甲烷直接氧化制甲醇研究进展概述

doi:10.1016/S1872-2067(15)61097-X

摘要/Abstract

摘要：

目前，天然气转化为高附加值化工产品的应用越来越受到人们关注.甲烷作为天然气的主要成分，其转化和应用是天然气化工领域的重要研究方向.而甲烷直接氧化制甲醇长久以来一直是研究重点.甲烷直接氧化制甲醇与传统的甲烷二步法间接转化相比，有节能和工艺简化的突出特点.然而，甲醇直接氧化制甲醇过程所面临的主要问题有：（1）甲烷分子的活化能很高，需要苛刻的操作条件才能活化参与反应；（2）反应进行的程度难以控制，生成的甲醇会进一步被氧化生成较多副产物，大大降低甲醇收率.因此，高效活化甲烷分子和抑制甲醇深度氧化是促进该过程工业化的重要研究内容.本文主要论述了非均相、气相均相和液相体系中甲烷直接氧化制甲醇的研究进展.在甲烷非均相氧化过程中，采用过渡金属氧化物作为催化剂在高温条件下催化甲烷部分氧化反应，其中，钼系和铁系催化剂的研究最为广泛.研究表明，MoO₃可作为催化剂的主要活性组分，尤以MoO₃/Ga₂O₃催化剂性能最好，得到甲醇收率最高.在铁系催化剂中，Fe-ZSM-5催化反应的甲醇选择性和收率都相对较高；但是每次反应后催化剂都需要重新活化，这种间歇性操作会增加成本，不利于工业化应用.总之，甲烷的非均相氧化过程存在易形成金属聚集体、催化剂选择性低以及甲醇收率低（5%）等问题，需要深入系统地研究解决.然而，与非均相氧化过程相比，操作较为简单的甲烷气相均相氧化作为目前最有工业前景的过程受到越来越多关注.在此过程中，影响反应的主要因素有反应器、反应条件（反应压力、反应温度和反应时间等）以及添加的介质等.反应器的特殊设计需要考虑的方面有反应产物的分离与转移、反应热的移除以有效提高甲烷的转化率，比如膜反应器对物质的分离作用.反应压力对反应过程的影响较为复杂.基于动力学因素，提高反应压力可以较大幅度地增加甲醇收率，同时最佳反应温度降低，但是，当压力高于8.0MPa时，设备成本消耗大幅增加.另外，研究表明，进料中加入NO_x作为添加介质可以提高甲烷转化率和甲醇选择性，同时降低初始反应温度.与前两个氧化体系相比，液相均匀氧化过程能够获得较高的甲烷转化率与甲醇选择性.但是液相体系中强腐蚀性介质的使用增加了设备成本，阻碍了该过程工业化的应用进程.因此，促进液相体系工业化的关键就是开发绿色高效的催化剂.

关键词: 甲烷, 直接氧化, 甲醇, 多相氧化, 气相均相氧化, 液相催化氧化

Abstract:

This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol (DMTM) with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal oxides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aqueous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the corrosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient catalysts.

Key words: Methane, Direct oxidation, Methanol, Heterogeneous oxidation, Gas-phase homogeneous oxidation, Aqueous catalyzed oxidation

韩宝斋, 杨扬, 许妍妍, U. J. Etim, 乔柯, 许本静, 阎子峰. 甲烷直接氧化制甲醇研究进展概述[J]. 催化学报, 2016, 37(8): 1206-1215.

Baozhai Han, Yang Yang, Yanyan Xu, U. J. Etim, Ke Qiao, Benjing Xu, Zifeng Yan. A review of the direct oxidation of methane to methanol[J]. Chinese Journal of Catalysis, 2016, 37(8): 1206-1215.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(15)61097-X

https://www.cjcatal.com/CN/Y2016/V37/I8/1206

参考文献

[1] V. S. Arutyunov, Direct Methane to Methanol: Foundations and Prospects of the Process, Elsevier, 2014.
[2] V. S. Arutyunov, Stud. Surf. Sci. Catal., 2007, 167, 269-274.
[3] S. Betteridge, C. R. A. Catlow, D. H. Gay, R. W. Grimes, J. S. J. Hargreaves, G. J. Hutchings, R. W. Joyner, Q. A. Pankhurst, S. H. Taylor, Top. Catal., 1994, 1, 103-110.
[4] V. I. Atroshchenko, Z. M. Shchedrinskaya, N. A. Gavrya, J. Appl. Chem., 1965, 38, 643-649.
[5] D. A. Dowden, G. T. Walker, British Patent 1 244 001, 1971.
[6] R. S. Liu, M. Iwamoto, J. H. Lunsford, J. Chem. Soc., Chem. Commun., 1982, 78-79.
[7] H. F. Liu, R. S. Liu, K. Y. Liew, R. E. Johnson, J. H. Lunsford, J. Am. Chem. Soc., 1984, 106, 4117-4121.
[8] T. Sugino, A. Kido, N. Azuma, A. Ueno, Y. Udagawa, J. Catal., 2000, 190, 118-127.
[9] K. J. Zhen, M. M. Khan, C. H. Mak, K. B. Lewis, G. A. Somorjai, J. Catal., 1985, 94, 501-507.
[10] N. D. Spencer, J. Catal., 1988, 109, 187-197.
[11] E. M. Coda, E. Mulhall, R. van Hoek, B. K. Hodnett, Catal. Today, 1989, 4, 383-387.
[12] M. A. Banares, J. L. G. Fierro, J. B. Moffat, J. Catal., 1993, 142, 406-417.
[13] Y. Barbaux, A. R. Elamrani, E. Payen, L. Gengembre, J. P. Bonnelle, B. Grzybowska, Appl. Catal., 1988, 44, 117-132.
[14] S. H. Taylor, J. S. J. Hargreaves, G. J. Hutchings, R. W. Joyner, C. W. Lembacher, Catal. Today, 1998, 42, 217-224.
[15] K. Otsuka, Y. Wang, Appl. Catal. A, 2001, 222, 145-161.
[16] V. A. Durante, D. W. Walker, S. M. Gussow, J. E. Lyons, US Patent 4 918 249, 1990.
[17] J. E. Lyons, P. E. Ellis, V. A. Durante, Stud. Surf. Sci. Catal., 1991, 67, 99-116.
[18] K. Otsuka, M. Hatano, J. Catal., 1987, 108, 252-255.
[19] Y. Wang, K. Otsuka, J. Chem. Soc., Chem. Commun., 1994, 2209-2210.
[20] X. X. Wang, Y. Wang, Q. H. Tang, Q. Guo, Q. H. Zhang, H. L. Wan, J. Catal., 2003, 217, 457-467.
[21] B. Michalkiewicz, Appl. Catal. A, 2004, 277, 147-153.
[22] E. V. Starokon, M. V. Parfenov, S. S. Arzumanov, L. V. Pirutko, A. G. Stepanov, G. I. Panov, J. Catal., 2013, 300, 47-54.
[23] M. V. Parfenov, E. V. Starokon, L. V. Pirutko, G. I. Panov, J. Catal., 2014, 318, 14-21.
[24] V. S. Arutyunov, O. V. Krylov, Russ. Chem. Rev., 2005, 74, 1111-1137.
[25] R. Palkovits, M. Antonietti, P. Kuhn, A. Thomas, F. Schüth, Angew. Chem. Int. Ed., 2009, 48, 6909-6912.
[26] J. H. Edwards, N. R. Foster, Fuel Sci. Technol. Int., 1986, 4, 365-390.
[27] J. W. M. H. Geerts, J. H. B. J. Hoebink, K. van der Wiele, Catal. Today, 1990, 6, 613-620.
[28] J. C. W. Kuo, C. T. Kresge, R. E. Palermo, Catal. Today, 1989, 4, 463-470.
[29] N. R. Foster, Appl. Catal., 1985, 19, 1-11.
[30] H. D. Gesser, N. R. Hunter, C. B. Prakash, Chem. Rev., 1985, 85, 235-244.
[31] M. J. Brown, N. D. Parkyns, Catal. Today, 1991, 8, 305-335.
[32] Q. J. Zhang, D. H He, Q. M. Zhu, J. Nat. Gas Chem., 2003, 12, 81-89.
[33] D. E. Walsh, D. J. Martenak, S. Han, R. E. Palermo, Ind. Eng. Chem. Res., 1992, 31, 1259-1262.
[34] J. W. Chun, R. G. Anthony, Ind. Eng. Chem. Res., 1993, 32, 259-263.
[35] J. W. Chun, R. G. Anthony, Ind. Eng. Chem. Res., 1993, 32, 796-799.
[36] D. W. Rytz, A. Baiker, Ind. Eng. Chem. Res., 1991, 30, 2287-2292.
[37] G. A. Foulds, B. F. Gray, S. A. Miller, G. S. Walker, Ind. Eng. Chem. Res., 1993, 32, 780-787.
[38] Q. J. Zhang, D. H. He, J. L. Li, B. Q. Xu, Y. Liang, Q. M. Zhu, Appl. Catal. A, 2002, 224, 201-207.
[39] X. Zhang, D. H. He, Q. J. Zhang, Q. M. Zhu, Petrochem. Technol., 2003, 32, 195-199.
[40] V. S. Arutyunov, Catal. Today, 2013, 215, 243-250.
[41] G. A. Foulds, B. F. Gray, Fuel Process. Technol., 1995, 42, 129-150.
[42] B. G. Charlton, G. A. Foulds, G. S. Walker, J. C. Jones, B. F. Gray, in: Chemeca 92: The Impact of Government Policy on the Process Industries, Official Conference Proceedings, Parkville, Royal Australian Chemical Institute, 1992, 67-73.
[43] J. W. Chun, R. G. Anthony, Ind. Eng. Chem. Res., 1993, 32, 788-795.
[44] D. J. Thomas, R. Willi, A. Baiker, Ind. Eng. Chem. Res., 1992, 31, 2272-2278.
[45] N. R. Hunter, H. D. Gesser, L. A. Morton, P. S. Yarlagadda, D. P. C. Fung, Appl. Catal., 1990, 57, 45-54.
[46] T. Baldwin, R. Burch, G. Squire, S. Tsang, Appl. Catal., 1991, 74, 137-152.
[47] N. Fukuoka, K. Omata, K. Fujimoto, in: Pacifichem '89, Abstract, Conference Proceedings, 1989, 135, 106-107.
[48] P. S. Yarlagadda, L. A. Morton, N. R. Hunter, H. D. Gesser, Ind. Eng. Chem. Res., 1988, 27, 252-256.
[49] V. S. Arutyunov, V. M. Rudakov, V. I. Savchenko, E. V. Sheverdenkin, O. G. Sheverdenkina, A. Yu. Zheltyakov, Theor. Found. Chem. Eng., 2002, 36, 472-476.
[50] R. S. Burch, G. D. Squire, S. C. Tsang, J. Chem. Soc., Faraday Trans.1, 1989, 85, 3561-3568.
[51] M. J. Foral, Preprints-American Chemical Society, Division of Petroleum Chemistry, 1992, 37, 34-40.
[52] V. S. Arutyunov, V. M. Rudakov, V. I. Savchenko, E. V. Sheverdenkin, Theoret. Found. Chem. Eng., 2005, 39, 487-492.
[53] I. G. Fokin, V. I. Savchenko, V. S. Arutyunov, Russ. J. Phys. Chem. B, 2014, 8, 148-151.
[54] Y. Teng, H. Sakurai, K. Tabata, E. Suzuki, Appl. Catal. A, 2000, 190, 283-289.
[55] T. Li, S. J. Wang, C. S. Yu, Y. C. Ma, K. L. Li, L. W. Lin, Appl. Catal. A, 2011, 398, 150-154.
[56] R. A. Periana, D. J. Taube, E. R. Evitt, D. G. Löffler, P. R. Wentrcek, G. Voss, T. Masuda, Science, 1993, 259, 340-343.
[57] X. Gang, H. Birch, Y. M. Zhu, H. A. Hjuler, N. J. Bjerrum, J. Catal., 2000, 196, 287-292.
[58] R. A. Periana, D. J. Taube, S. Gamble, H. Taube, T. Satoh, H. Fujii, Science, 1998, 280, 560-564.
[59] R. Palkovits, C. von Malotki, M. Baumgarten, K. Müllen, C. Baltes, M. Antonietti, P. Kuhn, J. Weber, A. Thomas, F. Schüth, ChemSusChem, 2010, 3, 277-282.
[60] R. A. Periana, O. Mirinov, D. J. Taube, S. Gamble, Chem. Commun., 2002, 2376-2377.
[61] X. Gang, Y. Zhu, H. Birch, H. A. Hjuler, N. J. Bjerrum, Appl. Catal. A, 2004, 261, 91-98.
[62] K. Cao, [MS Dissertation], Northwest University, Xi’an, 2004.
[63] C. J. Jones, D. Taube, V. R. Ziatdinov, R. A. Periana, R. J. Nielsen, J. Oxgaard, W. A. Goddard, Angew. Chem. Int. Ed., 2004, 43, 4626-4629.
[64] X. C. Zhang, K. Cao, L. Y. Chen, Y. Y. Han, Petrochem. Technol., 2004, 33, 813-815.
[65] G. C. Yin, Z. W. Xi, G. Y. Cao, X. F. Zhang, M. Li, Chin. J. Catal., 1997, 18, 402-405.
[66] L. Y. Chen, B. L. Yang, X. C. Zhang, D. Wu, X. P. Zhang, Chin. J. Catal., 2006, 27, 462-464.
[67] A. Sen, E. Gretz, T. F. Oliver, Z. Z. Jiang, New J. Chem., 1989, 13, 755-760.
[68] M. N. Vargaftik, I. P. Stolyarov, I. I. Moiseev, J. Chem. Soc., Chem. Commun., 1990, 1049-1050.
[69] I. Yamanaka, M. Soma, K. Oisuka, J. Chem. Soc., Chem. Commun., 1995, 2235-2236.
[70] M. Lin, T. Hogan, A. Sen, J. Am. Chem. Soc., 1997, 119, 6048-6053.
[71] E. Gretz, T. F. Oliver, A. Sen, J. Am. Chem. Soc., 1987, 109, 8109-8111.
[72] Z. J. An, X. L. Pan, X. M. Liu, X. W. Han, X. H. Bao, J. Am. Chem. Soc., 2006, 128, 16028-16029.
[73] J. L. Yuan, Y. Wang, C. J. Hao, Catal. Lett., 2013, 143, 610-615.
[74] N. F. Gol’dshleger, M. B. Tyabin, A. E. Shilov, A. A. Shteinman, Russ. J. Phys. Chem., 1969, 43, 1222.
[75] I. Bar-Nahum, A. M. Khenkin, R. Neumann, J. Am. Chem. Soc., 2004, 126, 10236-10237.
[76] A. B. Sorokin, E. V. Kudrik, L. X. Alvarez, P. Afanasiev, J. M. M. Millet, D. Bouchu, Catal. Today, 2010, 157, 149-154.
[77] C. Hammond, M. M. Forde, M. H. Ab Rahim, M. Hasbi, A. Thetford, Q. He, R. L. Jenkins, N. Dimitratos, J. A. Lopez-Sanchez, N. F. Dummer, D. M. Murchy, A. F. Carley, S. H. Taylor, D. J. Willock, E. E. Stangland, J. Kang, H. Hagen, C. J. Kiely, G. T. Hutchings, Angew. Chem. Int. Ed., 2012, 51, 5129-5133.
[78] A. E. Shilov, G. B. Shul'pin, Chem. Rev., 1997, 97, 2879-2932.
[79] G. V. Nizova, G. Süss-Fink, G. B. Shul'Pin, Tetrahedron, 1997, 53, 3603-3614.
[80] C. Li, L. Y. Chen, J. Zhang, T. Lei, P. Lei, Chem. Eng. (China), 2010, 38(7), 58-61.