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Chemical Engineering and Processing 62 (2012) 106113

Contents lists available at SciVerse ScienceDirect

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-


ence of an inert solvent have been studied. Although numerous
Vegetable oils are a valuable raw material for the chemical references concerning the inuence of reaction variables on in situ
industry, due to ability of their main constituents, triglycerides, to epoxidation of different vegetable oils such as soybean, cotton seed,
undergo various reactions. Epoxidation of vegetable oils, i.e. their palm, karanja, and mahua, and, more recently, canola, exist, a few
unsaturated triglycerides, is a commercially important reaction, deal with kinetics of the process. Besides the main reactions of
since the epoxides obtained from these renewable resources have percarboxylic acid and the epoxy ring formation, side reactions of
a wide application. They are used directly as plasticizers and poly- epoxy ring opening also occur in a reaction mixture. The predom-
mer stabilizers, as paint and coating components, as lubricants, but inant side-reaction is epoxy ring cleavage with acetic acid (A) [2].
also as intermediates for alcohols, glycols, alkanolamines, poly- Depending on the applied catalyst, the reaction system is either
ols and polymers (such as polyurethanes, polyesters, and epoxy two- (oilwater) or three-phase (oilwaterion exchange resin).
resins) production due to the high reactivity of the epoxy ring. Due to complexity of the reaction system, kinetic models that have
On an industrial scale, the epoxidation of vegetable oils is cur- been proposed are based on different simplications. The authors
rently carried out with a percarboxylic acid, such as performic of the rst kinetic models of in situ epoxidation, assumed, besides
or peracetic acid (P), usually obtained in situ through the acid homogeneity of the reaction mixture, that concentration of per-
catalyzed peroxidation of the corresponding organic acid with acetic acid in the mixture was low and constant due to the fact that
hydrogen peroxide (H). Soluble mineral acid, usually sulphuric rate of peracetic acid formation was slower than the rate of epoxy
acid, or acidic cation exchange resin, such as the sulphonated ring formation. Such an assumption implied that reaction of the
polystyrene-type Amberlite, are commonly used as catalyst for this double bond with peracetic acid was pseudo-rst order. The side
reaction [1]. reaction with acetic acid was considered as rst order in respect to
The process of epoxidation is signicantly inuenced by reac- both epoxy compound and acetic acid [3]. However, in some models
tion variables. Therefore, the effects of molar ratio of reactants, type 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
Corresponding author. Tel.: +381 021 485 3748; fax: +381 021 450 413. the reaction system is inadequate [6], such an approach has been
E-mail address: ssser@uns.ac.rs (S. Sinadinovic-Fiser). 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 107

Castor oil (CO) is a natural polyol which has about 90% of washed with distilled water (308 K) until it was acid-free, and then
monounsaturated hydroxy fatty acid, ricinoleic acid (12-hydroxy- dried by adding anhydrous Na2 SO4 . After ltration, ether, benzene
9-octadecenoic acid), in its fatty acid composition. Therefore, and water were evaporated at 333 K at 3.04.0 kPa. All samples
CO can be used for obtaining polyurethanes without previous were then analyzed for iodine number (IN) and epoxy oxygen con-
derivatization [11]. However, polyurethanes with higher degree of tent (EO). If the catalyst was reused, at the end of the reaction the
crosslinking may be obtained by introducing additional hydroxy ion exchange resin was ltered from the cooled reaction mixture,
groups in CO. They may be formed by opening of primary formed washed with water and diethyl ether, and air-dried.
epoxy groups. The rst brief report about in situ epoxidation of CO
with peracetic acid in the presence of an ion exchange resin was
2.3. Analytical methods
given in 2004 [12]. No reports about effects of the reaction variables
on the in situ epoxidation of CO with percarboxylic acid were found.
The iodine number and epoxy oxygen content of each sample
Concerning the kinetics of epoxidation of CO with in situ formed
were determined by the Hanus method and the standard HBr-acetic
performic and peracetic acid catalyzed by the ion exchange resin,
acid method [15], respectively.
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]. 3. Results and discussion
Because of the aforementioned, in this paper the epoxidation
of CO in benzene with peracetic acid generated in situ from acetic The experimentally measured initial iodine number (IN0 ) of the
acid and an aqueous solution of hydrogen peroxide in the presence castor oil was 81.5 meaning 0.321 mol of double bond (D) per 100 g
of a sulphonated polystyrene type acidic ion exchange resin as the of CO.
catalyst was investigated. The aim was to study the inuence of In order to determine the conditions under which the main reac-
some reaction variables on the process. The pseudo-homogenous tions of the epoxidation are favored, the effects of the reaction
model which, besides the main reactions, involves epoxy ring open- variables on the epoxidation were studied. Due to high viscos-
ing reaction with peracetic acid is proposed. The model also takes ity, caused by intermolecular hydrogen bonds formed between
into consideration occurrence of the reactions during incremental the hydroxy groups of ricinoleic acid, the epoxidation of castor
reactant addition, as well as all temperature stages of the process. oil is better performed in the presence of an inert solvent which
The model parameters were determined on the basis of the exper- enhances better phase contact by reducing the viscosity of the
imental data. The proposed model was compared with some of the reaction mixture. Moreover, side reactions of epoxy ring opening,
pseudo-homogeneous models found in the literature. 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
2. Experimental procedures
reduce the mass transfer resistance in the reaction system, con-
tinuous intensive stirring was performed. The stirring speed of
2.1. Materials
1500 rpm was applied, since increasing the speed beyond this value
offers no appreciable change in the rate of epoxidation [16].
Castor oil was kindly provided by Hemiprodukt (Novi Sad, R.
On the basis of preliminary studies it was concluded that sul-
Serbia). Glacial acetic acid (>99.5%), benzene, diethyl ether and
phuric acid is not suitable catalyst for epoxidation of castor oil with
30 wt% aqueous hydrogen peroxide solution were purchased from
peracetic acid. Regardless of the applied reaction variable values,
J.T. Backer, USA, while anhydrous sodium sulphate was from Fluka,
the polymerization of the reaction mixture occurred before signif-
Chemie GmbH, Germany. Sulphonated polystyrene-type cation
icant yield of epoxide was obtained. This is probably due to the
exchange resin Amberlite IR-120 from Rohm&Hass Co. (Philadel-
structure of castor oil triglycerides that are mainly triesters of rici-
phia, PA, USA) was used in its acid form.
noleic acid and, therefore, polyols. Thus, an ion exchange resin was
the catalyst of choice for the epoxidation of castor oil.
2.2. Epoxidation procedure The values of the reaction variables studied, along with achieved
conversion of double bond (X), relative epoxide yield (REY) and
The epoxidation of castor oil was carried out with peracetic selectivity (SE), are detailed in Table 1 only for the maximum epoxy
exp
acid formed in situ according to a method reported in the litera- oxygen content (EOmax , where EO is epoxy oxygen content, super-
ture [14]. In a 500 mL three-neck round bottom ask, placed in a script exp indicates experimentally determined value and subscript
water bath with controlled temperature within 1 K, and equipped max indicates maximum value) reached in each run.
with magnetic stirrer, thermometer, reux condenser and dropping The epoxidation was carried out with acetic acid as it is more
funnel, the oil (100 g) was mixed with an equal mass of benzene selective than formic acid when combined with the ion exchange
and an appropriate mass of glacial acetic acid before addition of resin in the in situ process [1719]. An acetic acid to double bond
an ion exchange resin. Subsequently, the hydrogen peroxide solu- molar ratio of 0.5 was applied in all epoxidations. Under this con-
tion was added dropwise to the reaction mixture at a constant rate dition, the quantity of acetic acid, which acts as an oxygen carrier
over the course of one hour. During the hydrogen peroxide addi- and regenerates once the epoxidation occurred, is sufcient for the
tion, the temperature of the mixture was maintained at 303 K for main reaction, whereas it is insufcient at the beginning of the pro-
the epoxidation carried out at 303 K and at 323 K for other runs. cess for the most likely side reaction with the formed epoxy ring
After the addition was completed, if necessary, the temperature that converts to hydroxy acetate [2,20].
was increased to the desired level. The reaction mixture was con- Since hydrogen peroxide is consumed during the process of
tinuously stirred at 1500 rpm so that a ne dispersion of oil was epoxidation, an excess relative to a double bond of oil is usually
achieved. The progress of the reaction was followed by withdraw- applied. Thus, the inuence of 1.1 and 1.5 mol of aqueous hydro-
ing 10 mL samples of the reaction mixture at dened time intervals. gen peroxide solution (30 wt%) per mole of double bond on the
The beginning of the addition of hydrogen peroxide was considered epoxidation of castor oil was studied at 323 K in the presence of
to be the zero time. After the quenching and centrifugation of the 5 wt% of ion exchange resin used as catalyst. The effect is presented
sample, the separation of oil and aqueous phases was performed. in Fig. 1. With an increase in hydrogen peroxide concentration, a
Prior to analysis, the oil phase sample was dissolved in diethyl ether, 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 and 15 wt% of Amberlite IR-120 when the molar ratio of double
maximum of epoxy oxygen content (Table 1). Also, higher selec- bond:acetic acid:hydrogen peroxide was 1:0.5:1.5. Since the for-
tivity was achieved when the molar ratio of hydrogen peroxide mation of peracetic acid is catalyzed by ion exchange resin, as
to double bond was 1.5. Due to the fact that hydrogen peroxide expected, its rate increased when higher concentration of catalyst
concentrations higher than 1.5 lead to a higher rate of epoxy ring was applied. At the same time, higher amount of external surface
decomposition, as concluded in most papers [1719], this molar active catalyst sites in the reaction mixture increased rate of the
ratio was accepted as optimum. Notice that the mass of catalyst in epoxy ring cleavage. The inuence of an increase in the catalyst
this work is expressed as the weight percentage of the sum of the load on the former reaction resulted in a shortening of the time
used weights of acetic acid and hydrogen peroxide. Therefore, the for reaching the maximum REY, while an inuence on the latter
amount of applied catalyst was higher when 1.5 mol of hydrogen caused a lowering in the selectivity of the process (Table 1). It was
peroxide was used. Since an increase of the hydrogen peroxide and also observed that an increase in the catalyst concentration resulted
the catalyst concentration in the reaction mixture both increase in an increase of the double bond conversion (X) and epoxy yield
the rate of the peracetic acid formation, and consequently, the rate (REY). The amount of the catalyst used for further study is, however,
of the reaction of epoxide formation, the inuence of the catalyst 10 wt% since maximum relative epoxy yield was only 0.52% lower
concentration on epoxidation was further studied separately. than that reached when 15 wt% of catalyst was used, whereas the
The effect of other epoxidation variables on the in situ epoxi- selectivity was the same. The effect of the catalyst concentration
dation of castor oil was examined in the following ranges: catalyst on the in situ epoxidation is illustrated in Fig. 2.
concentration, 515%, temperature, 303348 K, and reusability of
the catalyst, 13 times. 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 Fig. 2. Time dependency of experimentally determined (points) and calculated
(curves) iodine number (IN) and epoxy oxygen content (EO) for in situ epoxida- (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 tion of castor oil in benzene with peracetic acid, when molar ratio of double bond in
in oil:acetic acid:(30 wt%) hydrogen peroxide was 1:0.5:1.1 and 1:0.5:1.5, in the oil:acetic acid:(30 wt%) hydrogen peroxide was 1:0.5:1.5, at 323 K in the presence
presence of 5 wt% of Amberlite IR-120 at 323 K. 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- Unlike kinetic models reported in the literature, in this model
tion, all expressed as moles per 100 g of oil, t (min) is the reaction the application of Eq. (11) makes possible tting of data obtained
time, AJ is the atomic mass of iodine and AO is the atomic mass under the temperature variations during epoxidation. Thus, the
of oxygen. (d[H]/dt)r (mol/min) is the rate of hydrogen peroxide temperature change from that at which hydrogen peroxide solution
consumption in the reaction (1). Since the stirring was good, the is incrementally added into the reaction mixture until the desired
diffusional resistances in the reaction mixture could be ignored. reaction temperature, is taken into consideration. Additionally, by
Thus, if the uniform distribution of the catalyst and complete dis- considering the beginning of the hydrogen peroxide addition as
sociation of its sulpho groups in the liquid phase are assumed, i.e. if the zero reaction time, the proceeding of the epoxidation reactions
the catalyst behaves as it is dissolved in the pseudo-homogeneous during that dropwise addition was not ignored.
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: 4.1. Kinetic parameters
 d[H]   [P][W]

= m Cs k1 [A][H] (8) The variations in the concentration of double bond and epoxy
dt r K1 group with reaction time (t), calculated on the basis of experimen-
where m (g) is the mass of the catalyst, Cs (mol/g catalyst) indi- tally determined iodine number and epoxy oxygen content were
cates the concentration of catalytically active sites (sulpho groups), used to determine the model parameters. They were calculated
k1 ((100 g oil)2 /(mol2 min)) is the rate coefcient for the reac- assuming the rst or the second order of the reaction of epoxy
tion (1), and K1 is the equilibrium constant for reaction (1). ring cleavage (reaction (3)) with respect to acetic acid. In Table 2
Also, in the system of Eqs. (1)(7) k2 ((100 g oil)/(mol min)) is the are shown the calculated values of the constants of the reparam-
rate coefcient for the reaction (2), k3 ((100 g oil)/(mol min) or eterized Arrhenius equation (ki,o and ki,a ) for all three considered
(100 g oil)2 /(mol2 min)), depending of the reaction order (n) is the reactions together with the least sum of squares (objective function
rate coefcient for reaction (3), n indicates the order (rst or sec- F) calculated by Eq. (12), standard deviation (SD) and an average
ond) of epoxy ring cleavage with respect to acetic acid, and FH and absolute deviations for double bond concentration (AAD[D] ) and
FW (mol/min) are the molar ows of hydrogen peroxide and water epoxy group concentration (AAD[E] ). Since the objective function is
addition, respectively. Dropwise addition of the hydrogen peroxide slightly lower when the order of reaction (3) was assumed as sec-
solution to the reaction mixture is approximated with continuous ond, the temperature dependencies of kinetic parameters for such
ows: assumption are presented as follows:
 mH wH   1 
  141179.8 1
 MH tH t tH  k1 Cs = exp 4.24834 (13)
FH =   (9) R T Ta
0 t > tH

 1 
  8398.366 1
 mH (1 wH )  k2 = exp 1.436033 (14)
 t tH  R T Ta
FW =  M t  (10)
W H
  1 
0 t > tH  14437.99 1
k3 = exp 3.064781 (15)
R T Ta
where mH (g) is the mass of the hydrogen peroxide aqueous solu-
tion, wH is the mass fraction of hydrogen peroxide in its aqueous The increase of all three rate coefcients with temperature
solution, MH and MW (g/mol) are molecular masses of hydrogen indicates that in this work determined dependencies are satisfac-
peroxide and water, respectively, and tH (min) is the period of tory. Since all calculated reactant and product concentrations have
hydrogen peroxide solution addition. positive values, the viability of the kinetic model is additionally
The temperature dependency of kinetic model parameters is conrmed. The proposed pseudo-homogeneous model ts reason-
expressed by reparameterized Arrhenius equation: ably well the experimental values, as shown in Figs. 13 where the
 1  experimentally determined (points) and calculated (curves) iodine
ki,a 1
ki = exp ki,o (11) number and epoxy oxygen content changes over time during the
R T Ta in situ epoxidation of castor oil with peracetic acid in benzene in
the presence of Amberlite IR-120 at different reaction conditions
where ki is the rate coefcient for the reaction i, ki,o is a constant
are compared.
related to frequency coefcient, ki,a is a constant related to activa-
The approach that occurrence of the epoxidation reactions dur-
tion energy, T (K) is the reaction temperature, Ta (K) indicates an
ing the hydrogen peroxide addition into the reaction mixture must
average temperature of syntheses (accepted as Ta = 323 K), and R
be taken into consideration when establishing the kinetic model,
(8.3143 J/mol K) is the universal gas constant. The constants of the
as used in this work, was tested: the proposed model was applied
Arrhenius equation were determined by tting the experimental
under assumption that the completion of the addition of hydrogen
values of the double bond and epoxy group concentrations. The
peroxide was zero time. For that case, the least sum of squares (F)
Marquardt method [21] was used to t the data. The following
was about 32% higher than those calculated when the beginning of
objective function F was minimized:
the addition was considered to be zero time, for the rst order
NUj of the epoxy ring cleavage (Table 2). Assuming the second order

NS 
exp 2 exp 2
F= [([D]calc calc of the same reaction, the difference of objective functions for such
j,k [D]j,k ) + ([E]j,k [E]j,k ) ] (12)
comparison was slightly lower (about 26%). The lowest least sum
j=1 k=1
of squares of 0.01375 obtained for model proposed in this work
where NS indicates the number of syntheses used for tting (runs when the second order of the epoxy ring cleavage with respect
16 in Table 1) and NUj is the number of samples in synthesis j; to acetic acid was assumed, conrmed the correctness of applied
superscript calc indicates the calculated value. approach. The constants of the reparameterized Arrhenius equa-
A fourth-order RungeKutta method was applied for integrating tion calculated for aforementioned assumptions are also given in
the system of differential equations (1)(7). 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 acid, hydrogen peroxide and catalyst concentrations, on the rate of
in the literature epoxy ring formation was neglected.
Gan et al. [4] described in situ epoxidation with the following
The two pseudo-homogeneous kinetic models developed for the expression without giving any explanation:
in situ epoxidation of triglycerides and fatty acid esters, applied
dCE
by other authors, were compared with the model proposed in this = k1 (CH,0 CE )CA,0 (20)
work. dt
Wisniak et al. [3] assumed that the reaction of the double bond where CE (mol/L) is the epoxy group concentration, k1 (L/mol min)
with peracetic acid is pseudo-rst order whereas epoxy ring cleav- is the rate coefcient for reaction (1), CH,0 (mol/L) is the initial
age is rst order in respect to both epoxy compound and acetic acid. concentration of hydrogen peroxide and CA,0 (mol/L) is the initial
The model was described by the following equations: concentration of acetic acid. Eq. (20) can be derived if the epoxy
d[D] ring cleavage is ignored and if low and constant concentration of
= k2 [D] (16) the peracetic acid is assumed. Consequently, the reverse reaction
dt
of peracetic acid with water can be omitted. In such case, the con-
d[E] centration of acetic acid is constant and approximately the same as
= k2 [D] k3 [E][A] (17)
dt the initial concentration. For this model, it is only possible to con-
d[A] sider the completion of the addition of hydrogen peroxide into the
= k3 [E][A] (18)
dt reaction mixture as zero time. If the concentrations are expressed
d[HA] as moles per 100 g of oil, the model can be rewritten as follows:
= k3 [E][A] (19)
dt d[E]
= k1 ([H]0 [E])[A]0 (21)
where k2 (1/min) is the rate coefcient for reaction (2) and k3 dt
((100 g oil)/(mol min)) is the rate coefcient for reaction (3). This
d[D] d[E]
model correctly ts our experimental data giving positive values of = (22)
dt dt
all reactant/product concentrations and an increase of the k2 and k3
with temperature, when both rate coefcients were expressed by If, as in the previous model [3], the rate coefcient k1 was expressed
reparameterized Arrhenius equation. If the beginning of the addi- by reparameterized Arrhenius equation and if its constants were
tion of hydrogen peroxide into the reaction mixture was considered determined by tting the experimental data from this work, the
to be the zero time and if the rst order of the epoxy ring cleav- application of the model gave, for some runs, the calculated concen-
age was assumed when applying the above model, the least sum of trations of epoxy group higher than theoretical and thus, negative
squares was 4.7 times higher than that calculated for the model pro- values of the calculated concentrations of double bond. The nega-
posed in this work and for the same assumptions (Table 2). When tive values were obtained because of the conguration of Eq. (21):
the order of reaction (3) was, however, assumed to be second in the value of [E] can rise to the value of [H]0 , which is higher than
respect to acetic acid, slightly better result was obtained, i.e. the theoretical limitation of [E] if the hydrogen peroxide is used in
least sum of squares was 4.6 times higher. This was expected, since excess, before the d[E]/dt becomes zero. Additionally, the least sum
in the model reported in the literature the inuence of the rate of of squares was high (Table 2). When the inuence of the catalyst
peracetic acid formation, more precisely the inuence of the acetic 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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