Article

pubs.acs.org/IECR

Kinetics of the Epoxidation of Castor Oil with Peracetic Acid Formed

in Situ in the Presence of an Ion-Exchange Resin
Milovan R. Janković, Snežana V. Sinadinović-Fišer,* and Olga M. Govedarica
Faculty of Technology, University of Novi Sad, Bul. cara Lazara 1, 21000 Novi Sad, R. Serbia

ABSTRACT: The kinetics of the epoxidation of castor oil in benzene with peracetic acid formed in situ from acetic acid and
hydrogen peroxide in the presence of an ion-exchange resin as a catalyst was studied. Eighteen pseudo-two-phase models
are established that, besides the main reactions of peracid and epoxy ring formation, also consider the side reaction of epoxy ring
cleavage with acetic acid. Kinetic expressions for the heterogeneously catalyzed peracetic acid formation are developed on the
basis of Eley−Rideal and Langmuir−Hinshelwood−Hougen−Watson postulates. An equation derived for the temperature
dependency of the chemical equilibrium constant for peracetic acid formation is applied. Kinetic and adsorption parameters were
estimated by fitting experimental data using the Marquardt method. The best-fit model correctly interprets data of double bond
and epoxy group contents as a function of reactant ratios, catalyst concentrations, and temperatures applied during epoxidation.
The proposed model better fits experimental data than the pseudohomogeneous model reported in the literature.

1. INTRODUCTION Langmuir−Hinshelwood−Hougen−Watson postulates. The

Castor oil is a natural polyol because ∼90% of the fatty acid
chains in its triglycerides are monounsaturated hydroxy C18 acid
chains, namely 12-hydroxy-9-octadecenoic acid, i.e., ricinoleic
acid. This oil is used as a polyol component in polyurethane prod-
uction.1 However, a more cross-linked polyurethane network may
be formed by introducing additional hydroxy groups into fatty
acid chains of castor oil prior to polycondensation. That can
be achieved via epoxidation of castor oil triglyceride’s double
bonds followed by the transformation of epoxy groups to
hydroxy groups.
The epoxidation of vegetable oils with percarboxylic acid
generated in situ involves the acid-catalyzed percarboxylic acid
formation in the water phase, the uncatalyzed epoxy group for-
mation in the oil phase, and a few side reactions of acid-
catalyzed epoxy ring cleavage. The percaboxylic acid is formed
from hydrogen peroxide in an aqueous solution and a cor-
responding carboxylic acid, usually acetic acid. A mineral acid,
mainly sulfuric acid, or an acidic ion-exchange resin can be used
as a catalyst. This process is significantly influenced by reaction
variables; thus, it is necessary to establish a kinetic model for
its optimization. When an ion-exchange resin is used as the
catalyst, the reaction system for epoxidation of vegetable oil is a
three-phase, i.e., liquid−liquid−solid (oil−water−resin), sys-
tem. Because of the complexity of developing a rigorous
mathematical model describing such a system that must include
kinetic and thermodynamic, as well as mass transfer, param-
eters, different simplifications can be found in the literature.
The first kinetic model was based on an assumption of homo-
geneity of the epoxidation reaction system.2 Although their
inadequacy was discussed,3 pseudohomogeneous models are
still being used.4−6 The first pseudo-two-phase liquid−solid
model for vegetable oil epoxidation in the presence of an ion-
exchange resin as a catalyst was developed in 2001.7 Besides the
main reactions of peracetic acid and epoxy compound
formation, the model takes into consideration two epoxy ring
opening reactions, with water and acetic acid. The kinetics of
this heterogeneous catalytic process is described on the basis of
developed model was applied originally to experimental data
for soybean oil epoxidation and later for mahua,8 karanja,9
jatropha,10 and cotton11 oil epoxidation. In these cases, all
model parameters were determined simultaneously by fitting
the experimental data for the variation of component con-
centrations with reaction time. However, the fact that such
experimental data are inconvenient for the determination of the
chemical equilibrium constant for peracetic acid formation was
discussed, because the equilibrium of this reaction is shifted
to the right due to the constant consumption of peracetic acid
in the epoxidation reaction. Therefore, some model parameters
should be determined either using expressions derived by cor-
relating data of experiments designed for particular phenomena
or using expressions derived semitheoretically or theoret-
ically.12−15 Thus, a few authors who investigated peracetic acid
formation separately from the epoxidation process reported the
dependency of this reaction’s chemical equilibrium constant on
temperature.12,16−20
In this work, in established pseudo-two-phase (liquid−solid)
models for the epoxidation of castor oil in benzene with
peracetic acid generated in situ from acetic acid and hydrogen
peroxide in the presence of an acidic ion-exchange resin as a
catalyst, an expression for the temperature dependency of the
chemical equilibrium constant for peracetic acid formation in
an aqueous solution, derived on the basis of the van’t Hoff and
Kichoff equations, is used. Kinetic expressions for heteroge-
neously catalyzed peracetic acid formation were developed by
applying Eley−Rideal and Langmuir−Hinshelwood−Hougen−
Watson postulates. The models take into consideration the
occurrence of the reactions during the incremental addition of
reactants. Experimental data obtained for epoxidation of castor
Received: February 28, 2014
Revised: May 7, 2014
Accepted: May 9, 2014
Published: May 9, 2014

© 2014 American Chemical Society 9357 dx.doi.org/10.1021/ie500876a | Ind. Eng. Chem. Res. 2014, 53, 9357−9364
Industrial & Engineering Chemistry Research Article

oil were used to test the models that, besides the main reac- evaporated at 333 K under 3.0−4.0 kPa to remove benzene,
tions, involve the side reaction of epoxy ring cleavage with water, and ether. The sample was then analyzed for iodine
acetic acid. Among 18 proposed models, the best-fit model was number (IN) and epoxy oxygen content (EO).
chosen on the basis of the smallest deviation between the cal- 2.3. Analytical Methods. The oil phase of each sample was
culated and experimentally determined values of double bond analyzed in triplicate to determine the iodine number and
and epoxy group concentrations. The accepted model was epoxy oxygen content according to the Hanush and the standard
compared with one of the pseudohomogeneous models HBr−acetic acid methods.21
reported in the literature.
3. KINETIC MODEL
2. EXPERIMENTAL SECTION Epoxidation of vegetable oil with peracetic acid (P) generated
2.1. Chemicals. Castor oil was kindly provided by in situ in the presence of an ion-exchange resin is a hetero-
Hemiprodukt (Novi Sad, R. Serbia). Glacial acetic acid geneous catalytic process in which the formation of peracid
(>99.5%), benzene, diethyl ether, and a 30 wt % aqueous from acetic acid (A) and hydrogen peroxide (H) in an aqueous
hydrogen peroxide solution were purchased from J. T. Baker. solution is acid-catalyzed (reaction I in Figure 1). Peracetic
Anhydrous sodium sulfate was bought from Fluka, Chemie acid diffuses through the water (W) to the oil phase where it
GmbH. An acid form of sulfonated polystyrene-type cation- spontaneously reacts with the double bond (D) of the oil
exchange resin Amberlite IR-120 from Rohm and Hass Co. triglyceride forming an epoxy ring (E) (reaction II). Because of
(Philadelphia, PA) was used as a catalyst. the continuous consumption, by epoxidation, the concentration
2.2. Epoxidation Procedure. Castor oil was epoxidized of peracetic acid in the system is low; thus, its decomposition is
with peracetic acid formed in situ according to a method negligible. Among the few side reactions, the selectivity of the
reported in detail in the literature.6 Equal masses of oil and epoxidation is mainly reduced by the acid-catalyzed reaction of
benzene and appropriate masses of glacial acetic acid and an the epoxy ring with acetic acid, which yields hydroxyl acetate
ion-exchange resin were loaded in the reactor, a 500 mL three- (HA) (reaction III).22−24
neck round-bottom flask. The reactor equipped with a magnetic In this work, the reaction system of epoxidation of castor oil
stirrer, a thermometer, and a reflux condenser was placed in a is considered as a pseudo-two-phase liquid−solid system. The
water bath. To avoid an uncontrolled increase in temperature, a presence of a large amount of benzene in the reaction mixture
30% aqueous hydrogen peroxide solution was gradually charged reduces the viscosity of the oil phase. Therefore, under intense
into the reaction mixture at a constant rate over the course of stirring, an effective mixing is achieved and a mass diffusion
1 h. The reaction conditions for all runs are listed in Table 1. resistance can be neglected; consequently, the parameters
related to the mass transfer phenomenon are omitted from the
Table 1. Reaction Conditions Related to the Epoxidation of model. If only reactions I−III occur during the epoxidation, the
Castor Oil in Benzene with Peracetic Acid Formed in Situ whole process may be described with the following system of
from Acetic Acid (A) and Hydrogen Peroxide (H) in the first-order differential equations:
Presence of an Ion-Exchange Resin Used as a Catalyst ⎛ d[H] ⎞
d[H]
= FH + ⎜ ⎟
temp (K) dt ⎝ dt ⎠1 (1)
run Da:A:H molar ratio Amberlite (wt %)b H addition reaction
1 1:0.5:1.1 2.48 (5) 323 323 d[A] ⎛ d[H] ⎞
=⎜ ⎟ + k 2[P][D] − k 3[E][A]n
2 1:0.5:1.5 3.21 (5) 323 323 dt ⎝ dt ⎠1 (2)
3 1:0.5:1.5 6.43 (10) 323 323
4 1:0.5:1.5 9.64 (15) 323 323 d[P] ⎛ d[H] ⎞
= −⎜ ⎟ − k 2[P][D]
5 1:0.5:1.5 6.43 (10) 323 348
dt ⎝ dt ⎠1 (3)
6 1:0.5:1.5 6.43 (10) 303 303
a
The initial iodine number of the castor oil of 81.5 corresponds to d[W] ⎛ d[H] ⎞
0.321 mol of double bonds (D) per 100 g of oil. bCatalyst con- = FW − ⎜ ⎟
centration expressed as a percentage of oil weight and, in parentheses, dt ⎝ dt ⎠1 (4)
as a percentage of acetic acid and hydrogen peroxide weight.
d[D]
= −k 2[P][D]
The beginning of the addition of the hydrogen peroxide dt (5)
solution was considered to be the “zero reaction time”. The d[E]
temperature of hydrogen peroxide addition was 323 K, except = k 2[P][D] − k 3[E][A]n
dt (6)
as noted in Table 1. After addition, where applicable, the tem-
perature of reaction mixture was increased to the reaction tem- d[HA]
perature at a uniform rate over the course of 1 h. The fluctua- = k 3[E][A]n
dt (7)
tion of the reaction temperature, as well as of the hydrogen
peroxide addition temperature, was less than ±1 K. The where brackets denote the concentration of a compound or
reaction mixture was continuously stirred at 1500 rpm. At functional group in moles per 100 g of oil. The double bond
defined time intervals, 10 mL samples of the reaction mixture concentration is determined with the equation [D] = IN/(2AI),
were taken for determination of the extent of epoxidation. Each where AI is the atomic mass of iodine, while the epoxy group
sample was filtered to remove the catalyst, quenched, and concentration is calculated with the equation [E] = EO/
centrifuged. The oil phase of the sample was dissolved in (100AO), where AO is the atomic mass of oxygen. t (minutes) is
diethyl ether, washed with distilled water (308 K) until the pH the reaction time. FH (moles per minute per 100 g of oil) and
reached 7, and dried with anhydrous Na2SO4. Further, it was FW (moles per minute per 100 g of oil) are the molar flows of
9358 dx.doi.org/10.1021/ie500876a | Ind. Eng. Chem. Res. 2014, 53, 9357−9364
Industrial & Engineering Chemistry Research Article

Table 2. Assumptions Made in Modeling the Kinetics of

Peracetic Acid Formation on the Basis of Eley−Rideal or
Langmuir−Hinshelwood−Hougen−Watson Postulates
chemisorptionb
modela adsorptionc rate-determining step
aAP A, P adsorption of A
aAH A, H adsorption of A
aAHP A, H, P adsorption of A
Figure 1. Reaction system of vegetable oil epoxidation with peracetic aAHW A, H, W adsorption of A
acid generated in situ. Main reactions of peracetic acid (reaction I) and aAHPW A, H, P, W adsorption of A
epoxy ring (reaction II) formation and the predominant side reaction dAP A, P desorption of P
of epoxy ring cleavage with acetic acid (reaction III). dAHPW A, H, P, W desorption of P
rAP A, P surface reaction
hydrogen peroxide and water addition, respectively. (d[H]/dt)1 rAHPW A, H, P, W surface reaction
(moles per minute per 100 g of oil) is the rate of hydrogen
a
For the notation of the models, the first letter indicates the rate-
peroxide consumption in reaction I. k2 (100 g of oil per mole determining step for peracetic acid formation, where “a” is the
per minute) and k3 [(100 g of oil)n/(mol·min)n] are the rate adsorption of acetic acid, “d” is the desorption of peracetic acid, and
“r” is the surface chemical reaction, and uppercase letters are symbols
coefficients of reactions II and III, respectively. n is the order of
for chemisorbed compounds. bSteps of chemisorption, i.e., adsorption,
reaction III with respect to acetic acid. surface reaction, and desorption, are considered reversible. cAssociative
Dropwise addition of the hydrogen peroxide solution to the adsorption is assumed.
reaction mixture is approximated with continuous flows of
hydrogen peroxide (FH) and water (FW): [(kinetic factor)(driving force group)]/(adsorption group)
mHSwH (10)
t ≤ t HS
F = MHt HS
H
and they comprise kinetic, thermodynamic, and chemisorption
0 t > t HS parameters.
(8) Depending on an assumed rate-determining step, the ex-
pression for the “kinetic factor” includes a rate coefficient either
mHS(1 − wH)
t ≤ t HS for the adsorption of the reactant or product or for the surface
FW = MW t HS reaction. The temperature dependency of these rate coef-
0 t > t HS ficients, as well as of the rate coefficients for reactions II and III,
(9) is described by the Arrhenius equation. To avoid a strong
where mHS (grams per 100 g of oil) is the mass of the hydrogen correlation between its parameters, a reparameterized form of
peroxide aqueous solution, wH is the mass fraction of hydrogen this equation is used:
peroxide in its aqueous solution, MH and MW are molecular ⎡
masses of hydrogen peroxide and water, respectively, and tHS ki , Ea ⎛ 1 1 ⎞⎤
ki = exp⎢ki ,0 − ⎜ − ⎟⎥
(minutes) is the period of addition of the hydrogen peroxide ⎢⎣ R ⎝T Ta ⎠⎥⎦ (11)
solution.6
Of those occurring during the epoxidation process, reactions where ki is the rate coefficient for reaction i (ka,C, adsorption of
of epoxy ring (reaction II) and hydroxyl acetate (reaction III) component C; k1,sr, surface reaction related to reaction I; k2,
formation are considered homogeneous and pseudohomoge- reaction II; k3, reaction III). ki,0 and ki,Ea are constants related to
neous, respectively, while peracetic acid formation (reaction I) the frequency coefficient and the activation energy, respectively.
is considered heterogeneous. To establish a mathematical model R is the universal gas constant (8.3143 J mol−1 K−1); T (kelvin)
for the rate of hydrogen peroxide consumption in peracetic is the temperature, and Ta (kelvin) is the average temperature
acid formation (d[H]/dt)1, Eley−Rideal (ER) or Lagmuir− of the runs (accepted as 323 K).
Hinshelwood−Hougen−Watson (LHHW) approaches are “Driving force group” in eq 10 indicates a displacement
applied to describe a chemisorption of this heterogeneous from the chemical equilibrium. The equation derived for the
catalytic reaction. The reaction proceeds on active sites of temperature dependency of the chemical equilibrium constant
the catalyst in three steps: (i) adsorption of at least one of for peracetic acid formation, K1, in an aqueous solution is
the reactants onto the active site, (ii) surface chemical applied:12
reaction between adsorbed molecules or between adsorbed
and nonadsorbed reactant, and (iii) desorption of the prod- K1 = exp(12.2324 ln T − 0.0229913T + 9.70452
ucts. Nine models were established assuming that different × 10−6T 2 + 3045.76/T − 72.8758) (12)
reactants and products are chemisorbed on the catalyst sur-
face and that different steps control the overall reaction rate. “Adsorption group” in eq 10 denotes a decrease in the over-
In all models, the adsorption is considered associative, and all reaction rate due to occupation of catalytic active sites by
adsorption, surface reaction, and desorption are thought to chemisorbed compounds. The adsorption equilibrium constant
be reversible. The order of the surface reaction is considered for component C, KC, defined as the ratio of adsorption and de-
as the first with respect to both reactants. In Table 2 are sorption rate coefficients, is also presented as a reparameterized
listed assumptions made in developing the models. Arrhenius type of temperature dependency (eq 11).
Kinetic equations derived according to ER and LHHW By introducing the expression for (d[H]/dt)1, derived on the
postulates have the following general form: basis of ER or LHHW postulates, into the system of differential
9359 dx.doi.org/10.1021/ie500876a | Ind. Eng. Chem. Res. 2014, 53, 9357−9364
Industrial & Engineering Chemistry Research Article

Table 3. Comparison of the Numbers of Model Parameters, Discrimination Results, and Statistical Values of the Model
Parameters Determined for Pseudo-Two-Phase and Pseudohomogeneous Models of the Reaction System for Castor Oil
Epoxidation in Benzene with Peracetic Acid Formed in Situ in the Presence of Amberlite IR-120 as a Catalyst
modela no. of model parameters ki temperature profileb F SDc AAD[D]d AAD[E]e
Pseudo-Two-Phase Model
aAP1 10 correct 0.012516 0.010571 0.00886 0.00653
aAP2 10 correct 0.012181 0.010429 0.00887 0.00677
aAH1 10 k2 incorrect 0.012147 0.010414 0.00874 0.00649
aAH2 10 correct 0.012011 0.010356 0.00890 0.00691
aAHP1 12 k2 incorrect 0.011547 0.010154 0.00862 0.00623
aAHP2 12 correct 0.011839 0.010281 0.00879 0.00670
aAHW1 12 correct 0.011425 0.010100 0.00849 0.00612
aAHW2 12 correct 0.011719 0.010229 0.00870 0.00658
aAHPW1 14 correct 0.011358 0.010070 0.00849 0.00606
aAHPW2 14 correct 0.011610 0.010181 0.00866 0.00653
dAP1 10 k2 incorrect 0.021124 0.013733 0.01275 0.00820
dAP2 10 k2 incorrect 0.020140 0.013410 0.01293 0.00754
dAHPW1 14 k2 incorrect 0.015873 0.011905 0.01019 0.00672
dAHPW2 14 k2 incorrect 0.014774 0.011485 0.01000 0.00678
rAP1 10 correct 0.025211 0.015003 0.01343 0.00847
rAP2 10 correct 0.030974 0.016630 0.01480 0.00908
rAHPW1 14 correct 0.016803 0.012249 0.01164 0.00797
rAHPW2 14 k2 incorrect 0.016599 0.012174 0.01193 0.00778
Pseudohomogeneous Model
ref 6 6 correct 0.031620 0.016802 0.01495 0.00916
a
The notation of models is done by adding a digit that indicates the order of hydroxyl acetate formation with respect to acetic acid at the end of
the notation for the corresponding chemisorption model of the peracetic acid formation reaction. bModels in which any of the kinetic constants
(ki) decreased with an increase in temperature were eliminated. cStandard deviation: SD = [F/(2∑NR 1/2 d
k=1NSk)] . Average absolute deviation
NR NSk
for double bond concentration: AAD[D] = 1/(∑k=1NSk)∑k=1∑l=1 |[D]k,l − [D]k,l |. Average absolute deviation for epoxy group concentration:
NR calc exp e
NR NSk
AAD[E] = 1/(∑NR k=1NSk)∑k=1∑l=1 |[E]k,l − [E]k,l |.
calc exp

eqs 1−7 and by assuming the first or the second order of

hydroxyl acetate formation with respect to acetic acid, we
established 18 mathematical models for the reaction system of
vegetable oil epoxidation (Table 3).

4. RESULTS AND DISCUSSION

The time dependencies of experimentally determined values
of iodine number and epoxy oxygen content for castor oil
epoxidation in benzene with peracetic acid formed in situ from
acetic acid and hydrogen peroxide, in the presence of Amberlite
IR-120 as a catalyst, are shown as points in Figures 2−4. The
initial iodine number of the castor oil was measured as 81.5,
meaning 0.321 mol of double bond per 100 g of oil. Discussion
related to the influence of reaction conditions on the con-
version of double bonds, relative epoxy yield, and selectivity
of epoxidation is detailed in previous work.6 The variations
of double bond [D] and epoxy group [E] concentrations with Figure 2. Time dependency of the experimentally determined (points)
reaction time, calculated on the basis of experimentally and calculated (curves) iodine number (IN) and epoxy oxygen content
determined iodine number and epoxy oxygen content, were (EO) for castor oil epoxidation in benzene with peracetic acid formed
used to determine the model parameters. The following ob- in situ, at 323 K in the presence of 10 wt % Amberlite IR-120, when
jective function F was minimized using the Marquardt the double bond (D) in oil:acetic acid (A):30 wt % hydrogen peroxide
algorithm:25 (H) molar ratio was 1:0.5:1.1 and 1:0.5:1.5.
NR NSk
F= ∑ ∑ [([D]kcalc,l − [D]kexp 2 calc exp 2
, l ) + ([E]k , l − [E]k , l ) ] end of the incremental addition of the oxidizing agent as the
k=1 l=1 zero reaction time, the occurrence of the epoxidation reactions
(13) during that period is not neglected in established models. The
where NR is the number of runs and NSk is the number of addition of the hydrogen peroxide solution is described with
samples in run k. Superscripts calc and exp indicate calculated molar flows of hydrogen peroxide and water. Additionally, the
and experimentally determined values, respectively. direct determination of constants in the Arrhenius type
Unlike in pseudo-two-phase models reported in the temperature dependency of kinetic and adsorption parameters
literature,7−11 by considering the beginning instead of the (eq 11), when fitting the experimental data, allowed the
9360 dx.doi.org/10.1021/ie500876a | Ind. Eng. Chem. Res. 2014, 53, 9357−9364
Industrial & Engineering Chemistry Research Article

consideration of the difference in hydrogen peroxide addition work, the increase in temperature from that at which the
and reaction temperature. However, as just mass balances are hydrogen peroxide solution is added to the reaction mixture to
included, the developed mathematical models are applicable the reaction temperature was approximated with the following
when the temperature is defined over the reaction time. In this linear function of reaction time:

THS t ≤ t HS
Tr − THS
T= THS + (t HS + t TI − t ) t HS < t ≤ t HS + t TI
t TI
Tr t HS + t TI < t (14)

where THS (kelvin) is the temperature of hydrogen peroxide ka,H

H + s XoooY H·s
addition, Tr (kelvin) is the temperature of the reaction, and kd,H (16)
tTI (minutes) is the period of temperature increase. Also, the
direct determination of constants related to frequency factor k1,sr
and activation energy makes possible the fitting of an ex- A·s + H·s XooooY P ·s + W·s
k −1,sr (17)
perimental data set obtained for epoxidations conducted at
different reaction temperatures. kd,P
The chemical equilibrium constant for peracetic acid for- P ·s XoooY P + s
ka,P (18)
mation was the subject of a few studies. In some works, only
experimental values were determined,16,17 while in others, the kd,W
expression for the temperature dependency of the constant was W·s XoooY W + s
ka,W (19)
developed.12,19,20 Except in one case,16 the values of the chem-
ical equilibrium constant decrease with an increase in tem- where s is an active site of the catalyst and k−1,sr indicates the
perature. Also, the values are on the same order of magnitude in rate coefficient for the reverse surface reaction related to reac-
the investigated temperature ranges.12,17−20 Thus, in this work, tion I. The corresponding (d[H]/dt)1 expression for model
eq 12 developed by Janković et al.12 was selected to calculate aAHPW1 is as follows:
the chemical equilibrium constant.
⎛ d[H] ⎞ ⎡ ⎛ [P][W] ⎞⎤
The system of differential eqs 1−7 was integrated by a ⎜ ⎟ = − ⎢mCska,A ⎜[A] − ⎟⎥
fourth-order Runge−Kutta method. ⎝ dt ⎠1 ⎣⎢ ⎝ K1[H] ⎠⎥⎦
4.1. Model Selection and Kinetic Parameter Determi-
⎛ ⎞
nation. Once the experimental data had been fit, the pseudo- K [P][W]
⎜⎜1 + A + KH[H] + KP[P] + KW [W]⎟⎟
two-phase models were discriminated if estimated values of ⎝ K1[H] ⎠
their parameters or calculated results were nonviable. The (20)
models in which any of the rate coefficients (ki) decreased
with an increase in temperature were eliminated. For each of 11 where m (grams) is the mass of the catalyst and Cs (moles per
noneliminated models, the calculated values of the concen- gram of catalyst) indicates the concentration of catalytically
tration of all reactants and products were found to be positive. active sites.
Among these models, aAHPW1 was chosen as the best because According to eq 12, the values of the chemical equilibrium
of the lowest least sum of squares, F, of 0.011358. In Table 3 constant for peracetic acid formation were calculated as 2.701,
2.258, and 1.891 at 303, 323, and 348 K, respectively; i.e., values
are listed the numbers of model parameters and discrimination
of K1 decrease with an increase in temperature.
results, as well as the least sums of squares (objective func-
By fitting the experimental data with the accepted aAHPW1
tion F) calculated by eq 13, the standard deviations (SD), and
model, we determined the temperature dependencies of the
the average absolute deviations for double bond concentra- rate coefficient for acetic acid adsorption, rate coefficients for
tion (AAD[D]) and epoxy group concentration (AAD[E]) for reactions II and III, and adsorption equilibrium constants for
established models. acetic acid, hydrogen peroxide, peracetic acid, and water as
In accepted pseudo-two-phase kinetic model aAHPW1, ad- follows:
sorption of acetic acid, hydrogen peroxide, peracetic acid, and
water is assumed. The order of hydroxyl acetate formation is ⎡ 220417.3 ⎛ 1 1 ⎞⎤
Cska,A = exp⎢2.007861 − ⎜ − ⎟⎥
considered as the first with respect to acetic acid. Besides the ⎣ R ⎝T 323 ⎠⎦ (21)
associative adsorption, the reversibility of the adsorption of
reactants and desorption of products, as well as of the dual site ⎡ 3524.043 ⎛ 1 1 ⎞⎤
surface chemical reaction between acetic acid and hydrogen k 2 = exp⎢ −1.403134 − ⎜ − ⎟⎥
⎣ R ⎝T 323 ⎠⎦ (22)
peroxide, is accepted. The adsorption of acetic acid is thought
to be the rate-determining step. Thus, the chemisorption ⎡ 10566.0 ⎛ 1 1 ⎞⎤
mechanism of peracetic acid formation can be presented by the k 3 = exp⎢ −5.389409 − ⎜ − ⎟⎥
following equations: ⎣ R ⎝ T 323 ⎠⎦ (23)

ka,A ⎡ 89489.52 ⎛ 1 1 ⎞⎤
A + s XoooY A·s KA = exp⎢10.34923 − ⎜ − ⎟⎥
kd,A (15) ⎣ R ⎝ T 323 ⎠⎦ (24)

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Industrial & Engineering Chemistry Research Article

basis of double bond and epoxy group concentrations, re-

Figure 3. Time dependency of the experimentally determined (points)
and calculated (curves) iodine number (IN) and epoxy oxygen content
(EO) for castor oil epoxidation in benzene with peracetic acid formed
in situ, when the double bond in oil:acetic acid:30 wt % hydrogen
peroxide molar ratio was 1:0.5:1.5, at 323 K in the presence of 5, 10,
and 15 wt % Amberlite IR-120.
spectively, estimated with model aAHPW1, are presented as
curves in Figures 2−4. As shown, the proposed pseudo-two-
phase model fits well the corresponding experimental values
(points) measured during epoxidation of castor oil in benzene
with peracetic acid generated in situ in the presence of Amberlite
IR-120 at different reactant ratios, catalyst concentrations, and
temperatures (Table 1).
4.2. Comparison of the Proposed Pseudo-Two-Phase
Model with the Pseudohomogeneous Model Reported
in the Literature. The experimental data obtained for
epoxidations of castor oil in benzene with peracetic acid
formed in situ from acetic acid and a 30% aqueous hydrogen
peroxide solution in the presence of Amberlite IR-120, run
under defined reaction conditions (Table 1), were fit by a
pseudo-two-phase model proposed in this work and by a
pseudohomogeneous model reported in the literature.6 Like in
the accepted pseudo-two-phase aAHPW1 model, in the
pseudohomogeneous model the kinetic parameters are temper-
ature-dependent and the beginning of the addition of hydrogen
peroxide to the reaction mixture is considered as the zero
reaction time. The same expression that correlates the chemical
equilibrium constant and temperature is used. In the latter
model, the epoxy ring opening reaction with acetic acid is
considered as the second-order reaction, while in the aAHPW1
model, it is considered as the first-order reaction, in both
cases with respect to acetic acid. The least sum of squares of
0.011358 obtained for the model proposed in this work, which
is >2.5 times lower than the value of 0.031620 obtained for
the pseudohomogeneous model (Table 3), indicates that the
pseudo-two-phase model better describes the reaction system
for epoxidation of castor oil conducted under the investigated
conditions. In Figure 5 are illustrated the variations of the

Figure 4. Time dependency of the experimentally determined (points)

and calculated (curves) iodine number (IN) and epoxy oxygen content
(EO) for castor oil epoxidation with peracetic acid formed in situ,
when the double bond in oil:acetic acid:30 wt % hydrogen peroxide
molar ratio was 1:0.5:1.5, in the presence of 10 wt % Amberlite IR-120
at 303, 323, and 348 K.

⎡ 213104.1 ⎛ 1 1 ⎞⎤
KH = exp⎢0.7595751 + ⎜ − ⎟⎥
⎣ R ⎝ T 323 ⎠⎦ (25)

⎡ 132215.0 ⎛ 1 1 ⎞⎤ Figure 5. Comparison between the experimentally determined

KP = exp⎢8.022979 − ⎜ − ⎟⎥
⎣ R ⎝T 323 ⎠⎦ (26) (points) values of the iodine number (IN) and epoxy oxygen (EO)
content and the corresponding values calculated with the pseudoho-
mogeneous (···) model and the pseudo-two-phase () model
⎡ 155250.8 ⎛ 1 1 ⎞⎤
KW = exp⎢6.954228 − ⎜ − ⎟⎥ proposed in this work, for the in situ epoxidation of castor oil with
⎣ R ⎝T 323 ⎠⎦ (27) peracetic acid conducted in benzene at 323 K with a double bond in
oil:acetic acid:hydrogen peroxide ratio of 1:0.5:1.5 in the presence of
An increase in all reaction rate coefficients with an increase 15 wt % Amberlite IR-120.
in temperature proved the correctness of the determined
dependences. Obtained positive values of all calculated reactant experimentally determined values (points) as well as the values
and product concentrations additionally confirmed the viability calculated with pseudohomogeneous (dotted curve) and pseudo-
of the accepted kinetic model. The variations in iodine number two-phase (solid curve) models of the iodine number and epoxy
and epoxy oxygen content with reaction time, calculated on the oxygen content over time during the epoxidation of castor oil
9362 dx.doi.org/10.1021/ie500876a | Ind. Eng. Chem. Res. 2014, 53, 9357−9364
Industrial & Engineering Chemistry Research Article

(performed at 323 K with 0.5 mol of acetic acid and 1.5 mol
of a 30% aqueous hydrogen peroxide solution per mole of
double bond in oil in the presence of 15 wt % Amberlite
IR-120 as a catalyst) when the relative epoxy yield of 78.32%,
the highest compared to yields obtained under other examined
conditions,6 was achieved.
5. CONCLUSIONS
A pseudo-two-phase kinetic model for the epoxidation of vegetable
oil in an organic solvent with a perorganic acid generated in situ
from an organic acid and hydrogen peroxide in the presence of
an acidic ion-exchange resin, used as a catalyst, was established
assuming that only perorganic acid formation is heteroge-
neously catalyzed. To describe the kinetics of the latter reac-
tion, Langmuir−Hinshelwood−Hougen−Watson postulates
were applied. The model took into consideration the occurrence
of the reactions during incremental addition of the oxidizing
agent solution, as well as defined temperature changes over time
during the epoxidation process. The variation in temperature of
the chemical equilibrium constant for peracetic acid formation is
defined by applying the derived expression. The temperature
dependencies of the kinetic and adsorption parameters were
obtained simultaneously by fitting the experimentally determined
values of double bond and epoxy group contents. An increase in
all reaction rate coefficients with an increase in temperature and
low square deviation of the calculated and experimental values
of double bond and epoxy group concentrations indicated the
correctness of the developed kinetic model. A comparison was
made between the model proposed in this work and a pseudo-
homogeneous model reported in the literature. The application
of a more rigorous pseudo-two-phase model was recommended.
FW = molar flow of addition of water [mol min−1 (100 g of
oil)−1]
H = hydrogen peroxide
[H] = hydrogen peroxide concentration (mol/100 g of oil)
HA = hydroxy acetate
[HA] = hydroxy acetate concentration (mol/100 g of oil)
IN = iodine number (g of iodine/100 g of oil)
K1 = chemical equilibrium constant for reaction I
KC = adsorption equilibrium constant for component C
ki = rate coefficient for reaction i
ka,C = rate coefficient for adsorption of component C
kd,C = rate coefficient for desorption of component C
k1,sr = rate coefficient for surface reaction related to reaction I
ki,0 = constant of the reparameterized Arrhenius equation
related to the frequency coefficient
ki,Ea = constant of the reparameterized Arrhenius equation
related to activation energy
LHHW = Langmuir−Hinshelwood−Hougen−Watson
MC = molecular mass of component C
m = mass of the catalyst (g)
mHS = mass of the hydrogen peroxide aqueous solution (g)
NR = number of runs
NSk = number of samples in run k
P = peracetic acid
[P] = peracetic acid concentration (mol/100 g of oil)
R = universal gas constant (J mol−1 K−1)
SD = standard deviation
s = active site of the catalyst
T = temperature (K)
Ta = average temperature of runs (K)
THS = temperature of hydrogen peroxide addition (K)

■
Tr = temperature of the reaction (K)
t = reaction time (min)
AUTHOR INFORMATION tHS = period of addition of the hydrogen peroxide aqueous
Corresponding Author solution (min)
*E-mail: ssfiser@uns.ac.rs. Telephone: +381 (021) 485 3748. tTI = period of temperature increase (min)
Fax: +381 (021) 450 413. W = water
Notes [W] = water concentration (mol/100 g of oil)
The authors declare no competing financial interest. wH = mass fraction of hydrogen peroxide in its aqueous

■
solution
ACKNOWLEDGMENTS Subscript
This work is part of Project III45022 financially supported by A = acetic acid
the Ministry of Education, Science and Technological Develop- a = adsorption
ment of the Republic of Serbia. C = component

■
d = desorption
NOMENCLATURE H = hydrogen peroxide
P = peracetic acid
A = acetic acid sr = surface reaction
[A] = acetic acid concentration (mol/100 g of oil) W = water
AI = atomic mass of iodine
Superscript
AO = atomic mass of oxygen
AAD = average absolute deviation calc = calculated value
Cs = concentration of catalytically active sites (mol/g of exp = experimentally determined value
catalyst) n = order of reaction
D = double bond
[D] = double bond concentration (mol/100 g of oil)
E = epoxy group, i.e., ring
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