Chemical Engineering and Processing 62 (2012) 106113

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Chemical Engineering and Processing:

Process Intensication
journal homepage: www.elsevier.com/locate/cep

Epoxidation of castor oil with peracetic acid formed in situ in the presence of an
ion exchange resin
Snezana Sinadinovic-Fiser , Milovan Jankovic, Olga Borota
Faculty of Technology, University of Novi Sad, Bul. cara Lazara 1, 21000 Novi Sad, Serbia

a r t i c l e i n f o a b s t r a c t

Article history: The inuence of reaction variables on the epoxidation of castor oil (CO) in benzene with peracetic acid
Received 7 March 2012 (P) generated in situ from acetic acid (A) and hydrogen peroxide (H) in the presence of an ion exchange
Received in revised form 7 August 2012 resin as catalyst was examined. The highest relative epoxy yield (REY) of 78.32% was achieved at 323 K
Accepted 22 August 2012
after 8 h when 0.5 mol of acetic acid and 1.5 mol of 30 wt% aqueous hydrogen peroxide per mol of dou-
Available online 10 September 2012
ble bond in oil were used in the presence of 15 wt% of Amberlite IR-120. The experimental data were
tted by proposed pseudo-homogeneous kinetic model which considers the side reaction of epoxy ring
Keywords:
cleavage involving the formation of hydroxy acetate in addition to reactions of the peracetic acid and
Castor oil
In situ epoxidation
epoxy compound formation. Temperature dependency of the kinetic parameters is expressed by a repa-
Peracetic acid rameterized Arrhenius equation. The constants of the Arrhenius equation were determined by tting
Ion exchange resin experimental data using the Marquardt method. An increase of all rate coefcients for considered reac-
Reaction variable tions with temperature and good agreement of the calculated reactant and product concentrations with
Kinetic model experimental data, indicate the correctness of the proposed kinetic model. The model was compared
with pseudo-homogeneous models reported in the literature.
2012 Elsevier B.V. All rights reserved.

1. Introduction of catalyst, catalyst loading, temperature, stirring speed and pres-

Vegetable oils are a valuable raw material for the chemical
industry, due to ability of their main constituents, triglycerides, to
undergo various reactions. Epoxidation of vegetable oils, i.e. their
unsaturated triglycerides, is a commercially important reaction,
since the epoxides obtained from these renewable resources have
a wide application. They are used directly as plasticizers and poly-
mer stabilizers, as paint and coating components, as lubricants, but
also as intermediates for alcohols, glycols, alkanolamines, poly-
ols and polymers (such as polyurethanes, polyesters, and epoxy
resins) production due to the high reactivity of the epoxy ring.
On an industrial scale, the epoxidation of vegetable oils is cur-
rently carried out with a percarboxylic acid, such as performic
or peracetic acid (P), usually obtained in situ through the acid
catalyzed peroxidation of the corresponding organic acid with
hydrogen peroxide (H). Soluble mineral acid, usually sulphuric
acid, or acidic cation exchange resin, such as the sulphonated
polystyrene-type Amberlite, are commonly used as catalyst for this
reaction [1].
The process of epoxidation is signicantly inuenced by reac-
tion variables. Therefore, the effects of molar ratio of reactants, type
Corresponding author. Tel.: +381 021 485 3748; fax: +381 021 450 413.
E-mail address: ssser@uns.ac.rs (S. Sinadinovic-Fiser).
ence of an inert solvent have been studied. Although numerous
references concerning the inuence of reaction variables on in situ
epoxidation of different vegetable oils such as soybean, cotton seed,
palm, karanja, and mahua, and, more recently, canola, exist, a few
deal with kinetics of the process. Besides the main reactions of
percarboxylic acid and the epoxy ring formation, side reactions of
epoxy ring opening also occur in a reaction mixture. The predom-
inant side-reaction is epoxy ring cleavage with acetic acid (A) [2].
Depending on the applied catalyst, the reaction system is either
two- (oilwater) or three-phase (oilwaterion exchange resin).
Due to complexity of the reaction system, kinetic models that have
been proposed are based on different simplications. The authors
of the rst kinetic models of in situ epoxidation, assumed, besides
homogeneity of the reaction mixture, that concentration of per-
acetic acid in the mixture was low and constant due to the fact that
rate of peracetic acid formation was slower than the rate of epoxy
ring formation. Such an assumption implied that reaction of the
double bond with peracetic acid was pseudo-rst order. The side
reaction with acetic acid was considered as rst order in respect to
both epoxy compound and acetic acid [3]. However, in some models
epoxy ring opening reactions were ignored and the kinetics of these
reactions was studied separately from epoxidation [4,5]. Although
it was discussed that an assumption about pseudo-homogeneity of
the reaction system is inadequate [6], such an approach has been
used even nowadays [710].

0255-2701/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cep.2012.08.005
 S. Sinadinovic-Fiser et al. / Chemical Engineering and Processing 62 (2012) 106113
Castor oil (CO) is a natural polyol which has about 90% of
monounsaturated hydroxy fatty acid, ricinoleic acid (12-hydroxy-
9-octadecenoic acid), in its fatty acid composition. Therefore,
CO can be used for obtaining polyurethanes without previous
derivatization [11]. However, polyurethanes with higher degree of
crosslinking may be obtained by introducing additional hydroxy
groups in CO. They may be formed by opening of primary formed
epoxy groups. The rst brief report about in situ epoxidation of CO
with peracetic acid in the presence of an ion exchange resin was
given in 2004 [12]. No reports about effects of the reaction variables
on the in situ epoxidation of CO with percarboxylic acid were found.
Concerning the kinetics of epoxidation of CO with in situ formed
performic and peracetic acid catalyzed by the ion exchange resin,
only the simplest one-phase model, which assumes that the reac-
tion of double bond with peracetic acid is pseudo-rst order and
which neglects epoxy ring opening reactions, was reported [13].
Because of the aforementioned, in this paper the epoxidation
of CO in benzene with peracetic acid generated in situ from acetic
acid and an aqueous solution of hydrogen peroxide in the presence
of a sulphonated polystyrene type acidic ion exchange resin as the
catalyst was investigated. The aim was to study the inuence of
some reaction variables on the process. The pseudo-homogenous
model which, besides the main reactions, involves epoxy ring open-
ing reaction with peracetic acid is proposed. The model also takes
into consideration occurrence of the reactions during incremental
reactant addition, as well as all temperature stages of the process.
The model parameters were determined on the basis of the exper-
imental data. The proposed model was compared with some of the
pseudo-homogeneous models found in the literature.
2. Experimental procedures
2.1. Materials
Castor oil was kindly provided by Hemiprodukt (Novi Sad, R.
Serbia). Glacial acetic acid (>99.5%), benzene, diethyl ether and
30 wt% aqueous hydrogen peroxide solution were purchased from
J.T. Backer, USA, while anhydrous sodium sulphate was from Fluka,
Chemie GmbH, Germany. Sulphonated polystyrene-type cation
exchange resin Amberlite IR-120 from Rohm&Hass Co. (Philadel-
phia, PA, USA) was used in its acid form.
2.2. Epoxidation procedure
The epoxidation of castor oil was carried out with peracetic
acid formed in situ according to a method reported in the litera-
ture [14]. In a 500 mL three-neck round bottom ask, placed in a
water bath with controlled temperature within 1 K, and equipped
with magnetic stirrer, thermometer, reux condenser and dropping
funnel, the oil (100 g) was mixed with an equal mass of benzene
and an appropriate mass of glacial acetic acid before addition of
an ion exchange resin. Subsequently, the hydrogen peroxide solu-
tion was added dropwise to the reaction mixture at a constant rate
over the course of one hour. During the hydrogen peroxide addi-
tion, the temperature of the mixture was maintained at 303 K for
the epoxidation carried out at 303 K and at 323 K for other runs.
After the addition was completed, if necessary, the temperature
was increased to the desired level. The reaction mixture was con-
tinuously stirred at 1500 rpm so that a ne dispersion of oil was
achieved. The progress of the reaction was followed by withdraw-
ing 10 mL samples of the reaction mixture at dened time intervals.
The beginning of the addition of hydrogen peroxide was considered
to be the zero time. After the quenching and centrifugation of the
sample, the separation of oil and aqueous phases was performed.
Prior to analysis, the oil phase sample was dissolved in diethyl ether,
107
washed with distilled water (308 K) until it was acid-free, and then
dried by adding anhydrous Na2 SO4 . After ltration, ether, benzene
and water were evaporated at 333 K at 3.04.0 kPa. All samples
were then analyzed for iodine number (IN) and epoxy oxygen con-
tent (EO). If the catalyst was reused, at the end of the reaction the
ion exchange resin was ltered from the cooled reaction mixture,
washed with water and diethyl ether, and air-dried.
2.3. Analytical methods
The iodine number and epoxy oxygen content of each sample
were determined by the Hanus method and the standard HBr-acetic
acid method [15], respectively.
3. Results and discussion
The experimentally measured initial iodine number (IN0 ) of the
castor oil was 81.5 meaning 0.321 mol of double bond (D) per 100 g
of CO.
In order to determine the conditions under which the main reac-
tions of the epoxidation are favored, the effects of the reaction
variables on the epoxidation were studied. Due to high viscos-
ity, caused by intermolecular hydrogen bonds formed between
the hydroxy groups of ricinoleic acid, the epoxidation of castor
oil is better performed in the presence of an inert solvent which
enhances better phase contact by reducing the viscosity of the
reaction mixture. Moreover, side reactions of epoxy ring opening,
which are acid catalyzed, are reduced by dilution of the organic
phase, especially at higher temperatures. Therefore, 1:1 mass ratio
of CO and benzene was used in all experiments. Further, in order to
reduce the mass transfer resistance in the reaction system, con-
tinuous intensive stirring was performed. The stirring speed of
1500 rpm was applied, since increasing the speed beyond this value
offers no appreciable change in the rate of epoxidation [16].
On the basis of preliminary studies it was concluded that sul-
phuric acid is not suitable catalyst for epoxidation of castor oil with
peracetic acid. Regardless of the applied reaction variable values,
the polymerization of the reaction mixture occurred before signif-
icant yield of epoxide was obtained. This is probably due to the
structure of castor oil triglycerides that are mainly triesters of rici-
noleic acid and, therefore, polyols. Thus, an ion exchange resin was
the catalyst of choice for the epoxidation of castor oil.
The values of the reaction variables studied, along with achieved
conversion of double bond (X), relative epoxide yield (REY) and
selectivity (SE), are detailed in Table 1 only for the maximum epoxy
exp
oxygen content (EOmax , where EO is epoxy oxygen content, super-
script exp indicates experimentally determined value and subscript
max indicates maximum value) reached in each run.
The epoxidation was carried out with acetic acid as it is more
selective than formic acid when combined with the ion exchange
resin in the in situ process [1719]. An acetic acid to double bond
molar ratio of 0.5 was applied in all epoxidations. Under this con-
dition, the quantity of acetic acid, which acts as an oxygen carrier
and regenerates once the epoxidation occurred, is sufcient for the
main reaction, whereas it is insufcient at the beginning of the pro-
cess for the most likely side reaction with the formed epoxy ring
that converts to hydroxy acetate [2,20].
Since hydrogen peroxide is consumed during the process of
epoxidation, an excess relative to a double bond of oil is usually
applied. Thus, the inuence of 1.1 and 1.5 mol of aqueous hydro-
gen peroxide solution (30 wt%) per mole of double bond on the
epoxidation of castor oil was studied at 323 K in the presence of
5 wt% of ion exchange resin used as catalyst. The effect is presented
in Fig. 1. With an increase in hydrogen peroxide concentration, a
slight increase in the rate of epoxidation was observed, along with
108 S. Sinadinovic-Fiser et al. / Chemical Engineering and Processing 62 (2012) 106113

Table 1
exp
Values of the reaction variables and run properties for the maximum content of epoxy oxygen (EOmax ) reached in each run of the in situ epoxidation of castor oila in benzene
with peracetic acid in the presence of the ion exchange resin used as catalyst.
exp
Run Molar ratio Amberliteb T t IN Xc EOmax REYd SEe
D:A:H (wt%) (K) (h) (%) (%) (%)

1 1:0.5:1.1 5 [2.48] 323 10 13.7 83.2 3.46 70.75 0.85

2 1:0.5:1.5 5 [3.21] 323 10 11.6 85.8 3.61 73.82 0.86
3 1:0.5:1.5 10 [6.43] 323 9 7.1 91.3 3.81 77.91 0.85
4 1:0.5:1.5 15 [9.64] 323 8 6.4 92.8 3.83 78.32 0.85
5 1:0.5:1.5 10 [6.43] 348 8 8.4 89.7 3.75 76.69 0.85
6 1:0.5:1.5 10 [6.43] 303 25 26.1 68.0 2.26 46.22 0.68
7 1:0.5:1.5 10 [6.43](2 times) 323 10 7.5 90.8 3.73 76.28 0.84
8 1:0.5:1.5 10 [6.43](4 times) 323 11 7.3 91.0 3.65 74.64 0.82
a
Initial iodine number, IN0 = 81.5 with EOth = 4.89%. Theoretical epoxy oxygen content, EOth is dened as the theoretical maximum content of epoxy oxygen in 100 g of oil,
calculated as EOth = {(IN0 /2AJ )/[100 + (IN0 /2AJ ) AO ]} AO 100.
b
Value in square bracket represents the catalyst concentration expressed in percentage of oil weight.
c
Double bond conversion, X = [(IN0 IN)/IN0 ] 100.
exp
c
Relative epoxy yield, REY = (EOmax /EOth ) 100.
exp
d
Selectivity, SE = EOmax IN0 /[EOth (IN0 IN)].

a decrease in the residual iodine number and an increase in the
maximum of epoxy oxygen content (Table 1). Also, higher selec-
tivity was achieved when the molar ratio of hydrogen peroxide
to double bond was 1.5. Due to the fact that hydrogen peroxide
concentrations higher than 1.5 lead to a higher rate of epoxy ring
decomposition, as concluded in most papers [1719], this molar
ratio was accepted as optimum. Notice that the mass of catalyst in
this work is expressed as the weight percentage of the sum of the
used weights of acetic acid and hydrogen peroxide. Therefore, the
amount of applied catalyst was higher when 1.5 mol of hydrogen
peroxide was used. Since an increase of the hydrogen peroxide and
the catalyst concentration in the reaction mixture both increase
the rate of the peracetic acid formation, and consequently, the rate
of the reaction of epoxide formation, the inuence of the catalyst
concentration on epoxidation was further studied separately.
The effect of other epoxidation variables on the in situ epoxi-
dation of castor oil was examined in the following ranges: catalyst
concentration, 515%, temperature, 303348 K, and reusability of
the catalyst, 13 times.
and 15 wt% of Amberlite IR-120 when the molar ratio of double
bond:acetic acid:hydrogen peroxide was 1:0.5:1.5. Since the for-
mation of peracetic acid is catalyzed by ion exchange resin, as
expected, its rate increased when higher concentration of catalyst
was applied. At the same time, higher amount of external surface
active catalyst sites in the reaction mixture increased rate of the
epoxy ring cleavage. The inuence of an increase in the catalyst
load on the former reaction resulted in a shortening of the time
for reaching the maximum REY, while an inuence on the latter
caused a lowering in the selectivity of the process (Table 1). It was
also observed that an increase in the catalyst concentration resulted
in an increase of the double bond conversion (X) and epoxy yield
(REY). The amount of the catalyst used for further study is, however,
10 wt% since maximum relative epoxy yield was only 0.52% lower
than that reached when 15 wt% of catalyst was used, whereas the
selectivity was the same. The effect of the catalyst concentration
on the in situ epoxidation is illustrated in Fig. 2.
3.2. Effect of temperature

3.1. Effect of catalyst concentration The inuence of temperature on the course of epoxidation was
examined by carrying out runs at 303, 323 and 348 K. The reac-
The catalytic effect of the strong cationic exchange resin on tion temperature of 348 K was reached by raising the temperature
the epoxidation of CO at 323 K was investigated by using 5, 10

Fig. 1. Time dependency of experimentally determined (points) and calculated
(curves) iodine number (IN) and epoxy oxygen content (EO) for in situ epoxida-
tion of castor oil in benzene with peracetic acid, when molar ratio of double bond
in oil:acetic acid:(30 wt%) hydrogen peroxide was 1:0.5:1.1 and 1:0.5:1.5, in the
presence of 5 wt% of Amberlite IR-120 at 323 K.
Fig. 2. Time dependency of experimentally determined (points) and calculated
(curves) iodine number (IN) and epoxy oxygen content (EO) for in situ epoxida-
tion of castor oil in benzene with peracetic acid, when molar ratio of double bond in
oil:acetic acid:(30 wt%) hydrogen peroxide was 1:0.5:1.5, at 323 K in the presence
of 5, 10 and 15 wt% of Amberlite IR-120.
 S. Sinadinovic-Fiser et al. / Chemical Engineering and Processing 62 (2012) 106113 109

Fig. 3. Time dependency of experimentally determined (points) and calculated Fig. 4. Effect of the catalysts recycling (1, 2 and 4 times used) on the epoxidation
(curves) iodine number (IN) and epoxy oxygen content (EO) for in situ epoxida- of castor oil in benzene with peracetic acid, when molar ratio of double bond in
tion of castor oil in benzene with peracetic acid, when molar ratio of double bond in oil:acetic acid:(30 wt%) hydrogen peroxide was 1:0.5:1.5, in the presence of 10 wt%
oil:acetic acid:(30 wt%) hydrogen peroxide was 1:0.5:1.5, in the presence of 10 wt% of Amberlite IR-120 at 323 K.
of Amberlite IR-120 at 303, 323 and 348 K.
ion exchange resin involves an acid-catalyzed reaction of peracetic
after completion of the one hour hydrogen peroxide addition into acid formation (reaction (1)), an uncatalyzed reaction of epoxy ring
the reaction mixture. The addition was performed at lower tem- formation (reaction (2)) and also acid-catalyzed side reactions of
perature due to better control over the exothermic reactions of epoxy ring cleavage. Among latter, the most likely is the reaction of
epoxidation. The changes in the iodine number and epoxy oxygen an epoxy ring with acetic acid that leads to the formation of hydroxy
content with the reaction time at applied temperatures are pre- acetate by-product (reaction (3)) (Fig. 5) [2,20].
sented in Fig. 3. As expected, rates of main and side epoxidation
reactions increased with an increase in the temperature. Conse-
quently, the same values of relative epoxy yields were achieved
within a shorter reaction time, whereas a stability of epoxy ring was
reduced at higher temperatures. Therefore, at the highest temper-
ature studied (348 K), after initial increase, REY started gradually to
decrease, even below the REY values reached at 323 K. The highest
conversion of 77.91% to epoxide was achieved at medium temper-
ature (323 K) after a reaction time of 9 h (Table 1). Additionally, Fig. 5. Reaction scheme of epoxidation of unsaturated triglycerides with peracetic
the quality of yielded product at 323 K was slightly better, i.e. the acid formed in situ from acetic acid and hydrogen peroxide in the presence of an
residual IN was lower, compared to that obtained at 348 K. Thus, acidic ion exchange resin used as catalyst.

the former temperature was chosen as better for the epoxidation

of CO when the molar ratio of double bond:acetic acid:hydrogen Assuming homogeneity of the reaction system and that only
peroxide was 1:0.5:1.5 and when 10 wt% of catalyst was used. reactions (1)(3) occur during epoxidation, the following system of
the rst order differential equations that mathematically describes
3.3. Reusability of the catalyst the whole process may be written as:
d[H]
 d[H] 
= + FH (1)
Four syntheses were conducted under identical conditions using dt dt r
the same catalyst to assess the reusability of the Amberlite IR-120.
d[A]
 d[H] 
The epoxidations were carried out at 323 K when the molar ratio = + k2 [P][D] k3 [E][A]n (2)
of double bond:acetic acid:hydrogen peroxide was 1:0.5:1.5 and dt dt r

10 wt% of catalyst was used. The effect of once, twice and four times d[P]

d[H]

= k2 [P][D] (3)
used catalyst on epoxidation is presented in Fig. 4. Deterioration of dt dt r
the catalyst performance caused decrease of the epoxidation rate
d[W] d[H]
 
in each succeeding run. Therefore, reaching the maximum REY was = + FW (4)
prolonged (Table 1). Consequently, the selectivity of the process dt dt r

was reduced by increasing the number of resin reuses. The max- d[D]
= k2 [P][D] (5)
imum REY reached with fresh catalyst was about 4% higher than dt
that achieved with four times used catalyst after 2 h longer reac-
d[E]
tion time. Thus, it can be concluded that it is possible to recycle the = k2 [P][D] k3 [E][A]n (6)
dt
Amberlite IR-120, but the quality of the yielded product should be
slightly lower. d[HA]
= k3 [E][A]n (7)
dt
4. Kinetic model where [H] is the hydrogen peroxide concentration, [A] is the acetic
acid concentration, [P] is the peracetic acid concentration, [D] is the
Epoxidation of castor oil with peracetic acid formed in situ from double bond concentration determined as [D] = IN/[2AJ ], [E] is the
acetic acid and hydrogen peroxide in the presence of an acidic epoxy group concentration determined as [E] = EO/[100AO ], [W] is
110 S. Sinadinovic-Fiser et al. / Chemical Engineering and Processing 62 (2012) 106113
the water concentration and [HA] is the hydroxy acetate concentra-
tion, all expressed as moles per 100 g of oil, t (min) is the reaction
time, AJ is the atomic mass of iodine and AO is the atomic mass
of oxygen. (d[H]/dt)r (mol/min) is the rate of hydrogen peroxide
consumption in the reaction (1). Since the stirring was good, the
diffusional resistances in the reaction mixture could be ignored.
Thus, if the uniform distribution of the catalyst and complete dis-
sociation of its sulpho groups in the liquid phase are assumed, i.e. if
the catalyst behaves as it is dissolved in the pseudo-homogeneous
reaction mixture, and if the inuence of mass diffusion on the reac-
tion rate is neglected, the rate of hydrogen peroxide consumption
for reaction (1) can be written as follows:
 d[H]   [P][W]

= m Cs k1 [A][H]
dt r K1
where m (g) is the mass of the catalyst, Cs (mol/g catalyst) indi-
cates the concentration of catalytically active sites (sulpho groups),
k1 ((100 g oil)2 /(mol2 min)) is the rate coefcient for the reac-
tion (1), and K1 is the equilibrium constant for reaction (1).
Also, in the system of Eqs. (1)(7) k2 ((100 g oil)/(mol min)) is the
rate coefcient for the reaction (2), k3 ((100 g oil)/(mol min) or
(100 g oil)2 /(mol2 min)), depending of the reaction order (n) is the
rate coefcient for reaction (3), n indicates the order (rst or sec-
ond) of epoxy ring cleavage with respect to acetic acid, and FH and
FW (mol/min) are the molar ows of hydrogen peroxide and water
addition, respectively. Dropwise addition of the hydrogen peroxide
solution to the reaction mixture is approximated with continuous
ows:
 mH wH  
 
 MH tH t tH 
FH =   (9)
0 t > tH

 
 mH (1 wH )  k2 = exp 1.436033
 t tH 
FW =  M t  (10)
W H
 
0 t > tH 
where mH (g) is the mass of the hydrogen peroxide aqueous solu-
tion, wH is the mass fraction of hydrogen peroxide in its aqueous
solution, MH and MW (g/mol) are molecular masses of hydrogen
peroxide and water, respectively, and tH (min) is the period of
hydrogen peroxide solution addition.
The temperature dependency of kinetic model parameters is
expressed by reparameterized Arrhenius equation:
 1 
ki,a 1
ki = exp ki,o
R T Ta
where ki is the rate coefcient for the reaction i, ki,o is a constant
related to frequency coefcient, ki,a is a constant related to activa-
tion energy, T (K) is the reaction temperature, Ta (K) indicates an
average temperature of syntheses (accepted as Ta = 323 K), and R
(8.3143 J/mol K) is the universal gas constant. The constants of the
Arrhenius equation were determined by tting the experimental
values of the double bond and epoxy group concentrations. The
Marquardt method [21] was used to t the data. The following
objective function F was minimized:
NUj

NS 
exp 2 exp 2
F= [([D]calc calc
j,k [D]j,k ) + ([E]j,k [E]j,k ) ]
j=1 k=1
where NS indicates the number of syntheses used for tting (runs
16 in Table 1) and NUj is the number of samples in synthesis j;
superscript calc indicates the calculated value.
A fourth-order RungeKutta method was applied for integrating
the system of differential equations (1)(7).
Unlike kinetic models reported in the literature, in this model
the application of Eq. (11) makes possible tting of data obtained
under the temperature variations during epoxidation. Thus, the
temperature change from that at which hydrogen peroxide solution
is incrementally added into the reaction mixture until the desired
reaction temperature, is taken into consideration. Additionally, by
considering the beginning of the hydrogen peroxide addition as
the zero reaction time, the proceeding of the epoxidation reactions
during that dropwise addition was not ignored.
4.1. Kinetic parameters
(8) The variations in the concentration of double bond and epoxy
group with reaction time (t), calculated on the basis of experimen-
tally determined iodine number and epoxy oxygen content were
used to determine the model parameters. They were calculated
assuming the rst or the second order of the reaction of epoxy
ring cleavage (reaction (3)) with respect to acetic acid. In Table 2
are shown the calculated values of the constants of the reparam-
eterized Arrhenius equation (ki,o and ki,a ) for all three considered
reactions together with the least sum of squares (objective function
F) calculated by Eq. (12), standard deviation (SD) and an average
absolute deviations for double bond concentration (AAD[D] ) and
epoxy group concentration (AAD[E] ). Since the objective function is
slightly lower when the order of reaction (3) was assumed as sec-
ond, the temperature dependencies of kinetic parameters for such
assumption are presented as follows:
1 
141179.8 1
k1 Cs = exp 4.24834 (13)
R T Ta
 1 
8398.366 1
(14)
R T Ta
1 
14437.99 1
k3 = exp 3.064781 (15)
R T Ta
The increase of all three rate coefcients with temperature
indicates that in this work determined dependencies are satisfac-
tory. Since all calculated reactant and product concentrations have
positive values, the viability of the kinetic model is additionally
conrmed. The proposed pseudo-homogeneous model ts reason-
ably well the experimental values, as shown in Figs. 13 where the
experimentally determined (points) and calculated (curves) iodine
(11) number and epoxy oxygen content changes over time during the
in situ epoxidation of castor oil with peracetic acid in benzene in
the presence of Amberlite IR-120 at different reaction conditions
are compared.
The approach that occurrence of the epoxidation reactions dur-
ing the hydrogen peroxide addition into the reaction mixture must
be taken into consideration when establishing the kinetic model,
as used in this work, was tested: the proposed model was applied
under assumption that the completion of the addition of hydrogen
peroxide was zero time. For that case, the least sum of squares (F)
was about 32% higher than those calculated when the beginning of
the addition was considered to be zero time, for the rst order
of the epoxy ring cleavage (Table 2). Assuming the second order
of the same reaction, the difference of objective functions for such
(12)
comparison was slightly lower (about 26%). The lowest least sum
of squares of 0.01375 obtained for model proposed in this work
when the second order of the epoxy ring cleavage with respect
to acetic acid was assumed, conrmed the correctness of applied
approach. The constants of the reparameterized Arrhenius equa-
tion calculated for aforementioned assumptions are also given in
Table 2.
 S. Sinadinovic-Fiser et al. / Chemical Engineering and Processing 62 (2012) 106113 111

Table 2
Comparison of statistical values of the model parameters determination when beginning or completion of the hydrogen peroxide (H) addition was considered as zero time
and when the order of the epoxy ring cleavage was 1 or 2. The constants of the reparameterized Arrhenius equation determined for compared models are given.

Error Ref. [3] Ref. [4] This work

Zero time

Beginning of H addition Completion of H addition Beginning of H addition Completion of H addition

Order of the epoxy ring cleavage, n

1 2 1 2 1 2

F 0.06476 0.06275 0.64218 0.01385 0.01375 0.01826 0.01732

SDa 0.02713 0.02670 0.08543 0.01254 0.01250 0.01440 0.01403
AAD[D] b 0.02540 0.02562 0.07168 0.01086 0.01086 0.01270 0.01280
AAD[E] c 0.01615 0.01518 0.07046 0.00757 0.00767 0.00874 0.00797

Constants of the reparameterized Arrhenius equation

k1,o 4.810925 4.301984 4.24834 4.182599 4.127129
k1,a 26,385.41 140,439.7 141,179.8 143,031.0 143,638.6
k2,o 5.486298 5.463897 1.450605 1.436033 1.271119 1.249667
k2,a 78,686.81 79,804.24 7189.949 8398.366 5571.393 6667.735
k3,o 5.301376 3.130085 5.319622 3.064781 5.182954 2.899264
k3,a 18,620.32 27,979.90 11,326.97 14,437.99 10,260.04 13,223.35

a
Standard deviation, SD = FNS .
2 NUj
j=1


NS

NUj
 calc 
b
Average absolute deviation for double bond concentration, AAD[D] = NS1 [D]j,k [D]exp
j,k
.
NUj
j=1 j=1 k=1


NS

NUi
 calc 
c
Average absolute deviation for epoxy group concentration, AAD[E] = NS1 [E]j,k [E]exp
j,k
.
NUj
j=1 j=1 k=1

4.2. Comparison of proposed kinetic model with models reported
in the literature
The two pseudo-homogeneous kinetic models developed for the
in situ epoxidation of triglycerides and fatty acid esters, applied
by other authors, were compared with the model proposed in this
work.
Wisniak et al. [3] assumed that the reaction of the double bond
with peracetic acid is pseudo-rst order whereas epoxy ring cleav-
age is rst order in respect to both epoxy compound and acetic acid.
The model was described by the following equations:
d[D]
= k2 [D]
dt
d[E]
= k2 [D] k3 [E][A]
dt
d[A]
= k3 [E][A]
dt
d[HA]
= k3 [E][A]
dt
where k2 (1/min) is the rate coefcient for reaction (2) and k3
((100 g oil)/(mol min)) is the rate coefcient for reaction (3). This
model correctly ts our experimental data giving positive values of
all reactant/product concentrations and an increase of the k2 and k3
with temperature, when both rate coefcients were expressed by
reparameterized Arrhenius equation. If the beginning of the addi-
tion of hydrogen peroxide into the reaction mixture was considered
to be the zero time and if the rst order of the epoxy ring cleav-
age was assumed when applying the above model, the least sum of
squares was 4.7 times higher than that calculated for the model pro-
posed in this work and for the same assumptions (Table 2). When
the order of reaction (3) was, however, assumed to be second in
respect to acetic acid, slightly better result was obtained, i.e. the
least sum of squares was 4.6 times higher. This was expected, since
in the model reported in the literature the inuence of the rate of
peracetic acid formation, more precisely the inuence of the acetic
acid, hydrogen peroxide and catalyst concentrations, on the rate of
epoxy ring formation was neglected.
Gan et al. [4] described in situ epoxidation with the following
expression without giving any explanation:
dCE
= k1 (CH,0 CE )CA,0 (20)
dt
where CE (mol/L) is the epoxy group concentration, k1 (L/mol min)
is the rate coefcient for reaction (1), CH,0 (mol/L) is the initial
concentration of hydrogen peroxide and CA,0 (mol/L) is the initial
concentration of acetic acid. Eq. (20) can be derived if the epoxy
ring cleavage is ignored and if low and constant concentration of
(16) the peracetic acid is assumed. Consequently, the reverse reaction
of peracetic acid with water can be omitted. In such case, the con-
centration of acetic acid is constant and approximately the same as
(17)
the initial concentration. For this model, it is only possible to con-
sider the completion of the addition of hydrogen peroxide into the
(18)
reaction mixture as zero time. If the concentrations are expressed
as moles per 100 g of oil, the model can be rewritten as follows:
(19)
d[E]
= k1 ([H]0 [E])[A]0 (21)
dt
d[D] d[E]
= (22)
dt dt
If, as in the previous model [3], the rate coefcient k1 was expressed
by reparameterized Arrhenius equation and if its constants were
determined by tting the experimental data from this work, the
application of the model gave, for some runs, the calculated concen-
trations of epoxy group higher than theoretical and thus, negative
values of the calculated concentrations of double bond. The nega-
tive values were obtained because of the conguration of Eq. (21):
the value of [E] can rise to the value of [H]0 , which is higher than
theoretical limitation of [E] if the hydrogen peroxide is used in
excess, before the d[E]/dt becomes zero. Additionally, the least sum
of squares was high (Table 2). When the inuence of the catalyst
amount in the reaction system was taken into consideration by
112 S. Sinadinovic-Fiser et al. / Chemical Engineering and Processing 62 (2012) 106113

multiplying Eq. (21) with term (mCs ), the difference between the IN iodine number (g iodine/100 g oil)
calculated and experimental values was even higher. K1 equilibrium constant for reaction (1)
The model proposed in this work ts the experimental ki rate coefcient for reaction i
data obtained for in situ epoxidation of castor oil performed ki,a reparameterized Arrhenius equation constant related to
under described conditions better than both pseudo-homogeneous activation energy
kinetic models taken for comparison. ki,o reparameterized Arrhenius equation constant related to
frequency factor
5. Conclusions MH molecular mass of hydrogen peroxide
MW molecular mass of water
The epoxidation of castor oil with peracetic acid generated in m mass of the catalyst (g)
situ from acetic acid and hydrogen peroxide was carried out in mH mass of the hydrogen peroxide aqueous solution (g)
benzene in the presence of an acidic ion exchange resin used as NS number of syntheses
catalyst. It was found that the epoxidation occurred optimally at NUj number of samples in synthesis j
a temperature of 323 K when 0.5 mol of glacial acetic acid and P peracetic acid
1.5 mol of 30 wt% aqueous hydrogen peroxide solution per mol of [P] peracetic acid concentration (mol/100 g oil)
double bond of castor oil were used and catalyzed with 10 wt% of R universal gas constant (J/mol K)
the ion exchange resin. Under these conditions only 0.52% lower REY relative epoxy yield (%)
epoxy yield was obtained compared to maximum yield reached SD standard deviation
with 15 wt% of catalyst, under the same other conditions. The ion SE selectivity
exchange resin catalyst was found to be reusable. The achieved rel- t reaction time (h; min in the model)
ative epoxide yield indicated that it is possible to develop valuable tH period of hydrogen peroxide solution addition (min)
epoxy product from an inedible castor oil. T reaction temperature (K)
A mathematical model that described the kinetics of the reaction Ta average temperature of syntheses (K)
system for in situ epoxidation of vegetable oil with perorganic acid [W] water concentration (mol/100 g oil)
was developed assuming pseudo-homogeneity. For such a process, wH mass fraction of hydrogen peroxide in its aqueous solu-
for the rst time, the proposed model took into consideration the tion
occurrence of the reactions during the incremental addition of the X conversion of double bond (%)
hydrogen peroxide solution, as well as all temperature stages of the
epoxidation process. The temperature dependency of the kinetic Subscript
parameters was determined. A comparison was made between the 0 initial value
experimentally determined values of double bond and epoxy oxy- max maximum value
gen content and the corresponding calculated values. An increase th theoretical value
of the reaction rate coefcients with increment of temperature and
good agreement of the calculated and experimental values of reac- Superscript
tant and product concentrations indicated the correctness of the calc calculated value
proposed kinetic model. exp experimentally determined value
n order of reaction
Acknowledgement
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