CeO_2掺杂对CaO基吸收剂CO_2捕获性能的影响
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摘要
以P123作为软模板剂,通过均相沉淀法制备了CeO_2掺杂的CaO基吸收剂,研究了CeO_2掺杂对CO_2捕获的影响。结果表明,CeO_2掺杂可促进表面氧物种的生成,从而促进CaO与CO_2的碳酸化反应。CaO-CeO_2的相互作用一方面促进了从Ca到表面氧物种的电子转移;另一方面,由于部分Ca离子对晶格中Ce离子的取代,晶格的电中性被打破,有利于CeO_2中晶格氧的逸出,以及氧空位和O~(2-)的生成。本实验制备的纯CaO吸收剂的碳酸化反应活化能为28.1 kJ/mol,而掺杂CeO_2后活化能显著降低,且当Ce/Ca(物质的量比)为0.25时达到最低值10.2 kJ/mol。另外,CeO_2的掺杂有利于CaO的分散,进而减缓CaO烧结。CeO_2掺杂的吸收剂在碳酸化/煅烧循环中表现出良好的CO_2捕获性能和循环稳定性。
The CeO_2-doped CaO-based sorbent was prepared by the homogeneous precipitation method using P123 as the soft template. The influence of CeO_2 doping on the capture of CO_2 was investigated. The CeO_2 doping can promote the formation of surface oxygen species, and facilitate the carbonation reaction. The interactions in CaO-CeO_2 lead to the electrons transfer from Ca to surface oxygen species. Moreover, when Ce ions are substituted by Ca ions, the charge neutrality is destroyed in the CeO_2 crystal, which promotes the formation of oxygen vacancies and O~(2-). E_a is tested to be 28.1 kJ/mol for the carbonation reaction of pure CaO sorbent, while E_a decreases to the minimal value of 10.2 kJ/mol when adding CeO_2 to CaO sorbent with a Ce/Ca molar ratio of 0.25. Also, the doping of CeO_2 is beneficial to the high dispersion of CaO and prevention of CaO sintering. The Ce-doped sorbents exhibit a superior capture capacity and cyclic stability in carbonation/calcination cycles.
The CeO_2-doped CaO-based sorbent was prepared by the homogeneous precipitation method using P123 as the soft template. The influence of CeO_2 doping on the capture of CO_2 was investigated. The CeO_2 doping can promote the formation of surface oxygen species, and facilitate the carbonation reaction. The interactions in CaO-CeO_2 lead to the electrons transfer from Ca to surface oxygen species. Moreover, when Ce ions are substituted by Ca ions, the charge neutrality is destroyed in the CeO_2 crystal, which promotes the formation of oxygen vacancies and O~(2-). E_a is tested to be 28.1 kJ/mol for the carbonation reaction of pure CaO sorbent, while E_a decreases to the minimal value of 10.2 kJ/mol when adding CeO_2 to CaO sorbent with a Ce/Ca molar ratio of 0.25. Also, the doping of CeO_2 is beneficial to the high dispersion of CaO and prevention of CaO sintering. The Ce-doped sorbents exhibit a superior capture capacity and cyclic stability in carbonation/calcination cycles.
引文
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[6] 郭名女, 张力, 唐强, BO Feng, 杨仲卿. CaO/MgO和CaO/Ca9Al6O18同时捕集CO2/SO2的循环吸收特性[J]. 燃料化学学报, 2012, 40(6): 757-762. (GUO Ming-nv, ZHANG Li, TANG Qiang, BO Feng, YANG Zhong-qing. Cyclic adsorption characteristic of CaO/MgO and CaO/Ca9Al6O18 for simultaneous CO2 /SO2 capture[J]. J Fuel Chem Technol, 2012, 40(6): 757-762.)
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[8] GUO H, KOU X, ZHAO Y, WANG S, SUN Q, MA X. Effect of synergistic interaction between Ce and Mn on the CO2 capture of calcium-based sorbent: Textural properties, electron donation, and oxygen vacancy[J]. Chem Eng J, 2018, 334: 237-246.
[9] WU S, LAN P. A kinetic model of nano-CaO reactions with CO2 in a sorption complex catalyst[J]. AIChE J, 2012, 58(5): 1570-1577.
[10] 詹望成, 郭耘, 龚学庆, 郭杨龙, 王艳芹, 卢冠忠. 二氧化铈表面氧的活化及对氧化反应的催化作用[J]. 中国科学: 化学, 2012, (4): 433-445.(ZHAN Wang-cheng, GUO Yun, GONG Xue-qing, GUO Yang-long, WANG Yan-qin, LU Guan-zhong. Surface oxygen activation on CeO2 and its catalytic performances for oxidation reactions[J]. China Sci: Chem, 2012, (4): 433-445.)
[11] 赵芳, 田志茗. CaO/MgO混合催化剂的制备及催化合成生物柴油[J]. 工业催化, 2017, 25(3): 58-62.(ZHAO Fang, TIAN Zhi-ming. Preparation and catalytic properties of CaO /MgO mixed catalyst for biodiesel synthesis[J]. Ind Catal, 2017, 25(3): 58-62.)
[12] LIU B, LI C, ZHANG G, YAN L, LI Z. Direct synthesis of dimethyl carbonate from CO2 and methanol over CaO-CeO2 catalysts: the role of acid-base properties and surface oxygen vacancies[J]. New J Chem, 2017, 41(20): 12231-12240.
[13] 张雷, 张力, 闫云飞, 杨仲卿, 郭名女. 掺杂Ce、Zr对CO2钙基吸附剂循环特性的影响[J]. 化工学报, 2015, 66(2): 612-617.(ZHANG Lei, ZHANG Li, YAN Yun-fei, YANG Zhong-qing, GUO Ming-nv. Effect of Ce, Zr on cyclic performance of CaO-based CO2 sorbents[J]. J Chem Ind Eng, 2015, 66(2): 612-617.)
[14] WANG S, FAN S, FAN L, ZHAO Y, MA X. Effect of cerium oxide doping on the performance of CaO-based sorbents during calcium looping cycles[J]. Environ Sci Technol, 2015, 49(8): 5021-5027.
[15] YU X, WEN Z, LI H, TU S, YAN J. Transesterification of Pistacia chinensis oil for biodiesel catalyzed by CaO-CeO2 mixed oxides[J]. Fuel, 2011, 90(5): 1868-1874.
[16] FANG J, BI X, SI D, JIANG Z, HUANG W. Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides[J]. Appl Surf Sci, 2007, 253(22): 8952-8961.
[17] RODRIGUEZ J A, WANG X, HANSON J C, LIU G. The behavior of mixed-metal oxides: Structural and electronic properties of Ce1-xCaxO2 and Ce1-xCaxO [J]. J Chem Phys, 2003, 119(11): 5659-5669.
[18] PACCHIONI G, RICART J M, ILLAS F. Ab initio cluster model calculations on the chemisorption of CO2 and SO2 probe molecules on MgO and CaO (100) surfaces. A theoretical measure of oxide basicity[J]. J Am Chem Soc, 1994, 116(22): 10152-10158.
[19] 刘水刚, 李军平, 赵宁, 魏伟, 孙予罕. 一种新型固体碱高稳定性介孔CaO-ZrO2的制备及性能[J]. 化工进展, 2007, 26(11): 1626-1630.(LIU Shui-gang, LI Jun-ping, ZHAO Ning, WEI Wei, SUN Yu-han. Preparation and property of mesoporous CaO-ZrO2 solid base with high activity and stability[J]. Chem Ind Eng Prog, 2007, 26(11): 1626-1630.)
[20] PING S, GRACE J R, LIM C J, ANTHONY E J. Determination of intrinsic rate constants of the CaO-CO2 reaction[J]. Chem Eng Sci, 2008, 63(1): 47-56.
[21] AIHARA M, NAGAI T, MATSUSHITA J, NEGISHI Y, OHYA H. Development of porous solid reactant for thermal-energy storage and temperature upgrade using carbonation/decarbonation reaction[J]. Appl Energy, 2001, 69(3): 225-238.
[22] 韩龙, 王勤辉, 马强, 余春江, 骆仲泱, 岑可法. 加压条件下CaO碳酸化反应动力学研究[J]. 中国电机工程学报, 2009, 29(14): 41-46.(HAN Long, WANG Qin-hui, MA Qiang, YU Chun-jiang, LUO Zhong-yang, CEN Ke-fa. Kinetics study on CaO carbonation reaction at pressurized conditions[J]. Proc CSEE, 2009, 29(14): 41-46.)
[23] 任斌, 考宏涛, 李爱莉. 钙基吸收剂碳酸化实验研究[J]. 煤炭转化, 2012, 35(2): 85-88.(REN Bin, KAO Hong-tao, LI Ai-li. Study on the carbonation reaction of Ca-based absorbent[J]. Coal Convers, 2012, 35(2): 85-88.) Influence of cerium doping on CO2 capture of CaO-based sorbentsYANG Bin YU Zhong-liang LI Chun-yu ZHOU Xing GUO Shuai LI Guang ZHAO Jian-tao FANG Yi-tian CeO2掺杂的CaO基吸收剂在CO2捕获过程中的电子效应。J Fuel Chem Technol, 2019, 47(3): 352-360以椰壳生物质炭为燃料的直接炭固体氧化物燃料电池丘倩媛陈倩阳刘志军刘江
[2] 李振山, 蔡宁生, 黄煜煜. 吸收增强式甲烷水蒸气重整制氢实验研究[J]. 燃料化学学报, 2007, 35(1): 79-84.(LI Zhen-shan, CAI Ning-sheng, HUANG Yu-yu. Experimental research on hydrogen production from sorption enhanced steam methane reforming[J]. J Fuel Chem Technol, 2007, 35(1): 79-84.)
[3] 李振山, 蔡宁生. 吸收增强式甲烷水蒸气重整制氢循环反应模拟[J]. 燃料化学学报, 2008, 36(1): 99-103.(LI Zhen-shan, CAI Ning-sheng. Modeling of hydrogen production by sorption enhanced methane steam reforming reactions[J]. J Fuel Chem Technol, 2008, 36(1): 99-103.)
[4] RONG N, WANG Q, FANG M, CHENG L, LUO Z, CEN K. Steam hydration reactivation of CaO-based sorbent in cyclic carbonation/calcination for CO2 capture[J]. Energy Fuels , 2013, 27(9): 5332-5340.
[5] 乔春珍, 王宝利, 肖云汉. 不同钙基CO2吸收剂的循环特性研究[J]. 燃料化学学报, 2010, 38(4): 478-482.(QIAO Chun-zhen, WANG Bao-li, XIAO Yun-han. Characteristics of different Ca-based CO2 absorbents during cyclic calcination-carbonation[J]. J Fuel Chem Technol, 2010, 38(4): 478-482.)
[6] 郭名女, 张力, 唐强, BO Feng, 杨仲卿. CaO/MgO和CaO/Ca9Al6O18同时捕集CO2/SO2的循环吸收特性[J]. 燃料化学学报, 2012, 40(6): 757-762. (GUO Ming-nv, ZHANG Li, TANG Qiang, BO Feng, YANG Zhong-qing. Cyclic adsorption characteristic of CaO/MgO and CaO/Ca9Al6O18 for simultaneous CO2 /SO2 capture[J]. J Fuel Chem Technol, 2012, 40(6): 757-762.)
[7] 谢明霜. 改性钙基吸收剂循环煅烧/碳酸化捕集CO2反应特性及动力学分析[D]. 重庆: 重庆大学, 2013.(XIE Ming-shuang. Cyclic calcination/carbonation characteristic and kinetics of modified Ca-based sorbent for CO2[D]. Chongqing: Chongqing University, 2013.)
[8] GUO H, KOU X, ZHAO Y, WANG S, SUN Q, MA X. Effect of synergistic interaction between Ce and Mn on the CO2 capture of calcium-based sorbent: Textural properties, electron donation, and oxygen vacancy[J]. Chem Eng J, 2018, 334: 237-246.
[9] WU S, LAN P. A kinetic model of nano-CaO reactions with CO2 in a sorption complex catalyst[J]. AIChE J, 2012, 58(5): 1570-1577.
[10] 詹望成, 郭耘, 龚学庆, 郭杨龙, 王艳芹, 卢冠忠. 二氧化铈表面氧的活化及对氧化反应的催化作用[J]. 中国科学: 化学, 2012, (4): 433-445.(ZHAN Wang-cheng, GUO Yun, GONG Xue-qing, GUO Yang-long, WANG Yan-qin, LU Guan-zhong. Surface oxygen activation on CeO2 and its catalytic performances for oxidation reactions[J]. China Sci: Chem, 2012, (4): 433-445.)
[11] 赵芳, 田志茗. CaO/MgO混合催化剂的制备及催化合成生物柴油[J]. 工业催化, 2017, 25(3): 58-62.(ZHAO Fang, TIAN Zhi-ming. Preparation and catalytic properties of CaO /MgO mixed catalyst for biodiesel synthesis[J]. Ind Catal, 2017, 25(3): 58-62.)
[12] LIU B, LI C, ZHANG G, YAN L, LI Z. Direct synthesis of dimethyl carbonate from CO2 and methanol over CaO-CeO2 catalysts: the role of acid-base properties and surface oxygen vacancies[J]. New J Chem, 2017, 41(20): 12231-12240.
[13] 张雷, 张力, 闫云飞, 杨仲卿, 郭名女. 掺杂Ce、Zr对CO2钙基吸附剂循环特性的影响[J]. 化工学报, 2015, 66(2): 612-617.(ZHANG Lei, ZHANG Li, YAN Yun-fei, YANG Zhong-qing, GUO Ming-nv. Effect of Ce, Zr on cyclic performance of CaO-based CO2 sorbents[J]. J Chem Ind Eng, 2015, 66(2): 612-617.)
[14] WANG S, FAN S, FAN L, ZHAO Y, MA X. Effect of cerium oxide doping on the performance of CaO-based sorbents during calcium looping cycles[J]. Environ Sci Technol, 2015, 49(8): 5021-5027.
[15] YU X, WEN Z, LI H, TU S, YAN J. Transesterification of Pistacia chinensis oil for biodiesel catalyzed by CaO-CeO2 mixed oxides[J]. Fuel, 2011, 90(5): 1868-1874.
[16] FANG J, BI X, SI D, JIANG Z, HUANG W. Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides[J]. Appl Surf Sci, 2007, 253(22): 8952-8961.
[17] RODRIGUEZ J A, WANG X, HANSON J C, LIU G. The behavior of mixed-metal oxides: Structural and electronic properties of Ce1-xCaxO2 and Ce1-xCaxO [J]. J Chem Phys, 2003, 119(11): 5659-5669.
[18] PACCHIONI G, RICART J M, ILLAS F. Ab initio cluster model calculations on the chemisorption of CO2 and SO2 probe molecules on MgO and CaO (100) surfaces. A theoretical measure of oxide basicity[J]. J Am Chem Soc, 1994, 116(22): 10152-10158.
[19] 刘水刚, 李军平, 赵宁, 魏伟, 孙予罕. 一种新型固体碱高稳定性介孔CaO-ZrO2的制备及性能[J]. 化工进展, 2007, 26(11): 1626-1630.(LIU Shui-gang, LI Jun-ping, ZHAO Ning, WEI Wei, SUN Yu-han. Preparation and property of mesoporous CaO-ZrO2 solid base with high activity and stability[J]. Chem Ind Eng Prog, 2007, 26(11): 1626-1630.)
[20] PING S, GRACE J R, LIM C J, ANTHONY E J. Determination of intrinsic rate constants of the CaO-CO2 reaction[J]. Chem Eng Sci, 2008, 63(1): 47-56.
[21] AIHARA M, NAGAI T, MATSUSHITA J, NEGISHI Y, OHYA H. Development of porous solid reactant for thermal-energy storage and temperature upgrade using carbonation/decarbonation reaction[J]. Appl Energy, 2001, 69(3): 225-238.
[22] 韩龙, 王勤辉, 马强, 余春江, 骆仲泱, 岑可法. 加压条件下CaO碳酸化反应动力学研究[J]. 中国电机工程学报, 2009, 29(14): 41-46.(HAN Long, WANG Qin-hui, MA Qiang, YU Chun-jiang, LUO Zhong-yang, CEN Ke-fa. Kinetics study on CaO carbonation reaction at pressurized conditions[J]. Proc CSEE, 2009, 29(14): 41-46.)
[23] 任斌, 考宏涛, 李爱莉. 钙基吸收剂碳酸化实验研究[J]. 煤炭转化, 2012, 35(2): 85-88.(REN Bin, KAO Hong-tao, LI Ai-li. Study on the carbonation reaction of Ca-based absorbent[J]. Coal Convers, 2012, 35(2): 85-88.) Influence of cerium doping on CO2 capture of CaO-based sorbentsYANG Bin YU Zhong-liang LI Chun-yu ZHOU Xing GUO Shuai LI Guang ZHAO Jian-tao FANG Yi-tian CeO2掺杂的CaO基吸收剂在CO2捕获过程中的电子效应。J Fuel Chem Technol, 2019, 47(3): 352-360以椰壳生物质炭为燃料的直接炭固体氧化物燃料电池丘倩媛陈倩阳刘志军刘江