垃圾焚烧飞灰热处理过程中Zn的挥发机理研究
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摘要
试验在650～1350℃条件下探讨了温度和时间对飞灰中Zn的挥发率的影响,采用XAFs对飞灰及二次飞灰中Zn的赋存形态进行分析,运用吉布斯自由能理论推导了Zn的氯化反应途径,并开展了验证试验.结果表明:温度是影响Zn挥发的主要因素,其挥发趋势随温度先增加而后降低,在1000℃时挥发率达到最高,而时间对其挥发效果影响较小;Zn主要以氯化物形态挥发,从假设反应途径的吉布斯自由能理论计算及验证试验得出,热处理过程中Zn的氯化反应分两步进行,首先飞灰中氯化物与SiO_2反应生成Cl_2,而后与ZnO反应生成ZnCl_2,而小部分Cl_2可能与水蒸气反应形成HCl,再与ZnO反应生成ZnCl_2.
Under the condition of 650～1350℃, the effect of temperature and time on the volatilization rate of Zn in fly ash wasinvestigated in this experiment. XAFs were used to analyze the morphological and structuralof Zn in fly ash and secondary fly ash.The chlorination reaction pathway of Zn was deduced by using Gibbs free energy theory and the verification test was carried out. Theresults showed that the temperature was the main factor affecting on the volatilization of Zn. The volatilization trend increased firstwith temperature and then decreased. The volatilization rate reached the highest at 1000℃, while the time had little effect on itsvolatilization. Zn was mainly volatilized in the form of chloride, according to the theoretical calculation and verification test of Gibbsfree energy theory in each hypothetical reaction pathway, it was concluded that the chlorination reaction of Zn in the heat treatmentwas carried out in two steps. First, the chloride in the fly ash reacted with Si O_2 to form Cl_2, and then Zn O reacted with Cl_2 to formZn Cl_2, while a small part of Cl_2 may react with water vapor to form HCl, and then react with Zn O to form Zn Cl_2.
Under the condition of 650～1350℃, the effect of temperature and time on the volatilization rate of Zn in fly ash wasinvestigated in this experiment. XAFs were used to analyze the morphological and structuralof Zn in fly ash and secondary fly ash.The chlorination reaction pathway of Zn was deduced by using Gibbs free energy theory and the verification test was carried out. Theresults showed that the temperature was the main factor affecting on the volatilization of Zn. The volatilization trend increased firstwith temperature and then decreased. The volatilization rate reached the highest at 1000℃, while the time had little effect on itsvolatilization. Zn was mainly volatilized in the form of chloride, according to the theoretical calculation and verification test of Gibbsfree energy theory in each hypothetical reaction pathway, it was concluded that the chlorination reaction of Zn in the heat treatmentwas carried out in two steps. First, the chloride in the fly ash reacted with Si O_2 to form Cl_2, and then Zn O reacted with Cl_2 to formZn Cl_2, while a small part of Cl_2 may react with water vapor to form HCl, and then react with Zn O to form Zn Cl_2.
引文
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[2]Meawad A S,Bojinova D Y,Pelovski Y G.An overview of metals recovery from thermal power plant solid wastes[J].Waste Management,2010,30(12):2548-2559.
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[19]Fujimori T,Tanino Y,Takaoka M.Coexistence of Cu,Fe,Pb,and Zn oxides and chlorides as a determinant of chlorinated aromatics generation in municipal solid waste incinerator fly ash[J].Environmental Science&Technology,2014,48(1):85.
[20]Yu M,Tian S,Chu W,et al.Speciation of zinc in secondary fly ashes of municipal solid waste at high temperatures[J].Journal of Synchrotron Radiation,2009,16(4):528.
[21]刘敬勇,孙水裕.焚烧飞灰高温过程中重金属的挥发及其氯转化特征[J].环境科学,2012,33(9):3279-3287.Liu jingyong,Sun shuiyu.Chlorination transformation and volatilization of heavy metals in fly ash from the incineration during the disposal process with higher temperature[J].Environmental Science,2012,33(9):3279-3287.
[22]Chan C,Jia C Q,Graydon J W,et al.The behaviour of selected heavy metals in MSW incineration electrostatic precipitator ash during roasting with chlorination agents[J].Journal of Hazardous Materials,1996,50(1):1-13.
[23]Nowak B,Pessl A,Aschenbrenner P,et al.Heavy metal removal from municipal solid waste fly ash by chlorination and thermal treatment[J].Journal of Hazardous Materials,2010,179(1-3):323.
[24]Zhang Y.Effect of chlorine on the vaporization behavior of zinc and lead during high temperature treatment of dust and fly ash[J].Transactions of the Iron&Steel Institute of Japan,2007,44(9):1457-1468.
[25]Jie Y,Sun L,Ma C,et al.Mechanism on heavy metals vaporization from municipal solid waste fly ash by Mg Cl2?6H2O[J].Waste Management,2015,49:124-130.
[26]Miwa M,Morita K.Chloride capacities of Ca O-Si O2-Al2O3(-Fe O,Mg O,Mn O)slags and their application in the incineration processes[J].Isij International,2002,42(10):1065-1070.
[27]Morita K,Hirosumi T,Sano N.Effects of aluminum,silicon,and boron on the dissolution rate of nitrogen into molten iron[J].Metallurgical&Materials Transactions B,2000,31(5):899-904.
[28]田书磊,王琪,王伟.复合添加剂对垃圾焚烧飞灰熔融固化处理的影响[J].环境卫生工程,2009,17(3):1-3.Tian Shulei,Wang Qi,Wang Wei.Effect of compound additive on melting and solidification of fly ash from waste incinerator[J].Environmental Sanitation Engineering,2009,17(3):1-3.
[29]Zhu F,Takaoka M,Shiota K,et al.Chloride chemical form in various types of fly ash[J].Environmental Science&Technology,2008,42(11):3932-3937.
[30]Cahn R W.Materials science:melting and the surface[J].Nature,1986,323(6090):668-669.
[31]Yu J,Qiao Y,Jin L,et al.Removal of toxic and alkali/alkaline earth metals during co-thermal treatment of two types of MSWI fly ashes in China[J].Waste Management,2015,46:287.
[2]Meawad A S,Bojinova D Y,Pelovski Y G.An overview of metals recovery from thermal power plant solid wastes[J].Waste Management,2010,30(12):2548-2559.
[3]Zheng L,Song J,Li C,et al.Preferential policies promote municipal solid waste(MSW)to energy in China:Current status and prospects[J].Renewable&Sustainable Energy Reviews,2014,36(C):135-148.
[4]GB16889-2008生活垃圾填埋场污染控制标准[S].GB16889-2008 Standard for Pollution Control on the Landfill Site of Municipal Solid Waste[S].
[5]王雷,金宜英,聂永丰,等.添加剂和水洗对焚烧飞灰烧结过程中重金属迁移特性的影响[J].环境科学,2009,30(4):1232-1237.Wang lei,Jin yiying,Nie yongfeng,et al.Effect of additive and washing pre-treatment on heavy metal vaporization during sintering process of MSWI fly ash[J].Chinese Journal of Environmental Science,2009,30(4):1232-1237.
[6]白晶晶,张增强,闫大海,等.水洗对焚烧飞灰中氯及重金属元素的脱除研究[J].环境工程,2012,30(2):104-108.Bai jingjing,Zhang zengqiang,Yan dahai,et al.Study on the removal of chlorine and heavy metals in incineration fly ash during water-washing process[J].Enviromental Engineering,2012,30(2):104-108.
[7]朱芬芬,高冈昌辉,大下和徹,等.焚烧飞灰预处理工艺及其无机氯盐的行为研究[J].环境科学,2013,34(6):2473-2478.Zhu fenfen,Takaoka Masaki,Oshita Kazuyuki,et al.Pretreatment technology for fly ash from mswi and the corresponding study of chloride behavior[J].Environmental Science,2013,34(6):2473-2478.
[8]胡小英,田书磊,闫大海,等.氯化剂对垃圾焚烧飞灰中重金属挥发特性的影响[J].中国环境科学,2008,28(7):614-619.Hu xiaoying,Tian shulei,Yan dahai,et al.The effect of chlorination agents on the volatilization of heavy metals in fly ash from municipal solid wasteincinerator[J].China Environmental Science,2008,28(7):614-619.
[9]Gong B,Deng Y,Yang Y,et al.Effects of microwave-assisted thermal treatment on the fate of heavy metals in MSWI fly ash[J].Energy&Fuels,2017,31(11).
[10]Liu G,Jiang X,Wang M,et al.Comparison of PCDD/F levels and profiles in fly ash samples from multiple industrial thermal sources[J].Chemosphere,2015,133(1):68-74.
[11]Chen W,Kirkelund G M,Jensen P E,et al.Comparison of different MSWI fly ash treatment processes on the thermal behavior of As,Cr,Pb and Zn in the ash[J].Waste Management,2017,24(27):21591-21600.
[12]李润东,聂永丰,王雷,等.垃圾焚烧飞灰熔融过程重金属的迁移特性实验[J].中国环境科学,2004,24(4):97-100.Li rundong,Nie yongfeng,Wang lei,et al.Migration characteristics experiment of heavy metal in the vitrification course of fly ash from municipal solidwaste incineration[J].China Environmental Science,2004,24(4):480-483.
[13]冯军会,何品晶,章骅,等.二噁英类化合物在生活垃圾焚烧飞灰中的分布[J].中国环境科学,2005,25(6):99-103.Feng junhui,He pinjing,Zhang hua,et al.Distribution of dioxins-like compounds in air pollution control residues from municipal solid waste incinerator[J].China Environmental Science,2005,25(6):99-103.
[14]Ferone C,Colangelo F,Messina F,et al.Recycling of pre-washed municipal solid waste incinerator fly ash in the manufacturing of low temperature setting geopolymer materials[J].Materials,2013,6(8):3420.
[15]Nowak B,Rocha S F,Aschenbrenner P,et al.Heavy metal removal from MSW fly ash by means of chlorination and thermal treatment:Influence of the chloride type[J].Chemical Engineering Journal,2012,179(4):178-185.
[16]Jakob A,Stucki S,Kuhn P.Evaporation of heavy metals during the heat treatment of municipal solid waste incinerator fly ash[J].Environmental Science&Technology,1995,29(9):2429-2436.
[17]田书磊.垃圾焚烧飞灰重金属热分离工艺及挥发特性研究[D].哈尔滨:哈尔滨工业大学,2007.Tian shulei.Thermal-separation process and evaporation mechanism of heavy metal from mswi fly ash[D].Harbin:Harbin Institute of Technology,2007.
[18]Chan C C,Kirk D W.Behaviour of metals under the conditions of roasting MSW incinerator fly ash with chlorinating agents[J].Journal of Hazardous Materials,1999,64(1):75-89.
[19]Fujimori T,Tanino Y,Takaoka M.Coexistence of Cu,Fe,Pb,and Zn oxides and chlorides as a determinant of chlorinated aromatics generation in municipal solid waste incinerator fly ash[J].Environmental Science&Technology,2014,48(1):85.
[20]Yu M,Tian S,Chu W,et al.Speciation of zinc in secondary fly ashes of municipal solid waste at high temperatures[J].Journal of Synchrotron Radiation,2009,16(4):528.
[21]刘敬勇,孙水裕.焚烧飞灰高温过程中重金属的挥发及其氯转化特征[J].环境科学,2012,33(9):3279-3287.Liu jingyong,Sun shuiyu.Chlorination transformation and volatilization of heavy metals in fly ash from the incineration during the disposal process with higher temperature[J].Environmental Science,2012,33(9):3279-3287.
[22]Chan C,Jia C Q,Graydon J W,et al.The behaviour of selected heavy metals in MSW incineration electrostatic precipitator ash during roasting with chlorination agents[J].Journal of Hazardous Materials,1996,50(1):1-13.
[23]Nowak B,Pessl A,Aschenbrenner P,et al.Heavy metal removal from municipal solid waste fly ash by chlorination and thermal treatment[J].Journal of Hazardous Materials,2010,179(1-3):323.
[24]Zhang Y.Effect of chlorine on the vaporization behavior of zinc and lead during high temperature treatment of dust and fly ash[J].Transactions of the Iron&Steel Institute of Japan,2007,44(9):1457-1468.
[25]Jie Y,Sun L,Ma C,et al.Mechanism on heavy metals vaporization from municipal solid waste fly ash by Mg Cl2?6H2O[J].Waste Management,2015,49:124-130.
[26]Miwa M,Morita K.Chloride capacities of Ca O-Si O2-Al2O3(-Fe O,Mg O,Mn O)slags and their application in the incineration processes[J].Isij International,2002,42(10):1065-1070.
[27]Morita K,Hirosumi T,Sano N.Effects of aluminum,silicon,and boron on the dissolution rate of nitrogen into molten iron[J].Metallurgical&Materials Transactions B,2000,31(5):899-904.
[28]田书磊,王琪,王伟.复合添加剂对垃圾焚烧飞灰熔融固化处理的影响[J].环境卫生工程,2009,17(3):1-3.Tian Shulei,Wang Qi,Wang Wei.Effect of compound additive on melting and solidification of fly ash from waste incinerator[J].Environmental Sanitation Engineering,2009,17(3):1-3.
[29]Zhu F,Takaoka M,Shiota K,et al.Chloride chemical form in various types of fly ash[J].Environmental Science&Technology,2008,42(11):3932-3937.
[30]Cahn R W.Materials science:melting and the surface[J].Nature,1986,323(6090):668-669.
[31]Yu J,Qiao Y,Jin L,et al.Removal of toxic and alkali/alkaline earth metals during co-thermal treatment of two types of MSWI fly ashes in China[J].Waste Management,2015,46:287.