应用分布活化能模型分析伊敏褐煤丝炭腐植酸热解及氢气生成动力学

doi:10.3866/PKU.WHXB20122825

Abstract

Abstract: The thermal behavior of humic acids of fusain (F-HA) and humic acids of demineralized fusain (DF-HA) were investigated at heating rates of 5, 20, and 50 °C·min^-1 using an open system thermogravimetric analyzer coupled to a quadrupole thermogravimetry mass spectrometer (TG-MS). The pyrolytic and hydrogen generation kinetics were analyzed using the distributed activation energy model (DAEM) and the distribution functions of the activation energy were obtained. The results indicated: (1) the distribution function of the activation energy for F-HA has an asymptotic approximation to a Gaussian distribution during pyrolysis. Moreover, it has some symmetry properties and the same peak value as a standard Gaussian distribution. The distribution function of the activation energy for DF-HA has an asymptotic approximation to a Gaussian distribution during pyrolysis and its peak value is less than that of a standard Gaussian distribution. According to the conversion ratio vs temperature, activation energy relationships and the thermal mass loss features of humic acids, four and five stages of a general pyrolytic process were found for F-HA and DF-HA, respectively. The chemical reactions for each stage of the pyrolytic process are discussed in detail. (2) The distribution functions of the activation energy of hydrogen generation for F-HA and DF-HA have an asymptotic approximation to a Gaussian distribution during pyrolysis. The activation energy of hydrogen generation increased with an increase in the conversion yields but it also showed staged features. Based on the kinetic characteristics of their generation during pyrolysis their hydrogen generation processes can be divided into five stages, which reflect the different chemical reaction mechanisms. (3) The demineralization of Yimin fusain influences the thermal behavior, kinetics of the pyrolytic processes and the hydrogen generation of humic acid.

Key words: Humic Acid, Pyrolysis, Hydrogen generation, Distribution activation energy model, Kinetics, Fusain

WANG Chuan-Ge, ZENG Fan-Gui, PENG Zhi-Long, LI Xia, ZHANG Li. Kinetic Analysis of a Pyrolysis Process and Hydrogen Generation of Humic Acids of Yimin Lignite Fusain Using the Distributed Activation Energy Model[J].Acta Phys. -Chim. Sin., 2012, 28(01): 25-36.

References

(1) Han, D. X.; Yang, Q. Coal Geology of China; Coal Industry Press: Beijing, 1979; Vol.1, pp 14-15. [韩德馨, 杨起. 中国煤田地质学. 北京: 煤炭工业出版社, 1979: Vol.1, 14-15.]
(2) Huang, D. F.; Qin, K. Z.;Wang, T. G.; Zhao, X. G.; Xu, Y. Q. Oil from Coal: Formation and Mechanism; Petroleum Industry Press: Beijing, 1955; pp 5-29. [黄第藩, 秦匡宗, 王铁冠, 赵锡嘏, 许云秋. 煤成油的形成和成烃机理. 北京: 石油工业出版社, 1995: 5-29.]
(3) Cramer, B. Org. Geochem. 2004, 35, 379.

(4) Fu, J. M.; Qin, K. Z. Geochemistry of Kerogen; Science & Technology Press of Guangdong: Guangzhou, 1995; pp 268-269, 546-552. [傅家谟, 秦匡宗. 干酪根地球化学. 广州: 广东科技出版社, 1995: 268-269, 546-552.]
(5) Niksa, S.; Kerstein, A. R. Energy Fuels 1991, 5, 647.

(6) Niksa, S.; Kerstein, A. R. Energy Fuels 1991, 5, 665.

(7) Niksa, S.; Kerstein, A. R. Energy Fuels 1991, 5, 673.

(8) Niksa, S. Energy Fuels 1994, 8, 659.

(9) Niksa, S. Energy Fuels 1994, 8, 671.

(10) Niksa, S. Energy Fuels 1995, 9, 467.

(11) Niksa, S. Energy Fuels 1996, 10, 173.

(12) Solomon, P. R.; Hamblen, D. G.; Carangelo, R. M. Energy Fuels 1988, 2, 405.

(13) Solomon, P. R.; Hamblen, D. G.; Carangelo, R. M. Combust. Flame 1988, 71, 137.

(14) Grant, D. M.; Pugmire, R. J. Energy Fuels 1989, 3, 175.

(15) Fletcher, T. H.; Kerstein, A. R. Energy Fuels 1990, 4, 54.

(16) Arenillas, A.; Rubiera, F.; Pevida, C.; Pis, J. J. J. Anal. Appl. Pyrolysis. 2001, 58, 685.

(17) Vand, V. Proc. Phys. Soc. (London) 1942, A55, 222.
(18) Miura, K. Energy Fuels 1995, 9, 302.

(19) Hashimoto, K.; Miura, K.;Watanabe, T. AICHE J. 1982, 28, 737.

(20) Miura, K.; Maki, T. Energy Fuels 1998, 12, 864.

(21) Sonobe, T.;Worasuwannarak, H. N. Fuel 2008, 87, 414.

(22) Quan, C.; Li, A. M.; Gao, N. B. Waste Manage. 2009, 2353.
(23) Liu, X. G.; Li, B. Q. J. Fuel Chem. Technol. 2001, 29, 54. [刘旭光, 李保庆. 燃料化学学报, 2001, 29, 54.]
(24) Sun, B. Z.;Wang, H. G.; Guan, X. H. Chem. Eng. (China) 2007, 35, 26. [孙佰仲, 王海刚, 关晓辉. 化学工程, 2007, 35, 26.]
(25) Yan, J. H.; Zhu, H. M.; Jiang, X. G.; Chi, Y.; Cen, K. F. J. Hazard. Mater. 2009, 162, 646.

(26) Heidenreich, C. A.; Yan, H. M.; Zhang, D. K. Fuel 1999, 78, 557.

(27) Chen,W. M. Coal Sci. Technol. 1994, 22, 40. [陈文敏. 煤炭科学技术, 1994, 22, 40.]
(28) Yang, J. H.; Chen,W. M.; Duan, Y. L. Chemical Examination Manual of Coal; Coal Industry Press: Beijing, 2004; pp 584-592. [杨金和, 陈文敏, 段云龙. 煤炭化验手册. 北京: 煤炭工业出版社, 2004: 584-592. ]
(29) Swaine, D. Org. Geochem. 1992, 78, 259.
(30) Sugano, M.; Mashimo, K.;Wainai, T. Fuel 1999, 78, 945.

(31) Steel, K. M.; Besida, J.; O'Donnell, T. A.;Wood, D. G. Fuel Process. Technol. 2001, 70, 171.

(32) Arenillas, A.; Rubiera, F.; Pis, J. J. J. Anal. Appl. Pyrolysis. 1999, 50, 31.

(33) Shen, X. The Kinetics Study of Different Thermal, Thermo Gravimetry Analysis and Nonisothermal Solid Phase; Metallurgical Industry Press: Beijing, 1995; pp 68-70. [沈兴. 差热、热重分析与非等温固相反应动力学. 北京: 冶金工业出版社, 1995: 68-70.]
(34) Painter, P. C.; Opaprakasit, P.; Scaroni, A. Energy Fuels 2000, 14, 1115.

(35) Opaprakasit, P.; Scaroni, A.W.; Painter, P. C. Energy Fuels 2002, 16, 543.

(36) Zeng, F. G.; Jia, J. B. Acta Phys. -Chim. Sin. 2009, 25, 1117. [曾凡桂, 贾建波. 物理化学学报, 2009, 25, 1117.]
(37) Zhu, X. D.; Zhu, Z. B.; Han, C. J.; Tang, L. H. J. East China Univ. Sci. Technol. 2000, 26, 14. [朱学栋, 朱子彬, 韩崇家, 唐黎华. 华东理工大学学报, 2000, 26, 14.]
(38) Sun, Q. L.; Li,W.; Chen, H. K.; Li, B. Q. J. China Univ. Min. Eng. 2003, 32, 665. [孙庆雷, 李文, 陈皓侃, 李宝庆. 中国矿业大学学报, 2003, 32, 665.]
(39) Faure, P.; Jeanneau, L.; Lannuzel, F. Org. Geochem. 2006, 37, 1900.

(40) Chen, C. X.; Sun, X. X.; Ma, L. Y. Prog. Nat. Sci. 1995, 5, 83. [陈彩霞, 孙学信, 马毓义. 自然科学进展, 1995, 5, 83.]
(41) Porada, S. Fuel 2004, 83, 1191.

[1]	Jingjing Wang, Guiqiang Cao, Ruixian Duan, Xiangyang Li, Xifei Li. Advances in Single Metal Atom Catalysts Enhancing Kinetics of Sulfur Cathode [J]. Acta Phys. -Chim. Sin., 2023, 39(5): 2212005-0.
[2]	Na Lu, Xuedong Jing, Yao Xu, Wei Lu, Kuichao Liu, Zhenyi Zhang. Effective Cascade Modulation of Charge-Carrier Kinetics in the Well-Designed Multi-Component Nanofiber System for Highly-Efficient Photocatalytic Hydrogen Generation [J]. Acta Phys. -Chim. Sin., 2023, 39(4): 2207045-0.
[3]	Yifei Xu, Hanwen Yang, Xiaoxia Chang, Bingjun Xu. Introduction to Electrocatalytic Kinetics [J]. Acta Phys. -Chim. Sin., 2023, 39(4): 2210025-0.
[4]	Xiaoxiong Huang, Yingjie Ma, Linjie Zhi. Ultrathin Nitrogenated Carbon Nanosheets with Single-Atom Nickel as an Efficient Catalyst for Electrochemical CO₂ Reduction [J]. Acta Phys. -Chim. Sin., 2022, 38(2): 2011050-.
[5]	Kelin He, Rongchen Shen, Lei Hao, Youji Li, Peng Zhang, Jizhou Jiang, Xin Li. Advances in Nanostructured Silicon Carbide Photocatalysts [J]. Acta Phys. -Chim. Sin., 2022, 38(11): 2201021-.
[6]	Yunfei Wang, Jianhua Liu, Mei Yu, Jinyan Zhong, Qisen Zhou, Junming Qiu, Xiaoliang Zhang. SnO₂ Surface Halogenation to Improve Photovoltaic Performance of Perovskite Solar Cells [J]. Acta Phys. -Chim. Sin., 2021, 37(3): 2006030-.
[7]	Ning Ren,Fang Wang,Jianjun Zhang,Xinfang Zheng. Progress in Thermal Analysis Kinetics [J]. Acta Physico-Chimica Sinica, 2020, 36(6): 1905062-.
[8]	Ting Zhang,Cuicui Li,Wei Wang,Zhaoqi Guo,Aimin Pang,Haixia Ma. Construction of Three-Dimensional Hematite/Graphene with Effective Catalytic Activity for the Thermal Decomposition of CL-20 [J]. Acta Physico-Chimica Sinica, 2020, 36(6): 1905048-.
[9]	Jing Miao,Ruifeng Guo,Zhihong Liu. Preparation of BaO·4B₂O₃·5H₂O Nanomaterial and Evaluation of Its Flame Retardant Performance to PP by Thermal Decomposition Kinetics Method [J]. Acta Physico-Chimica Sinica, 2020, 36(6): 1905052-.
[10]	Wen Xie,Lianjiao Zhou,Juan Xu,Qinglian Guo,Fenglei Jiang,Yi Liu. Advances in Biothermochemistry and Thermokinetics [J]. Acta Physico-Chimica Sinica, 2020, 36(6): 1905051-.
[11]	Chengfang Qiao,Lei Lü,Wenfeng Xu,Zhengqiang Xia,Chunsheng Zhou,Sanping Chen,Shengli Gao. Synthesis, Thermal Decomposition Kinetics and Detonation Performance of a Three-Dimensional Solvent-Free Energetic Ag(I)-MOF [J]. Acta Physico-Chimica Sinica, 2020, 36(6): 1905085-.
[12]	Yucheng He, Kefeng Xie, Youhao Wang, Dongshan Zhou, Wenbing Hu. Characterization of Polymer Crystallization Kinetics via Fast-Scanning Chip-Calorimetry [J]. Acta Physico-Chimica Sinica, 2020, 36(6): 1905081-.
[13]	Haixia Li,Jiwei Wang,Lifang Jiao,Zhanliang Tao,Jing Liang. Spherical Nano-SnSb/C Composite as a High-Performance Anode Material for Sodium Ion Batteries [J]. Acta Physico-Chimica Sinica, 2020, 36(5): 1904017-.
[14]	Minyi Su,Huisi Liu,Haixia Lin,Renxiao Wang. Machine-Learning Model for Predicting the Rate Constant of ProteinLigand Dissociation [J]. Acta Physico-Chimica Sinica, 2020, 36(1): 1907006-.
[15]	Yan-Shuang MENG,Chen WANG,Lei WANG,Gong-Rui WANG,Jun XIA,Fu-Liang ZHU,Yue ZHANG. Efficient Synthesis of Sulfur and Nitrogen Co-Doped Porous Carbon by Microwave-Assisted Pyrolysis of Ionic Liquid [J]. Acta Phys. -Chim. Sin., 2017, 33(9): 1915-1922.

Kinetic Analysis of a Pyrolysis Process and Hydrogen Generation of Humic Acids of Yimin Lignite Fusain Using the Distributed Activation Energy Model

PDF

Like

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Metrics

Recommended 0