收稿日期: 2024-08-09
网络出版日期: 2024-11-27
基金资助
中海油CCUS重大专项二氧化碳制碳中性航空煤油技术研究项目(KJGG-2022-12-CCUS-030402)
Research progress of CO2 conversion via Reverse Water-Gas Shift reaction
Received date: 2024-08-09
Online published: 2024-11-27
逆水煤气变换（RWGS）反应，通过催化二氧化碳与氢气的反应，成为生成甲醇、低碳烯烃、芳烃、汽油等高附加值化学品和燃料的关键步骤。深入剖析了RWGS反应的两大机理：氧化还原机理和中间体机理。同时，对近年来RWGS反应的研究进展进行了详细综述，对应用于该反应的催化剂进行了系统的分类、分析和总结。这些催化剂涵盖了负载型金属催化剂、氧化物催化剂（混合氧化物、尖晶石和钙钛矿）及碳化物催化剂。此外，还对RWGS的工业应用进行了分析，并对RWGS反应的发展进行了展望。RWGS可耦合石脑油脱氢芳构化技术、乙苯脱氢制备苯乙烯技术、低碳烷烃脱氢制烯烃技术、二氧化碳捕集技术及合成电子燃料技术等实现二氧化碳资源化利用。这不仅为开发制备新型RWGS反应催化剂提供了理论依据和指导，也为未来RWGS反应的应用场景提供了可行的思路和参考。
侯章贵 , 吴冲冲 , 张斯然 . 二氧化碳逆水煤气变换的研究进展[J]. 无机盐工业, 2024 , 56(11) : 105 -115 . DOI: 10.19964/j.issn.1006-4990.2024-0445
The Reverse Water-Gas Shift（RWGS） reaction，facilitated by the catalytic reaction between carbon dioxide and hydrogen，has become a crucial step in the production of high-value chemicals and fuels such as methanol，low-carbon olefins，aromatics，and gasoline.This review presents an in-depth analysis of the two primary mechanisms of the RWGS reaction：the redox mechanism and the intermediate mechanism.Additionally，recent advancements in RWGS research were comprehensively reviewed，the catalysts employed in this reaction were systematically categorized，analyzed，and summarized.These catalysts encompassed supported metal catalysts，oxide catalysts（including mixed oxides，spinels，and perovskites），and carbide catalysts.Moreover，the industrial applications of the RWGS reaction was analyzed and its future development was prospected.RWGS reaction could serve as an efficient method for integrating technologies like naphtha dehydroaromatization，ethylbenzene dehydrogenation for styrene production，low-carbon alkane dehydrogenation for olefin production，carbon dioxide capture，and synthetic electronic fuel production to realize efficient utilization of CO2.It not only provided theoretical basis and guidance for developing new RWGS reaction catalysts but also offered feasible ideas and references for the future application scenarios of the RWGS reaction.
Key words： Reverse Water-Gas Shift; catalysts; reaction mechanism; CO2
| 1 | 王挺，章文文，毛庆，等.二氧化碳电还原制乙醇催化体系与材料研究进展［J］.无机盐工业，2024，56（7）：1-10，68. |
| WANG Ting， ZHANG Wenwen， MAO Qing，et al.Research progress of catalytic system and materials for electrocatalytic reduction of carbon dioxide to ethanol［J］.Inorganic Chemicals Industry，2024，56（7）：1-10，68. | |
| 2 | WU Qing， WU Chongchong.Mechanism insights on single-atom catalysts for CO2 conversion［J］.Journal of Materials Chemistry A，2023，11（10）：4876-4906. |
| 3 | GONZáLEZ-CASTA?O M， DORNEANU B， ARELLANO-GARCíA H.The reverse water gas shift reaction：A process systems engineering perspective［J］.Reaction Chemistry & Engineering，2021，6（6）：954-976. |
| 4 | WANG Huilin， BOOTHARAJU M S， KIM J H，et al.Synergistic interactions of neighboring platinum and iron atoms enhance reverse water-gas shift reaction performance［J］.Journal of the American Chemical Society，2023，145（4）：2264-2270. |
| 5 | HOU Hao， HOU Luman， YU Qiang，et al.Electroplating sludge-derived multiple-metal-doped spinel with superior CO selectivity in reverse water-gas-shift reaction［J］.ACS Sustainable Chemistry & Engineering，2022，10（6）：2214-2223. |
| 6 | KHOSHOOEI M A， WANG Xijun， VITALE G，et al.An active，stable cubic molybdenum carbide catalyst for the high-temperature reverse water-gas shift reaction［J］.Science，2024，384（6695）：540-546. |
| 7 | 王晓月，张伟敏，姚正阳，等.逆水煤气变换反应研究进展［J］.化工进展，2023，42（3）：1583-1594. |
| WANG Xiaoyue， ZHANG Weimin， YAO Zhengyang，et al.Research progress of reverse water gas shift reaction［J］.Chemical Industry and Engineering Progress，2023，42（3）：1583-1594. | |
| 8 | PANAGIOTOPOULOU P.Hydrogenation of CO2 over supported noble metal catalysts［J］.Applied Catalysis A：General，2017，542：63-70. |
| 9 | TRIVI?O M L T， ARRIOLA N C， KANG Y S，et al.Transforming CO2 to valuable feedstocks：Emerging catalytic and technological advances for the reverse water gas shift reaction［J］.Chemical Engineering Journal，2024，487：150369. |
| 10 | WANG Luhui， ZHANG Shaoxing， LIU Yuan.Reverse water gas shift reaction over co-precipitated Ni-CeO2 catalysts［J］.Journal of Rare Earths，2008，26（1）：66-70. |
| 11 | CHEN Xiaodong， CHEN Ya， SONG Chunyu，et al.Recent advances in supported metal catalysts and oxide catalysts for the reverse water-gas shift reaction［J］.Frontiers in Chemistry，2020，8：709. |
| 12 | ZHAO Zhiying， WANG Mingzhi， MA Peijie，et al.Atomically dispersed Pt/CeO2 catalyst with superior CO selectivity in reverse water gas shift reaction［J］.Applied Catalysis B：Environmental，2021，291：120101. |
| 13 | 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. |
| 14 | KOBAYASHI D， KOBAYASHI H， KUSADA K，et al.Boosting reverse water-gas shift reaction activity of Pt nanoparticles through light doping of W［J］.Journal of Materials Chemistry A，2021，9（28）：15613-15617. |
| 15 | ZHANG Yudong， LIANG Long， CHEN Ziyang，et al.Highly efficient Cu/CeO2-hollow nanospheres catalyst for the reverse water-gas shift reaction：Investigation on the role of oxygen vacancies through in situ UV-Raman and DRIFTS［J］.Applied Surface Science，2020，516：146035. |
| 16 | PRICE C A H， PASTOR-PEREZ L， REINA T R，et al.Yolk-Shell structured NiCo@SiO2 nanoreactor for CO2 upgrading via reverse water-gas shift reaction［J］.Catalysis Today，2022，383：358-367. |
| 17 | HAMEED G， GOKSU A， MERKOURI L P，et al.Experimental optimization of Ni/P atomic ratio for nickel phosphide catalysts in reverse water-gas shift［J］.Journal of CO2 Utilization，2023，77：102606. |
| 18 | LI Mo， PHAM T H MY，KO Y，et al.Support-dependent Cu-In bimetallic catalysts for tailoring the activity of reverse water gas shift reaction［J］.ACS Sustainable Chemistry & Engineering，2022，10（4）：1524-1535. |
| 19 | KHARAJI A G， SHARIATI A， OSTADI M.Development of Ni-Mo/Al2O3 catalyst for reverse water gas shift（RWGS） reaction［J］.Journal of Nanoscience and Nanotechnology，2014，14（9）：6841-6847. |
| 20 | WANG Luhui， LIU Hui， LIU Yuan，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. |
| 21 | PANARITIS C， EDAKE M， COUILLARD M，et al.Insight towards the role of ceria-based supports for reverse water gas shift reaction over RuFe nanoparticles［J］.Journal of CO2 Utilization，2018，26：350-358. |
| 22 | TORRES-SEMPERE G， GONZáLEZ-ARIAS J， PENKOVA A，et al.CO2 conversion via low-temperature RWGS enabled by multicomponent catalysts：Could transition metals outperform Pt？［J］.Topics in Catalysis，2024.Doi：10.1007/s11244-024-01935-7. |
| 23 | ZONETTI P C， LETICHEVSKY S， GASPAR A B，et al.The Ni x Ce0.75Zr0.25- x O2 solid solution and the RWGS［J］.Applied Catalysis A：General，2014，475：48-54. |
| 24 | SHEN Haidong， DONG Yujuan， YANG Shaowei，et al.Identifying the roles of Ce3+-OH and Ce-H in the reverse water-gas shift reaction over highly active Ni-doped CeO2 catalyst［J］.Nano Research，2022，15（7）：5831-5841. |
| 25 | GU Mengwei， DAI Sheng， QIU Runfa，et al.Structure-activity relationships of copper- and potassium-modified iron oxide catalysts during reverse water-gas shift reaction［J］.ACS Catalysis，2021，11（20）：12609-12619. |
| 26 | DAI Hui， ZHANG Anhang， XIONG Siqi，et al.The catalytic performance of Ga2O3-CeO2 composite oxides over reverse water gas shift reaction［J］.ChemCatChem，2022，14（6）：e202200049. |
| 27 | KANG Hefei， LIU Yajie， LU Ye，et al.Exploring the sustained release catalysis of CuAl2O4 spinel for highly effective CO2 conversion to CO［J］.Journal of Catalysis，2024，432：115427. |
| 28 | 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. |
| 29 | MATSUO H， KOBAYASHI M， NANIWA S，et al.Hydrogenation of CO2 over Mn-substituted SrTiO3 based on the reverse mars-van krevelen mechanism［J］.The Journal of Physical Chemistry C，2023，127（19）：8946-8952. |
| 30 | LE SACHé E， PASTOR-PéREZ L， HAYCOCK B J，et al.Switchable catalysts for chemical CO2 recycling：A step forward in the methanation and reverse water-gas shift reactions［J］.ACS Sustainable Chemistry & Engineering，2020，8（11）：4614-4622. |
| 31 | WANG Wei， ZHANG Yao， WANG Zongyuan，et al.Reverse water gas shift over In2O3-CeO2 catalysts［J］.Catalysis Today，2016，259：402-408. |
| 32 | SUN Fengman， YAN Changfeng， WANG Zhida，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. |
| 33 | SPENNATI E， GARBARINO G， RIANI P，et al.Alumina-supported cobalt catalysts in the hydrogenation of CO2 at atmospheric pressure［J］.International Journal of Hydrogen Energy，2023，48（64）：25006-25015. |
| 34 | SUN Shuzhuang， ZHANG Chen， CHEN Sining，et al.Integrated CO2 capture and reverse water-gas shift reaction over CeO2-CaO dual functional materials［J］.Royal Society Open Science，2023，10（4）：230067. |
| 35 | ORTEGA-TRIGUEROS A， CACCIA M， NARCISO J.Tuning activity and selectivity in catalyzed reactions of environmental and industrial importance with a high-surface area，mesoporous Mo2C catalyst［J］.Chemistry of Materials，2022，34（14）：6232-6239. |
| 36 | ZHANG Xiao， ZHU Xiaobing， LIN Lili，et al.Highly dispersed copper over β-Mo2C as an efficient and stable catalyst for the reverse water gas shift（RWGS） reaction［J］.ACS Catalysis，2017，7（1）：912-918. |
| 37 | LIU Xianyun， KUNKEL C，RAMíREZ DE LA PISCINA P，et al.Effective and highly selective CO generation from CO2 using a polycrystalline α-Mo2C catalyst［J］.ACS Catalysis，2017，7（7）：4323-4335. |
| 38 | PAJARES A， LIU Xianyun， BUSACKER J R，et al.Supported nanostructured Mo x C materials for the catalytic reduction of CO2 through the reverse water gas shift reaction［J］.Nanomaterials，2022，12（18）：3165. |
| 39 | LIU Xianyun， PAJARES A， CALINAO MATIENZO D D，et al.Preparation and characterization of bulk Mo x C catalysts and their use in the reverse water-gas shift reaction［J］.Catalysis Today，2020，356：384-389. |
| 40 | GAO Jiajian， WU Yue， JIA Chunmiao，et al.Controllable synthesis of α-MoC1- x and β-Mo2C nanowires for highly selective CO2 reduction to CO［J］.Catalysis Communications，2016，84：147- 150. |
| 41 | ZHANG Jiajun， FENG Kai， LI Zhengwen，et al.Defect-driven efficient selective CO2 hydrogenation with Mo-based clusters［J］.JACS Au，2023，3（10）：2736-2748. |
| 42 | KUHN A N， PARK R C， YU Siying，et al.Valorization of carbon dioxide into C1 product via reverse water gas shift reaction using oxide-supported molybdenum carbides［J］.Carbon Future，2024，1（2）：9200011. |
| 43 | 彭晓伟，王银斌，臧甲忠，等.金属改性甲醇芳构化催化剂的制备及性能研究［J］.无机盐工业，2021，53（9）：104-108. |
| PENG Xiaowei， WANG Yinbin， ZANG Jiazhong，et al.Research on preparation of metal modified catalysts and catalytic performances of methanol aromatization［J］.Inorganic Chemicals Industry，2021，53（9）：104-108. | |
| 44 | 刘永存，肖寒，王帅，等.Ni-Mo-P/Beta-ZSM-5催化剂对四氢萘加氢裂化性能的研究［J］.无机盐工业，2018，50（6）：81-85. |
| LIU Yongcun， XIAO Han， WANG Shuai，et al.Study on hydrocracking performance of tetralin over Ni-Mo-P/Beta-ZSM-5 catalyst［J］.Inorganic Chemicals Industry，2018，50（6）：81-85. | |
| 45 | 司智伟，丹少鹏，陈树伟，等.Co-Al2O3高效催化CO2氧化乙苯脱氢制苯乙烯［J］.燃料化学学报（中英文），2023，51（11）：1683-1690. |
| SI Zhiwei， DAN Shaopeng， CHEN Shuwei，et al.Highly efficient Co-Al2O3 catalysts for oxidative dehydrogenation of ethylbenzene to styrene with CO2 ［J］.Journal of Fuel Chemistry and Technology，2023，51（11）：1683-1690. | |
| 46 | WU Jiayi， ZHENG Yuhang， FU Jiali，et al.Synthetic Ni-CaO-CeO2 dual function materials for integrated CO2 capture and conversion via reverse water-gas shift reaction［J］.Separation and Purification Technology，2023，317：123916. |
/
| 〈 |
|
〉 |
