{"title":"基于多胺的甲苯二异氰酸酯焦油渣氨解:高效转化及机理探讨","authors":"Xu Chai, Shengxian Huang, Zhixian Huang, Chongfu Wu, Ping Lu, Changshen Ye, Ting Qiu","doi":"10.1021/acs.iecr.5c00745","DOIUrl":null,"url":null,"abstract":"Tar residue produced in the phosgenation process is one of the important hazardous wastes in the toluene diisocyanate (TDI) industry. The efficient degradation and utilization of TDI tar residue have become a tough challenge for TDI enterprises worldwide. Traditional landfill and incinerator processes do not properly use the organic resources in tar residue, and they also pose a danger of soil and air contamination. This study explores aminolysis using polyamines as a highly efficient alternative to TDI tar residue valorization. Aminolysis offers high degradation rates and TDA yields without requiring added catalysts or solvents, presenting a potentially atom-economical process. Using diethylenetriamine (DETA), a TDA yield of approximately 60% alongside the value-added coproduct 1-(2-aminoethyl)-2-imidazolidone (AEI) was achieved under optimized conditions. Density functional theory (DFT) calculations and experimental results support a three-step mechanism involving a sequential amine attack on urea linkages, followed by cyclization. This work demonstrates the potential of aminolysis as a cleaner and effective route for the chemical recycling of TDI tar residue.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"84 1","pages":""},"PeriodicalIF":3.9000,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Aminolysis of Toluene Diisocyanate Tar Residue Based on Polyamines: Efficient Conversion and Mechanism Exploration\",\"authors\":\"Xu Chai, Shengxian Huang, Zhixian Huang, Chongfu Wu, Ping Lu, Changshen Ye, Ting Qiu\",\"doi\":\"10.1021/acs.iecr.5c00745\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Tar residue produced in the phosgenation process is one of the important hazardous wastes in the toluene diisocyanate (TDI) industry. The efficient degradation and utilization of TDI tar residue have become a tough challenge for TDI enterprises worldwide. Traditional landfill and incinerator processes do not properly use the organic resources in tar residue, and they also pose a danger of soil and air contamination. This study explores aminolysis using polyamines as a highly efficient alternative to TDI tar residue valorization. Aminolysis offers high degradation rates and TDA yields without requiring added catalysts or solvents, presenting a potentially atom-economical process. Using diethylenetriamine (DETA), a TDA yield of approximately 60% alongside the value-added coproduct 1-(2-aminoethyl)-2-imidazolidone (AEI) was achieved under optimized conditions. Density functional theory (DFT) calculations and experimental results support a three-step mechanism involving a sequential amine attack on urea linkages, followed by cyclization. This work demonstrates the potential of aminolysis as a cleaner and effective route for the chemical recycling of TDI tar residue.\",\"PeriodicalId\":39,\"journal\":{\"name\":\"Industrial & Engineering Chemistry Research\",\"volume\":\"84 1\",\"pages\":\"\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-07-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Industrial & Engineering Chemistry Research\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.iecr.5c00745\",\"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":"Industrial & Engineering Chemistry Research","FirstCategoryId":"5","ListUrlMain":"https://doi.org/10.1021/acs.iecr.5c00745","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}
Aminolysis of Toluene Diisocyanate Tar Residue Based on Polyamines: Efficient Conversion and Mechanism Exploration
Tar residue produced in the phosgenation process is one of the important hazardous wastes in the toluene diisocyanate (TDI) industry. The efficient degradation and utilization of TDI tar residue have become a tough challenge for TDI enterprises worldwide. Traditional landfill and incinerator processes do not properly use the organic resources in tar residue, and they also pose a danger of soil and air contamination. This study explores aminolysis using polyamines as a highly efficient alternative to TDI tar residue valorization. Aminolysis offers high degradation rates and TDA yields without requiring added catalysts or solvents, presenting a potentially atom-economical process. Using diethylenetriamine (DETA), a TDA yield of approximately 60% alongside the value-added coproduct 1-(2-aminoethyl)-2-imidazolidone (AEI) was achieved under optimized conditions. Density functional theory (DFT) calculations and experimental results support a three-step mechanism involving a sequential amine attack on urea linkages, followed by cyclization. This work demonstrates the potential of aminolysis as a cleaner and effective route for the chemical recycling of TDI tar residue.
期刊介绍:
ndustrial & Engineering Chemistry, with variations in title and format, has been published since 1909 by the American Chemical Society. Industrial & Engineering Chemistry Research is a weekly publication that reports industrial and academic research in the broad fields of applied chemistry and chemical engineering with special focus on fundamentals, processes, and products.