草酸二甲酯加氢制乙醇酸甲酯反应网络分析及其多相加氢催化剂研究进展

doi:10.16085/j.issn.1000-6613.2022-0501

摘要/Abstract

摘要：

乙醇酸甲酯（MG）官能团丰富，是一种重要的精细化工中间体，而且经过缩聚反应可制得新一代可生物降解材料聚乙醇酸。采用合成气经草酸二甲酯（DMO）加氢路线可实现MG的规模化制备，而该技术工业化的关键是高性能加氢催化剂的开发，当前DMO加氢制MG催化剂正处于工业化前期阶段。本文分析了DMO加氢反应网络及各特征反应的热力学特点，重点概述了DMO多相加氢制MG催化剂的研究进展，包括铜基催化剂、银基催化剂、非铜/银基催化剂等，基于网络特点分析了各催化剂的研究重点及存在的难题，并从反应工艺控制、催化剂载体设计、助剂及活性组分选择等角度提出了改善工业化催化剂开发及性能的思路，建议近期将改性复合载体负载的铜基催化剂，或以银、镍等为第二助剂的复合铜基催化剂作为重点攻关方向，远期将新型非贵金属体系作为储备方向，期望能为开发我国自主知识产权的工业化催化剂提供有益参考。

关键词: 合成气, 乙醇酸甲酯, 多相催化剂, 乙二醇, 可降解材料, 加氢

Abstract:

Methyl glycolate(MG) is an important fine chemical intermediate with special functional groups, and a new biodegradable plastic of polyglycolic acid (PAG) can be synthesized by the polycondensation of MG. MG can be produced in large-scale via selective hydrogenation of dimethyl oxalate from syngas and the high-performance catalyst is the key, which however is still in the early stage of industrialization. The reaction network and reaction characteristics are analyzed in the work. Subsequently, the heterogeneous catalysts for the hydrogenation of DMO to MG is overviewed, including Cu-based catalysts, Ag-based catalysts, and other catalyst systems. The focuses and existing problems of current researches are discussed in detail, and some improvements for the MG catalysts are also suggested. This review will be a useful reference for the development of hydrogenation catalyst with independent intellectual property rights.

Key words: syngas, methyl glycolate, heterogeneous catalyst, ethylene glycol, biodegradable plastics, hydrogenation

中图分类号:

O643.36

张大洲, 卢文新, 商宽祥, 胡媛, 朱凡, 张宗飞. 草酸二甲酯加氢制乙醇酸甲酯反应网络分析及其多相加氢催化剂研究进展[J]. 化工进展, 2023, 42(1): 204-214.

ZHANG Dazhou, LU Wenxin, SHANG Kuanxiang, HU Yuan, ZHU Fan, ZHANG Zongfei. Reaction network analysis of dimethyl oxalate hydrogenation to methyl glycolate and recent progress in the heterogeneous catalysts[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 204-214.

图/表 8

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序号	催化剂	制备方法	压力/MPa	温度/℃	液时空速/h^-1	氢酯物质的量比	DMO转化率/%	MG选择性/%	稳定性	发表年份	参考文献
1	Cu/AC	蒸氨法	2.5	220	0.18	120	83	92	120h	2016	[15]
2	NaCu/SiO₂	蒸氨浸渍法	2.5	200	1.5	80	84	99.8	—	2020	[19]
3	Cu₃ /CeO₂	原子迁移法	2.5	200	6.0	80	100	95	—	2019	[17]
4	Cu/NASH	硬模版法	2.5	195	2.0	70	90	54	150h	2019	[17]
5	SP-Cu/SiO₂	等离子体轰击	3.0	240	0.5	150	16	80	30h	2018	[9]
6	20Cu-1Ni-3Ag/SiO₂	蒸氨法	2.0	220	0.7	80	89	83.9	—	2018	[20]
7	CuNi/SiO₂	水热法	2.0	200	0.5	150	90	90	100h	2017	[21]
8	Cu/HZSM5	蒸氨法	3.0	220	0.5	80	99.85	93.18	—	2016	[22]
9	CuAg/SiO₂	沉淀法	2.0	230	0.8	30	92.3	83.6	500h	2015	[23]
10	Cu/SiO₂	蒸氨法	2~2.5	200	0.3~0.7	40~60	≥80	≥80	—	2014	[24]
11	CuAg/SiO₂	不详	2.5	195	0.7	100	98.8	75.2	900h	2012	[25]
12	Cu/HPA	蒸氨法	2.5	210	0.4	150	85	75	120h	2015	[12]
13	CuAg/Ni-foam	浸渍法	2.5	210	0.25	200	96	96	200	2017	[26]
14	Cu/ZrO₂-SiO₂	蒸氨法	2.0	200	0.3	150	91.6	88.9	100h	2017	[13]
15	Cu/B-AC	浸渍法	2.4	230	1.0	180	73.4	65.9	130h	2020	[10]
16	Cu/RGO	超声浸渍	2.5	210	0.257	200	>90	>90	300h	2018	[14]
17	CuCe/SiO₂	蒸氨法	2.0	185	1.2	100	65.3	91	—	2021	[18]
18	Ag/AC-N	浸渍法	3.0	220	0.6	80	100	96	150h	2017	[27]
19	Ag-B/SiO₂	蒸氨-浸渍	1.5	220	0.28	150	100	88.3	300h	2018	[20]
20	负载型	不详	2.0	186	0.5	20	99.3	83.0	—	2018	[28]
21	Ag/SBA-15	浸渍法	3.0	200	0.6	100	99	94	100h	2013	[29]
22	15Ag/SiO₂	溶胶凝胶法	2.5	220	0.2	100	100	92	120h	2010	[30]
23	Ag-in/hCNT	浸渍法	3.0	220	0.6	80	>99%	>98%	200h	2016	[31]
24	Ag/Ti-KCC	浸渍法	3.0	200	1.75	100	98	95	100h	2019	[32]
25	Ru/AC-HNO₃	浸渍法	5	90	—	—	100	92.3	釜式	2021	[33]
26	Ni-Foam	水热法	2.5	230	0.44	180	99	95	1000h	2019	[34]
27	Ni₂P-TiO₂	浸渍法	3.0	230	0.1	300	100	76	3600h	2016	[35]
28	CoP/SiO₂	浸渍法	3.0	240	0.28	160	94.6	88.1	300h	2022	[36]
29	Au-Fe/ZrO₂	超声分解法	2.5	200	0.257	200	100	95	300h	2020	[37]
30	Ni₃P/RB-MSN	浸渍法	2.5	190	0.44	90	100	85	500h	2021	[38]

序号	催化剂	制备方法	压力/MPa	温度/℃	液时空速/h^-1	氢酯物质的量比	DMO转化率/%	MG选择性/%	稳定性	发表年份	参考文献
1	Cu/AC	蒸氨法	2.5	220	0.18	120	83	92	120h	2016	[15]
2	NaCu/SiO₂	蒸氨浸渍法	2.5	200	1.5	80	84	99.8	—	2020	[19]
3	Cu₃ /CeO₂	原子迁移法	2.5	200	6.0	80	100	95	—	2019	[17]
4	Cu/NASH	硬模版法	2.5	195	2.0	70	90	54	150h	2019	[17]
5	SP-Cu/SiO₂	等离子体轰击	3.0	240	0.5	150	16	80	30h	2018	[9]
6	20Cu-1Ni-3Ag/SiO₂	蒸氨法	2.0	220	0.7	80	89	83.9	—	2018	[20]
7	CuNi/SiO₂	水热法	2.0	200	0.5	150	90	90	100h	2017	[21]
8	Cu/HZSM5	蒸氨法	3.0	220	0.5	80	99.85	93.18	—	2016	[22]
9	CuAg/SiO₂	沉淀法	2.0	230	0.8	30	92.3	83.6	500h	2015	[23]
10	Cu/SiO₂	蒸氨法	2~2.5	200	0.3~0.7	40~60	≥80	≥80	—	2014	[24]
11	CuAg/SiO₂	不详	2.5	195	0.7	100	98.8	75.2	900h	2012	[25]
12	Cu/HPA	蒸氨法	2.5	210	0.4	150	85	75	120h	2015	[12]
13	CuAg/Ni-foam	浸渍法	2.5	210	0.25	200	96	96	200	2017	[26]
14	Cu/ZrO₂-SiO₂	蒸氨法	2.0	200	0.3	150	91.6	88.9	100h	2017	[13]
15	Cu/B-AC	浸渍法	2.4	230	1.0	180	73.4	65.9	130h	2020	[10]
16	Cu/RGO	超声浸渍	2.5	210	0.257	200	>90	>90	300h	2018	[14]
17	CuCe/SiO₂	蒸氨法	2.0	185	1.2	100	65.3	91	—	2021	[18]
18	Ag/AC-N	浸渍法	3.0	220	0.6	80	100	96	150h	2017	[27]
19	Ag-B/SiO₂	蒸氨-浸渍	1.5	220	0.28	150	100	88.3	300h	2018	[20]
20	负载型	不详	2.0	186	0.5	20	99.3	83.0	—	2018	[28]
21	Ag/SBA-15	浸渍法	3.0	200	0.6	100	99	94	100h	2013	[29]
22	15Ag/SiO₂	溶胶凝胶法	2.5	220	0.2	100	100	92	120h	2010	[30]
23	Ag-in/hCNT	浸渍法	3.0	220	0.6	80	>99%	>98%	200h	2016	[31]
24	Ag/Ti-KCC	浸渍法	3.0	200	1.75	100	98	95	100h	2019	[32]
25	Ru/AC-HNO₃	浸渍法	5	90	—	—	100	92.3	釜式	2021	[33]
26	Ni-Foam	水热法	2.5	230	0.44	180	99	95	1000h	2019	[34]
27	Ni₂P-TiO₂	浸渍法	3.0	230	0.1	300	100	76	3600h	2016	[35]
28	CoP/SiO₂	浸渍法	3.0	240	0.28	160	94.6	88.1	300h	2022	[36]
29	Au-Fe/ZrO₂	超声分解法	2.5	200	0.257	200	100	95	300h	2020	[37]
30	Ni₃P/RB-MSN	浸渍法	2.5	190	0.44	90	100	85	500h	2021	[38]

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