温室效应是人类面临的巨大挑战，温室气体的转化利用因而成为广泛研究的热点和难点课题。甲烷二氧化碳重整，即干重整制合成气因为可以同时将两种温室气体（CH4/CO2）转化为可用于清洁能源生产的合成气（H2/CO）而被认为是极具前景的先进技术。此技术目前仍未大规模工业化，其主要瓶颈在于尚未研发出合适的催化剂。过渡金属催化剂因其高活性和相对低廉的成本而被认为最具工业化前景，此前的研究主要集中在镍基催化剂，但是镍基催化剂易因表面积碳和金属烧结而快速失活。近年来，研究者发现钴基催化剂在甲烷二氧化碳重整中也具有良好的催化性能，并进行了初步的研究。本文将对钴基重整催化剂的研究现状进行简要综述。论文首先介绍了催化剂的活性组分、载体、助剂以及制备方法等对钴基催化剂重整性能的影响，接着阐述了钴基催化剂的重整反应机理以及积碳-消碳过程，最后对钴基重整催化剂的设计及未来研究方向进行了展望。
Greenhouse effect has been a pressing challenge for the mankind. The conversion and utilization of greenhouse gases become a difficult research topic with general interest all over the world. In this context, carbon dioxide (CO2) reforming of methane, namely dry reforming has been recognized as an advanced technology with great prospect because it can convert two potent greenhouse gases (CH4/CO2) into valuable synthesis gas (syngas, H2/CO). Commercialization of this technology remains unrealized mainly due to the lack of feasible catalysts. Considering the excellent activity and relatively low cost, transition metal based catalysts are regarded as the most promising candidates. The previous research mainly focuses on Ni-based catalysts. But the Ni-based catalysts are vulnerable to rapid deactivation due to carbon deposition and metal sintering. Recently, Co-based catalysts have been reported to possess excellent catalytic performance. Herein, the progress of Co-based catalysts for CO2 reforming of methane is reviewed. The first section addresses the role of active phases, supports, promoters and synthesis methodologies on catalytic performance. The second section discusses the catalytic mechanism and the formation of coke. The last section proposes the strategies for rational design of improving Co-based reforming catalysts and the research directions of Co-based reforming catalysts in the near future.
Contents
1 Introduction
2 The study of Co-based catalysts
2.1 The role of active phases
2.2 The role of supports
2.3 The role of promoters
2.4 The role of synthesis methodologies
3 Catalytic mechanisms and the formation of coke
3.1 Catalytic mechanisms
3.2 The formation of coke
4 Conclusion and outlook
[1] Wang W, Wang S P, Ma X B, Gong J L. Chem. Soc. Rev., 2011, 40:3703.
[2] Budiman A W, Song S H, Chang T S, Shin C H, Choi M J. Catal. Surv. Asia., 2012, 16:183.
[3] Wang Z J, Zhao Y, Cui L, Du H Y, Yao P, Liu C J. Green Chem., 2007, 9:554.
[4] Fischer F, Tropsch H. Brennstoff. Chem., 1928, 3:39.
[5] Pompeo F, Nichio N N, González M G, Montes M. Catal. Today, 2005, 107/108:856.
[6] Pakhare D, Spivey J. Chem. Soc. Rev., 2014, 43:7813.
[7] Liu C J, Ye J Y, Jiang J J, Pan Y X. ChemCatChem, 2011, 3:529.
[8] Sun J W, Wang S, Guo Y, Li M Z, Zou H K, Wang Z J. Catal. Commun., 2018, 104:53.
[9] Wen S P, Liang M L, Zou J M, Wang S, Zhu X D, Liu L, Wang Z J. J. Mater. Chem. A, 2015, 3:13299.
[10] Wang Z J, Yan Z, Liu C J, Goodman D W. ChemCatChem, 2011, 3:551.
[11] Wang Z J, Skiles S, Yang F, Yan Z, Goodman D W. Catal. Today, 2012, 181:75.
[12] Ruckenstein E, Wang H Y. J. Catal., 2002, 205:289.
[13] Ibrahim A A, Naeem M A, Fakeeha A H, Khan W U, Al-Fatesh A S, Abasaeed A E. Chem. Eng. Technol., 2015, 38:1397.
[14] Özkara-Aydinoglu S, Aksoylu A E. Catal. Commun., 2010, 11:1165.
[15] Mirzaei F, Rezaei M, Meshkani F, Fattah Z. J. Ind. Eng. Chem., 2015, 21:662.
[16] Wang H Y, Ruckenstein E. Appl. Catal. A:Gen., 2001, 209:207.
[17] 黄传敬(Huang C J). 浙江大学博士论文(Doctoral Dissertation of Zhejiang University), 2000.
[18] Fan M S, Abdullah A Z, Bhatia S. Appl. Catal. B:Environ., 2010, 100:365.
[19] Feng T C, Zheng W T, Sun K Q, Xu B Q. Catal. Commun., 2016, 73:54.
[20] Sengupta S, Ray K, Deo G. Int. J. Hydrogen Energy, 2014, 39:11462.
[21] Ferencz Z, Baán K, Oszkó A, Kónya Z, Kecskés T, Erdöhelyi A. Catal. Today, 2014, 228:123.
[22] Itkulova S S, Zhunusova K Z, Zakumbaeva G D. Bull. Korean Chem. Soc., 2005, 26:2017.
[23] San-José-Alonso D, Juan-Juan J, Illán-Gómez M J, Román-Martínez M C. Appl. Catal. A:Gen., 2009, 371:54.
[24] 马淳安(Ma C A). 上海大学博士论文(Doctoral Dissertation of Shanghai University), 2005.
[25] Shao H F, Kugler E L, Ma A W, Dadyburjor D B. Ind. Eng. Chem. Res., 2007, 44:4914.
[26] Shao H F, Kugler E L, Dadyburjor D B, Rykov S A, Chen J J G. Appl. Catal. A:Gen., 2009, 356:18.
[27] Cheng J M, Huang W. Fuel Process. Technol., 2010, 91:185.
[28] 王莉(Wang L), 敖先权(Ao X Q), 王诗瀚(Wang S H). 化学进展(Progress in Chemistry), 2012, 24:1696.
[29] Ruckenstein E, Wang H Y. Appl. Catal. A:Gen., 2000, 204:257.
[30] Abasaeed A E, Al-Fatesh A S, Naeem M A, Ibrahim A A, Fakeeha A H. Int. J. Hydrogen Energy, 2015, 40:6818.
[31] Ayodele B V, Khan M R, Cheng C K. Int. J. Hydrogen Energy, 2016, 41:198.
[32] Ayodele B V, Khan M R, Lam S S, Cheng C K. Int. J. Hydrogen Energy, 2016, 41:4603.
[33] Ayodele B V, Hossain S S, Lam S S, Osazuwa O U, Khan M R, Cheng C K. J. Nat. Gas Sci. Eng., 2016, 34:873.
[34] Zhang X H, Hu R J, Liu Y F, Zhao J W, Hou L N, Yang D, Hao Z M, Su H Q. Int. J. Hydrogen Energy, 2015, 40:10026.
[35] Djinovi Dc' P, Crnivec I G O, Erjavec B, Pintar A. Appl. Catal. B:Environ., 2012, 125:259.
[36] Kresge C, Leonowicz M, Roth W, Vartuli J, Beck J. Nature, 1992, 359:710.
[37] Abdollahifar M, Haghighi M, Sharifi M. Energ. Convers. Manage., 2015, 103:1101.
[38] Estephane J, Aouad S, Hany S, Khoury B E I, Gennequin C, Zakhem H EI, Nakat J EI, Aboukais A, Abi-Aad E. Int. J. Hydrogen Energy, 2015, 40:9201.
[39] Yuan Q, Yin A X, Luo C, Zhang Y W, Duan W T, Liu H C, Yan C H. J. Am. Chem. Soc., 2008, 130:3465.
[40] Liu S G, Guan L X, Li J P, Zhao N, Wei W, Sun Y H. Fuel, 2008, 87:2477.
[41] Xu L L, Zhao H H,Song H L, Chou L J. Int. J. Hydrogen Energy, 2012, 37:7497.
[42] Xu L L, Zhang X, Chen M D, Qi L, Nie D Y, Ma Y H. Int. J. Hydrogen Energy, 2016, 41:17348.
[43] Gennequin C, Safariamin M, Sihhert S, Aboukais A, Abi-Aad E. Catal. Today, 2011, 176:139.
[44] Cai W J, Qian L P, Yue B, Chen X Y, He H Y. Chinese Chem. Lett., 2013, 24:777.
[45] Zhang G J, Du Y N, Xu Y, Zhang Y F. J. Ind. Eng. Chem., 2014, 20:1677.
[46] Zhang G J, Qu J W, Su A T, Zhang Y F, Xu Y. J. Ind. Eng. Chem., 2015, 21:311.
[47] Zhang G J, Hao L X, Jia Y, Du Y N, Zhang Y F. Int. J. Hydrogen Energy, 2015, 40:12868.
[48] Aldashukurova G B, Mironenko A V, Mansurov Z A, Shikin N V, Yashnik S A, Kuznetsov V V, Ismagilov Z R. J. Energy Chem., 2013, 22:811.
[49] Guo Y, Zou J M, Shi X, Rukundo P, Wang Z J. ACS Sustainable Chem. Eng., 2017, 5:2330.
[50] San-José-Alonso D, Illán-Gómez M J, Román-Martínez M C. Catal. Today, 2011, 176:187.
[51] Usman M, Daud W M A W, Abbas H F. Renew. Sust. Energ. Rev., 2015, 45:710.
[52] Ewbank J L, Kovarik L, Kenvin C C, Sievers C. Green Chem., 2014, 16:885.
[53] Ji L, Tang S, Zeng H C, Lin J, Tan K L. Appl. Catal. A:Gen., 2001, 207:247.
[54] Lee J H, You Y W, Ahn H C, Hong J S, Kim S B, Chang T S, Suh J K. J. Ind. Eng. Chem., 2014, 20:284.
[55] Wang S B, Lu G Q. Energy Fuels, 1996,10:896.
[56] Fan M S, Abdullah A Z, Bhatia S. ChemCatChem, 2009, 1:192.
[57] Wang Z Y, Cao X M, Zhu J H, Hu P. J. Catal., 2014, 311:469.
[58] Budiman A W, Song S H, Chang T S, Choi M J. Adv. Powder Technol., 2016, 27:584.
[59] Foo S Y, Cheng C K, Nguyen T H, Adesina A A. Catal. Today, 2011, 164:221.
[60] Zhang J G, Wang H, Dalai A K. Ind. Eng. Res., 2009, 48:677.
[61] 姜洪涛(Jiang H T), 华炜(Hua W), 计建炳(Ji J B).化学进展(Progress in Chemistry), 2013, 25:859.
[62] Gadalla A M, Bower B. Chem. Eng. Sci., 1988, 43:3049.
[63] Goula M A, Lemonidou A A, Efstathiou A M E. J. Catal., 1996, 161:626.
[64] Shamsi A, Baltrus J R, Spivey J J. Appl. Catal. A:Gen. 2005, 293:145.
[65] 路勇(Lu Y), 邓存(Deng C), 丁雪加(Ding X J), 沈师孔(Shen S K). 催化学报(Chinese Journal of Catalysis), 1995, 16:447.
PDF
(941KB)
