1-十六烯烷基化降低煤沥青中毒性多环芳烃含量的研究
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摘要
因含烷基的芳烃特别是被长链烷基取代的芳烃,其潜在毒性显著降低,尝试用傅-克烷基化反应来转化煤沥青中的毒性多环芳烃(PAHs).选用蒽作为多环芳烃模型化合物来研究其烷基化反应条件,从5种烷基化剂和6种催化剂中分别筛选出1-十六烯和磷钨酸,优化反应温度为170℃,反应时间为2h,蒽的转化率达到100%,烷基蒽收率为35.46%.与煤沥青的反应表明:US EPA优先监控的16种多环芳烃总含量降低37.88%,利用Wiles毒性当量因子计算得到苯并[a]芘等量毒性降低率为45.97%.FTIR表征发现,改性后的沥青滤液中多环芳烃发生了烷基取代反应;TG表征说明改性后残渣结焦率上升,热稳定性提高.
Friedel-crafts alkylation was tried to reduce the content of toxic polycyclic aromatic hydrocarbons(PAHs)in coal-tar pitch(CTP),because the potential toxicity of alkyl aromatic compounds,especially the long chain alkyl substituted aromatics,dropped down dramatically.Anthracene,as a model compound of PAH,was used to investigate the reaction conditions of alkylation.From 5 kinds of alkylation agents and 6 kinds of catalysts,1-hexadecene and phosphotungstic acid are screened in alkylation of anthracene.The optimized reaction conditions are obtained as follows:the reaction temperature is 170 ℃,the reaction time is 2 h,and the anthracene conversion reaches 100%,the alkyl-anthracenes yield is 35.46%.The reaction with CTP shows that the content of the 16 kinds of US EPA priority PAHs is reduced by 37.88%,and the reduction rate of BaP equivalent calculated by Wiles toxic equivalence factor is 45.97%.The filtrate of modified CTP characterized by FTIR shows that PAHs have been substituted by alkyl groups,and TG analysis shows that the coking rate and thermal stability of the modified CTP residue both have gone up synchronously.
Friedel-crafts alkylation was tried to reduce the content of toxic polycyclic aromatic hydrocarbons(PAHs)in coal-tar pitch(CTP),because the potential toxicity of alkyl aromatic compounds,especially the long chain alkyl substituted aromatics,dropped down dramatically.Anthracene,as a model compound of PAH,was used to investigate the reaction conditions of alkylation.From 5 kinds of alkylation agents and 6 kinds of catalysts,1-hexadecene and phosphotungstic acid are screened in alkylation of anthracene.The optimized reaction conditions are obtained as follows:the reaction temperature is 170 ℃,the reaction time is 2 h,and the anthracene conversion reaches 100%,the alkyl-anthracenes yield is 35.46%.The reaction with CTP shows that the content of the 16 kinds of US EPA priority PAHs is reduced by 37.88%,and the reduction rate of BaP equivalent calculated by Wiles toxic equivalence factor is 45.97%.The filtrate of modified CTP characterized by FTIR shows that PAHs have been substituted by alkyl groups,and TG analysis shows that the coking rate and thermal stability of the modified CTP residue both have gone up synchronously.
引文
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[27]WANG Xionglei,SHEN Jun,NIU Yanxia,et al.Solvent Extracting Coal Gasification Tar Residue and the Extracts Characterization[J].Journal of Cleaner Production,2016,133:965-970.
[28]GARGIULO V,APICELLA B,ALFE M,et al.Structural Characterization of Large Polycyclic Aromatic Hydrocarbons(Part 1):The Case of Coal Tar Pitch and Naphthalene-derived Pitch[J].Energy and Fuels,2015,29(9):5714-5722.
[29]GARGIULO V,APICELLA B,STANZIONE F,et al.Structural Characterization of Large Polycyclic Aromatic Hydrocarbons(Part 2):Solvent-separated Fractions of Coal Tar Pitch and Naphthalene-derived Pitch[J].Energy and Fuels,2016,30(4):2574-2583.
[30]赵忠奎,乔卫红,李化民,等.U-甲基萘与长链烯烃烷基化研究[J].大连理工大学学报,2004,44(1):39-43.ZHAO Zhongkui,QIAO Weihong,LI Huamin,et al.Study of Long-chain Alkylation of U-methylnaphthalene with Olefins[J].Journal of Dalian University of Technology,2004,44(1):39-43.
[31]王颖,董亚威,钟存贵,等.机械振动对改性煤沥青制备针状焦结构影响的研究[J].新型炭材料,2017,32(5):467-473.WANG Ying,DONG Yawei,ZHONG Cungui,et al.The Effect of Mechanical Vibration on the Structure of Needle Coke Prepared from a Modified Coal Tar Pitch[J].New Carbon Materials,2017,32(5):467-473.
[2]GAN S,LAU E V,NG H K.Remediation of Soils Contaminated with Polycyclic Aromatic Hydrocarbons(PAHs)[J].Journal of Hazardous Materials,2009,172(2/3):532-549.
[3]李登新,高晋生,宋文.煤焦油沥青改质为辅路材料的研究进展[J].煤化工,1999(3):12-14.LI Dengxin,GAO Jinsheng,SONG Wen.Progress in Upgrading Coal Tar Pitch for Paving Materials[J].Coal Chemical Industry,1999(3):12-14.
[4]MAHLER B J,VAN METRE P C,FOREMAN W T,et al.Concentrations of Polycyclic Aromatic Hydrocarbons(PAHs)and Azaarenes in Runoff from Coal-tar-and Asphalt-sealcoated Pavement[J].Environmental Pollution,2014,188:81-87.
[5]MAHLER B J,VAN METRE P C,CRANE J L,et al.Coal-tar-based Pavement Sealcoat and PAHs:Implications for the Environment,Human Health,and Stormwater Management[J].Environmental Science and Technology,2012,46:3039-3045.
[6]WITTER A E,NGUYEN M H,BAIDAR S,et al.Coal-tar-based Sealcoated Pavement:a Major PAH Source to Urban Stream Sediments[J].Environmental Pollution,2014,185:59-68.
[7]YUAN Guoli,WU Lijuan,SUN Yong,et al.Polycyclic Aromatic Hydrocarbons in Soils of the Central Tibetan Plateau,China:Distribution,Sources,Transport and Contribution in Global Cycling[J].Environmental Pollution,2015,203:137-144.
[8]CHENG Xianglin,LI Guoning,PENG Yaoli,et al.Obtaining Needle Coke from Coal Liquefaction Residue[J].Chemistry and Technology and Fuels and Oils,2012,48(5):349-355.
[9]ZELLERHOFF R.Chemically and Physically Modified Coal Tar Pitches and Their Use:T-83-012[R].German,Rutgerwerke,Frank-furt:1988.
[10]ZHANG L F,LIU G,WANG Y G,et al.Modification of Coal Tar Pitch with P-phthalaldehyde to Reduce Toxic PAH Content[J].Energy Sources Part A:Recovery,Utilization,and Environmental Effects,2016,38(5):737-743.
[11]ZIELINSKI J.The Physical Chemistry and Thermodynamics of Semicolloidal Polymerbitumen Systems(PartⅡ):Polymers as Coal Par Pitch Modifies[J].Polimery,1998,43(1):17-23.
[12]KAUSHIK S,RAINA R K,BHATIA G,et al.Modification of Coal Tar Pitch by Chemical Method to Reduce Benzo[a]Pyrene[J].Current Science,2007,93(4):540-544.
[13]ZIELINSKI J,OSOWIECKA B,CIESINSKA W,et al.The Effect of a Polyester Resin or Polyoxyethylene Glycols as Coaltar Pitch Modifiers on Pitch’s Benzo[a]Pyrene Content[J].Polimery,1998,43(3):175-184.
[14]WANG Wenchao,LIU Gang,SHEN Jun,et al.Reducing Polycyclic Aromatic Hydrocarbons Content in Coal Tar Pitch by Potassium Permanganate Oxidation and Solvent Extraction[J].Journal of Environmental Chemical Engineering,2015,3(3):1513-1521.
[15]PRADO G H C,DE KLERK A.Alkylation of Asphaltenes Using a FeCl3Catalyst[J].Energy and Fuels,2015,29(8):4947-4955.
[16]PODGORSKI D C,CORILO Y E,NYADONG L,et al.Heavy Petroleum Composition(5):Compositional and Structural Continuum of Petroleum Revealed[J].Energy and Fuels,2013,27(3):1268-1276.
[17]陈曦,刘刚,牛艳霞,等.路用煤沥青中多环芳烃在水中浸出规律的研究[J].环境科学与技术,2016,39(10):36-41.CHEN Xi,LIU Gang,NIU Yanxia,et al.Research of Dissolving PAHs by Water from Road-paving Coal Tar Pitch[J].Environmental Science and Technology,2016,39(10):36-41.
[18]ALVAREZ P,GRANDA M,SUTIL J,et al.Preparation of Low Toxicity Pitches by Thermal Oxidative Condensation of Anthracene Oil[J].Environmental Science&Technology,2009,43(21):8126-8132.
[19]栗同林,刘希尧,朴玉玲,等.萘与不同烷基化试剂在沸石上的烷基化反应[J].催化学报,1998,19(2):181-183.LI Tonglin,LIU Xiyao,PIAO Yuling,et al.Alkylation of Naphthalene with Different Alkylating Agents over Some Zeolites[J].Chinese Journal of Catalysis,1998,19(2):181-183.
[20]佟惠娟,李工.不同分子筛的结构和酸性对苯与1-十二烯烷基化反应的影响[J].抚顺石油学院学报,2003,23(4):7-10.TONG Huijuan,LI Gong.Effect of Structure and Acidity of Different Molecular Sieves for Alkylation Reaction of Benzene with 1-dodecene[J].Journal of Fushun Petroleum Institute,2003,23(4):7-10.
[21]刘琪英,武文良,王军,等.不同沸石分子筛催化剂上萘与异丙醇的烷基化[J].南京工业大学学报,2004,26(3):12-14.LIU Qiying,WU Wenliang,WANG Jun,et al.Isopropylation of Naphthalene over Various Zeolite Catalysts[J].Journal of Nanjing University of Technology,2004,26(3):12-14.
[22]梁宇翔,焦广文.长链烷基萘合成工艺研究[J].石油炼制与化工,2009,40(3):22-25.LIANG Yuxiang,JIAO Guangwen.Study on the Preparation of Long Chain Alkylated Naphthalenes[J].Petroleum Processing and Petrochemicals,2009,40(3):22-25.
[23]温朗友,闵恩泽.固体杂多酸催化剂研究新进展[J].石油化工,2000,29(1):49-55.WEN Langyou,MIN Enze.New Progress of Solid Heteropoly Acid Catalyst[J].Petrochemical Technology,2000,29(1):49-55.
[24]王大飞,王平美,罗健辉,等.新型长链烷基蒽润滑油的合成及其热稳定性[J].合成化学,2013,21(5):572-574.WANG Dafei,WANG Pingmei,LUO Jianhui,et al.Synthesis and Thermal Stability of a Novel Long Chain Alkylanthracene Lubrication Oil[J].Chinese Journal of Synthetic Chemistry,2013,21(5):572-574.
[25]郭海涛,梁燕,乔卫红,等.HY分子筛催化合成长链烷基萘[J].石油化工,2003,32(3):182-186.GUO Haitao,LIANG Yan,QIAO Weihong,et al.Alkylation of Naphthalene with Long Chain Olefins on Zeolite Catalyst[J].Petrochemical Technology,2003,32(3):182-186.
[26]金英杰,任杰,袁兴东,等.苯-长链烯烃烷基化催化剂的稳定性和再生性能[J].燃料化学学报,1999,27(6):495-500.JIN Yingjie,REN Jie,YUAN Xingdong,et al.Stability and Regeneration Ability of Catalysts for Alkylation of Benzene with Long Chain Alkene[J].Journal of Fuel Chemistry and Technology,1999,27(6):495-500.
[27]WANG Xionglei,SHEN Jun,NIU Yanxia,et al.Solvent Extracting Coal Gasification Tar Residue and the Extracts Characterization[J].Journal of Cleaner Production,2016,133:965-970.
[28]GARGIULO V,APICELLA B,ALFE M,et al.Structural Characterization of Large Polycyclic Aromatic Hydrocarbons(Part 1):The Case of Coal Tar Pitch and Naphthalene-derived Pitch[J].Energy and Fuels,2015,29(9):5714-5722.
[29]GARGIULO V,APICELLA B,STANZIONE F,et al.Structural Characterization of Large Polycyclic Aromatic Hydrocarbons(Part 2):Solvent-separated Fractions of Coal Tar Pitch and Naphthalene-derived Pitch[J].Energy and Fuels,2016,30(4):2574-2583.
[30]赵忠奎,乔卫红,李化民,等.U-甲基萘与长链烯烃烷基化研究[J].大连理工大学学报,2004,44(1):39-43.ZHAO Zhongkui,QIAO Weihong,LI Huamin,et al.Study of Long-chain Alkylation of U-methylnaphthalene with Olefins[J].Journal of Dalian University of Technology,2004,44(1):39-43.
[31]王颖,董亚威,钟存贵,等.机械振动对改性煤沥青制备针状焦结构影响的研究[J].新型炭材料,2017,32(5):467-473.WANG Ying,DONG Yawei,ZHONG Cungui,et al.The Effect of Mechanical Vibration on the Structure of Needle Coke Prepared from a Modified Coal Tar Pitch[J].New Carbon Materials,2017,32(5):467-473.