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

Abstract

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

CLC Number:

TQ519

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.

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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

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