化学法改性煤沥青脱除苯并芘的研究
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摘要
在管式反应器中采用苯甲酸、聚乙二醇、固体古马隆树脂(S)、液体古马隆树脂(L)为添加剂来降低煤沥青中有害物质苯并芘的含量,以期使得煤沥青可绿色化应用。采用紫外-可见分光光度计分析煤沥青中苯并芘含量。考察了反应温度、反应时间、添加剂添加量、催化剂等工艺条件对添加剂脱除煤沥青中苯并芘的影响。结果表明,不同工艺条件能降低煤沥青中苯并芘的含量。在优化条件下,不同添加剂对苯并芘脱除率由高到低依次为:液体古马隆树脂、聚乙二醇、苯甲酸和固体古马隆树脂。分析其反应机理,这与催化剂的酸性相关,发生亲电取代反应。结果表明,液体古马隆树脂(L)在催化剂存在下对煤沥青中苯并芘脱除率可达73.0%,显示了良好的应用前景。
For the friendly environmental application of coal tar pitch,the benzoic acid,polyethylene glycol,solid coumarone resin( S) or liquid coumarone resin( L) were selected as a modifier to lower the content of harmful benzopyrene in coal tar pitch by chemical reaction in a tube furnace. The benzopyrene content was detected by an ultraviolet-visible spectrophotometer,and the influence of reaction temperature,reaction time,modifier contents and catalyst types on the benzopyrene content was investigated. The results show that the technical condition has an intimate relationship with the decrease of benzopyrene content owing to the electrophilic substitutive reaction at the existence of acidic catalyst. All modifiers tested have obvious effects on the decrease of benzopyrene content. Under the optimum conditions,the removal rates of benzopyrene by different additives decrease in proper sequence of liquid coumarone resin,polyethylene glycol,benzoic acid and solid coumarone resin. The highest benzopyrene removal rate of 73.0% is obtained by using liquid coumarone resin,showing a promising application prospect.
For the friendly environmental application of coal tar pitch,the benzoic acid,polyethylene glycol,solid coumarone resin( S) or liquid coumarone resin( L) were selected as a modifier to lower the content of harmful benzopyrene in coal tar pitch by chemical reaction in a tube furnace. The benzopyrene content was detected by an ultraviolet-visible spectrophotometer,and the influence of reaction temperature,reaction time,modifier contents and catalyst types on the benzopyrene content was investigated. The results show that the technical condition has an intimate relationship with the decrease of benzopyrene content owing to the electrophilic substitutive reaction at the existence of acidic catalyst. All modifiers tested have obvious effects on the decrease of benzopyrene content. Under the optimum conditions,the removal rates of benzopyrene by different additives decrease in proper sequence of liquid coumarone resin,polyethylene glycol,benzoic acid and solid coumarone resin. The highest benzopyrene removal rate of 73.0% is obtained by using liquid coumarone resin,showing a promising application prospect.
引文
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[9]王文超,牛艳霞,刘刚,申峻,李瑞丰,杜建奎,郭宝荣,杨志峰.煤沥青中多环芳烃的消减抑制研究[J].湖北大学学报:自然科学版,2015,37(4):400-406.(WANG Wen-chao,NIU Yan-xia,LIU Gang,SHEN Jun,LI Rui-feng,DU Jian-kui,GUO Bao-rong,YANG Zhi-feng.Reducing polycyclic aromatic hydrocarbons content in coal tar pitch[J].J Hubei Univ:Nat Sci Ed,2015,37(4):400-406.)
[10]ZIELI'N SKI J,OSOWIECKA B,LISZY'NSKA B,CIESINSKA W,POLACZEK J.Benzo[a]pyrene in coal tar pitch:Chemical conversion in situ by alky lation[J].Fuel,1996,75(13):1543-1548.
[11]HE D M,GUAN J,WU D,ZHAO S C,ZHANG Q M.Modification of coal tar pitch to reduce the carcinogenic polycyclic aromatic hydrocarbons[C].Applied Mechanics and Materials.Trans Tech Publications,2013,295:3098-3103.
[12]KAVSHIK S,RAINA R K,BHATIA G,VERMA G L,KHANDAL R K.Modification of coal tar pitch by chemical method to reduce benzo(a)pyrene[J].Curr Sci,2007,93(25):540-544.
[13]WANG W,LIU G,SHEN J,CHANG H H,LI R F,DU J K,YANG Z F,XU Q B.Reducing polycyclic aromatic hydrocarbons content in coal tar pitch by potassium permanganate oxidation and solvent extraction[J].J Environ Chem Eng,2015,3(3):1513-1521.
[2]宋健伟,李其祥,王红亮,王智勇,伍林.脱除煤沥青中3,4-苯并芘及其机理研究[J].化学与生物工程,2014,31(10):62-65.(SONG Jian-wei,LI Qi-xiang,WANG Hong-liang,WANG Zhi-yong,WU Lin.Removal of 3,4-benzopyren in coal tar pitch and mechanism research[J].Chem Bioeng,2014,31(10):62-65.)
[3]OUYOUNG C F,LI X Y,GAO Q,SH X Q.Reducing benzo(a)pyrene content of coal-tar-pitch modified by styrene-butadiene rubber through dynamic vulcanization[C]//Materials Science Forum.Trans Tech Publications,2013,743:292-300.
[4]黄大军.煤沥青与聚合物反应减少苯并[a]芘的研究[D].大连:大连理工大学,2006.(HUANG Da-jun.Reduce of benzo[a]pyrene in coal tar pitch by reacting with polymer[D].Dalian University of Technology,2016.)
[5]孙昱,廖志远,苏龙,曾鹏.溶剂效应对脱除煤沥青中3,4-苯并芘的影响[J].化工进展,2014,(8):2211-2214.(SUN Yu,LIAO Zhi-yuan,SU Long,ZENG Peng.Solvent effect on removal of benzo[a]pyrene in coal tar pitch[J].Chem Ind Eng Prog,2014,(8):2211-2214.)
[6]廖志远,孙昱,苏龙,曾鹏.聚乙二醇改性脱除煤沥青中3,4-苯并芘[J].燃料与化工,2014,45(4):37-39.(LIAO Zhi-yuan,SUN Yu,SU Long,ZENG Peng.Removal of benzo[a]pyrene from coal tar pitch with polyethylene glycol[J].Fuel Chem Prog,2014,45(4):37-39.)
[7]张秋民,黄大军,赵树昌.用聚合物试剂减少煤沥青中3,4-苯并芘的研究[J].煤化工,2007,35(1):58-60.(ZHANG Qing-ming,HUANG Da-jun,ZHAO Shu-chang.Decrease of benzo[a]pyrene in coal tar pitch by polymer[J].Coal Chem Ind,2007,35(1):58-60.)
[8]XUE Y B,GE Z F,LI F C,SU S,LI B Z.Modified asphalt properties by blending petroleum asphalt and coal tar pitch[J].Fuel,2017,207:64-70.
[9]王文超,牛艳霞,刘刚,申峻,李瑞丰,杜建奎,郭宝荣,杨志峰.煤沥青中多环芳烃的消减抑制研究[J].湖北大学学报:自然科学版,2015,37(4):400-406.(WANG Wen-chao,NIU Yan-xia,LIU Gang,SHEN Jun,LI Rui-feng,DU Jian-kui,GUO Bao-rong,YANG Zhi-feng.Reducing polycyclic aromatic hydrocarbons content in coal tar pitch[J].J Hubei Univ:Nat Sci Ed,2015,37(4):400-406.)
[10]ZIELI'N SKI J,OSOWIECKA B,LISZY'NSKA B,CIESINSKA W,POLACZEK J.Benzo[a]pyrene in coal tar pitch:Chemical conversion in situ by alky lation[J].Fuel,1996,75(13):1543-1548.
[11]HE D M,GUAN J,WU D,ZHAO S C,ZHANG Q M.Modification of coal tar pitch to reduce the carcinogenic polycyclic aromatic hydrocarbons[C].Applied Mechanics and Materials.Trans Tech Publications,2013,295:3098-3103.
[12]KAVSHIK S,RAINA R K,BHATIA G,VERMA G L,KHANDAL R K.Modification of coal tar pitch by chemical method to reduce benzo(a)pyrene[J].Curr Sci,2007,93(25):540-544.
[13]WANG W,LIU G,SHEN J,CHANG H H,LI R F,DU J K,YANG Z F,XU Q B.Reducing polycyclic aromatic hydrocarbons content in coal tar pitch by potassium permanganate oxidation and solvent extraction[J].J Environ Chem Eng,2015,3(3):1513-1521.