0.3MW(th)CFB锅炉烟道喷射生物质活性炭脱汞试验研究
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摘要
活性炭喷射(activated carbon injection,ACI)是燃煤电厂烟气高效脱汞技术。采用1%NH_4Br溶液对稻壳活性炭浸渍改性,制备NH_4Br改性稻壳活性炭(Br-RHC)脱汞吸附剂。利用比表面积分析仪(Brunauer-Emmet-Teller,BET)、扫描电子显微镜(scanning electron microscope,SEM)和X射线衍射(X-ray diffraction,XRD)等表征手段对吸附剂的理化性质进行了表征。在0.3MW(th)燃煤循环流化床锅炉中试装置上,进行了改性稻壳活性炭吸附剂烟气喷射脱汞试验研究。结果表明:吸附剂改性后的比表面积、微孔容积与总孔容积均有一定程度的增加;改性后吸附剂孔隙结构发达,石墨化程度较高,NH_4Br以非晶体形态担载在吸附剂表面。喷射脱汞效率随着喷射量的增大先增加后稳定,在碳汞比为16000时脱汞效率为79.44%。喷射脱汞效率随着喷射温度的升高而升高,由142℃的57.74%升高为200oC的79.48%。烟气中SO_2对喷射脱汞效率有抑制作用,NO对喷射脱汞效率有促进作用。汞排放浓度为0.35mg/m~3,污染物控制装置(air pollution control devices,APCDs)对烟气中Hg~0、Hg~(2+)与Hg~p的协同脱除率分别为98.83%、88.00%与100%。
Activated carbon injection(ACI) is known as high efficient mercury removal technique in coal-fired power plant. 1% NH_4 Br solution impregnation modified rice husk activated carbon(Br-RHC) was prepared as mercury adsorbent.Physicochemical characteristics of Br-RHC were investigated by using different analysis techniques of Brunauer-EmmetTeller(BET), scanning electron microscope(SEM) and X-ray diffraction(XRD). The sorbent injection for flue gas mercury removal experiment was carried out in a 0.3 MW(th) coal-fired circulating fluidized bed boiler system. The results showed that the specific surface area, micro pore volume and total pore volume increased, the pore structure of the adsorbent was developed, the degree of graphitization was high, and NH_4 Br was loaded on surface of the adsorbent in an amorphous form,after modification. The mercury removal efficiency of sorbent injection elevated first and then stabilized with increase of the injection amount, reaching 79.44% at a ratio of carbon to mercury of 16000. The mercury removal efficiency raised with increase of the flue gas temperature, which is from 57.74% at142℃ to 79.48% at 200℃. The mercury removal efficiency of sorbent injection is restrained by SO_2 concentration in the flue gas, while is promoted by NO. The total mercury emission concentration to the air was 0.35μg/m~3, and the synergistic removal rates of air pollution control devices(APCDs) for Hg~0, Hg~(2+) and Hg~p in flue gas were 98.83%, 88.00% and 100%, respectively.
Activated carbon injection(ACI) is known as high efficient mercury removal technique in coal-fired power plant. 1% NH_4 Br solution impregnation modified rice husk activated carbon(Br-RHC) was prepared as mercury adsorbent.Physicochemical characteristics of Br-RHC were investigated by using different analysis techniques of Brunauer-EmmetTeller(BET), scanning electron microscope(SEM) and X-ray diffraction(XRD). The sorbent injection for flue gas mercury removal experiment was carried out in a 0.3 MW(th) coal-fired circulating fluidized bed boiler system. The results showed that the specific surface area, micro pore volume and total pore volume increased, the pore structure of the adsorbent was developed, the degree of graphitization was high, and NH_4 Br was loaded on surface of the adsorbent in an amorphous form,after modification. The mercury removal efficiency of sorbent injection elevated first and then stabilized with increase of the injection amount, reaching 79.44% at a ratio of carbon to mercury of 16000. The mercury removal efficiency raised with increase of the flue gas temperature, which is from 57.74% at142℃ to 79.48% at 200℃. The mercury removal efficiency of sorbent injection is restrained by SO_2 concentration in the flue gas, while is promoted by NO. The total mercury emission concentration to the air was 0.35μg/m~3, and the synergistic removal rates of air pollution control devices(APCDs) for Hg~0, Hg~(2+) and Hg~p in flue gas were 98.83%, 88.00% and 100%, respectively.
引文
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[16]姚婷,段钰锋,朱纯,等.温度和氧含量对NH4Br改性稻壳焦汞氧化吸附特性的影响[J].化工学报,2016,67(4):1467-1474.Yao Ting,Duan Yufeng,Zhu Chun,et al.Effects of temperature and oxygen content on Hg0oxidation and adsorption by rice husk char impregnated with NH4Br[J].CIESC Journal,2016,67(4):1467-1474(in Chinese).
[17]佘敏,段钰锋,朱纯,等.CO2/H3PO4活化与NH4Br改性稻壳焦的脱汞性能实验研究[J].东南大学学报:自然科学版,2014,44(2):321-327.She Min,DuanYufeng,Zhu Chun,et al.Experimental study on mercury adsorption performances of rice husk chars activated by CO2/H3PO4 and modified by NH4Br[J].Journal of Southeast University:Natural Science Edition,2014,44(2):321-327(in Chinese).
[18]周强,冒咏秋,段钰锋,等.溴素改性活性炭汞吸附特性研究[J].工程热物理学报,2014,35(12):2531-2534.Zhou Qiang,Mao Yongqiu,DuanYufeng,et al.Studies on mercury adsorption on bromine modified activated carbon[J].Journal of Engineering Thermophysics,2014,35(12):2531-2534(in Chinese).
[19]段钰锋,江贻满,杨立国,等.循环流化床锅炉汞排放和吸附实验研究[J].中国电机工程学报,2008,28(32):1-5.Duan Yufeng,Jiang Yiman,Yang Liguo,et al.Experimental study on mercury emission and adsorption in circulating fluidized bed boiler[J].Proceedings of the CSEE,2008,28(32):1-5(in Chinese).
[20]Tang Nian,Pan Siwei.Study on mercury emission and migration from large-scale pulverized coal fired boilers[J].Journal of Fuel Chemistry and Technology,2013,41(4):484-490.
[21]Belkin H E,Finkelman R B,ZhengBaoshan.Mercury in people's republic of China coal[J].Geological Society of America Abstractwith Programs,2005,37(7):48.
[22]姜英.我国煤中氯的分布及其分级标准[J].煤质技术,1998(5):7-8,6.Jiang Ying.Distribution of chlorine in coal and its grading standards in China[J].Coal Quality Technology,1998(5):7-8,6(in Chinese).
[23]高连芬,刘桂建,Chou Chenlin,等.中国煤中硫的地球化学研究[J].矿物岩石地球化学通报,2005,24(1):79-87.GaoLianfen,Liu Guijian,ChouChenlin,et al.The study of sulfur geochemistry in Chinese coals[J].Bulletin of Mineralogy,Petrology and Geochemistry,2005,24(1):79-87(in Chinese).
[24]Zhao Shilin,Duan Yufeng,Yao Ting,et al.Study on the mercury emission and transformation in an ultra-low emission coal-fired power plant[J].Fuel,2017,199:653-661.
[25]Li Hailong,Wu Changyu,Li Ying,et al.CeO2-TiO2catalysts for catalytic oxidation of elemental mercury in low-rank coal combustion flue gas[J].Environmental Science&Technology,2011,45(17):7394-7400.
[26]López-Antón M A,Díaz-Somoano M,Martínez-Tarazona M R.Retention of elemental mercury in fly ashes in different atmospheres[J].Energy&Fuels,2007,21(1):99-103.
[27]丁建东,陈博,刁永发,等.碳汞比对燃煤烟气中Hg脱除影响的实验研究[J].环境工程,2012,30(1):58-61.Ding Jiandong,Chen Bo,DiaoYongfa,et al.The experimental study on the influence of C/Hg ratio on removal of elemental mercury in simulated flue gas[J].Environmental Engineering,2012,30(1):58-61(in Chinese).
[28]周强,段钰锋,洪亚光,等.模拟烟气活性炭喷射脱汞实验研究[J].中国电机工程学报,2013,33(35):36-43.Zhou Qiang,DuanYufeng,Hong Yaguang,et al.Experimental study on mercury capture using activated carbon injection in simulated flue gas[J].Proceedings of the CSEE,2013,33(35):36-43(in Chinese).
[29]Lee S H,Rhim Y J,Cho S P,et al.Carbon-based novel sorbent for removing gas-phase mercury[J].Fuel,2006,85(2):219-226.
[30]Yan Naiqiang,Liu Shouheng,Chang S G,et al.Method for the study of gaseous oxidants for the oxidation of mercury gas[J].Industrial&Engineering Chemistry Research,2005,44(15):5567-5574.
[31]Li Guoliang,Wu Qingru,Wang Shuxiao,et al.The influence of flue gas components and activated carbon injection on mercury capture of municipal solid waste incineration in China[J].Chemical Engineering Journal,2017,326:561-569.
[32]高洪亮,周劲松,骆仲泱,等.SO2对模拟燃煤烟气中汞形态分布影响的实验研究[J].环境科学学报,2004,24(2):204-209.Gao Hongliang,Zhou Jinsong,LuoZhongyang,et al.Effect of sulfur dioxide on the speciation of mercury in flue gases[J].ACTA Scientiae Circumstantiae,2004,24(2):204-209(in Chinese).
[33]Li Guoliang,Wu Qingru,Wang Shuxiao,et al.The influence of flue gas components and activated carbon injection on mercury capture of municipal solid waste incineration in China[J].Chemical Engineering Journal,2017,326:561-569.
[2]Pirrone N,Cinnirella S,Feng X,et al.Global mercury emissions to the atmosphere from anthropogenic and natural sources[J].Atmospheric Chemistry and Physics,2010,10(13):5951-5964.
[3]陈瑶姬.燃煤电厂超低排放系统中烟气汞的迁移规律研究[J].电力科技与环保,2017,33(1):9-11.Chen Yaoji.Migration law of flue gas mercury from coal-fired plant ULE system[J].Electric Power Environmental Protection,2017,33(1):9-11(in Chinese).
[4]Jew A D,Rupp E C,Geatches D L,et al.Mercury interaction with the fine fraction of coal-combustion fly ash in a simulated coal power plant flue gas stream[J].Energy&Fuels,2015,29(9):6025-6038.
[5]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB 13223-2011火电厂大气污染物排放标准[S].北京:中国环境科学出版社,2012.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China,Standardization Administration of the People's Republic of China.GB 13223-2011 Emission standard of air pollutants for thermal power plants[S].Beijing:China Environmental Science Press,2012(in Chinese).
[6]郑逸武,段钰锋,汤红健,等.燃煤烟气污染物控制装置协同脱汞特性研究[J].中国环境科学,2018(3):862-870.Zheng Yiwu,Duan Yufeng,Tang Hongjian,et al.Characteristics of the existing air pollutant control devices on Hg synergistic removal in a coal-fired power plant[J].China Environmental Science,2018(3):862-870(in Chinese).
[7]陈玲,孟德海,赵建新,等.同时脱硝脱汞催化剂的研究与应用[J].电力科技与环保,2018,34(3):27-29.Chen Ling,Meng Dehai,Zhao Jianxin,et al.Study and application of catalysts for simultaneous removal of NOx and mercury[J].Electric Power Environmental Protection,2018,34(3):27-29(in Chinese).
[8]Tang Hongjian,DuanYufeng,Zhu Chun,et al.Theoretical evaluation on selective adsorption characteristics of alkali metal-based sorbents for gaseous oxidized mercury[J].Chemosphere,2017,184:711-719.
[9]Sjostrom S,Durham M,Bustard C J,et al.Activated carbon injection for mercury control:overview[J].Fuel,2010,89(6):1320-1322.
[10]Granite E J,Pennline H W,Hargis R A.Novel sorbents for mercury removal from flue gas[J].Industrial&Engineering Chemistry Research,2000,39(4):1020-1029.
[11]周强,段钰锋,卢平.燃煤电厂吸附剂喷射脱汞技术的研究进展[J].化工进展,2018,37(11):4460-4467.Zhou Qiang,DuanYufeng,Lu Ping.Research progress on in-duct mercury removal by sorbent injection in power plant[J].Chemical Industry and Engineering Progress,2018,37(11):4460-4467(in Chinese).
[12]许静,段钰锋,姚婷,等.可再生脱汞吸附剂的研究进展[J].化工进展,2017,36(S1):442-448.Xu Jing,DuanYufeng,Yao Ting,et al.Research progress on regenerable mercury sorbents[J].Chemical Industry and Engineering Progress,2017,36(S1):442-448(in Chinese).
[13]朱纯,段钰锋,尹建军,等.卤化铵盐改性生物质稻壳焦的汞吸附特性[J].东南大学学报:自然科学版,2013,43(1):99-104.Zhu Chun,Duan Yufeng,Yin Jianjun,et al.Mercury adsorption by rice husk char sorbents modified by ammonium halide[J]Journal of Southeast University:Natural Science Edition,2013,43(1):99-104(in Chinese).
[14]Zeng Hancai,Jin Feng,Guo Jia.Removal of elemental mercury from coal combustion flue gas by chlorideimpregnated activated carbon[J].Fuel,2004,83(1):143-146.
[15]朱纯,段钰锋,冒咏秋,等.烟气组分对氯化铵改性活性炭汞吸附特性的影响[J].工程热物理学报,2013,34(10):1982-1985.Zhu Chun,Duan Yufeng,Mao Yongqiu,et al.Effect of flue gas components on mercury adsorption by ammonium Chloride modified activated carbon[J].Journal of Engineering Thermophysics,2013,34(10):1982-1985(in Chinese).
[16]姚婷,段钰锋,朱纯,等.温度和氧含量对NH4Br改性稻壳焦汞氧化吸附特性的影响[J].化工学报,2016,67(4):1467-1474.Yao Ting,Duan Yufeng,Zhu Chun,et al.Effects of temperature and oxygen content on Hg0oxidation and adsorption by rice husk char impregnated with NH4Br[J].CIESC Journal,2016,67(4):1467-1474(in Chinese).
[17]佘敏,段钰锋,朱纯,等.CO2/H3PO4活化与NH4Br改性稻壳焦的脱汞性能实验研究[J].东南大学学报:自然科学版,2014,44(2):321-327.She Min,DuanYufeng,Zhu Chun,et al.Experimental study on mercury adsorption performances of rice husk chars activated by CO2/H3PO4 and modified by NH4Br[J].Journal of Southeast University:Natural Science Edition,2014,44(2):321-327(in Chinese).
[18]周强,冒咏秋,段钰锋,等.溴素改性活性炭汞吸附特性研究[J].工程热物理学报,2014,35(12):2531-2534.Zhou Qiang,Mao Yongqiu,DuanYufeng,et al.Studies on mercury adsorption on bromine modified activated carbon[J].Journal of Engineering Thermophysics,2014,35(12):2531-2534(in Chinese).
[19]段钰锋,江贻满,杨立国,等.循环流化床锅炉汞排放和吸附实验研究[J].中国电机工程学报,2008,28(32):1-5.Duan Yufeng,Jiang Yiman,Yang Liguo,et al.Experimental study on mercury emission and adsorption in circulating fluidized bed boiler[J].Proceedings of the CSEE,2008,28(32):1-5(in Chinese).
[20]Tang Nian,Pan Siwei.Study on mercury emission and migration from large-scale pulverized coal fired boilers[J].Journal of Fuel Chemistry and Technology,2013,41(4):484-490.
[21]Belkin H E,Finkelman R B,ZhengBaoshan.Mercury in people's republic of China coal[J].Geological Society of America Abstractwith Programs,2005,37(7):48.
[22]姜英.我国煤中氯的分布及其分级标准[J].煤质技术,1998(5):7-8,6.Jiang Ying.Distribution of chlorine in coal and its grading standards in China[J].Coal Quality Technology,1998(5):7-8,6(in Chinese).
[23]高连芬,刘桂建,Chou Chenlin,等.中国煤中硫的地球化学研究[J].矿物岩石地球化学通报,2005,24(1):79-87.GaoLianfen,Liu Guijian,ChouChenlin,et al.The study of sulfur geochemistry in Chinese coals[J].Bulletin of Mineralogy,Petrology and Geochemistry,2005,24(1):79-87(in Chinese).
[24]Zhao Shilin,Duan Yufeng,Yao Ting,et al.Study on the mercury emission and transformation in an ultra-low emission coal-fired power plant[J].Fuel,2017,199:653-661.
[25]Li Hailong,Wu Changyu,Li Ying,et al.CeO2-TiO2catalysts for catalytic oxidation of elemental mercury in low-rank coal combustion flue gas[J].Environmental Science&Technology,2011,45(17):7394-7400.
[26]López-Antón M A,Díaz-Somoano M,Martínez-Tarazona M R.Retention of elemental mercury in fly ashes in different atmospheres[J].Energy&Fuels,2007,21(1):99-103.
[27]丁建东,陈博,刁永发,等.碳汞比对燃煤烟气中Hg脱除影响的实验研究[J].环境工程,2012,30(1):58-61.Ding Jiandong,Chen Bo,DiaoYongfa,et al.The experimental study on the influence of C/Hg ratio on removal of elemental mercury in simulated flue gas[J].Environmental Engineering,2012,30(1):58-61(in Chinese).
[28]周强,段钰锋,洪亚光,等.模拟烟气活性炭喷射脱汞实验研究[J].中国电机工程学报,2013,33(35):36-43.Zhou Qiang,DuanYufeng,Hong Yaguang,et al.Experimental study on mercury capture using activated carbon injection in simulated flue gas[J].Proceedings of the CSEE,2013,33(35):36-43(in Chinese).
[29]Lee S H,Rhim Y J,Cho S P,et al.Carbon-based novel sorbent for removing gas-phase mercury[J].Fuel,2006,85(2):219-226.
[30]Yan Naiqiang,Liu Shouheng,Chang S G,et al.Method for the study of gaseous oxidants for the oxidation of mercury gas[J].Industrial&Engineering Chemistry Research,2005,44(15):5567-5574.
[31]Li Guoliang,Wu Qingru,Wang Shuxiao,et al.The influence of flue gas components and activated carbon injection on mercury capture of municipal solid waste incineration in China[J].Chemical Engineering Journal,2017,326:561-569.
[32]高洪亮,周劲松,骆仲泱,等.SO2对模拟燃煤烟气中汞形态分布影响的实验研究[J].环境科学学报,2004,24(2):204-209.Gao Hongliang,Zhou Jinsong,LuoZhongyang,et al.Effect of sulfur dioxide on the speciation of mercury in flue gases[J].ACTA Scientiae Circumstantiae,2004,24(2):204-209(in Chinese).
[33]Li Guoliang,Wu Qingru,Wang Shuxiao,et al.The influence of flue gas components and activated carbon injection on mercury capture of municipal solid waste incineration in China[J].Chemical Engineering Journal,2017,326:561-569.
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