调节剂对UiO-66在糠醛转移加氢制糠醇反应中催化性能的影响

doi:10.16085/j.issn.1000-6613.2023-0020

摘要/Abstract

摘要：

糠醛高选择性催化转移加氢制糠醇是生物质高值化利用的重要途径之一，本文以甲酸、乙酸及三氟乙酸为调节剂制备了具有不同缺陷位点的UiO-66，利用XRD、SEM、NH₃-TPD、TG和N₂吸附脱附等手段进行详细表征，并以异丙醇为溶剂和氢供体，考察了UiO-66催化剂缺陷位、酸性和织构性质对催化糠醛转移加氢反应的影响。结果表明，UiO-66催化剂酸性的增强有利于糠醛转移加氢反应中糠醇选择性的提高，以甲酸为调节剂制备的UiO-66在160℃的反应温度下，反应1h后糠醛的转化率和对糠醇的选择性分别达到99.4%和98.9%。

关键词: UiO-66, 生物质, 糠醛, 醇, 催化, 转移加氢

Abstract:

The highly selective catalytic transfer hydrogenation of furfural to furfuryl alcohol is one of the important routes for high value utilization of biomass. Herein, UiO-66 catalysts with the different defect sites were prepared with formic acid, acetic acid and trifluoroacetic acid as regulators. The catalyst was characterized by XRD, SEM, NH₃-TPD, TG and N₂ adsorption and desorption. The effects of defects, acidity and textural properties of UiO-66 catalysts on the transfer hydrogenation of furfural were investigated with isopropanol as both solvent and hydrogen donor. The results showed that the enhancement of acidity of UiO-66 catalysts was beneficial to the improvement of furfuryl alcohol selectivity in furfural transfer hydrogenation reaction. The furfural conversion and selectivity to furfuryl alcohol over UiO-66 prepared with formic acid as regulator could reach 99.4% and 98.9% at 160℃ in 1h, respectively.

Key words: UiO-66, biomass, furfuryl, alcohol, catalysis, transfer hydrogenation

中图分类号:

TQ032.4

谢有为, 陈静, 于峰, 史秀锋, 范彬彬, 李瑞丰. 调节剂对UiO-66在糠醛转移加氢制糠醇反应中催化性能的影响[J]. 化工进展, 2023, 42(11): 5756-5763.

XIE Youwei, CHEN Jing, YU Feng, SHI Xiufeng, FAN Binbin, LI Ruifeng. Effect of regulators on the catalytic performance of UiO-66 in furfural transfer hydrogenation to furfuryl alcohol[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5756-5763.

图/表 12

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样品	BET比表面积/m²·g^-1	微孔面积/m²·g^-1	外表面积/m²·g^-1	总孔体积/cm²·g^-1	微孔体积/cm²·g^-1	介孔体积/cm²·g^-1
UiO-66-FD	942	882	60	0.39	0.34	0.05
UiO-66-AA	862	794	68	0.39	0.30	0.09
UiO-66-FA	938	876	62	0.42	0.34	0.09
UiO-66-TA	1034	957	77	0.42	0.36	0.07

样品	BET比表面积/m²·g^-1	微孔面积/m²·g^-1	外表面积/m²·g^-1	总孔体积/cm²·g^-1	微孔体积/cm²·g^-1	介孔体积/cm²·g^-1
UiO-66-FD	942	882	60	0.39	0.34	0.05
UiO-66-AA	862	794	68	0.39	0.30	0.09
UiO-66-FA	938	876	62	0.42	0.34	0.09
UiO-66-TA	1034	957	77	0.42	0.36	0.07

样品	脱附峰温度/℃	NH₃-TPD峰面积	总酸量
UiO-66-FD	124	4.3（45.7）	9.4
UiO-66-FD	177	5.1（54.3）	9.4
UiO-66-AA	123	6.1（35.5）	17.2
UiO-66-AA	195	11.1（64.5）	17.2
UiO-66-FA	129	7.7（37.9）	20.3
UiO-66-FA	198	12.6（62.1）	20.3
UiO-66-TA	123	2.8（26.2）	10.7
UiO-66-TA	190	7.9（73.8）	10.7

样品	脱附峰温度/℃	NH₃-TPD峰面积	总酸量
UiO-66-FD	124	4.3（45.7）	9.4
UiO-66-FD	177	5.1（54.3）	9.4
UiO-66-AA	123	6.1（35.5）	17.2
UiO-66-AA	195	11.1（64.5）	17.2
UiO-66-FA	129	7.7（37.9）	20.3
UiO-66-FA	198	12.6（62.1）	20.3
UiO-66-TA	123	2.8（26.2）	10.7
UiO-66-TA	190	7.9（73.8）	10.7

催化剂	溶剂	氢供体与糠醛摩尔比	反应温度/K	氢气压力/MPa	反应时间/h	糠醛转化率/%	糠醛转化率/%	参考文献
质量分数5% Pd/Al₂O₃	异丙醇	25.1	453	—	5	78	63	[13]
质量分数0.3% Pt-4	异丙醇	26	393	—	7.5	98.8	79.5	[14]
AuRu/La-ZrO₂	异丙醇	43.5	423	—	5	83	84	[15]
Cu/AC-SO₃H	异丙醇	65.3	378	0.4	2	99.9	99.9	[16]
Ni/AC-SO₃H	异丙醇	81.6	333	4	8	99.9	99.9	[17]
Fe₃O₄-12	异丙醇	389.9	433	—	5	97.5	92.5	[18]
UiO-66-FA	异丙醇	43.5	433	—	1	99.4	98.9	本工作