Gyula Novodárszki , Ferenc Lónyi , Balázs Csík , Magdolna R. Mihályi , Róbert Barthos , József Valyon , Anna Vikár , Dhanapati Deka , Zoltán Pászti , Yuting Shi , Hanna E. Solt
{"title":"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","authors":"Gyula Novodárszki , Ferenc Lónyi , Balázs Csík , Magdolna R. Mihályi , Róbert Barthos , József Valyon , Anna Vikár , Dhanapati Deka , Zoltán Pászti , Yuting Shi , Hanna E. Solt","doi":"10.1016/j.apcata.2024.119757","DOIUrl":null,"url":null,"abstract":"<div><p>Hydroconversion of guaiacol (GUA) over γ-Al<sub>2</sub>O<sub>3</sub> and phosphatized-γ-Al<sub>2</sub>O<sub>3</sub> (γ-Al<sub>2</sub>O<sub>3</sub>(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 H<sub>2</sub> 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-Al<sub>2</sub>O<sub>3</sub>(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<sup>+</sup>) – Lewis base (O<sup>–</sup>) pair surface sites of the γ-Al<sub>2</sub>O<sub>3</sub> support and, thereby, suppressed phenolate formation and hydrodeoxgenation.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7000,"publicationDate":"2024-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0926860X24002011/pdfft?md5=4defa8d3d96a187fdd47433abc8d2fc1&pid=1-s2.0-S0926860X24002011-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Hydroconversion of lignin-derived platform compound guaiacol to fuel additives and value-added chemicals over alumina-supported Ni catalysts\",\"authors\":\"Gyula Novodárszki , Ferenc Lónyi , Balázs Csík , Magdolna R. Mihályi , Róbert Barthos , József Valyon , Anna Vikár , Dhanapati Deka , Zoltán Pászti , Yuting Shi , Hanna E. Solt\",\"doi\":\"10.1016/j.apcata.2024.119757\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Hydroconversion of guaiacol (GUA) over γ-Al<sub>2</sub>O<sub>3</sub> and phosphatized-γ-Al<sub>2</sub>O<sub>3</sub> (γ-Al<sub>2</sub>O<sub>3</sub>(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 H<sub>2</sub> 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-Al<sub>2</sub>O<sub>3</sub>(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<sup>+</sup>) – Lewis base (O<sup>–</sup>) pair surface sites of the γ-Al<sub>2</sub>O<sub>3</sub> support and, thereby, suppressed phenolate formation and hydrodeoxgenation.</p></div>\",\"PeriodicalId\":243,\"journal\":{\"name\":\"Applied Catalysis A: General\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2024-04-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S0926860X24002011/pdfft?md5=4defa8d3d96a187fdd47433abc8d2fc1&pid=1-s2.0-S0926860X24002011-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Catalysis A: General\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0926860X24002011\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis A: General","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926860X24002011","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Hydroconversion of lignin-derived platform compound guaiacol to fuel additives and value-added chemicals over alumina-supported Ni catalysts
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.
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.