Al2O3性质诱导Cu-Al体系催化草酸二乙酯加氢合成醇醚酯

doi:10.3969/j.issn.2097-2806.2025.09.003

摘要/Abstract

摘要： 通过XRD、XPS、N₂O滴定以及²⁷Al MAS-NMR等多种表征技术，探讨了Cu/Al₂O₃催化剂在草酸二乙酯（DEO）加氢合成醇醚酯过程中的结构-性能关系。结果表明，当Al₂O₃的晶体构型相同时，增加比表面积可有效细化铜纳米粒子（Cu NPs）的尺寸，进而提高DEO的转化率。同时，γ-Al₂O₃（HSAl和SBAl）负载的Cu NPs尺寸较小，促进反应向深度加氢方向进行，生成乙醇（EtOH）和乙二醇（EG）。相比之下，无定形Al₂O₃（HTAl和SolAl）表面的Cu NPs尺寸较大，导致转化率降低，主要产物为乙醇酸乙酯（Egly）。尽管不同晶体结构的Al₂O₃中的Al³⁺离子配位形式存在差异，但实验数据表明Al³⁺离子配位差异并未对加氢反应的催化性能产生显著影响。醇醚酯化学品的形成关键在于Cu位点与酸性位点之间的相互作用。其中，EG和EtOH经SN2机制脱水形成2-乙氧基乙醇，Egly与EtOH则通过SN2机制形成乙氧基乙酸乙酯（EEA）。本研究为优化煤基乙二醇工艺以实现多样化产品组合提供了理论依据。

关键词: 草酸酯加氢, 醇醚酯, Cu-Al催化剂, SN2机制

Abstract:

The structure-performance relationship of Cu/Al₂O₃ catalysts in the hydrogenation of diethyl oxalate （DEO） for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD, XPS, N₂O titration, and ²⁷Al MAS-NMR. The results showed that when the crystal configurations of Al₂O₃ were the same, increasing the specific surface area could effectively refine the size of copper nanoparticles （Cu NPs）, and ultimately improve the conversion of DEO. Meanwhile, the smaller size of γ-Al₂O₃（HSAl and SBAl） loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol （EtOH） and ethylene glycol （EG）. Besides, the larger size of Cu NPs on the surface of amorphous Al₂O₃ （HTAl and SolAl） resulted in a lower conversion rate, where ethyl glycolate （Egly） is the main product. Despite there are differences in Al³⁺ ionic coordination in Al₂O₃ with different crystal structures, the experimental data showed that the differences in Al³⁺ ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction. The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites. Among them, EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism, while Egly and EtOH were reacted to form ethyl ethoxyacetate （EEA） via the SN2 mechanism. This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.

Key words: oxalate hydrogenation, alcohol ether esters, Cu-Al catalyst, SN2 mechanism

中图分类号:

TQ519

武鹏, 马丽娜, 郑昱, 罗莉, 苏立红, 栗俊田. Al₂O₃性质诱导Cu-Al体系催化草酸二乙酯加氢合成醇醚酯[J]. 日用化学工业（中英文）, 2025, 55(9): 1100-1111.

Peng Wu, Lina Ma, Yu Zheng, Li Luo, Lihong Su, Juntian Li. The synthesis of alcohol ether esters through the catalytic hydrogenation of diethyl oxalate in the Cu-Al systems induced by Al₂O₃ properties[J]. China Surfactant Detergent & Cosmetics, 2025, 55(9): 1100-1111.

图/表 18

参考文献 30

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Sample	N₂ isothermal adsorption and desorption			Coordination mode of Al³⁺/%
Sample	S_BET/ （m²/g）	V_P/ （cm³/g）	D_P/nm	Al³⁺_Octa	Al³⁺_Penta	Al³⁺_Terta
Sol	129.0	0.3	5.1	27.5	44.7	27.8
HT	187.5	0.3	10.1	29.1	42.2	28.7
HS	251.8	0.8	9.0	65.0	0	35.0
SB	256.1	0.5	5.6	100.0	0	0

Sample	N₂ isothermal adsorption and desorption			Cu loading^a/%	The ratio of Cu⁺/（Cu²⁺+Cu⁺） ^b/%
Sample	S_BET/ （m²/g）	V_P/ （cm³/g）	D_P/nm	Cu loading^a/%	The ratio of Cu⁺/（Cu²⁺+Cu⁺） ^b/%
SolCu	87.9	0.3	5.5	12.4	37.3
HTCu	118.3	0.2	11.0	12.4	43.4
SBCu	210.9	0.4	5.6	11.0	55.2
HSCu	209.1	0.7	8.7	12.1	68.6

Sample	Acidity/（mmol/g_cat）				N₂O titration
Sample	weak acid	medium-strong acid	strong acid	total acid quantity	D_Cu/%	S_{BET Cu}/（m²/g）	d_Cu/nm
SolAl	0.016	0.010	0	0.026	20.27	11.10	4.93
HTAl	0.014	0.017	0.001	0.032	29.94	16.31	3.34
SBAl	0.015	0.025	0.003	0.043	34.31	21.18	2.91
HSAl	0.010	0.021	0.005	0.036	35.70	23.28	2.80

Al₂O₃性质诱导Cu-Al体系催化草酸二乙酯加氢合成醇醚酯

The synthesis of alcohol ether esters through the catalytic hydrogenation of diethyl oxalate in the Cu-Al systems induced by Al₂O₃ properties

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