煤与废轮胎共热解行为及热解焦炭微晶结构研究  

Study on Co-pyrolysis Behavior of Coal and Waste Tires and Microcrystalline Structure of Pyrolytic Char

作　　者：徐靖 王雪 张代林[1] 张小勇[1] 曹银平[2] XU Jing;WANG Xue;ZHANG Dailin;ZHANG Xiaoyong;CAO Yinping(School of Chemistry and Chemical Engineering,Anhui University of Technology,243002 Ma’anshan,China;Baoshan Iron and Steel Company Limited,201900 Shanghai,China)

机构地区：[1]安徽工业大学化学与化工学院,安徽马鞍山243032 [2]宝山钢铁股份有限公司,上海201900

出　　处：《煤炭转化》2022年第5期53-62,共10页Coal Conversion

基　　金：安徽省煤清洁转化与高值化利用重点实验室开放基金资助项目(CHV19-02)

摘　　要：为探究在配煤方案中添加废轮胎对煤热解过程以及焦炭质量的影响,使用大容量热失重装置研究较大质量(4 g)样品的热解行为。考察了煤与废轮胎共热解行为,揭示煤与废轮胎在热解过程中协同效应,反映热解动力学参数的变化规律以及热解焦炭微晶结构的特征变化,为废轮胎用于配煤炼焦提供初步的指导作用。结果表明:在460℃~570℃之间,废轮胎与煤混合物的实验失重w_(exp)大于理论计算值w_(cal),存在着明显的协同效应;动力学分析表明废轮胎有着比煤低的活化能,热解焦炭的活化能随着废轮胎混合比例增多而减小;XRD研究表明添加废轮胎热解焦炭的d_(002,a),L_(c,a)和L_(c,a)/d_(002.a)都比煤热解焦炭的相应参数小,随着废轮胎的配比增加,热解焦炭样品X_(P)(无定形衍射峰峰面积占石墨化峰峰面积与无定形衍射峰峰面积之和的比值)明显减小,X_(G)(石墨化峰峰面积占无定形衍射峰峰面积与石墨化峰峰面积之和的比值)增大;通过Raman光谱分析,表明样品的I_(D1)/I_(G)随着轮胎配比增加而减少,而I_(G)/I_(all)则增加。这说明随着废轮胎的加入,热解焦炭样品中的碳向着更加有序的方向发展,Raman光谱检测到的碳结构演变与XRD是一致的;废轮胎的配入同样会使热解焦炭的孔结构发生改变,随着废轮胎配比增加,5μm~60μm的气孔含量增多,大于650μm的气孔含量减少。To investigate the effect of adding waste tires to the coal blending scheme on the coal pyrolysis process and coke quality,a large-capacity thermogravimetric analyzer was used to study the pyrolysis behavior of the mixing sample with a larger mass(4 g).The co-pyrolysis behavior was tested for waste tires and coal with different mixing ratios,revealing their synergistic effect in the pyrolysis process and reflecting a clear trend for kinetic parameters of pyrolysis reactions and the characteristic change of microcrystalline structure of pyrolytic char.This study can provide preliminary guidance for using waste tires for coal blending and coke making.The results show that there exist an apparent synergistic effect between waste tires and coal during the pyrolysis process at 460℃-570℃.The kinetic analysis indicates that the activation energy of waste tires is lower than that of coal.The activation energy decreases with the increase in the proportion of waste tires.XRD characterization shows that the d_(002,a),L_(c,a) and L_(c,a)/d_(002,a) of pyrolytic char are smaller than those of coal.With the addition of waste tires in coal,the proportion of X_(P)(area of amorphous diffraction peak to the plus of graphitization peak area and amorphous diffraction peak area)is significantly decreased,while the proportion of X_(G)(area of graphitization peak to the plus of amorphous diffraction peak and graphitization peak)is increased.Raman spectroscopic analysis revealed that the I_(D1)/I_(G) ratio of the pyrolytic char decreases with the increasing addition of waste tires,while the I_(G)/I_(all) ratio increases.The results indicate that with the increase of the addition of waste tires,the carbon structure of pyrolytic char can develop in a more ordered direction,and those structure evolutions detected by Raman spectroscopy are consistent with XRD characterization.The addition of waste tires also changes the pore structure of pyrolytic char.With the addition of waste tires,the content of pores of 5μm-60μm increases,but the

关 键 词：废轮胎 共热解 协同效应 动力学分析 微晶结构 

分 类 号：TQ530.2[化学工程—煤化学工程]