Ru-Ni/WO3催化剂的制备及其催化纤维素制乙二醇

doi:10.3969/j.issn.0253-2417.2023.04.013

摘要/Abstract

摘要：

以商业氧化钨(WO₃)为载体，通过调控制备工艺和活化方式制备了一系列钨基金属催化剂并探索其催化性能。研究结果表明：通过浸渍负载法制备并采用NaBH₄液相活化制备的Ru-Ni/WO₃催化剂，Ru和Ni的负载量分别为2%和20%，其表现出较好的纤维素氢解制乙二醇的催化性能，在240 ℃、4 MPa氢压下，反应4 h可以得到86.1%纤维素转化率和62.8%的乙二醇选择性。采用XRD、SEM、Raman和XPS等表征手段探讨了催化剂组成和结构对其催化性能和产物分布的影响机制，Ni和Ru分步浸渍、然后NaBH₄液相还原活化的双金属催化剂会比普通浸渍和氢气热还原活化的催化剂更易被还原，同时具有更大的比表面积和金属分散性，表现出更多的表面缺陷和酸活性位，从而有利于催化纤维素直接氢解转化制备乙二醇。

关键词: 生物质, 纤维素, 钨催化剂, 氢解, 乙二醇

Abstract:

Using commercial tungsten oxide as carrier, a series of tungsten fund metal catalysts were prepared and their catalytic properties were investigated by controlling the preparation process and activation method. Results showed that the Ru-Ni/WO₃ catalyst(Ru loading 2%, Ni loading 20%), which was first impregnated with Ni and then loaded with Ru using sodium borohydride liquid-phase activation, exhibited better catalytic properties for cellulosic hydrogenolysis to ethylene glycol(EG). 86% cellulosic conversion and 63% ethylene glycol selectivity were obtained at 240 ℃ and 4 MPa H₂ pressure for 4 h. Subsequently, the characterizations of XRD, SEM, Raman, and XPS also employed to investigate the mechanism of the influence of catalyst composition and structure on its catalytic performance and product distribution. The results showed that bimetallic catalyst with Ni and Ru dipped step by step, and then actived by sodium borohydride liquid-phase reduction was easier to be reduced than the catalyst with normal dipping and hydrogen thermal reduction activation, and showed higher surface area and better dispersion of metal, with more surface defects and acid sites, thus was conducive to the occurrence of cascade reaction for cellulose to ethylene glycol.

Key words: biomass, cellulose, tungsten catalysts, hydrogenolysis, ethylene glycol

中图分类号:

TQ352

张明威, 王晓龙, 翁育靖, 穆仕芳, 孙琦, 张玉龙. Ru-Ni/WO₃催化剂的制备及其催化纤维素制乙二醇[J]. 林产化学与工业, 2023, 43(4): 90-98.

Mingwei ZHANG, Xiaolong WANG, Yujing WENG, Shifang MU, Qi SUN, Yulong ZHANG. Preparation of Ru-Ni/WO₃ Multifunctional Catalyst and Its Catalytic Performance for Cellulose to Ethylene Glycol[J]. Chemistry and Industry of Forest Products, 2023, 43(4): 90-98.

图/表 9

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参考文献 20

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催化剂¹⁾ catalyst	比表面积/(m²·g^-1) specific surface area	孔体积/(cm³·g^-1) pore volume	孔径/nm) pore diameter
WO₃	2.9	0.010	19.6
Ru/WO₃	2.0	0.007	7 14.2
Ni/WO₃	2.5	0.020	24.6
Ru-Ni/WO₃	4.8	0.020	12.9

催化剂 catalyst	纤维素转化率 cellulose conversion	不同产物的产率the yield of different products
催化剂 catalyst	纤维素转化率 cellulose conversion	甲醇 methanol	乙醇 ethanol	正丙醇 propanol	乙二醇 ethylene glycol(EG)	丙二醇 propylene glycol(PG)
WO₃	51.4	0.9	0.6	1.0	0.5	0.3
Mo/WO₃	64.4	3.3	2.4	1.3	0.9	0.3
Mn/WO₃	59.2	1.1	1.1	0.5	1.1	0.2
Ni/WO₃	93.7	0.5	0.5	0.8	41.5	3.1
Fe/WO₃	42.9	0.3	0.6	0.2	0.5	0.2
Ag/WO₃	44.3	1.6	0.6	0.8	0.7	0.4
Cu/WO₃	47.4	1.6	1.0	0.9	1.0	0.1
Ru-Mo/WO₃	74.3	3.4	5.0	3.0	15.9	7.4
Ru-Mn/WO₃	78.1	2.3	5.6	2.8	37.5	2.3
Ru-Ni/WO₃	86.1	1.4	1.5	1.6	54.1	5.0
Ru-Fe/WO₃	73.8	1.7	3.5	2.6	26.4	3.4
Ru-Ag/WO₃	51.6	1.3	5.0	5.5	13.1	0.3
Ru-Cu/WO₃	90.4	1.7	5.6	2.0	50.6	3.1

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Ru-Ni/WO₃催化剂的制备及其催化纤维素制乙二醇

Preparation of Ru-Ni/WO₃ Multifunctional Catalyst and Its Catalytic Performance for Cellulose to Ethylene Glycol

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