储氢介质甲基环己烷研究进展

doi:10.16085/j.issn.1000-6613.2017.02.020

摘要/Abstract

摘要： 甲基环己烷（MCH）作为最佳的液态有机氢化物储氢介质，是甲基环己烷-甲基-氢气（MTH）循环体系中的重要组成部分，但MCH催化脱氢过程所使用催化剂因低温活性欠佳及高温不稳定的问题导致MTH循环无法大规模应用。本文综述了MTH循环系统的应用现状和该系统中MCH脱氢过程催化剂的研究现状。重点概述了单、双金属催化剂设计现状，比较了不同催化剂性能的优劣。此外，还比较了各类催化剂释氢速率以及反应条件和催化反应器结构特点。分析表明，研发出低温高活性或高温高稳定性的催化剂有利于MCH脱氢过程；此外，开发出既能打破反应平衡限制又能强化传质和传热效果以及保持催化剂稳定性的车载催化反应器将会加速MTH循环的社会化应用进程。

关键词: 催化剂, 催化剂载体, 反应器, 储氢, 甲基环己烷

Abstract: As the best liquid organic hydrides medium,methylcyclohexane is very important in the MTH circulation system. But the catalyst used in catalytic dehydrogenation process of MCH has the problems of the poor activity at low temperature and instability at high temperature,which limited the MTH circulation for large-scale application. This paper reviews the applications of MTH system and the research status about different kinds of catalysts applied in the process of the methylcyclohexane dehydrogenation. It also summarizes the design of the single and double metal catalysts and compares the performance of different catalysts. In addition,the hydrogen evolution rate,the reaction conditions and the structure characteristics of the catalyst are compared. Analysis shows that the catalysts with highly active at low temperature or good stability at high temperature is advantageous to the dehydrogenation process of MCH. In addition,the development of catalysts that could break the reaction equilibrium limit,strengthen the mass transfer and heat transfer and maintain the stability will prompt the applications of the MTH system.

Key words: catalyst, catalyst support, reactors, hydrogen storage, methylcyclohexane

中图分类号:

王锋, 杨运泉, 胡拥军, 曾永林. 储氢介质甲基环己烷研究进展[J]. 化工进展, 2017, 36(02): 538-547.

WANG Feng, YANG Yunquan, HU Yongjun, ZENG Yonglin. Advances in the development of methylcyclohexane as a hydrogen storage medium[J]. Chemical Industry and Engineering Progree, 2017, 36(02): 538-547.

参考文献

[1] OKADA Y,SASAKI E,WATANABE E,et al. Development of dehydrogenation catalyst for hydrogen generation in organic chemical hydride method[J]. Int. J. Hydrogen Energy,2006,31(10):1348-1356.
[2] PRADHAN A U,SHUKLA A,PANDE J V,et al. A feasibility analysis of hydrogen delivery system using liquid organic hydrides[J]. Int. J. Hydrogen Energy,2011,36(1):680-688.
[3] NAGATAKE S,HIGO T,OGO S,et al. Dehydrogenation of methylcyclohexane over Pt/TiO₂ catalyst[J]. Catal. Lett.,2016,146(1):54-60.
[4] ICHIKAWA M. Organic liquid carrier for hydrogen storage[J]. Solid-State Hydrogen Storage,2008,30(4):500-531.
[5] SCHERER G W H,NEWSON E. Analysis of the seasonal energy storage of hydrogen in liquid organic hydrides[J]. Int. J. Hydrogen Energy,1998,23(1):19-25.
[6] SCHERER G W H,NEWSON E,WOKAUN A. Economic analysis of the seasonal storage of electricity with liquid organic hydrides[J]. Int. J. Hydrogen Energy,1999,24(12):1157-1169.
[7] DELUCHI M A. Hydrogen vehicles:an evaluation of fuel storage,performance,safety,environmental impacts,and cost[J]. Int. J. Hydrogen Energy,1989,14(2):81-130.
[8] TAUBE M,RIPPIN D W T,CRESSWELL D L,et al. A system of hydrogen-powered vehicles with liquid organic hydrides[J]. Int. J. Hydrogen Energy,1983,8(3):213-225.
[9] TAUBE M,RIPPIN D,KNECHT W,et al. A prototype truck powered by hydrogen from organic liquid hydrides[J]. Int. J. Hydrogen Energy,1985,10(9):595-599.
[10] GRUNENFELDER N F,SCHUCAN T H. Seasonal storage of hydrogen in liquid organic hydrides:description of the second prototype vehicle[J]. Int. J. Hydrogen Energy,1989,14(8):579-586.
[11] KARIYA N,FUKUOKA A,ICHIKAWA M. Efficient evolution of hydrogen from liquid cycloalkanes over Pt-containing catalysts supported on active carbons under "wet-dry multiphase conditions"[J]. Appl. Catal:A,2002,233(1/2):91-102.
[12] KLVANA D,TOUZANI A,CHAOUKI J,et al. Dehydrogenation of methylcyclohexane in a reactor coupled to a hydrogen engine[J]. Int. J. Hydrogen Energy,1991,16(1):55-60.
[13] NEWSON E,HAUETER T,HOTTINGER P,et al. Seasonal storage of hydrogen in stationary systems with liquid organic hydrides[J]. Int. J. Hydrogen Energy,1998,23(10):905-909.
[14] BINIWALE R B,RAYALU S,DEVOTTA S,et al. Chemical hydrides:a solution to high capacity hydrogen storage and supply[J]. Int. J. Hydrogen Energy,2008,33(1):360-365.
[15] RAHIMPOUR M R,VAKILI R,POURAZADI E,et al. Enhancement of hydrogen production via coupling of MCH dehydrogenation reaction and methanol synthesis process by using thermally coupled heat exchanger reactor[J]. Int. J. Hydrogen Energy,2011,36(5):3371-3383.
[16] SHUKLA A A,GOSAVI P V,PANDE J V,et al. Efficient hydrogen supply through catalytic dehydrogenation of methylcyclohexane over Pt/metal oxide catalysts[J]. Int. J. Hydrogen Energy,2010,35(9):4020-4026.
[17] SHUKLA A,KARMAKAR S,BINIWALE R B. Hydrogen delivery through liquid organic hydrides:considerations for a potential technology[J]. Int. J. Hydrogen Energy,2012,37(4):3719-3726.
[18] GRETZ J,BASELT J P,ULLMANN O,et al. The 100 MW euro-Quebec hydro-hydrogen pilot project[J]. Int. J. Hydrogen Energy,1990,15(6):419-424.
[19] GRETZ J,DROLET B,KLUYSKENS D,et al. Status of the hydro-hydrogen pilot project (EQHHPP)[J]. Int. J. Hydrogen Energy,1994,19(2):169-174.
[20] 王锋,杨运泉,王威燕,等. 芳烃储氢技术研究进展[J]. 化工进展,2010,29(10):1877-1884. WANG F,YANG Y Q,WANG W Y,et al. Progress in hydrogen chemical storage technologies with aromatics[J]. Chemical Industry and Engineering Progress,2010,29(10):1877-1884.
[21] ZHANG C,LIANG X,LIU S. Hydrogen production by catalytic dehydrogenation of methylcyclohexane over Pt catalysts supported on pyrolytic waste tire char[J]. Int. J. Hydrogen Energy,2011,36(15):8902-8907.
[22] WANG Y,SHAH N,HUMAN G.Pure hydrogen production by partial dehydrogenation of cyclohexane and methylcyclohexane over nanotube-supported Pt and Pd catalysts[J]. Energy Fuels,2004,18(5):1429-1433.
[23] PHAM D T,TETSUYA S,MASAHIRO M. Continuous hydrogen evolution from cyclohexanes over platinum catalysts supported on activated carbon fibers[J]. Fuel Process Technol.,2008,89(4):415-418.
[24] CROMWELL D K,VASUDEVAN P T,PAWELEC B,et al. Enhanced methylcyclohexane dehydrogenation to toluene over Ir/USY catalyst[J]. Catal. Today,2016,259(1):119-129.
[25] Li X Y,Ma D,Bao X H. Dispersion of Pt catalysts supported on activated carbon and their catalytic performance in methyl cyclohexane dehydrogenation[J]. Chin. J. Catal.,2008,29(3):259-263.
[26] SAITO A,ARAMAKI K,HODOSHIMA S. Efficient hydrogen generation from organic chemical hydrides by using catalytic reactor on the basis of superheated liquid-film concept[J]. Chem. Eng. Sci.,2008,63(20):4935-4941.
[27] ALI J K,NEWSON E J,RIPPIN D W T. Exceeding equilibrium conversion with a catalytic membrane reactor for the dehydrogenation of methylcyclohexane[J]. Chem. Eng. Sci.,1994,49(13):2129-2134.
[28] TAUBE P,TAUBE M A. Liquid organic carrier of H₂ as a fuel for automobiles[J]. Adv. Hydrogen Energy,1981,2:1077-1083.
[29] KLVANA D,CHAOUKI J,KUSOHORSKY D,et al. Catalytic storage of hydrogen:hydrogenation of toluene over a nickel/silica aerogel catalyst in integral flow conditions[J]. Appl. Catal.,1988,42(1):121-130.
[30] GRÜNENFELDER N F,SCHUCAN T H. Seasonal storage of hydrogen in liquid organic hydrides:description of the second prototype vehicle[J]. Int. J. Hydrogen Energy,1989,14(8):579-586.
[31] YOLCULAR S,OLGUN O. Ni/Al₂O₃ catalysts and their activity in dehydrogenation of methylcyclohexane for hydrogen production[J]. Catal. Today,2008,138(3/4):198-202.
[32] 陈卓,杨运泉,包建国,等. 氢能载体甲基环己烷在Ni/γ-Al₂O₃上的脱氢反应[J]. 化工进展,2010,29(3):484-489. CHEN Z,YANG Y Q,BAO J G,et al. Catalytic performance of Ni/γ-Al₂O₃ for hydrogen carrier methylcyclohexane dehydrogenation[J]. Chemical Industry and Engineering Progress,2010,29(3):484-489.
[33] YOSHIMI O,EIJI S,WATANABE E,et al. Development of dehydrogenation catalyst for hydrogen generation in organic chemical hydride method[J]. Int. J. Hydrogen Energy,2006,31(10):1348-1356.
[34] JOUTHIMURUGESAN K,BHATIA S,SRIVASTAVA R D. Kinetics of dehydrogenation of methylcyclohexane over a platinum rhenium alumina catalyst in the presence of added hydrogen[J]. Ind. Eng. Chem. Fundamen,1985,24(4):433-438.
[35] COUGHLIN R W,KAWAKAMI K,HASAN A. Activity,yield patterns,and coking behavior of Pt and Pt-Re catalysts during dehydrogenation of methylcyclohexane:Ⅰ. In the absence of sulfur[J]. J. Catal.,1984,88(1):150-162.
[36] 王锋,杨运泉,王威燕. Ni-Pt/γ-Al₂O₃催化剂用于甲基环己烷催化脱氢的研究[J]. 燃料化学学报,2012,40(9):1128-1134. WANG F,YANG Y Q,WANG W Y. Catalytic performance of Ni-Pt/γ-Al₂O₃ in methylcyclohexane dehydrogenation[J]. Journal of Fuel Chemistry and Technology,2012,40(9):1128-1134.
[37] SHUKLA A A,GOSAVI P V,PANDE J V,et al. Efficient hydrogen supply through catalytic dehydrogenation of methylcyclohexane over Pt/metal oxide catalysts[J]. Int. J. Hydrogen Energy,2012,35(9):4020-4026.
[38] 陈进富,陆绍信,朱亚杰. K₂O对Pt-Sn/Al₂O₃催化剂表面酸性及MCH脱氢稳定性的影响[J]. 燃料化学学报,1998,26(6):543-547. CHEN J F,LU SH X,ZHU Y J. Influences of K₂O on acidity and MCH dehydrogenation stability of Pt-Sn/Al₂O₃ catalyst[J]. Journal of Fuel Chemistry and Technology,1998,26(6):543-547.
[39] 陈进富,俞英,蔡卫权. Li₂O对Pt-Sn/Al₂O₃催化剂表面酸性及MCH脱氢稳定性的影响[J]. 太阳能学报,2002,23(6):782-785. CHEN J F,YU Y,CAI W Q. Influences of Li₂O on acidity and MCH dehydrogenation performance of Pt-Sn/γ-Al₂O₃ catalyst[J]. Acta Energiae Solaris Sinic,2002,23(6):782-785.
[40] 苏君雅,丁梅,杨青. 用于脱氢反应的新型覆炭镍催化剂[J]. 石油化工,1996,25(6):391-395. SU J Y,DING M,YANG Q. Carbon-covered ni catalysts for dehydrogenation[J]. Petrochemical Technology,1996,25(6):391-395.
[41] 杨继涛,郝雪松,苏君雅,等. 覆炭载体Pt-Sn催化剂脱氢活性及抗结焦性能的研究[J]. 石油化工,2002,31(12):955-957. YANG J T,HAO X S,SU J Y,et al. Dehydrogenation activity and anti-coking performance of Pt-Sn catalyst supported on carbon covered alumina[J]. Petrochemical Technology,2002,31(12):955-957.
[42] 杨继涛,黄亚茹,苏君雅,等. 氧化铝覆炭载体的制备及抗结焦性能考察[J].石油大学学报(自然科学版),2003,27(2):98-104. YANG J T,HUANG Y R,SU J Y,et al. Preparation and anti-coking capability of carbon-covered alumina carrier[J]. Journal of the University of Petroleum,China(Edition of Natural Science),2003,27(2):98-104.
[43] 王锋,杨运泉,胡拥军,等. Ni-Cu/CCA用于甲基环己烷脱氢性能研究[J]. 现代化工,2015,35(10):66-70. WANG F,YANG Y Q,HU Y J,et al. Preparation and catalytic performance of Ni-Cu/CCA catalyst[J]. Modern Chemical Industry,2015,35(10):66-70.
[44] 贺恒,杨晨熹,欧阳键,等. Ni-Cu/γ-Al₂O₃催化剂的制备及其脱氢反应研究[J]. 精细化工,2011,28(7):675-684. HE H,YANG CH X,OU Y J,et al.Reparation of catalyst Ni-Cu/γ-Al₂O₃ and its research of dehydrogenation reaction[J]. Fine Chemicals,2011,28(7):675-684.
[45] KARIYA N,FUKUOKA A,UTAGAWA T,et al. Efficient hydrogen production using cyclohexane and decalin by pulse-spray mode reactor with Pt catalysts[J]. Appl. Catal. A:Gen.,2003,247(2):247-259.
[46] SHUKLA A,PANDE J V,BINIWALE R B. Dehydrogenation of methylcyclohexane over Pt/V₂O₅ and Pt/Y₂O₃ for hydrogen delivery applications[J]. Int. J. Hydrogen Energy,2012,37(4):3350-3357.
[47] ITOH N,WATANABE S,KAWASOE K,et al. A membrane reactor for hydrogen storage and transport system using cyclohexane-methylcyclohexane mixtures[J]. Desalination,2008,234(1/2/3):261-269.
[48] HODOSHIMA S,HIROSHI A,YASUKAZU S. Liquid-film-type catalytic decalin dehydrogeno-aromatization for long-term storage and long-distance transportation of hydrogen[J]. Int. J. Hydrogen Energy,2003,28(2):197-204.
[49] 朱刚利,杨伯伦. 液体有机氢化物储氢研究进展[J]. 化学进展,2009,21(12):2760-2770. ZHU G L,YANG B L. Hydrogen storage using liquid organic hydrides[J]. Progress in Chemistry,2009,21(12):2760-2770.
[50] SULTAN O,SHAW H. Study of automotive storage of hydrogen using recyclable liquid chemical carriers[EB/OL].[1975-06-01]. http://www.osti.gov/energycitations/product.biblio.jsp?osti_id=5000657.
[51] 姜召,徐杰,方涛. 新型有机液体储氢技术现状与展望[J]. 化工进展,2012,31(s1):315-322. JIANG ZH,XU J,FANG T. Current situation and prospect for hydrogen storage technology with new organic liqiud[J]. Chemical Industry and Engineering Progress,2012,31(s1):315-322.
[52] 闫云飞,张力,李丽仙,等. 膜催化反应器及其制氢技术的研究进展[J]. 无机材料学报,2011,26(12):1233-1242. YAN Y F,ZHANG L,LI L X,et al. Progress in catalytic membrane reactors for high purity hydrogen production[J]. Journal of Inorganic Materials,2011,26(12):1233-1242.
[53] ITOH N,TAMURA E,HARA S,et al. Hydrogen recovery from cyclohexane as a chemical hydrogen carrier using a palladium membrane reactor[J]. Catal. Today,2003,82(1/2/3/4):119-125.
[54] JEONG B H,SOTOW K I,KUSAKABE K. Catalytic dehydrogenation of cyclohexane in an FAU-type zeolite membrane reactor[J]. J. Membr. Sci.,2003,224(1):151-158.
[55] 陈雅萍,李永红. 纳米分子筛膜的研究进展[J]. 化工进展,2004,23(6):615-623. CEHN Y P,LI Y H. Development of studies on nano-zeolite membranes[J]. Chemical Industry and Engineering Progress,2004,23(6):615-623.
[56] BINIWALE R B,ICHIKAWA M. Thermal imaging of catalyst surface during catalytic dehydrogenation of cyclohexane under spray-pulsed conditions[J]. Chem. Eng. Sci.,2007,62(24):7370-7377.
[57] BINIWALE R B,KARIYA N,YAMASHIRO H,et al. Heat transfer and thermographic analysis of catalyst surface during multiphase phenomena under spray-pulsed conditions for dehydrogenation of cyclohexane over Pt catalysts[J]. J. Phys. Chem. B,2006,110(7):3189-3196.
[58] BINIWALE R B,MIZUNO A,ICHIKAWA M. Hydrogen production by reforming of iso-octane using spray-pulsed injection and effect of non-thermal plasma[J]. Appl. Catal.:A,2004,276(1/2):169-177.