溶胶-凝胶法制备高分散Ni-Cu/SiO2 促进间甲酚直接脱氧制甲苯

doi:10.16085/j.issn.1000-6613.2023-1009

摘要/Abstract

摘要：

在木质素生物质衍生的酚类化合物加氢脱氧生产芳烃中，Ni基催化剂兼具经济性与活性，然而，在温和条件下会受到C—C氢解的影响。在此，采用溶胶-凝胶法制备了高分散的Ni/SiO₂、Cu/SiO₂和不同Cu含量的双金属Ni-Cu催化剂，并在350℃和常压条件下对其进行间甲酚加氢脱氧性能测试。尽管Ni粒径约为2nm的单金属Ni/SiO₂表现出高的活性和甲苯选择性，但C—C氢解生成甲烷和苯的反应仍然显著。对于双金属Ni-Cu催化剂，Ni和Cu相互作用并在还原后形成Ni-Cu合金。在最佳的双金属催化剂（Cu/Ni摩尔比约为3）上，甲苯在所有转化水平上都是主要产物。当间甲酚转化率为97.2%时，甲苯和芳烃的收率分别达到85.0%和91.6%。本征反应速率和活化能分析表明，Cu的引入通过抑制竞争性的C—C氢解反应，促进了直接脱氧生成甲苯。

关键词: 催化, 生物质, 再生能源, 间甲酚, 加氢脱氧, Ni-Cu合金

Abstract:

Ni based catalysts are relatively cheap and active for hydrodeoxygenation (HDO) of lignin biomass derived phenolic compounds to produce aromatics, but they suffer from the C—C hydrogenolysis under mild conditions. Herein, highly dispersed Ni/SiO₂, Cu/SiO₂ and bimetallic Ni-Cu catalysts with different Cu content were prepared by sol-gel method, and tested for HDO of m-cresol at 350℃ and atmospheric pressure. Although bare Ni/SiO₂ with Ni size of 2nm showed high activity and toluene selectivity, significant C—C hydrogenolysis activity toward CH₄ and benzene were observed. Ni and Cu in bimetallic Ni-Cu catalysts could interact each other and form Ni-Cu alloy after reduced. Toluene were the dominant product over optimal bimetallic catalyst (Cu/Ni molar ratio of 3) at all conversion levels. At m-cresol conversion of 97.2%, the yields of toluene and aromatics reached 85.0% and 91.6%, respectively. Analysis of intrinsic reaction rate and activation energy indicates that the addition of Cu enhances the direct deoxygenation toward toluene by inhibiting the competitive C—C hydrogenolysis reaction.

Key words: catalysis, biomass, renewable energy, m-cresol, hydrodeoxygenation, Ni-Cu alloy

中图分类号:

王颖杰, 祝新利. 溶胶-凝胶法制备高分散Ni-Cu/SiO₂ 促进间甲酚直接脱氧制甲苯[J]. 化工进展, 2024, 43(7): 3824-3833.

WANG Yingjie, ZHU Xinli. Highly dispersed Ni-Cu/SiO₂ synthesized by sol-gel method for prompting direct deoxygenation of m-cresol to toluene[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3824-3833.

图/表 14

表1 Ni/SiO2、Cu/SiO2以及双金属Ni-Cu催化剂的比表面积、平均孔径、金属负载量以及H2/(Ni+Cu)摩尔比

样品	比表面积/m²·g^-1	平均孔径/nm	Ni负载量/%	Cu负载量/%	Cu/Ni摩尔比	H₂/(Ni+Cu)
Ni/SiO₂	676	2.94	1.0	—	—	1.00
Ni-Cu-1	653	2.95	0.4	0.8	1.9	0.98
Ni-Cu-2	565	2.96	0.3	1.0	3.1	1.01
Ni-Cu-3	515	2.99	0.3	1.5	4.6	1.04
Ni-Cu-4	512	3.06	0.3	1.9	5.8	0.95
Cu/SiO₂	557	2.94	—	1.0	—	0.96

图1 Ni/SiO2、Cu/SiO2以及双金属Ni-Cu催化剂的XRD谱图

图2 Ni/SiO2、Cu/SiO2以及双金属Ni-Cu催化剂的H2-TPR图

图3 500℃还原后催化剂的TEM图、粒径分布及HR-TEM图

图4 Ni-Cu-2的HAADF-STEM图和元素分析图，嵌入图为EDS线扫描结果

图5 还原温度对Ni-Cu-2上间甲酚转化率和甲苯收率的影响（反应条件：350℃，常压，空时=1h，反应时间0.5h）

图6 还原温度对Ni-Cu-2上产物选择性的影响（反应条件：350℃，常压，空时=1h，反应时间0.5h）

图7 不同催化剂的活性与甲苯选择性差异（反应条件：350℃，常压，反应时间0.5h）

图8 Ni/SiO2和双金属Ni-Cu催化剂上产物收率随转化率的变化关系（反应条件：350℃，常压，反应时间0.5h）

图9 350℃下Ni/SiO2和双金属Ni-Cu催化剂催化间甲酚HDO可能的反应路径

表2 常压条件下部分催化剂对酚类物质HDO的催化性能

催化剂	反应温度 /℃	反应物	空时 /h	转化率 /%	DDO选择性 /%	参考文献
Ni-Ga/SiO₂	300	苯甲醚	1	约70	约80	[13]
Ni-Mo/SiO₂	350	间甲酚	0.4	约92	约92	[33]
Ni-Zn/SiO₂	300	苯甲醚	0.5	48.6	89.4	[17]
Ni/TiO₂	350	间甲酚	4	约100	92.2	[11]
Ru_0.05Ce_0.95O₂	350	间甲酚	2	约100	78.2	[28]
Pd/ZrO₂	300	苯酚	0.16	约85	约85	[34]
Pd/Nb₂O₅	300	苯酚	约0.055	约55	约76	[35]
Ni-Cu-2	350	间甲酚	1.3	97.2	94.2	本文

表3 Ni/SiO2和双金属Ni-Cu催化剂上间甲酚HDO的本征反应速率

样品	反应速率/μmol·g^-1·min^-1
样品	间甲酚	甲苯	甲烷
Ni/SiO₂	63.4	26.8	17.8
Ni-Cu-1	57.2	43.5	3.8
Ni-Cu-2	35.7	27.5	1.2
Ni-Cu-3	22.3	17.6	0.8
Ni-Cu-4	19.8	15.5	0.8

图10 阿伦尼乌斯趋势图

图11 稳定性测试及Ni-Cu-2上主要产物收率随转化率的变化关系（空心图标表示在失活过程中获得的数据，实心图标表示调节空时获得的数据；反应条件：350℃，常压）

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溶胶-凝胶法制备高分散Ni-Cu/SiO₂ 促进间甲酚直接脱氧制甲苯

Highly dispersed Ni-Cu/SiO₂ synthesized by sol-gel method for prompting direct deoxygenation of m-cresol to toluene

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