Pyrolysis Characteristics and Properties of Thermal Conversion Products on Toluene Soluble Component from Medium Pitch
ZHU Yaming1, ZHAO Xuefei1, CHENG Junxia1, LIU Wei1, LU Jun1,2, WANG Ying3
1 Engineering Research Center of Advanced Coal Coking and Efficient Use of Coal Resources, University of Science and Technology Liaoning, Anshan 114051; 2 College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006; 3 Anshan Xingde Material Technology Co. Ltd, Anshan 114048
Abstract: Elemental composition, pyrolysis characteristics and microcrystalline structure of thermal conversion products on toluene soluble component from medium pitch were studied by elemental analysis, TG/DTG, polarizing microscope, X-ray diffraction, Raman spectrum and curve-fitting methods. The Flynn-Wall-Ozawa method and Kissinger-Akahira-Sunose method were used to calculate the pyrolysis activation energy of toluene soluble component. The Satava-Sastak method was used to investigate the pyrolysis kinetic parameters of toluene soluble component from medium pitch. Briefly, the activation energy (E) and pre-exponential factor (A) were E=88.48 kJ/mol and lgA=10.22, the reaction series was 2, and the pyrolysis mechanism model of toluene soluble is random nucleation and subsequent growth. What’s more, the optical microstructure of calcined thermal conversion product shows that the distribution of optical microstructure contents were mosaic structure (23.74%), crude fiber structure (14.80%), fine fiber structure (17.88%), and large structure (30.45%), respectively. Combined with XRD analysis and curve-fitting method, it was revealed that the content of ordered carbon crystallite (Ig) in the product was 41.86%. Raman spectrum and curve-fitted method proves that the content of ideal graphite carbon crystallite was 11.59%, the content of detect carbon crystallite was 79.31%, and the ratio of amorphous carbon was 9.10%. The thermal conversion product has a good graphitization ability.
1 Burchell T D. Carbon materials for advanced technologies[M].New York:Pergamon,1999. 2 Mora E, Santamaría R, Blanco C, et al. Mesophase development in petroleum and coal-tar pitches and their blends [J]. J Anal Pyrol,2003,68-69:409. 3 Gray R J, Krupinski K C, Marsh H. Introduction to carbon techno-logies[M]. Alicante: Universidad Alicante,1997:329. 4 Ramjee S, Rand B, Foche W W. Low shear rheological behaviour of two-phase mesophase pitch [J]. Carbon,2015,82:368. 5 Bhatia G, Fitzer E, Kompalik D. Mesophase formation in defined mixtures of coal tar pitch fractions [J]. Carbon,1986,24:489. 6 Sun Q, Wang B C, Zhang H P, et al. The influence of a magnetic field during carbonization on the microstructure and electrical conductivity of needle cokes [J]. New Carbon Mater,2011,26:429. 7 Li G N, Peng Y L, Song S L, et al. Obtaining needle coke from coal liquefaction residue [J]. Chem Tech Fuels Oils,2012,48:349. 8 Mochida I, Yoon S H, Takano N, et al. Microstructure of mesophase pitch-based carbon fiber and its control [J]. Carbon,1996,34:941. 9 Yu B J, Wang C Y, Chen M M, et al. Two-step chemical conversion of coal tar pitch to isotropic spinable pitch [J]. Fuel Process Tech-nol,2012,104:155. 10 Li T Q, Liu X J, Wang C Y, et al. Structural characteristics of mesophase spheres prepared from coal tar pitch modified by phenolic resin [J]. Chinese J Chem Eng,2006,14:660. 11 Yang Y S, Wang C Y, Chen M M, et al. The role of primary quinoline insoluble on the formation of mescarbon microbeads [J]. Fuel Process Technol,2011,92:154. 12 Han Y J, Kim J, Yeo J S, et al. Coating of graphite anode with coal tar pitch as an effective precursor for enhancing the rate performance in Li-ion batteries: Effects of composition and softening points of coal tar pitch [J]. Carbon,2015,94:432. 13 Knight S A. Analysis of aromatic petroleum fraction by means of absorption mode carbon-13N.M.R. spectroscopy [J]. Chem Ind,1967,11:1920. 14 Clutter D R, Leonidas P, Stenger R L, et al. Nuclear magnetic resonance spectrometry of petroleum frantions. Carbon-13 and proton nuclear magnetic resonance characterizations in terms of average molecule parameters[J]. Anal Chem,1972,44:1395. 15 Li Chunfeng, Zhang Pengzhou, Qian Shu’an. Structural analysis of some domestic petroleum heavy residues by combined 1H-NMR-IR spectroscopy [J]. J Fuel Chem Technol,1981,10(4):353(in Chinese). 李春锋, 张蓬洲, 钱树安.用1H-NMR结合IR光谱解析法对我国若干重质油组成结构的研究[J].燃料化学学报,1981,10(4):353. 16 Huang X N, Kocaefe D, Kocafe Y, et al. Interaction of bio-coke with different coal tar pitches [J]. Fuel,2016,179:179. 17 Öner F O, Yürüm A, Yürüm A. Structural characterization of semicokes produced from the pyrolysis of petroleum pitches [J]. J Anal Appl Pyrol, 2015,111:15. 18 Lee S, Eom Y, Kim B Y, et al. The thermotropic liquid crystalline behavior of mesophase pitches wit different chemical structures [J]. Carbon,2015,81:694. 19 Álvarez P, Granda M, Sutil J, et al. A unified process for preparing mesophase and isotropic material from anthracene oil-based pitch [J]. Fuel Process Technol,2011,92:421. 20 Asenjo N G, Botas C, Blanco C, et al. Synthesis of activated carbons by chemical activation of new anthracene oil-based pitches and their optimization by response surface methodology [J]. Fuel Process Technol,2011, 92:1987. 21 Díez N, Álvarez P, Santamaría R, et al. Optimisation of the melt-spinning of anthracene oil-based pitch for isotropic carbon fibre pre-paration [J]. Fuel Process Technol,2012,93:99. 22 Álvarez P, Granda M, Sutil J, et al. Characterization and pyrolysis behavior of novel anthracene oil derivatives [J]. Energy Fuels,2008,22:4077. 23 Morga R, Jolonek I, Kruszewska K, et al. Relationships between quality of coals, resulting cokes, and micro-Raman spectral characteristics of these cokes [J]. Int J Coal Geol,2015, 144-155:130. 24 Sadezky A, Muckenhuber H, Grothe H, et al. Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information [J]. Carbon,2005,43:1731. 25 Morga R. Micro-Raman spectroscopy of carbonized semifusinite and fusinite [J]. Int J Coal Geol,2011,87:253. 26 Beyssac O, Goffe B, Petitet J P, et al. On the characterization of disordered and heterogeneous carbonaceous materials by Raman spectroscopy [J]. Spectrochim Acta A,2003,59:2267. 27 Tian L, Tahmasebi A, Yu J L. An experimental study on thermal decomposition behavior of magnesite [J]. J Therm Anal Calorim,2014,118:1577. 28 Zhu Ganyu, Li Huiquan, Wu Huixiong, et al. Non-isothermal decomposition kinetics of Methyl N-Phenyl Carbamate for preparation of Phenyl isocyanate [J].Chinese J Process Eng,2012,12(4):608(in Chinese). 朱干宇,李会泉,邬慧雄,等. 苯氨基甲酸甲酯热解制备苯基异氰酸酯的非等温动力学 [J]. 过程工程学报,2012,12(4):608. 29 Trittschack R, Grobéty B, Brodard P. Kinetics of the chrysotile and brucite dehydroxylation reaction: A combined non-isothermal/isothermal thermogravimetric analysis and high-temperature X-ray powder diffraction study [J]. Phys Chem Minerals,2014,41:197. 30 Manoj B, Kunjomana A G. Study of stacking structure of amorphous carbon by X-ray diffraction technique [J]. Int J Electrochem Sci,2012,7:3127. 31 Rantitsch G, Bhattacharyya A, Schenk J, et al. Assessing the quality of metallurgical coke by Raman spectroscopy [J]. Int J Coal Geol,2014,130:1.
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2017, Vol. 31 
