基于CoFe_2O_4载氧体的生物质化学链气化热力学分析及实验研究
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摘要
对基于CoFe_2O_4载氧体的生物质化学链气化反应进行了热力学分析,研究了载氧体添加量、温度及水蒸气含量对气化反应特性的影响。同时应用热重分析仪对CoFe_2O_4和生物质的气化反应特性进行了实验研究,并利用XRD对反应前后载氧体的物相组成进行分析。热力学研究表明,CoFe_2O_4在气化反应中能够提供晶格氧,有效促进生物质气化,提高碳转化率。随着反应温度升高,合成气中H_2和CO的含量增加,CO_2的含量减少。随着水蒸气含量增加,H_2和CO_2含量会增加,CO含量减少。添加水蒸气能够提高合成气中H_2和CO的比值,改善合成气的品质。热重实验及XRD结果表明,钴优先于铁被还原,钴与铁存在协同作用,钴能够促进铁的进一步还原。随着载氧体添加量的增加,载氧体被还原的程度会降低,载氧体与生物质的最佳质量比为0.8。
The reactivity of biomass with CoFe_2O_4 oxygen carrier was investigated through thermodynamic analysis. The effects including amount of oxygen carrier, temperature and steam content on gasification characteristics of biomass were examined. Meanwhile, the reaction was experimentally investigated using thermogravimetric analysis. The phase of fresh and reacted oxygen carrier was characterized by X-ray diffraction(XRD).Thermodynamic analysis results show that CoFe_2O_4 can provide lattice oxygen and effectively improve gasification of biomass and carbon conversion efficiency. As the temperature goes up, amount of H_2 and CO increases, while CO_2 decreases. With amount of steam increases, H_2 and CO_2 yield increases while CO yield decreases. The ratio of H_2 to CO increases and high quality syngas can be obtained with the addition of steam. Thermogravimetric analysis and XRD results show that cobalt can be first reduced which can promote the further reduction of iron due to the synergistic effect. With the amount of oxygen carrier increases, reduction degree of oxygen carrier decreases. The optimal mass ratio of oxygen carrier to biomass is 0.8.
The reactivity of biomass with CoFe_2O_4 oxygen carrier was investigated through thermodynamic analysis. The effects including amount of oxygen carrier, temperature and steam content on gasification characteristics of biomass were examined. Meanwhile, the reaction was experimentally investigated using thermogravimetric analysis. The phase of fresh and reacted oxygen carrier was characterized by X-ray diffraction(XRD).Thermodynamic analysis results show that CoFe_2O_4 can provide lattice oxygen and effectively improve gasification of biomass and carbon conversion efficiency. As the temperature goes up, amount of H_2 and CO increases, while CO_2 decreases. With amount of steam increases, H_2 and CO_2 yield increases while CO yield decreases. The ratio of H_2 to CO increases and high quality syngas can be obtained with the addition of steam. Thermogravimetric analysis and XRD results show that cobalt can be first reduced which can promote the further reduction of iron due to the synergistic effect. With the amount of oxygen carrier increases, reduction degree of oxygen carrier decreases. The optimal mass ratio of oxygen carrier to biomass is 0.8.
引文
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[3] HUANG Z, HE F, FENG Y P, ZHAO K, ZHENG A, CHANG S, LI H B. Synthesis gas production through biomass direct chemical looping conversion with natural hematite as an oxygen carrier[J]. Bioresour Technol, 2013, 140(140C): 138-145.
[4] 黄振, 何方, 李新爱, 赵坤, 李海滨. Fe基载氧体的生物质化学链气化过程热力学分析及实验研究[J]. 太阳能学报, 2013, 34(11): 1943-1949.(HUANG Zhen, HE Fang, LI Xin-ai, ZHAO Kun, LI Hai-bin. Thermodynamic analysis and experimental study on biomass chemical looping gasification with iron-based oxygen carrier[J]. Acta Energ Sol Sin, 2013, 34(11): 1943-1949.)
[5] 戴金鑫, 刘晶, 刘丰. 化学链燃烧中H2S对NiFe2O4氧载体活性的影响机理[J]. 化工学报, 2017, 68(3): 1163-1169.(DAI Jin-xin, LIU Jing, LIU Feng. Influence mechanism of H2S on reactivity of NiFe2O4 oxygen carriers for chemical looping combustion[J]. CIESC J, 2017, 68(3): 1163-1169.)
[6] XU L, SCHWEBEL G L, KNUTSSON P, LEION H, LI Z S, CAI N S. Performance of industrial residues as low cost oxygen carriers[J]. Energy Procedia, 2017, 114: 361-370.
[7] WANG M J, LIU J, SHEN F H, CHENG H, DAI J X, LONG Y. Theoretical study of stability and reaction mechanism of CuO supported on ZrO2 during chemical looping combustion[J]. Appl Surf Sci, 2016, 367: 485-492.
[8] 宋洋博, 徐绍平, 李伶俐, 肖亚辉. Cu-橄榄石载氧体煤焦化学链气化实验研究[J]. 燃料化学学报, 2017, 45(8): 916-923.(SONG Yang-bo, XU Shao-ping, LI Ling-li, XIAO Ya-hui. Chemical looping gasification of coal char with Cu-olivine oxygen carriers[J]. J Fuel Chem Technol, 2017, 45(8): 916-923.)
[9] LIU F, LIU J, YANG Y J, WANG X F. A mechanistic study of CO oxidation over spinel MnFe2O4 surface during chemical-looping combustion[J]. Fuel, 2018, 230: 410-417.
[10] SONG Q L, XIAO R, DENG Z Y, SHEN L H, XIAO J, ZHANG M Y. Effect of temperature on reduction of CaSO4 oxygen carrier in chemical looping combustion of simulated coal gas in a fluidized bed reactor[J]. Ind Eng Chem Res, 2008, 47(21): 8148-8159.
[11] RYDENA M, LYNGFELTA A, MATTISSONA T, CHEN De, HOLMENB A, BJRGUMC E. Novel oxygen-carrier materials for chemical-looping combustion and chemical-looping reforming; LaxSr1-xFeyCo1-yO3-δ perovskites and mixed-metal oxides of NiO, Fe2O3 and Mn3O4[J]. Int J Greenhouse Gas Control, 2008, 2(1): 21-36.
[12] 程煜, 刘永卓, 田红景, 郭庆杰. 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.(CHENG Yu, LIU Yong-zhuo, TIAN Hong-jing, GUO Qing-jie. Characteristics and mechanism of coal chemical looping gasification with iron-based oxygen carrier[J]. CIESC J, 2013, 64(7): 2587-2595.)
[13] DERAZ N M. Glycine-assisted fabrication of nanocrystalline cobalt ferrite system[J]. J Anal Appl Pyrolysis, 2010, 88(2): 103-109.
[14] WANG B W, GAO C C, WANG W S, KONG F H, ZHENG C G. TGA-FTIR investigation of chemical looping combustion by coal with CoFe2O4 combined oxygen carrier[J]. J Anal Appl Pyrolysis, 2014, 105( 2): 369-378.
[15] LAURA S. Enhancement of redox properties of iron oxide through metal modification in catalyst assisted chemical looping[D]. Ghent: Ghent University, 2016.
[16] 张云鹏, 刘永卓, 杨勤勤, 郭庆杰. 废弃咖啡渣化学链气化反应特性[J]. 化工学报, 2016, 67(4): 1303-1312.(ZHANG Yun-peng, LIU Yong-zhuo, YANG Qin-qin, GUO Qing-jie. Reaction characteristics of chemical-looping gasification for waste coffee grounds[J]. CIESC J, 2016, 67(4): 1303-1312.)
[17] 郭万军, 张海峰, 葛晖骏, 沈来宏. 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, (3): 249-258.(GUO Wan-jun, ZHANG Hai-feng, GE Hui-jun, SHEN Lai-hong. Study of mechanism on biomass chemical looping gasification with iron ore as oxygen carrier[J]. J Therm Sci Technol, 2016, (3): 249-258.)
[18] WANG X, CHEN Z H, HU M, TIAN Y F, JIN X Y, MA S, XU T T, HU Z Q, LIU S M, GUO D B, XIAO B. Chemical looping combustion of biomass using metal ferrites as oxygen carriers[J]. Chem Eng J, 2017, 312: 252-262.
[19] 黄振, 刘帅, 李德波, 湛志钢, 何方, 李海滨. 基于Fe2O3载氧体的生物质化学链气化热力学模拟研究[J]. 太阳能学报, 2017, 38(5): 1421-1430.(HUANG Zhen, LIU Shuai, LI De-bo, ZHAN Zhi-gang, HE Fang, LI Hai-bin. Thermodynamic investigation on biomass chemical looping gasification with Fe2O3 oxygen carrier[J]. Acta Energ Sol Sin, 2017, 38(5): 1421-1430.)
[20] WANG K, YU Q B, QIN Q, HOU L M, DUAN W J. Thermodynamic analysis of syngas generation from biomass using chemical looping gasification method[J]. Int J Hydrogen Energy, 2015, 41(24): 10346-10353.
[21] 肖瑞瑞, 陈雪莉, 王辅臣, 于广锁. 生物质半焦CO2气化反应动力学研究[J]. 太阳能学报, 2012, 33(2): 236-242.(XIAO Rui-rui, CHEN Xue-li, WANG Fu-chen, YU Guang-suo. Research on kinetics characteristics of gasification biomass semi-char with CO2[J]. Acta Energ Sol Sin, 2012, 33(2): 236-242.)
[22] SCHEFFE J, ALLENDORF M, COKER E, BENJAMIN J. Hydrogen production via chemical looping redox cycles using atomic layer deposition-synthesized iron oxide and cobalt ferrites[J]. Chem Mater, 2011, 23(8): 2030-2038.
[23] 戴金鑫. 基于密度泛函理论的铁基复合氧载体与CO和H2S相互作用的机理研究[D]. 武汉: 华中科技大学, 2017.(DAI Jin-xin. Reaction mechanism between spinel ferrites and CO or H2S based on density functional theory[D]. Wuhan: Huazhong University of Science and Technology, 2017.)
[24] HUANG Z, DENG Z B, HE F, CHEN D Z, WEI G Q, ZHAO K, ZHENG A Q, ZHAO Z L, LI H B. Reactivity investigation on chemical looping gasification of biomass char using nickel ferrite oxygen carrier[J]. Int J Hydrogen Energy, 2017, 42(21): 14458-14470.
[25] HUANG Z, HE F, FENG Y P, ZHAO K, ZHENG A Q, CHANG S, WEI G Q, ZHAO Z L, LI H B. Biomass char direct chemical looping gasification using NiO-modified iron ore as an oxygen carrier[J]. Energy Fuels, 2013, 28(1): 183-191.Thermodynamic analysis and experimental studies on chemical looping gasification of biomass with CoFe2O4 as oxygen carrierWANG Xu-feng LIU Jing LIU Feng CoFe2O4能够提供晶格氧,有效促进生物质气化,提高碳转化率。J Fuel Chem Technol, 2019, 47(3): 312-317基于不同萃取剂的生物油常压蒸馏研究李时瑛朱谢飞张立强朱锡锋
[2] 魏国强, 何方, 赵增立, 赵伟娜, 黄振, 郑安庆, 赵坤, 冯宜鹏, 李海滨. 基于层状氢氧化物衍生复合载氧体的生物质化学链气化实验研究[J]. 燃料化学学报, 2016, 44(3): 349-356.(WEI Guo-qiang, HE Fang, ZHAO Zeng-li, ZHAO Wei-na, HUANG Zhen, ZHENG An-qing, ZHAO kun, FENG Yi-peng, LI Hai-bin. Chemical looping gasification of biomass based on the oxygen carrier derived from the layered double hydroxide (LDH) precursor[J]. J Fuel Chem Technol, 2016, 44(3): 349-356.)
[3] HUANG Z, HE F, FENG Y P, ZHAO K, ZHENG A, CHANG S, LI H B. Synthesis gas production through biomass direct chemical looping conversion with natural hematite as an oxygen carrier[J]. Bioresour Technol, 2013, 140(140C): 138-145.
[4] 黄振, 何方, 李新爱, 赵坤, 李海滨. Fe基载氧体的生物质化学链气化过程热力学分析及实验研究[J]. 太阳能学报, 2013, 34(11): 1943-1949.(HUANG Zhen, HE Fang, LI Xin-ai, ZHAO Kun, LI Hai-bin. Thermodynamic analysis and experimental study on biomass chemical looping gasification with iron-based oxygen carrier[J]. Acta Energ Sol Sin, 2013, 34(11): 1943-1949.)
[5] 戴金鑫, 刘晶, 刘丰. 化学链燃烧中H2S对NiFe2O4氧载体活性的影响机理[J]. 化工学报, 2017, 68(3): 1163-1169.(DAI Jin-xin, LIU Jing, LIU Feng. Influence mechanism of H2S on reactivity of NiFe2O4 oxygen carriers for chemical looping combustion[J]. CIESC J, 2017, 68(3): 1163-1169.)
[6] XU L, SCHWEBEL G L, KNUTSSON P, LEION H, LI Z S, CAI N S. Performance of industrial residues as low cost oxygen carriers[J]. Energy Procedia, 2017, 114: 361-370.
[7] WANG M J, LIU J, SHEN F H, CHENG H, DAI J X, LONG Y. Theoretical study of stability and reaction mechanism of CuO supported on ZrO2 during chemical looping combustion[J]. Appl Surf Sci, 2016, 367: 485-492.
[8] 宋洋博, 徐绍平, 李伶俐, 肖亚辉. Cu-橄榄石载氧体煤焦化学链气化实验研究[J]. 燃料化学学报, 2017, 45(8): 916-923.(SONG Yang-bo, XU Shao-ping, LI Ling-li, XIAO Ya-hui. Chemical looping gasification of coal char with Cu-olivine oxygen carriers[J]. J Fuel Chem Technol, 2017, 45(8): 916-923.)
[9] LIU F, LIU J, YANG Y J, WANG X F. A mechanistic study of CO oxidation over spinel MnFe2O4 surface during chemical-looping combustion[J]. Fuel, 2018, 230: 410-417.
[10] SONG Q L, XIAO R, DENG Z Y, SHEN L H, XIAO J, ZHANG M Y. Effect of temperature on reduction of CaSO4 oxygen carrier in chemical looping combustion of simulated coal gas in a fluidized bed reactor[J]. Ind Eng Chem Res, 2008, 47(21): 8148-8159.
[11] RYDENA M, LYNGFELTA A, MATTISSONA T, CHEN De, HOLMENB A, BJRGUMC E. Novel oxygen-carrier materials for chemical-looping combustion and chemical-looping reforming; LaxSr1-xFeyCo1-yO3-δ perovskites and mixed-metal oxides of NiO, Fe2O3 and Mn3O4[J]. Int J Greenhouse Gas Control, 2008, 2(1): 21-36.
[12] 程煜, 刘永卓, 田红景, 郭庆杰. 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.(CHENG Yu, LIU Yong-zhuo, TIAN Hong-jing, GUO Qing-jie. Characteristics and mechanism of coal chemical looping gasification with iron-based oxygen carrier[J]. CIESC J, 2013, 64(7): 2587-2595.)
[13] DERAZ N M. Glycine-assisted fabrication of nanocrystalline cobalt ferrite system[J]. J Anal Appl Pyrolysis, 2010, 88(2): 103-109.
[14] WANG B W, GAO C C, WANG W S, KONG F H, ZHENG C G. TGA-FTIR investigation of chemical looping combustion by coal with CoFe2O4 combined oxygen carrier[J]. J Anal Appl Pyrolysis, 2014, 105( 2): 369-378.
[15] LAURA S. Enhancement of redox properties of iron oxide through metal modification in catalyst assisted chemical looping[D]. Ghent: Ghent University, 2016.
[16] 张云鹏, 刘永卓, 杨勤勤, 郭庆杰. 废弃咖啡渣化学链气化反应特性[J]. 化工学报, 2016, 67(4): 1303-1312.(ZHANG Yun-peng, LIU Yong-zhuo, YANG Qin-qin, GUO Qing-jie. Reaction characteristics of chemical-looping gasification for waste coffee grounds[J]. CIESC J, 2016, 67(4): 1303-1312.)
[17] 郭万军, 张海峰, 葛晖骏, 沈来宏. 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, (3): 249-258.(GUO Wan-jun, ZHANG Hai-feng, GE Hui-jun, SHEN Lai-hong. Study of mechanism on biomass chemical looping gasification with iron ore as oxygen carrier[J]. J Therm Sci Technol, 2016, (3): 249-258.)
[18] WANG X, CHEN Z H, HU M, TIAN Y F, JIN X Y, MA S, XU T T, HU Z Q, LIU S M, GUO D B, XIAO B. Chemical looping combustion of biomass using metal ferrites as oxygen carriers[J]. Chem Eng J, 2017, 312: 252-262.
[19] 黄振, 刘帅, 李德波, 湛志钢, 何方, 李海滨. 基于Fe2O3载氧体的生物质化学链气化热力学模拟研究[J]. 太阳能学报, 2017, 38(5): 1421-1430.(HUANG Zhen, LIU Shuai, LI De-bo, ZHAN Zhi-gang, HE Fang, LI Hai-bin. Thermodynamic investigation on biomass chemical looping gasification with Fe2O3 oxygen carrier[J]. Acta Energ Sol Sin, 2017, 38(5): 1421-1430.)
[20] WANG K, YU Q B, QIN Q, HOU L M, DUAN W J. Thermodynamic analysis of syngas generation from biomass using chemical looping gasification method[J]. Int J Hydrogen Energy, 2015, 41(24): 10346-10353.
[21] 肖瑞瑞, 陈雪莉, 王辅臣, 于广锁. 生物质半焦CO2气化反应动力学研究[J]. 太阳能学报, 2012, 33(2): 236-242.(XIAO Rui-rui, CHEN Xue-li, WANG Fu-chen, YU Guang-suo. Research on kinetics characteristics of gasification biomass semi-char with CO2[J]. Acta Energ Sol Sin, 2012, 33(2): 236-242.)
[22] SCHEFFE J, ALLENDORF M, COKER E, BENJAMIN J. Hydrogen production via chemical looping redox cycles using atomic layer deposition-synthesized iron oxide and cobalt ferrites[J]. Chem Mater, 2011, 23(8): 2030-2038.
[23] 戴金鑫. 基于密度泛函理论的铁基复合氧载体与CO和H2S相互作用的机理研究[D]. 武汉: 华中科技大学, 2017.(DAI Jin-xin. Reaction mechanism between spinel ferrites and CO or H2S based on density functional theory[D]. Wuhan: Huazhong University of Science and Technology, 2017.)
[24] HUANG Z, DENG Z B, HE F, CHEN D Z, WEI G Q, ZHAO K, ZHENG A Q, ZHAO Z L, LI H B. Reactivity investigation on chemical looping gasification of biomass char using nickel ferrite oxygen carrier[J]. Int J Hydrogen Energy, 2017, 42(21): 14458-14470.
[25] HUANG Z, HE F, FENG Y P, ZHAO K, ZHENG A Q, CHANG S, WEI G Q, ZHAO Z L, LI H B. Biomass char direct chemical looping gasification using NiO-modified iron ore as an oxygen carrier[J]. Energy Fuels, 2013, 28(1): 183-191.Thermodynamic analysis and experimental studies on chemical looping gasification of biomass with CoFe2O4 as oxygen carrierWANG Xu-feng LIU Jing LIU Feng CoFe2O4能够提供晶格氧,有效促进生物质气化,提高碳转化率。J Fuel Chem Technol, 2019, 47(3): 312-317基于不同萃取剂的生物油常压蒸馏研究李时瑛朱谢飞张立强朱锡锋
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