Professional Documents
Culture Documents
Volume 10, Issue 03, March 2019, pp. 353–363, Article ID: IJMET_10_03_036
Available online at http://www.iaeme.com/ijmet/issues.asp?JType=IJMET&VType=10&IType=3
ISSN Print: 0976-6340 and ISSN Online: 0976-6359
ABSTRACT
Crude castor oil seems to have many industrial applications. However, its Iodine
value range <100 (82 - 88 gI2/100g) makes it not applicable in the paint industries
since it is considered a non-drying oil. Experimentally, dehydration of its fatty oil is
the only way of converting its non- drying attributes into a drying one. This process
involves heating the oil to a temperature of 250OC in the presence of catalyst such as
sulphuric acids, phosphoric acids, clays and metal oxides under an inert, atmospheric
or vacuum condition. Albeit a lot of research has been carried out on the different
catalyst used in dehydrating castor oil and the effect of catalyst percentage variation
in an overall continuous process, this study was however on the effect of sodium
bisulphate catalyst on a batch process. The change in the physiochemical properties
(hydroxyl, viscosity and iodine value) with respect to time and temperature was
considered. In the course of this study, Sodium bisulfate and Sodium bisulfite is chosen
as the catalyst and anti-polymerization agent respectively. The dehydration of castor
oil in the presence of catalyst speeds up the rate at which the maximum dehydration is
obtained (60min) but at the same time, speeds up the rate of polymerization. The
Iodine value rapidly decreases until it attains maximum dehydration wherein
polymerization (hardening of oil) takes place simultaneously. However, dehydration
reaction without catalyst takes longer time to reach maximum dehydration (180 min),
but does not readily polymerize when maximum dehydration is reached
Key words: Dehydration, Castor oil, Drying oil, Paint Industry
Cite this Article: Angela O. Mamudu, Enobong A. Charles, Francis Elehinafe,
Olayemi Odunlami and Damilola Akinneye, Effects of Sodium Bisulphate Catalyst on
the Dehydration of Castor Oil for the Paint Industry, International Journal of
Mechanical Engineering and Technology 10(3), 2019, pp. 353–363.
http://www.iaeme.com/IJMET/issues.asp?JType=IJMET&VType=10&IType=3
1. INTRODUCTION
Castor oil is a pale yellow non-edible vegetable oil extracted from the bean seeds of the
Castor oil plant (Ricinus Communis L.). The plant belongs to the spurge family
Euphorbiaceae. The family Euphorbiaceae is a wide, diverse and numerous group of the
angiosperm, including the species of great economic importance such as rubber tree (Hevea
Brasilens) and Cassava (Manihot Esculenta) [1]. Although Castor bean is very useful, it is
also considered one of the deadliest natural poison ever known to man due to the presence of
ricin: a very toxic substance to human, animals including insects. Its species include Gibsonii,
Carmencita pink, Carmencita Bright Red, Impala, Red Spire and Zanzibarensis [2]
Castor oil is commonly found in the South Eastern Mediterranean region, Eastern Africa,
and generally in the tropical and subtropical regions of the world [3,4,5 and 6].Currently India
is the world’s leading producer and exporters of castor seed. Other major producers include:
Brazil, China, Paraguay and Ethiopia [7]. In Nigeria, castor plant can be found growing in
Lagos, Ogun, Enugu, Ebonyi and most commonly in the North region (Daily Trust
Newspaper, 2018).
The percularity of castor oil is due to the presence of the hydroxyl fatty acid known as
ricin-oleic acid (C18H34O3); an 18- carbon hydro-xylated fatty acid having initially only one
double bond [8]. Generally, Castor oil consist of 89.5% ricin-oleic acid, 4.2% linoleic acid,
3% oleic acid, 1% stearic acid, palmitic acid(1.0%), Dihydroxystearic acid (0.7%), Linolenic
acid(0.3%) and Eicosanoic acid (0.3%). Previous research works have documented that
ricinoleic acid is the major constituent in the oil; over 89% [5]; 90.2% [9]; 89.2-94.9% [10];
about 70-90% by [11]; 87-90% [12].
The hydroxyl functional group of Ricinoleic acid (RA) gives castor oil specific properties
and attributes [13]. It makes the oil a natural polyol therefore giving it oxidative stability. It
gives castor oil a relative high shelf life by preventing the formation of peroxide. The
Hydroxyl group in ricinoleic acid also presents a functional group location in which various
chemical reactions such as dehydration, halogenation, alkoxylation, sulfation and
esterification can be performed [14]. According to [15] the high content of Ricin-oleic acid
and other physiochemical properties present, makes castor oil a very valuable commodity in
the medical, pharmaceutical and industrial sector at large (cosmetic, chemical ,petrochemical,
food, automobile and fuel).
Albeit, crude castor oil seems to have many industrial applications, its Iodine value range
<100 (82 - 88 gI2/100g) makes it not useful in the paint industries since it is considered a non-
drying oil. Generally, Oils are classified based on their Iodine value range into drying, semi-
drying and non-drying oils. Generally, as the iodine number increases, the drying capacity of
the oil increases
Non-drying oil iodine values fall below 100. When brought in contact with oxygen or
exposed to air, there is no appreciable drying. Examples include olive oil, argan oil, mineral
oil, babassu oil and coconut oil [16]. Semi-drying oil iodine values fall within the range of
100-130. These oils dry within acceptable limits that is partially dry when exposed to air.
Examples of semi-drying oil include sesame oil, cottonseed oil and corn oil [16].
Drying oil are oil that when spread into a film becomes hard, tough, and elastic upon
exposure to air (Britannica.com). They dry rapidly in contact with atmospheric oxygen and
usually have Iodine values within the range of 130-190. According to [17], Examples of
drying oil with their respective iodine value are Tung (234), Linseed (190.4), Catalpa (195.5)
and sunflower oil (139.1). These oils consist of glycerol tri-esters of fatty acids that are
characterised by high level of polyunsaturated fatty acids such as oleic acid, linoleic acid as
well as related saturated and unsaturated acids. The capacity of drying oil is related to the
amount of double bonds in its fatty acids, their positions in the molecule (conjugated or
isolated), and the geometric arrangement of the substituents around the double bonds (cis or
trans configuration).
Drying oils are the basic vehicles of oil paints. The hardening of drying oil is generally
considered to be due to the action of oxygen (oxidation). The primary reaction considered are
the formulation of unsaturated ester hydro-peroxides, the decomposition of these materials
and their subsequent cross-linking. The process begins when drying oil is exposed to
atmospheric oxygen. The oxygen molecule in air attaches itself to a carbon-hydrogen(C-H)
bond adjacent to one of the double bonds within the unsaturated fatty acid forming hydro-
peroxides. The hydro-peroxides formed are very reactive compounds that easily take part in
cross-linking reactions. Bonds form between neighbouring fatty acid chains result in a
polymer network. The polymer network is visible as skin like film formed on samples. In
summary, drying oils polymerize thereby forming a visible film [16].
atom. Therefore, the study of the disappearance or decrease in hydroxyl content with time
shows the course of dehydration [20]. Generally, as the hydroxyl group decreases, its
viscosity also reduces while the iodine value increases [20]. The elimination of every
hydroxyl group leads to the creation of a new double bond along with the already existing
double bonds thereby increasing the unsaturation level (Iodine value).
Viscosity is defined as the resistance of a liquid to flow. Castor oil is a vegetable oil with
relatively high viscosity in comparison to other oils. This is because of the presence of the
hydrogen bonds formed by the Hydroxyl groups [5]. The viscosity in this study is a parameter
that will be monitored in order to determine the rate of disappearance of the hydroxyl groups
during the dehydration reaction.
2. METHODOLOGY
2.1. Oil Extraction
White Big Size (WBS) Castor seeds were collected from Ogun State, Nigeria.
De-hulling: The seeds were de hulled manually by hand
Screening: The damaged seeds were sorted and selected from the good seeds by hand picking.
Damaged seeds are discarded.
Drying/Cooking: Selected seeds are further dried in an oven to a temperature of 60ᵒC in order
to reduce moisture content.
Grinding: Grinding to form paste was done using a manually operated grinding machine
of the extractor. The commercial hexane was heated to a constant temperature of 60 0C. This is
allowed to continue for four (4) hours. This procedure was repeated for eight (8) samples of
castor paste each weighing 200g. The samples are then removed from the tube, dried in the
oven and weighed again. The eight (8) samples of castor paste then underwent a second phase
of extraction known as the recycle extraction to further extract oil that left after the first phase.
25 ml each of Carbon tetrachloride and hanous solution each 25 ml were properly mixed and
added to the oil in the iodine flask. The content of the flask is also shaken well to ensure
complete mixing.
Standardized sodium thiosulfate solution is titrated against the content of the iodine flask.
The indicator used is standard potassium dichromate solution with starch
The same process was repeated for the non-catalyst samples
The iodine values of the different samples were calculated from equation (2) below
(2)
Where Z is the amount of Iodine consumed by the oil (ml), M1 the strength of thiosulfate,
A the weight of oil and bottle (gram) and B the weight of the bottle alone (gram)
reduced due to this reaction thereby rendering the oil unsuitable for biodiesel manufacture and
limiting its use in the chemical industry (Omari et al., 2015).
3.1.2. Percentage Yield
The percentage yield of the extraction process was calculated from equation 3 below
(3)
13.66%
Previous works have reported that the yield of Castor oil from the African castor bean
usually falls between the values of 35.7% to 51.9 %. For example, research was conducted on
the adaptation and performance capacity of 19 castor bean genotypes in Mediterranean
climate and reported that seed oil content depends on both genotype and environmental
conditions thereby giving a possible yield ranging from 44.5 to 54.2% [25] .As stated
previously, the productivity or yield varies depending on factors such as seed harvesting
practices, environment, genotype and extraction method (Tchuentu., 2017). Table 1 above
shows the number of extraction cycles that were performed. The resulting weight loss is
recorded after each extraction cycle. Therefore, substituting the required values into equation
3 we are able to calculate for the yield (13.66%). Continuous recycling will yield greater yield
value but for the sake of this experiment, 308.3g of oil is obtained by extracting 1700g of
castor paste.
split of are responsible for the thickness or viscosity of the castor oil. The viscosity of the oil
tends to decrease as the hydroxyl group present in the oil are eliminated. When
polymerization occurs due to crosslinking network formed by the hydro-peroxides, the
viscosity begins to increase
4000
3500
3000
VISCOSITY(cps)
2500
2000
1500
1000
500
0
0 20 40 60 80 100 120 140
TIME (min)
2000
1500
1000
500
0
0 50 100 150 200
TIME(min)
160
140
120
IODINE VALUE(cps)
100
80
60
40
20
0
0 20 40 60 80 100 120 140
TIME(min)
Figure 5 Variation of Iodine Value with time in a dehydration reaction with catalyst.
3.2.5. Dehydration Reaction without Catalyst (Iodine Value with Time)
Figure 4 below shows the change in Iodine value with time in a dehydration reaction without
catalyst. The Iodine value increases continuously with time. At the point where maximum
dehydration is attained, the Iodine value continues to increase. This is evidence to show that
polymerization does not occur simultaneously after maximum dehydration is reached.
Thereby it can be said that the presence of a catalyst is effective in promoting
polymerization. The viscosity of the oil tends to decrease as the hydroxyl group present in the
oil are eliminated. However, the viscosity begins to increase when polymerization occurs due
to crosslinking network formed by the hydro-peroxides. In the reaction without use of
catalyst, the Iodine value slowly and progressively increases until it attains a value above 130
thereby making it a drying oil. The rate of polymerization is reduced at the risk of reducing
the rate of dehydration. This is because the oil did not show signs of polymerization or
hardening though the colour of the oil darkened as continuous heat was being applied.
160
140
120
IODINE VALUE(cps)
100
80
60
40
20
0
0 50 100 150 200
TIME(min)
Figure 6 Variation of Iodine value with time in a dehydration reaction without catalyst
4. CONCLUSIONS
From the data obtained, it is evident that the dehydration of castor oil in the presence of
catalyst speeds up the rate at which the maximum dehydration was obtained (60min) but at
the same time, the rate of polymerization. If reaction is not carried out under typical
controlled situations where the limiting temperature mark is exceeded, the DCO required will
not be obtained.
However, dehydration reaction without catalyst takes longer time to reach maximum
dehydration (180 min), but does not readily polymerize when reached. Though the colour
changes are evident, it still produces castor oil of similar viscosity and Iodine value.
ACKNOWLEDGEMENT
I want to express my deep thanks to the management of Covenant University, Nigeria for
providing an enabling environment for this research. I also want to express my profound
gratitude to my co- authors for their wonderful contributions
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