化工进展2024,Vol.43Issue(7) :3824-3833.DOI:10.16085/j.issn.1000-6613.2023-1009

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

王颖杰 祝新利
化工进展2024,Vol.43Issue(7) :3824-3833.DOI:10.16085/j.issn.1000-6613.2023-1009

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

王颖杰 1祝新利1
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作者信息

  • 1. 天津大学化工学院,天津 300072
  • 折叠

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.

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.

关键词

催化/生物质/再生能源/间甲酚/加氢脱氧/Ni-Cu合金

Key words

catalysis/biomass/renewable energy/m-cresol/hydrodeoxygenation/Ni-Cu alloy

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基金项目

国家自然科学基金(22278299)

国家自然科学基金(21676194)

出版年

2024
化工进展
中国化工学会,化学工业出版社

化工进展

CSTPCD北大核心
影响因子:1.062
ISSN:1000-6613
参考文献量10
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