共沉淀法掺杂离子氧化钙吸收剂脱硫反应机理
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摘要
利用共沉淀法设计制备了晶格内掺有不同半径杂离子的CaO吸收剂,研究了杂离子类型对脱硫反应的影响;基于离子晶体内原子扩散的空位缺陷理论,获得了掺杂不同半径离子对硫化产物层离子扩散影响的整体规律,并利用傅氏转换红外线光谱分析仪(扫描电子显微镜)和X射线衍射仪对掺有不同半径杂离子的CaO吸收剂进行分析。结果表明:掺杂Ba~(2+)后的CaO吸收剂脱硫性能最佳,而掺杂Mg~(2+)的效果最差;设计样品中实现了杂离子与Ca~(2+)原子水平的掺混;杂原子掺入引起了CaO相应的晶格畸变,大半径杂离子能增加晶体中的空位点缺陷数量,提高吸收剂脱硫性能,而小半径杂离子则对产物层固态离子扩散无促进作用。
By co-precipitation method,CaO sorbents in which Ca~(2+) and hetero-ion(with different radius) were mixed in the crystalline lattice were prepared.The effect of hetero-ion type on desulfurization reaction was studied.On the basis of the vacancy defect theory in solid-state ions diffusion,the comprehensive rules about ion-doping promoting ion diffusion in sulfated product layer were obtained.The Fourier transform infrared spectroscopy(FTIR) and X-ray diffractometer were used to analyze the desulfurization performance of each sample.The result show that,the samples mixed with Ba~(2+) has the best desulphurization performance,while that with Mg~(2+) has the worst.The dopant ions were successfully mixed with Ca~(2+) at atom level.The dopant ions brought in lattice distortion.It concluded that the dopant ions which have a larger radius can increase the number of space point defects and improve the desulfurization ability of the sample,but the smaller radius dopant ions have no positive effect.
By co-precipitation method,CaO sorbents in which Ca~(2+) and hetero-ion(with different radius) were mixed in the crystalline lattice were prepared.The effect of hetero-ion type on desulfurization reaction was studied.On the basis of the vacancy defect theory in solid-state ions diffusion,the comprehensive rules about ion-doping promoting ion diffusion in sulfated product layer were obtained.The Fourier transform infrared spectroscopy(FTIR) and X-ray diffractometer were used to analyze the desulfurization performance of each sample.The result show that,the samples mixed with Ba~(2+) has the best desulphurization performance,while that with Mg~(2+) has the worst.The dopant ions were successfully mixed with Ca~(2+) at atom level.The dopant ions brought in lattice distortion.It concluded that the dopant ions which have a larger radius can increase the number of space point defects and improve the desulfurization ability of the sample,but the smaller radius dopant ions have no positive effect.
引文
[1]袁中山,吴迪镛,王树东.采用一体化燃煤添加剂的燃烧中固硫作用研究[J].燃料化学学报,2002,30(1):3-40.YUAN Zhongshan,WU Diyong,WANG Shudong.Study on sulfur retention of integrated additive during coal combustion[J].Journal of Fuel Chemistry and Technology,2002,30(1):36-40.
[2]DUO W,LAURSEN K,LIM J,GRACE J.Crystallization and fracture:product layer diffusion in sulfation of calcined limestone[J].Industrial&Engineering Chemistry Research,2004,43(18):5653-5662.
[3]武增华,许玲,陈昌和.添加剂对氧化钙固硫促进作用的机理探讨[J].煤炭转化,2000,23(3):72-76.WU Zenghua,XU Ling,CHEN Changhe,et al.Mechanism of additives on Ca O sulfation[J].Coal Conversion,2000,23(3):72-76.
[4]MAHULI S K,AGNIHOTRI R,CHAUK S,et al.Porestructure optimization of calcium carbonate for enhanced sulfation[J].AICh E Journal,1997,43(9):2323-2335.
[5]王春波,陈传敏.碳酸钙直接硫化反应产物层固态离子扩散机理研究[J].中国电机工程学报,2007,27(35):44-48.WANG Chunbo,CHEN Chuanmin.Investigation on solid-state ions diffusion in the product layer of direct sulfation reaction of limestone[J].Proceedings of the CSEE,2007,27(35):4-48.
[6]王春波,沈湘林.Na2CO3调质钙基脱硫剂硫化机理实验研究[J].工程热物理学报,2002,23(5):641-644.WANG Chunbo,SHEN Xianglin.The investigation on the sulfation mechanisms of Ca-based sorbent modified by Na2CO3[J].Journal of Engineering Thermophysics,2002,23(5):641-644.
[7]ALVAREZ E,GONZALEZ J F.High pressure thermogravimetric analysis of the direct sulfation of Spanish calcium based sorbents[J].Fuel,1999,78(3):341-348.
[8]FUERTES A B,VELASCO G,FUENTE E,ALVAREZ T.Study of the direct sulfation of limestone particles at high CO2 partial pressures[J].Fuel Processing Technology,1994,38(3):181-192.
[9]ZEVENHOVEN C A P,YRJAS K P,HUPA M M.Product layer development during sulfation andsulfidation of uncalcined limestone particles at elevated pressures[J].Industrial&Engineering Chemistry Research,1998,37(7):2639-2646.
[10]尚建宇,王松岭,王春波,等.脱硫Ca O团聚体晶粒产物层内Ca2+和SO42-的扩散行为[J].中国电机工程学报,2009,29(29):52-56.SHANG Jianyu,WANG Songling,WANG Chunbo,et al,The diffusion behavior of Ca2+and SO42-in Ca O sorbent aggregate crystal production layer[J].Proceedings of the CSEE,2009,29(29):52-56.
[11]王春波,陈鸿伟,吉云.调质钙基脱硫剂硫化特性研究[J].中国电机工程学报,2004,24(12):238-242.WANG Chunbo,CHEN Hongwei,JI Yun.Investigation on sulfation of modified ca-based sorbent[J].Proceedings of the CSEE,2004,24(12):238-242.
[12]WANG C,SHEN X,XU Y.Investigation on sulfation of modified Ca-based sorbent[J].Proceedings of the CSEE,2004,79(2):121-133.
[13]FILITZ R,KIERZKOWSKA A M,BRODA M,et al.Highly efficient CO2 sorbents:development of synthetic,calcium-rich dolomites[J].Environmental Science Technology,2012,46(1):559-565.
[14]王春波,李永华,陈鸿伟.调质脱硫剂硫化反应产物层固态离子扩散机理的研究[J].热能动力工程,2004,19(5):467-470.WANG Chunbo,LI Yonghua,CHEN Hongwei.An Investigation of the mechanism of solid state ion diffusion in the sulfidation reaction product layer of a modified desulfurization agent[J].Proceedings of the CSEE,2004,19(5):467-470.
[15]胡赓祥,蔡珣,戎咏华.材料科学基础[M].3版.上海:上海交通大学出版社,2010:157.HU Gengxiang,CAI Xun,RONG Yonghua.Foundations of materials science[M].3rd ed.Shanghai:Shanghai Jiao Tong University Press,2010:157(in Chinese).
[2]DUO W,LAURSEN K,LIM J,GRACE J.Crystallization and fracture:product layer diffusion in sulfation of calcined limestone[J].Industrial&Engineering Chemistry Research,2004,43(18):5653-5662.
[3]武增华,许玲,陈昌和.添加剂对氧化钙固硫促进作用的机理探讨[J].煤炭转化,2000,23(3):72-76.WU Zenghua,XU Ling,CHEN Changhe,et al.Mechanism of additives on Ca O sulfation[J].Coal Conversion,2000,23(3):72-76.
[4]MAHULI S K,AGNIHOTRI R,CHAUK S,et al.Porestructure optimization of calcium carbonate for enhanced sulfation[J].AICh E Journal,1997,43(9):2323-2335.
[5]王春波,陈传敏.碳酸钙直接硫化反应产物层固态离子扩散机理研究[J].中国电机工程学报,2007,27(35):44-48.WANG Chunbo,CHEN Chuanmin.Investigation on solid-state ions diffusion in the product layer of direct sulfation reaction of limestone[J].Proceedings of the CSEE,2007,27(35):4-48.
[6]王春波,沈湘林.Na2CO3调质钙基脱硫剂硫化机理实验研究[J].工程热物理学报,2002,23(5):641-644.WANG Chunbo,SHEN Xianglin.The investigation on the sulfation mechanisms of Ca-based sorbent modified by Na2CO3[J].Journal of Engineering Thermophysics,2002,23(5):641-644.
[7]ALVAREZ E,GONZALEZ J F.High pressure thermogravimetric analysis of the direct sulfation of Spanish calcium based sorbents[J].Fuel,1999,78(3):341-348.
[8]FUERTES A B,VELASCO G,FUENTE E,ALVAREZ T.Study of the direct sulfation of limestone particles at high CO2 partial pressures[J].Fuel Processing Technology,1994,38(3):181-192.
[9]ZEVENHOVEN C A P,YRJAS K P,HUPA M M.Product layer development during sulfation andsulfidation of uncalcined limestone particles at elevated pressures[J].Industrial&Engineering Chemistry Research,1998,37(7):2639-2646.
[10]尚建宇,王松岭,王春波,等.脱硫Ca O团聚体晶粒产物层内Ca2+和SO42-的扩散行为[J].中国电机工程学报,2009,29(29):52-56.SHANG Jianyu,WANG Songling,WANG Chunbo,et al,The diffusion behavior of Ca2+and SO42-in Ca O sorbent aggregate crystal production layer[J].Proceedings of the CSEE,2009,29(29):52-56.
[11]王春波,陈鸿伟,吉云.调质钙基脱硫剂硫化特性研究[J].中国电机工程学报,2004,24(12):238-242.WANG Chunbo,CHEN Hongwei,JI Yun.Investigation on sulfation of modified ca-based sorbent[J].Proceedings of the CSEE,2004,24(12):238-242.
[12]WANG C,SHEN X,XU Y.Investigation on sulfation of modified Ca-based sorbent[J].Proceedings of the CSEE,2004,79(2):121-133.
[13]FILITZ R,KIERZKOWSKA A M,BRODA M,et al.Highly efficient CO2 sorbents:development of synthetic,calcium-rich dolomites[J].Environmental Science Technology,2012,46(1):559-565.
[14]王春波,李永华,陈鸿伟.调质脱硫剂硫化反应产物层固态离子扩散机理的研究[J].热能动力工程,2004,19(5):467-470.WANG Chunbo,LI Yonghua,CHEN Hongwei.An Investigation of the mechanism of solid state ion diffusion in the sulfidation reaction product layer of a modified desulfurization agent[J].Proceedings of the CSEE,2004,19(5):467-470.
[15]胡赓祥,蔡珣,戎咏华.材料科学基础[M].3版.上海:上海交通大学出版社,2010:157.HU Gengxiang,CAI Xun,RONG Yonghua.Foundations of materials science[M].3rd ed.Shanghai:Shanghai Jiao Tong University Press,2010:157(in Chinese).