碳负载的超低汞乙炔加氢氯化催化剂中氮掺杂位点与金属氯化物的协同效应

IF 3.7 3区 工程技术 Q2 ENGINEERING, CHEMICAL
Yiyang Qiu , Chong Liu , Xueting Meng , Yuesen Liu , Jiangtao Fan , Guojun Lan , Ying Li
{"title":"碳负载的超低汞乙炔加氢氯化催化剂中氮掺杂位点与金属氯化物的协同效应","authors":"Yiyang Qiu ,&nbsp;Chong Liu ,&nbsp;Xueting Meng ,&nbsp;Yuesen Liu ,&nbsp;Jiangtao Fan ,&nbsp;Guojun Lan ,&nbsp;Ying Li","doi":"10.1016/j.cjche.2024.11.007","DOIUrl":null,"url":null,"abstract":"<div><div>Carbon-supported mercury catalysts are extensively employed in calcium carbide-based polyvinyl chloride (PVC) industries, but the usage of mercury-based catalysts can pose an environmental threat due to the release of mercury into the surrounding area during the operation period. In this study, a highly active and stable mercury-based catalyst was developed, utilizing the nitrogen atom of the support as the anchor site to enhance the interaction between active sites (HgCl<sub>2</sub>) and the carbon support (N-AC). Thermal loss rate testing and thermogravimetric analysis results demonstrate that, compared to commercial activated carbon, N-doped carbon can effectively increase the heat stability of HgCl<sub>2</sub>. The obtained mercury-based catalysts (HgCl<sub>2</sub>/N-AC) exhibit significant catalytic performance, achieving 2.5 times the C<sub>2</sub>H<sub>2</sub> conversion of conventional HgCl<sub>2</sub>/AC catalysts. Experimental analysis combined with theoretical calculations reveals that, contrary to the Eley-Rideal (ER) mechanism of HgCl<sub>2</sub>/AC, the HgCl<sub>2</sub>/N-AC catalyst follows the Langmuir-Hinshelwood (LH) adsorption mechanism. The nitrogen sites and HgCl<sub>2</sub> on the catalyst enhance the adsorption capabilities of the HCl and C<sub>2</sub>H<sub>2</sub>, thereby improving the catalytic performance. Based on the modification of the active center by these solid ligands, the loading amount of HgCl<sub>2</sub> on the catalyst can be further reduced from the current 6.5% to 3%. Considering the absence of successful industrial applications for mercury-free catalysts, and based on the current annual consumption of commercial mercury chloride catalysts in the PVC industry, the widespread adoption of this technology could annually reduce the usage of chlorine mercury by 500 tons, making a notable contribution to mercury compliance, reduction, and emissions control in China. It also serves as a bridge between mercury-free and low-mercury catalysts. Moreover, this solid ligand technology can assist in the application research of mercury-free catalysts.</div></div>","PeriodicalId":9966,"journal":{"name":"Chinese Journal of Chemical Engineering","volume":"79 ","pages":"Pages 145-154"},"PeriodicalIF":3.7000,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination\",\"authors\":\"Yiyang Qiu ,&nbsp;Chong Liu ,&nbsp;Xueting Meng ,&nbsp;Yuesen Liu ,&nbsp;Jiangtao Fan ,&nbsp;Guojun Lan ,&nbsp;Ying Li\",\"doi\":\"10.1016/j.cjche.2024.11.007\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Carbon-supported mercury catalysts are extensively employed in calcium carbide-based polyvinyl chloride (PVC) industries, but the usage of mercury-based catalysts can pose an environmental threat due to the release of mercury into the surrounding area during the operation period. In this study, a highly active and stable mercury-based catalyst was developed, utilizing the nitrogen atom of the support as the anchor site to enhance the interaction between active sites (HgCl<sub>2</sub>) and the carbon support (N-AC). Thermal loss rate testing and thermogravimetric analysis results demonstrate that, compared to commercial activated carbon, N-doped carbon can effectively increase the heat stability of HgCl<sub>2</sub>. The obtained mercury-based catalysts (HgCl<sub>2</sub>/N-AC) exhibit significant catalytic performance, achieving 2.5 times the C<sub>2</sub>H<sub>2</sub> conversion of conventional HgCl<sub>2</sub>/AC catalysts. Experimental analysis combined with theoretical calculations reveals that, contrary to the Eley-Rideal (ER) mechanism of HgCl<sub>2</sub>/AC, the HgCl<sub>2</sub>/N-AC catalyst follows the Langmuir-Hinshelwood (LH) adsorption mechanism. The nitrogen sites and HgCl<sub>2</sub> on the catalyst enhance the adsorption capabilities of the HCl and C<sub>2</sub>H<sub>2</sub>, thereby improving the catalytic performance. Based on the modification of the active center by these solid ligands, the loading amount of HgCl<sub>2</sub> on the catalyst can be further reduced from the current 6.5% to 3%. Considering the absence of successful industrial applications for mercury-free catalysts, and based on the current annual consumption of commercial mercury chloride catalysts in the PVC industry, the widespread adoption of this technology could annually reduce the usage of chlorine mercury by 500 tons, making a notable contribution to mercury compliance, reduction, and emissions control in China. It also serves as a bridge between mercury-free and low-mercury catalysts. Moreover, this solid ligand technology can assist in the application research of mercury-free catalysts.</div></div>\",\"PeriodicalId\":9966,\"journal\":{\"name\":\"Chinese Journal of Chemical Engineering\",\"volume\":\"79 \",\"pages\":\"Pages 145-154\"},\"PeriodicalIF\":3.7000,\"publicationDate\":\"2025-03-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chinese Journal of Chemical Engineering\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1004954125000084\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"ENGINEERING, CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chinese Journal of Chemical Engineering","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1004954125000084","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
引用次数: 0

摘要

碳负载汞催化剂广泛应用于以碳酸钙为基础的聚氯乙烯(PVC)工业,但使用汞基催化剂会对环境造成威胁,因为在运行期间汞会释放到周围地区。本研究开发了一种高活性稳定的汞基催化剂,利用载体的氮原子作为锚位,增强活性位点(HgCl2)与碳载体(N-AC)之间的相互作用。热损失率测试和热重分析结果表明,与商品活性炭相比,n掺杂碳能有效提高HgCl2的热稳定性。得到的汞基催化剂(HgCl2/N-AC)表现出显著的催化性能,其C2H2转化率是常规HgCl2/AC催化剂的2.5倍。实验分析结合理论计算表明,与HgCl2/AC的Eley-Rideal (ER)吸附机理相反,HgCl2/N-AC催化剂遵循Langmuir-Hinshelwood (LH)吸附机理。催化剂上的氮位和HgCl2增强了对HCl和C2H2的吸附能力,从而提高了催化性能。通过这些固体配体对活性中心的修饰,可以进一步将HgCl2在催化剂上的负载量从目前的6.5%降低到3%。考虑到无汞催化剂缺乏成功的工业应用,并基于目前PVC工业商用氯化汞催化剂的年消费量,该技术的广泛采用每年可减少500吨氯汞的使用量,为中国的汞合规、减排和排放控制做出显著贡献。它还可以作为无汞和低汞催化剂之间的桥梁。此外,该固体配体技术有助于无汞催化剂的应用研究。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination
Carbon-supported mercury catalysts are extensively employed in calcium carbide-based polyvinyl chloride (PVC) industries, but the usage of mercury-based catalysts can pose an environmental threat due to the release of mercury into the surrounding area during the operation period. In this study, a highly active and stable mercury-based catalyst was developed, utilizing the nitrogen atom of the support as the anchor site to enhance the interaction between active sites (HgCl2) and the carbon support (N-AC). Thermal loss rate testing and thermogravimetric analysis results demonstrate that, compared to commercial activated carbon, N-doped carbon can effectively increase the heat stability of HgCl2. The obtained mercury-based catalysts (HgCl2/N-AC) exhibit significant catalytic performance, achieving 2.5 times the C2H2 conversion of conventional HgCl2/AC catalysts. Experimental analysis combined with theoretical calculations reveals that, contrary to the Eley-Rideal (ER) mechanism of HgCl2/AC, the HgCl2/N-AC catalyst follows the Langmuir-Hinshelwood (LH) adsorption mechanism. The nitrogen sites and HgCl2 on the catalyst enhance the adsorption capabilities of the HCl and C2H2, thereby improving the catalytic performance. Based on the modification of the active center by these solid ligands, the loading amount of HgCl2 on the catalyst can be further reduced from the current 6.5% to 3%. Considering the absence of successful industrial applications for mercury-free catalysts, and based on the current annual consumption of commercial mercury chloride catalysts in the PVC industry, the widespread adoption of this technology could annually reduce the usage of chlorine mercury by 500 tons, making a notable contribution to mercury compliance, reduction, and emissions control in China. It also serves as a bridge between mercury-free and low-mercury catalysts. Moreover, this solid ligand technology can assist in the application research of mercury-free catalysts.
求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Chinese Journal of Chemical Engineering
Chinese Journal of Chemical Engineering 工程技术-工程:化工
CiteScore
6.60
自引率
5.30%
发文量
4309
审稿时长
31 days
期刊介绍: The Chinese Journal of Chemical Engineering (Monthly, started in 1982) is the official journal of the Chemical Industry and Engineering Society of China and published by the Chemical Industry Press Co. Ltd. The aim of the journal is to develop the international exchange of scientific and technical information in the field of chemical engineering. It publishes original research papers that cover the major advancements and achievements in chemical engineering in China as well as some articles from overseas contributors. The topics of journal include chemical engineering, chemical technology, biochemical engineering, energy and environmental engineering and other relevant fields. Papers are published on the basis of their relevance to theoretical research, practical application or potential uses in the industry as Research Papers, Communications, Reviews and Perspectives. Prominent domestic and overseas chemical experts and scholars have been invited to form an International Advisory Board and the Editorial Committee. It enjoys recognition among Chinese academia and industry as a reliable source of information of what is going on in chemical engineering research, both domestic and abroad.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信