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KINETICS STUDY OF ONE-STEP SYNTHESIS OF DME FROM SYNGAS

Chengyuan Cheng1, Dasheng Chen2, Haitao Zhang1, Weiyong Ying1,*, Dingye Fang1 1. Engineering Research Center of Large Scale Reactor Engineering and Technology, Ministry of Education, State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai China 200237 2. Shanghai Wujing Chemical Co. Ltd., Shanghai China 200241

Abstract: The intrinsic kinetics of the dimethyl ether (DME) synthesis process over a by-functional catalyst have been investigated at 220~260℃, 2~6MPa and 1000~2500mL/(g-cal h) using isothermal integral reactor. The bi-functional catalyst was prepared by physical mixing of commercial CuO/ZnO/Al2O3 as methanol synthesis catalyst and γ-alumina as methanol dehydration catalyst. The three reactions including methanol synthesis from CO and H2, CO2 and H2, and methanol dehydration were chosen as the independent reaction. The L-H kinetic model was presented for dimethyl ether synthesis and the parameters of the model were obtained by using Levenberg-Marquardt method. The model is reliable according to statistical analysis and residual error analysis. Also the effects of different parameters on the reactor performance have been investigated based on the presented kinetic model. Key words: Dimethyl ether; Syngas; One-step; Fixed-bed; Kinetics model

1. INTRODUCTION Dimethyl ether (DME) is a liquefied gas with handling characteristics similar to those of liquefied petroleum gas (LPG) (Semelsberger et al., 2005). It can be produced from a variety of feed-stock such as natural gas, crude oil, residual oil, coal, waste products and bio-mass. Many investigations have been carried out on DME to determine its suitability for use as a fuel in diesel-cycle engines (Arcoumanis et al., 2008). Compared to some of the other leading alternative fuel candidates (i.e., methane, methanol, ethanol, and Fischer-Tropsch fuels), dimethyl ether appears to have the largest potential impact on society, and should be considered as the fuel of choice for eliminating the dependency on petroleum. At the present time, DME is commercially prepared by dehydration of methanol using acidic porous catalysts such as zeolites, silica-alumina, alumina, etc. Recently, an original technique named STD (synthesis gas to dimethyl ether) process was developed for the direct synthesis of DME from synthesis gas (syngas) in a single reactor on bi-functional catalysts composed of copper-based
*

Correspondence to: Professor Wei-yong Ying, E-mail: wying@ecust.edu.cn

In order to better understand the process especially the relationship of CO and CO2 synthesis to methanol. 2. The catalyst is well mixed with quartz sand in the same size. and well mixed at mass ratio 1:1. investigate the intrinsic kinetics of one-step DME synthesis on the CuO-ZnO-Al2O3/γ-alumina catalyst in fixed-bed reactor. And there is no industry-scale slurry reactor has been built so far because the experience of scaling up is scarce for slurry reactor. The water is shifted by the WGSR reaction (4) forming carbon dioxide and hydrogen. (3) (1) (2) . The present study. However. Top and bottom of the catalyst bed is filled with quartz sand too. 2. one of the products of each step is a reactant for another. Then.1 Catalyst Bi-functional catalyst was prepared by admixing of the two catalysts. The combination of these reactions results in a synergistic effect relieving the unfavorable thermodynamic for methanol synthesis: methanol. The main reactions in the STD process can be shown as follow: Methanol synthesis: CO+2H2→CH3OH CO2+3H2→CH3OH+H2O Methanol dehydration: 2CH3OH→CH3OCH3+H2O Water gas shift: CO+H2O→H2+CO2 (4) Methanol is converted to DME by dehydration of methanol (Eq(3)) on the acid catalyst. product in the first and second step. the latter being a reactant for the methanol synthesis. space velocity is simulated by the proposed kinetic models. so the fixed-bed reactor could be easily rapidly built on industry-scale. the equilibrium conversion shifts toward the right-hand side of reaction (1) (2). Thus. This mass ratio obtained in previous study (Liu et al.2 Experimental set-up The STD reaction kinetic study was carried out in an isothermal integral reactor. Moreover. the catalyst was activated in situation by reduction using a flow of 5% H2 in N2 at 240℃ approached at 1℃/min from room temperature for 12 h. Before each kinetic test. the influence of different process parameters such as pressure. commercial methanol synthesis catalyst (CuO-ZnO-Al2O3) and methanol synthesis catalyst (γ-alumina). temperature.005g catalyst was filled in.methanol synthesis catalysts and dehydration catalyst. is consumed for reaction to DME and water. in which the 6. ensure that L/R>8. but in order to provide basic data for designing the reactor for plant or industry. the kinetics study of direct DME synthesis is necessary. there is much information available about the design and the operation on the fixed-bed reactor. This creates a strong driving force for the overall reaction allowing very high syngas conversion in one single pass.. The kinetics models for this process based on Longmuir-Hinshelwood mechanism. 2002). Two commercial catalyst were finely milled and sieved to size 150~180μm. EXPERIMENT 2. we do the intrinsic kinetic research and choose Eq(1) (2) and (4) as independent reaction. The research of direct DME synthesis is focused on the catalyst and the process at present.

cal ) 2 (8) Where yi is the mole fraction of key component and wi stands for the weight factor for response i.hydrogenat ion k1 f CO f H 2 (1 (1 K CO f CO k 2 f CO2 f H 2 (1 (1 K CO f CO k 3 f M (1 (1 3 K CO2 f CO2 K H2 f H2 )3 (5) rCO2 . Mass and heat transfer limitations were negligible during the experimental conditions chosen. 3. CO2. Several kinetic models for methanol synthesis and methanol dehydration reactions were tested (Ng et al. usually less than 5% and in 90% experiments the balances chose to within 2. The hydrogen rich CO lean syngas is best suit the fixed-bed reactor.exp yik . DME as three key component. SIMULATION AND PARAMETER ESTIMATE The simulation of DME synthesis reactions was based on a PFR model. so the H2/CO molar ratio = 2:1 to 4:1.. The intrinsic kinetics rate equations are blow: 2 2 f M / K f1 f CO f H 2 ) rCO .hydrogenat ion 3 f M f H 2O / K f 2 f CO f H 2 ) K CO2 f CO2 K H2 f H2 ) 4 (6) rMeOHdehydr ation 2 f DME f H 2O / K f 3 f M ) K M fM )2 (7) The fugacity of each component was calculated by SHBWR equation.2. From the initial screening. In order to carry out kinetic modeling. and Bi is the activation energy for rate constant or heat of adsorption for adsorption equilibrium constant. Choose CO. The parameters of the proposed . Moradi et al. Ai is the pre-exponential factor.5%. a broad range of experimental conditions have been carried out under the following reaction conditions: 220–260℃.. 1999. Kf is the equilibrium of reaction i Parameter estimation was based on the minimization of the objective function: I K S i 1 wi2 k 1 ( y ik . 1000-2500mL/(g-cat h) which was sufficiently far from equilibrium conditions.3 Experimental condition The kinetic experiments were always carried out under steady-state condition. The model for methanol synthesis proposed by Vanden Bussche and Froment (1996) based on a strictly sequential reaction mechanism of CO to CO2 to CH3OH via surface carbonate. 2–6MPa. The deviations were very small. the following equation was used: k i (T ) Ai exp Bi RT Where ki denotes a model parameter. were selected for analysis and simulation of the combined process. and the dehydration model proposed by Bercic and Levec(1992) based on reaction of dissociative adsorbed methanol. To establish the kinetic parameters as a function of temperature. For each experiment the carbon balances over the reactor were calculated. Both internal and external particle diffusion resistance were confirmed absent. This state was achieved within 20h from start up. 2008) under both independent and combined synthesis conditions.

Where M is number of the experiments. . Mp is number of parameters in the equation of model.kinetics models are given in table 1.

083 0.in (10) Fig.in YDME 4.235 -8.out (9) Fin yCO .232 16. SV=1500mL/(g-cat h). As is observed. pressure and space velocity.676×10 0. Fig.out Fin yCO .1 Effect of temperature Fout y DME.31585 4. when temperature is increased in the range from 220 to 260℃ the conversion of CO increases. These were defined as follows: X CO Fin yCO .72124 0.00004 0. and the thermodynamic influence becomes dominant in that case. higher temperature lead to an unfavorable effect on the equilibrium conversion of synthesis gas.842 11.Table 1 Kinetic parameter for DME synthesis Parameters k1 k2 k3 KCO KCO2 KH2 KM Ai 2. For the purposes of quantitative comparison with experimental result. The reaction is controlled by thermodynamic equilibrium at high temperature or low space velocity. ( □ )CO conversion. because the reactions rate is kinetically controlled in this region.1 shows the influence of temperature on the conversion of CO with results of kinetics model. the conversion of the feed carbon monoxide and yield of DME were used.732 47. (△)DME yield .963 -13.1 Effect of temperature on experimental result: P=5Mpa.in Fout yCO .167×10 1.41×10 3 3 3 Bi -20. Since methanol synthesis and methanol dehydration are both exothermic reactions.522 -44. RESULT AND DISCUSSION It is of interest to explore the dependence of kinetics of DME synthesis on the operating condition such as temperature.18417 0.

methanol synthesis is a mole-number-reducing reaction so that pressure enhancement favors the conversion of CO and yield of DME. The DME yield is decreasing less than CO conversion. (△)DME yield 4. the CO conversion and DME yield keep decreasing. As is observed. which is the logical consequence whereby methanol synthesis is the limiting step of the whole reaction. Fig. Fig.4. so the pressure has no effect on these reactions. when pressure is increased in the range from 2 to 6Mpa the CO conversion increases. Because higher space velocity means shorter residence time of reactants in contact with the catalyst. With increasing SV. (△)DME yield . (□)CO conversion.2 shows the CO conversion as a function of reaction pressure in the kinetics model. Also.3 shows the effect of space velocity on the performance of STD. This implies that the reaction of DME production may be carried out under a similar pressure as in the conversional synthesis of methanol. P=5MPa.3 Effect of space velocity Fig. and short residence time is unfavorable for the consecutive reactions.2 Effect of pressure Fig. Since the number of moles in the both sides of methanol dehydration and water-gas shift reactions are the same. SV=1500mL/(g-cat h). (□)CO conversion.1 Effect of pressure on experimental result: T=250℃.3 Effect of space velocity on experimental result: T=240℃.

Y. 3587-3592 Nie.H. J. H. K..Y. F. Liu.2005CB221205) and by 11th Five-year plan of China. W. 22-28. Yaripour. 3185-3192 Liu. Zhang. Eng. Chem. Eng. Xu. D. H.A. The simulation data was found to agree well with the experiment results over a wide range of experimental conditions. Eng. H.. Fang(2005) Intrinsic kinetics of dimethyl ether synthesis from syngas. H. 103-106 Moradi. 87. Beenackers. 14. This accurate kinetic model can be used in future reactor modeling and scaling-up. Ind.. Ying.5. (China).(2005) Calculation of equilibrium conversion and selectivity for dimethyl ether synthesis from syngas. J. Acknowledgements The authors gratefully acknowledge the financial support by National Basic Research Program of China (973 program) (No. Nat. Ahmadpour. 144.(2008) Intrinsic kinetics study of LPDME process from syngas over bi-functional catalyst. Dimethyl ether (DME) as an alternative fuel.(1988) Kinetics of low pressure methanol synthesis. 54. Fuel. L. Z. Fang(2002). E. D. Bae C and Crookes R (2008) The potential of dimethyl ether(DME) as an alternative fuel for compression-ignition engines: A review. 43. Journal of Power Sources... J. D. G. Tosland(1999) Kinetics and modeling of dimethyl ether synthesis from synthesis gas.M. Yang and W. Chadwick and B. The STD process was favorable at high temperature. T. Y.J. Chem. Chem. 497–511 Zhang. CONCLUSIONS A intrinsic kinetic model for the STD process over a CuO-ZnO-Al2O3/γ-alumina catalyst based on Longmuir-Hinshelwood mechanism are established. (China). Ying and D. D.& Eng. 156.G. Chem. Q. Gas Chem. A.L. 88-95 Ng. J. L..C. Chem. Semelsberger.. Rodney and H. Eng. J.. Stamhuis. 33. References Arcoumanis C. Sci. 53(1). A. Greene(2005). Direct synthesis of dimethyl ether from syngas in three-phase agitated reactors. pressure and low space velocity. T. R.A. G.. Liu. B. J. 1014-1030 Graaf. W. Y.. Sci. 64-68 .