determine the quality of palm kernel oil via its chemical properties using
locally made and refined palm kernel oils as study samples.
▪ To provide additional information on palm kernel oil in terms of its chemical
composition and therefore promote its use.

1.4 Scope and limitation


This work is strictly restricted to analyzing the chemical composition and properties
of palm kernel oil (Elaesis guineensis). These include the saponification value,
peroxide value, iodine value, and free fatty acid value.

1.5 Significance of study

In order to meet the increasing demand for vegetable oil for industrial and domestic
use, evaluating the chemical composition of palm kernel oil could serve as an
alternative for domestic and industrial use.

4
CHAPTER TWO

2.0 LITERATURE REVIEW

2.1 Historical Development of Palm Kernel Oil

The development of oil palm (Elaesis guineensis) starts about 2 weeks after a thesis
(WAA); at 8 WAA the endosperm of the seed is liquid and at 10 WAA, it is semi
gelatinous (Hartley et al, 1998): At 12 WAA oil start to deposit in the endosperm
and almost complete by 16 WAA. During this period the endosperm and endocarp
slowly harden and by 16 WAA the endocarp is a hard shell enclosing a hard whitish
endosperm which is known as the kernel, (Oo et al, 1985). Oil deposit in the
Mesocarp starts at about 15 WAA and continues until fruit maturity (about 20 WAA,
Bafor, and Osangie, 1986). Oo et al (1985), also observed that as the total lipid
progressively increases (0.1-48 %) in the mesocarp the moisture content decreases
(88-37 %) with increasing WAA.

The tree is generally believed to have originated in the jungle forests of East Africa
and there is some evidence that palm oil was used in Egypt at the time of the
pharaohs, some 5000 years ago (Cottrel, 1991) but now its cultivation is mostly in
South East Asia. There are three main varieties of oil palm distinguished by their
fruit characteristics. These are;

▪ Dura, which has a thin shell separating the pulp from the Kernels tends to be
large comprising 7-20 % fruit weight.
▪ Tenera has a thin shell between pulp and kernel, together with a fibrous large
round nut. The kernel is usually smaller comprising 3-15 % of the fruit. The oil
content is higher at 24-32 %.
▪ Pisifera, which has no shell and is very frequently female sterile, as a result,
Pisifera palms are not used for commercial planting.

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Figure 1. Palm kernel fruit
Source: Center for International Forestry Research/Iddy Farmer

In general, all crude palm oil extracting method includes a sterilization process
where the fruit is softened up usually by heat treatment, and a digesting stage where
the pulp is broken up to release the oil, an extraction process to release oil from
mashed fruit and a purification and clarification process where the oil is separated
from water and cell debris (sludge), fiber and shell. Further downstream kernel
obtained often the oil extraction process is separated from the fiber, cracked and
sold, or subjected to palm kernel oil extraction. The expert of palm kernel began in
1832 and by 1916 British West Africa alone exported 156,000 tons of which about
75 % from Nigeria (Smith 2009), Nigeria was the largest exporter until 1934 when
the country was surpassed by Malaysia Crest. Africa led the world in the production
and export of palm oil throughout the first half of the 20th century, led by Nigeria

6
and Zaire. By 1995, however, Malaysia and Indonesia have surpassed Africa’s total
palm oil production (Smith, 2009).

Figure 2. Global vegetable oil production (2011)


Source: Department of Food Technology Research, National Nutrition and Food Technology Research Institute,
University of Medical Sciences, Tehran.

The palm fruit looks like a plum, the outer flesh mesocarp gives the oil palm, while
the kernel which is inside a hard shell gives the palm kernel oil, and it’s rather strange
that the two oils from the same fruit are entirely different in fatty acid composition
and properties (Smith, 2009). Palm kernel oil is light yellowish fatty oil obtained
especially from crushed nuts of an African palm. It is composed of fatty acids and
esterifies with glycerol just like any ordinary fat (it is a triacylglycerol). The oil
gotten from the kernel by extraction is usually colorless or pale yellow. The oil is

7
more liquid than palm oil hence; it is composed of mainly unsaturated fatty acid
primary lauric (Ihekeronye and Ngoddy, 1985). The residue left after extracting oil
from the kernel usually referred to as palm kernel cake is used in the manufacture of
livestock feed.

2.2 Palm Kernel Oil and its Composition

2.2.1 Composition of Palm Kernel Oil

Palm kernel oil are less healthy than palm oil which is derived from the flesh of the
fruit itself, palm kernel oil is over 80 percent fat content, and 48 percent of this fat
is made up of lauric acid, with myristic and Oleic acid making up another 30 percent
of its fatty acid composition. It is because of this composition that palm kernel oil is
hard at room temperature and has a low melting point (Cottrel, 1998).
At room temperature, lipids can be oils or fat depending on the degree of
unsaturation of the fatty acid components. Those with a high percentage of saturated
fatty acids are solid at room temperature while those with a high percentage of
unsaturation are oils (i.e., liquids at room temperature) (Amira 2014). Palm kernel
oil (triglyceride) like other natural fats and oils is a chemical compound of one
molecule of glycerol, bonded to three molecules of fatty acids.

CH2 – OH + R – COOHCH2 – COOR

CH2 – OH + R – COOHCH – COOR + 3H2O

CH2 – OH + R – COOHCH2 – COOR

Glycerol fatty acid water

Triglyceride is the major form of lipid in the body of food. It is composed of fatty
acids and esterifies with glycerol, that is, glycerol with three fatty acids
(triacylglycerol) attached to the ester. Triglyceride molecules contain a “Backbone”

8
of three-carbon alcohol (glycerol). A fatty acid is attached to each of the hydroxyl
(OH) of glycerol. The molecules of water are released in the process of bonding fatty
acid to glycerol as shown above. The degree of saturation and the chain length of the
fatty acids in the triglycerides found in food is an important determinant of the
properties of the oil. The shortened chain fatty acids are of lower melting point and
are more soluble in water (Wolfong and Salmiab, 2007).

Table 1: Fatty Acid Composition of Palm Kernel Oil (2002)

Palm kernel oil % Fatty acid Structure


48% Lauric acid (12.0) CH3(CH2)10COOH
16% Myristic acid (14.0) CH3(CH2)12COOH
8% Palmitic acid (16.0) CH3(CH2)14COOH
2% Stearic acid (18.0) CH3(CH2)16COOH
15% Oleic acid (18.1) CH3(CH2)7CH=CH(CH2)7COOH
3% Linoleic acid (18.2) CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH

The heavy content of lauric acid gives palm kernel oil its sharp melting properties
meaning hardness at room temperature combined with low melting point (Pantzaria,
2000). In the presence of heat and water, the triglyceride (vegetable oil) breaks down
by a process known as hydrolysis to form raw fatty acids and glycerol.

Fats/Oil + H2O + catalyst → fatty acid + glycerol

Palm kernel oil can be fractionated into solid and liquid fractions known as stearin
and Olein respectively and then go for refining to give refined bleached deodorized
(RBD) (Pantzaris, 2000) which is of crucial importance to refiners. Moisture and dirt

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composition of palm kernel oil can be reduced by good milling and extraction but
normally it is in the range of 0.25 %

Other Moisture contents are:

▪ The Carotenoids /Antioxidants


▪ The tocopherols/vitamins
▪ The sterols (e.g., cholesterol)
▪ The polar lipids
▪ The phospholipids
▪ Hydrocarbons
▪ Other impurities

All the above are classified in one category because they are fatty in nature but not
really oils. They are referred to as unsaponifiable matters. These unsaponifiable
matters are defined as material left behind the oil and fat which after saponification
of the oil or fat by caustic alkali and extraction by a suitable solvent, remains non-
volatile on drying at 8°C (Loh 2010). Removal of these impurities is by degumming
the oil. Degumming of palm kernel oil is a process equally known as water refining.
This consists of treating the natural oil with small water, followed by centrifugal
separation. This is aimed at removing the gummy or waxy solids that are dissolved
in the oil (soluble organic matter). The essence of degumming is purification i.e., to
purify the oil (Sivasothy et al 1986).

2.2.2 Standardization of Fats and Oil

Standardization is the process of implementing and developing technical standards


based on the consensus of different parties that include firms, users, standard
organizations, and the government. It can help to maximize compatibility, safety,

10
repeatability, or quality. It can also facilitate the commoditization of formerly
custom processes (en.wikipedia.org)

The physicochemical properties of fats and oil are determined largely by the
properties of their component fatty acid. In cases of processed oil, it can be
influenced by other ingredients used and adapting methods of production.

Table 2: Recommended Standards for Some Vegetable Oils

Oils Palm oil Palm Soya Corn oil Groundnut Coconut


kernel beans oil oil oil
oil
Relative 0.30-0.89 0.89- 0.919- 0.917- 0.917- 0.915-
density 0.91 0.930 0.925 0.919 0.917
Saponificatio 195-205 245-255 189-195 - - -
n
value(mgKO
H/g)
Iodine value 45-58 14-18 120-143 - - -
(swiss)
Acid value 0.6 0.6 0.6 0.6 0.6 0.6
Peroxide 10 10 10 10 10 10
value
(meq/Kg)
%max 0.2 0.2 0.2 0.2 0.2 0.2
moisture
Source: (www.codex.org/standard-for-named-vegetable-oils)

2.3 Production of Palm Kernel Oil

2.3.1 Solvent Extraction of Palm Kernel Oil

Solvent extraction processes can be divided into three main unit operations: Kernel
pretreatment, oil extraction, and solvent recovery from the oil and meal. For the
purposes of small operations, it is sufficient to mention the solvent extraction process
11
is an alternative for high-capacity mills. However, the process is not recommended
for small enterprises. (Sivasothy, 2006).

2.3.2 Traditional Method of Palm kernel Extraction

Palm kernel extraction is a specialized operation undertaken by a completely


different set of processors. They are usually better organized as a group and are not
as dispersed as palm oil processors. The kernel processors have to go around the
palm oil processes during the peak season, when prices are lowest, to purchase the
nuts for drying. Nut processing and oil extraction are undertaken in the dry season.
When the pressure to obtain raw materials has subsided (Belge, 1955), traditional
palm oil processing starts with the shelling of the palm oil nuts. The shelling used to
be performed using two stones to crack each nut and separate the kernel and shell
simultaneously. This manual operation has been largely superseded by the use of
nut-cracking stations (Malaysia palm oil Board, Kuala Lumpur 1986). The
mechanical nut crackers deliver a mixture of kernels and shells that must be
separated. The kernel/shell separation is usually performed in a dry bath, which is a
concentrated viscous mixture of clay and water. The density of the clay bath is such
that the shells sink while the lighter kernels float to the top of the mixture. The
floating kernels are scooped into baskets, washed with clean water, and dried.
Periodically, the shells are scooped out of the bath and discarded.

The traditional oil extraction method is to fry palm kernels in old oil or simple heat
and dried nuts. The fried kernels are then pounded or ground to a paste in a motorized
grinder. The paste is mixed with a small quantity of water and heated to release the
palm kernel oil. The released oil is periodically skimmed from the top. Today, there
are stations in villages that will accept well-dried kernels for direct extraction of the
oil in mechanized, motorized expellers (Khairah, 2006).

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2.4 Uses of Palm Kernel Oil

2.4.1 Food Uses of Palm Kernel Oil

Processed foods in which trans fats have been replaced are often replaced with palm
kernel oil. Products like Margarine caramel, ice cream, vegetable shortening,
powdered milk, and milk whiteners are where palm kernel oil is most often found.
These processed foods are high in saturated fat and many health experts advise
consumers to stay away from such foods.

2.4.2 Hydrogenated Palm Kernel Oil

When palm kernel oil is hydrogenated, it can be blended with other high-fat oils and
used for very specific food applications, especially those in which “Mouth feel” is
important because it produces a non-greasy sensation on the tongue. Hydrogenated
palm kernel oil is more stable and can withstand being softened without melting,
making it ideal for use in foods such as chocolate candy bars and margarine,
(Podczasy et al, 1994).

2.4.3 Non-Food Uses of Palm Kernel Oil

Though palm kernel oil is used primarily in foods, it is also converted into biodiesel
as an alternative to traditional oil, and is found in soaps or other cleansing agents;
palm kernel oil is prized as a soap lauric acid. It lathers well and lends firmness to
soaps that are otherwise too soft to hold their shape, (Cornelius, 1997).

2.5 Classification of Palm Kernel Oil

What is the difference between palm oil and kernel oil? The specific fatty acids were
provided as current research suggests that they cannot simply classify all saturated
fat as being “bad”. What are saturated fats? The scientific definition of saturated fat
is having every carbon bound to as much hydrogen as possible, absence of double

13
bounds, saturated fat and saturated fatty acids may be used interchangeably. Often
saturated fatty acids, the length of the carbon chain differentiate saturated fatty acids.
The saturated fatty acids commonly found in a typical diet are lauric acid, myristic
acid, palmitic acid, and stearic acid. As a rule of thumb, the greater the saturated fat
in a food item, the more solid it will be at room temperature. The reverse is also true,
the greater the unsaturated fat in a food item, the more liquid it will be at room
temperature (Katan, M.B. et al 1994). There is scientific evidence that not all
saturated fats are equally cholesterol-elevating. Studies have found that compared to
other long-chain saturated fatty acids stearic acid appears to have a neutral effect on
total cholesterol; and low-density lipoprotein (LDL) otherwise known as the “bad”
cholesterol, studies has found that compared to palmitic acid, lauric acid and myristic
acid increase total blood cholesterol (the “bad” cholesterol) high-density lipoprotein
(HDL) the “good” cholesterol, and the LDL/HDL ratio in both non-human primates,
and normocholesterolemic men and women who consumed a typical western diet.
The myristic acid and lauric acid from coconut oil increased total blood cholesterol,
LDL, HDL, and triglycerides (Etherton et al, 1995). Another study found that
normocholesterolemic palmitic acid and oleic acid produced similar effects on LDL
and HDL metabolism. The finding was confirmed in studies with normolipidemic
humans who consumed a moderate-fat diet low in myristic acid and dietary
cholesterol, which found the effect of palmitic acid on total blood cholesterol and
LDL/HDL ratio to be comparable to that of Oleic acid. Oleic acid is a
monounsaturated fatty on total blood cholesterol, LDL, and HDL, in comparison
with saturated fats (Diersen-Schade, 1991).

In summary, the literature suggests that both stearic acid and palmitic acid, which
comprise virtually all the saturated fats in palm oil have a neutral to favorable impact
on serum lipid profits compared to lauric and myristic effect of dietary stearic acid

14
on plasma cholesterol and lipoprotein level. (Bonanome and Grundy, 1988). The
majority of unsaturated fat molecules are in the cis configuration thus having the
carbons on the same side of the double bond. Most unsaturated fats are cis except
for some naturally occurring trans in meats and milk. However, when hydrogenated,
taking a liquid fat and making it into a solid fat by the addition of hydrogen, then
trans fats are created; Trans-fat has carbons on the opposite side of the double bond.
Hydrogenation is used to remove the unsaturation of fatty acids in order to increase
the oxidative stability of oils and to raise their physical properties allowing for a
broader range of usage in the food industry. Hydrogenated oils are often used in
processed food due to their stability. Trans fat has been required on the food label,
since 2006, a product contains trans fatty acids if hydrogenated oil is listed under the
“ingredient” section of the food label. Research has shown a detrimental effect of
trans-fat or cholesterol (Sunkin et al, 1994). Extensive research on trans-fat has
occurred in the past decade. Numerous studies have suggested that trans-fat
consumption elevates low-density lipoprotein (LDL) cholesterol (the “bad”
cholesterol) and decreases the ratio of high-density lipoprotein resulting in a less
desirable cholesterol profile. In 1999, a meta-analysis of the comparative effects of
trans fats versus saturated fats on cholesterol was performed. This study found that
as the fat intake increased the LDL: HDL cholesterol ratio (a low value is desired)
also increased in a dose-dependent manner and that trans-fat consumption increased
this ratio by more than saturated fat consumption (Mutanen et al, 1997).

Tropical oils are generally thought of as having high saturated fat content and should
be avoided. Although palm oil is grown in the tropical region compared to other
tropical oils, its saturated fat content is approximately 30% less. Palm oil is often
confused with the more highly saturated palm kernel oil and coconut oil. Studies
have found that, unlike coconut oil, palm oil’s impact on serum lipid and lipoprotein

15
profiles compares favorably to corn oil, hydrogenated soybean oil, and olive oil. A
1995 study comparing the effect of palm Olein and Olive Oil diets on twenty-one
healthy, free-living normocholesterolemic subjects found no difference in total and
low-density lipoprotein (LDL) cholesterol levels. In sum, palm oil appears to affect
serum lipids more like a monounsaturated than saturated oil (Truswell, 1995).

2.5.1 Palm Acid Oil (PAO)

Palm Acid Oil (PAO) is a by-product from the chemical refining of palm oil. It
consists mainly of FFA over (50 % and neutral oil, with 2 - 3 % moisture and other
impurities. It is very similar to palm fatty acid distillate (PFAD), but its FFA is
generally lower, except for some special uses, the relative proportion of FFA to
neutral oil does not usually matter very much, as it does not affect its fitness for use.
In most cases, smell and colour are more important. The main uses of PAO are in
animal feed, soap making, and distilled fatty acid production. This product is not
now produced on any great scale outside Europe because in Malaysia and Indonesia
palm oil is refined by the physical process which gives (PFAD) rather than PAO
(Ataga et al, 1993).

2.5.2 Palm Fatty Acid Distilled (PFAD)

Palm fatty acid distilled (PFAD) is a by-product from the physical refining of palm
oil which is now the most widely used process in the major producing countries. Its
scale of production is large enough to support significant international trade in it.
(PFAD) has a very similar composition to palm acid oil (PAO) but it generally has
higher FFA (over 70 %), the balance being neutral oil and up to 1 % moisture and
impurities (Koh et al, 1981). Good quality material has a good smell and high colour
its main uses are in animal feeds, including some specialty products, in soap making,

16
and in the product of distilled fatty acids. This product is produced in much greater
volume than PAO.

2.5.3 Palm Kernel Oil (PKO)

Palm kernel oil (PKO) is derived from the kernel of the palm fruit and so it is a co-
product of palm oil production, Linoleic acid (12 %). However, refined blenched
deodorized (RBD) palm oleic oil POo is usually traded on the specification of FFA
0.1 % max SMP 24C Max and IV56min (Smith et al, 1986) on loading. There is a
good inverse correlation between the IV and the SMP and SFC of Oleic, and buyers
should aim for the highest value POo which is much more stable to Oxidation and
flavour deterioration than any of the major seed oils, its main disadvantage is its
tendency to become cloudy, or even semi-solid in a temperature climate.

2.5.4 Palm Stearin (Ps or POs)

Palm stearin is the harder fraction from the fractionation of palm oil, the softer
fraction being the Olein. The name stearin is usually abbreviated as PO s or Ps, with
the fish one more usually in technical writings. The demand for stearin is lower than
that for olein and so it has always been sold at discount to both Olein Oils. The main
characteristics of POs and SMP 47-54, IV 28 45 and SFC 25-71 % at 20oC its average
fatty acid composition is palmitic acid (57 %). Olein acid (20 %) and linolein acid
(7 %), (Atage et al 1998). However, refined blenched deodorized (RBD) PO s are
usually traded on the PORAM specification of FFA 0.2 % Max, SMP 44 c Min., and
IV48 Max on loading. In the past, there was much futile debate about whether oils
of such high melting would have reduced digestibility and indeed whether they could
be considered edible. POs are meant to be bleached with other softer oils and it is the
MP of the blend that counts more than that of its components. Palm stearin is very

17
useful in the formulation of pastry margarine, table margarine with
interesterification, and hard long-lasting soap.

2.5.5 Double Fractionated Palm Olein or Super Olein (POoo or DFPOo)

Double fractionated palm Olein, or Super Olein is a softer type of Olein Obtained
by fractionation of the standard Olein in order to achieve the maximum possible
fluidity. The name is POoo or DFPOothe first one more usual in technical writings.
This is a specialty product, for which there is no common standard such as PORAM,
and so there are differences according to the manufacturer. Its price is always at a
premium to standard Olein. The main characteristic of POoo are SMP 13-17°C IV
60-68 and SFC 0-26 % at 10oC. Its major fatty acids are palmitic acid (35 %), Olein
acid (45 %), and linoleic acid (13 %) (Ataga et al,1998). Different manufacturer set
their Limits within the above ranges. POoo is used for bottling, as it remains fully
liquid in tropical climates and also in temperate climates if blended with sufficient
seed oil. Its great advantage over the major seed oils is its much greater resistance to
oxidation.

But palm kernel oil (PKO) is a minor product and in World terms, about 8½ tons of
PO is produced for every tonne of PKO. This oil together with coconut oil composes
the lauric group. So named because their fatty acid composition is based
predominately on lauric acid, PKO has a slip melting point of 26-28°C, iodine value
of 16-19, and SFC (20oC) about 40 %. Its fatty acid composition consists mainly of
lauric acid (C 12:0) about 48 %, myristic and (C 14;0) 16 %, and Olein acid (18:0)
15 %, with total, saturates of about 82 % crude PKO usually traded on the basis of
FFA 5 % max. Moisture and impurities 1 % max and IV 19 max (Ataga et al 1998).
On loading, Palm kernel oil (PKO) is very similar to coconut oil and has very similar
uses, primarily in ice cream, sugar confectionary, substitute chocolate, special
bakery margarine, Oleochemical, and soap. A proportion of lauric oil is necessary
18
for soap formulations, to confer good lathering properties PKO is also fractionated
into PK stealin (used as CBS) PK Olein.

2.5.6 Palm Kernel Stearin (PKS)

As in the case of palm oil (PO) substantial quantities of palm kernel oil (PKO) are
fractionated in the producing countries and in Europe, into PKS and palm kernel
Olein (PKOo), but in this case, the stearin is the more valuable product, compared
with PKO, it has a higher melting point, lower IV and higher SFC at all temperatures.
Typical values are SMP 32-33oC, IV 6-8, SFC (20) about 82 %, and SFC (35) 0 %.
The lauric acid (C 12:0), content is about 57 % (Lumpur et al 1996). The
combination of very high SFC (20), low MP, and good Oxidative stability, makes
PKS excellent confectionery fat. Its main use is as a cocoa butter substitute (CBS)
either as it stands or after some hydrogenation. It is also used for other confectionery
products. High-quality biscuit creams, toppings, and similar products. In the past
when most of its production was concentrated in Western Europe, this fat is a rather
expensive specialty. But with rapidly increasing PKO production and fractionation
moving to S.E. Asia, it is becoming much more easily accessible, and competitively
priced.

2.5.7 Palm Kernel Olein

Palm Kernel Olein (PKOo) is the secondary product of PKO fractionate, normally
selly at a small discount to PKO. Compared with PKO the Olein has higher IV, and
lower melting point and SFC at all temperature. Typical values are IV 21-25, SMP
22-25C and SFC (20oC) about 17 %. Its major fatty acids are approximately lauric
acid (c 12:0) 45 % and Olein acid (C 18:1) 19 % (Sivasothy, 2006). PKO0 is very
suitable for rice cream making and also for soap production to provide the necessary
lauric acid when hydrogenated PKO and can be used for the same applications such

19
as biscuit and cake creams, sugar confectionery, chocolate flavored coating, filled
milk, coffee whiteners, vegetable cheese analogue, and similar products.

2.5.8 Palm Kernel Meal (PKM)

Palm kernel meal (PKM) is the meal left after removing the oil from the palm kernel,
which can be done by solvent extraction, or by pressing or both. Palm kernel
Expellers (PKE) refer to the particular grade of meal produced using expeller-types
crew processes. This grade has a higher fat content (6-86 % against 1-2 % for the
solvent-extracted meal) and no risk of residual solvent and so it is in greater demand
and sells at a higher price (Koh et al, 2007). PKE is the main grade imported by the
EU which is its biggest importer and user. PKM of all grades is used for animal feeds
especially cattle, either alone, or after compounding with other feed to produce a
more balanced food for the animal. It is classified as an energy feed and so it
competes on price with copra meal, barley, corn, tapioca, and similar, in contrast to
Soya beans meal, fish meal, etc which are “protein meals” and sell at much higher
prices. PKM also has the disadvantage of higher levels of indigestible fiber and
grittiness due to shell residues and aflatoxin contamination if improperly produced
or shipped. PKE usually contains 14-19 % protein and 6-8 % fat, but in international
trade, the main specification item is protein + fat 21 – 23 % (Alamu et al, 2007).

2.6 Physicochemical Properties of Palm Kernel Oil

Fats and oil have certain specific chemical and physical characteristics which vary
within a limited range.

2.6.1 Physical Properties

i. Colour and Solubility: Triglycerides are hydrophobic substances that are soluble
only in some organic solvents unlike many other types of complex lipids, they
possess no electric charges and are therefore referred to as neutral lipids.
20
a. Palm kernel oil is insoluble in water, but when agitated with water in the
presence of an emulsifying agent, they, however, form an emulsion.
b. They are soluble in most organic solvents such as ethyl ether, chloroform,
benzene, naphtha, carbon bisulphate carbon tetrachloride, etc. They are slightly
soluble in alcohol. The oil is yellowish in colour depending on the processing and
has a characteristic aroma of palm kernel oil due to methylyoxyketone (Esminger et
al, 1990).
ii. Density: Densities of fats in the liquid state do not differ much for most of the
common fats. The density of a material is given in cubic meters in the S.I. system of
units. This property is defined as the ratio of mass to volume of a substance.
Generally, the mass is measured in grams, and the volume in millimeters or cubic
centimeters. Density measurements of liquids are straightforward and sometimes can
aid in identifying pure substance mixtures that contain two or three known
components. They differ significantly in their individual densities.
iii. Specific Gravity: Specific gravity is a related quantity that is defined as the ratio of
the density of the analyte to the density of water at a specific temperature. Density
and specific gravity measurement rarely provide sufficient information to
qualitatively identify a pure analyte. They can be used as supporting evidence when
an essay is performed by another procedure.
iv.Viscosity and Oiliness: One of the most noticeable characteristics of vegetable oil
is its oiliness or ability to form lubricant films. Viscosity is a measure of internal
friction in molecules, the resistance of a substance to change a shape or resistance to
the flow of a liquid. This is measured by a viscometer. The higher the flow rate, the
lower the viscosity. The rate is expressed in centipoises. Fat and oil show relatively
high viscosities compared to other liquids because of the high intermolecular
attraction of the long alkyl chains of their glyceride molecules. Fat and oils behave

21
as Newtonian liquids except at a very high shear rate where degradation may begin
to occur.
v.In general, the viscosity of oil decreases slightly with an increase in the degree of
unsaturation and with an increase in average molecular weight thus viscosity is
increased by hydrogenation. The viscosity of oil increases by polymerization (Smith,
2009). Oiliness generally connotes a relative ability to operate under boundary
lubrication conditions. The term relates to a lubricant's tendency to wet and adhere
to a surface (Knothe et al, 2005).
vi. Melting and Solidification Point: Most mixtures and amorphous solids melt over
a range of temperatures. As heat is applied to a solid, its temperature will increase
until the melting point is reached. More heat then will convert the solid into a liquid
and the solid has melted thereby raising the temperature. Pure compounds usually
display sharp melting points and impure compounds show a broad melting point.
Triacylceride reflects the melting point of their constituent fatty acids. A low degree
of unsaturation, high molecular weight, and the presence of trans rather than cis-
Isomer of unsaturated acid all contributed to a relatively high melting point (Munack
et al, 2007).
vii. Refractive Index: Refractive index of a fat or oil is one of the most important acids
for classifying fatty oils since it is closely related to the nature of the product
(molecular weight and degree of unsaturation) and can be determined quickly with
great accuracy. In order to obtain values for both liquids and oils, most control
laboratories operate the instrument at increased temperature (48-60 oC).
viii. Surface and Interfacial Tension: The surface tension of refined oil such as cotton
seed oils is about 35 dyn/cm and the interfacial tension against water is about 30
dyn/cm at 60-70 oC. Surface tension increase in chain length and decrease with
increase in temperature (Schroder et al, 2001).

22
2.6.2 Chemical Properties

i. Saponification value: The saponification value measures the bonded and unbonded
acids present in the oil. It defines the exact potassium hydroxide (KOH) in
milligrams necessary to emulsify 1g of oil. The smaller the molar mass of the oil,
the higher its saponification value.
This also indicates the average molecular weight of fats and oils. Saponification
value may be defined as the number of milligrams of caustic potash required to
neutralize the fatty acids obtained by the complete hydrolysis of one gram of oil or
fat. Thus, saponification value gives us information on whether:
▪ An oil or fat contains a lower or higher proportion of some fatty acids.
▪ An oil or fat contains a high proportion of lower or higher fatty acids.
Since butter has a large proportion of lower fatty acids than lard and tallow, the
former has a high specification value. Coconut oil has a comparatively high
specification value (SV247), butter fat (SV225), oliver oil (SV200), and carrot oil
(SV180).
ii.Peroxide value: This indicates the degree of oxidation that takes place in the oil. It
is used for determining the peroxide oxygen (especially hydroperoxides). It is
expressed in milli equivalents of active oxygen per 1kg of oil/fat. As oxidation takes
place, the double bonds in the unsaturated fatty acid are attacked forming peroxides.
Thus, the peroxide value can therefore be used to estimate oxidation.
iii.Acid value: The acid value is a common parameter in the specification of fats and
oil. It is used to express the degree of acidity of the oil and it is the number of
potassium hydroxides required to neutralize the free acid in 1g of oil.
iv.Iodine value: iodine is a measure of the degree of unsaturation of the oil, this
represents the number of unsaturated C=C double bonds contained in the oil. It is
defined as the number of milligrams of iodine absorbed per gram of oil sample. The

23
greater the total unsaturation, the higher the iodine value. Iodine value determination
is important because depending on its value, oil can be classified into drying, semi-
drying, and non-drying oil. The ability of the oil to undergo oxygen-induced cross-
link reaction leads to the formation of a solid film known as drying (kirk et al, 2009).
v.Ester value: the ester value is a relative measure of the amount of ester present. It
is obtained by subtracting the acid value from the specification value therefore; it
is expressed in the same terms as the specification value and the acid value. The
process of esterification is when a fat that contains a mixture of triglyceride is
allowed to head in presence of an alkaline catalyst, a random exchange of acyl group
takes place between different glycerides, and a mixture of glyceride molecules is
obtained which is quite different from the mixture of glyceride originally presents.
vi.Rancidification: On long-term storage or in contact with air, vegetable oils undergo
low decomposition and develop an unpleasant smell, this process is known as
rancidification. Hydrolytic rancidity occurs under moisture, high temperatures, and
natural lipolytic enzymes.

24
CHAPTER THREE

3.0 MATERIALS AND METHOD

3.1 Collection and Preservation of Oil Sample

Palm kernel oil (crude and refined) which served as a sample for analysis were
purchased from High level and Wadata markets, Makurdi, Benue state on 17th April
2018. The two oil samples were properly kept in sealed plastic containers and
preserved from direct sunlight and heat. All chemicals used for this analysis were of
analytical grade.

3.1.1. Apparatus
● 25, 50, 100, and 250 ml Measuring cylinder
● Analytical Weighing balance
● conical flask
● Volumetric flask
● Glass rod
● Gas cylinder
● 25 ml pipette
● 100 ml flat bottom flask
● 50 ml burette
● Reagent bottles
● Beaker
● Spatula
● Dropper
● Cork
● Bunsen burner

25
3.1.2. Reagent
● Ethanol
● Diethyl ether
● Potassium hydroxide
● Phenolphthalein indicator
● Hydrochloric acid
● Distilled water
● Sodium thiosulphate solution
● Potassium iodide
● Starch solution
● Carbon tetrachloride
● Wij’s solution
● Acetic acid
● Chloroform

3.2 Physicochemical analysis

The oil will be subjected to the following analysis.


1. Free fatty acid (FFA)
2. Iodine value
3. Saponification value
4. Peroxide value
5. Moisture content
6. Specific gravity

3.2.1 Free Fatty Acid Value Determination

The method of analysis of the Association of Analytical Chemists (1984) will be


used. 1g of the oil sample was dissolved in 50 ml of neutral solvent (25ml of diethyl

26
ether and 25 ml of 95 % ethanol) in a conical flask. 2-3 drops of phenolphthalein
indicator were added and the solution was titrated with 0.1M alcoholic KOH until a
pink colour which persisted for 15 seconds was obtained. The titer value of the 0.1M
alcoholic KOH was then used to calculate the Free Fatty Acid as a percentage of
oleic acid.
𝑇×282
Percentage Free Fatty acid= × 100
1000×10𝑔

Where T= titer value of alcoholic KOH used

282= molecular weight of oleic acid

g= weight oil sample used

3.2.2 Iodine Value Determination

The American Oil Chemist’s Society (AOCS) method described by Onwuka (2005)
will be used. 0.2g of the oil weighed using a meter balance will be poured into a
250ml conical flask and 25.0mL wij’s solution will be added to each sample along
with 10.0mL carbon tetramethane, the flask was swirled and then placed in a dark
cupboard for 30 minutes. 15mL of 10% KI will be added followed by 100mL of
water. The resultant mixture will be titrated with 0.1M thiosulphates (Na2 SO4)
solution using 1 % starch as an indicator. A blank will be carried out without the oil.
The iodine value will be calculated as:

(𝐵−𝑆)×𝑀12.69
Iodine value =
𝐺

Where B= titer value of blank titration

S= titer value of sample titration

M= molarity of sodium thiosulphate

27
G= weight of oil sample

12.69 = equivalent of iodine

3.2.3 Saponification Value Determination

The Pearson’s method described by Onwuka (2005) will be used; 2g of the oil will
be weighed into a conical flask and 25 ml ethanolic potassium hydroxide solution
added to it. A reflux condenser will be attached to the conical flask after which the
flask content will be heated in boiling water for 1 hour with frequent shaking. About
1ml phenolphthalein (1 %) solution will be added and the alkali is titrated with 0.5M
HCl acid. The endpoint colour change from pink to yellow which disappears
completely after a few minutes. A blank titration will also be carried out without the
addition of the oil.

(𝑏−𝑎)×28.05
Saponification value =
𝑔

Where b= titer value of blank titration

a= titer value of sample titration

g= weight of the oil sample

28.05 = constant

3.2.4 Determination of Peroxide Value

The method described by Pearson (1976) will be used to determine the peroxide
value. 1.0g of the oil sample will be weighed into a clean conical flask followed by
1g of powdered KI and 20 ml of the solvent mixture (2 volumes glacial acetic acid
and 1 volume chloroform i.e., 3.1) the conical flask will be placed on a boiling water
bath to boil the mixture vigorously for a time not exceeding 30 seconds; 20 ml of KI
solution (5 %) will be added and the mixture titrated with 0.002M sodium

28
thiosulphate using (1 %) starch as an indicator. Peroxide value is given
by;
𝑇×𝑀
Peroxide value = × 100
𝑔

Where T= titer value of sodium thiosulphate solution

M= molarity of sodium thiosulphate solution

g= weight of oil sample used

3.2.5 Determination of Moisture Content

The hot oven method NAFDAC (1982) will be used in the determination of the
moisture content. The porcelain dish was thoroughly washed and dried in the oven
after which it was allowed to cool in the desiccators, then weighed (w1), about 5g of
the homogenous sample was weighed (w2) into the previously weighed dish and
placed in a thermostatic well-ventilated oven maintained at 105 oC for 4 hours. At
the end of the time, the dish was quickly transferred into the desiccator and allowed
to cool to room temperature. The weight of the dish and sample was recorded (w 3).
The process was repeated at an hour interval until a constant weight was obtained.
The percentage moisture content was calculated from the weight loss of the sample.
𝑤2 −𝑤3 100
% 𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒 𝑐𝑜𝑛𝑡𝑒𝑛𝑡 = ×
𝑤2 −𝑤1 1

W1 = Initial weight of empty crucible.

W2 = Weight of crucible and oil sample before drying.

W3 = Final weight of crucible and oil sample after drying.

CHAPTER FOUR

29
4.0 RESULTS AND DISCUSSION

4.1 Results

Table 4.1

Physicochemical Units Unrefined PKO Refined PKO


properties
Free fatty acid Mg/KOH/gm 5.20 3.30
Iodine value Mg/g 14.86 17.60
Peroxide value Mg/g 14.20 10
saponification Mg/g 206 249
Specific gravity S. G 0.903 0.90
Moisture content % 0.28 1.45

4.2 Discussion

4.2.1 Result of Saponification value

From the results obtained as presented in Table 4.1, the saponification value of
refined palm kernel oil (249 mg KOH/g) is higher than that obtained for crude palm
kernel oil (i.e.,206 mg KOH/g) and since the higher, the saponification value, the
higher the unsaturated level of the oil, it can thus be inferred that refined palm kernel
oil possesses more unsaturated fatty acids than the crude/unrefined palm kernel oil.
Pearson (1976) reported that a high saponification value contains a high proportion
of lower fatty acids. The saponification values obtained in this study are less than
the expected standard range of 318 to 319 mg KOH/g of oil for edible palm kernel
oils as specified by Nigeria Industrial Standard (NIS 1997). However, similar results
were presented by Atasie et al (2009). The results obtained were also comparable to
the standard range of 245-255 specified by SON (2000). Saponification values of
both oil samples are comparable to coconut oil (253 mg KOH/g) and butter fat (225
mg KOH/g) (Aremu et al., 2006). This quality in the oil quantifies its use in soap

30
production. It also indicates that the molecular weight of refined palm kernel oil is
higher than that of crude palm kernel oil (Theredore, 1983) hence it is preferable for
soap making.

4.2.2 Result of Iodine value

Iodine value is an index of the degree of unsaturation, which is one of the most
important analytical characteristics of the oil. It measures the level of unsaturation
of the oil and is, therefore a direct indicator of the oxidative stability of the oil. This
means an increase in iodine value indicates high susceptibility of oil to oxidative
degradation. From the table, the iodine value obtained for refined palm kernel oil
(i.e., 17.60 mgKOH/g) is higher than that obtained for the unrefined palm kernel oil
(14.86 mgKOH/g) depicting a higher level of unsaturation (Pearson, 1976). This
increase in the iodine value of refined palm kernel oil could be due to the detachment
of fatty acids which can lead to an increase in the degree of unsaturation of the lipid
(oil) and therefore, susceptible to oxidation. Hence, the addition of antioxidants may
be necessary to prolong the storage stability of this type of palm kernel oil. Duel
(1951) proposed that an iodine value above 100, makes oil dry and below 100 is
non-drying. The storage time, processing method, and the interaction between the
storage time and processing method of the palm kernel oil sample have a significant
effect on the iodine value.

4.2.3 Result of Peroxide value

The peroxide value determines the extent to which the oil has undergone rancidity,
thus it could be used as an indication of the quality and stability of fats and oils
(Ekwu and Nwagu, 2004). From the analysis, the peroxide value of crude/unrefined
palm kernel oil (i.e., 14.00 mEq/kg) is considerably much higher than that obtained

31
for refined palm kernel oil (10.00 mEq/kg) which is negligible. This is an indication
of the degree of spoilage of crude palm kernel oil which probably is more liable to
go rancid than refined palm kernel oil. This is not unexpected as a result of the
inferred higher level of unsaturation. Rancidity begins to be noticeable when the
peroxide value is well above 10 mEq/kg (Pearson, 1976). Furniss (1978) indicated
that the lower the molecular weight of oil, the higher its unsaturation.

4.2.4 Result of Free Fatty acid value

The free fatty acid value obtained for refined palm kernel oil (i.e., 3.30 mg KOH/g)
is lower than that obtained for crude palm kernel oil (i.e., 5.20 mg KOH/g) indicating
the lower level to which the glycerides in the oil had been decomposed by lipase
action (Pearson, 1975). Therefore, refined palm kernel oil is in good condition and
preferable for consumption since its acid value is less than the values obtained for
crude palm kernel oil. However, the values obtained were not within the range
reported by AOCS, (1996) and Swerm et al, (1964). The low FFA value of palm
kernel oil is an indication that the oils will be most suitable for biodiesel as an
alternative to traditional oil. Storage time and processing method have a significant
effect on the free fatty acid value. The table also showed that crude palm kernel oil
has a specific gravity of 0.903 compared to that of refined palm kernel oil (i.e.,
0.900) indicating that the molecular weight of crude palm kernel oil is lower than
that of refined palm kernel oil.

4.2.5 Result of Moisture

Moisture content is the quantity of water contained in a material such as oil, it is


used in a likely range of scientific and technical areas and it’s expressed as a ratio.
It ranges from zero, (completely dry) to the value of the material’s porosity at
saturation. The moisture content is one of the most important indicators of oil

32
determination. The increase in moisture content of the refined palm kernel oil as
observed from the table above, refined palm kernel oil’s (1.45 %) to crude palm
kernel oil (i.e., 0.28 %) indicates that there is a high amount of water present in the
refined PKO sample, this could be as a result of the storage environment of the oil.
This higher moisture content of the refined PKO indicates a high level of primary
oxidation in the oil (Tor, P.N et al). The moisture content value of crude PKO (0.28
%) is however within the standard value of 0.2 % given by NIS. The values obtained
from the results are however lower than the value (6.5%) reported by Atasie et al
(2009).

33
5.0 CHAPTER FIVE

5.1 CONCLUSION AND RECOMMENDATION

5.2 CONCLUSION

Based on the results of the chemical analysis of palm kernel oil, Elaesis guineensis,
it can be concluded that PKO could be a valuable industrial oil; also, the high quality
and nutritional value of the oil has potential application in foods. Hence from the
results obtained from the analysis, the saponification value of refined PKO is higher
(i.e.,249 Mg KOH/g), hence a higher molecular weight, compared to the
saponification value of crude PKO (i.e., 206 Mg KOH/g) which thus have lower
molecular weight, it can be concluded that the refined PKO with a higher molecular
weight is preferable for soap making. Also, from the results obtained, crude palm
kernel oil is not easily perishable since it contains a low moisture content of 0.28%.

This study has established that palm kernel oil, like most contemporary edible oils,
also contains a high amount of unsaturated fatty acids required by the human body
as essential fatty acids, hence the desirability of palm kernel oil in the human diet.
Additionally, its higher content of inorganic materials makes it stand head and
shoulders high above its contemporary cooking oils. Based on the results obtained
from this work, and for the fact that the refined palm kernel oil has a lower FFA
value of 3.30MgKOH/g compared to the crude unrefined PKO which has a higher
FFA value of 5.20MgKOH/g, on the basis of this finding, it can be concluded that
the refined palm kernel oil is preferable for edible purpose.

5.3 Recommendation

Due to the immense domestic and industrial applications of palm kernel oil, further
studies should be undertaken to compare the various types of crude PKO. Also, more
research work is needed to determine the fatty acid composition of the oil. Additional
34
economical and sustainability studies should be undertaken; as purifying methods
for extracting the oil. In light of this, it is however recommended that further research
be undertaken to improve the organoleptic properties of palm kernel oil.

35
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