Hydroconversion of lignin-derived platform compound guaiacol to fuel additives and value-added chemicals over alumina-supported Ni catalysts

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General Pub Date : 2024-04-26 DOI:10.1016/j.apcata.2024.119757

Gyula Novodárszki , Ferenc Lónyi , Balázs Csík , Magdolna R. Mihályi , Róbert Barthos , József Valyon , Anna Vikár , Dhanapati Deka , Zoltán Pászti , Yuting Shi , Hanna E. Solt

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引用次数: 0

Abstract

Hydroconversion of guaiacol (GUA) over γ-Al₂O₃ and phosphatized-γ-Al₂O₃ (γ-Al₂O₃(P)) supported Ni catalysts was initiated by Lewis-sites and active Ni sites. Conversion proceeded via transmethylation and hydrodemethylation/hydrodemethoxylation as major and minor pathways, respectively, resulting in mainly catechol and methylcatechols, and via series of consecutive hydrodehydroxylation (HDHY) and ring hydrogenation (HYD) reactions leading to partially and fully deoxygenated, saturated, and unsaturated products. High Ni-loading and high H₂ pressure promoted the formation of cyclohexane and methyl-substituted cyclohexanes; however, above 300 °C the hydrogenation–dehydrogenation equilibrium favored the formation of benzene and methyl-substituted benzenes. Ni/γ-Al₂O₃(P) showed suppressed HYD/HDHY activity resulting in pronounced formation of catechol and/or phenol and their methyl-substituted derivatives. Surface phenolate species were substantiated as surface intermediates of hydrodeoxygenation. Phosphatizing reduced the concentration of both basic OH and Lewis acid (Al⁺) – Lewis base (O^–) pair surface sites of the γ-Al₂O₃ support and, thereby, suppressed phenolate formation and hydrodeoxgenation.

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在氧化铝支撑的镍催化剂上将木质素衍生的平台化合物愈创木酚加氢转化为燃料添加剂和增值化学品

愈创木酚（GUA）在γ-Al2O3 和磷化-γ-Al2O3 (γ-Al2O3(P))载镍催化剂上的加氢转化是由路易斯位点和活性镍位点引发的。转化的主要途径和次要途径分别是跨甲基化和加氢脱甲基化/加氢脱甲氧基化，主要生成儿茶酚和甲基邻苯二酚，以及一系列连续的加氢脱羟基（HDHY）和环氢化（HYD）反应，生成部分和完全脱氧的饱和和不饱和产物。高 Ni-loading 和高 H2 压力促进了环己烷和甲基取代环己烷的形成；然而，在 300 °C 以上，氢化-氢化平衡有利于苯和甲基取代苯的形成。Ni/γ-Al2O3(P) 的 HYD/HDHY 活性受到抑制，从而明显形成了儿茶酚和/或苯酚及其甲基取代衍生物。表面苯酚类物质被证实是氢脱氧的表面中间产物。磷化降低了 γ-Al2O3 支持物的碱性 OH 和路易斯酸（Al+）-路易斯碱（O-）对表面位点的浓度，从而抑制了苯酚的形成和氢脱氧。

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来源期刊

Applied Catalysis A: General 化学-环境科学

CiteScore

9.00

自引率

5.50%

发文量

415

审稿时长

24 days

期刊介绍： Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications. Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.

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