铁离子液相催化氧化协同脱硫脱硝
|
摘要
在铁法脱硫的基础上,利用Fe(Ⅲ)离子可以催化氧化NO_x与SO_2溶于液相中形成的S(IV)化合物发生反应的特性,在鼓泡反应器中进行了铁离子液相催化氧化协同脱除烟气中SO_2和NO_x的实验研究,考察了吸收液pH值、温度、烟气中SO_2和NO_x的浓度比等因素对SO_2和NO_x脱除效率的影响。结果表明:实验条件下影响因素的改变并未对SO_2脱除效率产生影响,其脱除效率一直维持在95%以上;对NO_x的脱除效率影响较大,吸收液pH值在3.0左右时,NO_x脱除效率最高,其脱除率可达62%;温度和烟气中SO_2和NO_x的浓度比的增大都会在一定程度上提高NO_x的脱除效率。仅当吸收液温度增大到50℃以后,溶液中Fe(Ⅲ)离子水解生成絮凝状沉淀时,NO_x的脱除效率开始下降;另外,SO_2和NO_x的浓度比大于2.3∶1时,即可满足NO_x脱除的需要。
On the basis of iron( Ⅲ) ions catalyzed oxidation of sulfur( IV) compounds,a experiment of synergetic removing SO_2 and NO_x by iron-aqueous catalytic oxidation was carried out in a bubble column. Some factors of effects,including pH value of absorbing solution,temperature and the ratio of SO_2/ NO_x concentration in flue gas on removal efficiency of NO_x ,were investigated. Results show that factors change did not affect the SO_2 removal efficiency,its removal efficiency maintained at more than 95%,but had an considerable influence on NO_x removal efficiency. On the one hand,the best NO_x removal rate was 62% at the pH value around 3. 0. On the other hand,the removal rate of NO_x was positive correlation with the temperature and the ratio of SO_2/ NO_x concentration in a certain extent. Only when the absorption liquid temperature increased to 50 ℃,the solution of iron( Ⅲ) generated flocculation precipitation,NO_x removal efficiency began to decline. Besides,the ratio of SO_2 and NO_x concentration was greater than 2. 3 that can meet the need of NO_x removal.
On the basis of iron( Ⅲ) ions catalyzed oxidation of sulfur( IV) compounds,a experiment of synergetic removing SO_2 and NO_x by iron-aqueous catalytic oxidation was carried out in a bubble column. Some factors of effects,including pH value of absorbing solution,temperature and the ratio of SO_2/ NO_x concentration in flue gas on removal efficiency of NO_x ,were investigated. Results show that factors change did not affect the SO_2 removal efficiency,its removal efficiency maintained at more than 95%,but had an considerable influence on NO_x removal efficiency. On the one hand,the best NO_x removal rate was 62% at the pH value around 3. 0. On the other hand,the removal rate of NO_x was positive correlation with the temperature and the ratio of SO_2/ NO_x concentration in a certain extent. Only when the absorption liquid temperature increased to 50 ℃,the solution of iron( Ⅲ) generated flocculation precipitation,NO_x removal efficiency began to decline. Besides,the ratio of SO_2 and NO_x concentration was greater than 2. 3 that can meet the need of NO_x removal.
引文
[1]李金玉,闫静,宋光武,等.北京市工业锅炉脱硝系统运行状况分析.环境科学与管理,2012,37(8):120-124Li Jinyu,Yan Jing,Song Guangwu,et al.Operation condition of denitrification system of Beijing heating boilers.Environmental Science and Management,2012,37(8):120-124(in Chinese)
[2]薛永杰,李雄浩,韩旭,等.烟气脱硫副产物资源化利用现状与发展方向.电力环境保护,2009,25(4):47-49Xue Yongjie,Li Xionghao,Han Xu,et al.Application status quo and development for resource utilization of flue gas desulfurization byproduct.Electric Power Environmental Protection,2009,25(4):47-49(in Chinese)
[3]赵毅,郝润龙,齐萌,等.同时脱硫脱硝脱汞技术研究概述.中国电力,2013,46(10):155-158Zhao Yi,Hao Runlong,Qi Meng,et al.Overview of simultaneous desulfurization,denitrification and demercuration technologies.Electric Power,2013,46(10):155-158(in Chinese)
[4]Littlejohn D.,Hu K.Y.,Chang S.G.Kinetics of the reaction of nitric oxide with sulfite and bisulfite ions in aqueous solution.Inorganic Chemistry,1986,25(18):3131-3135
[5]Mendiara S.N.,Ghibaudi E.,Perissinotti L.J.,et al.Free radicals and diradicals in the reaction between nitrous acid and bisulfite in acid aqueous media.The Journal of Physical Chemistry,1992,96(20):8089-8091
[6]邢有权.从烟道气中除去SO2和NOx的LBL Pho-SNOX过程.国外环境科学技术,1993(4):59-65Xing Youquan.The process of LBL Pho-SNOX for remove SO2and NO from flue gas.The Abroad of Environmental Science and Technology,1993(4):59-65(in Chinese)
[7]Wang Li,Zhao Weirong,Wu Zhongbiao.Simultaneous absorption of NO and SO2by FeIIEDTA combined with Na2SO3solution.Chemical Engineering Journal,2007,132(1-3):227-232
[8]Nelli C.H.,Rochelle G.T.Simultaneous sulfur dioxide and nitrogen dioxide removal by calcium hydroxide and calcium silicate solids.Journal of the Air&Waste Management Association,1998,48(9):819-828
[9]Kustin K.,Taub I.A.,Weinstock E.A kinetic study of the formation of the ferrous-nitric oxide complex.Inorganic Chemistry,1995,5(6):1079-1082
[10]黎宝林,李明玉,刘海豪,等.络合-氧化-还原耦合方法脱除烟气中NOx的研究.中国环境科学,2014,34(5):1125-1130Li Baolin,Li Mingyu,Liu Haihao,et al.Removal of NOxin flue gas by complexation-oxidation-reduction coupling method.China Environmental Science,2014,34(5):1125-1130(in Chinese)
[11]Brandt C.,Van Eldik R.Transition metal-catalyzed oxidation of sulfur(IV)oxides.Atmospheric-relevant processes and mechanisms.Chemical Reviews,1995,95(1):119-190
[12]马双忱,赵毅,郑福玲,等.液相催化氧化脱除烟道气中SO2和NOx的研究.中国环境科学,2001,21(1):33-37Ma Shuangchen,Zhao Yi,Zheng Fuling,et al.Study on reducing SO2/NOxin flue gas by aqueous catalytic oxidation.China Environmental Science,2001,21(1):33-37(in Chinese)
[13]Lepentsiotis V.,Prinsloo F.F.,Eldik R.V.,et al.Influence of mixed sulfur-nitrogen oxides on the redox kinetics of iron ions in aqueous solution.Journal of the Chemical Society,Dalton Transactions,1996(10):2135-2141
[14]Colchev N.,Reddy K.B.,Van Eldik R.The synergistic effect of manganese(II)in the sulfite-induced autoxidation of metal ions and complexes in aqueous solution.Atmospheric Environment.Part A.General Topics,1992,26(13):2295-2300
[15]Brandt C.,Van Eldik R.Kinetics and mechanism of the iron(III)-catalyzed autoxidation of sulfur(IV)oxides in aqueous solution.The influence of p H,medium and aging.Transition Metal Chemistry,1998,23(6):667-675
[16]Martins C.R.,Cabral Neto C.A.,ALVES J.J.F.,et al.Oxidation of sulfur(IV)by oxygen in aqueous solution:Role of some metal ions.Journal of the Brazilian Chemical Society,1999,10(6):453-458
[17]赵庆庆,金晶,高新勇等.湿法烟气脱硫装置中铁锰离子对SO2催化氧化作用的试验研究.热能动力工程,2015,30(2):248-252Zhao Qingqing,Jin Jing,Gao Xinyong,et al.Experimental study of the action of iron and manganese ions in a wetmethod flue gas desulfurization device on the catalytic oxidization of SO2.Journal of Engineering for Thermal Energy and Power,2015,30(2):248-252(in Chinese)
[18]Karatza D.,Prisciandaro M.,Lancia A.,et al.Calcium bisulfite oxidation in the flue gas desulfurization process catalyzed by iron and manganese ions.Industrial&Engineering Chemistry Research,2004,43(16):4876-4884
[19]刘兆斌,童华,王京刚.锌、铁等离子对氧化锌烟气脱硫工艺中亚硫酸锌氧化的影响.环境工程学报,2014,8(1):290-293Liu Zhaobin,Tong Hua,Wang Jinggang.Effects of Zn and Fe ion on zinc sulfite oxidation in flue gas desulfurization with zinc oxide.Chinese Journal of Environmental Engineering,2014,8(1):290-293(in Chinese)
[20]Betterton E.A.On the p H-dependent formation constants of iron(III)-sulfur(IV)transient complexes.Journal of Atmospheric Chemistry,1993,17(4):307-324
[21]Stefánsson A.Iron(III)hydrolysis and solubility at 25℃.Environmental Science&Technology,2007,41(17):6117-6123
[22]Millero F.J.,Hershey J.P.,Johnson G.,et al.The solubility of SO2and the dissociation of H2SO3in Na Cl solutions.Journal of Atmospheric Chemistry,1989,8(4):377-389
[23]Ali M.,Saha S.K.,Banerjee P.Oxidation of sulfite and thiosulfate by the Cobalt(III)complex of dipicolinate in aqueous medium.Bulletin of the Chemical Society of Japan,1991,64(8):2497-2501
[2]薛永杰,李雄浩,韩旭,等.烟气脱硫副产物资源化利用现状与发展方向.电力环境保护,2009,25(4):47-49Xue Yongjie,Li Xionghao,Han Xu,et al.Application status quo and development for resource utilization of flue gas desulfurization byproduct.Electric Power Environmental Protection,2009,25(4):47-49(in Chinese)
[3]赵毅,郝润龙,齐萌,等.同时脱硫脱硝脱汞技术研究概述.中国电力,2013,46(10):155-158Zhao Yi,Hao Runlong,Qi Meng,et al.Overview of simultaneous desulfurization,denitrification and demercuration technologies.Electric Power,2013,46(10):155-158(in Chinese)
[4]Littlejohn D.,Hu K.Y.,Chang S.G.Kinetics of the reaction of nitric oxide with sulfite and bisulfite ions in aqueous solution.Inorganic Chemistry,1986,25(18):3131-3135
[5]Mendiara S.N.,Ghibaudi E.,Perissinotti L.J.,et al.Free radicals and diradicals in the reaction between nitrous acid and bisulfite in acid aqueous media.The Journal of Physical Chemistry,1992,96(20):8089-8091
[6]邢有权.从烟道气中除去SO2和NOx的LBL Pho-SNOX过程.国外环境科学技术,1993(4):59-65Xing Youquan.The process of LBL Pho-SNOX for remove SO2and NO from flue gas.The Abroad of Environmental Science and Technology,1993(4):59-65(in Chinese)
[7]Wang Li,Zhao Weirong,Wu Zhongbiao.Simultaneous absorption of NO and SO2by FeIIEDTA combined with Na2SO3solution.Chemical Engineering Journal,2007,132(1-3):227-232
[8]Nelli C.H.,Rochelle G.T.Simultaneous sulfur dioxide and nitrogen dioxide removal by calcium hydroxide and calcium silicate solids.Journal of the Air&Waste Management Association,1998,48(9):819-828
[9]Kustin K.,Taub I.A.,Weinstock E.A kinetic study of the formation of the ferrous-nitric oxide complex.Inorganic Chemistry,1995,5(6):1079-1082
[10]黎宝林,李明玉,刘海豪,等.络合-氧化-还原耦合方法脱除烟气中NOx的研究.中国环境科学,2014,34(5):1125-1130Li Baolin,Li Mingyu,Liu Haihao,et al.Removal of NOxin flue gas by complexation-oxidation-reduction coupling method.China Environmental Science,2014,34(5):1125-1130(in Chinese)
[11]Brandt C.,Van Eldik R.Transition metal-catalyzed oxidation of sulfur(IV)oxides.Atmospheric-relevant processes and mechanisms.Chemical Reviews,1995,95(1):119-190
[12]马双忱,赵毅,郑福玲,等.液相催化氧化脱除烟道气中SO2和NOx的研究.中国环境科学,2001,21(1):33-37Ma Shuangchen,Zhao Yi,Zheng Fuling,et al.Study on reducing SO2/NOxin flue gas by aqueous catalytic oxidation.China Environmental Science,2001,21(1):33-37(in Chinese)
[13]Lepentsiotis V.,Prinsloo F.F.,Eldik R.V.,et al.Influence of mixed sulfur-nitrogen oxides on the redox kinetics of iron ions in aqueous solution.Journal of the Chemical Society,Dalton Transactions,1996(10):2135-2141
[14]Colchev N.,Reddy K.B.,Van Eldik R.The synergistic effect of manganese(II)in the sulfite-induced autoxidation of metal ions and complexes in aqueous solution.Atmospheric Environment.Part A.General Topics,1992,26(13):2295-2300
[15]Brandt C.,Van Eldik R.Kinetics and mechanism of the iron(III)-catalyzed autoxidation of sulfur(IV)oxides in aqueous solution.The influence of p H,medium and aging.Transition Metal Chemistry,1998,23(6):667-675
[16]Martins C.R.,Cabral Neto C.A.,ALVES J.J.F.,et al.Oxidation of sulfur(IV)by oxygen in aqueous solution:Role of some metal ions.Journal of the Brazilian Chemical Society,1999,10(6):453-458
[17]赵庆庆,金晶,高新勇等.湿法烟气脱硫装置中铁锰离子对SO2催化氧化作用的试验研究.热能动力工程,2015,30(2):248-252Zhao Qingqing,Jin Jing,Gao Xinyong,et al.Experimental study of the action of iron and manganese ions in a wetmethod flue gas desulfurization device on the catalytic oxidization of SO2.Journal of Engineering for Thermal Energy and Power,2015,30(2):248-252(in Chinese)
[18]Karatza D.,Prisciandaro M.,Lancia A.,et al.Calcium bisulfite oxidation in the flue gas desulfurization process catalyzed by iron and manganese ions.Industrial&Engineering Chemistry Research,2004,43(16):4876-4884
[19]刘兆斌,童华,王京刚.锌、铁等离子对氧化锌烟气脱硫工艺中亚硫酸锌氧化的影响.环境工程学报,2014,8(1):290-293Liu Zhaobin,Tong Hua,Wang Jinggang.Effects of Zn and Fe ion on zinc sulfite oxidation in flue gas desulfurization with zinc oxide.Chinese Journal of Environmental Engineering,2014,8(1):290-293(in Chinese)
[20]Betterton E.A.On the p H-dependent formation constants of iron(III)-sulfur(IV)transient complexes.Journal of Atmospheric Chemistry,1993,17(4):307-324
[21]Stefánsson A.Iron(III)hydrolysis and solubility at 25℃.Environmental Science&Technology,2007,41(17):6117-6123
[22]Millero F.J.,Hershey J.P.,Johnson G.,et al.The solubility of SO2and the dissociation of H2SO3in Na Cl solutions.Journal of Atmospheric Chemistry,1989,8(4):377-389
[23]Ali M.,Saha S.K.,Banerjee P.Oxidation of sulfite and thiosulfate by the Cobalt(III)complex of dipicolinate in aqueous medium.Bulletin of the Chemical Society of Japan,1991,64(8):2497-2501