含钙和含铁矿物对粉煤气化堵渣的影响机理
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摘要
为了研究粉煤气化的堵渣机理,选取气流床粉煤气化过程中产生的工业渣样(正常渣样和非正常渣样)和在不同还原性气氛与温度下烧制的试验渣样,利用X-射线荧光光谱(XRF)、X-射线衍射仪(XRD)、扫描电子显微镜和能谱仪(SEM-EDX)等研究渣样的灰成分、晶体矿物组成、微观形貌和微区化学组成等性质,结果表明:非正常渣中钙长石的生成和铁的析出是导致堵渣的主要原因;熔渣析铁的主要原因是在还原性气氛下,赤铁矿被还原的中间产物FeO、FeSx转变的中间产物FeS形成Fe-O-S共熔体;气化炉操作温度的波动易导致钙长石晶体生成,而钙长石的大量析出与铁质矿物的富集和单质铁的析出存在内在联系。
In order to study the mechanism of slag blockage of pulverized coal gasification,the industrial slag samples( normal slag samples and unnormal slag samples) taken from coal gasification unit and the XZ coal ash slag samples( experimental slag samples) obtained from bench scale tube furnace in different temperature and reducing atmosphere were investigated.The ash chemical composition,crystal mineral composition,microscopic morphology and chemical composition of the micro-zone of slag samples were studied by X-ray Fluorescence( XRF),X-ray diffractometer( XRD) and Scanning Electronic Microscopy combined with energy Dispersive X-ray Spectrometer( SEMEDX) respectively.The results show that the main reasons of slag blockage of coal gasification is the formation of anorthite and iron precipation in slag samples.The iron precipation in slag under reducing atmosphere is caused by the formation Fe-O-S eutectic,which is converted by Fe O,Fe Sxand Fe S.The temperature fluctuations of gasifier operation is likely to lead to the formation of anorthite,and the massive formation of anorthite in slag is intrinsically linked to the enrichment of iron minerals and the precipitation of elemental iron.
In order to study the mechanism of slag blockage of pulverized coal gasification,the industrial slag samples( normal slag samples and unnormal slag samples) taken from coal gasification unit and the XZ coal ash slag samples( experimental slag samples) obtained from bench scale tube furnace in different temperature and reducing atmosphere were investigated.The ash chemical composition,crystal mineral composition,microscopic morphology and chemical composition of the micro-zone of slag samples were studied by X-ray Fluorescence( XRF),X-ray diffractometer( XRD) and Scanning Electronic Microscopy combined with energy Dispersive X-ray Spectrometer( SEMEDX) respectively.The results show that the main reasons of slag blockage of coal gasification is the formation of anorthite and iron precipation in slag samples.The iron precipation in slag under reducing atmosphere is caused by the formation Fe-O-S eutectic,which is converted by Fe O,Fe Sxand Fe S.The temperature fluctuations of gasifier operation is likely to lead to the formation of anorthite,and the massive formation of anorthite in slag is intrinsically linked to the enrichment of iron minerals and the precipitation of elemental iron.
引文
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[2]徐国壮,周红军,周广林,等.Shell粉煤气化装置主要运行问题的分析[J].煤化工,2010(3):15-19.XU Guozhuang,ZHOU Hongjun,ZHOU Guanglin,et al.The analy-sis of the main operation probliems exist in the shell coal gasifica-tion process(SCGP)plants[J]. Coal Chemical Industry,2010(3):15-19.
[3] BAI J,LI W,LI B Q.Characterization of low-temperature coal ashbehaviors at high temperatures under reducing atmosphere[J].Fu-el,2008,87(4/5):583-591.
[4]陶然,李寒旭,胡洋,等.铁钙比对煤灰中耐熔矿物生成的抑制机理研究[J].硅酸盐通报,2017,36(11):3810-3816.TAO Ran,LI Hanxu,HU Yang,et al. Inhibition mechanism of theratio of Fe2O3/CaO on formation of refractory mineral in coal ash[J]. Bulletin of the Chinese Ceramic Society,2017,36(11):3810-3816.
[5]李意,盛昌栋.神华煤中含铁矿物质及其在煤粉燃烧过程中的转化[J].动力工程,2008,28(2):259-264.LI Yi,SHENG Changdong.Iron-bearing minerals of Shenhua coalsand their conversion during pulverized coal combusti[J].Journal ofPower Engineeri,2008,28(2):259-264.
[6]熊金钰.高硫煤气化熔渣析铁机理研究[D].淮南:安徽理工大学,2015.
[7]李寒旭,李金知,张冬梅,等.还原性气氛下熔渣中铁的富集及析出机理研究[J].中国矿业大学学报,2015,44(1):144-150.LI Hanxu, LI Jinzhi, ZHANG Dongmei, et al. Study ofenrichment&iron precipitation in molten slag under reducing atmos-phere[J]. Journal of China University of Mining&Technology,2015,44(1):144-150.
[8] XIONG Jinyu,LI Hanxu,DONG Zhongbing,et al. Occurrence offerrum in ZX coal and its transformation in reducing atmosphere[J].Journal of the Energy Institute,2017,90(6):941-950.
[9] MATJIE R H,FRENCH D,WARD C R,et al. Behavior ofcoal mineral matter in sintering and slagging of ash duringthe gasification process[J].Fuel Processing Technology,2011,92(8):1426-1433.
[10] WU X J,ZHANG Z X,CHEN Y S,et al.Main mineral melting be-havior and mineral reaction mechanism at molecular level of blen-ded coal ash under gasification condition[J]. Fuel ProcessingTechnology,2010,91(11):1591-1600.
[11]黄镇宇,李燕,赵京,等.不同灰成分的低熔点煤灰熔融性调控机理研究[J].燃料化学学报,2012,40(9):1038-1043.HUANG Zhenyu,LI Yan,ZHAO Jing,et al. Ash fusion regula-tion mechanism of coal with low melting point and differentash compositions[J]. Journal of Fuel Chemistry and Technology,2012,40(9):1038-1043.
[12]张兆麟. Fe2O3被CO还原反应的探讨[J].化学教育,2002(2):43-45.ZHANG Zhaolin. Discussion on reduction reaction of Fe2O3byCO[J].Chemistry Education,2002(2):43-45.
[13] TOMECZEK J,PALUGNIOK H.Kinetics of mineral matter trans-formation during coal combustion[J]. Fuel,2002,81(5):1251-1258.
[14] CHEN Y,SHAH N,HUGGINS F E,et al.Investigation of primaryfine particulate matter from coal combustion by computer-con-trolled scanning electron microscopy[J].Fuel Processing Technol-ogy,2004,85(6/7):743-761.
[15]白进,李文,白宗庆,等.兖州煤中矿物质在高温下的变化[J].中国矿业大学学报,2008,37(3):369-372.BAI Jin,LI Wen,BAI Zongqing,et al. Transformation of miner-al matters in Yanzhou coal ash at high temperation[J].Journal ofChina University of Mining&Technology,2008,37(3):369-372.
[16] SONG Wenjia,TANG Lihua,ZHU Xuedong,et al.Flow propertiesand rheology of slag from coal gasification[J]. Fuel,2009,89:1709-1715.
[17]李寒旭,辛宇,张冬梅,等.还原性气氛下熔渣析铁的影响因素[J].煤炭学报,2014,39(7):1372-1378.LI Hanxu,XIN Yu,ZHANG Dongmei,et al.Influencing factors ofiron precipitation of slag unde reducing conditions[J]. Journal ofChina Coal Society,2014,39(7):1372-1378.
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