煤中伴生金属元素对煤低温氧化特性的影响
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摘要
为分析Na、Mg、Al、K、Ca、Mn、Zn七种金属元素对烟煤自燃特性的影响,选用含7种代表性的金属离子的氯盐与硫酸盐,每100 g许疃烟煤添加1 g无机盐;通过耗氧分析、差示扫描量热法(DSC)和阻化率测定对比各金属元素对煤低温氧化的阻化效果;计算氧化动力学参数,并结合自由基反应理论,分析了7种金属元素对煤自燃作用机制。研究结果表明,Mg、Zn、Ca、Al、K、Na等元素阻化率在9.5%～57.9%,在60～180℃的低温氧化活化能最大增加29.6%,上述金属无机盐与煤分子结合生成稳定的络合物,增强了煤中活性结构的稳定性,也可捕捉煤中羟基自由基等活性分子,抑制煤的氧化。Mn元素因多价态之间转换所造成的电子传递对煤自燃有一定的促进效果。
Two kinds of inorganic salts with 7 representative metal ions were selected for studying their inhibition effect on spontaneous combustion of coal.100 g Xutuan bituminous coal was treated by 1 g additives.Oxygen consumption,DSC and inhibition rate were compared before and after treatment for evaluating their inhibit effect during low-temperature stage.Oxidation kinetic parameters was calculated.Combined with free radical theory,the mechanism that metal elements influence on spontaneous combustion of coal was presented.The results showed that the inhibition ratios of Mg,Zn,Ca,Al,K and Na were between 9.5% and 57.9%.The maximum activation energy of low temperature during 30 ～ 180 ℃ increased by 29.6%.The mentioned metal inorganic salts reacted with coal molecules to form stable complexes and enhanced the stability of active structures.It can also inhibit coal oxidation by capturing active molecules such as hydroxyl radicals.Besides,the electron transfer caused by the conversion of manganese ion under polyvalent states has a certain promoting effect on coal spontaneous combustion.
Two kinds of inorganic salts with 7 representative metal ions were selected for studying their inhibition effect on spontaneous combustion of coal.100 g Xutuan bituminous coal was treated by 1 g additives.Oxygen consumption,DSC and inhibition rate were compared before and after treatment for evaluating their inhibit effect during low-temperature stage.Oxidation kinetic parameters was calculated.Combined with free radical theory,the mechanism that metal elements influence on spontaneous combustion of coal was presented.The results showed that the inhibition ratios of Mg,Zn,Ca,Al,K and Na were between 9.5% and 57.9%.The maximum activation energy of low temperature during 30 ～ 180 ℃ increased by 29.6%.The mentioned metal inorganic salts reacted with coal molecules to form stable complexes and enhanced the stability of active structures.It can also inhibit coal oxidation by capturing active molecules such as hydroxyl radicals.Besides,the electron transfer caused by the conversion of manganese ion under polyvalent states has a certain promoting effect on coal spontaneous combustion.
引文
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[3] BEAMISHA B Basil,AHMET Arisoy.Effect of mineral matter on coal self-heating rate[J].Fuel,2008,87:125-130.
[4]王德明,辛海会,戚绪尧,等.煤自燃中的各种基元反应及相互关系:煤氧化动力学理论及应用[J].煤炭学报,2014,29(8):1667-1674.WANG Deming,XIN Haihui,QI Xuyao,et al.Mechanism and relationships of elementary reactions in spontaneous combustionof coal:the coal oxidation kinetics theory and application[J]. Journal of China Coal Society,2014,39(8):1667-1674.
[5]邓军,宋佳佳,赵婧昱,等.高温氧化条件下风化煤自燃特性试验研究[J].煤炭科学技术,2017,45(1):73-77,105.DENG Jun,SONG Jiajia,ZHAO Jingyu,et al.Experiment study on spontaneous combustion features of weathered coal under condition of high temperature oxidation[J]. Coal Science and Technology,2017,45(1):73-77,105.
[6] ZHANG Weiqing,JIANG Shuguang,WANG Kai,et al. Thermogravimetric dynamics and FTIR analysis on oxidation properties of low rank coal at low and moderate temperatures[J]. International Journal of Coal Preparation and Utilization,2014,35(1):39-50.
[7] ZHANG Yaqing,LIANG Peng,JIAO Tiantian,et al. Effect of foreign minerals on sulfur transformation in the step conversion of coal pyrolysis and combustion[J]. Journal of Analytical&Applied Pyrolysis,2017,127:240-245.
[8] LI Wen,BAI Zongqing,BAI Jin,et al.Transformation and roles of inherent mineral matter in direct coal liquefaction:a mini-review[J].Fuel,2017,197:209-216.
[9] WANG Yafeng,TANG Yuegang,LIU Shuqin,et al. Behavior of trace elements and mineral transformations in the super-high organic sulfur Ganhe coal during gasification[J]. Fuel Processing Technology,2018,177:140-151.
[10] WIWIK Sujanti,ZHANG Dongke.A laboratory study of spontaneous combustion of coal:the influence of inorganic matter and reactor size[J].Fuel,1999,78(9):549-556.
[11] ZHANG Lanjun,LI Zenghua,HE Wenjing,et al. Study on the change of organic sulfur forms in coal during low-temperature oxidation process[J].Fuel,2018,222:350-361.
[12] REN Deyi,ZHAO Fenghua,WANG Yunquan,et al.Distributions of minor and trace elements in Chinese coals[J]. International Journal of Coal Geology,1999,40:109-118.
[13] ZHAO Jiyao,TANG Xiuyi,HUANG Wenhui.Abundance of trace elements in coal of China[J]. Coal Geology of China,2002,14:5-13.
[14]贺飞,王继仁,郝朝瑜,等.脱氧型阻化剂对煤自燃的抑制效果[J].煤炭学报,2016,41(11):2780-2785.HE Fei,WANG Jiren,HAO Chaoyu,et al. Experimental study on the effect of oxygen consuming inhibitor in inhibiting coal spontaneous combustion[J]. Journal of China Coal Society,2016,41(11):2780-2785.
[15]张辛亥,丁峰,张玉涛,等.LDHs复合阻化剂对煤阻化性能的试验研究[J].煤炭科学技术,2017,45(1):84-88.ZHANG Xinhai,DING Feng,ZHANG Yutao,et al. Experimental study on LDHs composite inhibitor to coal resistance property[J].Coal Science and Technology,2017,45(1):84-88.
[16] TANG Yibo,XUE Sheng. Laboratory study on the spontaneous combustion propensity of lignite undergone heating treatment at low temperature in inert and low-oxygen environments[J].Energy&Fuels,2015,29:4683-4689.
[17]王雪峰,王继仁,邓存宝,等.金属钙离子对煤中含硫活性基团的阻化效果研究[J].计算机与应用化学,2015,32(5):534-538.WANG Xuefeng,WANG Jiren,DENG Cunbao,et al. Effect of Ca2+on sulfur contained active groups in coal[J].Computers and Applied Chemistry,2015,32(5):534-538.
[18] CHEN Xiaolang,YU Jie,GUO Shaoyun,et al.Surface modification of magnesium hydroxide and its application in flame retardant polypropylene composites[J]. Journal of Materials Science,2009,44(5):1324-1332.
[19] TANG Yibo.Experimental investigation of a novel Zn foam for preventing the spontaneous combustion of coal[J]. Journal of Chemical Engineering of Japan,2017,50(7):527-534.
[20] TANG Yibo.The influences of manganese and phosphorus on the low-temperature oxidation of coal[J]. International Journal of Coal Preparation and Utilization,2015,35(2):63-75.
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