Epoxidation of Vegetable Oils - A Review

International Journal of Advanced Engineering Technology
E-ISSN 0976-3945
Research Article
EPOXIDATION OF VEGETABLE OILS: A REVIEW

Tayde Saurabh.a*, Patnaik M.b, Bhagt S.L.a, Renge V.C.a
Address for Correspondence

a
Department Of Chemical Engineering College Of Engineering And Technology. NH-6, Murtizapur Road,
Babhulgaon (Jh) AKOLA 444104, Maharashtra State. INDIA.
b
Chemical Industries Division. Mahatma Gandhi Institute of Rural Industrialization, Maganwadi, Wardha442001, Maharashtra State. INDIA.
ABSTRACT
Vegetable oils are the fats and lipids containing triglyceride molecules. Most of the vegetable oils have high contents of
unsaturated fatty acid and can be converted into epoxy fatty acid by conventional epoxidation, catalytic acidic ion exchange
resin, metal catalyst epoxidation or using chemoenzymatic epoxidation. Nowadays epoxidized vegetable oil is having great
concern as they obtain from sustainable, renewable natural resource and are environmental friendly. Epoxidized vegetable
oil (EVO) can act as a raw material for synthesis of variety of chemicals including polyols, glycol, carbonyl compound,
lubricants, plasticizers for polymer etc. because of their respectable oxirane oxygen content and high reactivity of oxirane
ring. This paper presents an overview of epoxidation of different vegetable oils.
KEY WORDS Epoxidation, EVO, Oxirane Oxygen Content
INTRODUCTION
This review focused on the finding of the potential
utility of epoxidized vegetable oil and developing
newer means for its widespread applications.
Vegetable oil finds sustainable and renewable source
of raw material. The unsaturation present in
vegetable oils can be chemically modified to a value
added product by a complicated reaction called
epoxidation. Due to the high reactivity of the
oxirane ring epoxides can also act as a raw material
for synthesis of variety of chemicals such as alcohols
(polyols), glycols, olefinic compounds, lubricants,
plasticizer and stabilizer for polymers and their
demand is increasing day by day. Vegetable oil
represents one of the cheapest and most abundant
biological feedstock available in large quantities and
its use as starting material offers numerous
advantages such as low toxicity and inherent
biodegradability[1].Thus the economic value of the
vegetable oil could be increased by converting the
vegetable oil into epoxidized vegetable oil. The
double bonds in the vegetable oil are used as reactive
sites in the coatings and they can also be
functionalized by epoxidation. Thus the high
molecular weight products can be obtained by
increasing the cross linking. Now due to the
increasing levels of awareness regarding environment
is driving the development of sustainable green
materials. Petrochemical based resin such as epoxy,
polyester and vinyl ester find more engineering
application because of their advantageous material
properties such as high stiffness and strength.
However these resins have serious drawbacks in
terms of biodegradability, initial processing cost,
energy
consumption
and
health
hazards.
Consequently there is a requirement to develop novel
biobased product from renewable feedstock.
Therefore a number of researchers have been studied
IJAET/Vol.II/ Issue IV/October-December, 2011/
vegetable oils as alternative feedstock to substitute

for petroleum[2-5]. Hence it needs to be explored for
the various applications in chemical industry
VEGETABLE OILS: STRUCTURE,
COMPOSITION, PROPERTIES AND
EXTRACTION
Vegetable oils are predominantly the triglyceride
molecules. Triglycerides are also known by the name
triacylglycerol (TAG). In vegetable oil glycerol
molecule is attached to the three fatty acid chains of
unsaturated and saturated fatty acids. The saturated
fatty acids contain only single bond between two
carbon-carbon atoms while the unsaturated fatty
acids contain many double or triple bond between
two carbon atoms. A generalized structure of
triglyceride is shown in the following figure1.
Fig1. Structure of a typical triglyceride molecule[6].

1) COMPOSITION AND PROPERTIES
Many naturally occurring fats are containing fatty
acids with variation in chain length between 14-22
carbon atoms and single to triple bonds between two
carbon atoms. The unsaturated fatty acids present in
vegetable oil are oleic acid, linoleic acid and linolenic
acid containing one, two and three double bonds
between two carbon atoms respectively. The
functionality present in vegetable oil is in terms of
double bonds thus the C=C acts as a reaction site for
chemical modification in vegetable oil[7].
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Table1. Chemical Structure of Common Fatty Acid[8]

Fatty Acid
Lauric
Myristic
Palmitic
Stearic
Arachidic
Behenic
Lignoceric
Oleic
Linoleic
Linolenic
Erucic
Systematic Name
Dodecanoic
Tetradecanoic
Hexadecanoic
Octadecanoic
Eicosanoic
Docosanoic
Teracosanoic
cis-9-octadecanoic
cis-9, cis-12- octadecadienoic
cis-9, cis-12, cis-15-Octadecatrienoic
cis-13-Docosenoic
Structure
12:0
14:0
16:0
18:0
20:0
22:0
24:0
18:1
18:2
18:3
22:1
Formula
C12H24O2
C14H28O2
C16H32O2
C18H36O2
C20H40O2
C22H44O2
C24H48O2
C18H34O2
C18H32O2
C18H30O2
C22H42O2
Table 2.Chemical Composition of Vegetable Oila [8-9]

Vegetable Oil
Corn
Cottonseed
Crambe
Linseed
Peanut
Rapseed
Safflower
H.O.Safflower
Sesame
Soybean
Sunflower
Tr= Traces
14:0
0
0
0
0
0
0
0
Tr
0
0
0
16:0
12
28
2
5
11
3
9
5
13
12
6
18:0
2
1
1
2
2
1
2
2
4
3
3
Fatty Acid Composition, Wt %

20:0
22:0
24:0
18:1
Tr
0
0
25
0
0
0
13
2
1
1
19
0
0
0
20
1
2
1
48
0
0
0
64
0
0
0
12
Tr
0
0
79
0
0
0
53
0
0
0
23
0
0
0
17
22:1
0
0
59
0
0
0
0
0
0
0
0
18:2
6
58
9
18
32
22
78
13
30
55
74
18:3
Tr
0
7
55
1
8
0
0
0
6
0
Table 3.Chemical Composition of Vegetable Oilb [8-9]

Vegetable Oil
Rice-Bran
Sal
Mahua
Neem
Karanjia
14:0
0.4-0.6
0.2-0.26
-
16:0
11.7-16.5
4.5-8.6
16.0-28.2
13.6-16.2
3.7-7.9
Fatty Acid Composition, Wt %

18:0
20:0
24:0
1.7-2.5
0.4-0.6
0.4-0.9
34.2-44.8
6.3-12.2
20.0-25.1
0.0-3.3
14.4-24.1
0.8-3.4
2.4-8.9
1.1-3.5
18:1
39.2-43.7
34.2-44.8
41.0-51.0
49.1-61.9
44.5-71.3
18:2
26.4-35.1
2.7
8.9-13.7
2.3-15.8
10.8-18.3
Table 4.Properties of Vegetable Oil [10-11]

Vegetable Oil
Corn
Cottonseed
Linseed
Peanut
Rapeseed
Safflower
Sesame
Soybean
Sunflower
Palm
Kinematic
Viscosity
(at 38 0C mm2 /s)
34.9
33.5
27.2
39.6
37.0
31.3
35.5
32.6
33.9
39.6
2) EXTRACTION OF OIL FROM OILSEEDS

Oilseeds usually have the oil encased in minute
cells that are deeply embedded in fibrous
structures. Most oilseeds, therefore, require grinding
or flaking to rupture the cells and heat treatment,
sometimes cooking and drying, to help release the
oil. Vegetable oilseed could either be processed by
traditional crude method of crushing seed without
delinting in undecorticated from or by scientific
process which involves removal of linter,
decortications, separation of hull, expelling, solvent
extraction and refining of oil. The chief
disadvantages of solvent extraction are the high
initial cost of the equipment and the fact that some oil
seeds disintegrate under the influence of the solvent
and consequently are difficult to handle. However,
Density (kg/l)
0.9095
0.9148
0.9236
0.9026
0.9115
0.9144
0.9133
0.9138
0.9161
0.9180
Iodine Value
Gms of I2 /100
gms of oil
127-133
98-118
170-204
86-107
97-108
141-147
104-120
120-141
118-141
50-55
extraction with solvents constitutes the most efficient

method for the recovery of oil from any oil-bearing
material. The minimum oil content to which oil cake
can be reduced by mechanical expression is
approximately the same for all oil seeds, ie. about 23%. Consequently, the oil unrecoverable by
mechanical expression, in terms of percentage of the
total oil, increases progressively as the oil content of
the seed decreases Substitution of solvent extraction
for pressing methods increases the yield of oil [12].
PROCESS OF EPOXIDATION
The double bonds in the vegetable oils are used as
reactive sites in coatings and they can also be
functionalized by epoxidation. The utilization of
epoxidized vegetable oil has become more common
in the past few years. Moreover, plasticizers and

additives for polymer PVC derived from vegetable
oil based have been shown to have improved
performance in terms of high resistance to heat and
light[13]. Epoxidized oil contains epoxide groups or
oxirane rings. The term epoxide can be defined as
cyclic ethers which consist of three elements in the
epoxide ring. The general process for the synthesis of
the epoxide groups is known as an epoxidation
reaction wherein an alkene is reacted with an organic
peroxy acid.
Established methods of epoxidation are as follows:
Epoxidation by Conventional Method
Epoxidation using acid ion exchange
resin(AIER)
Epoxidation using enzymes
Epoxidation using metal catalyst
Other Systems
I) CONVENTIONAL CHEMICAL TREATMENT
It is the most widely used process of epoxidation. For
safety point of view these epoxidation are usually
carried out using peracids formed in-situ, by reacting
a carboxylic acid with concentrated hydrogen
peroxide. This process performs industrially on large
scale.
In 2008, Dinda et al; worked on the epoxidation
kinetics of cottonseed oil using a hydrogen peroxide
catalysed by liquid inorganic acids i.e. HCl, H2SO4,
HNO3 and H3PO4. They used carboxylic acid i.e.
CH3COOH and HCOOH as oxygen carrier but they
found that acetic acid is more effective oxygen
carrier than formic acid. Out of all liquid inorganic
acid studied as catalyst, H2SO4 was found to be most
efficient and effective [14].
In the same year Meyer et al. (2008), worked on the
epoxidation of the soybean oil and jatropha oil by
conventional method. They carried out the
epoxidation reaction at 50 0C and atmospheric
pressure for about 10 hours. The maximum reaction
conversion was 83.3% for epoxidation of soybean oil
as catalyst[17].
Similarly Cai et al. (2008), worked on the kinetics of
in-situ epoxidation of soybean oil, sunflower oil and
corn oil by peroxyacetic acid catalysed H2SO4. In this
work they found that soybean oil has greatest
conversion rate and lowest activation energy for
epoxidation using peroxyacetic acid [18].
and 87.4% for epoxidation of jatropha oil[15]. An
epoxidation reaction of mahua oil using hydrogen
peroxide was done by Goud et al. (2005). In order to
optimize the process they studied various parameter
and factors including catalyst type, temperature,
reactants molar ratio and mixing speed on the
epoxidation reaction. Also they stated that the
economic value of mahua oil could be increased by
converting oil to epoxidized mahua oil. They used
H2O2 as oxygen donar and glacial acetic acid as
oxygen carrier in the presence of catalytic inorganic
acid i.e.H2SO4 and HNO3 but they concluded that
sulphuric acid is the best inorganic catalyst for this
system producing a high conversion of double bonds
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to oxirane groups when the epoxidation reaction

performed at the intermediate temperature of 55 0C to
65 0C to reduce the hydrolysis reaction[16].
In 2010, Jia Liankun et al. worked on the synthesis of
vegetable oil based polyether polyols via epoxidation
followed by ring-opening reaction. In this study,
epoxidation of cottonseed oil with epoxy oxygen
content from 5.25 wt% to 6.15 wt% was first
produced by peroxyformic acid generated in-situ
from hydrogen peroxide and formic acid, they used
HBF4 (40 wt%) The presence of strong mineral
inorganic acid such as H2SO4 as acid catalyst leads to
many side reactions such as oxirane ring opening to
diols, hydroxyl esters, estelloids and other dimer
formation[19]. The presence of this side reaction in
commercial preparation of fatty epoxide diminishes
their attractiveness as a starting material for further
elaboration, as producers may require expensive
purification[20].
II) ACID ION EXCHANGE RESIN (AIER)
METHOD
Acidic Ion Exchange Resin (AIER) is an insoluble
gel type catalyst in the form of small yellowish
organic polymer beads. Peroxy acid is obtained by
reaction
of
H2O2
with
carboxylic
acid
(HCOOH/CH3COOH). The peroxy acid interacts
with the catalyst by way of entering the pores of the
catalyst. Thus when AIER loaded into the reactor its
pores get filled with peroxy acid. It leads to low
oxirane degradation as triglyceride couldnt enter into
the gel type structure of AIER[21].
It is investigated that the conversion of unsaturated
fatty acids to oxirane ring using peroxy acid either
peroxyformic acid or peroxyacetic acid in the
presence of AIER shows different conversion for
different vegetable oil. Petrovic et al. worked on the
epoxidation kinetics and side reactions of soybean oil
in toluene with peroxyacetic acid and peroxy formic
acid in the presence of AIER as a catalyst. They
found that peroxyacetic acid is less efficient than
peroxy formic acid. Acidic ion exchange resin can be
used as catalyst to synthesize peroxy acids followed
by in-situ epoxidation of vegetable oils. While
studying the kinetics of in-situ epoxidation of
soybean oil in bulk catalyzed by ion exchange resin,
they find that AIER has prominent advantages over
conventional chemical method of epoxidation of
vegetable oil is that by improving the selectivity and
undesirable side reactions can be reduced to certain
level[22]. Goud et al. in 2006 worked on in-situ
epoxidation of karanja oil with aqueous hydrogen
peroxide and acetic acid in presence of Amberlite IR120 acidic ion exchange resin as catalyst. The
variables studied were stirring speed, hydrogen
peroxide to ethylenic unsaturation molar ratio, acetic
acid to ethylenic unsaturation molar ratio,
temperature and catalyst loading. The effects of this
parameter on the conversion to epoxidized oil were
studied at the optimum condition for the maximum
oxirane content was established. They reported that

the intermediate temperature in the range of 550C to
65 0C gives maximum conversion of double bonds to
oxirane groups and the reaction time was minimized.
Further they added that molar ratio of acetic acid to
karanja oil is 0.5 mol and a mole ratio of 1.5 for
hydrogen peroxide to oil was the optimal
concentration for the epoxidation reaction[23].
Mungroo et al. worked on the epoxidation of canola
oil with H2O2 as oxygen donar, acetic acid as oxygen
carrier and AIER (22 % loading) as catalyst. The
heterogeneous catalyst, AIER, was found to be
reusable and exhibited a negligible loss in activity.
The formation of epoxy adduct of canola oil was
confirmed by FTIR and 1H NMR spectral
analysis[24].
Sinadinovic-Fiser et al. worked on the kinetics of
epoxidation of soybean oil in bulk by peracetic acid
formed in situ, in the presence of an ion exchange
resin as the catalyst. The catalytic reaction of the
peracetic acid formation was characterized by
adsorption of only acetic acid and peracetic acid on
the active catalyst sites and irreversible surface
reaction was the overall rate determining step. They
investigated
that
increasing
the
catalyst
concentration, reaction temperature and acetic acid to
ethylenic unsaturation molar ratio increases the
reaction rate and oxirane content[25].
Dinda et al. investigated the kinetics of epoxidation
of cottonseed oil by peroxyacetic acid (PAA)
generated in situ from hydrogen peroxide and glacial
acetic acid (AA) in the presence of acidic ion
exchange resin (AIER) catalysts, namely Amberlite
IR-120. The effect of several variables including
temperature, stirring speed, catalyst loading, and
particle size, concentration of hydrogen peroxide and
AA on oxirane conversion was studied. A
satisfactory level of oxirane conversion (greater than
65%) with high selectivity (greater than 90%) could
be obtained if the epoxidation was carried out at
optimum conditions, using in situ generated PAA.
The LangmuirHinshelwoodHougenWatson (L
HHW) kinetic model approach has been adopted
for the development of overall reaction rate
equations, and the proposed kinetic model includes
the major side reactions for the estimation of kinetic
parameters. Kinetic parameters were estimated by
fitting experimental data using a nonlinear regression
method. From the estimated kinetic constants, the
activation energy for the AIER catalysed epoxidation
of cottonseed oil was found to be 10.1 kcal
mol1[26].
III) ENZYMATIC METHOD
To avoid side reactions and to make the process more
environmental friendly, enzyme catalyst are
preferred. Immobilized Candida Antarctica lipase
was used as the catalyst. The epoxidation reaction
can be improved by adding the lipase step wisely.
Enzymatic catalyst for epoxidation is a good
alternative to chemical treatment. The main limitation
however is the low stability of the lipase under the
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reaction conditions. The parameters affecting the

lipase activity and operational lifetime during
chemoenzymatic epoxidation of fatty acids were
investigated [27].
It is found that in biocatalyzed reactions, enzymatic
activity may also be lost due to elevated
concentrations of hydrogen peroxide or to
temperature effects. However, some recent papers
have shown that Candida antarctica B lipase
remained stable above 50 C, although this was not
favorable, mainly due to the decomposition of
hydrogen peroxide. Furthermore, at higher
temperatures, the enzyme acquires a more open
conformation, possibly increasing the accessibility to
sensitive amino acids in the inner regions of the
enzyme, and thus decreasing its catalytic activity
[28].
In 1990, Bjorkling et al. published the first results
related to chemo-enzymatic epoxidation. Later,
progress was made towards reducing the limitations
of industrial scale syntheses by making the procedure
a more environmentally acceptable alternative for
vegetable oil transformations [29] .While studying
the new synthesis with oil and fats as a renewable
raw material for the chemical industry, Ursula et al.
had stated that the lipase catalyst exhibited excellent
stability and activity during the epoxidation process
and can reuse many times[30].
Shangde Sun et al. (2011) worked on enzymatic
epoxidation of Sapindus mukorossi seed oil. The
Sapindus mukorossi seed oil (SMSO) was epoxidized
using hydrogen peroxide as oxygen donar and Stearic
acid as active oxygen carrier in the presence of
immobilized Candida antartica lipase B. The effect of
the amount of Stearic acid on the enzymatic
epoxidation was investigated. The variables of the
reaction temperature and enzyme load were the most
significant in the process. They compared with
reaction time and substrate ratio, reaction temperature
and enzyme load had significant effects on the
epoxidation and reaction temperature had a negative
effect on the enzyme activity at higher temperatures
[31].
Klass. M. Warwel, S worked on the complete and
partial epoxidation of plant oils by lipase-catalysed
perhydrolysis. They studied epoxidation of plant oils
such as rapeseed, sunflower, soybean and linseed
using immobilized lipase catalyst. They find that the
epoxidation using lipase biocatalyst was very
selective and epoxidation conversion rate was
exceeding 90%[32].
Vlcek and Petrovic worked on the Optimization of
chemoenzymatic epoxidation of soybean oil. In this
work they find that the rate of reaction is affected by
the concentration of lipase biocatalyst. Along with
the catalyst loading (not more than 4 wt% of catalyst
loading) reaction temperature, molar ratio of
hydrogen peroxide to ethylenic unsaturation , oleic
acid concentration and solvent concentration[33].

Rosana de Cassia et al. worked on the ChemoEnzymatic Epoxidation of Sunflower Oil Methyl
Esters. They investigated the chemo-enzymatic
epoxidation of the methyl esters of sunflower oil with
lipase from Candida antarctica B and aqueous H2O2
in the presence and absence of an acyl donor. The
biphasic system (CH2Cl2/H2O) comprised Candida
antarctica B lipase (CALB, 1000 u g-1) and 30%
(v/v) aqueous hydrogen peroxide. In some cases the
conversion was higher than 99%. The best results
were obtained for the biphasic system after 16 h of
reaction, at 30 C, using 10 mol of octanoic acid in
relation to 1 g of the oil, 6 mL of dichlomethane and
5 mL of water[34].
IV) METAL CATALYST METHOD
Researchers and scientist are always in search of
some new method and techniques to improve the
existing technology. In the same line many workers
and co-workers have given their contribution to
increase the oxirane content and improve the
efficiency of epoxidation reaction. Various metal
catalysts such as titanium, molybdenum, tungsten.
The peracid oxidant is obtained in situ when a
carboxylic acid (usually acetic acid) reacts with
hydrogen peroxide in the presence of mineral acids
that act as catalysts. Several drawbacks must be
improved in the peracid process, including: (i) the
selectivity to epoxidized products is relatively low
due to acid catalysed oxirane ring-opening; (ii) the
separation of acidic byproducts, whose presence may
be detrimental for further applications, is not easy;
(iii) the handling of highly concentrated hydrogen
peroxide and strong acids is dangerous and causes
corrosion problems. Thus, in recent years several
papers have dealt with the setting up of catalytic
processes aimed at overcoming such disadvantages,
using more sustainable compounds and technologies.
Campanella et al. worked on the epoxidation of
soybean oil and soybean methyl esters with hydrogen
peroxide in dilute solution (6 wt %) using an
amorphous heterogeneous Ti/SiO2 catalyst in the
presence of tert-butyl alcohol. Under the
experimental conditions employed in this work, no
degradation of the oxirane ring was observed.
Recently it has been shown that the incorporation of
Ti on an amorphous silica support produces oxidation
catalysts that are highly effective in epoxidation
reactions with hydrogen peroxide [35].
Mohamed et al worked on the epoxidation kinetics of
sunflower oil using tungsten as a catalyst. But in this
case they got less conversion as compared to peroxy
acid system[36].
REACTION MECHANISM
In situ epoxidation of vegetable oil with carboxylic
acid in the presence of suitable catalyst in which
peracetic acid formation is an acid-catalyzed reaction.
H+
RCOOH + H2O2
RCOOOH + H2O [1]
Whereas the main reaction involving the epoxy group
formation is an uncatalyzed reaction:
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O
R1CH=CHR2 + RCOOOH
R1CHCHR2
+ RCOOH [2]
Precisely it can be represented as[37].
The followings are the possible side reactions of the

epoxy ring cleavage that may take place are acidcatalyzed [38].
Fig.2. Epoxidation Side Reactions

KINETICS OF EPOXIDATION
There are two major reactions involved in the
epoxidation reaction as mentioned above. During the
first stage, peroxy acid is formed from the reaction of
formic or acetic acid and hydrogen peroxide while in
second stage epoxidized oil is produced from the
reaction between peracid and double bond in the
oil[39].
Considering hydrogen peroxide as oxygen donar and
acetic acid as oxygen carrier, we can write following
steps[40]:
Step I: Formation of Peroxyacetic acid
PAA
AA + H2O2
Step II: Epoxidation Reaction
DB + PAA
EO + AA
Where,
AA = Acetic Acid
PAA = Peroacetic Acid
DB = Double Bonds
EO = Epoxidized Oil
K1, K2, K3 = Reaction Rate Constant
The reaction was found to be overall second order

and a one step mechanism (Step 2) has been
proposed[41]. Kinetic studies of epoxidation of
soybean oil with peroxoacetic acid and peroxoformic
acid have been reported and found to be pseudo-first
order with respect to both double bonds as well as
peroxy acid.
If the first step is considered rate determining and the
concentration of peroxy acetic acid is assumed
constant throughout the reaction then following rate
laws can be applied:
= K3 [DB]n1 [PAA]n2

Where,
[DB] = Molar Concentration of Double Bond
[PAA] = Molar Concentration of Peroxyacetic Acid
K3 = Reaction rate constant
n1 = Reaction order with respect to double bonds
concentration.
n2= Reaction order with respect to Peroxyacetic Acid
concentration.
If it is assumed that the reaction is pseudofirst order

with respect to double bonds, the rate equation for the
pseudofirst order can be expressed as:
= K [DB]n1
K = K3 [PAA]n2
Then the rate equation data for the epoxidation
reaction using peroxyacetic acid is fitted with the
equation above. If X is expressed as the conversion
of double bonds in the oil, after integration the
equation above and defines
[DB] = [DB]0 (1 X)
the equation above can be simplified as
= K [DB]
= K [DB]0 (1 X)
[DB] 0
= K [DB]0 (1 X)
= K (1 X)
= K dt
Integration at t=0 X=0 and t=t X=X
=
= K.t
ln
The rate constant (K) value for each temperature can
be determined as slope of plot of ln
Vs. reaction
time (t).
THERMODYNAMIC PROPERTIES OF THE
EPOXIDIZED VEGETABLE OIL
The enthalpy of activation can be calculated using
following equation[43].
H = Ea RT
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cal/ (mol K) and F = 30.6 kcal/mol. Similarly Dinda

et al. worked on epoxidation of cottonseed oil. While
doing this the thermodynamic parameters such as
enthalpy, entropy, and free energy of activation were
determined to be of 11.0 kcal /mol, -51.4 cal/(mol.K)
and 28.1 kcal/mol, respectively. The thermodynamic
properties show that, the present reaction is
endothermic in nature because the enthalpy of
activation is positive and hence an increase in the
reaction temperature may lead to an increase in the
conversion to oxirane oxygen. As the free energy of
activation is positive, the reaction is non spontaneous
under the present experimental conditions. With an
increase of temperature, the nonspontaneity of the
reaction should increase since F will be more
positive and hence, at any particular time instant, the
yield of oxirane will increase. However, the net
conversion to oxirane will maximize if the in situ
epoxidation occurs at optimum temperature, which
depends on the type of catalyst used in such process
[14].
INDUSTRIAL MANUFACTURING PROCESSES
There are many processes available for the
manufacturing of epoxidized vegetable oil. The most
widely used method of epoxidation of unsaturated
vegetable oil is pre or in-situ epoxidation. Although
the epoxidation of unsaturated oils using continuous
epoxidation process is limited.
1) IN-SITU EPOXIDATION
In-situ epoxidation using hydrogen peroxide as
oxygen donar and acetic or formic acid as the
peroxygen carrier has achieved commercial
importance [43]. With hydrogen peroxide and acetic
acid, however, acid catalysts, such as sulfuric acid or
strong cation exchange resins, are needed to speed up
peracid formation, whereas performic acid formation
requires no strong acid. The reaction is always
carried out under isothermal condition. The
schematic flow diagram for the in-situ epoxidation
can be given in following manner [44].
Where, Ea = Activation Energy

T= Temperature
R= Universal Gas Constant
The entropy of activation (S) and free energy of

activation (F) were calculated at the same
temperature using following equation [43]
k=
F = H T S
Where, k = Rate Constant
N = Avogadro Constant
h = Planks constant
S = Entropy of activation, Cal/ (mol.K).
F = Free energy of activation, Cal/mole.
Goud et al. worked on epoxidation of mahua oil, they

determined the thermodynamic parameters such as
enthalpy, entropy, and free energy of activation and
were found to be H = 13.8 kcal /mol, S = -51.1
Fig. 3 Schematic Flow Diagram of In-Situ

Epoxidation.

2) CONTINUOUS EPOXIDATION FLOW
PROCESS
This process includes three or four stirred-tank
epoxidation reactors with the same volume, a
continuous feed and sampling outlet, and temperature
and stirring controllers. Unsaturated oil, formic acid,
and hydrogen peroxide were continuously introduced
into the first reactor, then the reaction mixture was
continuously fed to the next reactor, and finally the
crude product from the last reactor was placed in a
separator. The aqueous layer was drawn off, and the
ester layer was washed in successive steps until acidfree. The final product was analyzed for the iodine
and oxirane values according to standard methods
[45]. As compared with a batch process, a continuous
process has three advantages: (i) stable product
quality; (ii) convenience, because of use of automatic
control; and (iii) lower production costs. Also, the
continuous process is useful for controlling by
product formation and improving reaction selectivity
and yield by changing material contacting time and
reaction temperature.
Fig 2. Continuous Flow Stirred Tank Cascade

Epoxidation Process.1, 2, 3, stirred-tank reactor; 4, storage
tank; 5, sedimentation tank; 6, washing tank; 7, pump.
VEGETABLE OIL
Epoxidized vegetable oil has unlimited and bright
future prospects as it is found to be potential and
renewable biobased material. Increasing the concern
about environmental issues and limiting supply of
petroleum and fossil fuel again adds the importance
to epoxidized vegetable oil. Epoxidized vegetable oil
possesses epoxy ring in their backbone chain and
produces flexibility and elasticity when it is treated
with thermoplastic or thermosetting polymer along
with suitable curing agent. Because of this special
kind of application EVO can easily replace the
phthalates which are petroleum based. Looking
forward this it is expected that EVO oil has a great
future.
ECONOMIC FEASIBILITY OF EPOXIDIZED
VEGETABLE OIL
India used to grow and has rich forest resources with
a wide range of plants and oilseeds. The economic
feasibility of the epoxidized vegetable oil depends on
the price of crude petroleum oil. It is very certain that
the cost of crude petroleum is increasing day by day
due to increase in its demand and limited supply.
The cost of epoxidized vegetable oil can be
considerably reduced if we consider non-edible oil,
used frying oil and acid oils instead of edible oils.
The non-edible oils such as babassu, mahua, neem,
karanja, jatropha etc. are easily available in many
E-ISSN 0976-3945
parts of the world including India and are very cheap

as compared to edible oil. In many countries
including Australia, Netherland, U.S.A,Germany,
Belgium, Austria and Japan the used frying oils are
discarded that can be used for epoxidation purpose.
CONCLUSION
The potential utility of epoxidized vegetable oil has
begun to be realized in industrial applications with
increasing the concern of research in aspirants to
develop value added products from the available
plant oils. Vegetable oil could be epoxidized
successfully by peroxy acid generated in-situ by
reacting formic or acetic acid with hydrogen peroxide
at isothermal temperature condition. The epoxidation
can be confirmed by iodine value, FTIR analysis and
NMR analysis. In-situ epoxidation of vegetable oil is
more convenient and economically viable method for
large scale epoxidation which shows utility especially
in plasticizer and stabilizer used in polymers.
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