烷基化法降低煤焦油沥青中毒性多环芳烃含量的研究进展  

Progress of decreasing toxic polycyclic aromatic hydrocarbons content in coal-tar pitch by alkylation method

作　　者：张文硕 申峻[1] 王玉高[1] 刘刚[1] 李瑞丰[1] 徐青柏 ZHANG Wenshuo;SHEN Jun;WANG Yugao;LIU Gang;LI Ruifeng;XU Qingbai(College of Chemistry and Chemical Engineering,Taiyuan University of Technology,Taiyuan 030024,China;Dalian Research Institute of Petroleum and Petrochemicals,China Petroleum&Chemical Corporation,Dalian 116045,China)

机构地区：[1]太原理工大学化学化工学院,山西太原030024 [2]中国石油化工股份有限公司大连石油化工研究院,辽宁大连116045

出　　处：《煤炭科学技术》2023年第3期271-280,共10页Coal Science and Technology

基　　金：国家自然科学基金资助项目(U1610223,21706172);山西省科技攻关资助项目(201903D321061)。

摘　　要：煤焦油沥青(简称“煤沥青”)是高温煤焦油常减压蒸馏后的残余物,尽管煤沥青在中国产量很大,但由于其具有较高毒性,因此限制了它的广泛应用。通过固体^(13)C NMR和气相色谱/质谱联用等技术发现煤沥青的毒性来源于其含有大量的毒性多环芳烃(PAHs),包括美国环保署(EPA)优先监控的16种PAHs,如荧蒽、芘和苯并[a]芘等。介绍了煤沥青的各种抑毒改性方法,包括化学交联法和物理化学法,现有的研究主要集中在化学交联法;通过对比煤沥青与石油沥青的分子结构,发现石油沥青中具有较高的脂肪族烃类,提出通过长链烯烃烷基化的方法,在PAHs上加上烷基侧链,生成无毒的长链烷基取代PAHs,以抑制煤沥青的毒性。因此重点阐述了烷基化交联改性方法,详细总结该方法的反应原理、所使用的催化剂,并对国内外有关改性试验结果和理论研究工作进行了综合分析,首先使用高斯模拟16种PAHs与烯烃的烷基化反应,得出其反应的一般规律;其次选取模型化合物进行烷基化反应,探讨在煤沥青改性过程中相关PAHs可能发生的反应及反应机理;最后将模型化合物烷基化实验所得到的反应条件应用到真实煤沥青体系,并分析改性前后煤沥青中美国环保署优先监控16种PAHs的降低情况,以及煤沥青抑毒改性后的沥青烟释放物和水可溶物变化情况等内容,同时对该方法的下一步研究应用热点和发展进行了展望,希望为国内外煤沥青的环境友好利用提供参考。Coal-tar pitch(CTP)is a substance produced by ambient and/or vacuum distillation of high-temperature coal tar,although CTP has a large yield in China,however its wide application is limited due to its high toxicity.It was found that the toxicity of CTP was derived from its large amount of toxic Polycyclic Aromatic Hydrocarbons(PAHs)by ^(13)C NMR and gas chromatography/mass spectrometer,including 16 PAHs monitored by the United States Environmental Protection Agency(EPA),such as fluoranthene、pyrene and benzo[a]pyrene.Various anti-toxic modification methods of CTP are introduced in the article,including chemical crosslinking method and physical chemistry method.The existing research mainly focuses on the former;by comparing the molecular structure of CTP and petroleum pitch,it is found that petroleum pitch has higher aliphatic hydrocarbons,it is proposed to add alkyl side chains to PAHs by alkylation of long-chain olefins to generate non-toxic long-chain alkyl substituted PAHs and inhibit the toxicity of CTP.Thus the method of alkylation cross-linking modification is focused on.The principle of the method and the catalysts used were summarized,the domestic and foreign related modification experiment results and theoretical research work were analyzed;Firstly,the alkylation of 16 kinds of PAHs with olefins was simulated by Gaussian,and the general rules of the reaction were obtained;Secondly,model compounds were selected for alkylation reaction,the possible reaction and its reaction mechanism of PAHs in the process of CTP modification were discussed;Finaly,the reaction conditions obtained from alkylation experiments of model compounds were applied to real CTP system,including 16 U.S.Environmental Protection Agency priority monitoring PAHs reduction in the modified coal tar pitch,as well as the changes of asphalt fume emissions and water soluble matter after modification in CTP,meanwhile the future research and application hot-spots and development of this method were prospected,it is hoped to provide reference for

关 键 词：煤焦油沥青 多环芳烃 烷基化 模型化合物 

分 类 号：TQ53[化学工程—煤化学工程]