高盐水条件下亚硫酸盐氧化特性实验研究
|
摘要
在"水十条"背景下,脱硫废水零排放已是大势所趋,利用烟气余热浓缩脱硫废水将脱硫废水减量化引起业内关注。在烟气预浓缩过程中有较少的SO_2转移至液相,产生SO_3~(2-)、HSO_3~-、SO_4~(2-)。其中亚硫酸盐性质不稳定,会影响后续处理。为探究此过程中高盐水条件下亚硫酸盐的氧化特性,通过氧化还原电位(ORP)和溶解氧联合监控,对亚硫酸盐的氧化特性进行研究。研究发现:烟气含氧量促进亚硫酸盐氧化;脱硫废水浓缩倍率同ORP值呈正相关,有利于亚硫酸盐的氧化;烟气预浓缩过程中亚硫酸盐氧化情况较好,氧化率可达94.7%,不需要进行强制氧化。此研究对烟气浓缩过程中控制结垢及减少对后续处理的不良影响具有重要的价值。
Under the background of"Water pollution control action plan",zero discharge of desulfurization wastewater has become the development trend of the era.The use of flue gas waste heat concentrated desulfurization wastewater to reduce desulfurization wastewater has attracted industry attention.During the pre-concentration of the flue gas,less SO_2is transferred to the liquid phase to produce SO_3~(2-),HSO_3~-,SO_4~(2-).The sulfite nature is unstable and subsequent treatment will be affected.To explore the oxidation characteristics of sulfite under high salt water conditions in this process,the oxidation characteristics of sulfites were studied by oxidation-reduction potential(ORP)and dissolved oxygen.The study found that flue gas oxygen content promoted sulfite oxidation.The concentration ratio of desulfurization wastewater is positively correlated with the ORP value,which is beneficial to the oxidation of sulfite.Better sulfite oxidation during pre-concentration of flue gas,the oxidation rate can reach94.7%,and no forced oxidation is required.This study is of great significance for controlling fouling during flue gas enrichment and reducing adverse effects on subsequent treatment.
Under the background of"Water pollution control action plan",zero discharge of desulfurization wastewater has become the development trend of the era.The use of flue gas waste heat concentrated desulfurization wastewater to reduce desulfurization wastewater has attracted industry attention.During the pre-concentration of the flue gas,less SO_2is transferred to the liquid phase to produce SO_3~(2-),HSO_3~-,SO_4~(2-).The sulfite nature is unstable and subsequent treatment will be affected.To explore the oxidation characteristics of sulfite under high salt water conditions in this process,the oxidation characteristics of sulfites were studied by oxidation-reduction potential(ORP)and dissolved oxygen.The study found that flue gas oxygen content promoted sulfite oxidation.The concentration ratio of desulfurization wastewater is positively correlated with the ORP value,which is beneficial to the oxidation of sulfite.Better sulfite oxidation during pre-concentration of flue gas,the oxidation rate can reach94.7%,and no forced oxidation is required.This study is of great significance for controlling fouling during flue gas enrichment and reducing adverse effects on subsequent treatment.
引文
[1]张秀云,郑继成.国内外烟气脱硫技术综述[J].电站系统工程,2010,26(4):1-2.Zhang X Y,Zheng J C.Summary of domestic and abroad FGDtechnology[J].Power System Engineering,2010,26(4):1-2.
[2]潘丹萍,郭彦鹏,黄荣廷,等.石灰石-石膏法烟气脱硫过程中细颗粒物形成特性[J].化工学报,2015,66(11):4618-4625.Pan D P,Guo Y P,Huang R T,et al.Formation of fine particles in flue gas desulphurization process using limestone-gypsum[J].CIESC Journal,2015,66(11):4618-4625.
[3]董继红,李占印,吴俊,等.燃煤电厂烟气脱硫技术综述[J].化工设计,2017,27(6):3-6.Dong J H,Li Z Y,Wu J,et al.Summary of flue gas desulfurization technology for coal-fired power plants[J].Chemical Engineering Design,2017,27(6):3-6.
[4]马双忱,杨静,张立男,等.湿法脱硫浆液的氧化控制缺陷及对策[J].化工进展,2016,35(8):2547-2552.Ma S C,Yang J,Zhang L N,et al.Defects and counter measures of slurry oxidation control in the Wet-FGD[J].Chemical Industry and Engineering Progress,2016,35(8):2547-2552.
[5]吴薇,王建中,杜慧玲,等.亚硫酸钠对铬渣水泥固化体的影响研究[J].辽宁化工,2008,37(2):89-91.Wu W,Wang J Z,Du H L,et al.Effects of Na2SO3on chromium residue cement solidified body[J].Liaoning Chemical Industry,2008,37(2):89-91.
[6]王昕,颜碧兰,刘晨,等.亚硫酸钙对水泥性能影响及其优化方法研究[J].硅酸盐通报,2010,29(6):1421-1428.Wang X,Yan B L,Liu C,et al.Effect of calcium sulfite on cement properties and its optimization method[J].Bulletin of the Chinese Ceramic Society,2010,29(6):1421-1428.
[7]杜谦,吴少华,朱群益,等.湿法烟气脱硫锰催化对亚硫酸钙氧化的影响[J].哈尔滨工业大学学报,2004,36(3):391-394.Du Q,Wu S H,Zhu Q Y,et al.Mn-catalyzed oxidation kinetics of calcium sulfite in wet FGD process[J].Journal of Harbin Institute of Technology,2004,36(3):391-394.
[8]Das P K,Anand S,Das R P.Comparative study on the catalytic influence of Cu(Ⅱ),Co(Ⅱ),Ag(Ⅰ)and Ni(Ⅱ)on oxidation of(NH4)2SO3using O2gas[J].Scandinavian Journal of Metallurgy,1995,24:152-158.
[9]Li Q,Yang Y,Wang L,et al.Mechanism and kinetics of magnesium sulfite oxidation catalyzed by multiwalled carbon nanotube[J].Applied Catalysis B Environmental,2017,203:851-858.
[10]Wang L,Wang J,Xu P,et al.Selectivity of transition metal catalysts in promoting the oxidation of solid sulfites in flue gas desulfurization[J].Applied Catalysis A General,2015,508:52-60.
[11]Lancia A,Musmarra D,Prisciandaro M,et al.Catalytic oxidation of calcium bisulfite in the wet limestone-gypsum flue gas desulfurization process[J].Chemical Engineering Science,1999,54(15/16):3019-3026.
[12]Barron C H,O'Hern H A.Reaction kinetics of sodium sulfite oxidation by the rapid-mixing method[J].Chemical Engineering Science,1966,21(5):397-404.
[13]汪黎东,赵毅,李蔷薇,等.湿法脱硫中亚硫酸盐非催化氧化本征动力学[J].化学学报,2007,65(22):2618-2622.Wang L D,Zhao Y,Li Q W,et al.Intrinsic kinetics of noncatalytic oxidation of sulfite in wet desulfurization[J].Acta Chimica Sinica,2007,65(22):2618-2622.
[14]Hjuler K,Dam-Johansen K.Wet oxidation of residual product from spray absorption of sulphur dioxide[J].Chemical Engineering Science,1994,49(24):4515-4521.
[15]杜谦,吴少华,朱群益,等.湿法烟气脱硫环境下亚硫酸钙的非催化氧化[J].化工学报,2003,54(10):1490-1493.Du Q,Wu S H,Zhu Q Y,et al.Non-catalytic oxidation kinetics of calcium sulfite in wet limestone-gypsum FGD process[J].Journal of Chemical Industry and Engineering(China),2003,54(10):1490-1493.
[16]Mo J S,Wu Z B,Cheng C J,et al.Oxidation inhibition of sulfite in dual alkali flue gas desulfurization system[J].Journal of Environmental Sciences,2007,19(2):226-231.
[17]Karatza D,Prisciandaro M,Lancia A,et al.Reaction rate of sulfite oxidation catalyzed by cuprous ions[J].Chemical Engineering Journal,2008,145(2):285-289.
[18]Brown L C,Baillod R C.Modeling and interpreting oxygen transfer data[J].Journal of the Environmental Engineering Division,1982,108(4):607-628.
[19]Whiteman W G.The two-film theory of gas absorption[J].Chemistry and Metal Engineering,1923,29(1):147-157.
[20]张东平,李乾军,刘献锋,等.湿法烟气脱硫石膏-飞灰浆液的浸出与传质特性[J].动力工程学报,2011,31(10):761-767.Zhang D P,Li Q J,Liu X F,et al.Mass transfer and leaching behavior of gypsum-fly ash slurry for wet flue gas desulphurization[J].Chinese Journal of Power Engineering,2011,31(10):761-767.
[21]B?ckstr?m H L J.The chain-reaction theory of negative catalysis[J].Journal of the American Chemical Society,1927,49(6):1460-1472.
[22]魏刚,熊蓉春,张小冬.某些物质对亚硫酸盐氧化的阻滞作用[J].水处理技术,1999,(5):277-280.Wei G,Xiong R C,Zhang X D.Blocking effect of certain substances on sulfite oxidation[J].Water Treatment Technology,1999,(5):277-280.
[23]Brown S R,Devault R F,Johnson D B.ORP as a predictor of WFGD chemistry and wastewater treatment[J].Power,2013,157(7):40-42.
[24]杜谦,吴少华,朱群益,等.石灰石/石灰湿法烟气脱硫系统的结垢问题[J].电站系统工程,2004,20(5):41-44.Du Q,Wu S H,Zhu Q Y,et al.Scaling problem of wet limestone/lime flue gas desulfurization[J].Power System Engineering,2004,20(5):41-44.
[25]Huang R L,Goh S H,Ong S H.自由基化学[M].穆光照,甘礼雅,陈敏为,译.上海:上海科技出版社,1983:69-77.Huang R L,Goh S H,Ong S H.The Chemistry of Free Radicals[M].Mu G Z,Gan L Y,Chen M W,trans.Shanghai:Shanghai Science and Technology Press,1983:69-77.
[26]Wang L D,Zhao Y,Li Q W,et al.Non-catalyzed intrinsic oxidation kinetics of sulfite in wet desulfurization process[J].Acta Chimica Sinica,2007,65(22):2618-2622.
[27]刘启旺,禾志强,陈江平,等.Fe3+离子催化与微生物代谢在烟气脱硫中的协同作用[J].环境工程,2005,23(5):42-44.Liu Q W,He Z Q,Chen J P,et al.The cooperative effect of Fe3+ion catalysis and microbial metabolism on flue gas desulfurization[J].Environmental Engineering,2005,23(5):42-44.
[28]赖庆柯,张永奎,梁斌,等.酸性Fe(Ⅲ)溶液催化氧化S(Ⅳ)的研究[J].环境科学学报,2004,24(6):1091-1097.Lai Q K,Zhang Y K,Liang B,et al.Study on catalytic oxidation of S(Ⅳ)by acidic Fe(Ⅲ)solution[J].Acta Scientiae Circumstantiae,2004,24(6):1091-1097.
[29]虞哲,张燕,姜茗馨,等.含盐度对溶解氧的影响[J].科学咨询,2014,(9):39-40.Yu Z,Zhang Y,Jiang M X,et al.Effect of salinity on dissolved oxygen[J].Scientific Consult,2014,(9):39-40.
[30]Ruen-Ngam D,Wongsuchoto P,Limpanuphap A,et al.Influence of salinity on bubble size distribution and gas-liquid mass transfer in airlift contactors[J].Chemical Engineering Journal,2008,141(1/2/3):222-232.
[2]潘丹萍,郭彦鹏,黄荣廷,等.石灰石-石膏法烟气脱硫过程中细颗粒物形成特性[J].化工学报,2015,66(11):4618-4625.Pan D P,Guo Y P,Huang R T,et al.Formation of fine particles in flue gas desulphurization process using limestone-gypsum[J].CIESC Journal,2015,66(11):4618-4625.
[3]董继红,李占印,吴俊,等.燃煤电厂烟气脱硫技术综述[J].化工设计,2017,27(6):3-6.Dong J H,Li Z Y,Wu J,et al.Summary of flue gas desulfurization technology for coal-fired power plants[J].Chemical Engineering Design,2017,27(6):3-6.
[4]马双忱,杨静,张立男,等.湿法脱硫浆液的氧化控制缺陷及对策[J].化工进展,2016,35(8):2547-2552.Ma S C,Yang J,Zhang L N,et al.Defects and counter measures of slurry oxidation control in the Wet-FGD[J].Chemical Industry and Engineering Progress,2016,35(8):2547-2552.
[5]吴薇,王建中,杜慧玲,等.亚硫酸钠对铬渣水泥固化体的影响研究[J].辽宁化工,2008,37(2):89-91.Wu W,Wang J Z,Du H L,et al.Effects of Na2SO3on chromium residue cement solidified body[J].Liaoning Chemical Industry,2008,37(2):89-91.
[6]王昕,颜碧兰,刘晨,等.亚硫酸钙对水泥性能影响及其优化方法研究[J].硅酸盐通报,2010,29(6):1421-1428.Wang X,Yan B L,Liu C,et al.Effect of calcium sulfite on cement properties and its optimization method[J].Bulletin of the Chinese Ceramic Society,2010,29(6):1421-1428.
[7]杜谦,吴少华,朱群益,等.湿法烟气脱硫锰催化对亚硫酸钙氧化的影响[J].哈尔滨工业大学学报,2004,36(3):391-394.Du Q,Wu S H,Zhu Q Y,et al.Mn-catalyzed oxidation kinetics of calcium sulfite in wet FGD process[J].Journal of Harbin Institute of Technology,2004,36(3):391-394.
[8]Das P K,Anand S,Das R P.Comparative study on the catalytic influence of Cu(Ⅱ),Co(Ⅱ),Ag(Ⅰ)and Ni(Ⅱ)on oxidation of(NH4)2SO3using O2gas[J].Scandinavian Journal of Metallurgy,1995,24:152-158.
[9]Li Q,Yang Y,Wang L,et al.Mechanism and kinetics of magnesium sulfite oxidation catalyzed by multiwalled carbon nanotube[J].Applied Catalysis B Environmental,2017,203:851-858.
[10]Wang L,Wang J,Xu P,et al.Selectivity of transition metal catalysts in promoting the oxidation of solid sulfites in flue gas desulfurization[J].Applied Catalysis A General,2015,508:52-60.
[11]Lancia A,Musmarra D,Prisciandaro M,et al.Catalytic oxidation of calcium bisulfite in the wet limestone-gypsum flue gas desulfurization process[J].Chemical Engineering Science,1999,54(15/16):3019-3026.
[12]Barron C H,O'Hern H A.Reaction kinetics of sodium sulfite oxidation by the rapid-mixing method[J].Chemical Engineering Science,1966,21(5):397-404.
[13]汪黎东,赵毅,李蔷薇,等.湿法脱硫中亚硫酸盐非催化氧化本征动力学[J].化学学报,2007,65(22):2618-2622.Wang L D,Zhao Y,Li Q W,et al.Intrinsic kinetics of noncatalytic oxidation of sulfite in wet desulfurization[J].Acta Chimica Sinica,2007,65(22):2618-2622.
[14]Hjuler K,Dam-Johansen K.Wet oxidation of residual product from spray absorption of sulphur dioxide[J].Chemical Engineering Science,1994,49(24):4515-4521.
[15]杜谦,吴少华,朱群益,等.湿法烟气脱硫环境下亚硫酸钙的非催化氧化[J].化工学报,2003,54(10):1490-1493.Du Q,Wu S H,Zhu Q Y,et al.Non-catalytic oxidation kinetics of calcium sulfite in wet limestone-gypsum FGD process[J].Journal of Chemical Industry and Engineering(China),2003,54(10):1490-1493.
[16]Mo J S,Wu Z B,Cheng C J,et al.Oxidation inhibition of sulfite in dual alkali flue gas desulfurization system[J].Journal of Environmental Sciences,2007,19(2):226-231.
[17]Karatza D,Prisciandaro M,Lancia A,et al.Reaction rate of sulfite oxidation catalyzed by cuprous ions[J].Chemical Engineering Journal,2008,145(2):285-289.
[18]Brown L C,Baillod R C.Modeling and interpreting oxygen transfer data[J].Journal of the Environmental Engineering Division,1982,108(4):607-628.
[19]Whiteman W G.The two-film theory of gas absorption[J].Chemistry and Metal Engineering,1923,29(1):147-157.
[20]张东平,李乾军,刘献锋,等.湿法烟气脱硫石膏-飞灰浆液的浸出与传质特性[J].动力工程学报,2011,31(10):761-767.Zhang D P,Li Q J,Liu X F,et al.Mass transfer and leaching behavior of gypsum-fly ash slurry for wet flue gas desulphurization[J].Chinese Journal of Power Engineering,2011,31(10):761-767.
[21]B?ckstr?m H L J.The chain-reaction theory of negative catalysis[J].Journal of the American Chemical Society,1927,49(6):1460-1472.
[22]魏刚,熊蓉春,张小冬.某些物质对亚硫酸盐氧化的阻滞作用[J].水处理技术,1999,(5):277-280.Wei G,Xiong R C,Zhang X D.Blocking effect of certain substances on sulfite oxidation[J].Water Treatment Technology,1999,(5):277-280.
[23]Brown S R,Devault R F,Johnson D B.ORP as a predictor of WFGD chemistry and wastewater treatment[J].Power,2013,157(7):40-42.
[24]杜谦,吴少华,朱群益,等.石灰石/石灰湿法烟气脱硫系统的结垢问题[J].电站系统工程,2004,20(5):41-44.Du Q,Wu S H,Zhu Q Y,et al.Scaling problem of wet limestone/lime flue gas desulfurization[J].Power System Engineering,2004,20(5):41-44.
[25]Huang R L,Goh S H,Ong S H.自由基化学[M].穆光照,甘礼雅,陈敏为,译.上海:上海科技出版社,1983:69-77.Huang R L,Goh S H,Ong S H.The Chemistry of Free Radicals[M].Mu G Z,Gan L Y,Chen M W,trans.Shanghai:Shanghai Science and Technology Press,1983:69-77.
[26]Wang L D,Zhao Y,Li Q W,et al.Non-catalyzed intrinsic oxidation kinetics of sulfite in wet desulfurization process[J].Acta Chimica Sinica,2007,65(22):2618-2622.
[27]刘启旺,禾志强,陈江平,等.Fe3+离子催化与微生物代谢在烟气脱硫中的协同作用[J].环境工程,2005,23(5):42-44.Liu Q W,He Z Q,Chen J P,et al.The cooperative effect of Fe3+ion catalysis and microbial metabolism on flue gas desulfurization[J].Environmental Engineering,2005,23(5):42-44.
[28]赖庆柯,张永奎,梁斌,等.酸性Fe(Ⅲ)溶液催化氧化S(Ⅳ)的研究[J].环境科学学报,2004,24(6):1091-1097.Lai Q K,Zhang Y K,Liang B,et al.Study on catalytic oxidation of S(Ⅳ)by acidic Fe(Ⅲ)solution[J].Acta Scientiae Circumstantiae,2004,24(6):1091-1097.
[29]虞哲,张燕,姜茗馨,等.含盐度对溶解氧的影响[J].科学咨询,2014,(9):39-40.Yu Z,Zhang Y,Jiang M X,et al.Effect of salinity on dissolved oxygen[J].Scientific Consult,2014,(9):39-40.
[30]Ruen-Ngam D,Wongsuchoto P,Limpanuphap A,et al.Influence of salinity on bubble size distribution and gas-liquid mass transfer in airlift contactors[J].Chemical Engineering Journal,2008,141(1/2/3):222-232.