非平衡负离子与ZnO-ZrO2固溶体协同催化CO2与H2O反应制甲醇

doi:10.16085/j.issn.1000-6613.2021-0083

摘要/Abstract

摘要：

近年，CO₂加氢制甲醇技术初步克服了催化剂选择性低和稳定性差的难题，实现了工业化生产。然而作为氢源，氢气的廉价替代品却极少被报道。本文利用二元金属氧化物ZnO-ZrO₂固溶体作为催化剂，在负电晕等离子体的辅助下将CO₂和水蒸气转化为甲醇。结果表明，甲醇产量达到33.56μmol/h，是单独等离子体和单独催化剂条件下甲醇产量之和的1.4倍，催化剂与等离子体联用产生协同性。甲醇产量随反应电流和水蒸气流量的增大而增大，随CO₂流量的增加而降低。X射线衍射（XRD）、X射线光电子能谱分析（XPS）和CO₂-程序升温脱附（CO₂-TPD）表征发现，催化剂在负电晕等离子体反应条件下晶面间距增大，氧空位增多，这增强了催化剂的CO₂吸附性能。CO₂-漫反射傅里叶红外光谱（CO₂-DRIFTs）分析结果表明，负电晕等离子体处理后的催化剂反应过程中会产生羧酸盐（COO^-），是形成甲醇的主要中间物种。

关键词: 二氧化碳, 等离子体, 催化剂, 甲醇, 协同作用, 醇

Abstract:

CO₂ and water vapor was converted into methanol with the catalyst of ZnO-ZrO₂ solid solution and the aid of negative corona plasma, which provided synergistic effect when employed together. The yield of methanol was 33.56μmol/h, which was 1.4 times of the sum of those under plasma alone and catalyst alone. The methanol yield increased with the increase of reaction current and steam flow rate, but decreased with the increase of CO₂ flow rate. The results of XRD, XPS and CO₂-TPD showed that the crystal plane spacing and oxygen vacancies of the catalyst increased under negative corona plasma condition, which enhanced the CO₂ adsorption on the catalyst. The CO₂-DRIFTs results showed that carboxylate (COO^-) was the main intermediate species during the methanol formation.

Key words: carbon dioxide, plasma, catalyst, methanol, synergy, alcohol

中图分类号:

TQ531.7

徐瑞, 杨凡, 贾显枝, 刘璐, 赵彬然, 马晓迅. 非平衡负离子与ZnO-ZrO₂固溶体协同催化CO₂与H₂O反应制甲醇[J]. 化工进展, 2021, 40(12): 6714-6720.

XU Rui, YANG Fan, JIA Xianzhi, LIU Lu, ZHAO Binran, MA Xiaoxun. Preparation of methanol from CO₂ and H₂O catalyzed by non-equilibrium anion and ZnO-ZrO₂ solid solution[J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6714-6720.

图/表 10

表1 不同反应条件的甲醇产量

项目	C^①									P^②	（P+C）^③
温度/℃	110	130	150	170	210	230	250	270	290	150	150
甲醇产量/μmol·h^-1	2.00	2.07	2.66	2.62	2.07	2.53	2.67	2.21	1.43	21.09	33.56
甲醇产量^④/μmol·g $c a t - 1$ ·h^-1	6.67	6.90	8.87	8.73	6.90	8.43	8.90	7.37	4.77		111.86

表1 不同反应条件的甲醇产量

项目	C^①									P^②	（P+C）^③
温度/℃	110	130	150	170	210	230	250	270	290	150	150
甲醇产量/μmol·h^-1	2.00	2.07	2.66	2.62	2.07	2.53	2.67	2.21	1.43	21.09	33.56
甲醇产量^④/μmol·g $c a t - 1$ ·h^-1	6.67	6.90	8.87	8.73	6.90	8.43	8.90	7.37	4.77		111.86

图1 不同摩尔分数催化剂中CO2流量对甲醇产量的影响

图2 CO2流量对醇类产物产量的影响

图3 反应电流对甲醇产量的影响

图4 水蒸气流量对甲醇产量的影响

图5 ZnO-ZrO2催化剂的XRD图

图6 ZnO-ZrO2催化剂的XPS图

图7 7%ZnO-ZrO2催化剂反应前后的CO2-TPD图

图8 等离子反应后催化剂的CO2-DRIFTs表征结果

图9 等离子体联合催化剂合成甲醇机理图

参考文献 30

1	BETTS R A, JONES C D, KNIGHT J R, et al. El Niño and a record CO₂ rise[J]. Nature Climate Change, 2016, 6(9): 806-810.
2	HEPBURN C, ADLEN E, BEDDINGTON J, et al. The technological and economic prospects for CO₂ utilization and removal[J]. Nature, 2019, 575(7781): 87-97.
3	LI J, ZHANG X, SHEN J, et al. Dissociation of CO₂ by thermal plasma with contracting nozzle quenching[J]. Journal of CO₂ Utilization, 2017, 21: 72-76.
4	PERATHONER S, CENTI G. CO₂ recycling: a key strategy to introduce green energy in the chemical production chain[J]. ChemSusChem, 2014, 7(5): 1274-1282.
5	WANG W, QU Z, SONG L, et al. CO₂ hydrogenation to methanol over Cu/CeO₂ and Cu/ZrO₂ catalysts: tuning methanol selectivity via metal-support interaction[J]. Journal of Energy Chemistry, 2020, 40(1): 22-30.
6	王有和, 吴成成, 刘忠文, 等. 甲醇制烯烃反应工艺、反应机理及其动力学研究进展[J]. 工业催化, 2018, 26(1): 13-21.
	WANG Youhe, WU Chengcheng, LIU Zhongwen, et al. Progresses in reaction processes, mechanism and kinetics of methanol to olefins[J]. Industrial Catalysis, 2018, 26(1): 13-21.
7	WANG S, WEI Z, CHEN Y, et al. Methanol to Olefins over H-MCM-22 zeolite: theoretical study on the catalytic roles of various pores[J]. ACS Catalysis, 2015, 5(2): 1131-1144.
8	KAR S, KOTHANDARAMAN J, GOEPPERT A, et al. Advances in catalytic homogeneous hydrogenation of carbon dioxide to methanol[J]. Journal of CO₂ Utilization, 2018, 23: 212-218.
9	高鹏, 李枫, 赵宁, 等. 以类水滑石为前驱体的Cu/Zn/Al/(Zr)/(Y)催化剂制备及其催化CO₂加氢合成甲醇的性能[J]. 物理化学学报, 2014, 30(6): 1155-1162.
	GAO Peng, LI Feng, ZHAO Ning, et al. Preparation of Cu/Zn/Al/(Zr)/(Y) catalysts from hydrotalcite-like precursors and their catalytic performance for the hydrogenation of CO₂ to methanol[J]. Acta Physico-Chimica Sinica, 2014, 30(6): 1155-1162.
10	BAHRUJI H, BOWKER M, HUTCHINGS G, et al. Pd/ZnO catalysts for direct CO₂ hydrogenation to methanol[J]. Journal of Catalysis, 2016, 343: 133-146.
11	BONGERS W, BOUWMEESTER H, WOLF B, et al. Plasma-driven dissociation of CO₂ for fuel synthesis[J]. Plasma Processes and Polymers, 2017, 14(6): 1600126.
12	BELOV I, VERMEIREN V, PAULUSSEN S, et al. Carbon dioxide dissociation in a microwave plasma reactor operating in a wide pressure range and different gas inlet configurations[J]. Journal of CO₂ Utilization, 2018, 24: 386-397.
13	WANG L, YI Y, WU C, et al. One-step reforming of CO₂ and CH₄ into high-value liquid chemicals and fuels at room temperature by plasma-driven catalysis[J]. Angewandte Chemie, 2017, 56(44): 13679-13683.
14	陈亮, 鲁群苟, 胡辉, 等. 直流电晕等离子体重整甲烷二氧化碳制取合成气的研究[J]. 应用化工, 2018, 47(9): 1947-1951.
	CHEN Liang, LU Qungou, HU Hui, et al. Study on CO₂ reforming of CH₄ to make synthesis gas by DC corona plasma[J]. Applied Chemical Industry, 2018, 47(9): 1947-1951.
15	CHEN P, SHEN J, RAN T, et al. Investigation of operating parameters on CO₂ splitting by dielectric barrier discharge plasma[J]. Plasma Science and Technology, 2017, 19(12): 123-128.
16	DURME J V, DEWULF J, LEYS C, et al. Combining non-thermal plasma with heterogeneous catalysis in waste gas treatment: a review[J]. Applied Catalysis B: Environmental, 2008, 78(3/4): 324-333.
17	CHE F, GRAY J T, HA S, et al. Catalytic water dehydrogenation and formation on nickel: dual path mechanism in high electric fields[J]. Journal of Catalysis, 2015, 332: 187-200.
18	MEI D, ZHU X, WU C, et al. Plasma-photocatalytic conversion of CO₂ at low temperatures: understanding the synergistic effect of plasma-catalysis[J]. Applied Catalysis B: Environmental, 2016, 182: 525-532.
19	CHEN G, BRITUN N, GODFROID T, et al. An overview of CO₂ conversion in a microwave discharge: the role of plasma-catalysis[J]. Journal of Physics D: Applied Physics, 2017, 50(8): 084001.
20	MICHIELSEN I, UYTDENHOUWEN Y, PYPE J, et al. CO₂ dissociation in a packed bed DBD reactor: first steps towards a better understanding of plasma catalysis[J]. Chemical Engineering Journal, 2017, 326: 477-488.
21	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.
22	郭利, 向小凤, 伍星, 等. 非平衡碘负离子转化二氧化碳[J]. 化工学报, 2012, 63(10): 3297-3303.
	GUO Li, XIANG Xiaofeng, WU Xing, et al. Conversion of carbon dioxide with non-equilibrium electronegative ions of iodine[J]. CIESC Journal, 2012, 63(10): 3297-3303.
23	ZHAO B, LIU Y, ZHU Z, et al. Highly selective conversion of CO₂ into ethanol on Cu/ZnO/Al₂O₃ catalyst with the assistance of plasma[J]. Journal of CO₂ Utilization, 2018, 24: 34-39.
24	GUO L, MA X, XIA Y, et al. A novel method of production of ethanol by carbon dioxide with steam[J]. Fuel, 2015, 158: 843-847.
25	CIMINO A, STONE F S. Oxide solid solutions as catalysts[J]. Advances in Catalysis, 2002, 47: 141-306.
26	SINGHAL A. Study of electronic and magnetic properties of vacuum annealed Cr doped ZnO[J]. Journal of Alloys and Compounds, 2012, 515(1): 12-15.
27	VELU S, SUZUKI K, GOPINATH C S, et al. XPS, XANES and EXAFS investigations of CuO/ZnO/Al₂O₃/ZrO₂ mixed oxidecatalysts[J]. Physical Chemistry Chemical Physics, 2002, 4(10): 1990-1999.
28	JIN Y, CUI Q, WEN G, et al. XPS and Raman scattering studies of room temperature ferromagnetic ZnO: Cu[J]. Journal of Physics D: Applied Physics, 2009, 42(21): 215007.
29	SUN J, ZHU K, GAO F, et al. Direct conversion of bio-ethanol to isobutene on nanosized Zn_xZr_yO_zmixed oxides with balanced acid-base sites[J]. Journal of the American Chemical Society, 2011, 133(29): 11096-11099.
30	MILLAR G J, ROCHESTER C H, BAILEY S, et al. Combined temperature-programmed desorption and fourier-transform infrared spectroscopy study of CO₂, CO and H₂ interactions with model ZnO/SiO₂, Cu/SiO₂ and Cu/ZnO/SiO₂ methanol synthesis catalysts[J]. Journal of the Chemical Society, Faraday Transactions, 1993, 89(7): 1109-1115.

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非平衡负离子与ZnO-ZrO₂固溶体协同催化CO₂与H₂O反应制甲醇

Preparation of methanol from CO₂ and H₂O catalyzed by non-equilibrium anion and ZnO-ZrO₂ solid solution

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