燃煤及烟气脱硫工艺的探索性研究
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摘要
当前,因二氧化硫气体的排放造成的环境污染已经越来越受到各国政府的重视。我国每年因此千万的社会经济损失超过100亿人民币。为此,我国已经在“十一五”期间启动了“燃煤电厂烟气脱硫工程”项目。石灰石等以其丰富的资源、低廉的价格而被作为首选脱硫剂。
本文首先用氧化钙、氢氧化钙和碳酸钙进行脱硫实验,然后选择不同的物质作为脱硫添加剂进行实验。实验结果表明：钙硫比、添加剂的种类及添加量均会对脱硫剂的脱硫效果产生一定影响。不同的添加剂及添加量对脱硫率以及脱硫产物的影响不同。在后序喷水增湿过程中,喷水量的多少也在一定程度上决定了脱硫过程中的脱硫效果。
在实验的基础上,还用流程模型软件PROⅡ对整个脱硫过程进行了模拟。通过选用合适的反应器模型、热力学状态方程以及正确的动力学模型,可以准确地反映出实际脱硫过程中各因素对脱硫效果的影响。
At present, the environmental pollution caused by the emissions of sulfur dioxide has drawn the attention of governments. Our country loss more than 10 billion yuan every year. Therefore, the government started the project of Power Plant's Flue Gas Desulfurization during the Eleventh Five-Year plan Period. Limestone is the preferred desulfurizer because of its abundant resources and low prices.
First this article use CaO, Ca(OH)2, CaCO3 as desulfurizer for desulfurization experiences, and then choose different kinds of compounds as additives. The results showed that calcium sulfur ratio, the kind of additive and its quantity has certain effects on the desulfurization efficiency; different additive has different effect on desulfurization efficiency and desulfurization products. The effect of spraying water on flue gas desulfurization efficiency has been experimentally investigated.
Based on the experiences, the desulfurization process was simulated with PROⅡ. By selecting the right unit operation models, proper thermodynamics equation and kinetic equation, the simulation results can reflect accurately the effect of various factors on desulfurization efficiency.
本文首先用氧化钙、氢氧化钙和碳酸钙进行脱硫实验,然后选择不同的物质作为脱硫添加剂进行实验。实验结果表明：钙硫比、添加剂的种类及添加量均会对脱硫剂的脱硫效果产生一定影响。不同的添加剂及添加量对脱硫率以及脱硫产物的影响不同。在后序喷水增湿过程中,喷水量的多少也在一定程度上决定了脱硫过程中的脱硫效果。
在实验的基础上,还用流程模型软件PROⅡ对整个脱硫过程进行了模拟。通过选用合适的反应器模型、热力学状态方程以及正确的动力学模型,可以准确地反映出实际脱硫过程中各因素对脱硫效果的影响。
At present, the environmental pollution caused by the emissions of sulfur dioxide has drawn the attention of governments. Our country loss more than 10 billion yuan every year. Therefore, the government started the project of Power Plant's Flue Gas Desulfurization during the Eleventh Five-Year plan Period. Limestone is the preferred desulfurizer because of its abundant resources and low prices.
First this article use CaO, Ca(OH)2, CaCO3 as desulfurizer for desulfurization experiences, and then choose different kinds of compounds as additives. The results showed that calcium sulfur ratio, the kind of additive and its quantity has certain effects on the desulfurization efficiency; different additive has different effect on desulfurization efficiency and desulfurization products. The effect of spraying water on flue gas desulfurization efficiency has been experimentally investigated.
Based on the experiences, the desulfurization process was simulated with PROⅡ. By selecting the right unit operation models, proper thermodynamics equation and kinetic equation, the simulation results can reflect accurately the effect of various factors on desulfurization efficiency.
引文
[1]邢佰英.中国煤炭工业协会会长王显政预计2010年煤炭需求量将达30亿吨.信息荟萃,2009,25(6)：57.
[2]国家酸雨和二氧化硫污染防治“十一五”规划.中国环保产业,2008.2：15.
[3]Yu Zhao, Shuxiao Wang, Lei Duan, Yu Lei, Pengfei Cao, Jiming Hao, Primary air pollutant emissions of coal-fired power plants in China: Current status and future prediction, Atmospheric Environment.2008,42:8442-8452
[4]K. C. Hackley, D. H. Buchanan, K. Coombs, C.Chaven, C. W. Kruse.Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes. Fuel Process. Techno.1990,24(1-3):431-436.
[5]智红梅.煤焦全硫测定方法的比较.科技情报开发与经济,2005,15(22)：146-147.
[6]郭琳霞.煤中全硫测定方法的探讨.山西焦煤科技,2004,9：3740.
[7]何有光,张亚凤.燃煤固硫剂固硫效率测定方法的探讨.环境保护,1997,5：29-31
[8]邹其明.煤焦中全硫测定方法的改进与统一.燃料化工,1993,11：279-280
[9]李丽,冯有利,郭景会.国内外燃煤脱硫技术的现状及对策.山西能源与节能,2006,3：9-13.
[10]姜彦立,周新华,郝宇.国内外燃煤脱硫技术的研究进展.矿业快报,2007,1：7-9.
[11]Hill, F. F.flue Gas. Desulfurization by Spray Dry Absorption, Chem. Eng, Process, 2000,39:45-53.
[12]P. Ollero, F. J. Gutie'rrez Ortiz, A. Cabanillas, etal. Flue-Gas Desulfurization in Circulation Fluidized Beds:AnEmpirical Model from an Experimental Pilot-Plant Study [J]. Ind. Eng. Chem. Res.2001,40(23):5640-5648.
[13]赵鹏高.火电厂烟气脱硫关键技术与设备国产化规划要点.电力环境保护,2000,16(2)：28-32.
[14]赵卷,张少峰,张占锋.半干法烟气脱硫技术新进展.河北工业大学学报,2003,32(5)：81-86.
[15]蒋欣,黄玲,武秀文,等.烟气脱硫技术的应用研究.环境污染与防治,2003,4(3)：83.
[16]韩琪,李忠华.石灰石/石膏湿法烟气脱硫的化学过程研究.电力环境保护,2002,18(1)：1.
[17]张基伟.国外燃煤电厂烟气脱硫技术综述.中国电力,1999,32(7)：61-66.
[18]王丽英.LIFAC系统对锅炉运行性能的影响.锅炉技术,2003,34(2)：61-63.
[19]石林,陈定盛,汪碧容,等.提高LIFAC法脱硫效率的工程实例.环境污染法理技 术与设备,2005,6(11)：92-94.
[20]董清梅,郭建明.炉内喷钙尾部增湿脱硫的影响因素探讨.电站系统工程,2006,22(1)：21-22.
[21]He Bailei, Song Qiang, Chem Changhe, et al. Investigations on mechanism of soot formation during combustion and control of soot emission [A]. The 5th international symposium on combustion [C],2003:1-5.
[22]Jinliang Ma, Thomas H, Brent W. Webb. Effect of flame environment on soot formation in coal combustion [A]. International conference on coal science [C],1995:869-872.
[23]Liu Shiling. On soot inception in nonpremixed flames and the effects of flame structure [D].2001.
[24]Rengui Guan, Wen Li, Baoqing Li,Effects of Ca-based additives on desulfurization during coal pyrolysis, Fuel.2003,82:1961-1966.
[25]Irvan Dahlan, Keat Teong Lee, Azlina Harun Kamaruddin, Abdul Rahman Mohamed,Evaluation of various additives on the preparation of rice husk ash (RHA)/CaO-based sorbent for flue gas desulfurization (FGD) at low temperature, Journal of Hazardous Materials.2009,161:570-574.
[26]Jinliang Ma, Thomas H. Fletcher, and Brent W. webb. Effect of flame environment on soot formation in coal combustion. International conference on coal science.1995,869-872.
[27]Thomas H. Fletcher, Jinliang Ma, James R. Rigby ea tl. Soot in Coal Combustion Systems.Prog. Energy Combust. Sci.1997,23:283-301
[28]刘彦,徐江荣,李德忠,等.炉内钙基脱硫两种反应过程机理研究.锅炉技术,2006,37：68-70.
[29]Ian M, Kennedy. Models of Soot Formation and Oxidation. Prog. Energy Combust. Sci. 1997,23:95-132
[30]J.Rigby, J. Ma, B. W. Webb, et al. Transformations of coal-derived soot at elevated temperature. Energy&Fuels.2001,15:52-59.
[31]J. Rigby, J. Ma, B. W. Webb. et al. Transformations of coal-derived soot at elevated temperature [J]. Energy & Fuels,2001, (15):52-59.
[32]Seeker, W. R., Samuelson, G. S., et al. Eighteenth Symposium (international) on Combustion [C]. The combustion institute, Pittsburgh,1980,1213.
[33]任有中.洁净型煤中提高脱硫性能的新技术.工程热物理学报,1999,20(1)：125-128.
[34]周俊虎,范浩杰,姚强,等.氧化钙燃烧固硫添加剂的研究.环境科学学报,1997,17(3)：284-288.
[35]David A. Jozewicz W. Structural changes in surfactant-modified sorbents during furnace injection. AIChE J,1989,35(3):500-506.
[36]肖佩林,沈迪新,林国珍,等.高温固硫反应中锶化合物的促进作用.环境化学,1994,13(5)：389-394.
[37]R. T. Yang. Direct sulfation of calcium carbonate. Ind.Eng. Chem. Res.1988,27(2): 268-273.
[38]袁中山,吴迪镛,谭志诚,等.燃煤固硫及催化燃烧一体化添加剂的催化作用机理研究.燃料化学学报,2005,33(3)：267-272
[39]M.C. Macias-Perez et al,SO2 retention on CaO/activated carbon sorbents. Part Ⅲ. Study of the retention and regeneration conditions. Fuel.2008,87:3170-3175.
[40]M. C. Macias-Perez et al,SO2 retention on CaO/activated carbon sorbents. Part Ⅱ:E□ect of the activated carbon support, Fuel.2008,87:2544-2550.
[41]L. Chen et al, Oxidation of FGD-CaSO3 and effect on soil chemical properties when applied to the soil surface, Fuel.2009,88:1167-1172.
[42]Sen Li, Tongmo Xu, Peng Sun, et al. NOX and SOX emissions of a high sulfur self-retention coal during air-staged combustion, Fuel.2008,87:723-731.
[43]J. Cheng. Sulfur removal at high temperature during coal combustion in furnaces:a review. Progress in Energy and Combustion Science.2003,29:381-405.
[44]朱光俊,梁中渝,邓能运.燃煤固硫剂及添加剂的研究现状.工业加热,2004,33：21-24.
[45]M.A. Lopez-Anton et al.Retention of arsenic and selenium compounds present in coal combustion and gasification flue gases using activated carbons, Fuel Processing Technology.2007,88:799-805.
[46]A. Bueno-Lopez. Regenerable CaO sorbents for SO2 retention:carbonaceous versusinorganic dispersants, Fuel.2002,8:2435-2438.
[47]刘诗词,陈金凤,黄清华.锅炉燃煤量空气量和烟气量的估算.河南电力,2007,1：30-33.
[48]孟志浩,俞保云.燃煤锅炉烟气量及NOx排放量计算方法的探讨.环境污染与防治,2009,31(11)：107-109.
[2]国家酸雨和二氧化硫污染防治“十一五”规划.中国环保产业,2008.2：15.
[3]Yu Zhao, Shuxiao Wang, Lei Duan, Yu Lei, Pengfei Cao, Jiming Hao, Primary air pollutant emissions of coal-fired power plants in China: Current status and future prediction, Atmospheric Environment.2008,42:8442-8452
[4]K. C. Hackley, D. H. Buchanan, K. Coombs, C.Chaven, C. W. Kruse.Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes. Fuel Process. Techno.1990,24(1-3):431-436.
[5]智红梅.煤焦全硫测定方法的比较.科技情报开发与经济,2005,15(22)：146-147.
[6]郭琳霞.煤中全硫测定方法的探讨.山西焦煤科技,2004,9：3740.
[7]何有光,张亚凤.燃煤固硫剂固硫效率测定方法的探讨.环境保护,1997,5：29-31
[8]邹其明.煤焦中全硫测定方法的改进与统一.燃料化工,1993,11：279-280
[9]李丽,冯有利,郭景会.国内外燃煤脱硫技术的现状及对策.山西能源与节能,2006,3：9-13.
[10]姜彦立,周新华,郝宇.国内外燃煤脱硫技术的研究进展.矿业快报,2007,1：7-9.
[11]Hill, F. F.flue Gas. Desulfurization by Spray Dry Absorption, Chem. Eng, Process, 2000,39:45-53.
[12]P. Ollero, F. J. Gutie'rrez Ortiz, A. Cabanillas, etal. Flue-Gas Desulfurization in Circulation Fluidized Beds:AnEmpirical Model from an Experimental Pilot-Plant Study [J]. Ind. Eng. Chem. Res.2001,40(23):5640-5648.
[13]赵鹏高.火电厂烟气脱硫关键技术与设备国产化规划要点.电力环境保护,2000,16(2)：28-32.
[14]赵卷,张少峰,张占锋.半干法烟气脱硫技术新进展.河北工业大学学报,2003,32(5)：81-86.
[15]蒋欣,黄玲,武秀文,等.烟气脱硫技术的应用研究.环境污染与防治,2003,4(3)：83.
[16]韩琪,李忠华.石灰石/石膏湿法烟气脱硫的化学过程研究.电力环境保护,2002,18(1)：1.
[17]张基伟.国外燃煤电厂烟气脱硫技术综述.中国电力,1999,32(7)：61-66.
[18]王丽英.LIFAC系统对锅炉运行性能的影响.锅炉技术,2003,34(2)：61-63.
[19]石林,陈定盛,汪碧容,等.提高LIFAC法脱硫效率的工程实例.环境污染法理技 术与设备,2005,6(11)：92-94.
[20]董清梅,郭建明.炉内喷钙尾部增湿脱硫的影响因素探讨.电站系统工程,2006,22(1)：21-22.
[21]He Bailei, Song Qiang, Chem Changhe, et al. Investigations on mechanism of soot formation during combustion and control of soot emission [A]. The 5th international symposium on combustion [C],2003:1-5.
[22]Jinliang Ma, Thomas H, Brent W. Webb. Effect of flame environment on soot formation in coal combustion [A]. International conference on coal science [C],1995:869-872.
[23]Liu Shiling. On soot inception in nonpremixed flames and the effects of flame structure [D].2001.
[24]Rengui Guan, Wen Li, Baoqing Li,Effects of Ca-based additives on desulfurization during coal pyrolysis, Fuel.2003,82:1961-1966.
[25]Irvan Dahlan, Keat Teong Lee, Azlina Harun Kamaruddin, Abdul Rahman Mohamed,Evaluation of various additives on the preparation of rice husk ash (RHA)/CaO-based sorbent for flue gas desulfurization (FGD) at low temperature, Journal of Hazardous Materials.2009,161:570-574.
[26]Jinliang Ma, Thomas H. Fletcher, and Brent W. webb. Effect of flame environment on soot formation in coal combustion. International conference on coal science.1995,869-872.
[27]Thomas H. Fletcher, Jinliang Ma, James R. Rigby ea tl. Soot in Coal Combustion Systems.Prog. Energy Combust. Sci.1997,23:283-301
[28]刘彦,徐江荣,李德忠,等.炉内钙基脱硫两种反应过程机理研究.锅炉技术,2006,37：68-70.
[29]Ian M, Kennedy. Models of Soot Formation and Oxidation. Prog. Energy Combust. Sci. 1997,23:95-132
[30]J.Rigby, J. Ma, B. W. Webb, et al. Transformations of coal-derived soot at elevated temperature. Energy&Fuels.2001,15:52-59.
[31]J. Rigby, J. Ma, B. W. Webb. et al. Transformations of coal-derived soot at elevated temperature [J]. Energy & Fuels,2001, (15):52-59.
[32]Seeker, W. R., Samuelson, G. S., et al. Eighteenth Symposium (international) on Combustion [C]. The combustion institute, Pittsburgh,1980,1213.
[33]任有中.洁净型煤中提高脱硫性能的新技术.工程热物理学报,1999,20(1)：125-128.
[34]周俊虎,范浩杰,姚强,等.氧化钙燃烧固硫添加剂的研究.环境科学学报,1997,17(3)：284-288.
[35]David A. Jozewicz W. Structural changes in surfactant-modified sorbents during furnace injection. AIChE J,1989,35(3):500-506.
[36]肖佩林,沈迪新,林国珍,等.高温固硫反应中锶化合物的促进作用.环境化学,1994,13(5)：389-394.
[37]R. T. Yang. Direct sulfation of calcium carbonate. Ind.Eng. Chem. Res.1988,27(2): 268-273.
[38]袁中山,吴迪镛,谭志诚,等.燃煤固硫及催化燃烧一体化添加剂的催化作用机理研究.燃料化学学报,2005,33(3)：267-272
[39]M.C. Macias-Perez et al,SO2 retention on CaO/activated carbon sorbents. Part Ⅲ. Study of the retention and regeneration conditions. Fuel.2008,87:3170-3175.
[40]M. C. Macias-Perez et al,SO2 retention on CaO/activated carbon sorbents. Part Ⅱ:E□ect of the activated carbon support, Fuel.2008,87:2544-2550.
[41]L. Chen et al, Oxidation of FGD-CaSO3 and effect on soil chemical properties when applied to the soil surface, Fuel.2009,88:1167-1172.
[42]Sen Li, Tongmo Xu, Peng Sun, et al. NOX and SOX emissions of a high sulfur self-retention coal during air-staged combustion, Fuel.2008,87:723-731.
[43]J. Cheng. Sulfur removal at high temperature during coal combustion in furnaces:a review. Progress in Energy and Combustion Science.2003,29:381-405.
[44]朱光俊,梁中渝,邓能运.燃煤固硫剂及添加剂的研究现状.工业加热,2004,33：21-24.
[45]M.A. Lopez-Anton et al.Retention of arsenic and selenium compounds present in coal combustion and gasification flue gases using activated carbons, Fuel Processing Technology.2007,88:799-805.
[46]A. Bueno-Lopez. Regenerable CaO sorbents for SO2 retention:carbonaceous versusinorganic dispersants, Fuel.2002,8:2435-2438.
[47]刘诗词,陈金凤,黄清华.锅炉燃煤量空气量和烟气量的估算.河南电力,2007,1：30-33.
[48]孟志浩,俞保云.燃煤锅炉烟气量及NOx排放量计算方法的探讨.环境污染与防治,2009,31(11)：107-109.