用硅钨酸催化臭氧氧化降解聚乙烯醇模拟废水
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摘要
以臭氧氧化不易生物降解的聚乙烯醇(PVA)模拟废水,考察典型杂多酸(HPA)对臭氧氧化的催化作用.先在3种典型杂多酸中筛选出对臭氧氧化PVA具有催化效果的硅钨酸(HSiW),考察反应时间、臭氧质量浓度、体系pH值、催化剂用量和反应温度对PVA去除率的影响,再通过正交实验确定去除PVA的最佳条件.结果表明:体系的pH值对PVA去除率影响最大,催化剂用量的影响最小;HSiW催化臭氧氧化体系去除PVA的最佳条件为ρ(O_3)=25mg/L,反应温度30℃,体系pH=8.3,催化剂用量250mg/L,在该条件下降解反应5 min,PVA去除率即可达98.3%;HSiW未改变臭氧氧化降解PVA的基本途径,HSiW可促进臭氧分解,生成更多的HO·,并可催化臭氧与PVA的直接反应.
The catalytic effect of typical heteropolyacids(HPA)on ozonation was investigated by ozonation of polyvinyl alcohol(PVA)which was not easily biodegradable.First,silicotungstic acid(HSiW)with catalytic effect on ozonation PVA was screened out among three typical heteropoly acids,and the effects of reaction time,ozone mass concentration,pH value of the system,catalyst dosage and reaction temperature on removal rate of PVA were investigated.Then,the optimal conditions for removing PVA were determined by orthogonal experiments.The results show that the pH value of the system has the greatest influence on the removal rate of PVA,and the effect of catalyst dosage is small.The optimal conditions for the removal of PVA by the silicotungstic acid catalytic ozonation system are:ρ(O_3)=25 mg/L,reaction temperature of 30℃,pH=8.3,catalyst dosage of 250 mg/L.Under this condition,the degradation experiment was carried out for 5 min,and the removal rate of PVA can reach 98.3%,the addition of silicotungstic acid does not change the basic pathway for ozonation to degrade PVA,the silicotungstic acid can promote ozone decomposition to generate more HO·,and can also catalyze the direct reaction between ozone and PVA.
The catalytic effect of typical heteropolyacids(HPA)on ozonation was investigated by ozonation of polyvinyl alcohol(PVA)which was not easily biodegradable.First,silicotungstic acid(HSiW)with catalytic effect on ozonation PVA was screened out among three typical heteropoly acids,and the effects of reaction time,ozone mass concentration,pH value of the system,catalyst dosage and reaction temperature on removal rate of PVA were investigated.Then,the optimal conditions for removing PVA were determined by orthogonal experiments.The results show that the pH value of the system has the greatest influence on the removal rate of PVA,and the effect of catalyst dosage is small.The optimal conditions for the removal of PVA by the silicotungstic acid catalytic ozonation system are:ρ(O_3)=25 mg/L,reaction temperature of 30℃,pH=8.3,catalyst dosage of 250 mg/L.Under this condition,the degradation experiment was carried out for 5 min,and the removal rate of PVA can reach 98.3%,the addition of silicotungstic acid does not change the basic pathway for ozonation to degrade PVA,the silicotungstic acid can promote ozone decomposition to generate more HO·,and can also catalyze the direct reaction between ozone and PVA.
引文
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[14]SUN Weihua,CHEN Lujun,ZHANG Yongming,et al.Synergistic Effect of Ozonation and Ionizing Radiation for PVA Decomposition[J].Journal of Environmental Sciences,2015,34(1):63-67.
[15]ARSLAN-ALATON I.Novel Catalytic Photochemical and Hydrothermal Treatment Processes for Acid Dye Wastewater[J].Journal of Environmental Science and Health,Part A:Toxic/Hazardous Substances&Environmental Engineering,2003,38(8):1615-1627.
[16]MENA E,REY A,ACEDO B,et al.On Ozone-Photocatalysis Synergism in Black-Light Induced Reactions:Oxidizing Species Production in Photocatalytic Ozonation versus Heterogeneous Photocatalysis[J].Chemical Engineering Journal,2012,204/205/206:131-140.
[17]ZHU Zhirong,TIAN Ruan,RHODES C.A Study of the Decomposition Behaviour of 12-Tungstophosphate Heteropolyacid in Solution[J].Canadian Journal of Chemistry,2003,81(10):1044-1050.
[18]ESPLUGAS S,GIMENEZ J,CONTRERAS S,et al.Comparison of Different Advanced Oxidation Processes for Phenol Degradation[J].Water Research,2002,36(4):1034-1042.
[19]荆国华,周作明,李艳,等.臭氧氧化及其他强化技术协同降解聚乙烯醇[J].环境工程学报,2008,2(12):1594-1598.(JING Guohuan,ZHOU Zuoming,LI Yan,et al.Degradation of Polyvinyl Alcohol with Ozonation and Other Synergic Oxidation[J].Chinese Journal of Environmental Engineering,2008,2(12):1594-1598.)
[20]高孝恢,肖慎修,陈天朗,等.杂多化合物的合成与结构性能研究的近代发展[J].化学研究与应用,1999,11(4):22-29.(GAO Xiaohui,XIAO Shenxiu,CHEN Tianlang,et al.Recent Development on Study of Synthesis,Structure and Properties of Heteropoly Compounds[J].Chemical Research and Application,1999,11(4):22-29.)
[21]SHIN H S,YOO K S,KWON J C,et al.Degradation Mechanism of PVA and Hec by Ozonation[J].Environmental Technology,1999,20(3):325-330.
[22]KOZHEVNIKOV I V.Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions[J].Chemical Reviews,1998,98(1):171-198.
[23]MAHMOODI N M.Photocatalytic Ozonation of Dyes Using Copper Ferrite Nanoparticle Prepared by Co-precipitation Method[J].Desalination,2011,279(1/2/3):332-337.
[24]周康民,王璇.正交试验在实验设计中的应用[J].江苏地质,1998,22(4):213-215.(ZHOU Kangmin,WANGXuan.Application of Orthogonal Test in the Geological Experimental Design[J].Jiangsu Geology,1998,22(4):213-215.)
[25]YE Bei,LI Yue,CHEN Zhou,et al.Degradation of Polyvinyl Alcohol(PVA)by UV/Chlorine Oxidation:Radical Roles,Influencing Factors,and Degradation Pathway[J].Water Research,2017,124(1):381-387.
[2]XIAO Yutang,XU Shuangshuang,LI Zhihua.Degradation of Polyvinyl-Alcohol Wastewater by Fenton’s Reagent:Condition Optimization and Enhanced Biodegradability[J].Journal of Central South University of Technology,2011,18(1):96-100.
[3]董德明,曹珍,闫征楚,等.臭氧-超声联用处理聚乙烯醇废水[J].吉林大学学报(地球科学版),2016,46(4):1191-1198.(DONG Deming,CAO Zhen,YAN Zhengchu,et al.Treatment Research of Polyvinyl Alcohol Wastewater by Ozone/Ultrasound Oxidation Process[J].Journal of Jilin University(Earth Science Edition),2016,46(4):1191-1198.)
[4]XIAO Jiadong,XIE Yongbing,CAO Hongbin.Organic Pollutants Removal in Wastewater by Heterogeneous Photocatalytic Ozonation[J].Chemosphere,2015,121:1-17.
[5]MEHRJOUEI M,MüLLER S,MOLLER D.A Review on Photocatalytic Ozonation Used for the Treatment of Water and Wastewater[J].Chemical Engineering Journal,2015,263(1):209-219.
[6]KASPRZYK-HORDERN B,ZIOLEK M,NAWROCKI J.Catalytic Ozonation and Methods of Enhancing Molecular Ozone Reactions in Water Treatment[J].Applied Catalysis B:Environmental,2003,46(4):639-669.
[7]SATHICQ A G,ROMANELLI G P,PALERMO V,et al.Heterocyclic Amine Salts of Keggin Heteropolyacids Used as Catalyst for the Selective Oxidation of Sulfides to Sulfoxides[J].Tetrahedron Letters,2008,49(9):1441-1444.
[8]向诗银,杨水金.杂多酸(盐)催化氧化反应研究进展[J].精细石油化工进展,2017,18(3):30-33.(XIANG Shiyin,YANG Shuijin.Progress of Research on Heteropoly Acids or Polyoxometalates Catalyzed Oxidation Reaction[J].Advances in Fine Petrochemicals,2017,18(3):30-33.)
[9]REZVANI M A,HARUTYUNYAN R,HERAVI M.Aerobic Oxidation of Thioles to Disulfides Catalyzed by Mixed-Addenda Vanadium(Ⅴ)Substituted Heteropolyacids[J].Synthesis and Reactivity in Inorganic and MetalOrganic Chemistry,2012,42(9):1232-1236.
[10]DIZAJI A K,MORTAHEB H R,MOKHTARANI B.Extractive-Catalytic Oxidative Desulfurization with Graphene Oxide-Based Heteropolyacid Catalysts:Investigation of Affective Parameters and Kinetic Modeling[J].Catalysis,2019,149(1):259-271.
[11]李保山,戴仲娟.铜取代杂多金属氧酸盐对催化裂化柴油氧化脱硫的催化作用[J].石油炼制与化工,2008,39(9):17-20.(LI Baoshan,DAI Zhongjuan.Catalysis of Copper Substituted Heteropolyoxometalate in Oxidative Desulphurization of Catalytic Cracked Diesel Fuel[J].Petroleum Processing and Petrochemicals,2008,39(9):17-20.)
[12]王丽娟,高美玲,周业剑,等.Zn-杂多酸合物催化降解碱性藏花红实验研究[J].环境科学与技术,2008,31(5):119-121.(WANG Lijuan,GAO Meiling,ZHOU Yejian,et al.Experimental Study on Degradation of Safranine T by Zn1.5PW12O40Catalyzed Dioxygen Oxidation[J].Environmental Science&Technology,2008,31(5):119-121.)
[13]赵燕.多金属氧酸盐催化臭氧氧化油品深度脱硫的研究[D].济南:山东大学,2013.(ZHAO Yan.Study on Deep Desulfurization of Ozonated Oil by Polyoxometalate[D].Jinan:Shandong University,2013.)
[14]SUN Weihua,CHEN Lujun,ZHANG Yongming,et al.Synergistic Effect of Ozonation and Ionizing Radiation for PVA Decomposition[J].Journal of Environmental Sciences,2015,34(1):63-67.
[15]ARSLAN-ALATON I.Novel Catalytic Photochemical and Hydrothermal Treatment Processes for Acid Dye Wastewater[J].Journal of Environmental Science and Health,Part A:Toxic/Hazardous Substances&Environmental Engineering,2003,38(8):1615-1627.
[16]MENA E,REY A,ACEDO B,et al.On Ozone-Photocatalysis Synergism in Black-Light Induced Reactions:Oxidizing Species Production in Photocatalytic Ozonation versus Heterogeneous Photocatalysis[J].Chemical Engineering Journal,2012,204/205/206:131-140.
[17]ZHU Zhirong,TIAN Ruan,RHODES C.A Study of the Decomposition Behaviour of 12-Tungstophosphate Heteropolyacid in Solution[J].Canadian Journal of Chemistry,2003,81(10):1044-1050.
[18]ESPLUGAS S,GIMENEZ J,CONTRERAS S,et al.Comparison of Different Advanced Oxidation Processes for Phenol Degradation[J].Water Research,2002,36(4):1034-1042.
[19]荆国华,周作明,李艳,等.臭氧氧化及其他强化技术协同降解聚乙烯醇[J].环境工程学报,2008,2(12):1594-1598.(JING Guohuan,ZHOU Zuoming,LI Yan,et al.Degradation of Polyvinyl Alcohol with Ozonation and Other Synergic Oxidation[J].Chinese Journal of Environmental Engineering,2008,2(12):1594-1598.)
[20]高孝恢,肖慎修,陈天朗,等.杂多化合物的合成与结构性能研究的近代发展[J].化学研究与应用,1999,11(4):22-29.(GAO Xiaohui,XIAO Shenxiu,CHEN Tianlang,et al.Recent Development on Study of Synthesis,Structure and Properties of Heteropoly Compounds[J].Chemical Research and Application,1999,11(4):22-29.)
[21]SHIN H S,YOO K S,KWON J C,et al.Degradation Mechanism of PVA and Hec by Ozonation[J].Environmental Technology,1999,20(3):325-330.
[22]KOZHEVNIKOV I V.Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions[J].Chemical Reviews,1998,98(1):171-198.
[23]MAHMOODI N M.Photocatalytic Ozonation of Dyes Using Copper Ferrite Nanoparticle Prepared by Co-precipitation Method[J].Desalination,2011,279(1/2/3):332-337.
[24]周康民,王璇.正交试验在实验设计中的应用[J].江苏地质,1998,22(4):213-215.(ZHOU Kangmin,WANGXuan.Application of Orthogonal Test in the Geological Experimental Design[J].Jiangsu Geology,1998,22(4):213-215.)
[25]YE Bei,LI Yue,CHEN Zhou,et al.Degradation of Polyvinyl Alcohol(PVA)by UV/Chlorine Oxidation:Radical Roles,Influencing Factors,and Degradation Pathway[J].Water Research,2017,124(1):381-387.