基于石灰石法脱硫浆液的K_2S_2O_8氧化Hg~0性能
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摘要
利用改进的Hg~0液相氧化反应器,考察脱硫浆液pH、K2S2O8浓度、金属离子浓度、入口烟气Hg~0和SO2质量浓度对氧化Hg~0性能的影响。研究结果表明:低pH有利于K2S2O8高效氧化Hg~0,p H在5.0左右时,Hg~0氧化效率能维持在83%以上。K2S2O8浓度在5 mmol/L时,Hg~0氧化效率高于90%并呈现很好的运行稳定性。Mn2+,Ag+或Co2+的存在均可提高Hg~0氧化性能,但提高K2S2O8浓度至5 mmol/L也能达同等效果。Hg~0氧化效率随浆液Fe3+浓度的增加先增加后趋于稳定,当Fe3+浓度增至2.0mmol/L以上时,Hg~0氧化效率再次增加;Mg2+的存在反而使Hg~0性能有所降低。Hg~0氧化效率随烟气SO2质量浓度的升高先增加后逐渐下降,最高可达85.57%,且SO2的存在增强了系统Hg~0氧化的稳定性。
The effects of slurry pH, K2 S2 O8 concentration, metallic ion concentration, inlet flue gas Hg~0 and SO2 mass concentration on Hg~0 oxidation were studied based on the modified liquid reactor. The results show that low value of slurry pH is propitious to oxidize Hg~0, and the oxidation efficiency can maintain above 83% when the value of pH keeps around 5.0. The oxidation efficiency of Hg~0 can be higher than 90% and keeps stable steadily when K2 S2 O8 concentration reaches 5 mmol/L. The existence of Mn2+, Ag+ or Co2+ can improve the Hg~0 oxidation capability while it can acquire the same outcome through increasing the K2 S2 O8 concentration to 5 mmol/L. With the increase of Fe3+ concentration, the Hg~0 oxidation efficiency rises firstly, then becomes steady, but the efficiency rises again when the Fe3+ concentration is higher than 2.0 mmol/L. The existence of Mg2+ does not enhance the Hg~0 oxidation but weakens the oxidation capability. Hg~0 oxidation efficiency rises firstly and then descends gradually, and the highest efficiency can reach 85.57% with the increase of flue gas SO2 mass concentration. The existence of SO2 can enhance the stabilization of the system about Hg~0 oxidation.
The effects of slurry pH, K2 S2 O8 concentration, metallic ion concentration, inlet flue gas Hg~0 and SO2 mass concentration on Hg~0 oxidation were studied based on the modified liquid reactor. The results show that low value of slurry pH is propitious to oxidize Hg~0, and the oxidation efficiency can maintain above 83% when the value of pH keeps around 5.0. The oxidation efficiency of Hg~0 can be higher than 90% and keeps stable steadily when K2 S2 O8 concentration reaches 5 mmol/L. The existence of Mn2+, Ag+ or Co2+ can improve the Hg~0 oxidation capability while it can acquire the same outcome through increasing the K2 S2 O8 concentration to 5 mmol/L. With the increase of Fe3+ concentration, the Hg~0 oxidation efficiency rises firstly, then becomes steady, but the efficiency rises again when the Fe3+ concentration is higher than 2.0 mmol/L. The existence of Mg2+ does not enhance the Hg~0 oxidation but weakens the oxidation capability. Hg~0 oxidation efficiency rises firstly and then descends gradually, and the highest efficiency can reach 85.57% with the increase of flue gas SO2 mass concentration. The existence of SO2 can enhance the stabilization of the system about Hg~0 oxidation.
引文
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[18]HEIDELB,HILBERM,SCHEFFKNECHTG.Impactofadditives for enhanced sulfur dioxide removal on re-emissions ofmercury in wet flue gas desulfurization[J]. Applied Energy, 2014,114:485-491.
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[20]CHENGChinmin,CAOYan,KAIZhang.Co-effectsofsulfurdioxideloadandoxidationaironmercuryre-emissioninforced-oxidationlimestonefluegasdesulfurizationwetscrubber[J]. Fuel, 2013, 106:505-511.
[21]TAOYe,ZHUOYuqun,ZHANGLiang.Impactoffluegasspeciesandtemperatureonmercuryoxidation[J].TsinghuaScience and Technology, 2010, 15(4):418-425.
[22]MA Yongpeng, QU Zan, XU Haomiao. Investigation on mercuryremovalmethodfromfluegasinthepresenceofsulfurdioxide[J]. Journal of Hazardous Materials, 2014, 279:289-295.
[2]中国环境保护部.国家重金属污染综合防治“十二五”规划[EB/OL].[2011-02-19]. http://www.zhb.gov.cn.ChinaEnvironmentalProtectionDepartment.Comprehensivepreventionandcontrolofheavymetalpollutioninthestate“Twelfth Five Year Plan”[EB/OL].[2011-02-19]. http://www.zhb.gov.cn.
[3]中国环境保护部.《汞污染防治技术政策编制说明》征求意见稿[EB/OL].[2013-12-08]. http://www.zhb.gov.cn/gkml/hbb/bgth/201301/t20130123_245431.htm.ChinaEnvironmentalProtectionDepartment.Draftoftechnicalpolicy for prevention and control of mercury pollution[EB/OL].[2013-12-08].http://www.zhb.gov.cn/gkml/hbb/bgth/201301/t20130123_245431.htm.
[4]梁大镁.湿法脱硫系统协同脱除汞的实验研究[D].武汉:华中科技大学煤燃烧国家重点实验室, 2011:27-35.LIANGDamei.Experimentalstudyofmercuryremovalwithwetfluegasdesulfurizationsystem[D].Wuhan:HuazhongUniversity of Science and Technology. State Key Laboratory ofCoal Combustion, 2011:27-35.
[5]武成利.燃煤烟气中汞再析出及抑制研究[D].淮南:安徽理工大学化学工程学院, 2010:75-112.WUChengli.Studyonthere-emissionandsuppressionofmercuryinthefluegas[D].Huainan:AnhuiUniversityofScience and Technology. School of Chemical Engineering, 2010:75-112.
[6]王岳军.气相零价汞催化氧化及二价汞液相吸收、还原过程研究[D].杭州:浙江大学环境与资源学院, 2011:32-62.WANGYuejun.Catalyticoxidationofgas-phaseelementalmercuryandbivalentmercuryaqueousabsorption-reductionbehaviorstudy[D].Hangzhou:ZhejiangUniversity.CollegeofEnvironmental and Resource, 2011:32-62.
[7]陈传敏,张建华,俞立.湿法烟气脱硫浆液中汞再释放特性研究[J].中国电机工程学报, 2011, 31(5):48-51.CHENChuanmin,ZHANGJianhua,YULi.Studyonthecharacteristicsofmercuryreemissionfromwetfluegasdesulfurizationsolution[J].ProceedingsoftheCSEE,2011,31(5):48-51.
[8]SUNMingyang,LOUZimo,CHENGGuanghuan.Processmigrationandtransformationofmercuryinsimulatedwetfluegas desulfurization slurry system[J]. Fuel, 2015, 140:136-142.
[9]WANGYunjun,DUANYufeng,YANGLiguo.Experimentalstudy on mercury transformation and removal in coal-fired boilerflue gases[J]. Fuel Processing Technology, 2009, 90:643-651.
[10]田立江,张甜甜,王艳芳,等.脱硫浆液钙基组分对K2S2O8氧化Hg0的影响[J].中国矿业大学学报, 2016, 45(4):779-784.TIANLijiang,ZHANGTiantian,WANGYanfang,etal.ResearchonHg0oxidationbyK2S2O8basedontheCa-basedcomponentsofdesulfurizationslurry[J].JournalofChinaUniversity of Mining and Technology, 2016, 45(4):779-784.
[11]康新园.燃煤烟气脱硫脱硝一体化技术研究进展[J].洁净煤技术, 2014, 20(6):115-118.KANGXinyuan.Researchprogressofcoal-firedfluegassimultaneousdesulfurizationanddenitrification[J].CleanCoalTechnology, 2014, 20(6):115-118.
[12]刘嘉宇,刘亚明,郝雅洁,等.湿法脱硫塔内脱硫浆液运动特性[J].中南大学学报(自然科学版), 2016, 47(1):330-337.LIUJiayu,LIUYaming,HAOYajie,etal.Motioncharacteristicsofgypsumslurryinwet-typedesulphurizationtower[J].JournalofCentralSouthUniversity(ScienceandTechnology), 2016, 47(1):330-337.
[13]YE Zhuang, PAVLISH J H, LENTZ N B. Mercury measurementandcontrolinaCO2-enrichedfluegas[J].InternationalJournalof Greenhouse Gas Control, 2011, 5(S1):S136-S142.
[14]FARRS,HEIDELB,HILBERM,etal.Influenceoffluegascomponents on mercury removal and retention in dual loop fluegas desulfurization[J]. Energy and Fuels, 2015, 29:4418-4427.
[15]BAWNCEH,MARGERISOND.Moleculardissociationprocessesinsolution.Part4:therateofdecompositionofpersulphate ion and its catalysis by metal ions[J]. Transactions ofthe Faraday Society, 1955, 51:925-934.
[16]睢辉,张梦泽,董勇,等.燃煤烟气中单质汞吸附与氧化机理研究进展[J].化工进展, 2014, 33(6):1582-1588.SUIHui,ZHANGMengze,DONGYong,etal.Researchprogressofadsorptionandoxidationmechanismofelementalmercuryfromcoal-firedfluegas[J].ChemicalIndustryandEngineering Progress, 2014, 33(6):1582-1588.
[17]WUHui,ZHANGBi,QIUYong,etal.Experimentalstudyonmercurymigrationacrosswetfluegasdesulfurizationslurryunderoxy-coalcombustionatmosphere[J].Fuel,2016,181:1184-1190.
[18]HEIDELB,HILBERM,SCHEFFKNECHTG.Impactofadditives for enhanced sulfur dioxide removal on re-emissions ofmercury in wet flue gas desulfurization[J]. Applied Energy, 2014,114:485-491.
[19]SUNMingyang,HOUJiaai,CHENGGuanghuan.Therelationship between speciation and release ability of mercury influegasdesulfurization(FGD)gypsum[J].Fuel,2014,125:66-72.
[20]CHENGChinmin,CAOYan,KAIZhang.Co-effectsofsulfurdioxideloadandoxidationaironmercuryre-emissioninforced-oxidationlimestonefluegasdesulfurizationwetscrubber[J]. Fuel, 2013, 106:505-511.
[21]TAOYe,ZHUOYuqun,ZHANGLiang.Impactoffluegasspeciesandtemperatureonmercuryoxidation[J].TsinghuaScience and Technology, 2010, 15(4):418-425.
[22]MA Yongpeng, QU Zan, XU Haomiao. Investigation on mercuryremovalmethodfromfluegasinthepresenceofsulfurdioxide[J]. Journal of Hazardous Materials, 2014, 279:289-295.