掺杂钙钛矿催化剂的制备及其催化合成气直接转化制C2+醇性能研究
Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C2+ alcohols
- 低碳化学与化工 2024, 49(1): 25-32.
- 作者机构：
1.中国科学院 大连化学物理研究所 洁净能源国家实验室，辽宁 大连 116023
2.中国科学院大学，北京 100049
- 作者简介：
徐晶（1996—），博士研究生，研究方向为合成气直接制高碳含氧化合物，E-mail：ahajxu1996@dicp.ac.cn。
葛庆杰（1971—），博士，研究员，博士生导师，研究方向为CO2加氢、合成气催化转化， E-mail：geqj@dicp.ac.cn；
孙剑（1982—），博士，研究员，研究方向为CO2加氢、合成气催化转化，E-mail：sunj@dicp.ac.cn。
- 基金信息：国家重点研发计划(2022YFA1504702)
DOI：10.12434/j.issn.2097-2547.20230091
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徐晶,葛庆杰,孙剑.掺杂钙钛矿催化剂的制备及其催化合成气直接转化制C2+醇性能研究[J].低碳化学与化工,2024,49(01):25-32.
XU Jing,GE Qingjie,SUN Jian.Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C2+ alcohols[J].Low-carbon Chemistry and Chemical Engineering,2024,49(01):25-32.
徐晶,葛庆杰,孙剑.掺杂钙钛矿催化剂的制备及其催化合成气直接转化制C2+醇性能研究[J].低碳化学与化工,2024,49(01):25-32. DOI： 10.12434/j.issn.2097-2547.20230091.
XU Jing,GE Qingjie,SUN Jian.Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C2+ alcohols[J].Low-carbon Chemistry and Chemical Engineering,2024,49(01):25-32. DOI： 10.12434/j.issn.2097-2547.20230091.
摘要
由合成气直接转化制C,2+,醇（碳链中含两个及两个以上碳原子的醇类）是目前最有前景的醇类化合物合成路线之一，而钙钛矿结构的催化剂可用于提高该过程中的C,2+,醇合成性能。采用共沉淀法分别制备了Co、Mn掺杂的钙钛矿LFC和LFM催化剂（L、F、C和M分别指金属La、Fe、Co和Mn），系统考察了不同焙烧温度和掺杂元素对钙钛矿催化剂的C,2+,醇合成性能的影响。多种表征结果显示，低焙烧温度可优化LF-600（“-”后的数字指焙烧温度）催化剂的结构和吸附行为，在LF-600催化剂上，CO解离和非解离位点的耦合有助于提高反应的CO转化率和总醇的选择性，分别达16.9%和31.2%（质量分数），且Co和Mn的掺杂可改变LF-600催化剂的产物分布和活性。与LF-600催化剂相比，LFC-600催化剂的H,2,吸附能力低，有利于反应链增长，从而将C,2+,醇在总醇中的比例从60.4%提高至71.6%。LFM-600催化剂具有更多的低温H,2,吸附位点，导致醇类产物以甲醇为主，而Mn掺杂导致的颗粒团聚及Mn和O元素聚集会降低LFM-600催化剂的活性。
Abstract
Direct conversion of syngas to C,2+, alcohols (alcohols with two or more carbon atoms) is currently one of the most promising routes for the synthesis of alcohols, and perovskite-structured catalysts can be used to improve the performance for the synthesis of C,2+, alcohols in this process. Co and Mn doped perovskite LFC and LFM catalysts (L, F, C and M refer to metal La, Fe, Co and Mn, respectively) were prepared by co-precipitation method, respectively, and the effects of different calcination temperatures and doped elements on the catalytic performance of perovskite catalysts were systematically investigated in C,2+, alcohols synthesis. Results of various characterizations show that the low calcination temperature can optimize the structural properties and adsorption behaviors of LF-600 (the numbers after “-” refer to the calcination temperature) catalyst, and the coupling of CO dissociation and non-dissociation sites on LF-600 catalyst helps to increase CO conversion and total alcohol selectivity to 16.9% and 31.2% (mass fraction), respectively. The doping of Co and Mn can change the product distribution and activity of LF-600 catalyst. Compared with LF-600 catalyst, LFC-600 catalyst promotes the chain growth due to the low H,2, adsorption capacity, thereby increasing the proportion of C,2+, alcohols in total alcohols from 60.4% to 71.6%. LFM-600 catalyst has more low-temperature H,2, adsorption sites leading to methanol being the main alcohol product, while particle agglomeration and Mn and O aggregation caused by Mn doping can reduce the activity of LFM-600 catalyst.
关键词
合成气C2+醇钙钛矿催化剂B位掺杂焙烧温度
Keywords
syngasC2+ alcoholsperovskite catalystsB-site dopingcalcination temperature
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