添加煤灰及混合氧化物对石油焦CO_2高温气化反应的影响
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摘要
以化学组成相近的燃烧煤灰、气化煤灰和混合氧化物为添加剂,分别通过干混法和湿混法加入石油焦中,并借助热重分析仪在1200-1400℃下进行CO_2气化实验,研究高温下煤灰掺混方式、含量及物相组成对石油焦CO_2气化的影响,并使用混合氧化物替代实际煤灰研究其对石油焦的高温气化催化作用。结果表明,石油焦气化反应速率随煤灰添加量的增加而提升;气化温度为1200、1300℃时,使用干混法和气化煤灰对石油焦的气化促进作用较弱;但气化温度为1400℃时,改变煤灰和石油焦的掺混方式及其中活性金属存在方式,对石油焦气化反应几乎没有影响。这是高温下煤灰熔融,导致液态熔体与石油焦表面接触良好、活性金属自由度高以及传质阻力增加共同作用的结果。此时混合氧化物的催化指数与混合物中铁钙含量具有线性关系,即添加高铁钙含量的煤灰可以促进石油焦CO_2气化反应。
Three additives(combustion coal ash,coal gasification ash and oxide mixture) with similar chemical composition were added into petcoke by dry mixing and wet mixing. Their gasification reactivities under CO_2 atmosphere were investigated by a Thermo gravimetric Analyzer(TGA) at 1200-1400℃. The influence of mixing method,coal ash content and phase components on petcoke catalytic gasification was studied. The oxide mixture was used to simulate the catalytic effect of actual coal ash at high temperature. The results indicate that gasification reaction rate of petroleum coke is accelerated with increasing amount of coal ash. Dry mixing and gasification coal ash has less obvious effects on catalytic activity at 1200 and 1300 ℃. But the mixing method and mode of active metal has little influence on gasification reaction of petcoke at 1400 ℃. It is because the molten ash keeps good contact with petcoke,which makes reactive metals more freely and enhances mass transfer resistance. The catalytic index of the oxide mixtures has linear relationship with content of Fe_2O_3 and CaO during petcoke gasification at high temperature. This means coal ashes with high content of Fe and Ca could accelerate CO_2 gasification reactivity of petcoke.
Three additives(combustion coal ash,coal gasification ash and oxide mixture) with similar chemical composition were added into petcoke by dry mixing and wet mixing. Their gasification reactivities under CO_2 atmosphere were investigated by a Thermo gravimetric Analyzer(TGA) at 1200-1400℃. The influence of mixing method,coal ash content and phase components on petcoke catalytic gasification was studied. The oxide mixture was used to simulate the catalytic effect of actual coal ash at high temperature. The results indicate that gasification reaction rate of petroleum coke is accelerated with increasing amount of coal ash. Dry mixing and gasification coal ash has less obvious effects on catalytic activity at 1200 and 1300 ℃. But the mixing method and mode of active metal has little influence on gasification reaction of petcoke at 1400 ℃. It is because the molten ash keeps good contact with petcoke,which makes reactive metals more freely and enhances mass transfer resistance. The catalytic index of the oxide mixtures has linear relationship with content of Fe_2O_3 and CaO during petcoke gasification at high temperature. This means coal ashes with high content of Fe and Ca could accelerate CO_2 gasification reactivity of petcoke.
引文
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[15]HU X F,GUO Q H,LIU X.Ash fusion and viscosity behavior of coal ash with high content of Fe and Ca[J].J Fuel Chem Technol,2016,44(7):769-776.
[16]MAHINPEY N,GOMEZ A.Review of gasification fundamentals and new findings:Reactors,feedstock,and kinetic studies[J].Chem Eng Sci,2016,148:14-31.
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[19]ZHAN X L,JIA J,ZHOU Z J.Influence of blending methods on the co-gasification reactivity of petroleum coke and lignite[J].Energ Convers M anage,2011,52(4):1810-1814.
[20]黄胜.石油焦的理化性质及其催化气化反应特性研究[D].上海:华东理工大学,2013.(HUANG Sheng.Studies on physico-chemical properties and catalytic gasification characteristics of petroleum coke[D].Shanghai:East China University of Science and Technology,2013.)
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[22]刘鑫.热处理及金属催化对石油焦气化过程的影响研究[D].上海:华东理工大学,2012.(LIU Xin.The research of the influence of pyrolysis and metal on petroleum coke gasification reactivity[D].Shanghai:East China University of Science and Technology,2012.)
[23]JIANG M Q,RONG Z,JIE H.Calcium-promoted catalytic activity of potassium carbonate for steam gasification of coal char:Influences of calcium species[J].Fuel,2012,99(9):64-71.
[24]ASAMI K,SEARS R,FURIMSKY E,OHTSUKA Y.Gasification of brown coal and char with carbon dioxide in the presence of finely dispersed iron catalysts[J].Fuel Process Technol,1996,47:139-151.
[25]KIM R-G,HWNAG C-W,JEON C-H.Kinetics of coal char gasification with CO2:Impact of internal/external diffusion at high temperature and elevated pressure[J].Appl Energy,2014,129:299-307.
[26]ZHOU Z J,HU Q J,LIU X.Effect of iron species and calcium hydroxide on high-sulfur petroleum coke CO2gasification[J].Energy and Fuels,2012,26(3):1489-1495.
[2]CHEN J H,LU X F.Progress of petroleum coke combusting in circulating fluidized bed boilers-A review and future perspectives[J].Resour Conserv Recy,2007,49(3):203-216.
[3]唐黎华,陈冬霞,朱学栋,吴勇强,倪燕慧,朱子彬.石油焦高温气化反应性[J].燃料化学学报,2005,33(6):687-691.(TANG Li-hua,CHEN Dong-xia,ZHU Xue-dong,WU Yong-qiang,NI Yan-hui,ZHU Zi-bin.Gasification reactivity of petroleum coke at high temperature[J].J Fuel Chem Technol,2005,33(6):687-691.)
[4]刘建锟,杨涛,郭蓉,方向晨.解决高硫石油焦出路的措施分析[J].化工进展,2017,36(7):2417-2427.(LIU Jian-kun,YANG Tao,GUO Rong,FANG Xiang-chen.Analysis of measures to solve high sulfur petroleum coke[J].Prog Chem,2017,36(7):2417-2427.)
[5]LI Y,YANG H P,HU J H.Effect of catalysts on the reactivity and structure evolution of char in petroleum coke steam gasification[J].Fuel,2014,117,Part B:1174-1180.
[6]MALEKSHAHIAN M,HILL J M.Potassium catalyzed CO2gasification of petroleum coke at elevated pressures[J].Fuel Process Technol,2013,113:34-40.
[7]刘骥.钾盐的高温挥发及其与矿物质的固相反应机理研究[D].武汉:华中科技大学,2014.(LIU Ji.The high-temperature volatilization and solid reaction mechanism between sylvite and mineral[D].Wuhan:Huazhong University of Science and Technology,2014.)
[8]任立伟,魏蕊娣,高玉红,辛景.石油焦高温催化气化的可行性研究[J].石油学报(石油加工),2017,33(5):893-900.(REN Li-wei,WEI Rui-di,GAO Yu-hong,XIN Jing.Feasibility study on catalytic gasification of petroleum coke at high temperatures[J].Acta Pet Sin(Pet Process Sect),2017,33(5):893-900.)
[9]ZHOU Z J,HU Q J,LIU X.Effect of iron species and calcium hydroxide on high-sulfur petroleum coke CO2gasification[J].Energy Fuels,2012,26(3):1489-1495.
[10]李庆峰,房倚天,张建民,王洋,时铭显,孙国刚.煤灰对石油焦水蒸气气化的影响[J].燃烧科学与技术,2004,10(4):359-362.(LI Qing-feng,FANG Yi-tian,ZHANG Jian-min,WANG Yang,SHI Ming-xian,SUN Guo-gang.Gasification of petroleum coke with additional coal ash[J].J Combust Sci Techno,2004,10(4):359-362.)
[11]邹建辉,周志杰,代正华,刘海峰,王辅臣,于遵宏.三种工业废料对石油焦CO2气化动力学的影响[J].燃料化学学报,2008,36(3):279-285.(ZOU Jian-hui,ZHOU Zhi-jie,DAI Zheng-hua,LIU Hai-feng,WANG Fu-chen,YU Zun-hong.Effects of three industrial wastes on kinetic characteristics of petroleum coke CO2gasification[J].J Fuel Chem Technol,2008,36(3):279-285.)
[12]HUANG S,WU S Y,WU Y Q.Steam cogasification of petroleum coke and different rank coals for enhanced coke reactivity and hydrogenrich gas production[J].Energy Fuels,2014,28(6):3614-3622.
[13]REN L W,WEI R D,GAO Y H.Co-gasification reactivity of petcoke and coal at high temperature[J].Fuel,2017,190:245-252.
[14]胡启静,周志杰,刘鑫等.氯化铁对高硫石油焦-CO2气化的催化作用[J].石油学报(石油加工),2012,28(3):463-469.(HU Qi-jing,ZHOU Zhi-jie,LIU Xin,YU Guang-suo.Catalytic activity of ferric chloride for high-sulfur petroleum coke-carbon dioxide gasification[J].Acta Pet Sin(Pet Process Sect),2012,28(3):463-469.)
[15]HU X F,GUO Q H,LIU X.Ash fusion and viscosity behavior of coal ash with high content of Fe and Ca[J].J Fuel Chem Technol,2016,44(7):769-776.
[16]MAHINPEY N,GOMEZ A.Review of gasification fundamentals and new findings:Reactors,feedstock,and kinetic studies[J].Chem Eng Sci,2016,148:14-31.
[17]BAI J,LI W,LI C Z.Influences of minerals transformation on the reactivity of high temperature char gasification[J].Fuel Process Technol,2010,91(4):404-409.
[18]孙雪莲,王黎,张占涛.煤气化复合催化剂研究及机理探讨[J].煤炭转化,2006,29(01):15-18.(SUN Xue-lian,WANG Li,ZHANG Zhan-tao.Study on compound catalyst for gasification and its mechanism[J].Coal Convers,2006,29(01):15-18.)
[19]ZHAN X L,JIA J,ZHOU Z J.Influence of blending methods on the co-gasification reactivity of petroleum coke and lignite[J].Energ Convers M anage,2011,52(4):1810-1814.
[20]黄胜.石油焦的理化性质及其催化气化反应特性研究[D].上海:华东理工大学,2013.(HUANG Sheng.Studies on physico-chemical properties and catalytic gasification characteristics of petroleum coke[D].Shanghai:East China University of Science and Technology,2013.)
[21]李文,白进.煤的灰化学[M].北京:科学出版社,2013:34-72.(LI wen,BAI Jin.Chemistry of Ash from Coal[M].Beijing:Science Press,2013:34-72.)
[22]刘鑫.热处理及金属催化对石油焦气化过程的影响研究[D].上海:华东理工大学,2012.(LIU Xin.The research of the influence of pyrolysis and metal on petroleum coke gasification reactivity[D].Shanghai:East China University of Science and Technology,2012.)
[23]JIANG M Q,RONG Z,JIE H.Calcium-promoted catalytic activity of potassium carbonate for steam gasification of coal char:Influences of calcium species[J].Fuel,2012,99(9):64-71.
[24]ASAMI K,SEARS R,FURIMSKY E,OHTSUKA Y.Gasification of brown coal and char with carbon dioxide in the presence of finely dispersed iron catalysts[J].Fuel Process Technol,1996,47:139-151.
[25]KIM R-G,HWNAG C-W,JEON C-H.Kinetics of coal char gasification with CO2:Impact of internal/external diffusion at high temperature and elevated pressure[J].Appl Energy,2014,129:299-307.
[26]ZHOU Z J,HU Q J,LIU X.Effect of iron species and calcium hydroxide on high-sulfur petroleum coke CO2gasification[J].Energy and Fuels,2012,26(3):1489-1495.