石油基中间相沥青的研制
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摘要
以石油基中温沥青为原料,经过热聚合-氢化-热处理制备中间相含量大于80%的广域流线型的中间相沥青,对处理过程中沥青的组分和结构变化进行了表征,探讨了低温长时间和高温短时间处理对中间相沥青形态的影响规律.结果表明,原料通过热聚合,沥青中的甲苯不溶物含量和芳环数提高;再经过加氢改性,沥青分子中的脂环烃增加,流动性改善;最后经高温短时间或低温长时间热处理形成含侧链或环烷结构的稠环芳烃分子,低温长时间处理更有利于中间相分子充分发展,易获得广域流线型的中间相.
The petroleum asphalt was used to prepare the mesophase pitch through three steps treatment including polymerization,hydrogenation and heat treatment.The mesophase content in the obtained product is more than 80%.The composition and structure of asphalt in the three-step process were characterized.Besides,the influence of heat treatment conditions,like low temperature with a long time and high temperature with a short time,on mesophase pitch morphology was investigated.The results showed that the content of toluene insoluble and the number of aromatic rings in the asphalt were improved by thermal polymerization.After modified by hydrogenation,the alicyclic hydrocarbons in the asphalt molecules was increased and the mobility was improved.Finally,after thermal treatment,the polycyclic aromatic molecules were formed with side chains or naphthenic structure.The treatment by low temperature with long time was favorable to the development of mesophase molecules and obtaining wide-area streamlined mesophase.
The petroleum asphalt was used to prepare the mesophase pitch through three steps treatment including polymerization,hydrogenation and heat treatment.The mesophase content in the obtained product is more than 80%.The composition and structure of asphalt in the three-step process were characterized.Besides,the influence of heat treatment conditions,like low temperature with a long time and high temperature with a short time,on mesophase pitch morphology was investigated.The results showed that the content of toluene insoluble and the number of aromatic rings in the asphalt were improved by thermal polymerization.After modified by hydrogenation,the alicyclic hydrocarbons in the asphalt molecules was increased and the mobility was improved.Finally,after thermal treatment,the polycyclic aromatic molecules were formed with side chains or naphthenic structure.The treatment by low temperature with long time was favorable to the development of mesophase molecules and obtaining wide-area streamlined mesophase.
引文
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[12]孙磊,郑长征,马丽斯,等.煤沥青及其改性后中间相的转化行为研究[J].煤炭转化,2010,33(1):82-85.Sun L,Zheng C Z,Ma L S,et al.Study on the Mesophase Transformations of Coal-tar Pitch and Modified Coal-tar Pitch[J].Coal Conversion,2010,33(1):82-85.
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[15]Mochida I,Yoon S H,Korai Y.Mesoscopic Structure and Properties of Liquid Crystalline Mesophase Pitch and Its Transformation into Carbon Fiber[J].Chem.Rec.,2002,2(2):81-101.
[16]Miyake M,Ida T,Yoshida H,et al.Effects of Reductively Introduced Alkyl Groups and Hydrogen to Mesophase Pitch on Carbonization Properties[J].Carbon,1993,31(5):705-714.
[17]Li M,Liu D,Du H.Preparation of Mesophase Pitch by Aromatics-rich Distillate of Naphthenic Vacuum Gas Oil[J].Appl.Petrochem.Res.,2015,5(4):339-346.
[18]Zhang J,Guo S,Wang Y,et al.Effect of Electrolytic Systems on Electrochemical Hydrogenation of Mesophase Coal Tar Pitch[J].Fuel Process.Technol.,2003,80(1):81-90.
[19]Mochida I,Shimizu K,Fujiyama S.Preparation of Mesophase Pitch from Aromatic Hydrocarbons by the Aid of HF/BF3[J].Carbon,1990,28(2):311-319.
[20]Korai Y,Nakamura M,Mochida I.Mesophase Pitches Prepared from Methylnaphthalene by the Aid of HF/BF3[J].Carbon,1991,29(4):561-567.
[21]舒欣,姚艳波,夏文丽,等.同步氢化/热缩聚法制备中间相沥青[J].功能材料,2011,42(12):2185-2188.Shu X,Yao Y B,Xia W L,et al.Preparation of Mesophase Pitch by Simultaneous Hydrogenation-thermal Condensation[J].Journal of Functional Materials,2011,42(12):2185-2188.
[22]Wazir A H,Kakakhel L.Preparation and Characterization of Pitch-based Carbon Fiber[J].New Carbon Mater.,2009,24(1):83-88.
[23]Li P P,Xiong J M,Ge M L.Preparation of Pitch-based General Purpose Carbon Fibers from Catalytic Slurry Oil[J].Fuel Process.Technol.,2015,140:231-235.
[24]Cheng X L,Zha Q F,Li X J.Modified Characteristics of Mesophase Pitch Prepared Fromcoal Tar Pitch by Adding Waste Polystyrene[J].Fuel Process.Technol.,2008,89(12):1436-1441.
[25]袁靖,迟伟东,沈曾民,等.采用加压-真空两段热缩聚法制备中间相沥青炭纤维的原料[J].炭素,2002,(4):8-14.Yuan J,Chi W D,Shen Z M,et al.Manufacture Raw of Mesophase-pitch Carbon Fiber by Two-stage Thermal Condensation Method under Pressure-Vacuum[J].Carbon,2002,(4):8-14.
[26]盛英,李克健,李文博.煤直接液化残留物制备中间相沥青[J].煤炭学报,2009,34(8):1125-1128.Sheng Y,Li K J,Li W B.Preparation of Mesophase Pitch Using Coal Liquefaction Residue[J].Journal of China Coal Society,2009,34(8):1125-1128.
[27]李伏虎,沈曾民,迟伟东.两种不同原料中间相沥青分子结构的研究[J].炭素技术,2009,28(1):4-8.Li F H,Shen Z M,Chi W D.Molecular Structures of Mesophase Pitches Prepared from Different Raw Materials[J].Carbon Techniques,2009,28(1):4-8.
[2]李新贵.中介相沥青液晶熔体纺丝[J].合成纤维工业,1997,20(2):42-46.Li X G.Liquid Crystalline Melt Spinning of Mesophase Pitch[J].China Synthetic Fiber Industry,1997,20(2):42-46.
[3]李新贵,黄美荣.高性能沥青基碳纤维制造一氧化碳化石墨化[J].合成纤维,1997,26(2):25-29.Li X G,Huang M R.Manufacturing of High Performance Pitch-based Carbon Fiber-Oxidization,Carbonization and Graphitization[J].Synthetic Fiber in China,1997,26(2):25-29.
[4]李新贵,黄美荣.中介相沥青基碳纤维的力学性能[J].材料导报,1997,11(1):46-49.Li X G,Huang M R.Mechanical Property of Mesophase Pitch-based Carbon Fiber[J].Materials Review,1997,11(1):46-49.
[5]李新贵,黄美荣.中介相沥青基碳纤维的性能[J].材料科学与工程,1997,15(4):69-71.Li X G,Huang M R.Properties of Carbon Fibre Based Upon Mesophase Pitch[J].Materials Science&Engineering,1997,15(4):69-71.
[6]李新贵,黄美荣.高性能中介相沥青基碳微球及碳片[J].材料科学与工艺,1997,5(3):92-96.Li X G,Huang M R.High Performance Carbon Microbeads and Sheets Based Upon Mesophase Pitch[J].Material Science&Technology,1997,5(3):92-96.
[7]LüY G,Wu D,Zha Q F,et al.Skin-Core Structure in Mesophase Pitch-based Carbon Fibers:Causes and Prevention[J].Carbon,1998,36(12):1719-1724.
[8]查庆芳,郭燕生,吴明铂,等.减压渣油与FCC油浆共炭化的化学组成变化[J].新型炭材料,2002,17(2):4-8.Zha Q F,Guo Y S,Wu M B,et al.Composition Changes in the Co-carbonization of FCC Slurry and VR[J].New Carbon Materials,2002,17(2):4-8.
[9]宋怀河,刘朗,张碧江.均四甲苯基中间相沥青纤维不熔化行为的研究[J].新型炭材料,1999,14(1):13-18.Song H H,Liu L,Zhang B J.Stabilization of Mesophase Pitch Fibers from Durene Methylene-bridged Oligomers[J].New Carbon Materials,1999,14(1):13-18.
[10]Otani S,Watanabe S,Ogino H.High Modulus Carbon Fibers from Pitch Materials[J].Bull.Chem.Soc.Jpn.,1972,45(12):3710-3714.
[11]Mora E,Blanco C,Santamaria R,et al.A Novel Method to Obtain a Petroleum-derived Mesophase Pitch Suitable as Carbon Fiber Precursor[J].Carbon,2003,41(3):445-452.
[12]孙磊,郑长征,马丽斯,等.煤沥青及其改性后中间相的转化行为研究[J].煤炭转化,2010,33(1):82-85.Sun L,Zheng C Z,Ma L S,et al.Study on the Mesophase Transformations of Coal-tar Pitch and Modified Coal-tar Pitch[J].Coal Conversion,2010,33(1):82-85.
[13]王惠,乔占平,冉新权,等.石油沥青制备中间相沥青[J].材料科学与工程,2001,19(2):58-60.Wang H,Qiao Z P,Ran X Q,et al.Study on Mesophase Pitch Made by Using Petroleum Pitch[J].Materials Science and Engineering,2001,19(2):58-60.
[14]黄美荣,李新贵.中间相沥青的制备与应用[J].石油化工,1998,27(1):62-66.
[15]Mochida I,Yoon S H,Korai Y.Mesoscopic Structure and Properties of Liquid Crystalline Mesophase Pitch and Its Transformation into Carbon Fiber[J].Chem.Rec.,2002,2(2):81-101.
[16]Miyake M,Ida T,Yoshida H,et al.Effects of Reductively Introduced Alkyl Groups and Hydrogen to Mesophase Pitch on Carbonization Properties[J].Carbon,1993,31(5):705-714.
[17]Li M,Liu D,Du H.Preparation of Mesophase Pitch by Aromatics-rich Distillate of Naphthenic Vacuum Gas Oil[J].Appl.Petrochem.Res.,2015,5(4):339-346.
[18]Zhang J,Guo S,Wang Y,et al.Effect of Electrolytic Systems on Electrochemical Hydrogenation of Mesophase Coal Tar Pitch[J].Fuel Process.Technol.,2003,80(1):81-90.
[19]Mochida I,Shimizu K,Fujiyama S.Preparation of Mesophase Pitch from Aromatic Hydrocarbons by the Aid of HF/BF3[J].Carbon,1990,28(2):311-319.
[20]Korai Y,Nakamura M,Mochida I.Mesophase Pitches Prepared from Methylnaphthalene by the Aid of HF/BF3[J].Carbon,1991,29(4):561-567.
[21]舒欣,姚艳波,夏文丽,等.同步氢化/热缩聚法制备中间相沥青[J].功能材料,2011,42(12):2185-2188.Shu X,Yao Y B,Xia W L,et al.Preparation of Mesophase Pitch by Simultaneous Hydrogenation-thermal Condensation[J].Journal of Functional Materials,2011,42(12):2185-2188.
[22]Wazir A H,Kakakhel L.Preparation and Characterization of Pitch-based Carbon Fiber[J].New Carbon Mater.,2009,24(1):83-88.
[23]Li P P,Xiong J M,Ge M L.Preparation of Pitch-based General Purpose Carbon Fibers from Catalytic Slurry Oil[J].Fuel Process.Technol.,2015,140:231-235.
[24]Cheng X L,Zha Q F,Li X J.Modified Characteristics of Mesophase Pitch Prepared Fromcoal Tar Pitch by Adding Waste Polystyrene[J].Fuel Process.Technol.,2008,89(12):1436-1441.
[25]袁靖,迟伟东,沈曾民,等.采用加压-真空两段热缩聚法制备中间相沥青炭纤维的原料[J].炭素,2002,(4):8-14.Yuan J,Chi W D,Shen Z M,et al.Manufacture Raw of Mesophase-pitch Carbon Fiber by Two-stage Thermal Condensation Method under Pressure-Vacuum[J].Carbon,2002,(4):8-14.
[26]盛英,李克健,李文博.煤直接液化残留物制备中间相沥青[J].煤炭学报,2009,34(8):1125-1128.Sheng Y,Li K J,Li W B.Preparation of Mesophase Pitch Using Coal Liquefaction Residue[J].Journal of China Coal Society,2009,34(8):1125-1128.
[27]李伏虎,沈曾民,迟伟东.两种不同原料中间相沥青分子结构的研究[J].炭素技术,2009,28(1):4-8.Li F H,Shen Z M,Chi W D.Molecular Structures of Mesophase Pitches Prepared from Different Raw Materials[J].Carbon Techniques,2009,28(1):4-8.