{"title":"二氧化硅支撑镓催化剂上的轻烷脱氢反应","authors":"Yury A. Agafonov, Oleg L. Eliseev","doi":"10.1016/j.mcat.2024.114646","DOIUrl":null,"url":null,"abstract":"<div><div>The present work is devoted to the studies of Ga/Silica catalysts in the paraffins dehydrogenation of natural gas - propane and ethane to produce valuable products - olefins and hydrogen. The gallium oxide supported on silica gel (2–10 %wt. of Ga) have been studied using XRD, TPR-H<sub>2</sub> and STEM/EDS methods, it has been shown that the dispersion of gallium oxide over the silica surface is very effective, the support actively reacts with a gallium salt to form surface particles that are more easily reduced than pure gallium oxide. Under steady and no-stationary state the negative effect of oxidative pre-treatment and the addition of CO<sub>2</sub> to the reaction mixture on catalytic activity was detected. On the contrary, pre-treatment of the catalysts in hydrogen (at 650–700 °C) or CO addition to the reaction mixture was accompanied by an increase in their propane dehydrogenation activities and stabilities at 600 °C. In the ethane dehydrogenation conditions (650 to 700 °C) catalysts is effective treated by hydrogen during the experiment. At 700 °C, the Ga/Silica activity may even increase during ethane dehydrogenation. By TPR-H<sub>2</sub> it was observed that with an increase in the temperature of pre-treatment of Ga/Silica in hydrogen from 650 to 700 °C, the proportion of oxidized Ga-containing phase significantly decreases.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114646"},"PeriodicalIF":3.9000,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Light alkanes dehydrogenation over silica supported gallium catalysts\",\"authors\":\"Yury A. Agafonov, Oleg L. Eliseev\",\"doi\":\"10.1016/j.mcat.2024.114646\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The present work is devoted to the studies of Ga/Silica catalysts in the paraffins dehydrogenation of natural gas - propane and ethane to produce valuable products - olefins and hydrogen. The gallium oxide supported on silica gel (2–10 %wt. of Ga) have been studied using XRD, TPR-H<sub>2</sub> and STEM/EDS methods, it has been shown that the dispersion of gallium oxide over the silica surface is very effective, the support actively reacts with a gallium salt to form surface particles that are more easily reduced than pure gallium oxide. Under steady and no-stationary state the negative effect of oxidative pre-treatment and the addition of CO<sub>2</sub> to the reaction mixture on catalytic activity was detected. On the contrary, pre-treatment of the catalysts in hydrogen (at 650–700 °C) or CO addition to the reaction mixture was accompanied by an increase in their propane dehydrogenation activities and stabilities at 600 °C. In the ethane dehydrogenation conditions (650 to 700 °C) catalysts is effective treated by hydrogen during the experiment. At 700 °C, the Ga/Silica activity may even increase during ethane dehydrogenation. By TPR-H<sub>2</sub> it was observed that with an increase in the temperature of pre-treatment of Ga/Silica in hydrogen from 650 to 700 °C, the proportion of oxidized Ga-containing phase significantly decreases.</div></div>\",\"PeriodicalId\":393,\"journal\":{\"name\":\"Molecular Catalysis\",\"volume\":\"570 \",\"pages\":\"Article 114646\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2024-11-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Molecular Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2468823124008289\",\"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":"Molecular Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2468823124008289","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
本研究致力于镓/二氧化硅催化剂在天然气(丙烷和乙烷)石蜡脱氢过程中的应用研究,以生产有价值的产品(烯烃和氢)。使用 XRD、TPR-H2 和 STEM/EDS 方法研究了硅胶上的氧化镓(镓含量为 2-10%wt.),结果表明氧化镓在硅胶表面的分散非常有效,支撑物会与镓盐积极反应,形成比纯氧化镓更容易还原的表面颗粒。在稳定和非稳定状态下,氧化预处理和在反应混合物中加入二氧化碳对催化活性有负面影响。相反,在氢气(650-700 °C)中对催化剂进行预处理或在反应混合物中加入 CO 的同时,催化剂的丙烷脱氢活性和在 600 °C 下的稳定性都有所提高。在乙烷脱氢条件下(650 至 700 °C),催化剂在实验过程中经过了有效的氢气处理。在 700 °C 的乙烷脱氢过程中,镓/二氧化硅的活性甚至会增加。通过 TPR-H2 可以观察到,随着镓/二氧化硅在氢气中的预处理温度从 650 ℃ 升高到 700 ℃,氧化的含镓相的比例明显降低。
Light alkanes dehydrogenation over silica supported gallium catalysts
The present work is devoted to the studies of Ga/Silica catalysts in the paraffins dehydrogenation of natural gas - propane and ethane to produce valuable products - olefins and hydrogen. The gallium oxide supported on silica gel (2–10 %wt. of Ga) have been studied using XRD, TPR-H2 and STEM/EDS methods, it has been shown that the dispersion of gallium oxide over the silica surface is very effective, the support actively reacts with a gallium salt to form surface particles that are more easily reduced than pure gallium oxide. Under steady and no-stationary state the negative effect of oxidative pre-treatment and the addition of CO2 to the reaction mixture on catalytic activity was detected. On the contrary, pre-treatment of the catalysts in hydrogen (at 650–700 °C) or CO addition to the reaction mixture was accompanied by an increase in their propane dehydrogenation activities and stabilities at 600 °C. In the ethane dehydrogenation conditions (650 to 700 °C) catalysts is effective treated by hydrogen during the experiment. At 700 °C, the Ga/Silica activity may even increase during ethane dehydrogenation. By TPR-H2 it was observed that with an increase in the temperature of pre-treatment of Ga/Silica in hydrogen from 650 to 700 °C, the proportion of oxidized Ga-containing phase significantly decreases.
期刊介绍:
Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are:
Heterogeneous catalysis including immobilized molecular catalysts
Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis
Photo- and electrochemistry
Theoretical aspects of catalysis analyzed by computational methods