太阳燃料甲醇合成

doi:10.16085/j.issn.1000-6613.2022-0244

化工进展 ›› 2022, Vol. 41 ›› Issue (3): 1309-1317.DOI: 10.16085/j.issn.1000-6613.2022-0244

• 可再生能源的开发利用 • 上一篇下一篇

太阳燃料甲醇合成

王集杰¹(), 韩哲¹, 陈思宇¹^,², 汤驰洲¹^,², 沙峰¹^,³, 唐珊¹^,², 姚婷婷¹, 李灿¹()

^1.中国科学院大连化学物理研究所，催化基础国家重点实验室，辽宁大连 116023
^2.中国科学院大学，北京 100049
^3.南开大学材料科学与工程学院，天津 300350

收稿日期:2022-02-16 修回日期:2022-03-04 出版日期:2022-03-23 发布日期:2022-03-28
通讯作者: 李灿
作者简介:王集杰（1985—），男，研究员，研究方向为液态阳光及二氧化碳资源化利用。E-mail：jjwang@dicp.ac.cn。
基金资助:
人工光合成基础科学中心(22088102);国家自然科学基金(22172160);中国科学院A类先导专项(XDA21090200);中国科学院青年创新促进会项目(2019183)

Liquid sunshine methanol

WANG Jijie¹(), HAN Zhe¹, CHEN Siyu¹^,², TANG Chizhou¹^,², SHA Feng¹^,³, TANG Shan¹^,², YAO Tingting¹, LI Can¹()

^1.State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^2.University of Chinese Academy of Sciences, Beijing 100049, China
^3.School of Materials Science and Engineering and National Institute for Advanced Materials, Nankai University, Tianjin, 300350, China

Received:2022-02-16 Revised:2022-03-04 Online:2022-03-23 Published:2022-03-28
Contact: LI Can

摘要/Abstract

摘要：

我国将力争于2060年前实现碳中和，而实现碳中和的根本途径是能源利用形式由化石能源向可再生能源转变。本文指出太阳燃料甲醇合成（又称“液态阳光”）是利用太阳能等可再生能源分解水制取绿氢，再将二氧化碳与绿氢结合转化为甲醇的综合性技术，它不仅可将再生能源存储在液体燃料甲醇中，还可解决重要领域如冶金、建材、化工中的刚性二氧化碳排放，是实现碳中和目标切实可行的技术路线和有力手段。本文就作者团队研究发展的液态阳光水分解制氢和二氧化碳加氢制甲醇技术进行总结，并对当前液态阳光技术的工业应用进行了介绍。

关键词: 液态阳光, 水分解制氢, 绿色氢能, 二氧化碳加氢, 绿色甲醇合成

Abstract:

We will strive to achieve carbon neutrality by 2060. The fundamental route to achieve carbon neutrality is to transform energy use form from fossil energy to renewable energy. Liquid sunshine is an integrated technology, which utilizing solar energy or other renewable energy to produce green hydrogen from water splitting, then converting CO₂ with green hydrogen into methanol. It is not only a new energy storage form for renewable energy, but also an effective way to solve the problem of rigid CO₂ emissions from industry, such as metallurgy, and building materials, chemical industry. In this paper, the latest research progress of liquid sunshine is summarized, including two key technologies: hydrogen production from water splitting and CO₂ hydrogenation to methanol. Finally, the industrial application of liquid sunshine technology is briefly introduced.

Key words: liquid sunshine, water splitting, green hydrogen, CO₂ hydrogenation, green methanol synthesis

中图分类号:

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.

WANG Jijie, HAN Zhe, CHEN Siyu, TANG Chizhou, SHA Feng, TANG Shan, YAO Tingting, LI Can. Liquid sunshine methanol[J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1309-1317.

图/表 7

参考文献 53

1	STOCKER T F, QIN D, G-K PLATTNER, et al. Climate change 2013: the physical science basis[R]. New York: Intergovernmental Panel on Climate Change, 2014.
2	OLAH George A. Beyond oil and gas: the methanol economy[J]. Angewandte Chemie International Edition, 2005, 44(18): 2636-2639.
3	SHIH Choon Fong, ZHANG Tao, LI Jinghai, et al. Powering the future with liquid sunshine[J]. Joule, 2018, 2(10): 1925-1949.
4	ZHANG Jian, WANG Tao, LIU Pan, et al. Efficient hydrogen production on MoNi₄ electrocatalysts with fast water dissociation kinetics[J]. Nature Communications, 2017, 8: 15437.
5	ZHANG Jian, WANG Tao, LIU Pan, et al. Engineering water dissociation sites in MoS₂ nanosheets for accelerated electrocatalytic hydrogen production[J]. Energy & Environmental Science, 2016, 9(9): 2789-2793.
6	ZHANG Zhicheng, LIU Guigao, CUI Xiaoya, et al. Crystal phase and architecture engineering of lotus-thalamus-shaped Pt-Ni anisotropic superstructures for highly efficient electrochemical hydrogen evolution[J]. Advanced Materials, 2018, 30(30): e1801741.
7	YE Sheng, DING Chunmei, LIU Mingyao, et al. Water oxidation catalysts for artificial photosynthesis[J]. Advanced Materials, 2019, 31(50): e1902069.
8	ZOU Xiaoxin, ZHANG Yu. Noble metal-free hydrogen evolution catalysts for water splitting[J]. Chemical Society Reviews, 2015, 44(15): 5148-5180.
9	KING Laurie A, HUBERT McKenzie A, CAPUANO Christopher, et al. A non-precious metal hydrogen catalyst in a commercial polymer electrolyte membrane electrolyser[J]. Nature Nanotechnology, 2019, 14(11): 1071-1074.
10	LI Ailong, KONG Shuang, GUO Chenxi, et al. Enhancing the stability of cobalt spinel oxide towards sustainable oxygen evolution in acid[J]. Nature Catalysis, 2022, 5(2): 109-118.
11	何泽兴, 史成香, 陈志超, 等. 质子交换膜电解水制氢技术的发展现状及展望[J]. 化工进展, 2021, 40(9): 4762-4773.
	HE Zexing, SHI Chengxiang, CHEN Zhichao, et al. Development status and prospects of proton exchange membrane water electrolysis[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 4762-4773.
12	LI Ailong, SUN Yimeng, YAO Tingting, et al. Earth-abundant transition-metal-based electrocatalysts for water electrolysis to produce renewable hydrogen[J]. Chemistry, 2018, 24(69): 18334-18355.
13	NAKAMURA J, CHOI Y, FUJITANI T. On the issue of the active site and the role of ZnO in Cu/ZnO methanol synthesis catalysts[J]. Topics in Catalysis, 2003, 22(3/4): 277-285.
14	KUNKES Edward L, STUDT Felix, Frank ABILD-PEDERSEN, et al. Hydrogenation of CO₂ to methanol and CO on Cu/ZnO/Al₂O₃: is there a common intermediate or not? [J]. Journal of Catalysis, 2015, 328: 43-48.
15	FICHTL Matthias B, SCHLERETH David, JACOBSEN Nikolas, et al. Kinetics of deactivation on Cu/ZnO/Al₂O₃ methanol synthesis catalysts[J]. Applied Catalysis A: General, 2015, 502: 262-270.
16	WANG Jijie, LI Guanna, LI Zelong, et al. A highly selective and stable ZnO-ZrO₂ solid solution catalyst for CO₂ hydrogenation to methanol[J]. Science Advances, 2017, 3(10): e1701290.
17	WANG Jijie, TANG Chizhou, LI Guanna, et al. High-performance M_aZrO _x (M_a = Cd, Ga) solid-solution catalysts for CO₂ hydrogenation to methanol[J]. ACS Catalysis, 2019, 9(11): 10253-10259.
18	YE Jingyun, LIU Changjun, GE Qingfeng. DFT study of CO₂ adsorption and hydrogenation on the In₂O₃ surface[J]. The Journal of Physical Chemistry C, 2012, 116(14): 7817-7825.
19	YE Jingyun, LIU Changjun, MEI Donghai, 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.
20	SUN Kaihang, FAN Zhigang, YE Jingyun, et al. Hydrogenation of CO₂ to methanol over In₂O₃ catalyst[J]. Journal of CO₂ Utilization, 2015, 12: 1-6.
21	MARTIN Oliver, MARTÍN Antonio J, MONDELLI Cecilia, et al. Indium oxide as a superior catalyst for methanol synthesis by CO₂ hydrogenation[J]. Angewandte Chemie International Edition, 2016, 55(21): 6261-6265.
22	JIANG Xiao, NIE Xiaowa, GUO Xinwen, et al. Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis[J]. Chemical Reviews, 2020, 120(15): 7984-8034.
23	KATTEL Shyam, RAMÍREZ Pedro J, CHEN Jingguang, et al. Active sites for CO₂ hydrogenation to methanol on Cu/ZnO catalysts[J]. Science, 2017, 355(6331): 1296-1299.
24	KATTEL Shyam, RAMÍREZ Pedro J, CHEN Jingguang, et al. Response to comment on “active sites for CO₂ hydrogenation to methanol on Cu/ZnO catalysts”[J]. Science, 2017, 357(6354): eaan8210.
25	BEHRENS Malte, STUDT Felix, KASATKIN Igor, et al. The active site of methanol synthesis over Cu/ZnO/Al₂O₃ industrial catalysts[J]. Science, 2012, 336(6083): 893-897.
26	LUNKENBEIN Thomas, SCHUMANN Julia, BEHRENS Malte, et al. Formation of a ZnO overlayer in industrial Cu/ZnO/Al₂O₃ catalysts induced by strong metal-support interactions[J]. Angewandte Chemie International Edition, 2015, 54(15): 4544-4548.
27	NAKAMURA Junji, FUJITANI Tadahiro, KULD Sebastian, et al. Comment on “active sites for CO₂ hydrogenation to methanol on Cu/ZnO catalysts”[J]. Science, 2017, 357(6354): eaan8074.
28	BANSODE Atul, TIDONA Bruno, ROHR Philipp Rudolf VON, et al. Impact of K and Ba promoters on CO₂ hydrogenation over Cu/Al₂O₃ catalysts at high pressure[J]. Catalysis Science & Technology, 2013, 3(3): 767-778.
29	BAN Hongyan, LI Congming, ASAMI Kenji, 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.
30	NOMURA Naofumi, TAGAWA Tomohiko, GOTO Shigeo. Effect of acid-base properties on copper catalysts for hydrogenation of carbon dioxide[J]. Reaction Kinetics and Catalysis Letters, 1998, 63(1): 21-25.
31	PHONGAMWONG Thanaree, CHANTAPRASERTPORN Usanee, WITOON Thongthai, et al. CO₂ hydrogenation to methanol over CuO-ZnO-ZrO₂-SiO₂ catalysts: effects of SiO₂ contents[J]. Chemical Engineering Journal, 2017, 316: 692-703.
32	ARENA F, MEZZATESTA G, ZAFARANA G, et al. How oxide carriers control the catalytic functionality of the Cu-ZnO system in the hydrogenation of CO₂ to methanol[J]. Catalysis Today, 2013, 210: 39-46.
33	Mei Kee KOH, KHAVARIAN Mehrnoush, CHAI Siang Piao, et al. The morphological impact of siliceous porous carriers on copper-catalysts for selective direct CO₂ hydrogenation to methanol[J]. International Journal of Hydrogen Energy, 2018, 43(19): 9334-9342.
34	WANG Guannan, CHEN Limin, SUN Yuhai, et al. Carbon dioxide hydrogenation to methanol over Cu/ZrO₂/CNTs: effect of carbon surface chemistry[J]. RSC Advances, 2015, 5(56): 45320-45330.
35	TISSERAUD Céline, COMMINGES Clément, HABRIOUX Aurélien, et al. Cu-ZnO catalysts for CO₂ hydrogenation to methanol: morphology change induced by ZnO lixiviation and its impact on the active phase formation[J]. Molecular Catalysis, 2018, 446: 98-105.
36	LI Molly M J, CHEN Chunping, Ayvalı TUĞÇE, et al. CO₂ hydrogenation to methanol over catalysts derived from single cationic layer CuZnGa LDH precursors[J]. ACS Catalysis, 2018, 8(5): 4390-4401.
37	ZHANG Chen, YANG Haiyan, GAO Peng, 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.
38	BEHRENS Malte. Coprecipitation: an excellent tool for the synthesis of supported metal catalysts—From the understanding of the well known recipes to new materials[J]. Catalysis Today, 2015, 246: 46-54.
39	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.
40	DANG Shanshan, QIN Bin, YANG Yong, et al. Rationally designed indium oxide catalysts for CO₂ hydrogenation to methanol with high activity and selectivity[J]. Science Advances, 2020, 6(25): eaaz2060.
41	TSOUKALOU Athanasia, ABDALA Paula M, STOIAN Dragos, et al. Structural evolution and dynamics of an In₂O₃ catalyst for CO₂ hydrogenation to methanol: an operando XAS-XRD and in situ TEM study[J]. Journal of the American Chemical Society, 2019, 141(34): 13497-13505.
42	RUI Ning, WANG Zongyuan, SUN Kaihang, et al. CO₂ hydrogenation to methanol over Pd/In₂O₃: effects of Pd and oxygen vacancy[J]. Applied Catalysis B: Environmental, 2017, 218: 488-497.
43	YE Jingyun, LIU Changjun, MEI Donghai, et al. Methanol synthesis from CO₂ hydrogenation over a Pd₄/In₂O₃ model catalyst: a combined DFT and kinetic study[J]. Journal of Catalysis, 2014, 317: 44-53.
44	HAN Zhe, TANG Chizhou, WANG Jijie, et al. Atomically dispersed Pt ⁿ ⁺ species as highly active sites in Pt/In₂O₃ catalysts for methanol synthesis from CO₂ hydrogenation[J]. Journal of Catalysis, 2021, 394: 236-244.
45	SUN Kaihang, RUI Ning, ZHANG Zhitao, et al. A highly active Pt/In₂O₃ catalyst for CO₂ hydrogenation to methanol with enhanced stability[J]. Green Chemistry, 2020, 22(15): 5059-5066.
46	WANG Jing, SUN Kaihang, JIA Xinyu, et al. CO₂ hydrogenation to methanol over Rh/In₂O₃ catalyst[J]. Catalysis Today, 2021, 365: 341-347.
47	RUI Ning, ZHANG Feng, SUN Kaihang, et al. Hydrogenation of CO₂ to methanol on a Au ^δ ⁺-In₂O_3- _x catalyst[J]. ACS Catalysis, 2020, 10(19): 11307-11317.
48	JIA Xinyu, SUN Kaihang, WANG Jing, et al. Selective hydrogenation of CO₂ to methanol over Ni/In₂O₃ catalyst[J]. Journal of Energy Chemistry, 2020, 50: 409-415.
49	BAVYKINA Anastasiya, YARULINA Irina, ABDULGHANI Abdullah J AL, et al. Turning a methanation Co catalyst into an In-Co methanol producer[J]. ACS Catalysis, 2019, 9(8): 6910-6918.
50	HAN Zhe, TANG Chizhou, SHA Feng, et al. CO₂ hydrogenation to methanol on ZnO-ZrO₂ solid solution catalysts with ordered mesoporous structure[J]. Journal of Catalysis, 2021, 396: 242-250.
51	HALPER Mark. Forget storing carbon; re-use it: a company in Iceland is turning CO₂ into methanol to power cars[J]. Renewable Energy Focus, 2011, 12(1): 56-58.
52	SINGH Surinder P, HAO Pingjiao, LIU Xiao, et al. Large-scale affordable CO₂ capture is possible by 2030[J]. Joule, 2019, 3(9): 2154-2164.
53	姬加良. 煤与不同原料重整气化制甲醇对CO₂排放的影响[J]. 能源科技, 2020, 18(2): 62-66.
	JI Jialiang. Effect of reforming gasification to methanol by coal and different raw materials on carbon dioxide emission[J]. Energy Science and Technology, 2020, 18(2): 62-66.

成本	工艺名称	煤制甲醇 /×10⁸CNY	液态阳光甲醇 /×10⁸CNY
固定资产	造气	6.60
	空分	4.20
	变换	0.84
	净化	1.88
	电解水装置		5.70^①
	其他/公用工程等	21.08	14.05^②
	小计	34.60	19.75
运行成本	煤消耗	9.00^③
	空分	1.80
	制氢电耗		9.11^①
	二氧化碳的捕获		1.34^④
	其他	1.50	1.50
	小计	12.30	11.95
甲醇成本		2627CNY/t	2321CNY/t
考虑碳税成本		2777CNY/t^⑤	2261CNY/t^⑥

成本	工艺名称	煤制甲醇 /×10⁸CNY	液态阳光甲醇 /×10⁸CNY
固定资产	造气	6.60
	空分	4.20
	变换	0.84
	净化	1.88
	电解水装置		5.70^①
	其他/公用工程等	21.08	14.05^②
	小计	34.60	19.75
运行成本	煤消耗	9.00^③
	空分	1.80
	制氢电耗		9.11^①
	二氧化碳的捕获		1.34^④
	其他	1.50	1.50
	小计	12.30	11.95
甲醇成本		2627CNY/t	2321CNY/t
考虑碳税成本		2777CNY/t^⑤	2261CNY/t^⑥

煤制甲醇		液态阳光甲醇
煤炭价格 /CNY·t^-1	甲醇成本 /CNY·t^-1	可再生能源发电成本/CNY·（kW·h^-1）	甲醇成本 /CNY·t^-1
500	1800	0.1	1600
1000	2600	0.2	2600
1500	3300	0.3	3600
2000	4100	0.4	4600

煤制甲醇		液态阳光甲醇
煤炭价格 /CNY·t^-1	甲醇成本 /CNY·t^-1	可再生能源发电成本/CNY·（kW·h^-1）	甲醇成本 /CNY·t^-1
500	1800	0.1	1600
1000	2600	0.2	2600
1500	3300	0.3	3600
2000	4100	0.4	4600

[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]	刘畅, 刘忠文. CO₂加氢一步制二甲醚展望[J]. 化工进展, 2022, 41(3): 1115-1120.
[3]	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.

太阳燃料甲醇合成

Liquid sunshine methanol

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 53

相关文章 3

编辑推荐

Metrics

本文评价