铬助剂对Cu/ZrO2/CNTs-NH2催化剂催化CO2加氢合成甲醇性能的影响

doi:10.3866/PKU.WHXB201403051

Abstract

Abstract:

A series of Cu/ZrO₂/CNTs-NH₂ catalysts with various chromium dopings were prepared using a coprecipitation method for the synthesis of methanol by the hydrogenation of CO₂. The impact of the addition of chromium on the catalytic performance of the Cu/ZrO₂/CNTs-NH₂ catalyst was investigated in a fixed-bed plug flow reactor. When the chromium loading was set to 1% of the total amount of Cu²⁺ and Zr⁴⁺, the methanol yield increased to a maximum of 7.78% (reaction conditions: 3.0 MPa, 260 ℃, V(H₂):V(CO₂):V(N₂)=69:23:8 and gaseous hourly space velocity (GHSV)=3600 mL·h^-1·g^-1). The catalysts were characterized by N₂ physisorption, X-ray diffraction (XRD), temperature-programmed desorption of H₂ (H₂-TPD), X-ray photoelectron spectroscopy (XPS), temperature- programmed desorption of CO₂ (CO₂-TPD), differential thermal analysis (DTA), and scanning electron microscopy (SEM). The results of these analyses indicated that the introduction of chromium reduced the size of the Cu nanoparticles, enhanced the dispersion of the Cu species, inhibited the phase transformation and sintering of ZrO₂, increased the specific surface area, enhanced the amount of CO₂ adsorbed, and promoted the conversion of weakly adsorbed CO₂ species to strongly adsorbed CO₂ species. Taken together, these factors lead to a high methanol yield. However, when the chromium loading was greater than 1%, the amount Cu and Zr on the surface, as well as the size of the Cu nanoparticle reduced considerably, which led to a significant reduction in the adsorption of CO₂ species. This effect also facilitated the formation of strongly adsorbed CO₂ species, leading to lower methanol yields.

Key words: CNTs-NH₂, Chromium, Copper, Zirconia, Methanol synthesis, Carbon dioxide hydrogenation

WANG Guan-Nan, CHEN Li-Min, GUO Yuan-Yuan, FU Ming-Li, WU Jun-Liang, HUANG Bi-Chun, YE Dai-Qi. Effect of Chromium Doping on the Catalytic Behavior of Cu/ZrO₂/CNTs-NH₂ for the Synthesis of Methanol from Carbon Dioxide Hydrogenation[J]. Acta Phys. -Chim. Sin. 2014, 30(5), 923-931. doi: 10.3866/PKU.WHXB201403051

References

(1) Guo, X. M.; Mao, D. S.; Lu, G. Z.; Wang, S.; Wu, G. S. J. Catal. 2010, 271, 178. doi: 10.1016/j.jcat.2010.01.009
(2) Liu, X. M.; Lu, G. Q.; Yan, Z. F.; Beltramini, J. Ind. Eng. Chem. Res. 2003, 42, 6518. doi: 10.1021/ie020979s
(3) Olah, G. A.; Goeppert, A.; Prakash, G. J. Org. Chem. 2009, 74, 487. doi: 10.1021/jo801260f
(4) Guo, X. M.; Mao, D. S.; Lu, G. Z.; Wang, S. Acta Phys. -Chim. Sin. 2012, 28, 170. [郭晓明, 毛东森, 卢冠忠, 王嵩. 物理化学学报, 2012, 28, 170.] doi: 10.3866/PKU.WHXB201228170
(5) Liang, X. L.; Dong, X.; Lin, G. D.; Zhang, H. B. Appl. Catal. B 2009, 88, 315. doi: 10.1016/j.apcatb.2008.11.018
(6) Natesakhawat, S.; Lekse, J.W.; Baltrus, J. P.; Ohodnicki, P. R., Jr.; Howard, B. H.; Deng, X.; Matranga, C. ACS Catalysis 2012, 2, 1667. doi: 10.1021/cs300008g
(7) Guo, X. M.; Mao, D. S.; Lu, G. Z.; Wang, S.; Wu, G. S. J. Mol. Catal. A-Chem. 2011, 345, 60. doi: 10.1016/j.molcata.2011.05.019
(8) Tang, Q. L.; Hong, Q. J.; Liu, Z. P. J. Catal. 2009, 263, 114. doi: 10.1016/j.jcat.2009.01.017
(9) Keskitalo, T. J.; Niemela, M.; Krause, A. Langmuir 2007, 23, 7612. doi: 10.1021/la7009868
(10) Jung, K. T.; Bell, A. T. Catal. Lett. 2002, 80, 63. doi: 10.1023/A:1015326726898
(11) Kilo, M.; Weigel, J.; Wokaun, A.; Koeppel, R. A.; Stoeckli, A.; Baiker, A. J. Mol. Catal. A-Chem. 1997, 126, 169. doi: 10.1016/S1381-1169(97)00109-X
(12) Wang, D. S.; Tan, Y. S.; Han, Y. Z.; Noritatsu, T. Chin. J. Catal. 2008, 29, 63. [王东升, 谭猗生, 韩怡卓, 椿范立. 催化学报, 2008, 29, 63.]
(13) Wang, W. H.; Huang, B. C.; Wang, L. S.; Ye, D. Q. Surf. Coat. Tech. 2011, 205, 4896. doi: 10.1016/j.surfcoat.2011.04.100
(14) Wang, L. S.; Huang, B. C.; Su, Y. X.; Zhou, G. Y.; Wang, K. L.; Luo, H. C.; Ye, D. Q. Chem. Eng. J. 2012, 192, 232. doi: 10.1016/j.cej.2012.04.012
(15) Chen, L. M.; Ma, D.; Zhang, Z.; Guo, Y. Y.; Ye, D. Q.; Huang, B. C. ChemCatChem 2012, 4, 1960.
(16) Chen, L. M.; Ma, D.; Zhang, Z.; Guo, Y. Y.; Ye, D. Q.; Huang, B. C. Catal. Lett. 2012, 142, 975. doi: 10.1007/s10562-012-0850-0
(17) Chen, L. M.; Ma, D.; Bao, X. H. J. Phys. Chem. C 2007, 111, 2229.
(18) Pan, X. L.; Fan, Z. L.; Chen, W.; Ding, Y. J.; Luo, H. Y.; Bao, X. H. Nat. Mater. 2007, 6, 507. doi: 10.1038/nmat1916
(19) Dong, X.; Liang, X. L.; Li, H. Y.; Lin, G. D.; Zhang, P.; Zhang, H. B. Catal. Today 2009, 147, 158. doi: 10.1016/j.cattod.2008.11.025
(20) Zhang, H. B.; Liang, X. L.; Dong, X.; Li, H. Y.; Lin, G. D. Catal. Sur. Asia 2009, 13, 41. doi: 10.1007/s10563-009-9066-8
(21) Sloczynski, J.; Grabowski, R.; Kozlowska, A.; Olszewski, P.; Lachowska, M.; Skrzypek, J.; Stoch, J. Appl. Catal. A-Gen. 2003, 249, 129. doi: 10.1016/S0926-860X(03)00191-1
(22) Pokrovski, K. A.; Rhodes, M. D.; Bell, A. T. J. Catal. 2005, 235, 368. doi: 10.1016/j.jcat.2005.09.002
(23) 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, 孙予罕, 何鸣元. 催化学报, 2004, 25, 591.]
(24) Zhang, L. X.; Zhang, Y. C.; Chen, S. Y. Appl. Catal. A-Gen. 2012, 415, 118.
(25) Saito, M.; Murata, K. Catal. Sur. 2004, 8, 285. doi: 10.1007/s10563-004-9119-y
(26) Alwin, M.; Mathias, P.; Karl, W. Production of Oxygenated Organic Compounds. US Patent 15585591, 1925-10-27.
(27) Kim, D. H.; Cha, J. E. Catal. Lett. 2003, 86, 107. doi: 10.1023/A:1022671327794
(28) Hao, A. X.; Yu, Y.; Chen, H. B.; Mao, C. P.; Wei, S. X.; Yin, Y. S. Acta Phys. -Chim. Sin. 2013, 29, 2047. [郝爱香, 于杨, 陈海波, 毛春鹏, 魏士新, 殷玉圣. 物理化学学报, 2013, 29, 2047.] doi: 10.3866/PKU.WHXB201306211
(29) Esposito, S.; Turco, M.; Bagnasco, G.; Cammarano, C.; Pernice, P.; Aronne, A. Appl. Catal. A-Gen. 2010, 372, 48. doi: 10.1016/j.apcata.2009.10.006
(30) Chen, H. B.; Liao, D.W.; Yu, L. J.; Lin, Y. J.; Yi, J.; Zhang, H. B.; Tsai, K. R. Appl. Surf. Sci. 1999, 147, 85. doi: 10.1016/S0169-4332(99)00081-1
(31) Hoang, D. L.; Dittmar, A.; Radnik, J.; Brzezinka, K.W.; Witke, K. Appl. Catal. A-Gen. 2003, 239, 95. doi: 10.1016/S0926-860X(02)00375-7
(32) Jones, S. D.; Hagelin-Weaver, H. E. Appl. Catal. B-Environ. 2009, 90, 195. doi: 10.1016/j.apcatb.2009.03.013
(33) Avgouropoulos, G.; Ioannides. T.; Matralis, H. Appl. Catal. BEnviron. 2005, 56, 87. doi: 10.1016/j.apcatb.2004.07.017
(34) Avgouropoulos, G.; Ioannides, T. Appl. Catal. A-Gen. 2003, 244, 155. doi: 10.1016/S0926-860X(02)00558-6
(35) Xu, L.Y.; Wang, Q. X.; Liang, D. B.; Wang, X.; Lin, L.W.; Cui, W.; Xu, Y. D. Appl. Catal. A 1998, 173 , 19.
(36) Li, J. T.; Zhang, W. D.; Chen, M. K.; Ou, Z. T. Nat. Gas Chem. Ind. 1998, 23, 14. [李基涛, 张伟德, 陈明口, 区泽棠. 天然气化工, 1998, 23, 14.]
(37) Zhang, L. X. Investigation of Modification of Catalyst CuOZnO-Al2O3 for Methanol Synthesis from CO2 Catalytic Hydrogenation. Ph. D. Dissertation, Dalian University of Technology, Dalian, 2012. [张鲁湘. CO2 催化加氢合成甲醇催化剂CuO-ZnO-Al2O3 改性的研究[D]. 大连: 大连理工大学, 2012.]
(38) Li, M. J.; Yao, Z. C.; Zhang, J.; Ying, P. L.; Xin, Q.; Li, C. Chin. J. Catal. 2003, 5, 861. [李美俊, 冯兆池, 张静, 应品良, 辛勤, 李灿. 催化学报, 2003, 5, 861.]
(39) Li, M. J.; Feng, Z. C.; Ying, P. L.; Xin, Q.; Li, C. Phys. Chem. Chem. Phys. 2003, 5, 5326. doi: 10.1039/b310284j

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Effect of Chromium Doping on the Catalytic Behavior of Cu/ZrO₂/CNTs-NH₂ for the Synthesis of Methanol from Carbon Dioxide Hydrogenation

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Effect of Chromium Doping on the Catalytic Behavior of Cu/ZrO2/CNTs-NH2 for the Synthesis of Methanol from Carbon Dioxide Hydrogenation

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Effect of Chromium Doping on the Catalytic Behavior of Cu/ZrO₂/CNTs-NH₂ for the Synthesis of Methanol from Carbon Dioxide Hydrogenation