二氧化碳加氢制甲醇铜基催化剂性能的研究进展

doi:10.16085/j.issn.1000-6613.2019-1740

摘要/Abstract

摘要：

二氧化碳（CO₂）加氢制甲醇对于解决CO₂排放和能源紧缺问题具有重要意义，催化剂的研究是这项技术的关键。铜基催化剂因高效廉价而被广泛研究，但目前的生产效率离实现工业化仍有距离。本文针对铜基催化剂，首先探讨了活性中心的存在形式，然后从活性组分负载量、载体、助剂、制备方法及条件、预处理条件这5个方面，分别分析其对催化剂的活性、选择性以及稳定性等的影响，以期为CO₂高值转化为甲醇的铜基催化剂的制备和筛选提供参考。按照广泛接受的双位点机理可知，CO₂转化率与铜表面积密切相关，甲醇选择性与强碱位点含量密切相关。因此，各方面因素通过影响催化剂比表面积、铜表面积、铜分散度、碱性位点、铜与载体的协同作用等物理化学参数，进而影响CO₂转化率与甲醇选择性。

关键词: 二氧化碳加氢, 甲醇, 铜基催化剂, 铜表面积, 铜分散度

Abstract:

CO₂ hydrogenation to methanol is an important technique to solve the problems of CO₂ emission and energy shortage and the catalyst is the key. Cu-based catalysts have been extensively studied due to their low cost and good performance, but the current production efficiency is still not high enough for its industrialization. In this paper, the existing forms of the active centers of Cu-based catalysts are discussed firstly. Then, the effects of the loading active component, carrier, promoter, preparation method and conditions, pretreatment conditions on the activity, selectivity and stability of the catalysts are reviewed in order to provide a reference for the preparation and selection of Cu-based catalysts for conversion of CO₂ to methanol. According to the double site mechanism, the conversion of CO₂ is closely related to the Cu surface area, and the selectivity of methanol is closely related to the strong basic sites. Therefore, the above factors affect the CO₂ conversion and methanol selectivity by affecting the specific surface area, Cu surface area, Cu dispersion, basic site of the catalyst, and the interaction between Cu and carriers.

Key words: CO₂hydrogenation, methanol, Cu-based catalyst, Cu surface area, Cu dispersion

中图分类号:

TQ426

贾晨喜, 邵敬爱, 白小薇, 肖建军, 杨海平, 陈汉平. 二氧化碳加氢制甲醇铜基催化剂性能的研究进展[J]. 化工进展, 2020, 39(9): 3658-3668.

Chenxi JIA, Jing’ai SHAO, Xiaowei BAI, Jianjun XIAO, Haiping YANG, Hanping CHEN. Review on Cu-based catalysts for CO₂ hydrogenation to methanol[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3658-3668.

参考文献

1	BORETTI A. Renewable hydrogen to recycle CO₂ to methanol[J]. International Journal of Hydrogen Energy, 2013, 38(4): 1806-1812.
2	BEHRENS M, STUDT F, KASATKIN I, et al. The active site of methanol synthesis over Cu/ZnO/Al₂O₃industrial catalysts[J]. Science, 2012, 336(6083): 893.
3	RIVAROLO M, BELLOTTI D, MAGISTRI L, et al. Feasibility study of methanol production from different renewable sources and thermo-economic analysis[J]. International Journal of Hydrogen Energy, 2016, 41(4): 2105-2116.
4	LI X, FAGHRI A. Development of a direct methanol fuel cell stack fed with pure methanol[J]. International Journal of Hydrogen Energy, 2012, 37(19): 14549-14556.
5	KATTEL S, YAN B, YANG Y, et al. Optimizing binding energies of key intermediates for CO₂hydrogenation to methanol over oxide-supported copper[J]. Journal of the American Chemical Society, 2016, 138(38): 12440-12450.
6	KANDEMIR T, FRIEDRICH M, PARKER S F, et al. Different routes to methanol: inelastic neutron scattering spectroscopy of adsorbates on supported copper catalysts[J]. Physical Chemistry Chemical Physics, 2016, 18(26): 17253-17258.
7	LIU Y M, LIU J T, LIU S Z, et al. Reaction mechanisms of methanol synthesis from CO/CO₂ hydrogenation on Cu₂O(111): comparison with Cu(111)[J]. Journal of CO₂ Utilization, 2017, 20: 59-65.
8	LEE J S, LEE K H, LEE S Y, et al. A comparative study of methanol synthesis from CO₂/H₂ and CO/H₂ over a Cu/ZnO/Al₂O₃catalyst[J]. Journal of Catalysis, 1993, 144(2): 414-424.
9	ANGELO L, KOBL K, TEJADA L M M, et al. Study of CuZnMO_x oxides (M= Al, Zr, Ce, CeZr) for the catalytic hydrogenation of CO₂ into methanol[J]. Comptes Rendus Chimie, 2015, 18(3): 250-260.
10	FUJITANI T, NAKAMURA J. The chemical modification seen in the Cu/ZnO methanol synthesis catalysts[J]. Applied Catalysis A: General, 2000, 191(1/2): 111-129.
11	GAO P, YANG H, ZHANG L, et al. Fluorinated Cu/Zn/Al/Zr hydrotalcites derived nanocatalysts for CO₂hydrogenation to methanol[J]. Journal of CO₂ Utilization, 2016, 16: 32-41.
12	MARTIN O, MONDELLI C, CURULLA-FERRé D, et al. Zinc-rich copper catalysts promoted by gold for methanol synthesis[J]. ACS Catalysis, 2015, 5(9): 5607-5616.
13	YANG Y, MIMS C A, MEI D H, et al. Mechanistic studies of methanol synthesis over Cu from CO/CO₂/H₂/H₂O mixtures: the source of C in methanol and the role of water[J]. Journal of Catalysis, 2013, 298: 10-17.
14	KLIER K, CHATIKAVANIJ V, HERMAN R, et al. Catalytic synthesis of methanol from CO/H₂: IV. The effects of carbon dioxide[J]. Journal of Catalysis, 1982, 74(2): 343-360.
15	杨盼盼, 孙琦, 张玉龙, 等. 甲醇合成中CO₂作用的研究进展[J]. 化工进展, 2018, 37(S1): 94-101.
15	YANG P P, SUN Q, ZHANG Y L, et al. Research progress of the role of CO₂ in methanol synthesisl[J]. Chemical Industry and Engineering Progress, 2018, 37(S1): 94-101.
16	ARENA F, ITALIANO G, BARBERA K, et al. Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO₂ catalysts in the CO₂ hydrogenation to CH₃OH[J]. Applied Catalysis A： General, 2008, 350(1): 16-23.
17	GAO P, LI F, ZHAO N, et al. Influence of modifier (Mn, La, Ce, Zr and Y) on the performance of Cu/Zn/Al catalysts via hydrotalcite-like precursors for CO₂hydrogenation to methanol[J]. Applied Catalysis A: General, 2013, 468: 442-452.
18	WANG G, MAO D, GUO X, et al. Methanol synthesis from CO₂ hydrogenation over CuO-ZnO-ZrO₂-M_xO_y catalysts (M=Cr, Mo and W)[J]. International Journal of Hydrogen Energy, 2019, 44(8): 4197-4207.
19	GUO X, MAO D, LU G, et al. The influence of La doping on the catalytic behavior of Cu/ZrO₂ for methanol synthesis from CO₂ hydrogenation[J]. Journal of Molecular Catalysis A: Chemical, 2011, 345(1-2): 60-68.
20	LI F, ZHAN H, ZHAO N, et al. CO₂ hydrogenation to methanol over La-Mn-Cu-Zn-O based catalysts derived from perovskite precursors[J]. International Journal of Hydrogen Energy, 2017, 42(32): 20649-20657.
21	ARENA F, BARBERA K, ITALIANO G, et al. Synthesis, characterization and activity pattern of Cu-ZnO/ZrO₂ catalysts in the hydrogenation of carbon dioxide to methanol[J]. Journal of Catalysis, 2007, 249(2): 185-194.
22	KARELOVIC A, RUIZ P. The role of copper particle size in low pressure methanol synthesis via CO₂ hydrogenation over Cu/ZnO catalysts[J]. Catalysis Science & Technology, 2015, 5(2): 869-881.
23	CHANG K, WANG T, CHEN J G. Hydrogenation of CO₂to methanol over CuCeTiO_x catalysts[J]. Applied Catalysis B: Environmental, 2017, 206: 704-711.
24	ZHANG C, YANG H, GAO P, et al. Preparation and CO₂ hydrogenation catalytic properties of alumina microsphere supported Cu-based catalyst by deposition-precipitation method[J]. Journal of CO₂ Utilization, 2017, 17: 263-272.
25	HORNEBECQ V, KNOEFEL C, BOULET P, et al. Adsorption of carbon dioxide on mesoporous zirconia: microcalorimetric measurements, adsorption isotherm modeling, and density functional theory calculations[J]. Journal of Physical Chemistry C, 2011, 115(20): 10097-10103.
26	樊钰佳, 吴素芳. 二氧化碳加氢合成甲醇反应铜基催化剂研究进展[J]. 化工进展, 2016, 35(S1): 159-166.
26	FAN Y J, WU S F. Advances in copper-based catalyst for the methanol synthesis from CO₂ hydrogenation[J]. Chemical Industry and Engineering Progress, 2016, 35(S1): 159-166.
27	李基涛, 区泽棠, 陈明旦, 等. CO₂加氢合成甲醇催化剂中Al₂O₃的作用[J]. 天然气化工, 1997, 21(5): 13-16.
27	LI J T, AU Z T, CHEN M D, et al. The role of Al₂O₃ in CO₂ hydrogenation to methanol over a CuO/ZnO/Al₂O₃ catalyst[J]. Natural Gas Chemical Industry, 1997, 21(5): 13-16.
28	TURSUNOV O, KUSTOV L, TILYABAEV Z. Methanol synthesis from the catalytic hydrogenation of CO₂ over CuO-ZnO supported on aluminum and silicon oxides[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 78: 416-422.
29	KARELOVIC A, GALDAMES G, MEDINA J C, et al. Mechanism and structure sensitivity of methanol synthesis from CO₂ over SiO₂-supported Cu nanoparticles[J]. Journal of Catalysis, 2019, 369: 415-426.
30	BONURA G, ARENA F, MEZZATESTA G, et al. Role of the ceria promoter and carrier on the functionality of Cu-based catalysts in the CO₂-to-methanol hydrogenation reaction[J]. Catalysis Today, 2011, 171(1): 251-256.
31	WITOON T, CHALORNGTHAM J, DUMRONGBUNDITKUL P, et al. CO₂ hydrogenation to methanol over Cu/ZrO₂ catalysts: effects of zirconia phases[J]. Chemical Engineering Journal, 2016, 293: 327-336.
32	TADA S, KATAGIRI A, KIYOTA K, et al. Cu species incorporated into amorphous ZrO₂ with high activity and selectivity in CO₂-to-methanol hydrogenation[J]. The Journal of Physical Chemistry C, 2018, 122(10): 5430-5442.
33	LI S, GUO L, ISHIHARA T. Hydrogenation of CO₂ to methanol over Cu/AlCeO catalyst[J]. Catalysis Today, 2020, 339: 352-361.
34	LI S, WANG Y, YANG B, et al. A highly active and selective mesostructured Cu/AlCeO catalyst for CO₂ hydrogenation to methanol[J]. Applied Catalysis A: General, 2019, 571: 51-60.
35	XIONG S, LIAN Y, XIE H, et al. Hydrogenation of CO₂ to methanol over Cu/ZnCr catalyst[J]. Fuel, 2019, 256: 115975.
36	DIN I U, SHAHARUN M S, NAEEM A, et al. Revalorization of CO₂for methanol production via ZnO promoted carbon nanofibers based Cu-ZrO₂ catalytic hydrogenation[J]. Journal of Energy Chemistry, 2019, 39: 68-76.
37	FANG X, MEN Y, WU F, et al. Improved methanol yield and selectivity from CO₂ hydrogenation using a novel Cu-ZnO-ZrO₂ catalyst supported on Mg-Al layered double hydroxide (LDH)[J]. Journal of CO₂ Utilization, 2019, 29: 57-64.
38	MUREDDU M, FERRARA F, PETTINAU A. Highly efficient CuO/ZnO/ZrO₂@SBA-15 nanocatalysts for methanol synthesis from the catalytic hydrogenation of CO₂[J]. Applied Catalysis B: Environmental, 2019, 258: 117941.
39	LIU C H, GUO X M, GUO Q S, et al. Methanol synthesis from CO₂ hydrogenation over copper catalysts supported on MgO-modified TiO₂[J]. Journal of Molecular Catalysis A: Chemical, 2016, 425: 86-93.
40	GAO P, LI F, ZHAN H, et al. Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. Journal of Catalysis, 2013, 298: 51-60.
41	REN H, XU C H, ZHAO H Y, et al. Methanol synthesis from CO₂ hydrogenation over Cu/γ-Al₂O₃ catalysts modified by ZnO, ZrO₂and MgO[J]. Journal of Industrial and Engineering Chemistry, 2015, 28: 261-267.
42	LI M J, ZENG Z, LIAO F, et al. Enhanced CO₂ hydrogenation to methanol over CuZn nanoalloy in Ga modified Cu/ZnO catalysts[J]. Journal of Catalysis, 2016, 343: 157-167.
43	MELIAN-CABRERA I, GRANADOS M L, FIERRO J J C L. Effect of Pd on Cu-Zn catalysts for the hydrogenation of CO₂ to methanol: stabilization of Cu metal against CO₂ oxidation[J]. Catalysis Letters, 2002, 79(1/2/3/4): 165-170.
44	BAN H, LI C, ASAMI K, et al. Influence of rare-earth elements (La, Ce, Nd and Pr) on the performance of Cu/Zn/Zr catalyst for CH₃OH synthesis from CO₂[J]. Catalysis Communications, 2014, 54: 50-54.
45	VENUGOPAL A, PALGUNADI J, DEOG J K, et al. Dimethyl ether synthesis on the admixed catalysts of Cu-Zn-Al-M (M=Ga, La, Y, Zr) and γ-Al₂O₃: the role of modifier[J]. Journal of Molecular Catalysis A: Chemical, 2009, 302(1): 20-27.
46	NATESAKHAWAT S, OHODNICKI P R, HOWARD B H, et al. Adsorption and deactivation characteristics of Cu/ZnO-based catalysts for methanol synthesis from carbon dioxide[J]. Topics in Catalysis, 2013, 56(18-20): 1752-1763.
47	贾淼尧, 高文桂, 王华, 等. 助剂二氧化硅对CO₂加氢制备甲醇 CuO-ZnO-Al₂O₃-ZrO₂催化剂性能的影响[J]. 化工进展, 2015, 34(2): 407-412.
47	JIA M Y, GAO W G, WANG H, et al. Effect of promoter silica on performance of CuO-ZnO-Al₂O₃-ZrO₂catalyst for methanol synthesis from CO₂ hrdrogenation[J]. Chemical Industry and Engineering Progress, 2015, 34(2): 407-412.
48	PHONGAMWONG T, CHANTAPRASERTPORN U, WITOON T, et al. CO₂ hydrogenation to methanol over CuO-ZnO-ZrO₂-SiO₂catalysts: effects of SiO₂ contents[J]. Chemical Engineering Journal, 2017, 316: 692-703.
49	SAMEI E, TAGHIZADEH M, BAHMANI M J F P T. Enhancement of stability and activity of Cu/ZnO/Al₂O₃catalysts by colloidal silica and metal oxides additives for methanol synthesis from a CO₂-rich feed[J]. Fuel Processing Technology, 2012, 96: 128-133.
50	GAO P, LI F, ZHANG L, et al. Influence of fluorine on the performance of fluorine-modified Cu/Zn/Al catalysts for CO₂ hydrogenation to methanol[J]. Journal of CO₂ Utilization, 2013, 2: 16-23.
51	GAO P, LI F, ZHAN H, et al. Fluorine-modified Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. Catalysis Communications, 2014, 50: 78-82.
52	ZHUANG H D, BAI S F, LIU X M, et al. Structure and performance of Cu/ZrO₂ catalyst for the synthesis of methanol from CO₂ hydrogenation[J]. Journal of Fuel Chemistry and Technology, 2010, 38(4): 462-467.
53	XIAO S, ZHANG Y, GAO P, et al. Highly efficient Cu-based catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. Catalysis Today, 2017, 281: 327-336.
54	程鹏泽, 高文桂, 纳薇, 等. 不同沉淀剂对CO₂加氢合成甲醇Cu-ZnO-ZrO₂催化剂性能的影响[J]. 化工进展, 2017, 36(8): 2955-2961.
54	CHENG P Z, GAO W G, NA W, et al. Influence of different precipitants on the properties of Cu-ZnO-ZrO₂catalyst for methanol synthesis through CO₂ hydrogenation[J]. Chemical Industry and Engineering Progress, 2017, 36(8): 2955-2961.
55	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.
56	LO I C, WU H S. Methanol formation from carbon dioxide hydrogenation using Cu/ZnO/Al₂O₃ catalyst[J]. Journal of the Taiwan Institute of Chemical Engineers, 2019, 98: 124-131.
57	LI L, MAO D, YU J, et al. Highly selective hydrogenation of CO₂ to methanol over CuO-ZnO-ZrO₂catalysts prepared by a surfactant-assisted co-precipitation method[J]. Journal of Power Sources, 2015, 279: 394-404.
58	DONG X, LI F, ZHAO N, et al. CO₂ hydrogenation to methanol over Cu/ZnO/ZrO₂ catalysts prepared by precipitation-reduction method[J]. Applied Catalysis B: Environmental, 2016, 191: 8-17.
59	CAI W J, DE LA PISCINA P R, TOYIR J, et al. CO₂hydrogenation to methanol over CuZnGa catalysts prepared using microwave-assisted methods[J]. Catalysis Today, 2015, 242: 193-199.
60	RAMLI M Z, SYED-HASSAN S S A, HADI A. Performance of Cu-Zn-Al-Zr catalyst prepared by ultrasonic spray precipitation technique in the synthesis of methanol via CO₂ hydrogenation[J]. Fuel Processing Technology, 2018, 169: 191-198.
61	DASIREDDY V D B C, LIKOZAR B. The role of copper oxidation state in Cu/ZnO/Al₂O₃ catalysts in CO₂ hydrogenation and methanol productivity[J]. Renewable Energy, 2019, 140: 452-460.
62	BONURA G, CORDARO M, CANNILLA C, et al. The changing nature of the active site of Cu-Zn-Zr catalysts for the CO₂ hydrogenation reaction to methanol[J]. Applied Catalysis B: Environmental, 2014, 152: 152-161.
63	GUO X, MAO D, LU G, et al. Glycine-nitrate combustion synthesis of CuO-ZnO-ZrO₂catalysts for methanol synthesis from CO₂ hydrogenation[J]. Journal of Catalysis, 2010, 271(2): 178-185.
64	张明宇, 王华, 高文桂. 真空冷冻干燥法制备 CuO-ZnO-ZrO₂甲醇合成催化剂[J]. 化工进展, 2013, 32(6): 1290-1295.
64	ZHANG M Y, WANG H, GAO W G. Preparation of CuO-ZnO-ZrO₂catalysts for methanol synthesis by vacuum freeze drying[J]. Chemical Industry and Engineering Progress, 2013, 32(6): 1290-1295.
65	刘祥志, 朴玲钰, 毛立娟, 等. 真空冷冻干燥制备高比表面积纳米氧化铝[J]. 物理化学学报, 2010, 26(4): 1171-1176.
65	LIU X Z, PIAO L Y, MAO L J, et al. Preparation of high specific surface srea nano-alumina by vacuum freeze drying[J]. Acta Physico-Chimica Sinica, 2010, 26(4): 1171-1176.
66	WITOON T, NUMPILAI T, PHONGAMWONG T, et al. Enhanced activity, selectivity and stability of a CuO-ZnO-ZrO₂ catalyst by adding graphene oxide for CO₂ hydrogenation to methanol[J]. Chemical Engineering Journal, 2018, 334: 1781-1791.
67	DEERATTRAKUL V, LIMPHIRAT W, KONGKACHUICHAY P. Influence of reduction time of catalyst on methanol synthesis via CO₂ hydrogenation using Cu-Zn/N-rGO investigated by in situ XANES[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 80: 495-502.
68	HUANG C, WEN J, SUN Y, et al. CO₂ hydrogenation to methanol over Cu/ZnO plate model catalyst: effects of reducing gas induced Cu nanoparticle morphology[J]. Chemical Engineering Journal, 2019, 374: 221-230.

[1]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[2]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[3]	舒斌, 陈建宏, 熊健, 吴其荣, 喻江涛, 杨平. 碳中和目标下推动绿色甲醇发展的必要性分析[J]. 化工进展, 2023, 42(9): 4471-4478.
[4]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.
[5]	王子健, 柯明, 宋昭峥, 李佳涵, 童燕兵, 孙巾茹. 分子筛催化汽油烷基化降苯技术研究进展[J]. 化工进展, 2023, 42(5): 2371-2389.
[6]	萧垚鑫, 张军, 胡升, 单锐, 袁浩然, 陈勇. 甲醇供氢体系铜锌双金属催化糠醛加氢转化[J]. 化工进展, 2023, 42(3): 1341-1352.
[7]	黄起中, 刘冰, 马红鹏, 吕文杰. 基于新型微通道分离技术的甲醇制烯烃废水处理[J]. 化工进展, 2023, 42(2): 669-676.
[8]	郭晓宇, 李冬晨, 赵炜, 杜朕屹, 李晓良. Au-Pd/MnO₂催化剂的制备及其苯甲醇氧化性能[J]. 化工进展, 2023, 42(10): 5223-5231.
[9]	郭峰, 张尚杰, 蒋羽佳, 姜万奎, 信丰学, 章文明, 姜岷. 一碳资源在酵母中的利用与转化[J]. 化工进展, 2023, 42(1): 30-39.
[10]	刘鹏龙, 许雄飞, 张玮, 许鑫, 张侃, 王俊文. 甲醇制芳烃K-means-PSO-SVR局部建模及优化[J]. 化工进展, 2022, 41(9): 4691-4700.
[11]	向晟, 王超, 庄钰, 顾偲雯, 张磊, 都健. 变压精馏分离乙酸甲酯-甲醇-乙酸乙酯体系的设计与控制[J]. 化工进展, 2022, 41(8): 4065-4076.
[12]	张嘉琪, 林丽娜, 高文桂, 祝星. CeO₂的形貌对CuO/CeO₂催化剂CO₂加氢制甲醇性能的影响[J]. 化工进展, 2022, 41(8): 4213-4223.
[13]	李贵贤, 张军强, 杨勇, 范学英, 王东亮. 基于PX选择性强化的短流程甲苯甲醇甲基化PX生产新工艺[J]. 化工进展, 2022, 41(6): 2939-2947.
[14]	王集杰, 韩哲, 陈思宇, 汤驰洲, 沙峰, 唐珊, 姚婷婷, 李灿. 太阳燃料甲醇合成[J]. 化工进展, 2022, 41(3): 1309-1317.
[15]	常斐, 詹国雄, 史森森, 曾少娟, 张香平. 离子液体电还原CO₂合成甲醇过程评价与分析[J]. 化工进展, 2022, 41(3): 1256-1264.