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Ind. Eng. Chem. Res. 2009, 48, 1084010844

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

Mehmet Riza Altiokka* and Sema Akyalcin
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 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 commonly 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 purication 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 ionexchange resin,10-12 and niobium oxide supported on R-alumina13 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 ltration. 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 uidized 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 types of ion-exchange resins were used as heterogeneous carriers 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, t the rst-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 xed-bed tube reactor using a cross-linked styrene-divinylbenzene (styreneDVB) 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 nd 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 M) 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.

10.1021/ie901037w CCC: $40.75 2009 American Chemical Society Published on Web 10/23/2009

Ind. Eng. Chem. Res., Vol. 48, No. 24, 2009

Table 1. Properties of Ion-Exchange Resins Amberjet 4200 manufacturer functional group % moisture total exchange capacity (equiv/L) particle size (mm) polymer type Rohm and Haas Co. -[Ph-CH2-N(CH3)3]+ 53.2 >1.3 0.425-0.850 Gelular Lewatit MonoPlus M500 LANXESS Germany GmbH. -[Ph-CH2-N(CH3)3]+ 48-55 >1.3 0.62 Gelular Dowex SBR Dow Chemical Co. -[Ph-CH2-N(CH3)3]+ 50-56 1.4 0.3-1.2 Gelular

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Dowex Marathon A Dow Chemical Co. -[Ph-CH2-N(CH3)3]+ 50-60 1.2 0.525-0.625 Gelular

Table 2. Experimental Data Obtained at 348 K, W/EtO ) 4.5/1, Catalyst Loading ) 0.15 mol of HCO3-/L in Equivalent time (min) 0 5 10 20 CEtO (mol/L) 7.557 7.045 6.614 5.889 time (min) 30 45 65 90 CEtO (mol/L) 5.267 4.401 3.582 2.742 time (min) 125 160 213 CEtO (mol/L) 2.022 1.549 0.803

the solution by treating the catalyst with 10% NaCl solution,11 and then the solution was titrated with 0.1 N HCl solution.16 Results and Discussion The effects of the parameters, such as temperature, catalyst loading, and reactant molar ratio, on the reaction rate were studied. As seen in Figure 1, the reaction rate doubles for every 10 K increase in temperature. Therefore, it is reasonable to accept that the overall reaction is controlled by the surface reaction step since a chemical change is more temperature sensitive than a physical change. That is, the effects of external and internal pore diffusion can be neglected, considering that they are physical steps.17 As an example, the calculation of the average reaction rate 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: Using the experimental data given in Table 2, k1, k2, and k3 were calculated from eqs 3a-3d by the Methods of Averages.18 Taking the initial ratio of W/EtO to be 5/1, concentration and time values were recalculated by the solution of eqs 3a-3d with the known values of k1, k2, and k3. These data were used to obtain the concentration-time curve, given in Figure 2. Thus, the reaction rates under the same condition and conversion level were obtained at different temperatures.

Table 3. Time-Concentration-Rate Relation Obtained from Figure 2 time (min) 0 7 21 46 CEtO (mol/L) 7 6.423 5.458 4.055 -dCEtO/dt 0.0836 0.0764 0.0644 0.047 time (min) 91 137 160 207 CEtO (mol/L) 2.461 1.438 1.146 0.695 -dCEtO/dt 0.0275 0.0161 0.0122 0.00724

2.2. Apparatus and Procedure. The experiments were carried out in a stainless steel, high-pressurized, 450 mL batch reactor obtained from Parr Instrument Co. The reactor (PARR 4562) was equipped with a heating jacket, a cooling coil, a sampling line, two oblong windows, and a catalyst basket with uniow stirrer. A Parr 4843 controller was used for the temperature and stirrer speed control and for monitoring the reactor pressure. 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 temperature, 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 of a liquid sample was withdrawn from the reactor at predetermined intervals for the analysis. MEG, DEG, and TEG concentrations in all samples were determined by HP 7890 gas chromatograph (GC) equipped with ame 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 concentration, rst the bicarbonate anions were transferred into

Figure 1. Average reaction rate vs reaction temperature: W/EtO ) 5/1; catalyst loading ) 0.15 mol HCO3-/L in equivalent; conversion of EtO ) 0.90.

Figure 2. Example reaction, T ) 348 K, water/EtO ) 5/1, catalyst loading ) 0.15 mol HCO3-/L in equivalent.

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Table 4. Calculated Values of k1, k2, and k3 for the Uncatalyzed Hydration Reaction at Different Temperatures temperature (K) 358 373 388 k1 104 (L/(mol min)) 0.9070 2.1439 5.3516 k2 104 (L/(mol min)) 1.688 4.019 11.070 k3 104 (L/(mol min)) 1.604 3.684 11.00

Applying the Arrhenius equation to the values given in Table 4, the temperature dependencies of the rate constants were found to be k1/[L/(mol min)] ) exp(13.62 - 8220/T) k2/[L/(mol min)] ) exp(15.57 - 8700/T) k3/[L/(mol min)] ) exp(16.06 - 8900/T) (4a) (4b) (4c)

The reaction rate of EtO, as the slope of the curve given in Figure 2, was also tabulated in Table 3. Then, using the values given in Table 3, eq 1 was evaluated numerically to obtain the average reaction rate under prescribed conditions. For this particular example, it was found to be 0.0448 mol/(L min).

-rEtO,av )

Co

- rEtO dC C - Co (1)

The average reaction rates under the other conditions, therefore, can be calculated similarly. 3.1. Reaction Mechanism and Kinetics. The experiments were carried out in a batch reactor to observe the effects of the parameters on reaction rate. For each experiment, the parameter under investigation was changed while keeping the others constant. The preliminary experimental data show that the formation of a higher level of polyethylene glycol is negligible. Therefore, the ethylene oxide-water reaction was considered to be a seriesparallel reaction in three steps:2,19 W + EtO 9 MEG 8 MEG + EtO 9 DEG 8 DEG + EtO 9 TEG 8
k3 k2 k1

(2a) (2b) (2c)

where T is absolute temperature in kelvin. 3.3. Efcacy of Various Catalysts. Four types of catalysts, namely, Amberjet 4200, Lewatit MonoPlus 500, Dowex SBR, and Dowex Marathon A, were compared with each other in 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 catalyst containing the same equivalent amount of HCO3(corresponding to 0.23 mol/L). Under these conditions the reaction was allowed to complete up to 90% conversion of EtO. The average reaction rates calculated by eq 1 and MEG selectivity are given in Table 5. Table 5 shows that the reaction rate and MEG selectivity, for the reactions without catalyst, are much lower than those of the reactions with catalyst. On the other hand, although MEG selectivity for each catalyst is close to each other, Amberjet 4200/HCO3- accelerates the reaction rate most. Therefore, Amberjet 4200/HCO3-, among the tested catalysts, can be recommended as a proper catalyst for the hydration of EtO. 3.4. Effect of Catalyst Loading. The experiments were carried out at different Amberjet 4200/HCO3- loadings with 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 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 rate versus catalyst loading is shown in Figure 3. As it can be seen from this gure, the average reaction rate is linearly increasing with catalyst loading, as expected, since the active surface area is proportional to the amount of catalyst. This is a further conrmation 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 dt dCDEG ) k2CMEGCEtO - k2CDEGCEtO dt dCTEG ) k3CDEGCEtO dt (3b) (3c) (3d)
Figure 3. Effect of catalyst loading on the average reaction rate with water/ EtO molar ratio of 5/1 at 358 K. Table 5. Average Reaction Rate and MEG Selectivity for Different Catalyst Types with Water/EtO Molar Ratio of 5/1 and 0.23 mol of HCO3-/L at 358 K catalyst type
uncatalyzed Amberjet 4200 /HCO3Lewatit MonoPlus M500 /HCO3Dowex SBR /HCO3Dowex Marathon A /HCO3-

where k1, k2, and k3 are the reaction rate constants. Applying these equations to the experimental data, reaction rate constants were determined by the method of averages at different temperatures. 3.2. Reaction Rate without Catalyst. The uncatalyzed reactions were performed with the W/EtO molar ratio of 5/1 at 358, 373, and 388 K. The calculated reaction rate constants are given in Table 4.

conversion (-rEtO)av MEG range [mol/(L min)] selectivity (%)

0-0.90 0-0.90 0-0.90 0-0.90 0-0.90 0.0128 0.118 0.1065 0.1040 0.0969 73.7 94.0 94.3 93.9 93.8

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k1/[L/(mol min)] ) exp(19.60 - 10446/T) k2/[L/(mol min)] ) exp(20.19 - 10421/T) k3/[L/(mol min)] ) exp(19.06 - 10018/T)

(7a) (7b) (7c)

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 (K)
338 348 358 368

k1 104 (L/(mol min))

1.6603 3.4716 7.8438 16.471

k2 104 (L/(mol min))

0.5292 1.1142 2.7136 6.0055

k3 104 (L/(mol min))

0.5355 1.5238 2.9197 5.8241

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 ) (CEtO0)2(1 - xEtO)[k1(H - xEtO) + dt k2(M + xEtO) + k3(D + xEtO)] (8)

-rEtO ) CEtO0

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 (5)

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 gure, 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) (6a) (6b) (6c)

A numerical integration of eq 8 by Polymath 6.10 program gives 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 ve 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 fth-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

Figure 5. Experimental points and calculated curve at 358 K and prescribed conditions. Table 7. Average Reaction Rates Depending on Reused Catalyst no. of usage rst usage (fresh) third usage fth usage -rEtO,av 0.0395 0.0368 0.04346 a ) -rEtO,at time t/-rEtO,fresh catalyst 1 0.93 1.100

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

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a)

-rEtO,at time t -rEtO,with fresh catalyst

(9)

V ) volume of the reaction mixture (L) W ) water xi ) mole fraction of component i Subscripts av ) average 0 ) at initial condition

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 fth 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 ionexchange 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 Scientic Research Project Commission of Anadolu University (Project No. 060212). S.A. acknowledges nancial support through The Scientic and Technological Research Council of Turkey (TUBYTAK BYDEB) 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

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; WileyVCH: 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 Monoethylene Glycol (MEG). Catal. Today 2007, 123, 310. (8) Reed, L. M.; Wenzel, L. A.; OHara, 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 Esterication 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; PrenticeHall: 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