Steam Reforming of Dimethyl Ether over Coupled Catalysts of CuO-ZnO-Al2O3-ZrO2 and Solid-acid Catalyst

Abstract

Abstract: Steam reforming(SR) of dimethyl ether(DME) was investigated for the production of hydrogen for fuel cells.The activity of a series of solid acids for DME hydrolysis was investigated.The solid acid catalysts were ZSM-5 [Si/Al=25, 38 and 50:denoted Z(Si/Al)] and acidic alumina(γ-Al₂O₃) with an acid strength order that was Z(25)>Z(38)>Z(50)>γ-Al₂O₃.Stronger acidity gave higher DME hydrolysis conversion.Physical mixtures containing a CuO-ZnO-Al₂O₃-ZrO₂ catalyst and solid acid catalyst to couple DME hydrolysis and methanol SR were used to examine the acidity effects on DME SR.DME SR activity strongly depended on the activity for DME hydrolysis.Z(25) was the best solid acid catalyst for DME SR and gave a DME conversion>90% [T=24℃, n(H₂O)/n(DME)=3.5, space velocity=1179 ml·(g cat)^-1·h^-1, and P=0.1MPa].The influences of the reaction temperature, space velocity and feed molar ratio were studied.Hydrogen production significantly depended on temperature and space velocity.A bifunctional catalyst of CuO-ZnO-Al₂O₃-ZrO₂ catalyst and ZSM-5 gave a high H₂ production rate and CO₂ selectivity.

Key words: hydrogen production, dimethyl ether, steam reforming, hydrolysis, solid-acid catalyst, CuO-ZnO catalyst

摘要： Steam reforming(SR) of dimethyl ether(DME) was investigated for the production of hydrogen for fuel cells.The activity of a series of solid acids for DME hydrolysis was investigated.The solid acid catalysts were ZSM-5 [Si/Al=25,38 and 50:denoted Z(Si/Al)] and acidic alumina(γ-Al₂O₃) with an acid strength order that was Z(25)>Z(38)>Z(50)>γ-Al₂O₃.Stronger acidity gave higher DME hydrolysis conversion.Physical mixtures containing a CuO-ZnO-Al₂O₃-ZrO₂ catalyst and solid acid catalyst to couple DME hydrolysis and methanol SR were used to examine the acidity effects on DME SR.DME SR activity strongly depended on the activity for DME hydrolysis.Z(25) was the best solid acid catalyst for DME SR and gave a DME conversion>90% [T=24℃,n(H₂O)/n(DME)=3.5,space velocity=1179 ml·(g cat)^-1·h^-1,and P=0.1MPa].The influences of the reaction temperature,space velocity and feed molar ratio were studied.Hydrogen production significantly depended on temperature and space velocity.A bifunctional catalyst of CuO-ZnO-Al₂O₃-ZrO₂ catalyst and ZSM-5 gave a high H₂ production rate and CO₂ selectivity.

关键词: hydrogen production, dimethyl ether, steam reforming, hydrolysis, solid-acid catalyst, CuO-ZnO catalyst

FENG Dongmei, ZUO Yizan, WANG Dezheng, WANG Jinfu. Steam Reforming of Dimethyl Ether over Coupled Catalysts of CuO-ZnO-Al₂O₃-ZrO₂ and Solid-acid Catalyst[J]. , 2009, 17(1): 64-71.

冯冬梅, 左宜赞, 王德峥, 王金福. Steam Reforming of Dimethyl Ether over Coupled Catalysts of CuO-ZnO-Al₂O₃-ZrO₂ and Solid-acid Catalyst[J]. , 2009, 17(1): 64-71.

References

1 Liu, Z.Q., Mao, Z.Q., Xu, J.M., “Operation conditions optimization of hydrogen production by propane autothermal reforming for PEMFC applications”, Chin. J. Chem. Eng., 14, 729-735 (2006).
2 Wang, Z.L., Diao, J., Wang, J.F., Jing, Y., “Study on synergy effect in dimethyl ether synthesis from syngas”, Chin. J. Chem. Eng., 9,412-416 (2001).
3 Tanaka, Y., Kikuchi, R., Takeguchi, T., Equchi, K., “Steam reforming of dimethyl ether over composite catalysts of γAl₂O₃ and Cubased spinel”, Appl. Catal. B Environ., 57, 211-222 (2005).
4 Faungnawakij, K., Tanaka, Y., Shimoda, N., Fukunaga, T., Kawashima, S., Kikuchi, R., Eguchi, K., “Influence of solid-acid catalysts on steam reforming and hydrolysis of dimethyl ether for hydrogen production”, Appl. Catal. A Gen., 304, 40-48 (2006).
5 Semelsberger, T.A., Ott, K.C., Borup, R.L., Greene, H.L., “Generating hydrogen-rich fuel-cell feeds from dimethyl ether (DME) using Cu/Zn supported on various solid-acid substrates”, Appl. Catal. A Gen., 309, 210-223 (2006).
6 Kawabata, T., Matsuoka, H., Shishido, T., Li, D., Tian, Y., Sano, T., Takehira, K., “Steam reforming of dimethyl ether over ZSM-5 coupled with Cu/ZnO/Al₂O₃ catalyst prepared by homogeneous precipitation”, Appl. Catal. A Gen., 308, 82-90 (2006).
7 Semelsberger, T.A., Ott, K.C., Borup, R.L., Greene, H.L., “Generating hydrogen-rich fuel-cell feeds from dimethyl ether (DME) using physical mixtures of a commercial Cu/Zn/Al₂O₃ catalyst and several solid-acid catalysts”, Appl. Catal. A Gen., 65, 291-300 (2006).
8 Faungnawakij, K., Tanaka, Y., Shimoda, N., Fukunaqa, T., Kikuchi, R., Equchi, K., “Hydrogen production from dimethyl ether steam reforming over composite catalysts of copper ferrite spinel and alumina”, Appl. Catal. B Environ., 74, 144-151 (2007).
9 Laosiripojana, N., Assaburnrngrat, S., “Catalytic steam reforming of dimethyl ether (DME) over high surface area Ce-ZrO₂ at SOFC temperature: The possible use of DME in indirect internal reforming operation (IIR-SOFC)”, Appl. Catal. A Gen., 320, 105-113 (2007).
10 Takeishi, K., Suzuki, H., “Steam reforming of dimethyl ether”, Appl. Catal. A Gen., 260, 111-117 (2004).
11 Badmaev, S.D., Volkova, G.G., Belyaev, V.D., Sobyanin, V.A., “Steam reforming of dimethyl ether to hydrogen-rich gas”, Reac. Kinet. Catal. Lett., 90, 205-211 (2007).
12 Semelsberger, T.A., Borup, R.L., “Thermodynamic equilibrium calculations of dimethyl ether steam reforming and dimethyl ether hydrolysis”, J. Power Sources., 152, 87-96 (2005).
13 Faungnawakij, K., Tanaka, Y., Shimoda, N., Fukunaqa, T., Kikuchi, R., Equchi, K., “Thermodynamic analysis of carbon formation boundary and reforming performance for steam reforming of dimethyl ether”, J. Power Sources., 164, 7-79 (2007).
14 Agell, J., Birgersson, H., Boutonnet, M., “Steam reforming of methanol over a Cu/ZnO/Al₂O₃ catalyst: a kinetic analysis and strategies for suppression of CO formation”, J. Power Sources., 106,249-257 (2002).
15 Peppley, B.A., Amphlett, J.C., Kearns, L.M., “ Methanol-steam reforming on Cu/ZnO/Al₂O₃ . Part 1: the reaction network”, Appl. Catal. A Gen., 197, 21-29 (1999).
16 Peppley, B.A., Amphlett, J.C., Kearns, L.M., “ Methanol-steam reforming on Cu/ZnO/Al₂O₃ catalysts. Part 2. A comprehensive kinetic model”, Appl. Catal. A Gen., 197, 31-49 (1999).
17 Jiang, C.J., Trimm, D.L., Wainwright, M.S., “Kinetic study of steam reforming of methanol over copper-based catalysts”, Appl. Catal. A Gen., 97, 145-158 (1993).
18 Mastalir, A., Frank, B., Szizybalski, A., Soerijanto, H., Deshpande, A., Niederbergere, M., Schomacker, R., Schlogl, R., Ressler, T., “Steam reforming of methanol over Cu/ZrO₂ /CeO₂ catalysts: a kinetic study”, J. Catal., 230, 464-475 (2005).
19 Agrell, J., Birgersson, H., Boutonnet, M., “Steam reforming of methanol over a Cu/ZnO/Al₂O₃ catalysts: a kinetic analysis and strategies for suppression of CO formation”, J. Power Sources., 106,249-257 (2002).
20 Xie, F., Li, H.S., Zhao, X.L., “Adsorption and dehydration of methanol on Al₂O₃ catalyst”, Chin. J. Catal., 25, 403-408 (2004). (in Chinese)
21 Wang, Z.L., Wang, J.F., Diao, J., Jin, Y., “The synergy effect of process coupling for dimethyl ether synthesis in slurry reactors”, Chem. Eng. Tech., 24, 507-511 (2001).
22 Ren, F., Li, H.S., Wang, J.F., Wang, D.Z., “Methanol synthesis from syngas in a slurry reactor”, In: 226th National Meeting of the American Chemical Society, 575 (2003).
23 An, X., F, Ren., Li, J.L., Wang, D.Z., Wang, J.F., “A highly active Cu/ZnO/Al₂O₃ nanofiber catalyst for methanol synthesis through CO₂ and CO hydrogenation”, Chin. J. Catal., 26, 729-735 (2005). (in Chinese)
24 An, X., Li, J.L., Zuo, Y.Z., Zhang, Q., Wang, D.Z., Wang, J.F., “A CuO-ZnO-Al₂O₃ -ZrO₂ fibrous catalyst that is an improved CO₂ hydrogenation to methanol catalyst”, Catal. Lett., 118, 264-269 (2007).
25 Chen, J.H., Li, W.Z., Wang, D.Z., “Electrochemical characterization of carbon nanotubes as electrode in electrochemical double-layer capacitors”, Carbon, 40, 1193-1197 (2002).
26 Wang, D.Z., Wei, F., Wang, J.F., “Method and apparatus to measure gas amounts adsorbed on a powder sample”, US Pat., 6981426 (2006)
27 Faungnawakij, K., Tanaka, Y., Shimoda, N., Fukunaqa, T., Kikuchi, R., Equchi, K., “A comparative study of solid acids in hydrolysis and steam reforming of dimethyl ether”, Appl. Catal. A Gen., 333,114-121 (2007).

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Steam Reforming of Dimethyl Ether over Coupled Catalysts of CuO-ZnO-Al₂O₃-ZrO₂ and Solid-acid Catalyst

Steam Reforming of Dimethyl Ether over Coupled Catalysts of CuO-ZnO-Al₂O₃-ZrO₂ and Solid-acid Catalyst

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