石油沥青对煤焦油沥青焦结构和电性能的影响
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摘要
为了研究石油沥青(PP)作为煤沥青添加剂对沥青焦结构及导电性能的影响,将精制煤沥青(RCTP)与PP混合共炭化,同时在机械搅拌的作用下制焦,并对共炭化过程中PP和机械作用产生的影响机理进行了探讨和分析.采用偏光显微镜、X射线衍射仪、热重分析仪、比表面分析仪对所制半焦的结构进行了分析,利用电化学石英晶体微天平及电阻率仪对所制针状焦的性能进行了考察.结果表明:当PP质量分数为10%、搅拌速率为100 r/min、以间歇搅拌方式所制针状焦,其纤维组织占比达到了67.9%,电阻率降为676Ω·mm~2/m,即PP和机械搅拌二者联合作用存在下可显著增加中间相各向异性组织和纤维组织的含量,有利于改善半焦结构,使其结构更加趋于有序,所得针状焦电阻率也得到明显降低.
In order to study the effect of petroleum pitch(PP) as a coal tar pitch additive on the structure and electrical conductivity of pitch coke,the refined coal tar pitch(RCTP) was mixed with PP and cocarbonization.,and t The coke was prepared with the help ofunder mechanical agitation.Meanwhile At the same time,the influence mechanism of PP and mechanical action in the process of co-carbonization was elaborateddiscussed and analyzed.The structure of the semi-coke was analyzed by polarizing microscope,X-ray diffraction,thermogravimetric analyzer and specific surface analyzer.The properties of the needle-like coke werecoke were studied by electrochemical quartz crystal microbalance and resistivity meter.The results showed that when the proportion of PP was 10% and the stirring speed was 100 rpm,the content of fiber was67.9% and the resistivity was 676 Ω·mm~2/m,for the case of 67.9 wt.% PP,and 100 rpm stirring speed.This suggested that Namely,in the presence of both PP and mechanical agitation can significantly improve the,the content of mesophase anisotropic tissue and fibrous tissue can be significantly increased,,and then facilitate the formation of homogeneousand the semi-coke structure is greatly improved.Meanwhile,the resistivity of obtainedresulting needle-like coke can also be obviously reduced.
In order to study the effect of petroleum pitch(PP) as a coal tar pitch additive on the structure and electrical conductivity of pitch coke,the refined coal tar pitch(RCTP) was mixed with PP and cocarbonization.,and t The coke was prepared with the help ofunder mechanical agitation.Meanwhile At the same time,the influence mechanism of PP and mechanical action in the process of co-carbonization was elaborateddiscussed and analyzed.The structure of the semi-coke was analyzed by polarizing microscope,X-ray diffraction,thermogravimetric analyzer and specific surface analyzer.The properties of the needle-like coke werecoke were studied by electrochemical quartz crystal microbalance and resistivity meter.The results showed that when the proportion of PP was 10% and the stirring speed was 100 rpm,the content of fiber was67.9% and the resistivity was 676 Ω·mm~2/m,for the case of 67.9 wt.% PP,and 100 rpm stirring speed.This suggested that Namely,in the presence of both PP and mechanical agitation can significantly improve the,the content of mesophase anisotropic tissue and fibrous tissue can be significantly increased,,and then facilitate the formation of homogeneousand the semi-coke structure is greatly improved.Meanwhile,the resistivity of obtainedresulting needle-like coke can also be obviously reduced.
引文
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[20]梁基照,杨铨铨.高分子基导电复合材料非线性导电行为及其机理(Ⅱ)量子力学隧道效应理论[J].上海塑料,2010(1):1-5.LIANG Jizhao,YANG Shuanshuan.Conductive polymer matrix composites nonlinear conduction behavior and Mechanism(Ⅱ)quantum mechanical tunneling theory[J].Shanghai Plastic,2010(1):1-5.
[21]孙权,王保成,张怀平,等.碳化过程中的磁场作用对针状焦结构及导电性能的影响[J].新型碳材料,2011,26(6):429-434.SUN Quan,WANG Baocheng,ZHANG Huaiping,et al.Effect of magnetic field on the structure and electrical conductivity of needle coke in carbonization process[J].New Carbon Materials,2011,26(6):429-434.
[22]张文龙,仲利东,吴月,等.纳米Mg O制备方法对Mg O/LDPE纳米复合材料介电性能的影响[J].材料科学与工艺,2014,22(6):113-117.ZHANG Wenlong,ZHONG Lidong,WU Yue,et al.The influence of preparation methods of nano-Mg O on Mg O/LDPE nanocomposite dielectric properties[J].Materials Science and Technology,2014,22(6):113-117.
[2]GUL A,YARDIM M F.Preparation and characterization of mesophase pitch based carbon foam produced at low pressure[J].Journal of Porous Materials,2015,22(4):851-857.
[3]ZHAO Z,CANNON F S,NIETO-DELGADO C,et al.Lignin/collagen hybrid biomaterials as binder substitute for specialty graphites and electrodes[J].Carbon,2016,108:303-317.
[4]LIN Q,SU W,XIE Y.Effect of rosin to coal-tar pitch on carbonization behavior and optical texture of resultant semi-cokes[J].Journal of Analytical and Applied Pyrolysis,2009,86(1):8-13.
[5]MELENDI S,DIEZ M A,ALVAREZ R,et al.Plastic wastes,lube oils and carbochemical products as secondary feed stocks for blast-furnace coke production[J].Fuel Processing Technology,2011,92(3):471-478.
[6]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 Xingui,HUANG Meirong.Mechanical property of mesophase pitch-based carbon fiber[J].Materials Review,1997,11(1):46-49.
[7]BROOKS J D,TAYLOR G H.The formation of graphitizing carbons from the liquid phase[J].Carbon,1965,3(2):185-193.
[8]何曼君,陈维孝,董西侠.高分子物理修订版[M].上海:复旦大学出版社,2007:97-107.
[9]MORIYAMA R,HAYASHI J,SUZUKI K,et al.Analysis and modeling of mesophase sphere generation,growth and coalescence upon heating of a coal tar pitch[J].Carbon,2002,40(1):53-64.
[10]KOVAC C A,LEWIS I C.Magnetic orientation studies of synthetic mesophase pitches[J].Carbon,1978,16(6):433-437.
[11]MIYAKE M,SATOH J,IZUMI T,et al.Application of electric field to pitch containing mesophase spherules[C]//International Symposium of Carbon.Tokyo:[s.n.],1998:248-249.
[12]解小玲,曹青,张俊花.电场对改性煤沥青中间相形成的影响[J].功能材料,2013,44(1):28-31.XIE Xiaoling,CAO Qing,ZHANG Junhua.Effect of electric field on mesophase formation of modified coal[J].Functional Materials,2013,44(1):28-31.
[13]李同起,王成扬.影响碳质中间相形成和发展的因素-Ⅰ.原料和热缩聚条件[J].炭素技术,2007,26(1):34-40.LI Tongqi,WANG Chengyang.Factors of influencing the formation and development of carbonaceous mesophase:Ⅰ.raw materials and pyrolysis conditions[J].Carbon Techniques,2007,26(1):34-40.
[14]CAO Q,XIE X,LI J,et al.A novel method for removing quinoline insolubles and ash in coal tar pitch using electrostatic fields[J].Fuel,2012,96:314-318.
[15]BRZOZOWSKA T,ZIELINSKI J,MACHNIKOWSKI J.Effect of polymeric additives to coal tar pitch on carbonization behaviour and optical texture of resultant cokes[J].Journal of Analytical and Applied Pyrolysis,1998,48(1):45-58.
[16]刘杰,关华,宋东明.包覆赤磷的制备及其热安定性研究[J].材料科学与工艺,2016,24(3):9-14.LIU Jie,GUAN Hua,SONG Dongming.Study on the preparation and thermal stability of microencapsulated[J].Materials Science and Technology,2016,24(3):9-14.
[17]ZHANG Ni,LIU Huiling,LI Junjing,et al.Preparation and properties of composite membrane of bisphenol Abased sulfonated poly(arylene ether sulfone)and phosphotungstic acid for proton exchange membranes[J].Journal of Harbin Institute of Technology,2010,17(5):636-640.
[18]李劼,宋海申,李荐,等.沥青调制温度对活性碳材料结构及电容特性的影响[J].中国有色金属学报,2007,17(3):481-486.LI Jie,SONG Haishen,LI Jian,et al.Effects of temperature modification of mesophase pitches on structure and electrochemical performance of activated carbons[J].Transactions of Nonferrous Metals Society of China,2007,17(3):481-486.
[19]KANEKO K,ISHII C,RUIKE M.Origin of superhigh surface area and microcrystalline graphitic structures of activated carbons[J].Carbon,1992,30(7):1075-1088.
[20]梁基照,杨铨铨.高分子基导电复合材料非线性导电行为及其机理(Ⅱ)量子力学隧道效应理论[J].上海塑料,2010(1):1-5.LIANG Jizhao,YANG Shuanshuan.Conductive polymer matrix composites nonlinear conduction behavior and Mechanism(Ⅱ)quantum mechanical tunneling theory[J].Shanghai Plastic,2010(1):1-5.
[21]孙权,王保成,张怀平,等.碳化过程中的磁场作用对针状焦结构及导电性能的影响[J].新型碳材料,2011,26(6):429-434.SUN Quan,WANG Baocheng,ZHANG Huaiping,et al.Effect of magnetic field on the structure and electrical conductivity of needle coke in carbonization process[J].New Carbon Materials,2011,26(6):429-434.
[22]张文龙,仲利东,吴月,等.纳米Mg O制备方法对Mg O/LDPE纳米复合材料介电性能的影响[J].材料科学与工艺,2014,22(6):113-117.ZHANG Wenlong,ZHONG Lidong,WU Yue,et al.The influence of preparation methods of nano-Mg O on Mg O/LDPE nanocomposite dielectric properties[J].Materials Science and Technology,2014,22(6):113-117.