Perspective on catalyst investigation for reverse water-gas shift reactin（RWGS）

doi:10.16085/j.issn.1000-6613.2016-2074

Abstract

Abstract: CO₂ can be converted into syngas via reverse water-gas shift (RWGS) reaction,followed by the F-T reaction to produce C_xH_y fuels or oxygenated chemicals,which have a significant impact on the environment and the energy structure of the future society and the catalyst plays a key role.The catalyst systems of RWGS reaction are reviewed,especially for the effect of interaction between metal and support,the preparation methods,and the electronic effect of doping elements on RWGS reaction performance of the corresponding catalyst are analyzed.Further,the application of Ce-based catalyst in RWGS reaction was discussed.Optimizing the active component can effectively improve the RWGS reaction performance of the corresponding catalysts for the hydrogenation reduction of CO₂ into syngas,and provide a foundation for the industrialization of RWGS reaction.The differences between noble metal and non-noble metal catalysts are also evaluated from points of the preparation methods,reaction conditions,and RWGS reaction performance.The development of novel catalyst material is the key to the industrial application of the RWGS reaction.

Key words: carbon dioxide, catalyst, syngas, reverse water-gas shift reaction, resource utilization

摘要： CO₂经逆水煤气变换（RWGS）反应制得合成气（CO和H₂），通过费托反应合成C_xH_y燃料和含氧化学品，将对环境与未来能源结构产生重大影响，且催化剂起着决定性作用。本文概述了RWGS反应催化剂体系研究现状，详细介绍了Pt、Pd、Cu、Ni和Fe基等催化剂的RWGS反应性能，尤其是对金属与载体间的相互作用、制备方法和掺杂元素的电子效应等对相应催化剂的RWGS反应性能进行了分析，进而探讨了Ce基催化剂在RWGS反应中的应用。通过催化剂活性组分的优化能有效地调控相应催化剂的RWGS反应性能，实现CO₂有效氢化还原制得合成气，为RWGS反应工业化奠定基础。最后对比总结了贵金属与非贵金属催化剂在制备方法、反应条件及RWGS反应性能间的差异，提出新型催化剂材料开发是RWGS反应工业化应用的关键。

关键词: 二氧化碳, 催化剂, 合成气, 逆水煤气变换, 资源化

CLC Number:

DAI Bican, ZHOU Guilin. Perspective on catalyst investigation for reverse water-gas shift reactin（RWGS）[J]. Chemical Industry and Engineering Progress, 2017, 36(07): 2473-2480.

代必灿, 周桂林. 逆水煤气变换（RWGS）催化剂研究进展[J]. 化工进展, 2017, 36(07): 2473-2480.

References

[1] 邵光印,张玉龙,张征湃,等. 不同硅铝比ZSM-5负载铁基催化剂二氧化碳加氢性能[J]. 化工学报,2017,68(2):670-679. SHAO G Y,ZHANG Y L,ZHANG Z P,et al. CO₂ hydrogenation over Fe catalysts supported on ZSM-5 zeolite with different ratios of Si/Al[J]. CIESC Journal,2017,68(2):670-679.
[2] 刘昌俊,郭秋婷,叶静云,等. 二氧化碳转化催化剂研究进展及相关问题思考[J]. 化工学报,2016,67(1):6-8. LIU C J,GUO Q T,YE J Y,et al. Perspective on catalyst investigation for CO₂ conversion and related issues[J]. CIESC Journal,2016,67(1):6-8.
[3] 巩金龙. CO₂化学转化研究进展概述[J]. 化工学报,2017,68(4):1282-1285. GONG J L. A brief overview on recent progress on chemical conversion of CO₂[J]. CIESC Journal,2017,68(4):1282-1285.
[4] 靳治良,钱玲,吕功煊. 二氧化碳化学-现状及展望[J]. 化学进展,2010,22(6):1102-1115. JIN Z L,QIAN L,LÜ G X. CO₂ chemistry-actuality and expectation[J]. Progress in Chemistry,2010,22(6):1102-1115.
[5] 吴川,张华民,衣宝廉. 化学制氢技术研究进展[J]. 化学进展,2005,17(3):423-429. WU C,ZHANG H M,YI B L. Recent advances in hydrogen generation with chemical methods[J]. Progress in Chemistry,2005,17(3):423-429.
[6] AHMAD H,KAMARUDIN S K,MINGGU L J,et al. Hydrogen from photo-catalytic water splitting process:a review[J]. Renewable and Sustainable Energy Reviews,2015,43:599-610.
[7] ZHOU G L,WU T,XIE H M,et al. Effects of structure on the carbon dioxide methanation performance of Co-based catalysts[J]. International Journal of Hydrogen Energy,2013,38(24):10012-10018.
[8] 崔凯凯,周桂林,谢红梅. 二氧化碳甲烷化催化剂的研究进展[J]. 化工进展,2015,34(3):724-730. CUI K K,ZHOU G L,XIE H M. Research progress in CO₂ methanation catalysts[J]. Chemical Industry and Engineering Progress,2015,34(3):724-730.
[9] ZHOU G L,LIU H R,CUI K K,et al. Role of surface Ni and Ce species of Ni/CeO₂ catalyst in CO₂ methanation[J]. Applied Surface Science,2016,383(15):248-252.
[10] GARBRINO G,RIANI P,MAGISTRI L,et al. A study of the methanation of carbon dioxide on Ni/Al₂O₃ catalysts at atmospheric pressure[J]. International Journal of Hydrogen Energy,2014,39(22):11557-11565.
[11] JOO O S,JUNG K D,MOON I,et al. Carbon dioxide hydrogenation to form methanol via a Reverse-Water-Gas-Shift reaction(the CAMERE Process)[J]. Industrial & Engineering Chemistry Research,1999,38(5):1808-1812.
[12] MARTIN O,MART?N A J,MONDELLI C,et al. Indium oxide as a superior catalyst for methanol synthesis by CO₂ hydrogenation[J]. Angewandte Chemie International Edition,2016,55(21):6261-6265.
[13] OSHIMA K,SHINAGAWA T,NOGAMI Y,et al. Low temperature catalytic reverse water gas shift reaction assisted by an electric field[J]. Catalysis Today,2014,232:27-32.
[14] DAI B C,ZHOU G L,GE S B,et al. CO₂ reverse water-gas shift reaction on mesoporous M-CeO₂ catalysts[J]. The Canadian Journal of Chemical Engineering,2017,95:634-642.
[15] 徐海成,戈亮. 二氧化碳加氢逆水汽变换反应的研究进展[J]. 化工进展,2016,35(10):3180-3190. XU H C,GE L. Progress on the catalytic hydrogenation of CO₂ via reverse water gas shift reaction[J]. Chemical Industry and Engineering Progress,2016,35(10):3180-3190.
[16] 张晶,孙显锋,乔婧,等. 合成气制芳烃研究进展[J]. 化工进展,2013,32(s1):13-15. ZHANG J,SUN X F,QIAO J,et al. Research advancement of syngas to aromatics[J]. Chemical Industry and Engineering Progress,2013,32(s1):13-15.
[17] 陈维苗,丁云杰,薛飞,等. CO加氢制C₂含氧化合物Rh基催化剂中常见助剂的作用[J]. 物理化学学报,2015,31(1):1-10. CHEN W M,DING Y J,XUE F,et al. Role of common promoters in Rh-based catalysts for CO hydrogenation to C₂-oxygenates[J]. Acta Physico-Chimica Sinica,2015,31(1):1-10.
[18] YOSHIHARA J,PARKER S C,SCHAFER A,et al. Methanol synthesis and reverse water-gas shift kinetics over clean polycrystalline copper[J]. Catalysis Letters,1995,31(4):313-324.
[19] GOGUET A,MEUNIER F,BREEN J P,et al. Study of the origin of the deactivation of a Pt/CeO₂ catalyst during reverse water gas shift (RWGS)reaction[J]. Journal of Catalysis,2004,226(2):382-392.
[20] WANG L C,TAHVIDAR KHAZANEH M,WIDMANN D,et al. TAP reactor studies of the oxidizing capability of CO₂ on a Au/CeO₂ catalyst-a first step toward identifying a redox mechanism in the Reverse Water-Gas Shift reaction[J]. Journal of Catalysis,2013,302:20-30.
[21] PETTIGREW D J,TRIMM D L. The effects of rare earth oxides on the reverse water-gas shift reaction on palladium/alumina[J]. Catalysis Letters,1994,28(2):313-319.
[22] KIM S S,LEE H H,HONG S C. The effect of the morphological characteristics of TiO₂ supports on the reverse water-gas shift reaction over Pt/TiO₂ catalysts[J]. Applied Catalysis B:Environmental,2012,119/120:100-108.
[23] MATSUBU J C,ZHANG S,DERITA L,et al. Adsorbate-mediated strongmetal-support interactions in oxide-supported Rh catalysts[J]. Nature Chemistry,2017,9:120-127.
[24] KIM S S,LEE H H,HONG S C. A study on the effect of support's reducibility on the reverse water-gas shift reaction over Pt catalysts[J]. Applied Catalysis A:General,2012,423/424:100-107.
[25] ARANIFARD S,AMMAL S C,HEYDEN A. On the importance of metal-oxide interface sites for the water-gas shift reaction over Pt/CeO₂ catalysts[J]. Journal of Catalysis,2014,309:314-324.
[26] PANAGIOTOPOULOU P,KONDARIDES D L. Effects of alkali promotion of TiO₂ on the chemisorptive properties and water-gas shift activity of supported noble metal catalysts[J]. Journal of Catalysis,2009,267(1):57-66.
[27] KIM S S,PARK K H,HONG S C. A study of the selectivity of the reverse water-gas-shift reaction over Pt/TiO₂ catalysts[J]. Fuel Processing Technology,2013,108:47-54.
[28] CHEN C S,CHENG W H,LIN S S. Enhanced activity and stability of a Cu/SiO₂ catalyst for the reverse water gas shift reaction by an iron promoter[J]. Chemical Communications,2001(18):1770-1771.
[29] CHEN C S,CHENG W H,LIN S S. Study of reverse water gas shift reaction by TPD,TPR and CO hydrogenation over potassium-promoted Cu/SiO₂ catalyst[J]. Applied Catalysis A:General,2003,238(1):55-67.
[30] CHEN C S,CHENG W H,LIN S S. Study of iron-promoted Cu/SiO₂ catalyst on high temperature reverse water gas shift reaction[J]. Applied Catalysis A:General,2004,257(1):97-106.
[31] STONE F S,WALLER D. Cu-ZnO and Cu-ZnO/Al₂O₃ catalysts for the reverse water-gas shift reaction. The effect of the Cu/Zn ratio on precursor characteristics and on the activity of the derived catalysts[J]. Topics in Catalysis,2003,22(3):305-318.
[32] WANG L H,ZHANG S X,LIU Y. Reverse water gas shift reaction over co-precipitated Ni-CeO₂ catalysts[J]. Journal of Rare Earths,2008,26(1):66-70.
[33] WANG L H,LIU H,LIU Y,et al. Influence of preparation method on performance of Ni-CeO₂ catalysts for reverse water-gas shift reaction[J]. Journal of Rare Earths,2013,31(6):559-564.
[34] WANG L H,LIU H,LIU Y,et al. Effect of precipitants on Ni-CeO₂ catalysts prepared by a co-precipitation method for the reverse water-gas shift reaction[J]. Journal of Rare Earths,2013,31(10):969-974.
[35] LU B,KAWAMOTO K. Preparation of monodispersed NiO particles in SBA-15,and its enhanced selectivity for reverse water gas shift reaction[J]. Journal of Environmental Chemical Engineering,2013,1(3):300-309.
[36] LU B,KAWAMOTO K. Preparation of mesoporous CeO₂ and monodispersed NiO particles in CeO₂,and enhanced selectivity of NiO/CeO₂ for reverse water gas shift reaction[J]. Materials Research Bulletin,2014,53:70-78.
[37] SUN F M,YAN C F,WANG Z D,et al. Ni/Ce-Zr-O catalyst for high CO₂ conversion during reverse water gas shift reaction (RWGS)[J]. International Journal of Hydrogen Energy,2015,40(46):15985-15993.
[38] ZONETTI P C,LETICHEVSKY S,GASPAR A B,et al. The Ni_XCe_0.75Zr_0.25-XO₂ solid solution and the RWGS[J]. Applied Catalysis A:General,2014,475:48-54.
[39] KIM D H,HAN S W,YOON H S,et al. Reverse water gas shift reaction catalyzed by Fe nanoparticles with high catalytic activity and stability[J]. Journal of Industrial and Engineering Chemistry,2015,23:67-71.
[40] KHARAJI A G,SHARIATI A,TAKASSI M A. A novel-alumina supported Fe-Mo bimetallic catalyst for reverse water gas shift reaction[J]. Chinese Journal Chemical Engineering,2013,21(9):1007-1014.
[41] PENA M A,FIERRO J L G. Chemical structures and performance of perovskite oxides[J]. Chemical Reviews,2001,101(7):1981-2017.
[42] YAMAZOE N,TERAOKA Y,SEIYAMA T. TPD and XPS study on thermal behavior of absorbed oxygen in La_1-XSr_XCoO₃[J]. Chemistry Letters,1981,11:1767-1770.
[43] DAZA Y A,KENT R A,YUNG M M,et al. Carbon dioxide conversion by reverse water-gas shift chemical looping on perovskite-type oxides[J]. Industrial & Engineering Chemistry Research,2014,53(14):5828-5837.
[44] KIM D H,PARK J L,PARK E J,et al. Dopant effect of barium zirconate-based perovskite-type catalysts for the intermediate-temperature reverse water gas shift reaction[J]. ACS Catalysis,2014,4(9):3117-3122.
[45] 李永强,朱华星. 铈基氧化物用于VOCS催化燃烧的研究进展[J]. 重庆工商大学学报(自然科学版),2016,33(2):1-5. LI Y Q,ZHU H X. Research progress in ceria based oxides for catalytic combustion of volatile organic compounds[J]. Journal Chongqing Technology Business University (Nat Sci Ed),2016,33(2):1-5.
[46] LIU Y J,LI Z F,XU H B,et al. Reverse water-gas shift reaction over ceria nanocube synthesized by hydrothermal method[J]. Catalysis Communications,2016,76:1-6.
[47] 黄仲涛,耿建铭. 工业催化[M]. 2版. 北京:化学工业出版社,2006:85. HUANG Z T,GENG J M. Industrial catalysis[M]. 2nd ed. Beijing:Chemical Industry Press,2006:85.
[48] CHEN C S,CHENG W H,LIN S S. Mechanism of CO formation in reverse water-gas shift reaction over Cu/Al₂O₃ catalyst[J]. Catalysis Letters,2000,68:45-48.