叶知远,饶娜,夏菖佑,刘硕,梁希
YE Zhiyuan,RAO Na,XIA Changyou,LIU Shuo,LIANG Xi

• 1:广东南方碳捕集与封存产业中心
• 2:江西省科学院能源研究所
• 3:宁夏回族自治区电力设计院有限公司
• 4:伦敦大学学院

摘要(Abstract)：

甲醇是重要的有机化工原料和优质燃料。在气候危机、能源危机背景下，发展甲醇经济利于实现化工、能源和交通运输行业绿色低碳转型，保障能源供应安全。系统地介绍了两步法、一步法CO_2加氢制甲醇工艺路线，分析、归纳和梳理了铜基、铟基、固溶体与贵金属催化剂性能表现。由数据可知4类催化剂反应条件集中分布在200～300℃,1.5～5.0 MPa。铜基催化剂是目前研究和应用最广的催化剂，其CO_2转化率和甲醇选择性中位数分别为13.6和69.2。与铜基催化剂相比，铟基催化剂和固溶体催化剂CO_2转化率和甲醇选择性与铜基催化相当，但稳定性更优。而贵金属催化剂CO_2转化率(最佳值66,最小值0.6)和甲醇选择性(最佳值100,最小值11)极值差别大且少见稳定性相关的数据。固溶体催化剂在工业条件表现出优异的催化性能和稳定性，可能成为未来规模化应用的催化剂种类之一。此外，梳理了国内和国际现有CO_2加氢制甲醇的项目与技术路线。目前国内外二氧化碳加氢制甲醇项目数量不断增多，其中部分已建成投产，甲醇生产能力从4 000 t/a到200 000 t/a不等。目前这些项目甲醇生产碳源主要来自工业排放源CO_2捕集装置，而氢气主要通过电解水获取。碳中和目标下，CO_2加氢制甲醇技术的重要性愈发显著，建议从CO_2加氢制甲醇催化剂技术研发和项目产业化应用方面加大支持力度。
Methanol is a crucial organic raw material and fuel, particularly in the context of the climate and energy crisis. Developing a methanol economy is crucial to promoting a green, low-carbon transformation of the chemical, energy, and transportation sectors while ensuring a secure energy supply. A comprehensive overview of the CO_2 hydrogenation process routes to methanol was offered, including an analysis and summary of the performance of copper-based, indium-based, solid solution, and noble metal catalysts. The data show that the reaction conditions of all four types of catalysts are concentrated at 200-300 ℃ and 1.5-5.0 MPa. While copper-based catalysts were the most widely studied and applied, with a median CO_2 conversion and methanol selectivity of 13.6 and 69.2,respectively,indium-based catalysts and solid solution catalysts have comparable CO_2 conversion and methanol selectivity but exhibit better stability. The extreme values of CO_2 conversion and methanol selectivity for noble metal catalysts vary significantly, with limited data related to stability. Solid solution catalysts demonstrate exceptional catalytic performance and stability under industrial conditions, making them a promising catalyst type for large-scale application in the future. Furthermore, this paper provides an overview of existing CO_2 hydrogenation to methanol projects and technical routes both domestically and abroad. The number of carbon dioxide hydrogenation to methanol projects is increasing, with production capacities ranging from 4 000 t/a to 200 000 t/a. Industrial emission source CO_2 capture devices as the carbon source and electrolytic water as the primary source of hydrogen were primarily relied on. As the goal of carbon neutralization becomes increasingly critical, the CO_2 hydrogenation to methanol technology becomes even more vital. Therefore, it is recommended that research and development of CO_2 hydrogenation to methanol catalyst technology receive greater support, as well as industrial application of the project.

关键词(KeyWords)： CCUS;甲醇;碳利用;催化剂;二氧化碳
CCUS;methanol;carbon utilization;catalyst;CO_2

Abstract:

Keywords:

基金项目(Foundation): 宁夏回族自治区发展改革委资助项目(GDCCUS2022041901)

作者(Author): 叶知远,饶娜,夏菖佑,刘硕,梁希
YE Zhiyuan,RAO Na,XIA Changyou,LIU Shuo,LIANG Xi

DOI: 10.13226/j.issn.1006-6772.23030103

参考文献(References)：

• [1] Change I P C C.Climate change 2021:The physical science basis [M].Cambridge:Cambridge University Press,2023.
• [2] IRENA.Innovation Outlook:Renewable Methanol [R].Abu Dhabi:IRENA,2021:12-32.
• [3] WENDER I.Reactions of synthesis gas [J].Fuel Processing Tech-nology,1996,48(3):189-297.
• [4] LIU G,WILLCOX D,GARLAND M,et al.The role of CO2 in methanol synthesis on Cu-Zn oxide:An isotope labeling study [J].Journal of Catalysis,1985,96(1):251-260.
• [5] KATTEL S,RAMíREZ P J,CHEN J G,et al.Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts [J].Science,2017,355(6331):1296-1299.
• [6] YANG Y,LOUISIA S,YU S,et al.Operando studies reveal active Cu nanograins for CO2 electroreduction [J].Nature,2023,614(7947):262-269.
• [7] SLOTBOOM Y,BOS M J,PIEPER J,et al.Critical assessment of steady-state kinetic models for the synthesis of methanol over an industrial Cu/ZnO/Al2O3 catalyst [J].Chemical Engineering Journal,2020,389:124181.
• [8] PAVLI?I C A,HU?M,PRA?NIKAR A,et al.Multiscale modelling of CO2 reduction to methanol over industrial Cu/ZnO/Al2O3 heterogeneous catalyst:Linkingab initio surface reaction kinetics with reactor fluid dynamics [J].Journal of Cleaner Production,2020,275:122958.
• [9] ZHAO F,FAN L,XU K,et al.Hierarchical sheet-like Cu/Zn/Al nanocatalysts derived from LDH/MOF composites for CO2 hydrogenation to methanol [J].Journal of CO2 Utilization,2019,33:222-232.
• [10] LIANG Z,GAO P,TANG Z,et al.Three dimensional porous Cu-Zn/Al foam monolithic catalyst for CO2 hydrogenation to methanol in microreactor [J].Journal of CO2 Utilization,2017,21:191-199.
• [11] GODINI H R,KHADIVI M,AZADI M,et al.Multi-scale analysis of integrated C1 (CH4 and CO2) utilization catalytic processes:Impacts of catalysts characteristics up to industrial-scale process flowsheeting,part I:Experimental analysis of catalytic low-pressure CO2 to methanol conversion [J].Catalysts,2020,10(5):505.
• [12] REN S,SHOEMAKER W R,WANG X,et al.Highly active and selective Cu-ZnO based catalyst for methanol and dimethyl ether synthesis via CO2 hydrogenation [J].Fuel,2019,239:1125-1133.
• [13] DONG X,LI F,ZHAO N,et al.CO2 hydrogenation to methanol over Cu/Zn/Al/Zr catalysts prepared by liquid reduction [J].Chinese Journal of Catalysis,2017,38(4):717-725.
• [14] GAO P,YANG H,ZHANG L,et al.Fluorinated Cu/Zn/Al/Zr hydrotalcites derived nanocatalysts for CO2 hydrogenation to methanol [J].Journal of CO2 Utilization,2016,16:32-41.
• [15] CAI W,CHEN Q,WANG F,et al.Comparison of the promoted CuZnMxOy(M:Ga,Fe) catalysts for CO2 hydrogenation to methanol [J].Catalysis Letters,2019,149(9):2508-2518.
• [16] HENGNE A M,YUAN D J,DATE N S,et al.Preparation and activity of copper-gallium nanocomposite catalysts for carbon dioxide hydrogenation to methanol [J].Industrial & Engineering Chemistry Research,2019,58(47):21331-21340.
• [17] CHEN K,FANG H,WU S,et al.CO2 hydrogenation to methanol over Cu catalysts supported on La-modified SBA-15:The crucial role of Cu-LaOx interfaces [J].Applied Catalysis B:Environmental,2019,251:119-129.
• [18] HU X,ZHAO C,GUAN Q,et al.Selective hydrogenation of CO2 over a Ce promoted Cu-based catalyst confined by SBA-15 [J].Inorganic Chemistry Frontiers,2019,6(7):1799-1812.
• [19] WANG G,MAO D,GUO X,et al.Methanol synthesis from CO2 hydrogenation over CuO-ZnO-ZrO2-MxOy catalysts (M=Cr,Mo and W) [J].International Journal of Hydrogen Energy,2019,44(8):4197-4207.
• [20] LEUNG A H M,GARCíA-TRENCO A,PHANOPOULOS A,et al.Cu/M:ZnO (M=Mg,Al,Cu) colloidal nanocatalysts for the solution hydrogenation of carbon dioxide to methanol [J].Journal of Materials Chemistry A,2020,8(22):11282-11291.
• [21] GAO J,SONG F,LI Y,et al.Cu2In nanoalloy enhanced performance of Cu/ZrO2 catalysts for the CO2 hydrogenation to methanol [J].Industrial & Engineering Chemistry Research,2020,59(27):12331-12337.
• [22] YE H,NA W,GAO W,et al.Carbon-modified CuO/ZnO catalyst with high oxygen vacancy for CO2 hydrogenation to methanol [J].Energy Technology,2020,8(6):2000194.
• [23] MARTIN O,MARTíN A J,MONDELLI C,et al.Indium oxide as a superior catalyst for methanol synthesis by CO2 hydrogenation [J].Angewandte Chemie (International Ed in English),2016,55(21):6261-6265.
• [24] YE J,LIU C,MEI D,et al.Active oxygen vacancy site for methanol synthesis from CO2 hydrogenation on In2O3(110):A DFT study [J].ACS Catalysis,2013,3(6):1296-1306.
• [25] FREI M S,CAPDEVILA-CORTADA M,GARCíA-MUELAS R,et al.Mechanism and microkinetics of methanol synthesis via CO2 hydrogenation on indium oxide [J].Journal of Catalysis,2018,361:313-321.
• [26] YE J,LIU C,GE Q.DFT study of CO2 adsorption and hydrogenation on the In2O3 surface [J].The Journal of Physical Chemistry C,2012,116(14):7817-7825.
• [27] GAO P,LI S,BU X,et al.Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst [J].Nature Chemistry,2017,9(10):1019-1024.
• [28] PRINS R.Hydrogen spillover.Facts and fiction [J].Chemical Reviews,2012,112(5):2714-2738.
• [29] TRIWAHYONO S,JALIL A A,TIMMIATI S N,et al.Kinetics study of hydrogen adsorption over Pt/MoO3[J].Applied Catalysis A:General,2010,372(1):103-107.
• [30] RUI N,WANG Z,SUN K,et al.CO2 hydrogenation to methanol over Pd/In2O3:Effects of Pd and oxygen vacancy [J].Applied Catalysis B:Environmental,2017,218:488-497.
• [31] WANG J,LI G,LI Z,et al.A highly selective and stable ZnO-ZrO2 solid solution catalyst for CO2 hydrogenation to methanol [J].Science Advances,2017,3(10):e1701290.
• [32] FANG X,MEN Y,WU F,et al.Promoting CO2 hydrogenation to methanol by incorporating adsorbents into catalysts:Effects of hydrotalcite [J].Chemical Engineering Journal,2019,378:122052.
• [33] FANG X,XI Y,JIA H,et al.Tetragonal zirconia based ternary ZnO-ZrO2-MOx solid solution catalysts for highly selective conversion of CO2 to methanol at High reaction temperature [J].Journal of Industrial and Engineering Chemistry,2020,88:268-277.
• [34] WANG J,TANG C,LI G,et al.High-performance MaZrOx (Ma=Cd,Ga) solid-solution catalysts for CO2hydrogenation to methanol [J].ACS Catalysis,2019,9(11):10253-10259.
• [35] LI W,WANG K,HUANG J,et al.MxOy-ZrO2 (M=Zn,Co,Cu) solid solutions derived from schiff base-bridged UiO-66 composites as high-performance catalysts for CO2 hydrogenation [J].ACS Applied Materials &Interfaces,2019,11(36):33263-33272.
• [36] 何珍红，李竹惠，王忠宇，等.Pt/ZSM-5水相催化二氧化碳加氢制甲醇[J].陕西科技大学学报，2021,39(2):67-71,78.HE Zhenhong,LI Zhuhui,WANG Zhongyu,et al.Aqueous CO2 hydrogenation to methanol over Pt/ZSM-5 catalysts [J].Journal of Shaanxi University of Science & Technology,2021,39(2):67-71,78.
• [37] OJELADE O A,ZAMAN S F,DAOUS M A,et al.Optimizing Pd:Zn molar ratio in PdZn/CeO2 for CO2 hydrogenation to methanol [J].Applied Catalysis A:General,2019,584:117185.
• [38] 王集杰，韩哲，王欢，等.TiO2负载的高分散Cd团簇催化剂高效催化CO2加氢制甲醇[J].催化学报，2022,43(3):761-770.WANG Jijie,HAN Zhe,WANG Huan,et al.Highly dispersed Cd cluster supported on TiO2 as an efficient catalyst for CO2 hydrogenation to methanol[J].Chinese Journal of Catalysis,2022,43(3):761-770.
• [39] LI X,LIU G,XU D,et al.Confinement of subnanometric PdZn at a defect enriched ZnO/ZIF-8 interface for efficient and selective CO2 hydrogenation to methanol [J].Journal of Materials Chemistry A,2019,7(41):23878-23885.
• [40] GUTTER?D E S,LAZZARINI A,FJERMESTAD T,et al.Hydrogenation of CO2 to methanol by Pt nanoparticles encapsulated in UiO-67:Deciphering the role of the metal-organic framework [J].Journal of the American Chemical Society,2020,142(2):999-1009.
• [41] MANRIQUE R,RODRíGUEZ-PEREIRA J,RINCóN-ORTIZ S A,et al.The nature of the active sites of Pd-Ga catalysts in the hydrogenation of CO2 to methanol [J].Catalysis Science & Technology,2020,10(19):6644-6658.
• [42] OTA A,KUNKES E L,KASATKIN I,et al.Comparative study of hydrotalcite-derived supported Pd2Ga and PdZn intermetallic nanoparticles as methanol synthesis and methanol steam reforming catalysts [J].Journal of Catalysis,2012,293:27-38.
• [43] FUJITANI T,SAITO M,KANAI Y,et al.Development of an act-ive Ga2O3 supported palladium catalyst for the synthesis of methanol from carbon dioxide and hydrogen [J].Applied Catalysis A:General,1995,125(2):L199-L202.
• [44] ZABILSKIY M,SUSHKEVICH V L,PALAGIN D,et al.The unique interplay between copper and zinc during catalytic carbon dioxide hydrogenation to methanol [J].Nature Communications,2020,11(1):2409.
• [45] LIU T,HONG X,LIU G.In situgeneration of the Cu@3D-ZrOxframework catalyst for selective methanol synthesis from CO2/H2[J].ACS Catalysis,2020,10(1):93-102.
• [46] WANG Y,KATTEL S,GAO W,et al.Exploring the ternary interactions in Cu-ZnO-ZrO2 catalysts for efficient CO2 hydrogenation to methanol [J].Nature Communications,2019,10(1):1166.
• [47] LI L,MAO D,YU J,et al.Highly selective hydrogenation of CO2 to methanol over CuO-ZnO-ZrO2 catalysts prepared by a surfactant-assisted co-precipitation method [J].Journal of Power Sources,2015,279:394-404.
• [48] STAWOWY M,CIESIELSKI R,MANIECKI T,et al.CO2 hydrogenation to methanol over Ce and Zr containing UiO-66 and Cu/UiO-66 [J].Catalysts,2019,10(1):39.
• [49] HU B,YIN Y,ZHONG Z,et al.Cu@ZIF-8 derived inverse ZnO/Cu catalyst with sub-5 nm ZnO for efficient CO2 hydrogenation to methanol [J].Catalysis Science & Technology,2019,9(10):2673-2681.
• [50] JIANG Y,YANG H,GAO P,et al.Slurry methanol synthesis from CO2 hydrogenation over micro-spherical SiO2 support Cu/ZnO catalysts [J].Journal of CO2 Utilization,2018,26:642-651.
• [51] TOYIR J,DE LA PISCINA P R,FIERRO J L G,et al.Highly effective conversion of CO2 to methanol over supported and promoted copper-based catalysts:Influence of support and promoter [J].Applied Catalysis B:Environmental,2001,29(3):207-215.
• [52] PHONGAMWONG T,CHANTAPRASERTPORN U,WITOON T,et al.CO2 hydrogenation to methanol over CuO-ZnO-ZrO2-SiO2 catalysts:Effects of SiO2 contents [J].Chemical Engineering Journal,2017,316:692-703.
• [53] XIONG S,LIAN Y,XIE H,et al.Hydrogenation of CO2 to methanol over Cu/ZnCr catalyst [J].Fuel,2019,256:115975.
• [54] CHOU C Y,LOBO R F.Direct conversion of CO2 into methanol over promoted indium oxide-based catalysts [J].Applied Catalysis A:General,2019,583:117144.
• [55] DANG S,QIN B,YANG Y,et al.Rationally designed indium oxide catalysts for CO2 hydrogenation to methanol with high activity and selectivity [J].Science Advances,2020,6(25):eaaz2060.
• [56] JIANG H,LIN J,WU X,et al.Efficient hydrogenation of CO2 to methanol over Pd/In2O3/SBA-15 catalysts [J].Journal of CO2 Utilization,2020,36:33-39.
• [57] SHA F,TANG C,TANG S,et al.The promoting role of Ga in ZnZrOx solid solution catalyst for CO2 hydrogenation to methanol [J].Journal of Catalysis,2021,404:383-392.
• [58] FIORDALISO E M,SHARAFUTDINOV I,CARVALHO H W P,et al.Evolution of intermetallic GaPd2/SiO2 catalyst and optimization for methanol synthesis at ambient pressure [J].Science and Technology of Advanced Materials,2019,20(1):521-531.
• [59] COLLINS S E,DELGADO J J,MIRA C,et al.The role of Pd-Ga bimetallic particles in the bifunctional mechanism of selective methanol synthesis via CO2 hydrogenation on a Pd/Ga2O3 catalyst [J].Journal of Catalysis,2012,292:90-98.
• [60] KOIZUMI N,JIANG X,KUGAI J,et al.Effects of mesoporous silica supports and alkaline promoters on activity of Pd catalysts in CO2 hydrogenation for methanol synthesis [J].Catalysis Today,2012,194(1):16-24.
• [61] KIM C H,LEE J S,TRIMM D L.The preparation and characterisation of Pd-ZnO catalysts for methanol synthesis [J].Topics in Catalysis,2003,22(3):319-324.
• [62] LIANG X L,DONG X,LIN G D,et al.Carbon nanotube-supported Pd-ZnO catalyst for hydrogenation of CO2 to methanol [J].Applied Catalysis B:Environmental,2009,88(3/4):315-322.
• [63] PANAGIOTOPOULOU P.Hydrogenation of CO2 over supported noble metal catalysts [J].Applied Catalysis A:General,2017,542:63-70.
• [64] CRI.First Production of Fuel From CO2 at Industrial Scale [EB/OL].(2022-05-01)[2023-03-01].https://www.carbonrecycling.is/project-goplant.
• [65] CRI.Our Projects [EB/OL].(2022-05-01)[2023-03-01].https://www.carbonrecycling.is/projects.
• [66] BAILEY M.Celanese announces expansion of methanol produ-ction using recycled CO2 feedstock [EB/OL].(2021-03-26)[2023-03-01].https://www.chemengonline.com/celanese-announces-expansion-of-methanol-production-using-recycled-CO2-feedstock/.
• [67] U.S.JV to increase production of methanol derived from CO2[EB/OL].(2021-03-26)[2023-03-01].https://www.mitsui.com/jp/en/topics/2021/1240906_12171.html.
• [68] 陈升华.2021—2022年度中国甲醇行业市场分析报告(中) [J].广州化工，2022,50(4):1-3.CHEN Shenghua.Market analysis report of methanol industry in China in 2021-2022 (Ⅱ) [J].Guangzhou Chemical Industry,2022,50(4):1-3.
• [69] 周紫璇，杨海艳，孙予罕，等.二氧化碳加氢制甲醇多相催化剂研究进展[J].高等学校化学学报，2022,43(7):11-23.ZHOU Zixuan,YANG Haiyan,SUN Yuhan,et al.Recent progress in heterogeneous catalysts for the hydrogenation of carbon dioxide to methanol [J].Chemical Journal of Chinese Universities,2022,43(7):11-23.
• [70] 任霄鹏.全球首套规模化太阳燃料合成示范项目试车成功[EB/OL].(2020-04-07)[2023-03-01].https://www.cas.cn/jh/202005/t20200506_4744560.shtml.
• [71] 钱伯章.江苏斯尔邦石化有限公司将在中国建造15万t/a CO2制甲醇工厂[J].石化技术与应用，2021,39(6):461.QIAN Bozhang.Jiangsu Sierbang Petrochemical Co.,Ltd.will build a 150 000 t/a CO2 to methanol plant in China[J].Petrochemical Technology & Application,2021,39(6):461.