高温燃烧热导法测定煤中碳氢氮硫
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摘要
对煤中碳、氢、氮、硫同时测定的报道多采用近红外光谱或中红外光谱法。实验控制称样量为80~120mg,选择三氧化钨与试样的质量比为3∶1,建立了高温燃烧热导法同时测定煤中碳、氢、氮、硫的方法。实验表明,当称样量为80、100和120mg时,两个煤样中4种元素的测定值与认定值基本一致,方差值在0.000133~0.0621之间,F值在0.71~3.00之间,F值均小于在95%置信限下的F_(0.05)=5.05,这说明3种称样量条件的精密度彼此无显著性差异。方法的检出限分别为碳0.026mg、氢0.015mg、氮0.004mg、硫0.044mg;方法的测定下限分别为碳0.194mg、氢0.037mg、氮0.096mg、硫0.185mg。方法应用于煤标准物质中碳、氢、氮、硫这4种元素的测定,测定值与认定值基本一致,相对标准偏差(RSD,n=6)在0.12%~2.8%范围。
The simultaneous determination of carbon,hydrogen,nitrogen and sulfur in coal mostly adopts near-infrared spectrometry or middle-infrared spectrometry in existing reports.When the sample amount was controlled at 80-120 mg and the mass ratio of tungsten trioxide to sample was 3∶1,a simultaneous determination method of carbon,hydrogen,nitrogen and sulfur in coal by high temperature combustion thermal conductivity was established.The experiments showed that the determination results of four elements in two coal samples were consistent with the certified values when the sample amount was 80,100 and 120 mg.The variances were between 0.000 133 and 0.062 1 and Fvalues were between 0.71 and 3.00.F values were all less than F_(0.05)=5.05 within 95% confidence limit,indicating that the precision under three sampling conditions had no significant difference.The detection limit of method for carbon,hydrogen,nitrogen and sulfur was 0.026,0.015,0.004 and 0.044 mg,respectively.The lower determination limit for carbon,hydrogen,nitrogen and sulfur was 0.194,0.037,0.096 and 0.185 mg,respectively.The proposed method was applied for the determination of four elements including carbon,hydrogen,nitrogen and sulfur in certified reference materials of coal.The results were basically consistent with the certified values,and the relative standard deviations(RSD,n=6)were between 0.12% and 2.8%.
The simultaneous determination of carbon,hydrogen,nitrogen and sulfur in coal mostly adopts near-infrared spectrometry or middle-infrared spectrometry in existing reports.When the sample amount was controlled at 80-120 mg and the mass ratio of tungsten trioxide to sample was 3∶1,a simultaneous determination method of carbon,hydrogen,nitrogen and sulfur in coal by high temperature combustion thermal conductivity was established.The experiments showed that the determination results of four elements in two coal samples were consistent with the certified values when the sample amount was 80,100 and 120 mg.The variances were between 0.000 133 and 0.062 1 and Fvalues were between 0.71 and 3.00.F values were all less than F_(0.05)=5.05 within 95% confidence limit,indicating that the precision under three sampling conditions had no significant difference.The detection limit of method for carbon,hydrogen,nitrogen and sulfur was 0.026,0.015,0.004 and 0.044 mg,respectively.The lower determination limit for carbon,hydrogen,nitrogen and sulfur was 0.194,0.037,0.096 and 0.185 mg,respectively.The proposed method was applied for the determination of four elements including carbon,hydrogen,nitrogen and sulfur in certified reference materials of coal.The results were basically consistent with the certified values,and the relative standard deviations(RSD,n=6)were between 0.12% and 2.8%.
引文
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[14]孙冠中,李薇,付正辉,等.高温燃烧红外热导法测定固体生物质燃料元素的试验研究[J].太阳能学报,2016,37(8):2123-2128.SUN Guan-zhong,LI Wei,FU Zheng-hui.Experiment research of high temperature combusion and infrared thermal conduction method for determination of fuel elements in solid biofuel[J].Acta Energiae Solaris Sinica,2016,37(8):2123-2128.
[15]刘攀,杜丽丽,聂富强,等.惰气熔融-红外吸收/热导法在无机固态材料气体分析中的应用[J].冶金分析,2014,34(6):42-48.LIU Pan,DU Li-li,NIE Fu-qiang,et al.Application of inert gas fusion-infrared absorption or thermal conductivity method for gas analysis in inorganic solid materials[J].Metallurgical Analysis,2014,34(6):42-48.
[16]朱卫华,孙宇光.用煤标准样品校准-脉冲熔融样品-热导法测定炼钢用增碳剂中的氮含量[J].理化检验:化学分册,2014,50:720-724.ZHU Wei-hua,SUN Yu-guang.Thermo-conductometric determination of nitrogen in carburetants for steelmaking with fusion of sample by electrio-impulse heating and instrumental calibration by coal standard samples[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2014,50:720-724.
[17]李英华.煤质分析应用技术指南[M].2版.北京:中国标准出版社,2009:111.
[2]李小莉,安树清,于兆水,等.高压制样X-射线荧光光谱法测定煤样品中17种元素和灰分[J].分析化学,2014,42(2):283-287.LI Xiao-Li,AN Shu-Qing,YU Zhao-Shui,et al.Determination multi-elements and ash in coal sample by X-Ray fluorescence spectrometer with high pressure pelletised sample[J].Chinese Journal of Analytical Chemistry,2014,42(2):283-287.
[3]宋义,郭芬,谷松海.X射线荧光光谱法同时测定煤中砷硫磷氯[J].岩矿测试,2006,25(3):285-287.SONG Yi,GUO Fen,GU Song-hai.Determination of As,P,S,Cl in coal by X-ray fluorescence spectrometry[J].Rock and Mineral Analysis,2006,25(3):285-287.
[4]刘瑾,刘凯.高频燃烧-红外吸收法测定煤及焦炭中硫含量[J].冶金分析,2008,28(2):75-77.LIU Jin,LIU Kai.Determination of sulfur content in coal and coke by high frequency combustion-infrared absorption method[J].Metallurgical Analysis,2008,28(2):75-77.
[5]朱卫华.煤、焦碳及其复合物中碳硫的红外分析方法探讨[J].理化检验:化学分册,2003,39(12):732-733.ZHU Wei-hua.On the direct-combustion IR-spectrometric determination of carbon and sulfur in coal,charcoal and some other compound materials[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2003,39(12):732-733.
[6]龙亚平.半微量开氏法和红外热导法测试煤中氮的比较[J].洁净煤技术,2015,21(4):39-41.LONG Ya-ping.Comparison of nitrogen in coal by semimicro Kjeldahl method and infrared thermal conductivity method[J].Clean Coal Technology,2015,21(4):39-41.
[7]冀雪妮.测定煤中碳氢氮元素的试验研究[J].煤质技术,2016(6):36-38.JI Xue-ni.Experimental research on determination of CHN elements in coal[J].Coal Quality Technology,2016(6):36-38.
[8]李婷.称样量对红外-热导联合法测量结果的影响[J].煤质技术,2011,17(5):85-89.LI Ting.Influence of sample weight on measurement results by infrared-thermoconductive method[J].Coal Quality Technology,2016,(6):36-38.
[9]Andrés J M,Bona M T.Analysis of coal by diffuse reflectance near-infrared spectroscopy[J].Analytica Chimica Acta,2005,535(1-2):123-132.
[10]Bona M T,Andrés J M.Application of chemometric tools for coal classification and multivariate calibration by transmission and drift mid-infrared spectroscopy[J].Analytica Chimica Acta,2008,624(1):68-78.
[11]Bona M T,Andrés J M.Coal analysis by diffuse reflectance near-infrared spectroscopy:Hierarchical cluster and linear discriminant analysis[J].Talanta,2007,72(4):1423-1431.
[12]Andrés J M,Bona M T.ASTM clustering for improving coal analysis by near-infrared spectroscopy[J].Talanta,2006,70(4):711-719.
[13]王宽,周恺,李波,等.惰气熔融-红外/热导法同时测定锆合金中氧和氮[J].冶金分析,2017,37(1):81-84.WANG Kuan,ZHOU Kai,LI Bo,et al.Simultaneous determination of oxygen and nitrogen in zirconium alloy by Inert gas fusion-infrared thermal conductivity method[J].Metallurgical Analysis,2017,37(1):81-84.
[14]孙冠中,李薇,付正辉,等.高温燃烧红外热导法测定固体生物质燃料元素的试验研究[J].太阳能学报,2016,37(8):2123-2128.SUN Guan-zhong,LI Wei,FU Zheng-hui.Experiment research of high temperature combusion and infrared thermal conduction method for determination of fuel elements in solid biofuel[J].Acta Energiae Solaris Sinica,2016,37(8):2123-2128.
[15]刘攀,杜丽丽,聂富强,等.惰气熔融-红外吸收/热导法在无机固态材料气体分析中的应用[J].冶金分析,2014,34(6):42-48.LIU Pan,DU Li-li,NIE Fu-qiang,et al.Application of inert gas fusion-infrared absorption or thermal conductivity method for gas analysis in inorganic solid materials[J].Metallurgical Analysis,2014,34(6):42-48.
[16]朱卫华,孙宇光.用煤标准样品校准-脉冲熔融样品-热导法测定炼钢用增碳剂中的氮含量[J].理化检验:化学分册,2014,50:720-724.ZHU Wei-hua,SUN Yu-guang.Thermo-conductometric determination of nitrogen in carburetants for steelmaking with fusion of sample by electrio-impulse heating and instrumental calibration by coal standard samples[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2014,50:720-724.
[17]李英华.煤质分析应用技术指南[M].2版.北京:中国标准出版社,2009:111.
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