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 DENG Cunbao,DAI Fengwei,DENG Hanzhong,et al.Influence of water solvent effect on oxidation characteristics of coal[J].JOURNAL OF SAFETY SCIENCE AND TECHNOLOGY,2016,12(2):88-93.[doi:10.11731/j.issn.1673-193x.2016.03.016]





Influence of water solvent effect on oxidation characteristics of coal
邓存宝1戴凤威1 邓汉忠2武司苑1
(1.辽宁工程技术大学 安全科学与工程学院,辽宁 阜新 123000;2.辽宁工程技术大学 材料科学与工程学院,辽宁 阜新 123000)
DENG Cunbao1 DAI Fengwei1 DENG Hanzhong2 WU Siyuan1
(1. College of Safety Science and Engineering, Liaoning Technical University, Fuxin Liaoning 123000, China; 2. College of Materials Science and Engineering, Liaoning Technical University, Fuxin Liaoning 123000, China)
coal oxidizability water solvent effect
水既可以隔绝空气,又可以吸热降温,是防火、灭火的绝好材料。但经过大量的煤矿现场应用及实验研究发现:很多情况下,注水不仅不能预防煤炭自燃灾害,反而易于灾害发生。为了揭示煤矿井下注水易引起煤自燃的原因,应用Gaussian09程序,采用含时密度泛函理论(TD-DFT),在B3LYP/6-31G (d,p)水平上,分析水溶剂效应对煤氧化特性的影响。由计算结果可知:煤各模型的HOMO与O2的LUMO对称性相同,且能级差均小于0.4 eV,符合前线轨道理论提出的反应条件,所以煤HOMO轨道的电子将流向O2未占据的LUMO轨道,从而发生氧化反应,氧化反应剧烈时将引起煤炭自燃;当煤浸泡在水中,煤分子与水分子间将产生静电相互作用,氢键及孔洞能等相互作用,这些相互作用影响了煤分子的核外电子排布,改变了煤的前线轨道能级,煤各模型的HOMO与O2的LUMO能级差比在气相中更小,因此,被水浸泡的煤更容易发生氧化自燃。
Water is a good material for fire prevention and extinguishment, which plays the roles of air isolation and heat absorbing for cooling. However, after a large number of field application in coal mine and experimental research, it was found that in many cases, water injection not only cannot prevent the spontaneous combustion of coal, but also be vulnerable to the occurrence of accident. In order to reveal the reason that water injection is easy to cause the spontaneous combustion of coal, through using the Gaussian 09 program, the influence of water solvent effect on oxidation characteristics of coal was analyzed by adopting the time-dependent density functional theory (TD-DFT) at the B3LYP / 6-31G (d, p) levels. The results showed that the highest occupied molecular orbital (HOMO) of each coal model and the lowest unoccupied molecular orbital (LUMO) of O2 have the same symmetry, and both the energy difference are less than 0.4eV, which are in accord with the reaction conditions proposed by frontier orbital theory. So the electrons on HOMO orbit of coal flow to the unoccupied LUMO orbit of O2, then the oxidation reaction occurs. When the oxidation reaction is intense, it will cause the spontaneous combustion of coal. When coal is soaked in water, electrostatic interaction, hydrogen bond, cavity formation energy and other interactions are produced between coal molecule and water molecule. These interactions will influence the extranuclear electron configuration of coal molecule, and change the frontier orbital energy levels of coal. The energy difference between the HOMO of every coal model and the LUMO of O2 is smaller than that in the gas phase, therefore, oxidation and spontaneous combustion are easy to occur for coal soaked in water.


[1]谢克昌. 煤的结构与反应性[M]. 北京: 科学出版社, 2002.

[2]刘英学. 清水灌注抑制易燃采空区遗煤氧化及自燃的机理研究与应用[J]. 煤炭学报,2002(3):237-241.LIU Yingxue. Study on the mechanism and appl ication of fresh water pouring for prevention of oxidation and spontaneous combustion of residual coal in goaf[J]. Journal of China Coal Society,2002(3):237-241.?
[3]王雪峰,邓汉忠,邓存宝,等. 煤自燃阻化剂选择及喷洒工艺研究[J]. 中国安全科学学报,2013,22(10):105-109.WANG Xuefeng, DENG Hanzhong, DENG Cunbao, et al. Research on selection of coal spontaneous combustion inhibitors and spraying process[J]. China Safety Science Journal,2013,22(10):105-109.
[4]Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 09, Revision D.01[M]. Inc., Wallingford, CT, 2009.
[5]Rosa L, Michelangelo P, Carmine G, et al. Conformational equilibria of methyl α-L-arabinopyranosides in solution[J]. Journal of the Chemical Society, 1996(4): 505-510.
[6]Józef S K, Jerzy L. Molecular structure and vibrational IR spectra of the 2-hydroxypyridine/2(1H)-pyridinone system and its thio and seleno analogs: density functional theory versus conventional ab initio calculations[J]. Journal of Molecular Structure, 1996, 376: 325-342.
[7]Miertu S, Scrocco E, Tomasi J. Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects[J]. Chemical Physics, 1981,55(1): 117-129.
[8]Cancès E, Mennucci B, Tomasi J. A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics[J]. The Journal of Chemical Physics, 1997, 107(8): 3032.
[9]Cossi M, Barone V, Mennucci B. Ab initio study of ionic solutions by a polarizable continuum dielectric model[J]. Chemical Physics Letters, 1998, 286: 253-260.
[10]刘江燕,武书彬. 化学图文设计与分子模拟计算[M].广州:华南理工大学出版社,2009.
[11]Lu Tian, Chen Feiwu. Multiwfn: A multifunctional wavefunction analyzer[J]. Journal of Computational Chemistry, 2012, 33(5): 580-592.
[12]Xin Haihui, Wang Deming, Dou guolan, et al. The infrared characterization and mechanism of oxygen adsorption in coal[J]. Spectroscopy Letters, 2014(47):664-675.
[13]邢孟文,李凡.原煤中可抽提噻吩硫的研究[J]. 煤炭转化,2011(4):1-4,49.XING Mengwen, LI Fan.Experimental study on the ignition temperature of hydrogen-carbon monoxide-methane-carbon dioxide mixtures[J]. Coal Conversion,2011(4):1-4,49.
[14]雷加锦,盛国英,彭平安. 高有机硫煤抽提物中含硫化合物的组成与热演化特征[J]. 沉积学报,1998(2):20-23.LEI Jiajin, SHENG Guoying, PENG Pingan. Thermal evolution characteristics and sulphur-bearing compound composition in extract from high organosulphur Coal[J]. Acta Sedimentologica Sinica,1998(2):20-23.
[15]许金钩,王尊本. 荧光分析法[M].北京: 科学出版社,2006.
[16]周公度, 段连运. 结构化学基础[M]. 北京: 北京大学出版社, 2004.


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 DENG Cunbao,DAI Fengwei,DENG Hanzhong,et al.Influence of water solvent effect on oxidation characteristics of coal[J].JOURNAL OF SAFETY SCIENCE AND TECHNOLOGY,2016,12(2):88.[doi:10.11731/j.issn.1673-193x.2016.03.016]


国家自然科学基金项目(51274112, 51174108);国家科技支撑计划项目 (2013BAK06B07-2)
更新日期/Last Update: 2016-04-18