基于降解氯源活性的烧结过程二噁英生成抑制技术研究进展
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摘要
高效低成本减少铁矿烧结工序二噁英排放是当前钢铁企业急需解决的重大难题。氯元素作为二噁英生成的必要因素,其活性决定二噁英的生成行为。基于此,首先介绍了烧结过程二噁生成的2种机制,确立了"从头合成"是二噁英生成的主要方式;其次,系统分析烧结料层内氯元素的演化行为,明晰了Cl_2、HCl等高活性氯化物的生成机制;在此基础上,介绍了料层内生石灰、石灰石等碱性钙质熔剂和尿素、碳酸肼等含氮阻滞剂对上述高活性氯化物的降解机制及其减排二噁英效果,并对进一步强化料层内抑制二噁英生成提出了展望。本文评述可为钢铁行业减少铁矿烧结工序二噁英排放提供有效参考。
How to cost-effectively reduce dioxins emission of iron ore sintering process is a new challenge for iron and steel industry at present. The activity of Cl element is one of the major factors, which determines the formation of dioxins. In this paper, two formation mechanisms of dioxins in the sintering process were firstly discussed. It was concluded that de novo synthesis was the main path. Then, the evolution behaviors of Cl element in sintering bed were analyzed. The formation mechanisms of high activity chlorides such as Cl_2 and HCl were clarified. Moreover, the degradation mechanism of high activity chlorides and the reduction of dioxins emission by alkaline calcium fluxes in sintering mixture such as quicklime/limestone and the nitrogen-containing retarders such as urea/carbohydrazide, were discussed in detail. In addition,the development directions of inhibiting dioxins formation were proposed. This review provides an effective reference for steel industry to reduce dioxins emission in iron ore sintering process.
How to cost-effectively reduce dioxins emission of iron ore sintering process is a new challenge for iron and steel industry at present. The activity of Cl element is one of the major factors, which determines the formation of dioxins. In this paper, two formation mechanisms of dioxins in the sintering process were firstly discussed. It was concluded that de novo synthesis was the main path. Then, the evolution behaviors of Cl element in sintering bed were analyzed. The formation mechanisms of high activity chlorides such as Cl_2 and HCl were clarified. Moreover, the degradation mechanism of high activity chlorides and the reduction of dioxins emission by alkaline calcium fluxes in sintering mixture such as quicklime/limestone and the nitrogen-containing retarders such as urea/carbohydrazide, were discussed in detail. In addition,the development directions of inhibiting dioxins formation were proposed. This review provides an effective reference for steel industry to reduce dioxins emission in iron ore sintering process.
引文
[1]程琳.关注钢铁行业二噁英污染,重视烧结烟气污染物协同治理[C]//中国金属学会.第八届中国钢铁年会论文集.北京:冶金工业出版社, 2011.
[2]闫晓淼,李玉然,朱廷钰,等.钢铁烧结烟气多污染物排放及协同控制概述[J].环境工程技术学报, 2015, 5(2):85-90.
[3] Kuo Y C, Chen Yucheng, Yang Chiwei, et al. Identification the content of the windbox dust related to the formation of PCDD/Fs during the iron ore sintering process[J]. Aerosol and Air Quality Resarch, 2011, 11(4):351-359.
[4]岳昌盛,彭犇,王晟,等.除尘灰水洗对烟气颗粒物组成和二噁英的影响[J].工程科学学报, 2018, 40(10):1208-1214.
[5] Xhrouet C, Pirard C, De Pauw E. De novo synthesis of polychlorinated dibenzo-p-dioxins and dibenzofurans on fly ash from a sintering process[J]. Environmental Science&Technology, 2001, 35(8):1616-1623.
[6] Kawaguchi T, Matsumura M, Kasai E, et al. Effect of properties of solid fuel on dioxin concentration of the exhaust gas in the iron ore sintering process[J]. Tetsu-to-Hagané, 2002, 88(7):378-385.
[7] Kawaguchi T, Matsumura M, Kasai E, et al. Promoter material and inhibitor material for dioxins formation in sintering process[J]. Tetsu-to-Hagané, 2002, 88(7):370-377.
[8]苍大强,魏汝飞,张玲玲,等.钢铁工业烧结过程二噁英的产生机理与减排研究进展[J].钢铁, 2014, 49(8):1-8.
[9] Hung Paochen, Lo Weichiao, Chi K H, et al. Reduction of dioxin emission by a multi-layer reactor with bead-shaped activated carbon in simulated gas stream and real flue gas of a sinter plant[J]. Chemosphere, 2011, 82(1):72-77.
[10]李强.太钢烧结烟气二噁英减排技术应用及分析[J].环境工程, 2013, 31(4):93-96.
[11]何晓蕾,李咸伟,俞勇梅.烧结烟气减排二噁英技术的研究[J].宝钢技术, 2008(3):25-28.
[12]孟庆立,李昭祥,杨其伟,等.台湾中钢SCR触媒在烧结场脱硝与脱二噁英中的应用[J].武汉大学学报(工学版),2012, 45(6):751-756.
[13] Suzuki K, Kasai E, Aono T, et al. De novo formation characteristics of dioxins in the dry zone of an iron ore sintering bed[J]. Chemosphere, 2004, 54(1):97-104.
[14] Tuppurainen K, Halonen I, Ruokoj?rvi P, et al. Formation of PCDDs and PCDFs in municipal waste incineration and its inhibition mechanisms:a review[J]. Chemosphere, 1998, 36(7):1493-1511.
[15] Addink R, Olie K. Mechanisms of formation and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans in heterogeneous systems[J]. Environmental science&technology, 1995, 29(6):1425-1435.
[16] Kasai E, Aono T. Behavior of dioxins in the sintering process of iron ores[J]. Tetsu-to-Hagané, 2001, 87(5):228-237.
[17] Kasama S, Yamamura Y, Watanabe K. Investigation on the dioxin emission from a commercial sintering plant[J]. ISIJ International, 2006, 46(7):1014-1019.
[18] Cieplik M K, Carbonell J P, Mu?oz C, et al. On dioxin formation in iron ore sintering[J]. Environmental science&technology, 2003, 37(15):3323-3331.
[19] Ooi T C, Lu Liming. Formation and mitigation of PCDD/Fs in iron ore sintering[J]. Chemosphere, 2011, 85(3):291-9.
[20] Tan Pengfu, Neuschütz D. Study on polychlorinated dibenzop-dioxin/furan formation in iron ore sintering process[J]. Metallurgical and Materials Transactions B, 2004, 35(5):983-991.
[21]贾汉忠,宋存义,戴振中,等.烧结过程中二噁英的产生机理和控制[J].烧结球团, 2008, 33(1):25-30.
[22] Altarawneh M, Dlugogorski B Z, Kennedy E M, et al. Mechanisms for formation, chlorination, dechlorination and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs)[J]. Progress in Energy and Combustion Science, 2009, 35(3):245-274.
[23] Stieglitz L, Zwick G, Beck J, et al. Carbonaceous particles in fly ash-a source for the de-novo-synthesis of organochlorocompounds[J]. Chemosphere, 1989, 19(1-6):283-290.
[24] Stieglitz L, Eichberger M, Schleihauf J, et al. The oxidative degradation of carbon and its role in the de-novo-synthesis of organohalogen compounds in fly ash[J]. Chemosphere, 1993,27(1-3):343-350.
[25] Qian Lixin, Chun Tiejun, Long Hongming, et al. Emission reduction research and development of PCDD/Fs in the iron ore sintering[J]. Process Safety and Environmental Protection,2018, 117:82-91.
[26] Nakano M, Hosotani Y, Kasai E. Observation of behavior of dioxins and some relating elements in iron ore sintering bed by quenching pot test[J]. ISIJ international, 2005, 45(4):609%%%%%%-617.
[27] Kawaguchi T, Matsumura M. Method of sinter pot test of evaluation for dioxins formation on iron ore sintering[J]. Tetsuto-Hagané, 2002, 88(1):16-22.
[28]王梦京,吴素愫,高新华,等.铁矿石烧结行业二噁英类形成机制与排放水平[J].环境化学, 2014, 33(10):1723-1732.
[29] Wang Yafeng, Wang Linchi, Hsieh L T, et al. Effect of temperature and CaO addition on the removal of polychlorinated dibenzo-p-dioxins and dibenzofurans in fly ash from a medical waste incinerator[J]. Aerosol and Air Quality Research,2012, 12(2):191-199.
[30] Long Hongming, Li Jiaxin, Wang Ping, et al. Emission reduction of dioxin in iron ore sintering by adding urea as inhibitor[J]. Ironmaking&Steelmaking, 2013, 38(4):258-262.
[31]吴雪健,龙红明,春铁军,等.基于添加尿素的铁矿烧结过程二噁英减排技术研究[J].环境污染与防治, 2016, 38(5):61-66.
[32]谈琰,戴帆,李咸伟,等.碳酰肼对烧结过程二噁英生成的抑制作用[J].环境污染与防治, 2012, 34(5):48-53.
[33]龙红明,李家新,王平,等.尿素对减少铁矿烧结过程二噁英排放的作用机理[J].过程工程学报, 2010, 10(5):944-949.
[34]戴帆,谈琰,李咸伟,等.两种抑制剂对铁矿石烧结过程二噁英减排研究[J].中国环境科学, 2012, 32(5):822-828.
[2]闫晓淼,李玉然,朱廷钰,等.钢铁烧结烟气多污染物排放及协同控制概述[J].环境工程技术学报, 2015, 5(2):85-90.
[3] Kuo Y C, Chen Yucheng, Yang Chiwei, et al. Identification the content of the windbox dust related to the formation of PCDD/Fs during the iron ore sintering process[J]. Aerosol and Air Quality Resarch, 2011, 11(4):351-359.
[4]岳昌盛,彭犇,王晟,等.除尘灰水洗对烟气颗粒物组成和二噁英的影响[J].工程科学学报, 2018, 40(10):1208-1214.
[5] Xhrouet C, Pirard C, De Pauw E. De novo synthesis of polychlorinated dibenzo-p-dioxins and dibenzofurans on fly ash from a sintering process[J]. Environmental Science&Technology, 2001, 35(8):1616-1623.
[6] Kawaguchi T, Matsumura M, Kasai E, et al. Effect of properties of solid fuel on dioxin concentration of the exhaust gas in the iron ore sintering process[J]. Tetsu-to-Hagané, 2002, 88(7):378-385.
[7] Kawaguchi T, Matsumura M, Kasai E, et al. Promoter material and inhibitor material for dioxins formation in sintering process[J]. Tetsu-to-Hagané, 2002, 88(7):370-377.
[8]苍大强,魏汝飞,张玲玲,等.钢铁工业烧结过程二噁英的产生机理与减排研究进展[J].钢铁, 2014, 49(8):1-8.
[9] Hung Paochen, Lo Weichiao, Chi K H, et al. Reduction of dioxin emission by a multi-layer reactor with bead-shaped activated carbon in simulated gas stream and real flue gas of a sinter plant[J]. Chemosphere, 2011, 82(1):72-77.
[10]李强.太钢烧结烟气二噁英减排技术应用及分析[J].环境工程, 2013, 31(4):93-96.
[11]何晓蕾,李咸伟,俞勇梅.烧结烟气减排二噁英技术的研究[J].宝钢技术, 2008(3):25-28.
[12]孟庆立,李昭祥,杨其伟,等.台湾中钢SCR触媒在烧结场脱硝与脱二噁英中的应用[J].武汉大学学报(工学版),2012, 45(6):751-756.
[13] Suzuki K, Kasai E, Aono T, et al. De novo formation characteristics of dioxins in the dry zone of an iron ore sintering bed[J]. Chemosphere, 2004, 54(1):97-104.
[14] Tuppurainen K, Halonen I, Ruokoj?rvi P, et al. Formation of PCDDs and PCDFs in municipal waste incineration and its inhibition mechanisms:a review[J]. Chemosphere, 1998, 36(7):1493-1511.
[15] Addink R, Olie K. Mechanisms of formation and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans in heterogeneous systems[J]. Environmental science&technology, 1995, 29(6):1425-1435.
[16] Kasai E, Aono T. Behavior of dioxins in the sintering process of iron ores[J]. Tetsu-to-Hagané, 2001, 87(5):228-237.
[17] Kasama S, Yamamura Y, Watanabe K. Investigation on the dioxin emission from a commercial sintering plant[J]. ISIJ International, 2006, 46(7):1014-1019.
[18] Cieplik M K, Carbonell J P, Mu?oz C, et al. On dioxin formation in iron ore sintering[J]. Environmental science&technology, 2003, 37(15):3323-3331.
[19] Ooi T C, Lu Liming. Formation and mitigation of PCDD/Fs in iron ore sintering[J]. Chemosphere, 2011, 85(3):291-9.
[20] Tan Pengfu, Neuschütz D. Study on polychlorinated dibenzop-dioxin/furan formation in iron ore sintering process[J]. Metallurgical and Materials Transactions B, 2004, 35(5):983-991.
[21]贾汉忠,宋存义,戴振中,等.烧结过程中二噁英的产生机理和控制[J].烧结球团, 2008, 33(1):25-30.
[22] Altarawneh M, Dlugogorski B Z, Kennedy E M, et al. Mechanisms for formation, chlorination, dechlorination and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs)[J]. Progress in Energy and Combustion Science, 2009, 35(3):245-274.
[23] Stieglitz L, Zwick G, Beck J, et al. Carbonaceous particles in fly ash-a source for the de-novo-synthesis of organochlorocompounds[J]. Chemosphere, 1989, 19(1-6):283-290.
[24] Stieglitz L, Eichberger M, Schleihauf J, et al. The oxidative degradation of carbon and its role in the de-novo-synthesis of organohalogen compounds in fly ash[J]. Chemosphere, 1993,27(1-3):343-350.
[25] Qian Lixin, Chun Tiejun, Long Hongming, et al. Emission reduction research and development of PCDD/Fs in the iron ore sintering[J]. Process Safety and Environmental Protection,2018, 117:82-91.
[26] Nakano M, Hosotani Y, Kasai E. Observation of behavior of dioxins and some relating elements in iron ore sintering bed by quenching pot test[J]. ISIJ international, 2005, 45(4):609%%%%%%-617.
[27] Kawaguchi T, Matsumura M. Method of sinter pot test of evaluation for dioxins formation on iron ore sintering[J]. Tetsuto-Hagané, 2002, 88(1):16-22.
[28]王梦京,吴素愫,高新华,等.铁矿石烧结行业二噁英类形成机制与排放水平[J].环境化学, 2014, 33(10):1723-1732.
[29] Wang Yafeng, Wang Linchi, Hsieh L T, et al. Effect of temperature and CaO addition on the removal of polychlorinated dibenzo-p-dioxins and dibenzofurans in fly ash from a medical waste incinerator[J]. Aerosol and Air Quality Research,2012, 12(2):191-199.
[30] Long Hongming, Li Jiaxin, Wang Ping, et al. Emission reduction of dioxin in iron ore sintering by adding urea as inhibitor[J]. Ironmaking&Steelmaking, 2013, 38(4):258-262.
[31]吴雪健,龙红明,春铁军,等.基于添加尿素的铁矿烧结过程二噁英减排技术研究[J].环境污染与防治, 2016, 38(5):61-66.
[32]谈琰,戴帆,李咸伟,等.碳酰肼对烧结过程二噁英生成的抑制作用[J].环境污染与防治, 2012, 34(5):48-53.
[33]龙红明,李家新,王平,等.尿素对减少铁矿烧结过程二噁英排放的作用机理[J].过程工程学报, 2010, 10(5):944-949.
[34]戴帆,谈琰,李咸伟,等.两种抑制剂对铁矿石烧结过程二噁英减排研究[J].中国环境科学, 2012, 32(5):822-828.