基于CuFe_2O_4载氧体的羊肠煤化学链气化特性
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摘要
以羊肠煤为燃料,CuFe_2O_4为载氧体,通过热重-质谱联用技术研究CuFe_2O_4载氧体的氧传递过程。同时考察羊肠煤(YC)与CuFe_2O_4载氧体的反应性能和循环稳定性。结果表明:CuFe_2O_4载氧体具有提供晶格氧和催化分解CO_2的双功能,其氧传递过程是CuFe_2O_4载氧体先被还原为Cu和Fe_3O_4,然后Fe_3O_4继续被还原生成Fe。对比YC/Al_2O_3,CuFe_2O_4载氧体的加入提高了YC的气化速率。在还原过程中CuFe_2O_4载氧体形成的氧缺位材料CuFe_2O_(4-δ)提高气化产物中CO和CH_4的摩尔累积量。通过XRD、BET和SEM-EDS分析10次循环前后载氧体的表面形貌和物质组成,表明CuFe_2O_4载氧体的反应活性和催化活性良好。
Oxygen transfer mechanism of CuFe_2O_4 oxygen carrier and characteristics of Chemical Looping gasification reaction of Yangchang coal(YC) were investigated with a thermogravimetric analyzer. In addition, the reaction performance and cycle stability of Yangchang coal with CuFe_2O_4 oxygen carrier were also studied. Experimental results indicated that CuFe_2O_4 oxygen carrier is dual functional. It can provide lattice oxygen and catalyze decomposition of CO_2 simultaneously. During oxygen transport process, CuFe_2O_4 oxygen carrier is reduced to Cu and Fe_3O_4 at the first step, and then Fe_3O_4 is further reduced to metal iron. In comparison with YC/Al_2O_3gasification, it was found that CuFe_2O_4 oxygen carrier could increase the gasification rate of char. Meanwhile, CuFe_2O_4 also can form some deficient materials, i.e., CuFe_2O_(4-δ), which can improve molar accumulation of CO and CH_4. Moreover, surface morphology and composition of the CuFe_2O_4 oxygen carrier before and after 10 cycles were characterized by means of XRD, BET and SEM-EDS. Characterization results demonstrate that CuFe_2O_4 oxygen carrier has very good reactivity and catalytic activity.
Oxygen transfer mechanism of CuFe_2O_4 oxygen carrier and characteristics of Chemical Looping gasification reaction of Yangchang coal(YC) were investigated with a thermogravimetric analyzer. In addition, the reaction performance and cycle stability of Yangchang coal with CuFe_2O_4 oxygen carrier were also studied. Experimental results indicated that CuFe_2O_4 oxygen carrier is dual functional. It can provide lattice oxygen and catalyze decomposition of CO_2 simultaneously. During oxygen transport process, CuFe_2O_4 oxygen carrier is reduced to Cu and Fe_3O_4 at the first step, and then Fe_3O_4 is further reduced to metal iron. In comparison with YC/Al_2O_3gasification, it was found that CuFe_2O_4 oxygen carrier could increase the gasification rate of char. Meanwhile, CuFe_2O_4 also can form some deficient materials, i.e., CuFe_2O_(4-δ), which can improve molar accumulation of CO and CH_4. Moreover, surface morphology and composition of the CuFe_2O_4 oxygen carrier before and after 10 cycles were characterized by means of XRD, BET and SEM-EDS. Characterization results demonstrate that CuFe_2O_4 oxygen carrier has very good reactivity and catalytic activity.
引文
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[16] NIU X,SHEN L,JIANG S,et al.Combustion performance of sewage sludge in chemical looping combustion with bimetallic Cu-Fe oxygen carrier[J].Chemical Engineering Journal,2016,294:185-192.
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[20] GU Z,XIANG X,FAN G,et al.Facile synthesis and characterization of cobalt ferrite nanocrystals via a simple reduction-oxidation route[J].The Journal of Physical Chemistry C,2008,112(47):18459-18466.
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[22] 付晓娟,曾尚红,苏海全.用于甲烷二氧化碳重整新型催化材料的研究进展[J].化工进展,2012,31(S1):168-175.(FU Xiaojuan,ZENG Shanghong,SU Haiquan.Advance in catalytic materials for CO2 reforming of methane:A review[J].Chemical Industry and Engineering Progress,2012,31(S1):168-175.)
[23] WANG J H,LI F,CHANG L P,et al.The structure characteristics and reactivity of Lingwu coal and its macerals in western China[J].Energy Sources,2010,32(20):1869-1877.
[24] WANG J,DU J,CHANG L,et al.Study on the structure and pyrolysis characteristics of Chinese western coals[J].Fuel Processing Technology,2010,91(4):430-433.
[25] TSUJI M,NISHIZAWA K,YOSHIDA T,et al.Methanation reactivity of carbon deposited directly from CO2 on to the oxygen deficient magnetite[J].Journal of Materials Science,1994,29(20):5481-5484.
[26] RUBER A,YI Z,NEATHERY J K,et al.Comparative study of the effect of different coal fly ashes on the performance of oxygen carriers for chemical looping combustion[J].Energy & Fuels,2012,26(6):3156-3161.
[27] BAO J H,LI Z,CAI N.Interaction between iron-based oxygen carrier and four coal ashes during chemical looping combustion[J].Applied Energy,2014,115(4):549-558.Chemical Looping Gasification of Yangchang Coal With CuFe2O4 as Oxygen CarrierAN Mei MA Jingjing WU Wei REN Tian HU XiudeGUO QingjieComprehensive studies of reaction products from CuFe2O4 with YC and oxygen transfer mechanism of CuFe2O4 oxygen carrier were performed.CuFe2O4 is a good oxygen carrier for coal chemical looping gasification.CuFe2O4 oxygen carrier is dual functional.It can provide both lattice oxygen and catalyzing decomposition of CO2.
[2] 陈文,刘自俭.宁东能源化工基地煤炭资源保障能力分析[J].中国煤炭地质,2009,21(11):24-27.(CHEN Wen,LIU Zijian.Ningdong energy and chemical industrial base coal resource support analysis[J].Coal Geology of China,2009,21(11):24-27.)
[3] FAN L,ZENG L,LUO S,et al.Chemical looping technology platform[J].AIChE Journal,2015,61(1):2-22.
[4] 刘永卓,郭庆杰,田红景.煤化学链转化技术研究进展[J].化工进展,2014,33(6):1357-1364.(LIU Yongzhuo,GUO Qingjie,TIAN Hongjing.Advance in the coal chemical looping conversion technology[J].Chemical Industry and Engineering Progress,2014,33(6):1357-1364.)
[5] NANDY A,LOHA C,GU S,et al.Present status and overview of chemical looping combustion technology[J].Renewable and Sustainable Energy Reviews,2016,59:597-619.
[6] WANG P,MEANS N,SHEKHAWAT D,et al.Chemical looping combustion and gasification of coals and oxygen carrier development:A brief review[J].Energies,2015,8(10):10605-10635.
[7] 罗四维,李军,张然,等.固体原料化学链技术研究进展与展望[J].石油学报(石油加工),2015,31(2):426-435.(LUO Siwei,LI Jun,ZHANG Ran,et al.Status and perspective of solid-fueled chemical looping technology[J].Acta Petrolei Sinica (Petroleum Processing Section),2015,31(2):426-435.)
[8] 王博,刘永卓,王东营,等.废弃活性炭化学链气化制富氢合成气[J].化工学报,2017,68(9):3541-3550.(WANG Bo,LIU Yongzhuo,WANG Dongying,et al.Chemical looping gasification of waste activated carbon for hydrogen-enriched syngas production[J].CIESC Journal,2017,68(9):3541-3550.)
[9] 郭万军,张海峰,葛晖骏,等.基于铁矿石载氧体的生物质化学链气化机理研究[J].热科学与技术,2016,15(3):249-258.(GUO Wanjun,ZHANG Haifeng,GE Huijun,et al.Mechanism study of bimass chemical looping gasification based on iron ore as oxygen carrier[J].Journal of Thermal Science and Technology,2016,15(3):249-258)
[10] HUANG Z,HE F,ZHAO K,et al.Natural iron ore as an oxygen carrier for biomass chemical looping gasification in a fluidized bed reactor[J].Journal of Thermal Analysis & Calorimetry,2014,116(3):1315-1324.
[11] 程煜,刘永卓,田红景,等.铁基复合载氧体煤化学链气化反应特性及机理[J].化工学报,2013,64(7):2587-2595.(CHEN Yu,LIU Yongzhuo,TIAN Hongjing,et al.Chemical looping gasification on reaction characteristics and mechanism of coal and Fe-based composite oxygen carriers[J].CIESC Journal,2013,64(7):2587-2595.)
[12] CHEN L,YANG L,LIU F,et al.Evaluation of multi-functional iron-based carrier from bauxite residual for H2-rich syngas production via chemical looping gasification[J].Fuel Processing Technology,2017,156:185-194.
[13] 胡修德,贾伟华,刘永卓,等.K2CO3修饰钙基载氧体的煤化学链气化反应特性[J].高校化学工程学报,2015,29(1):108-115.(HU Xiude,JIA Weihua,LIU Yongzhuo,et al.Coal Chemical looping gasification of Ca-based oxygen carriers decorated by K2CO3[J].Journal of Chemical Engineering of Chinese Universities,2015,29(1):108-115.)
[14] KSEPKO E,SCIAZKO M,BABINSKI P,et al.Studies on the redox reaction kinetics of Fe2O3-CuO/Al2O3 and Fe2O3/TiO2 oxygen carriers[J].Applied Energy,2014,115(4):374-383.
[15] WEI G,HE F,ZHAO Z,et al.Performance of Fe-Ni bimetallic oxygen carriers for chemical looping gasification of biomass in a 10 kWth interconnected circulating fluidized bed reactor[J].International Journal of Hydrogen Energy,2015,40(46):16021-16032.
[16] NIU X,SHEN L,JIANG S,et al.Combustion performance of sewage sludge in chemical looping combustion with bimetallic Cu-Fe oxygen carrier[J].Chemical Engineering Journal,2016,294:185-192.
[17] WANG X,CHEN Z,HU M,et al.Chemical looping combustion of biomass using metal ferrites as oxygen carriers[J].Chemical Engineering Journal,2017,312:252-262.
[18] WANG B,WANG W,MA Q,et al.In-depth investigation of chemical looping combustion of a Chinese bituminous coal with CuFe2O4 combined oxygen carrier[J].Energy & Fuels,2016,30(3):2285-2294.
[19] WANG B,MA Q,WANG W,et al.Effect of reaction temperature on the chemical looping combustion of coal with CuFe2O4 combined oxygen carrier[J].Energy & Fuels,2017,31(5):5233-5245.
[20] GU Z,XIANG X,FAN G,et al.Facile synthesis and characterization of cobalt ferrite nanocrystals via a simple reduction-oxidation route[J].The Journal of Physical Chemistry C,2008,112(47):18459-18466.
[21] 张平,于波,张磊.铁酸铜在形成氧缺位体过程中的失氧机理[J].中国科学,2008,38(7):624-630.(ZHANG Pin,YU Bo,ZHANG Lei,et al.The mechanism of oxygen loss in the process of oxygen deficiency in copper ferrites[J].Science in China,2008,38(7):624-630.)
[22] 付晓娟,曾尚红,苏海全.用于甲烷二氧化碳重整新型催化材料的研究进展[J].化工进展,2012,31(S1):168-175.(FU Xiaojuan,ZENG Shanghong,SU Haiquan.Advance in catalytic materials for CO2 reforming of methane:A review[J].Chemical Industry and Engineering Progress,2012,31(S1):168-175.)
[23] WANG J H,LI F,CHANG L P,et al.The structure characteristics and reactivity of Lingwu coal and its macerals in western China[J].Energy Sources,2010,32(20):1869-1877.
[24] WANG J,DU J,CHANG L,et al.Study on the structure and pyrolysis characteristics of Chinese western coals[J].Fuel Processing Technology,2010,91(4):430-433.
[25] TSUJI M,NISHIZAWA K,YOSHIDA T,et al.Methanation reactivity of carbon deposited directly from CO2 on to the oxygen deficient magnetite[J].Journal of Materials Science,1994,29(20):5481-5484.
[26] RUBER A,YI Z,NEATHERY J K,et al.Comparative study of the effect of different coal fly ashes on the performance of oxygen carriers for chemical looping combustion[J].Energy & Fuels,2012,26(6):3156-3161.
[27] BAO J H,LI Z,CAI N.Interaction between iron-based oxygen carrier and four coal ashes during chemical looping combustion[J].Applied Energy,2014,115(4):549-558.Chemical Looping Gasification of Yangchang Coal With CuFe2O4 as Oxygen CarrierAN Mei MA Jingjing WU Wei REN Tian HU XiudeGUO QingjieComprehensive studies of reaction products from CuFe2O4 with YC and oxygen transfer mechanism of CuFe2O4 oxygen carrier were performed.CuFe2O4 is a good oxygen carrier for coal chemical looping gasification.CuFe2O4 oxygen carrier is dual functional.It can provide both lattice oxygen and catalyzing decomposition of CO2.