乙醇酸甲酯选择性氧化制备乙醛酸甲酯研究进展

doi:10.3969/j.issn.1000-5641.2023.01.011

摘要/Abstract

摘要：

乙醛酸甲酯在有机合成和化工生产中应用广泛, 传统的制备方法存在成本高、效率低、易造成环境污染等缺点. 乙醇酸甲酯是煤基合成气经草酸二甲酯加氢制乙二醇工艺的中间产物且可高选择性控制合成, 以其为原料选择性氧化制备乙醛酸甲酯具有较好的工业应用前景, 但目前为止, 研究较为有限. 本文综述了乙醛酸甲酯的应用、传统制备方法及乙醇酸甲酯氧化法的研究现状, 也总结了相关醇类 (如乙醇) 选择性氧化制醛酮的研究进展.

关键词: 乙醇酸甲酯, 乙醛酸甲酯, 选择氧化, 分子氧, 醇氧化

Abstract:

Methyl glyoxylate is widely used in organic synthesis and chemical production. The application of traditional preparation methods is limited by high cost, low efficiency, and significant environmental pollution. During the coal to ethylene glycol process, methyl glycolate is produced as an intermediate product of the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol. Methyl glycolate can be selectively obtained from DMO via hydrogenation, and therefore, has the potential to serve as raw material for methyl glyoxylate. However, only few studies have considered this process. Herein , the applications, traditional preparation methods, and state-of-the-art research progress of methyl glycolate oxidation are reviewed. Recent research on selective oxidation of related alcohols (such as ethanol) to aldehydes and ketones is also summarized.

Key words: methyl glycolate, methyl glyoxylate, selective oxidation, molecular oxygen, alcohol oxidation

中图分类号:

O643

王浩, 赵国锋, 路勇. 乙醇酸甲酯选择性氧化制备乙醛酸甲酯研究进展[J]. 华东师范大学学报（自然科学版）, 2023, 2023(1): 104-113.

Hao WANG, Guofeng ZHAO, Yong LU. Progress in synthesis of methyl glyoxylate by selective oxidation of methyl glycolate with molecular oxygen[J]. Journal of East China Normal University(Natural Science), 2023, 2023(1): 104-113.

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催化剂	Ag /(wt%)	反应条件			乙醇转化率 /%	乙醛选择性 /%	文献
催化剂	Ag /(wt%)	GHSV^a /(mL·g_cat^–1·h^–1)	T/℃	EtOH/O₂ (摩尔比)	乙醇转化率 /%	乙醛选择性 /%	文献
Ag/CeO₂	1.0	13500(137)	350	1/1	36	90	[35]
Ag/HAP	0.5	7200(570)	250	4/1	18	100	[28]
Ag/OMS	5.0	100000(72)	170	1/9	53	58	[36]
Ag-Li/Al₂O₃	1.9	2500 (75)	350	1/1	100	95	[37]
Ag-Ce/SiO₂	1.0	18000 (72)	240	1/9	98	82	[29]
Ag/MgCuCr₂O₄	1.0	36000(1515)	250	1/3	10	99	[38]

催化剂	Au/(wt%)	反应条件			乙醇转化率 /%	乙醛选择性 /%	文献
催化剂	Au/(wt%)	GHSV^a /(mL·g_cat^–1·h^–1)	T/℃	EtOH/O₂ (摩尔比)	乙醇转化率 /%	乙醛选择性 /%	文献
Au/MgCuCr₂O₄	1.0	100000(1515)	250	1/3	100	95	[51]
Au/CuSiO₃	1.0	100000(1515)	250	1/3	98	93	[52]
Au/MoO₃	1.0	20000(154)	240	1/3	95	95	[53]
Au/Silicon-1	1	30000(1436)	200	1/1	50	98	[54]
Au-Fe/MnO₂	1	100000(2500)	200	1/1	89	96	[55]
Au-CuO_x/SiO₂	3.6	6000(2300)	300	1/3	90	90	[56]

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