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Acta Phys. Chim. Sin.  2011, Vol. 27 Issue (11): 2651-2658    DOI: 10.3866/PKU.WHXB20111018
CATALYSIS AND SURFACE SCIENCE     
Dimethyl Ether Synthesis from CO2 Hydrogenation over CuO-TiO2-ZrO2/HZSM-5 Catalysts
WANG Song, MAO Dong-Sen, GUO Xiao-Ming, LU Guan-Zhong
Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 200235, P. R. China
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Abstract  A series of CuO-TiO2-ZrO2 mixed oxides with different CuO mass fractions (50%-80%) were prepared by co-precipitation and characterized by X-ray diffraction (XRD), N2 physisorption, temperatureprogrammed reduction of hydrogen (H2-TPR), temperature-programmed desorption of carbon dioxide (CO2-TPD) and hydrogen (H2-TPD), and reactive N2O adsorption techniques. The prepared CuO-TiO2-ZrO2 samples were mixed physically with HZSM-5 zeolite to synthesize dimethyl ether (DME) from CO2 hydrogenation in a fixed bed reactor at 250°C, 3.0 MPa, gas hourly space velocity (GHSV) of 1500 mL·g-1· h-1, and volume ratio of 2.8 for H2 to CO2. We found that the conversion of CO2 increased with an increase in CuO content, reached a maximum at a CuO content of 70% and then decreased. The selectivity of DME increased with an increase in CuO content initially and remained essentially constant when the CuO content was ≥70%. Thus, the yield of DME reached a maximum of 13.2% at 70% CuO content. The productivity of the oxygenated compounds (including methanol and DME) on the CuO-TiO2-ZrO2/HZSM-5 catalysts is closely related to the metallic copper surface area.

Key wordsHydrogenation of CO2      Dimethyl ether      CuO-TiO2-ZrO2 mixed oxide      Zeolite HZSM-5      Bifunctional catalyst     
Received: 09 May 2011      Published: 19 August 2011
MSC2000:  O643  
Fund:  

The project was supported by the Science and Technology Commission of Shanghai Municipality, China (08520513600), Leading Academic Discipline Project of Shanghai Education Committee, China (J51503) and Shanghai Special Fund for Outstanding Young Teachers, China (yyy10078).

Corresponding Authors: MAO Dong-Sen     E-mail: dsmao@sit.edu.cn
Cite this article:

WANG Song, MAO Dong-Sen, GUO Xiao-Ming, LU Guan-Zhong. Dimethyl Ether Synthesis from CO2 Hydrogenation over CuO-TiO2-ZrO2/HZSM-5 Catalysts. Acta Phys. Chim. Sin., 2011, 27(11): 2651-2658.

URL:

http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/10.3866/PKU.WHXB20111018     OR     http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/Y2011/V27/I11/2651

(1) Mao, D. S.;Wang, S.; Lu, G. Z. Petrochem. Technol. 2007, 36, 1172.
[毛东森, 王嵩, 卢冠忠. 石油化工, 2007, 36, 1172.]
(2) Jin, Z. L.; Qian, L.; Lü, G. X. Progress Chem. 2010, 22, 1102.
[靳治良, 钱玲, 吕功煊. 化学进展, 2010, 22,1102.]
(3) Naik, S. P.; Bui, V.; Ryu, T.; Miller, J.D.; Zmierczak,W. Appl. Catal. A-Gen. 2010, 381, 183,
(4) Zhao, Y. Q.; Chen, J. X.; Zhang, J. Y. Chem. React. Eng. Technol. 2007, 23, 456.
[赵彦巧, 陈吉祥, 张继炎. 化学反应工程与工艺, 2007, 23, 456.]
(5) Zhao, Y. Q.; Chen, J. X.; Zhang, J. X.; Zhang, J. Y. J. Fuel Chem. Technol. 2005, 33, 334.
[赵彦巧, 陈吉祥, 张建祥, 张继炎. 燃料化学学报. 2005, 33, 334.]
(6) Arena, F.; Barbera, K.; Italiano,G.; Bonura,G.; Spadaro, L.; Frusteri, F. J. Catal. 2007, 249, 185.  
(7) Arena, F.; Italiano, G.; Barbera, K.; Bonura, G.; Spadaro, L.; Frusteri, F. Catal. Today 2009, 143, 80.  
(8) Liu, X. M.; Yan, Z. F.; Lu, G. Q. Chin. Sci. Bull. 2004, 49, 522.
[刘欣梅, 阎子峰, 逯高清. 科学通报, 2004, 49, 522.]
(9) Liu, X. M.; Lu, G. Q.; Yan, Z. F. Appl. Catal. A- Gen. 2005, 279, 24.
(10) Zhao, Y. P.; Tian, J. Z.; Jin, T. J. Qiqihar Univ. 2006, 22, 1.
[赵云鹏, 田景芝, 荆涛. 齐齐哈尔大学学报. 2006, 22, 1.]
(11) S?oczyński, J.; Grabowski, R.; Olszewski, P.; Koz?owska, A.; Stoch, J.; Lachowska, M.; Skrzypek, J. Appl. Catal. A- Gen. 2006, 310, 127.  
(12) Guo, X. M.; Mao, D. S.;Wang, S.;Wu, G. S.; Lu, G. Z. Catal. Commun. 2009, 10, 166.1
(13) Guo, X. M.; Mao, D. S.; Lu, G. Z.;Wang, S.;Wu, G. S. J. Catal. 2010, 271, 178.  
(14) Ge, Q. J.; Huang, Y. M.; Qiu, F. Y.; Zhang, C.W. J. Nat. Gas Chem. 1999, 8, 280.
(15) Wang, J. Y.; Zeng, C. Y. Petro. Process. Petrochem. 2004, 35, 13.
[王继元, 曾崇余. 石油炼制与化工, 2004, 35, 13.]
(16) Arena, F.; Spadaro, L.; Di Blasi, O.; Bonura, G.; Frusteri, F. Stud. Surf. Sci. Catal. 2004, 147, 385.  
(17) Chen, G. M.;Wang, H.; Gao,W. G.; Zhang, J.;Wei, G. Mater. Rev. 2010, 24, 104.
[陈高明, 王华, 高文桂, 张健, 魏刚. 材料导报, 2010, 24, 104.]
(18) Mao, D. S.; Chen, Q. L.; Lu, G. Z. Appl. Catal. A- Gen. 2003, 244, 273.  
(19) Mao, D. S.; Lu, G. Z.; Chen, Q. L. Chin. J. Catal. 2004, 24, 501.
[毛东森, 卢冠忠, 陈庆龄. 催化学报, 2004, 24, 501.]
(20) Wang, S.; Mao, D. S.; Guo, X. M.; Lu, G. Z. Catal. Commun. 2009, 10, 1367.  
(21) Fujiwara, M.; Ando, H.; Tanaka, M.; Souma, Y. Bull. Chem. Soc. Jpn. 1994, 67, 546.  
(22) Sun, Q.; Zhang, Y. L.; Chen, Y.; Deng, J. F.;Wu, D.; Chen, S. Y. J. Catal. 1997, 167, 92.  
(23) Dubois, J. L.; Sayama, K.; Arakawa, H. Chem. Lett. 1992, 21, 1115.
(24) Ge, Q. J.; Huang, Y. M.; Qiu, F. Y.; Li, S. B. J. Mol. Catal. (China) 1997, 11, 297.
[葛庆杰, 黄友梅, 邱凤炎, 李树本. 分子催化, 1997, 11, 297.]
(25) Li, Z. X.; Feng, Y. L.;Wang, R. J.; Zhang, J. Y.;Wang, Y. J.; Han, S. Chin. J . Catal. 1998, 19, 367
[李增喜, 冯玉龙, 王日杰, 张继炎, 王延吉, 韩森. 催化学报, 1998, 19, 367.]
(26) Deng, S. Y.; Chu,W.; Xu, H. Y.; Shi, L. M.; Huang, L. H. J. Nat. Gas Chem. 2008, 17, 369.  
(27) Chary, K. V. R.; Sagar, G. V.; Naresh, D.; Seela, K. K.; Sridhar, B. J. Phys. Chem. B, 2005, 109, 9437.  
(28) Ding, G. H.; Jiang, X. Y.;Wang, Y. J.; Zheng, X. M. Chin. J. Inorg. Chem. 2004, 20, 805.
[丁光辉, 蒋晓原, 王月娟, 郑小明. 无机化学学报. 2004, 20, 805.]
(29) Batyrev, E. D.; van den Heuvel, J. C.; Beckers, J.; Jansen,W.P. A.; Castricum, H.L. J. Catal. 2005, 229, 136.  
(30) S?oczyński, J.; Grabowski, R.; Koz?owska, A.; Olszewski, P. K.; Stoch, J. Phys. Chem. Chem. Phys. 2003, 5, 463.1.
(31) Yang, Z. Q.; Mao, D. S.; Guo, Q. S.; Gu, L. Acta Phys .-Chim. Sin. 2010, 26, 3278.
[杨志强, 毛东森, 郭强胜, 顾蕾. 物理化学学报, 2010, 26, 3278.]
(32) Yang, Z. Q.; Mao, D. S.;Wu, R. C.; Yu, J.;Wang, Q. Acta Phys . -Chim. Sin. 2011, 27, 1163.
[杨志强, 毛东森, 吴仁春, 俞俊, 王倩. 物理化学学报, 2011, 27, 1163.]
(33) Bando, K. K.; Sayama, K.; Kusama, H.; Okabe, K.; Arakawa, H. Appl. Catal. A- Gen. 1997, 165, 391.  
(34) Arena, F.; Italiano, G.; Barbera, K.; Bordiga, S.; Bonura, G.; Spadaro, L.; Frusteri, F. Appl. Catal. A- Gen. 2008, 350, 16.  
(35) Lin, M. G.; Yang, C.;Wu, G. S.;Wei,W.; Li,W. H.; Shan, Y. K.; Sun, Y. H.; He, M. Y. Chin. J. Catal. 2004, 25, 591.
[林明桂, 杨成, 吴贵升, 魏伟, 李文怀, 单永奎, 孙罕宇, 何鸣元. 催化学报, 2004, 25, 591.]
(36) Bianchi, D.; Gass, J.L.; Khalfallah, M. S.; Teichner, J. Appl. Catal. A- Gen. 1993, 101, 297
(37) Fisher, I. A.; Bell, A.T. J. Catal. 1997, 172, 222.  
(38) Nitta, Y.; Fujimatsu, T.; Okamoto, Y.; Imanaka, T. Catal. Lett. 1993, 17, 157.  
(39) Nitta, Y.; Suwata, O.; Ikeda, Y.; Okamoto, Y.; Imanaka. T. Catal. Lett. 1994, 26, 345.  
(40) Koeppel, R. A.; Baiker, A.;Wokaun, A. Appl. Catal. A- Gen. 1992, 84, 77.  
(41) Nomura, N.; Tagawa, T.; Goto, S. React. Kinet. Catal. Lett. 1998, 63, 21.  
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