10840 Ind. Eng. Chem. Res.

2009, 48, 10840–10844

Kinetics of the Hydration of Ethylene Oxide in the Presence of Heterogeneous

Catalyst
Mehmet Riza Altiokka* and Sema Akyalçin
Department of Chemical Engineering, Anadolu UniVersity, 26555 Eskisehir, Turkey

Kinetic data on the hydration of ethylene oxide was obtained from both uncatalyzed and heterogeneously
catalyzed reactions using a pressurized batch reactor. Amberjet 4200/HCO3- was used as the heterogeneous
catalyst, which was found to be the most effective among the four types of cross-linked styrene-divinylbenzene
anion-exchange resins tested. The reactions were proved to follow a series-parallel irreversible homogeneous
mechanism under both catalyzed and uncatalyzed conditions. Thus the corresponding rate expression can be
given as -rEtO ) k1CWCEtO + k2CMEGCEtO + k3CDEGCEtO. The rate constants were determined by applying the
method of averages at different temperatures. The temperature dependency of the rate constants was found
to be k1/[L/(mol · min)] ) exp(13.62 - 8220/T), k2/[L/(mol · min)] ) exp(15.57 - 8700/T), and k3/[L/(mol · min)]
) exp(16.06 - 8900/T) for the uncatalyzed reactions and k1/[L/(mol · min)] ) exp(19.60 - 9580/T), k2/[L/
(mol · min)] ) exp(20.19 - 10171/T), and k3/[L/(mol · min)] ) exp(19.06 - 9743/T) in the presence of catalyst
of 0.15 mol of HCO3-/L in equivalent, where T is the absolute temperature in kelvin.

Introduction types of ion-exchange resins were used as heterogeneous carriers

Monoethylene glycol (MEG) is an important raw material
for industrial applications. MEG is used in the manufacture of
polyester resins, antifreezes, and solvents, etc. MEG is com-
monly produced by the hydration of ethylene oxide (EtO).
During the reaction, diethylene glycol (DEG) and triethylene
glycol (TEG) are also produced as byproduct. Both DEG and
TEG are also used for the manufacture of many chemicals,
especially in the production of various of polymers.1,2
EtO can be hydrolyzed either noncatalytically or catalytically.
Noncatalytic hydration of EtO for the production of MEG is a
well-known process in which a large amount of water is
required. This increases the purification cost of products.
Furthermore, the reaction has to be carried out at high
temperature to increase the reaction rate appreciably, which
causes high energy consumption. Contrarily, the hydration of
EtO can also be performed catalytically without using a large
amount of water and high temperature. Additionally, MEG
selectivity can be increased by using the proper catalyst.
Both homogeneous and heterogeneous catalysts can be used
for catalytic EtO hydration. While sulfuric acid,3 salts of some
acids,4-6 and cyclic amines7 are used as homogeneous catalysts,
a strongly acid ion-exchange resin,3,8,9 a strongly basic ion-
exchange resin,10-12 and niobium oxide supported on R-alu-
mina13 can serve as heterogeneous catalysts. The use of
heterogeneous catalyst has the inherent advantages over catalysis
affected by dissolved electrolytes since they eliminate the
corrosive environment and can be easily removed from the
reaction mixture by decantation and filtration. It is also claimed
that heterogeneous catalyst suppresses side reactions, leading
to higher purity of product.14
The hydration of EtO was studied in the presence of
heterogeneous catalysis by many researchers. Othmer and
Thakar developed a continuous process for making glycol from
EtO using Amberlite IR-120 as an acid ion-exchange resin in a
fluidized solid-liquid bed. They reported that the maximum
MEG yield was found to be 95.4% at 70 °C, 24.4/1 water (W)/
EtO molar ratio, and 95% conversion of EtO.3 The same reaction
has also been studied by Reman and Van Kruchten using
immobilized anions of salts on heterogeneous carriers. Various
10.1021/ie901037w CCC: $40.75  2009 American Chemical Society
Published on Web 10/23/2009
in their studies. They tested immobilized anions of salts, such
as bicarbonate, bisulfate, and formate, on Lewatit M 500 WS,
Amberlite 400, and Duolite A 368. They found that the highest
MEG selectivity was obtained in the presence of Lewatit M
500 WS/HCO3-.10 The kinetics of selective hydration of
ethylene and propylene oxides in concentrated aqueous solutions
was also studied using sodium bicarbonate as a homogeneous
catalyst. It was shown that the kinetic data, obtained from the
isothermal batch autoclave, fit the first-order rate expression. It
was also reported that 97.9% MEG yield was obtained at 94
°C when the W/EtO molar ratio was 25.6/1.6 Shvets et al.
studied the EtO hydration process in a catalytic fixed-bed tube
reactor using a cross-linked styrene-divinylbenzene (styrene-
DVB) anion-exchange resin in the HCO3-/CO32- form as a
catalyst. They developed a mathematical model of the reactor
describing the rate of reaction, product distribution, and catalyst
deactivation and swelling.11,12 The hydration of EtO was
investigated in the presence of amine, bifunctional, and Salen
compounds as homogeneous catalysts. It was concluded that
there was a correlation between catalyst performance and its
acidity/basicity. Although strong acid and strong base catalysts
accelerate the reaction rate, they are not selective toward MEG
formation.7 In the case of heterogeneous catalyst, it was reported
that the acidic catalyst lowers the MEG selectivity without
affecting the EtO conversion.15
This work aimed to find the kinetic model representing the
hydration of EtO in the presence of Amberjet 4200/HCO3-,
which was found to be the most effective among the tested four
types of cross-linked styrene-DVB anion-exchange resins. The
kinetic model was rearranged for the formation of MEG, DEG,
and TEG.
Experimental Section
2.1. Materials. Ethylene oxide of 99.9% purity (Linde Gas)
and deionized water (18.2 MΩ) were used as reactants in all
experiments. The bicarbonate forms of Amberjet 4200 beads,
Lewatit MonoPlus M500, Dowex SBR, and Dowex Marathon
A were used as heterogeneous catalysts.10 The properties of
these ion-exchange resins are given in Table 1.
 Ind. Eng. Chem. Res., Vol. 48, No. 24, 2009 10841
Table 1. Properties of Ion-Exchange Resins
Amberjet 4200 Lewatit MonoPlus M500 Dowex SBR Dowex Marathon A
manufacturer Rohm and Haas Co. LANXESS Germany GmbH. Dow Chemical Co. Dow Chemical Co.
functional group -[Ph-CH2-N(CH3)3]+ -[Ph-CH2-N(CH3)3]+ -[Ph-CH2-N(CH3)3]+ -[Ph-CH2-N(CH3)3]+
% moisture 53.2 48-55 50-56 50-60
total exchange capacity (equiv/L) >1.3 >1.3 1.4 1.2
particle size (mm) 0.425-0.850 0.62 0.3-1.2 0.525-0.625
polymer type Gelular Gelular Gelular Gelular

Table 2. Experimental Data Obtained at 348 K, W/EtO ) 4.5/1, the solution by treating the catalyst with 10% NaCl solution,11
Catalyst Loading ) 0.15 mol of HCO3-/L in Equivalent and then the solution was titrated with 0.1 N HCl solution.16
time CEtO time CEtO time CEtO
(min) (mol/L) (min) (mol/L) (min) (mol/L)
Results and Discussion
0 7.557 30 5.267 125 2.022
5 7.045 45 4.401 160 1.549 The effects of the parameters, such as temperature, catalyst
10 6.614 65 3.582 213 0.803 loading, and reactant molar ratio, on the reaction rate were
20 5.889 90 2.742 studied. As seen in Figure 1, the reaction rate doubles for every
Table 3. Time-Concentration-Rate Relation Obtained from 10 K increase in temperature. Therefore, it is reasonable to
Figure 2 accept that the overall reaction is controlled by the surface
time CEtO CEtO reaction step since a chemical change is more temperature
(min) (mol/L) -dCEtO/dt time (min) (mol/L) -dCEtO/dt sensitive than a physical change. That is, the effects of external
and internal pore diffusion can be neglected, considering that
0 7 0.0836 91 2.461 0.0275
7 6.423 0.0764 137 1.438 0.0161
they are physical steps.17
21 5.458 0.0644 160 1.146 0.0122 As an example, the calculation of the average reaction rate
46 4.055 0.047 207 0.695 0.00724 for the reaction realized at 348 K, W/EtO molar ratio of 5/1,
and the amount of catalyst of 0.15 mol of HCO3-/L in equivalent
is given as follows:
2.2. Apparatus and Procedure. The experiments were Using the experimental data given in Table 2, k1, k2, and k3
carried out in a stainless steel, high-pressurized, 450 mL batch were calculated from eqs 3a-3d by the “Methods of Aver-
reactor obtained from Parr Instrument Co. The reactor (PARR ages”.18 Taking the initial ratio of W/EtO to be 5/1, concentra-
4562) was equipped with a heating jacket, a cooling coil, a tion and time values were recalculated by the solution of eqs
sampling line, two oblong windows, and a catalyst basket with 3a-3d with the known values of k1, k2, and k3. These data were
uniflow stirrer. A Parr 4843 controller was used for the used to obtain the concentration-time curve, given in Figure
temperature and stirrer speed control and for monitoring the 2. Thus, the reaction rates under the same condition and
reactor pressure. conversion level were obtained at different temperatures.

A predetermined amount of liquid EtO withdrawn from

pressurized cylinder was dissolved in a known amount of
deionized water in the reactor, and the total volume was kept
at 150 mL in all experiments. A known amount of the catalyst
was loaded into a catalyst basket, and the reaction vessel was
closed. The gas cap was purged with nitrogen at 3.4 barg
pressure, and it was taken to be the initial pressure of the
reaction. The reactor content was heated to the desired tem-
perature, and it was kept constant during the reaction. After a
steady-state value of the desired temperature was attained, the
sample was taken in a cold trap and analyzed to determine the
initial composition of the reaction mixture. Thereafter, 3 mL
Figure 1. Average reaction rate vs reaction temperature: W/EtO ) 5/1;
of a liquid sample was withdrawn from the reactor at prede- catalyst loading ) 0.15 mol HCO3-/L in equivalent; conversion of EtO )
termined intervals for the analysis. 0.90.

MEG, DEG, and TEG concentrations in all samples were

determined by HP 7890 gas chromatograph (GC) equipped with
flame ionization detector (FID), and the compounds were
separated by a capillary column (HP-INNOwax). The column
temperature was programmed with a 1 min initial hold at 100
°C, followed by a 20 °C · min-1 ramp-up to 220 °C, held for 10
min. The internal standard used was 1,3-butanediol (g99.0%).
The concentration of EtO and water was determined by the mass
balance on the basis of the stoichiometric equations given in
eqs 2a-2c. Thus, the initial concentration of EtO would be able
to be calculated from the concentration of the products obtained
when the reaction was completed. To determine the bicarbonate Figure 2. Example reaction, T ) 348 K, water/EtO ) 5/1, catalyst loading
concentration, first the bicarbonate anions were transferred into ) 0.15 mol HCO3-/L in equivalent.
10842 Ind. Eng. Chem. Res., Vol. 48, No. 24, 2009

Table 4. Calculated Values of k1, k2, and k3 for the Uncatalyzed Applying the Arrhenius equation to the values given in Table
Hydration Reaction at Different Temperatures 4, the temperature dependencies of the rate constants were found
temperature k1 × 104 k2 × 104 k3 × 104 to be
(K) (L/(mol · min)) (L/(mol · min)) (L/(mol · min))
358 0.9070 1.688 1.604
k1/[L/(mol · min)] ) exp(13.62 - 8220/T) (4a)
373 2.1439 4.019 3.684
388 5.3516 11.070 11.00 k2/[L/(mol · min)] ) exp(15.57 - 8700/T) (4b)
k3/[L/(mol · min)] ) exp(16.06 - 8900/T) (4c)
The reaction rate of EtO, as the slope of the curve given in
Figure 2, was also tabulated in Table 3. where T is absolute temperature in kelvin.
Then, using the values given in Table 3, eq 1 was evaluated 3.3. Efficacy of Various Catalysts. Four types of catalysts,
numerically to obtain the average reaction rate under prescribed namely, Amberjet 4200, Lewatit MonoPlus 500, Dowex SBR,
conditions. For this particular example, it was found to be 0.0448 and Dowex Marathon A, were compared with each other in
mol/(L · min). this work. The reaction was realized at the same temperature
of 358 K and W/EtO molar ratio of 5/1 in the presence of each
∫
C
- rEtO dC catalyst containing the same equivalent amount of HCO3-
Co
-rEtO,av ) (1) (corresponding to 0.23 mol/L). Under these conditions the
C - Co reaction was allowed to complete up to 90% conversion of EtO.
The average reaction rates calculated by eq 1 and MEG
The average reaction rates under the other conditions, therefore, selectivity are given in Table 5.
can be calculated similarly. Table 5 shows that the reaction rate and MEG selectivity,
3.1. Reaction Mechanism and Kinetics. The experiments for the reactions without catalyst, are much lower than those of
were carried out in a batch reactor to observe the effects of the the reactions with catalyst. On the other hand, although MEG
parameters on reaction rate. For each experiment, the parameter selectivity for each catalyst is close to each other, Amberjet
under investigation was changed while keeping the others 4200/HCO3- accelerates the reaction rate most. Therefore,
constant. Amberjet 4200/HCO3-, among the tested catalysts, can be
The preliminary experimental data show that the formation recommended as a proper catalyst for the hydration of EtO.
of a higher level of polyethylene glycol is negligible. Therefore, 3.4. Effect of Catalyst Loading. The experiments were
the ethylene oxide-water reaction was considered to be a series- carried out at different Amberjet 4200/HCO3- loadings with
parallel reaction in three steps:2,19 W/EtO molar ratio of 5/1 at 358 K. The catalyst loading was
varied over a range of 0-0.23 mol of HCO3-/L in equivalent
k1
W + EtO 98 MEG (2a) in the reaction mixture. The reaction was allowed to complete
90% conversion of EtO. Under these conditions, the average
reaction rates were calculated by eq 1. The average reaction
k2
MEG + EtO 98 DEG (2b) rate versus catalyst loading is shown in Figure 3. As it can be
seen from this figure, the average reaction rate is linearly
increasing with catalyst loading, as expected, since the active
k3
DEG + EtO 98 TEG (2c) surface area is proportional to the amount of catalyst. This is a
further confirmation of the negligibility of the internal and
external diffusion effects.20
Each step given in eqs 2a-2c can be assumed as an
irreversible, bimolecular, and constant density reaction. The rate
expressions, with this assumption, can be given by

dCEtO
- ) k1CWCEtO + k2CMEGCEtO + k3CDEGCEtO
dt
(3a)
dCMEG
) k1CWCEtO - k2CMEGCEtO (3b)
dt
dCDEG
) k2CMEGCEtO - k2CDEGCEtO (3c)
dt
dCTEG Figure 3. Effect of catalyst loading on the average reaction rate with water/
) k3CDEGCEtO (3d) EtO molar ratio of 5/1 at 358 K.
dt
Table 5. Average Reaction Rate and MEG Selectivity for Different
where k1, k2, and k3 are the reaction rate constants. Applying Catalyst Types with Water/EtO Molar Ratio of 5/1 and 0.23 mol of
HCO3-/L at 358 K
these equations to the experimental data, reaction rate constants
were determined by the method of averages at different conversion (-rEtO)av MEG
catalyst type range [mol/(L · min)] selectivity (%)
temperatures.
3.2. Reaction Rate without Catalyst. The uncatalyzed uncatalyzed 0-0.90 0.0128 73.7
reactions were performed with the W/EtO molar ratio of 5/1 at Amberjet 4200 /HCO3- 0-0.90 0.118 94.0
Lewatit MonoPlus M500 /HCO3- 0-0.90 0.1065 94.3
358, 373, and 388 K. The calculated reaction rate constants are Dowex SBR /HCO3- 0-0.90 0.1040 93.9
given in Table 4. Dowex Marathon A /HCO3- 0-0.90 0.0969 93.8

Figure 4. Effect of the W/EtO molar ratio on the reaction rate and MEG
selectivity.
Table 6. Calculated Values of the Rate Constants in the Presence of
Catalyst in Equivalent of 0.15 mol of HCO3-/L at Different
Temperatures
temperature k1 × 104 k2 × 104 k3 × 104
(K) (L/(mol · min)) (L/(mol · min)) (L/(mol · min))
338 1.6603 0.5292 0.5355
348 3.4716 1.1142 1.5238
358 7.8438 2.7136 2.9197
368 16.471 6.0055 5.8241
Figure 3 also shows that the average reaction rate, under
expressed conditions, can be given by
(-rEtO)av / [mol/ (L · min)] ) 0.4798CHCO3- + 0.0144
where 0.0144 mol/(L · min) corresponds to the uncatalyzed
reaction rate.
3.5. Effect of Reactants Mole Ratio. Experiments were
carried out at constant catalyst loading of 0.15 mol of HCO3-/L
in equivalent and 358 K, while the W/EtO molar ratio was varied
as 1.61/1, 4.68/1, 7.92/1, and 10.44/1. The reaction was allowed
to complete 90% conversion of EtO. The MEG selectivity and
average reaction rate values obtained under these conditions are
given in Figure 4. As seen in this figure, while MEG selectivity
increases, the average reaction rate decreases by increasing
reactant molar ratio. This is an expected result since the reaction
given in eqs 2b and 2c will be suppressed due to the low
concentrations of EtO, MEG, and DEG in dilute solution.
Similarly, the conversion rate of EtO will not increase with high
W/EtO molar ratio because, as seen in eqs 2a-2c, a high
concentration of water will be balanced by a low concentration
of EtO, MEG, and DEG.
3.6. Effect of Temperature. The reactions were realized in
the presence of catalyst in equivalent of 0.15 mol of HCO3-/L
at different temperatures. The calculated reaction rate constants
at different temperatures are given in Table 6.
Applying the Arrhenius equation to the values given in Table
6, the temperature dependencies of the rate constants were found
to be
k1/[L/(mol · min)] ) exp(19.60 - 9580/T)
k2/[L/(mol · min)] ) exp(20.19 - 10171/T)
k3/[L/(mol · min)] ) exp(19.06 - 9743/T)
where T is in kelvin.
Uncatalyzed reaction rate constants given in eqs 4a-4c were
rearranged by equalizing their corresponding frequency factors
with those given in eqs 6a-6c. These are
Ind. Eng. Chem. Res., Vol. 48, No. 24, 2009 10843
k1/[L/(mol · min)] ) exp(19.60 - 10446/T) (7a)
k2/[L/(mol · min)] ) exp(20.19 - 10421/T) (7b)
k3/[L/(mol · min)] ) exp(19.06 - 10018/T) (7c)
where T is in kelvin.
Comparison of eqs 6a-6c and 7a-7c shows that the
activation energies for k1, k2, and k3 decrease by 7.20, 2.08,
and 2.29 kJ/mol, respectively, with catalyst in equivalent amount
of 0.15 mol of HCO3-/L. This result, considered together with
eqs 2a-2c, shows that the reaction rate and MEG selectivity
increase in the presence of catalyst. Furthermore, it also indicates
that the MEG selectivity decreases with temperature in the
presence of the same amount of catalyst.
3.7. Integrated Rate Expressions. If the reaction rate given
in eq 3a is expressed in terms of conversion of EtO, the
following equation can be obtained:
dxEtO
-rEtO ) CEtO0 ) (CEtO0)2(1 - xEtO)[k1(H - xEtO) +
dt
k2(M + xEtO) + k3(D + xEtO)] (8)
A numerical integration of eq 8 by Polymath 6.10 program gives
(5) several points (xi,ti) which allow us to plot the calculated curve
together with the experimental points. As an example, Figure 5
is obtained at 358 K and under the conditions of H ) CW0/CEtO0
) 5.00, M ) CMEG0/CEtO0 ) 0.0840, D ) CDEG0/CEtO0 ) 6.403
× 10-4, CEtO0 ) 6.872 mol/L, and catalyst loading ) 0.15 mol
of HCO3-/L in equivalent. As it can be seen in Figure 5, good
agreement between the calculated curve and experimental points
is observed.
3.8. Catalyst Deactivation. Experiments were carried out
in the presence of catalyst of 0.19 mol of HCO3-/L in equivalent
at 343 K which is below the maximum operating temperature
of the resin. The catalyst was reused five times at the W/EtO
molar ratio of 5/1. For each experiment, the reaction was allowed
to complete up to 100% conversion of EtO. The average reaction
rates in the presence of fresh and third- and fifth-used catalysts
were calculated by eq 1. The results are shown in Table 7. It is
known that the activity of a catalyst, a, is given by21
(6a)
(6b)
Figure 5. Experimental points and calculated curve at 358 K and prescribed
conditions.
(6c)
Table 7. Average Reaction Rates Depending on Reused Catalyst
no. of usage -rEtO,av a ) -rEtO,at time t/-rEtO,fresh catalyst
first usage (fresh) 0.0395 1
third usage 0.0368 0.93
fifth usage 0.04346 1.100
10844 Ind. Eng. Chem. Res., Vol. 48, No. 24, 2009
-rEtO,at time t
a) (9)
-rEtO,with fresh catalyst
Equation 9 implies that if there is no deactivation, activity
will be unity.
As seen from Table 7, there is no deactivation up to the fifth
usage, which takes approximately 65 h as long as the reaction
temperature is kept below the maximum operating temperature
of the resin.
Conclusions
The kinetics of hydration of EtO has been studied with and
without catalyst in a high-pressure batch reactor. It has been
indicated that the reaction conducted with and without catalyst
follows a serial-parallel irreversible reaction model in which
the reaction rate, toward the consumption of EtO, will be given
by -dCEtO/dt ) k1CWCEtO + k2CMEGCEtO + k3CDEGCEtO. It was
also shown that the temperature dependencies of the rate
constants appearing in this equation will be given by eqs 4a-4c
for the uncatalyzed reactions and by eqs 6a-6c for the catalyzed
reaction with 0.15 mol of HCO3-/L in equivalent. On the other
hand, it was shown that the reaction rate increases linearly with
catalyst loading in accordance with the equation of
(-rEtO)av / [mol/ (L · min)] ) 0.4798CHCO3- + 0.0144
where 0.0144 mol/(L · min) corresponds to the uncatalyzed
reaction rate.
As a result, the Amberjet 4200/ HCO3-, as an anionic ion-
exchange resin, is a suitable catalyst for the hydration of EtO
since it reduces the activation energy of the MEG production
by 7.20 kJ/mol in the presence of it amounting to 0.15 mol
HCO3-/L in equivalent. Furthermore, there is no deactivation
if the temperature is kept below the maximum operating
temperature of the resin.
Acknowledgment
This project was supported by the Scientific Research Project
Commission of Anadolu University (Project No. 060212). S.A.
acknowledges financial support through The Scientific and
Technological Research Council of Turkey (TÜBÝTAK-
BÝDEB) for Ph.D. Scholarship.
Nomenclature
D ) CDEG0/CEtO0
DEG ) diethylene glycol
EtO ) ethylene oxide
H ) CW0/CEtO0
k ) rate constant
m ) catalyst mass (mol)
M ) CMEG0/CEtO0
MEG ) monoethylene glycol
R ) 8.314 (J · mol-1 · K-1)
s ) standard deviation
T ) temperature (K)
TEG ) triethylene glycol
V ) volume of the reaction mixture (L)
W ) water
xi ) mole fraction of component i
Subscripts
av ) average
0 ) at initial condition
Literature Cited
(1) Kirk, R. E.; Othmer, D. F. In Encyclopedia of Chemical Technology;
Seidel, A., Ed.; John Wiley and Sons: New York, 2005; pp 644-660.
(2) Weissermel, K.; Arpe, H.-J. Industrial Organic Chemistry; Wiley-
VCH: New York, 1993.
(3) Othmer, D. F.; Thakar, M. S. Glycol ProductionsHydration of
Ethylene Oxide. Ind. Eng. Chem. 1958, 50, 1235.
(4) Keen, B. T. Carbon Dioxide-Enhanced Monoalkylene Glycol
Production. U.S. Patent 4,578,524, 1986.
(5) Masuda, T.; Asona, K.; Hori, N.; Ando, S. Method for Preparing
Ethylene Glycol and/or Propylene Glycol. U.S. Patent 4,937,393, 1990.
(6) Kozlovsky, I. A.; Kovzlovsky, R. A.; Koustov, A. V.; Makarov,
M. G.; Suchkov, J. P.; Shvets, V. F. Kinetics and Products Distribution of
Selective Catalytic Hydration of Ethylene and Propylene Oxides in
Concentrated Aqueous Solutions. Org. Process Res. DeV. 2002, 6, 660.
(7) Van Hal, J. W.; Ledford, J. S.; Zhang, X. Investigation of Three
Types of Catalysts for the Hydration of Ethylene Oxide (EO) to Monoet-
hylene Glycol (MEG). Catal. Today 2007, 123, 310.
(8) Reed, L. M.; Wenzel, L. A.; O’Hara, J. B. Catalytic Hydration of
Ethylene Oxide: Applying Ion Exchange Resins as Catalysts. Ind. Eng.
Chem. 1956, 48, 205.
(9) Johnson, F. L.; Watts, L. W. Process for the Production of Alkylene
Glycols. U.S. Patent 4,393,254, 1983.
(10) Reman, W. G.; Van Kruchten, E. M. G. A. Process for the
Preparation of Alkylene Glycols. U.S. Patent 5,488,184, 1996.
(11) Shvets, V. F.; Kozlovskiy, R. A.; Kozlovskiy, I. A.; Makarov,
M. G.; Suchkov, J. P.; Koustov, A. V. The Model of Catalytic Reactor of
Ethylene Glycol Production. Org. Process Res. DeV. 2005, 9, 768.
(12) Shvets, V. F.; Kozlovskiy, R. A.; Kozlovskiy, I. A.; Makarov,
M. G.; Suchkov, J. P.; Koustov, A. V. The Cause and Quantitative
Description of Catalyst Deactivation in the Ethylene Oxide Hydration
Process. Chem. Eng. J. 2005, 107, 199.
(13) Li, Y.; Yan, S.; Yue, B.; Yang, W.; Xie, Z.; Chen, Q.; He, H.
Selective Catalytic Hydration of Ethylene Oxide over Niobium Oxide
Supported on R-Alumina. Appl. Catal., A 2004, 272, 305.
(14) Altiokka, M. R.; Citak, A. Kinetics Study of Esterification of Acetic
Acid with Isobutanol in the Presence of Amberlite Catalyst. Appl. Catal.,
A 2003, 239, 141.
(15) Van Kruchten, E. M. G. A.; Kunin, R.; Lemansaki, M. F. Catalyst
Stabilising Additive in the Hydrolysis of Alkylene Oxides. WO Patent
0035841, 2000.
(16) Skoog, D. A.; West, D. M.; Holler, F. J. Fundamentals of Analytical
Chemistry; Saunders College: Orlando, FL, 1996.
(17) Fogler, H. S. Elements of Chemical Reaction Engineering; Prentice-
Hall: Englewood Cliffs, NJ, 1992.
(18) Jenson, V. G.; Jeffreys, G. V. Mathematical Methods in Chemical
Engineering; Academic Press: New York, 1977.
(19) Mcclellan, P. P. Manufacture and Uses of Ethylene Oxide and
Ethylene Glycol. Ind. Eng. Chem. 1950, 42, 2402.
(20) Madon, R. J.; Boudart, M. Experimental Criterion for the Absence
of Artifacts in the Measurement of Rates of Heterogeneous Catalytic
Reactions. Ind. Eng. Chem. Fundam. 1982, 21, 438.
(21) Levenspiel, O. Chemical Reaction Engineering; John Wiley and
Sons: New York, 1999.
ReceiVed for reView June 26, 2009
ReVised manuscript receiVed September 24, 2009
Accepted October 5, 2009
IE901037W