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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.
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 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 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 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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