咪唑类离子液体抑制煤自燃特性的研究
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摘要
为了考察咪唑类离子液体对煤自燃特性的影响,开展热重-差热同步热分析试验测试.结果表明:离子液体对煤自燃的失重过程有明显的减弱作用,且不同离子液体的作用效果不同.效果最好的为[BMIM][BF_4],抑制百分比约7.9%.同种阴离子([BF_4]~-)下,[BMIM]~+的抑制效果比[EMIM]~+强;同种阳离子([BMIM]~+)下,[BF_4]~-的抑制效果比[NO_3]~-和[I]~-强.差热结果显示:[BMIM][BF_4]处理煤样峰值温度提高28℃,放热量明显变低.通过采用热动力学分析方法,计算出煤样自燃过程中的表观活化能(E_a)和指前因子(A),得出煤样增重阶段的活化能均高于对应失重阶段的活化能,说明煤在失重阶段更容易氧化自燃,[BMIM][BF_4]处理煤的平均表观活化能高于其他煤样,说明其抑制效果较好.
To investigate the effect of imidazolium-based ionic liquids(ILs)on the oxidation characterisitcs of coal,an experimental analysis involving a synchronous thermal analyzer(TG-DSC)was performed.The results show that ILs have a significant weakening effect in the mass loss process of coal spontaneous combustion.The best effect is[BMIM][BF_4]with an inhibiting percent of about 7.9%.For a given anion([BF_4]~-),the inhibitory effect of[BMIM]~+is stronger than that of[EMIM]~+.Moreover,for a given cation([BMIM]~+),the inhibitory effect of[BF_4]~-is stronger than that of[NO_3]~-and[I]~-.The results of differential thermal analysis show that the peak temperature of the[BMIM][BF_4]treated coal sample increases by 28℃,and its heat release becomes significantly lower.To research the inhibiting effect of ILs on the oxidation reaction thermokinetics of coal,the apparent activation energy(E_a)and preexponential factor(A)were calculated.The results show that the E_avalues in the primary oxidation are higher than those in the combustion,and the coal treated with ILs has higher values of E_athan that of IL-untc,indicating that the spontaneous combustion of coal is more likely to occur in the weight loss stage,and[BMIM][BF_4]has better inhibition effect.
To investigate the effect of imidazolium-based ionic liquids(ILs)on the oxidation characterisitcs of coal,an experimental analysis involving a synchronous thermal analyzer(TG-DSC)was performed.The results show that ILs have a significant weakening effect in the mass loss process of coal spontaneous combustion.The best effect is[BMIM][BF_4]with an inhibiting percent of about 7.9%.For a given anion([BF_4]~-),the inhibitory effect of[BMIM]~+is stronger than that of[EMIM]~+.Moreover,for a given cation([BMIM]~+),the inhibitory effect of[BF_4]~-is stronger than that of[NO_3]~-and[I]~-.The results of differential thermal analysis show that the peak temperature of the[BMIM][BF_4]treated coal sample increases by 28℃,and its heat release becomes significantly lower.To research the inhibiting effect of ILs on the oxidation reaction thermokinetics of coal,the apparent activation energy(E_a)and preexponential factor(A)were calculated.The results show that the E_avalues in the primary oxidation are higher than those in the combustion,and the coal treated with ILs has higher values of E_athan that of IL-untc,indicating that the spontaneous combustion of coal is more likely to occur in the weight loss stage,and[BMIM][BF_4]has better inhibition effect.
引文
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[21]肖旸,钟凯琪,解萌玥,等.离子液体抑制煤自燃的程序升温试验研究[J].西安科技大学学报,2017,37(3):396-402.XIAO Yang,ZHONG Kaiqi,XIE Mengyue,et al.Experimental research on ionic liquid inhibitors to inhibit coal spontaneous combustion[J].Journal of Xi’an University of Science and Technology,2017,37(3):396-402.
[22]胡荣祖.热分析动力学[M].北京:科学出版社,2008:116-117.HU Rongzu.Thermal analysis kinetics[M].Beijing:Science Press,2008:116-117.
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[25]BENFELL K E,BEAMISH B B,RODGERS K A.Thermogravimetric analytical procedures for characterizing New Zealand and Eastern Australian coals[J].Thermochimica Acta,1996,286(1):67-74.
[26]KIZGUT S,YILMAZ S.Characterization and non-isothermal decomposition kinetics of some Turkish bituminous coals by thermal analysis[J].Fuel Process Technology,2004,85(2):103-111.
[27]王凯.陕北侏罗纪煤氧化自燃特性试验研究[D].西安:西安科技大学,2013:36-41.WANG Kai.Study on the oxidation and spontaneous combustion characteristics of Jurassic coal in northern Shaanxi[D].Xi’an:Xi’an Technology University,2013:36-41.
[28]苏怀兴.褐煤中水分存在形式的试验研究[D].鞍山:辽宁科技大学,2014:2-5.SU Huaixing.An experimental study on the existing form of water in lignite[D].Anshan:Liaoning University of Science and Technology,2014:2-5.
[29]SUDHIR N V K.How polar are room-temperature communications[J].Chemical Communications,2001(5):413-414.
[30]HANKE C G,JOHANSSON A,HARPER J B,et al.Why are aromatic compounds more soluble than aliphatic compounds in dimethyimidazolium ionic liquids?A simulation study[J].Chemical Physics Letters,2003,374(1):85-90.
[2]郑兰芳.抑制煤氧化自燃的盐类阻化剂性能分析[J].煤炭科学技术,2010,38(5):70-72.ZHENG Lanfang.Test and analysis on salty retardants performance to restrain coal oxidized spontaneous combustion[J].Coal Science and Technology,2010,38(5):70-72.
[3]于水军,谢锋承,路长,等.不同还原程度煤的氧化与阻化特性[J].煤炭学报,2010,35(增1):136-140.YU Shuijun,XIE Fengcheng,LU Chang,et al.Oxidation and inhibition characteristic of coal with different deoxidization degree[J].Journal of China Coal Society,2010,35(Sup 1):136-140.
[4]杨胜强.氢氧化钙对高硫煤的阻化试验及机理分析[J].中国矿业大学学报,1996,25(4):68-72.YANG Shengqiang.Experiment study and mechanism analysis of Ca(OH)2as the retarder of high-sulphur coal[J].Journal of China University of Mining&Technology,1996,25(4):68-72.
[5]XU Y L,WANG D M,WANG L Y,et al.Experimental research on inhibition performances of the sandsuspended colloid for coal spontaneous combustion[J].Safety Science,2012,50:822-827.
[6]DEBASIS R.Application of inhibitors to prevent spontaneous heating of coal[J].Rourkela:National Institute of Technology Rourkela,2012,209:743-750.
[7]肖旸,吕慧菲,邓军,等.煤自燃阻化机理及其应用技术的研究进展[J].安全与环境工程,2017,24(1):176-182.XIAO Yang,LHuifei,DENG Jun,et al.Progress on inhibition mechanism and application technology for coal spontaneous combustion[J].Safety and Environmental Engineering,2017,24(1):176-182.
[8]ZHAN J,WANG H H,SONG S N,et al.Role of an additive in retarding coal oxidation at moderate temperatures[J].Proceedings of the Combustion Institute,2011,33(2):2515-2522.
[9]WIJAYA N,ZHANG L.A critical review of coal demineralization and its implication on understanding the speciation of organically bound metals and submicrometer mineral grains in coal[J].Energy Fuel,2011,25(25):1-16.
[10]PINTO F,GULYURTLU I,LOBO L S,et al.Effect of coal pre-treatment with swelling solvents on coal liquefaction[J].Fuel,1999,78(6):629-634.
[11]ROGERS R D,SEDDON K R.Chemistry.Ionic liquids:Solvents of the future?[J].Science,2003,302(5646):792-793.
[12]ANDERSON J L,DING J,WELTON T,et al.Characterizing ionic liquids on the basis of multiple solvation interactions[J].Journal of the American Chemical Society,2002,124(47):14247-14254.
[13]HAYES R,WARR G G,ATKIN R.Structure and nanostructure in ionic liquids[J].Chemical Society Reviews,2015,115(13):6357-6426.
[14]刘宇佳.离子液体的固定化及其在蛋白质分离中的应用[D].沈阳:东北大学,2009:4-5.LIU Yujia.Immobilization of ionic liquid and application in protein isolation[D].Shenyang:Northeastern University,2009:4-5.
[15]王兰云,蒋曙光,吴征艳,等.离子液体抑制煤炭自燃的新设想[J].煤矿安全,2009(8):90-92.WANG Lanyun,JIANG Shuguang,WU Zhengyan,et al.A new idea of inhibition on coal spontaneous combustion by ionic liquid[J].Coal Mine Safety,2009(8):90-92.
[16]WANG L Y,XU Y L,JIANG S G,et al.Imidazolium based ionic liquids affecting functional groups and oxidation properties of bituminous coal[J].Safety Science,2012,5(7):1528-1534.
[17]ZHANG Weiqing,JIANG Shuguang,WANG Kai,et al.Study on coal spontaneous combustion characteristic structures affected by ionic liquids[J].Procedia Engineering,2011,26(4):480-485.
[18]CUMMINGS J,TREMAIN P,SHAH K,et al.Modification of lignites via low temperature ionic liquid treatment[J].Fuel Process Technology,2017,155:51-58.
[19]王兰云,徐永亮,姬宇鹏,等.含氧取代咪唑类离子液体影响煤结构及其氧化性质的试验研究[J].煤炭学报,2012,37(7):1190-1194.WANG Lanyun,XU Yongliang,JI Yupeng,et al.Effect of ionic liquids with imidazolium based cations substituted bydifferent oxygen-containing groups on coal oxidation[J].Journal of China Coal Society,2012,37(7):1190-1194.
[20]邓军,白祖锦,肖旸.离子液体抑制煤自燃的研究进展[J].煤矿安全,2017,48(10):39-42.DENG Jun,BAI Zujin,XIAO Yang.Research progress of ionic liquids inhibiting coal spontaneous combustion[J].Safety in Coal Mines,2017,48(10):39-42.
[21]肖旸,钟凯琪,解萌玥,等.离子液体抑制煤自燃的程序升温试验研究[J].西安科技大学学报,2017,37(3):396-402.XIAO Yang,ZHONG Kaiqi,XIE Mengyue,et al.Experimental research on ionic liquid inhibitors to inhibit coal spontaneous combustion[J].Journal of Xi’an University of Science and Technology,2017,37(3):396-402.
[22]胡荣祖.热分析动力学[M].北京:科学出版社,2008:116-117.HU Rongzu.Thermal analysis kinetics[M].Beijing:Science Press,2008:116-117.
[23]QI X,LI Q,ZHANG H,et al.Thermodynamic characteristics of coal reaction under low oxygen concentration conditions[J].Journal of the Energy Institute,2017,90(4):544-555.
[24]张卫清,蒋曙光,吴征艳,等.离子液体对煤中氢键反应活性的影响[J].中国矿业大学学报,2013,42(2):200-205.ZHANG Weiqing,JIANG Shuguang,WU Zhengyan,et al.Study of the effect ionic liquids have on hydrogen bonds of coal[J].Journal of China University of Mining&Technology,2013,42(2):200-205.
[25]BENFELL K E,BEAMISH B B,RODGERS K A.Thermogravimetric analytical procedures for characterizing New Zealand and Eastern Australian coals[J].Thermochimica Acta,1996,286(1):67-74.
[26]KIZGUT S,YILMAZ S.Characterization and non-isothermal decomposition kinetics of some Turkish bituminous coals by thermal analysis[J].Fuel Process Technology,2004,85(2):103-111.
[27]王凯.陕北侏罗纪煤氧化自燃特性试验研究[D].西安:西安科技大学,2013:36-41.WANG Kai.Study on the oxidation and spontaneous combustion characteristics of Jurassic coal in northern Shaanxi[D].Xi’an:Xi’an Technology University,2013:36-41.
[28]苏怀兴.褐煤中水分存在形式的试验研究[D].鞍山:辽宁科技大学,2014:2-5.SU Huaixing.An experimental study on the existing form of water in lignite[D].Anshan:Liaoning University of Science and Technology,2014:2-5.
[29]SUDHIR N V K.How polar are room-temperature communications[J].Chemical Communications,2001(5):413-414.
[30]HANKE C G,JOHANSSON A,HARPER J B,et al.Why are aromatic compounds more soluble than aliphatic compounds in dimethyimidazolium ionic liquids?A simulation study[J].Chemical Physics Letters,2003,374(1):85-90.