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Ind. Eng. Chem. Res.

2006, 45, 4589-4596 4589

Limonene Epoxidation: Diffusion and Reaction over PW-Amberlite in a


Triphasic System

R. Barrera Zapata, A. L. Villa,* and C. Montes de Correa

Departamento de Ingenierı́a Quı́mica, UniVersidad de Antioquia, Calle 67 N° 53-108, Medellı́n, Colombia

The effect of several reaction parameters on limonene epoxidation and hydrogen peroxide decomposition
over PW-Amberlite was studied. Parameters evaluated were as follows: amount of catalyst (8-28 g/L),
average particle diameter (110-720 µm), and concentrations of acetonitrile (7.4-15.7 mol/L), limonene
(0.27-1.04 mol/L), hydrogen peroxide (0.73-1.92 mol/L), water (5.84-7.39 mol/L), and limonene epoxide
(0-0.17 mol/L). The initial limonene reaction rate exhibits a maximum at 71 wt % acetonitrile (18 wt %
hydrogen peroxide), 6.5 times higher than that obtained under biphasic conditions. According to Weisz-
Prater criterion, mass transfer limitations were insignificant for catalyst particle sizes smaller than 425 µm.
External mass transfer limitations were avoided by using a stirring speed of 1000 rpm. The apparent acti-
vation energy of limonene epoxidation was 25 kJ/mol, three times lower than that previously found in a
biphasic system. Empirical reaction rates of limonene epoxidation and hydrogen peroxide decomposition are
proposed.

1. Introduction 2. Experimental Section

Limonene is an abundant monoterpene extracted from citrus 2.1. Materials. All commercial products were used without
oil, which is usually epoxidized for obtaining fragrances, further purification. Products used include aqueous hydrogen
perfumes, and food additives.1 High limonene conversion peroxide (30 wt %, J. T. Baker), (R)-(+) limonene (97 wt %,
(>80%) and limonene epoxide selectivity (>90%) have been Sigma-Aldrich), acetonitrile (99.5 wt %, Merck), Amberlite
obtained over PW-Amberlite using aqueous H2O2 as the IRA-900 ionic form chloride (Sigma), tetrabutylammonium
oxidizing agent and acetonitrile as the solvent.2 A kinetic study hydrogen sulfate (97 wt %, Aldrich), tungstic acid (99 wt %,
of limonene epoxidation over PW-Amberlite using a homoge- Aldrich), phosphoric acid (85 wt %, Merck), sodium nitrate (95
neous liquid phase, i.e., biphasic system, was previously wt %, Merck), and acetone (99.8 wt %, Merck).
reported.3 Upon addition of 81 wt % acetonitrile, reaction rate 2.2. Catalyst Preparation. PW-Amberlite catalyst was
is first order with respect to limonene, oxidant, and catalyst synthesized as reported elsewhere.7 First, the complex PW4O24-
concentration. Notwithstanding, because of environmental and [(C4H9)4N]3 was prepared and heterogenized on previously
economic reasons, it is desirable to minimize the amount of crushed and sieved NO3-Amberlite IRA-900, taking care of
solvent so a triphasic reaction system consisting of two liquid preserving complex peroxo groups. Following this procedure,
phases and a solid catalyst may be obtained. Overall reaction 0.55 mmol of PW4 (active complex, S) per gram of dry material
over PW-Amberlite should be different in a triphasic system were heterogenized.3,7
compared to that observed in a biphasic one. Catalytic activity 2.3. PW-Amberlite Swelling Experiments. Ion-exchange
differences in biphasic and triphasic systems have been reported. resins are functionalized cross-linked polymers. They are glassy
Bhaumik and Kumar4 found higher benzyl alcohol oxidation in their dry form and become rubberlike in contact with polar
with H2O2 over TS-1 under triphasic (89.6%) compared to solvents; the swelling degree depends on the interaction between
biphasic conditions (12.5%). Product selectivities were also solvent and resin.8 The relationship between swelling and
dependent on the number of phases. In another report, it was reaction mixture composition was determined as follows: 0.1
found that reaction rate for benzene hydroxylation with H2O2 g of dry catalyst was placed into a glass cylinder (70 × 7.0
over TS-15 increases between 15 and 25 times when a biphasic mm) and, after compacting by centrifugation, solid height was
system is used in comparison to a triphasic system. However, measured (ho); then, the homogeneous liquid phase (see Table
in certain organic substrate oxidations over TS-1,6 reaction rate 1) was added and the final solid height (hf) was measured after
increased 3-10 times when a triphasic system was used instead ∼8 days when no changes were observed. The percentage of
of a biphasic one. Here, we report the influence of several swelling, % H, was estimated according to eq 1.
reaction parameters for limonene epoxidation with aqueous H2O2
over PW-Amberlite in a triphasic system. Parameters studied hf
%H ) × 100% (1)
were as follows: temperature, limonene and hydrogen peroxide ho
concentrations, solvent, catalyst amount, catalyst recycling, and
the presence of water and limonene epoxide. Internal mass 2.4. Catalyst Density. The density of catalyst samples having
transfer limitations were tested following the Weisz-Prater different particle sizes was determined by placing a known
criterion. amount of sample in a 5 mL graduated cylinder filled with water.
Once catalyst was fully swollen (∼8 days), the displaced volume
* Corresponding author. Tel.: +574 2106606. Fax: +574 2106609. of water was measured. This value was taken as a rough estimate
E-mail: alvilla@udea.edu.co. of the catalyst volume.
10.1021/ie060098b CCC: $33.50 © 2006 American Chemical Society
Published on Web 05/28/2006
4590 Ind. Eng. Chem. Res., Vol. 45, No. 13, 2006

Table 1. Swelling of PW-Amberlite


limonene
water mass limonene acetonitrile epoxide
fraction mass fraction mass fraction mass fraction swelling
(wt/wt), W (wt/wt), L (wt/wt), A (wt/wt), E (% H)
0.042 0.089 0.868 0 16.7
0.223 0.375 0.057 0.345 30.1
1 0 0 0 45.5
0 1 0 0 9.1
0 0 1 0 6.8
0 0 0 1 1.5
0 0.126 0.874 0 18.3
0.076 0.321 0.176 0.426 33.9
0.105 0.036 0.860 0 22.0
0.146 0 0.853 0 14.8 Figure 1. Effect of stirring speed on initial limonene epoxidation rate over
PW-Amberlite: [C10H16]0 ) 0.66 mol/L, [H2O2]0 ) 1.33 mol/L, [H2O] )
5.84 mol/L, [cat] ) 18 g/L, catalyst particle size ) 250-425 µm, [CH3CN]
2.5. Catalytic Experiments. Typically, required amounts of ) 14.05 mol/L, 306 K.
limonene, acetonitrile, and hydrogen peroxide were mixed at
room temperature and added to 8 mL magnetically stirred glass Table 2. Effect of Catalyst Particle Size on the Initial Reaction
flasks immersed in a thermally controlled oil bath at the desired Rates of Limonene Epoxidation over PW-Amberlite
temperature; then, catalyst was added to start the reaction. initial reaction rate of
Temperature was maintained within (0.5 K using an IKA ETS- limonene epoxidation,
D4 fuzzy controller. Flasks were sampled at different times, mmol/(h g) dry cata
between 0 and 120 min. Catalytic tests were carried out using particle size average diameter, aqueous organic
catalyst samples of average particle diameter between 110 and fraction range (µm) 2rdry catalyst (µm) phase phase bulk
720 µm and concentrations varying between 8 and 28 g/L; I 600-830 715 3.77 3.8 7.57
acetonitrile (7.4-15.7 mol/L), limonene (0.27-1.04 mol/L), II 425-600 512 3.78 3.54 7.32
III 250-425 337 4.13 3.77 7.9
hydrogen peroxide (0.73-1.92 mol/L), water (5.84-7.39 mol/ IV 180-250 215 4.15 3.78 7.93
L), and limonene epoxide (0-0.17 mol/L) were used. An V 125-180 152 4.11 3.80 7.91
electronic balance accurate to (0.1 mg was employed for VI 90-125 107 3.98 3.85 7.83
weighing. After reaction, samples from each liquid phase a Reaction conditions: [C H ] ) 0.66 mol/L, [H O ] ) 1.33 mol/L,
10 16 0 2 2 0
(aqueous and organic) were carefully taken by means of syringes [H2O] ) 5.84 mol/L, [cat] ) 18 g/L, [CH3CN] ) 14.05 mol/L, 306 K.
and analyzed by gas chromatography.
2.6. Catalyst Recycling. Catalyst was recovered by filtration, disappearance reaction rate of H2O2, -rPb, can be expressed by
washed with acetone, and dried at room temperature before eq 4.
being recycled.
2.7. Analyses. Liquid samples were analyzed using a gas -rPb ) -rP2 + (-rP3) (4)
chromatograph (Varian Star, 3400) equipped with a flame
On the other hand, assuming that only limonene epoxide is
ionization detector (FID). A 50 m DB-1 capillary column was
obtained, H2O2 consumed by limonene oxidation (-rP2) is
used to separate limonene and its epoxide; column temperature
estimated from eq 5 and H2O2 decomposition rate (-rP3) is
was increased from 120 to 160 °C at a heating rate of 10 °C/
estimated from eq 4.
min; injector temperature was 200 °C; and nitrogen (7.7 cm3/
min) was used as carrier gas. Each sample (1.0 µL) was analyzed -rP2 ) -rLa + (-rLo) (5)
three times. A confidence interval of 95% and a normal
distribution of data were assumed. Uncertainties were estimated 3. Results and Discussion
by calculating standard deviation, using a factor of 1.960,
recommended by the NIST (National Institute of Standard and 3.1. Mass Transfer Resistances. First, internal and external
Technology)9,10 for a confidence interval of 95%. Estimated diffusion limitations on initial reaction rate were investigated.
uncertainties in initial reaction rate of limonene disappearance Stirring speed was varied (see Figure 1) for determining external
(mol/(h g)) were (1.5 × 10-4 and (4.32 × 10-4 for organic mass transfer resistances. Above 800 rpm, no effects on
and aqueous phase, respectively. H2O2 concentration at different limonene epoxidation with aqueous H2O2 over PW-Amberlite
times was determined by cerimetric titration using a 0.1 N under triphasic conditions were observed. Thus, stirring speed
CeSO4 aqueous solution. Limonene epoxide was the only was set at 1000 rpm for all further experiments in order to avoid
product detected; therefore, we assumed that H2O2 was con- external mass transfer resistances. The effect of internal diffusion
sumed in two reactions (see eqs 2 and 3). The uncertainty in on initial reaction rates was determined by measuring reaction
the determination of H2O2 decomposition (mol/(h g)) rate was rates for different average catalyst particle sizes (see Table 2).
estimated as (2.65 × 10-4. It was observed that initial reaction rates did not vary when
catalyst particle sizes were smaller than 425 µm.
H2O2 + C10H16 f C10H16O + H2O (2) 3.1.1. Weisz-Prater Criterion. The Weisz-Prater criterion
was used to estimate intraparticle mass-transfer limitations. The
1 “true” particle radius (R) was determined from swelling experi-
H2O2 f H2O + O2(g) (3) ments (see Table 1). An empirical correlation, between swelling
2
(percent) and mixture composition was obtained by multiple
If -rLa and -rLo represent initial limonene reaction rates for linear regression using Polymath 5.1 (see eq 6). The correlation
limonene epoxidation in the aqueous and the organic phase, coefficient (0.92) was greater than that reported by Pääkkönen
respectively, and -rP2 and -rP3 represent H2O2 disappearance and Krause11 (0.42) for isoamylene etherification over a cation-
reaction rates for reactions 2 and 3, respectively, the total exchange resin. As is observed in Table 1, limonene epoxide
Ind. Eng. Chem. Res., Vol. 45, No. 13, 2006 4591

[ ( )]
Table 3. Estimated Densities of Swollen PW-Amberlite (g/mL) ( (8.2 × 10-8)T 3V2 2/3
0.08 for Different Particle Sizes D°1-2(cm2/s) ) 1+ (10)
µ2V11/3 V1
particle size range (µm) density
600-830 2.23
425-600 2.30
where µ is the viscosity (cP) and T is the temperature (K).
250-425 2.25 Viscosity at the reaction temperature, 306 K, was estimated
180-250 2.35 by the Reid equation12 (eq 11).
125-180 2.20
90-125 2.20 T - Tref
µ-0.2661 ) µref-0.2661 + (11)
Table 4. Molar Volumes and Viscosities of Limonene, Water, and 233
Acetonitrile at 293 K
where µref is the known viscosity at Tref.
molar volume
component (cm3/mol) ref viscosity (cP) ref
To avoid nonideality implicit in estimations of diffusion
coefficients at infinite dilution,17-19 the Vignes equation20 (eq
limonene 192.2 12 1.08 13
12) was used to correct liquid-phase activities.
water 18.11 12 1.0 14

[( ) ]( )
acetonitrile 57.4 12 0.35 15
D°2-1 x1
d ln a
D1-2 ) D° (12)
does not appreciably contribute to resin swelling; so, it was not D°1-2 d ln X 1-2
considered in this correlation.
where a and X denote liquid-phase activity and molar fraction
%H ) 44.7W + 9.2L + 14.9A (6) of solute in reaction mixture, respectively. Liquid-phase activi-
ties were calculated using the UNIQUAC model.21 The equation
where W, L, and A denote mass fraction of water, limonene, of Kooijman and Taylor19 (eq 13) was further used for
and acetonitrile, respectively. estimating diffusion coefficients of a multicomponent mixture:
In the isoamylene etherification study,11 the true particle
radius R was calculated by eq 7. Dij ) (D°ij)Xj(D°ji)Xi ∏
k)1
(D°ikD°jk)X /2
k
(13)
k*i,j

x
3
swelling (%)
R) × where i, j, and k are mixture components limonene (L), water
swelling in pure methanol ()113%) (W), and acetonitrile (A), respectively. For example, the
mean radius of the fractions (7) calculated limonene bulk diffusion coefficient in water and
acetonitrile (DL-W,A) was 5.06 × 10-6 cm2/s. Pore volume (Vp
where swelling (%) was calculated with an empirical correlation ) 0.42 cm3/g) obtained from N2 adsorption was used for the
similar to eq 6 and swelling in pure methanol (113%) corre- porosity calculation, and a value of 0.48 was obtained by eq
sponds to the maximum swelling that was obtained with a pure 14.22
compound in the swelling experiments.11 Notwithstanding, we
found that, depending on the composition of the reaction mVp
)
( )
mixture, eq 7 may give a value of the swollen resin radius (14)
m
smaller than that of the dry resin, which has no physical mVp +
Fpart
meaning. Thus, R was calculated from eq 8, which gives a good
representation of resin swelling phenomena. where Fpart is particle density in g/cm3 and m is amount of
catalyst used during N2 adsorption (0.0411 g). A tortuosity
%H
(
R ) rdry catalyst 1 + )
100
(8) factor, τ, of 2.17 was estimated using a model proposed by Dogu
and Dogu23,24 (eq 15) recommended for solid porosities, ,
higher than 0.476.
where rdry catalyst was obtained from Table 2.
The highest PW-Amberlite swelling was 45.5% (see Table 
τ) (15)
1). From Table 3, a catalyst density, Fpart, of 2.23 g/cm3 was 3 2/3
used as a representative value. [
1 - π (1 - )
4π ]
The effective diffusion coefficient of limonene-water and
acetonitrile-water, required to estimate Weisz-Prater criterion, The effective diffusion coefficient was determined by eq 16,
was determined using the Othmer-Thakar equation16 (eq 9) obtaining a value of 1.24 × 10-6 cm2/s.
recommended for diluted aqueous solutions.12

DeL ) DL-W,A (16)
τ
D°1-2 (cm2/s) ) (14 × 10-5)µw -1.1V1-0.6 (9)
The Weisz-Prater criterion (Φ), eq 17, establishes that, if Φ
where D°1-2 (cm2/s) is the diffusivity coefficient at infinite , 1, there are not diffusional problems.11,18,25
dilution of solute (1) in water (2), µw is the water viscosity (cP),
and V is the molar volume (cm3/mol). Table 4 lists molar -robsFpartR2
Φ) (17)
volumes and viscosities of reaction mixture components at 293 DeiCi
K.
The Scheibel equation17 (eq 10) recommended for solutions where -robs is the bulk observed reaction rate in mol/(g s), R is
of nonaqueous solvents11,12 was used to estimate the binary in cm, Fpart is in g/cm3, Dei is the effective diffusivity of
diffusivities of water-limonene and water-acetonitrile, as well component i in the reaction mixture (cm2/s), and Ci is the
as those of acetonitrile-limonene and limonene-acetonitrile. concentration of component i in mol/cm3.
4592 Ind. Eng. Chem. Res., Vol. 45, No. 13, 2006

Figure 2. Estimated Weisz-Prater criterion: [C10H16]0 ) 0.66 mol/L,


[H2O2]0 ) 1.33 mol/L, [H2O] ) 5.84 mol/L, [cat] ) 18 g/L, [CH3CN] )
14.05 mol/L, 306 K.

Table 5. Estimated Weisz-Prater Criterion and Effectiveness


Factors at 306 Ka
particle size [CH3CN] swelling R rate
range (µm) (mol/L) (%) (cm) (mmol/(g h)) Weisz η
600-830 14.7 19.0 0.043 3.10 1.73 0.53
425-600 14.4 19.7 0.031 7.34 1.63 0.93
250-425 14.3 19.5 0.020 7.20 0.72 1.00
180-250 14.4 19.7 0.013 7.93 0.31 1.00
125-180 14.4 19.7 0.009 7.91 0.16 1.00
90-125 14.4 19.7 0.006 7.83 0.08 0.99
a Reaction conditions: [C H ] ) 0.66 mol/L, [H O ] ) 1.33 mol/L, Figure 3. Effect of reaction temperature on (a) the initial reaction rate of
10 16 0 2 2 0
limonene epoxidation over PW-Amberlite and (b) H2O2 decomposition
[H2O] ) 5.84 mol/L, [cat] ) 18 g/L.
rate: [C10H16]0 ) 0.66 mol/L, [H2O2]0 ) 1.33 mol/L, [H2O] ) 5.84 mol/
L, [cat] ) 18 g/L, catalyst particle size ) 250-425 µm, [CH3CN] ) 14.05
Figure 2 shows the Weisz-Prater criterion profile vs catalyst mol/L.
particle sizes. It is observed that, for particles with average
diameters smaller than 425 µm, the Weisz-Prater criterion is in the absence of limonene, we assume that both limonene and
<1, so particle sizes from fraction III (see Table 2) were used hydrogen peroxide species are adsorbed on the catalytic surface
in further reactions. and compete for PW-Amberlyte active sites.
3.1.2. Calculation of the Effectiveness Factor. Effectiveness 3.2.1. Effect of Reaction Temperature. The initial reaction
factors, η, were estimated by eq 18, and results are shown in rate of limonene epoxidation increased with temperature (Figure
Table 5. 3a); however, the higher the temperature, the higher is the rate
of hydrogen peroxide decomposition (Figure 3b). According to
-robs Figure 3b, at temperatures < 306 K, the hydrogen peroxide
η) (18)
-rCs decomposition rate is approximately constant.
3.2.2. Effect of Acetonitrile Concentration. Acetonitrile
-rCs is the reaction rate that would result if the entire surface concentration was varied between 7.4 and 15.7 mol/L (Figure
were exposed to the external surface concentration Cs, i.e., the 4). Just one liquid phase was obtained for acetonitrile concentra-
intrinsic reaction rate. In our system, it corresponds to the tions higher than 15.62 mol/L. Parts a and b of Figure 4 show
reaction rates using catalyst particle sizes in the range 250- a maximum at 14.1 mol/L of acetonitrile (71 wt % CH3CN, 18
425 µm. wt % H2O2), independent of catalyst particle size (Figure 4a).
The effectiveness factor varies between 0.53 and 1 (Table As reported by Fu and Kaliaguine,26 the volume of the aqueous
5). It decreases by increasing particle size under identical phase increased by increasing the amount of solvent, while the
temperature and reactant concentrations. However, for catalyst volume of the organic phase decreased. Gallot et al.27 suggested
particle sizes smaller than 425 µm, it is constant, at a value of that the presence of a maximum is due to the solubility increase
1, suggesting that, under those conditions, no diffusional of organic compounds in the aqueous phase, where reaction is
problems are present. supposed to occur. As a consequence, H2O2 concentration in
3.2. Catalytic Experiments. The effect of temperature and the aqueous phase decreases. The same trend was observed for
concentration of reaction mixture was investigated on the initial the liquid-liquid equilibrium (LLE) of the limonene + water
reaction rate of limonene epoxidation and hydrogen peroxide + acetonitrile system.21 The maximum initial reaction rate of
decomposition over PW-Amberlite when three phases (S-L- limonene epoxidation under thriphasic conditions is ∼6.5 times
L) were present. Under our reaction conditions, there was no higher that the value obtained under biphasic conditions. Kumar
significant hydrogen peroxide decomposition due to thermal and Bhaumik6 reported similar results for hydroxylation of some
effects. At 306 K and in the absence of catalyst, no significant aromatic compounds over TS-1 and H2O2. Figure 4c shows that
H2O2 decomposition was detected by cerimetric titration at short the amount of solvent does not seem to affect hydrogen peroxide
reaction times (i.e., <2 h). However, H2O2 decomposition rate decomposition rate; so, acetonitrile might not significantly
increased in the presence of catalyst, and it was higher when adsorb on the catalyst surface.
no limonene was added to reaction mixture. H2O2 decomposition 3.2.3. Effect of Limonene Concentration. Initial reaction
rate was 2.05 mmol/(g h) in the presence of limonene and 4.68 rates of limonene epoxidation and H2O2 decomposition were
mmol/(g h) when no limonene was added. Thus, taking into determined at different limonene concentrations (0.27 and 1.04
account that decomposition rate of hydrogen peroxide increases mol/L), and they are shown in parts a and b of Figure 5,
Ind. Eng. Chem. Res., Vol. 45, No. 13, 2006 4593

Figure 5. Effect of limonene concentration on (a) the initial limonene


epoxidation rate over PW-Amberlite and (b) H2O2 decomposition rate:
[C10H16]0 ) 0.27-1.04 mol/L, [H2O2]0 ) 1.33 mol/L, [H2O] ) 5.84 mol/
L, [cat] ) 18 g/L, catalyst particle size in the 250-425 µm range, [CH3CN]
) 14.05 mol/L, 306 K.

Figure 4. Effect of solvent concentration and catalyst particle size on the


initial reaction rate of limonene epoxidation over PW-Amberlite: (a) bulk
reaction mixture, (b) catalyst particle size ) 250-425 µm, and (c) H2O2
decomposition. Reaction conditions: limonene 0.5 g, aqueous hydrogen
peroxide 0.83 g, catalyst 0.1 g, [CH3CN] ) 7.4-15.7 mol/L, 306 K.

respectively. It is observed that the initial reaction rate of


limonene epoxidation increased as limonene concentration
increased, but H2O2 decomposition rate decreased. These results
support the idea that both limonene and hydrogen peroxide are
adsorbed on the catalyst surface. Since the initial reaction rate
of limonene epoxidation is higher than that of hydrogen peroxide
decomposition, it is likely that hydrogen peroxide is preferably
consumed in limonene epoxidation (eq 2) rather than in H2O2
decomposition (eq 3).
3.2.4. Effect of Hydrogen Peroxide Concentration. H2O2
concentration was varied between 0.73 and 1.92 mol/L, while
catalyst and limonene concentrations were kept constant (Figure
Figure 6. Effect of hydrogen peroxide concentration on (a) the initial
6). When hydrogen peroxide concentration increased, the initial
limonene epoxidation rate over PW-Amberlite and (b) H2O2 decomposition
reaction rate of limonene epoxidation decreased (Figure 6a); rate: [C10H16]0 ) 0.66 mol/L, [H2O2]0 ) 0.73-1.92 mol/L, [H2O] ) 5.84
this may be explained from the LLE of the water + limonene mol/L, [cat] ) 18 g/L with a catalyst particle size in the 250-425 µm
+ acetonitrile system,21 which shows limonene dilution in the range, [CH3CN] ) 14.05 mol/L, 306 K.
aqueous phase with the addition of hydrogen peroxide. In the
biphasic3 system, the reaction rate increases with hydrogen show that the initial reaction rate of limonene epoxidation and
peroxide concentration. Figure 6b shows that hydrogen peroxide hydrogen peroxide decomposition rate increased with catalyst
decomposition rate increases by increasing its concentration. concentration since the available catalytic sites for reaction are
This behavior may be explained by dilution of limonene, which increased.
competes with hydrogen peroxide for catalyst active sites. 3.2.6. Effect of Water and Limonene Epoxide Concentra-
3.2.5. Catalyst Amount. The initial concentration of catalyst tion. Under biphasic conditions, PW-Amberlite catalyst was
was varied between 8 and 28 g/L. Parts a and b of Figure 7 poisoned by limonene epoxide and the presence of water did
4594 Ind. Eng. Chem. Res., Vol. 45, No. 13, 2006

Table 7. Effect of Limonene Epoxide Concentration on the Initial


Limonene Epoxidation Ratea
initial limonene
epoxidation rate (mmol/(g h)) initial H2O2
[C10H16O]0 aqueous organic bulk reaction decomposition
(mol/L) phase phase mixture rate (mmol/(g h))
0.0 4.40 3.62 8.02 1.47
0.06 2.83 2.00 4.83 0.56
0.12 1.74 1.10 2.84 0.29
0.17 0.67 0.43 1.10 0.09
a Reaction conditions: [C H ] ) 0.66 mol/L, [H O ] ) 1.33 mol/L,
10 16 0 2 2 0
[H2O] ) 5.84 mol/L, [cat] ) 18 g/L, [C10H16O]0 ) 0-0.17 mol/L, catalyst
particle size ) 250-425 µm, [CH3CN] ) 14.05 mol/L, 306 K.

Figure 7. Effect of catalyst concentration on (a) the initial limonene Figure 8. Initial limonene reaction rate for limonene epoxidation under
epoxidation rate over PW-Amberlite and (b) H2O2 decomposition rate: triphasic conditions: [C10H16]0 ) 0.66 mol/L, [H2O2]0 ) 1.33 mol/L, [H2O]
[C10H16]0 ) 0.66 mol/L, [H2O2]0 ) 1.33 mol/L, [H2O] ) 5.84 mol/L, [cat] ) 5.84 mol/L, [cat] ) 18 g/L, catalyst particle size ) 250-425 µm,
) 8-28 g/L, catalyst particle size ) 250-425 µm, [CH3CN] ) 14.05 mol/ [CH3CN] ) 14.05 mol/L, 306 K.
L, 306 K.

Table 6. Effect of Water Concentration on the Initial Limonene


3.2.7. Catalyst Recycling. PW-Amberlite was recycled up
Epoxidation Ratea to three times under the same reaction conditions. Catalytic
activity was recovered after washing the catalyst with acetone;
initial limonene
epoxidation rate (mmol/(g h)) no significant changes on the initial limonene reaction rates were
initial H2O2
[H2O]0 aqueous organic bulk reaction decomposition
observed (Figure 8). The initial reaction rate for limonene
(mol/L) phase phase mixture rate (mmol/(g h)) epoxidation over fresh catalyst was 8 × 10-3 mol/(h g), and
after three reactions, it decreased to 7 × 10-3 mol/(h g).
5.84 4.44 3.62 8.06 1.47
6.39 3.12 2.10 5.22 3.78 3.2.8. Empirical Reaction Rates. Empirical reaction rate
6.92 2.80 1.70 4.50 3.98 expressions for limonene epoxidation and hydrogen peroxide
7.39 1.50 0.78 2.28 5.63 decomposition are estimated in terms of concentrations. To
a Reaction conditions: [C H ] ) 0.66 mol/L, [H O ] ) 1.33 mol/L,
10 16 0 2 2 0
account for the nonideal character of liquid mixtures, it was
[H2O] ) 5.84-7.39 mol/L, [cat] ) 18 g/L, catalyst particle size ) 250- also estimated in terms of activities. Parameters were estimated
425 µm, [CH3CN] ) 14.05 mol/L, 306 K. from experimental data (Figures 3-6) using the optimization
toolbox slqnonlin from Matlab 6. Empirical kinetic parameters
not affect the reaction rate.3 Because 30 wt % aqueous hydrogen for limonene epoxidation and hydrogen peroxide decomposition
peroxide was used, water was always present in our reaction are listed in Table 8.
system at an initial concentration of 5.84 mol/L. To determine Equations 19 and 20 are expressed in terms of concentration,
the effect of water on the catalytic activity, water concentration for limonene epoxidation and hydrogen peroxide decomposition,
was increased to 7.39 mol/L, while limonene and hydrogen respectively.
peroxide concentration, catalyst amount, and catalyst particle
size were kept constant. The effect of limonene epoxide was -rL ) k[C10H16]R[H2O2]β (19)
determined by varying its concentration from 0 to 0.67 mol/L.
All other reaction conditions were kept constant. As can be
observed in Tables 6 and 7, initial limonene epoxidation rate -rdecomp H2O2 ) k[H2O2]β (20)
decreased when water and limonene epoxide concentration
increased. Initial H2O2 decomposition rate increased with water where [C10H16] and [H2O2] are limonene and hydrogen peroxide
concentration and decreased with limonene epoxide concentra- concentrations (mol/L), respectively.
tion. Thus, limonene epoxide appears to poison the catalyst, as The liquid-phase activity of each species was calculated using
was observed in the biphasic system.3 Therefore, as limonene eq 21.28
epoxide concentration increases, initial limonene epoxidation
and hydrogen peroxide decomposition rates decrease. On the ai ) χiγi (21)
other hand, it appears that water does not adsorb on the catalyst
surface but dilutes limonene in the aqueous phase, decreasing where ai is the activity, xi denotes the mole fraction, and
limonene epoxidation rate and increasing hydrogen peroxide γi is the activity coefficient of component i in the reaction
decomposition rate. mixture.
Ind. Eng. Chem. Res., Vol. 45, No. 13, 2006 4595

Table 8. Estimated Parameter Values for Kinetic Expressions of Initial Limonene Epoxidation and Hydrogen Peroxide Decomposition Ratesa
parameter with 95% confidence interval
equation SSR × 105 SE × 103 k R β
19 3.7 1.4 0.021 ( 0.007 1.934 ( 0.006 -1.410 ( 0.005
20 3.1 1.1 (3.274 ( 0.006) × 10-3 1.669 ( 0.006
22 6.2 1.2 (9.479 ( 0.001) × 10-7 2.869 ( 0.017 -2.407 ( 0.043
23 3.3 1.3 1.287 ( 0.008 2.447 ( 0.021
a SSR ) square sum of residuals; SE ) standard error.

Equations 22 and 23 give reaction rate, in terms of activities limitations were confirmed by the Weisz-Prater criterion. A
for limonene epoxidation and hydrogen peroxide decomposition, maximum initial reaction rate was found at 71 wt % acetonitrile
respectively. concentration and 18 wt % hydrogen peroxide. The maximum
reaction rate was ∼6.5 times higher in a triphasic system, and
-rL ) k(aC10H16)R(aH2O2)β (22) the apparent activation energy was three times lower than for
the biphasic system. Empirical kinetic pseudohomogeneous
expressions were obtained for limonene epoxidation and hy-
-rdecomp H2O2 ) k(aH2O2)β (23) drogen peroxide decomposition based on concentrations and
activities. PW-Amberlite was recycled three times, and no
where aC10H16 and aH2O2 are the activities of limonene and significant decrease on catalytic activity was detected.
hydrogen peroxide, respectively. The activity coefficients were
calculated for different reaction mixture compositions using Acknowledgment
UNIQUAC binary parameters reported for the ternary system
water + acetonitrile + limonene.21 Because of similar physical This work was sponsored by Colciencias/UdeA through
chemical properties of water and hydrogen peroxide, hydrogen CENIVAM RC No. 432 and Colciencias/SENA/UdeA, Project
peroxide activities were calculated using binary interaction 1115-05-12426.
parameters of water. This assumption was validated with the
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