Nickel based ethanol steam reforming catalysts: mechanism, deactivation and structure-activity relationship

doi:10.16085/j.issn.1000-6613.2017-0962

Abstract

Abstract: According to the trend of hydrogen utilization, ethanol steam reforming reaction (ESR) have attracted more and more research interest. Nickel based ESR catalyst exhibits great potential for industrial application due to its high activity, selectivity and low cost. Nevertheless, there is still room for enhancing its stability, lowering the reaction temperature and increasing the yield of hydrogen. Comprehensive understanding of the reaction mechanism, deactivation mechanism and activitystructure relationship is necessary for preparing more efficient catalysts. Herein, the research progress of nickel based ESR catalyst has been reviewed. Firstly, new insights into reaction mechanism based on results of in-situ spectroscopy, kinetic analysis and theoretical calculation was introduced. Next, the reason for ESR catalyst deactivation was elucidated. Then we discussed the deactivation, active phase, size effect, promoter effect and bimetallic effect issues. Finally, the progress of novel catalysts arisen with the fundamental researches mentioned above was summarized in brief. Our perspective on the future development of nickel based ESR catalysts were presented. The operando/in-situ characterization methods are believed to bring in new understanding of the reaction mechanism and structure-activity relationship of nickel based catalysts, while the application of novel materials, such as molybdenum carbide, may prompt the catalytic properties of nickel based catalysts.

Key words: hydrogen production, ethanol steam reforming, nickel based catalyst, reaction mechanism, deactivation, bimetallic catalyst, catalyst support, promoter

摘要： 为了应对潜在的氢能利用需求，乙醇水汽重整反应受到了越来越多的关注。镍基催化剂因其高活性、高选择性以及成本优势而极具应用前景，同时在提高催化剂稳定性、降低反应温度、提高氢气收率等方面仍然有进一步发展的空间。更深入认识反应机理、失活机制和催化剂的构效关系是开发高效催化剂的关键。本文对近年来镍基乙醇重整催化剂的研究进展进行了整理总结，首先介绍了通过原位光谱、动力学以及理论计算等手段取得对反应中间物种与反应机理的新认识，分析了催化剂失活的主要原因，并且讨论了镍基催化剂的活性相、尺寸效应、助剂效应，双金属效应等问题，最后简单介绍了得益于基础研究进展的催化剂合成方面的成果，并提出对镍基乙醇水蒸气重整（ESR）剂未来发展的看法：在线/原位表征技术和理论计算将有助于真正理解镍基ESR催化剂的构效关系和反应机理，而新材料，如碳化钼的应用可能在提高催化剂反应性能方面起到作用。

关键词: 制氢, 乙醇水蒸气重整, 镍基催化剂, 反应机理, 失活, 双金属催化剂, 催化剂载体, 助剂

CLC Number:

O643.3

ZHAO Huabo, LI Min, LUO Gang. Nickel based ethanol steam reforming catalysts: mechanism, deactivation and structure-activity relationship[J]. Chemical Industry and Engineering Progress, 2018, 37(02): 419-428.

赵华博, 李民, 罗刚. 镍基乙醇水汽重整催化剂:机理、失活与构效关系[J]. 化工进展, 2018, 37(02): 419-428.

References

[1] 孙道安,李春迎,张伟,等. 典型碳氢化合物水蒸气重整制氢研究进展[J]. 化工进展, 2012, 31(4):801-806. SUN Daoan, LI Chunying, ZHANG Wei, et al. Progress in hydrogen production from the steam reforming of typical hydrocarbons[J]. Chemical Industry and Engineering Progress, 2012, 31(4):801-806
[2] 郭勇,张永光,蔺建民,等. 甘油水相重整制氢研究进展[J]. 化工进展, 2014, 33(1):50-55. GUO Yong, ZHANG Yongguang, LIN Jianmin, et al. Progress in hydrogen production by the aqueous-phase reforming of glycerol[J]. Chemical Industry and Engineering Progress, 2014, 33(1):50-55.
[3] 王东旭,肖显斌,李文艳. 乙酸蒸汽催化重整制氢的研究进展[J]. 化工进展, 2017, 36(5):1658-1665. WANG Dongxu, XIAO Xianbin, LI Wenyan. A review of literatures on catalytic steam reforming of acetic acid for hydrogen production[J]. Chemical Industry and Engineering Progress, 2017, 36(5):1658-1665.
[4] FISHTIK I, ALEXANDER A, DATTA R, et al. A thermodynamic analysis of hydrogen production by steam reforming of ethanol via response reactions[J]. International Journal of Hydrogen Energy, 2000, 25(1):31-45.
[5] BHANDE R S. Significance of temperature on conversion of ethanol for hydrogen production by steam reforming——an experimental study[J]. International Journal of Chemical and Physical Sciences, 2013, 2(s1):25-31.
[6] BHANDE R S, GOIKAR S S. An experimental study:effect of molar ratios on conversion of ethanol to hydrogen by steam reforming[J]. International Journal of Chemical and Physical Sciences, 2013, 2(s1):18-24.
[7] CAVALLARO S. Ethanol steam reforming on Rh/Al₂O₃ catalysts[J]. Energy & Fuels, 2000, 14(6):1195-1199.
[8] BREEN J P, BURCH R, COLEMAN H M. Metal-catalysed steam reforming of ethanol in the production of hydrogen for fuel cell applications[J]. Applied Catalysis B:Environmental, 2002, 39(1):65-74.
[9] ZHANG B, TANG X, LI Y, et al. Steam reforming of bio-ethanol for the production of hydrogen over ceria-supported Co, Ir and Ni catalysts[J]. Catalysis Communications, 2006, 7(6):367-372.
[10] HARYANTO A, FERNANDO S, MURALI N A, et al. Current status of hydrogen production techniques by steam reforming of ethanol:a review[J]. Energy & Fuels, 2005, 19(5):2098-2106.
[11] 刘承伟,石秋杰,李彬. 负载型金属催化剂在乙醇水蒸气重整制氢中的应用[J]. 化工进展, 2008, 27(9):1336-1341. LIU Chengwei, SHI Qiujie, LI Bin. Application of supported metallic catalysts in hydrogen production from steam reforming of ethanol[J]. Chemical Industry and Engineering Progress, 2008, 27(9):1336-1341.
[12] AUPRETRE F, DESCORME C, DUPREZ D. Bio-ethanol catalytic steam reforming over supported metal catalysts[J]. Catalysis Communications, 2002, 3(6):263-267.
[13] 贾英桂,吴洪达,殷宇. 乙醇水蒸气重整制氢反应机理的研究进展[J]. 化工进展, 2012, 31(2):274-282. JIA Yinggui, WU Hongda, YIN Yu. Reaction mechanism research on hydrogen production from ethanol steam reforming[J]. Chemical Industry and Engineering Progress, 2012, 31(2):274-282.
[14] ZENG G, LI Y, OLSBYE U. Kinetic and process study of ethanol steam reforming over Ni/Mg(Al)O catalysts:the initial steps[J]. Catalysis Today, 2016, 259(2):312-322.
[15] FATSIKOSTAS A N, VERYKIOS X E. Reaction network of steam reforming of ethanol over Ni-based catalysts[J]. Journal of Catalysis, 2004, 225(2):439-452.
[16] FRENI S, MONDELLO N, CAVALLARO S, et al. Hydrogen production by steam reforming of ethanol:a two step process[J]. Reaction Kinetics, Mechanisms and Catalysis, 2000, 71(1):143-152.
[17] VINCI A, CHIODO V, PAPAGERIDIS K, et al. Ethanol steam reforming in a two-step process. short-time feasibility tests[J]. Energy & Fuels, 2013, 27(3):1570-1575.
[18] XU W, LIU Z, JOHNSTONPECK A C, et al. steam reforming of ethanol on Ni/CeO₂:reaction pathway and Interaction between Ni and the CeO₂ support[J]. ACS Catalysis, 2013, 3(5):975-984.
[19] VICENTE J, EREÑA J, MONTERO C, et al. Reaction pathway for ethanol steam reforming on a Ni/SiO₂ catalyst including coke formation[J]. International Journal of Hydrogen Energy, 2014, 39(33):18820-18834.
[20] LIMA S M D, SILVA A M D, COSTA L O O D, et al. Evaluation of the performance of Ni/La₂O₃, catalyst prepared from LaNiO₃, perovskite-type oxides for the production of hydrogen through steam reforming and oxidative steam reforming of ethanol[J]. Applied Catalysis A:General, 2010, 377(1/2):181-190.
[21] RESINI C, VENKOV T, HADJⅡVANOV K, et al. An FTIR study of the dispersed Ni species on Ni-YSZ catalysts[J]. Applied Catalysis A:General, 2009, 353(1):137-143.
[22] LIU Z, SENANAYAKE S D, RODRIGUEZ J A. Elucidating the interaction between Ni and CeO_x, in ethanol steam reforming catalysts:a perspective of recent studies over model and powder systems[J]. Applied Catalysis B:Environmental, 2016, 197:184-197.
[23] BARATTINI L, RAMIS G, RESINI C, et al. Reaction path of ethanol and acetic acid steam reforming over Ni-Zn-Al catalysts. Flow reactor studies.[J]. Chemical Engineering Journal, 2009, 153(1/2/3):43-49.
[24] WANG S R, GUO W W, LONG G, et al. Experimental and subsequent mechanism research on the steam reforming of ethanol over a Ni/CeO₂ catalyst[J]. International Journal of Green Energy, 2015, 12(7):694-701.
[25] 刘利平,李静,马晓建. 乙醇水蒸气重整制氢反应机理及动力学研究进展[J]. 天然气化工(C1化学与化工), 2013, 38(1):78-83. LIU Liping, LI Jing, MA Xiaojian. Research status and outlook on mechanism and kinetics of ethanol steam reforming for hydrogen production[J]. Natural Gas Chemistry Industry, 2013, 38(1):78-83.
[26] AKANDE A, ABOUDHEIR A, IDEM R, et al. Kinetic modeling of hydrogen production by the catalytic reforming of crude ethanol over a co-precipitated Ni-Al₂O₃ catalyst in a packed bed tubular reactor[J]. International Journal of Hydrogen Energy, 2006, 31(12):1707-1715.
[27] PATEL M, JINDAL T K, PANT K K. Kinetic study of steam reforming of ethanol on Ni-based ceria-zirconia catalyst[J]. Industrial & Engineering Chemistry Research, 2013, 52(45):15763-15771.
[28] WU Y J, SANTOS J C, PING L, et al. Simplified kinetic model for steam reforming of ethanol on a Ni/Al₂O₃, catalyst[J]. Canadian Journal of Chemical Engineering, 2014, 92(1):116-130.
[29] WU C, WILLIAMS P T. Effect of process conditions on the steam reforming of ethanol with a nano-Ni/SiO₂ catalyst[J]. Environmental Technology, 2012, 33(6):631-638.
[30] GALETTI A E, BARROSO M N, GOMEZ M F, et al. Promotion of Ni/MgAl₂O₄, catalysts with rare earths for the ethanol steam reforming reaction[J]. Catalysis Letters, 2012, 142(12):1461-1469.
[31] SILVA A A A D, COSTA L O O D, MATTOS L V, et al. The study of the performance of Ni-based catalysts obtained from LaNiO₃, perovskite-type oxides synthesized by the combustion method for the production of hydrogen by reforming of ethanol[J]. Catalysis Today, 2013, 213(37):25-32.
[32] ALBERTON A L, SOUZA M M V M, SCHMAL M. Carbon formation and its influence on ethanol steam reforming over Ni/Al₂O₃, catalysts[J]. Catalysis Today, 2007, 123(1/2/3/4):257-264.
[33] VICENTE J, MONTERO C, EREÑA J, et al. Coke deactivation of Ni and Co catalysts in ethanol steam reforming at mild temperatures in a fluidized bed reactor[J]. International Journal of Hydrogen Energy, 2014, 39(24):12586-12596.
[34] MONTERO C, OCHOA A, CASTANO P, et al. Monitoring Ni⁰, and coke evolution during the deactivation of a Ni/La₂O₃-αAl₂O₃, catalyst in ethanol steam reforming in a fluidized bed[J]. Journal of Catalysis, 2015, 331:181-192.
[35] GATES S M, ROSSELL JR J N, YANTES JR J T. Bond activation sequence observed in the chemisorption and surface reaction of ethanol on Ni(111)[J]. Surface Science Letters, 1986, 171(1):111-134.
[36] MARINO F, BARONETTI G, JOBBAGY M, et al. Cu-Ni-K/γ-Al₂O₃ supported catalysts for ethanol steam reforming:formation of hydrotalcite-type compounds as a result of metal-support interaction[J]. Applied Catalysis A:General, 2003, 238(1):41-54.
[37] CHEN L C, LIN S D. Effects of the pretreatment of CuNi/SiO₂, on ethanol steam reforming:influence of bimetal morphology[J]. Applied Catalysis B:Environmental, 2014, s 148/149(17):509-519.
[38] ABELLO S, BOLSHAK E, MONTANE D. Ni-Fe catalysts derived from hydrotalcite-like precursors for hydrogen production by ethanol steam reforming[J]. Applied Catalysis A:General, 2013, 450(2):261-274.
[39] NAGAI M, AKIYAMA M, OKI Y. Carburized cesium-doped Ni/ZrO₂ for efficient hydrogen production and less carbon deposition during ethanol steam reforming[J]. Journal of the Japan Petroleum Institute, 2012, 55(1):67-68.
[40] LIU Z, DUCHON T, WANG H, et al. Mechanistic insights of ethanol steam reforming over Ni-CeO_x(111):the importance of hydroxyl groups for suppressing coke formation[J]. Journal of Physical Chemistry C, 2015, 119(32):18248-18256.
[41] LIU Z, DUCHON T, WANG H, et al. Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni-CeO₂(111) catalysts:an in situ study of C-C and O-H bond scission[J]. Physical Chemistry Chemical Physics, 2016, 18(25):16621-16628.
[42] ZHAO X, LU G. Modulating and controlling active species dispersion over Ni-Co bimetallic catalysts for enhancement of hydrogen production of ethanol steam reforming[J]. International Journal of Hydrogen Energy, 2016, 41(5):3349-3362.
[43] EBIAD M,ABDELHAFIZ D,ELSALAMONY R,et al. Ni supported high surface area CeO₂-ZrO₂ catalysts for hydrogen production from ethanol steam reforming[J]. RSC Advances, 2012, 2(21):8145-8156.
[44] GALETTI A E, GOMEZ M F, ARRUA L A, et al. Ethanol steam reforming over Ni/ZnAl₂O₄-CeO₂. Influence of calcination atmosphere and nature of catalytic precursor[J]. Applied Catalysis A:General, 2011, 408(1/2):78-86.
[45] OSORIO-VARGAS P, FLORES-GONZALEZ N A, NAVARRO R M, et al. Improved stability of Ni/Al₂O₃, catalysts by effect of promoters (La₂O₃, CeO₂) for ethanol steam-reforming reaction[J]. Catalysis Today, 2015, 259:27-38.
[46] CAMPOS C H, OSORIO-VARGAS P, FLORES-GONZALEZ N, et al. Effect of Ni loading on lanthanide(La and Ce) promoted γ-Al₂O₃, catalysts applied to ethanol steam reforming[J]. Catalysis Letters, 2016, 146(2):433-441.
[47] 吴倩,陈豪慧,李佟茗. 稀土金属氧化物在乙醇重整制氢催化剂中的应用[J]. 化工进展, 2008, 27(2):187-189. WU Qian, CHEN Haohui, LI Tongming. Application of rare earth metal in steam reforming of ethanol[J]. Chemical Industry and Engineering Progress, 2008, 27(2):187-189.
[48] LI D, ZENG L, LI X, et al. Ceria-promoted Ni/SBA-15 catalysts for ethanol steam reforming with enhanced activity and resistance to deactivation[J]. Applied Catalysis B:Environmental, 2015, 176/177:532-541.
[49] SENANAYAKE S D, RODRIGUEZ J A, STACCHIOLA D. Electronic metal-support interactions and the production of hydrogen through the water-gas shift reaction and ethanol steam reforming:fundamental studies with well-defined model catalysts[J]. Topics in Catalysis, 2013, 56(15):1488-1498.
[50] MORAWETZ C S, LUDWIG D. In situ and theoretical studies for the dissociation of water on an active Ni/CeO₂, catalyst:importance of strong metal-support interactions for the cleavage of O-H bonds[J]. Angewandte Chemie, 2015, 54(13):3917-3921.
[51] ZHOU G, BARRIO L, AGNOLI S, et al. High activity of Ce_1-xNi_xO_2-y for H₂ production through ethanol steam reforming:tuning catalytic performance through metal-oxide interactions[J]. Angewandte Chemie, 2010, 49(50):9680-9684.
[52] LIU Z, XU W, YAO S, et al. Superior performance of Ni-W-Ce mixed-metal oxide catalysts for ethanol steam reforming:synergistic effects of W-and Ni-dopants[J]. Journal of Catalysis, 2014, 321:90-99.
[53] LAOSIRIPOJANA N, ASSABUMRUNGRAT S. Catalytic steam reforming of ethanol over high surface area CeO₂:The role of CeO₂, as an internal pre-reforming catalyst[J]. Applied Catalysis B:Environmental, 2006, 66(1/2):29-39.
[54] SÁNCHEZ-SÁNCHEZ M C, NAVARRO R M, FIERRO J L G. Ethanol steam reforming over Ni/La-Al₂O₃, catalysts:influence of lanthanum loading[J]. Catalysis Today, 2007, 129(3/4):336-345.
[55] RAMÍREZ-HERNÁNDEZ G Y, VIVEROS-GARCÍA T, FUENTES-RAMÍREZ R, et al. Promoting behavior of yttrium over nickel supported on alumina-yttria catalysts in the ethanol steam reforming reaction[J]. International Journal of Hydrogen Energy, 2016, 41(22):9332-9343.
[56] FRUSTERI F, FRENI S, CHIODO V, et al. Potassium improved stability of Ni/MgO in the steam reforming of ethanol for the production of hydrogen for MCFC[J]. Journal of Power Sources, 2004, 132(1):139-144.
[57] RASS-HANSEN J, CHRISTENSEN C H, SEHESTED J, et al. Renewable hydrogen:carbon formation on Ni and Ru catalysts during ethanol steam-reforming[J]. Green Chemistry, 2007, 9(9):1016-1021.
[58] DENIS A, GRZEGORCZYK W, GAC W, et al. Steam reforming of ethanol over Ni/support catalysts for generation of hydrogen for fuel cell applications[J]. Catalysis Today, 2008, 137(2):453-459.
[59] CHOONG C K S,ZHONG Z,LIN H,et al. Effect of calcium addition on catalytic ethanol steam reforming of Ni/Al₂O₃:Ⅰ.Catalytic stability, electronic properties and coking mechanism[J]. Applied Catalysis A:General, 2011, 407(1/2):145-154.
[60] CHOONG C K S, HUANG L, ZHONG Z, et al. Effect of calcium addition on catalytic ethanol steam reforming of Ni/Al₂O₃:Ⅱ.Acidity/basicity, water adsorption and catalytic activity[J]. Applied Catalysis A:General, 2011, 407(1):155-162.
[61] SONG J H, HAN S J, YOO J, et al. Effect of Sr content on hydrogen production by steam reforming of ethanol over Ni-Sr/Al₂O₃-ZrO₂, xerogel catalysts[J]. Journal of Molecular Catalysis A:Chemical, 2016, 418/419:68-77.
[62] SANCHEZ-SANCHEZ M C, NAVARRO R M, ESPARTERO I, et al. Role of Pt in the activity and stability of PtNi/CeO₂-Al₂O₃ catalysts in ethanol steam reforming for H₂ production[J]. Topics in Catalysis, 2013, 56:1672-1685.
[63] ROGATIS L D, MONTINI T, LORENZUT B, et al. Ni_xCu_y/Al₂O₃ based catalysts for hydrogen production[J]. Energy & Environmental Science, 2008, 1(4):501-509.
[64] LORENZUT B, MONTINI T, ROGATIS L D, et al. Hydrogen production through alcohol steam reforming on Cu/ZnO-based catalysts[J]. Applied Catalysis B:Environmental, 2011, 101(3/4):397-408.
[65] CHEN L C, LIN S D. The ethanol steam reforming over Cu-Ni/SiO₂, catalysts:effect of Cu/Ni ratio[J]. Applied Catalysis B:Environmental, 2011, 106(3/4):639-649.
[66] ANJANEYULU C, COSTA L O O D, RIBEIRO M C, et al. Effect of Zn addition on the performance of Ni/Al₂O₃, catalyst for steam reforming of ethanol[J]. Applied Catalysis A:General, 2016, 519(5):85-98.
[67] CARRERO A, CALLES J A, VIZCAÍNO A J. Hydrogen production by ethanol steam reforming over Cu-Ni/SBA-15 supported catalysts prepared by direct synthesis and impregnation[J]. Applied Catalysis A:General, 2007, 327(1):82-94.
[68] LINDO M, VIZCAÍNO A J, CALLES J A, et al. Ethanol steam reforming on Ni/Al-SBA-15 catalysts:effect of the aluminium content[J]. International Journal of Hydrogen Energy, 2010, 35(11):5895-5901.
[69] LI M, WANG X, LI S, et al. Hydrogen production from ethanol steam reforming over nickel based catalyst derived from Ni/Mg/Al hydrotalcite-like compounds[J]. International Journal of Hydrogen Energy, 2010, 35(13):6699-6708.
[70] GU R, ZENG G, SHAO J, et al. Sustainable H₂, production from ethanol steam reforming over a macro-mesoporous Ni/Mg-Al-O catalytic monolith[J]. Frontiers of Chemical Science and Engineering, 2013, 7(3):270-278.
[71] LIN L, ZHOU W, GAO R, et al. Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts[J]. Nature, 2017, 544(7648):80.