在双碱法烟气脱硫系统的亚硫酸盐氧化的抑制作用

OXIDATIONINHIBITIONOFSULFITEINDUALALKALIFLUEGASDESULFURIZATIONSYSTEMABSTRACTALABORATORYSCALEWELLMIXEDTHERMOSTATICREACTORWITHCONTINUOUSLYBLASTINGAIRWASUSEDTOINVESTIGATETHEOXIDATIONINHIBITIONOFSULFITEINDUALALKALIFLUEGASDESULFURIZATIONFGDSYSTEMTHEEFFECTSOFOPERATINGPARAMETERSSUCHASPHVALUEANDCATALYSTCONCENTRATIONONTHEOXIDATIONWERESTUDIEDSODIUMTHIOSULFATEWASUSEDINTHESYSTEM,ANDWASFOUNDTHATITSIGNIFICANTLYINHABITEDTHESULFITEOXIDATIONINTHEABSENCEOFCATALYST,SODIUMTHIOSULFATEAT1267MMOL/LHADANINISIBITIONEFFICIENCYOFAPPROXIMATELY98WHILEINTHEPRESENCEOFCATALYST,SODIUMTHIOSULFATEAT2672MMOL/LHADANINHIBITIONEFFICIENCYLESSTHAN850THEOXIDATIONREACTIONORDEROFSULFITEINTHESODIUMTHIOSULFATEWASDETERMINEDTOBE190AND055INTHEABSENCEANDPRESENCEOFTHECATALYST,RESPECTIVELYAPPARENTACTIVATIONENERGYOFOXIDATIONINHIBITIONWASCALCULATEDTOBE539KJ/MOLPILOTTESTSSHOWEDTHATTHECONSUMPTIONRATEOFTHIOSULFATEAGREEDWELLWITHTHELABORATORYSCALEEXPERIMENTALRESULTSKEYWORDSDUALALKALISODIUMSULFITEOXIDATIONINHIBITIONSODIUMTHIOSULFATEINTRODUCTIONCSIVISTHECONCENTRATIONOFS,CMISTHECONCENTRATIONOFCATALYSTANDC02ISOXYGENPRESSURETHEPARAMETERSSUCHASOXYGENCONCENTRATIONANDSULFITECONCENTRATIONWERECONFIRMEDCONSISTENTLYBOTHINHOMOGENEOUSANDHETEROGENEOUSSYSTEMBYTHEORETICALANDEXPERIMENTALSTUDIESHOWEVER,THEREAREFEWWORKHAVEBEENDONEONTHEEFFECTOFTHECATALYSTCONCENTRATIONANDPHVALUEONOXIDATIONRATESODIUMTHIOSULFATEWASDEMONSTRATEDTOBEANEFFECTIVEOXIDATIONINHIBITOR,WHICHISWIDELYUSEDININDUSTRYPILOTTESTSWEREMADEONSODIUMTHIOSULFATEOXIDATIONINHABITATIONINTHESODIUMSULFITE/BISULFITESOLUTIONFORALIMESTONEREGENERATEDDUALALKALISYSTEMCHANGANDKAPLAN,1983THESUCCESSFULAPPLICATIONHADBEENPERFORMEDINAMAGNESIUMENHANCEDLIMESYSTEMATTHEPHILIPSSTATIONOFDUQUESNELIGHTTVASHAWNEESTATIONTESTEDSODIUMTHIOSULFATEINAPROTOTYPESPRAYTOWERITWASFOUNDTHATONLY100MG/RN3OFTHIOSULFATEWASNEEDEDTOREDUCETHESULFATESATURATIONANDSCALEFREEOPERATIONCHANGANDBRNA,1986CHANGANDBMA1986FOUNDTHATTHECONCENTRATIONOFTHIOSULFATEIONFROM100TO200MG/RN3COULDEFFECTIVELYAVOIDSCALINGANDITWASALSOCONCLUDEDTHATTHECONSUMPTIONRATETOACHIEVETHEOXIDATIONINHIBITIONEFFECTSHOULDBEINTHERANGEOFITO3MMOLNA2S203/MOLSO2ABSORBEDBOTHINLIMEANDLIMESTONESYSTEMSLATERSULFURINSTEADOFSODIUMTHIOSULFATEASANINHIBITORHASBEENSTUDIEDFORCOMMERCIALPURPOSEOWENSETA,1988THIOSULFATEWASPRODUCEDBYSULFURREACTINGWITHTHESULFITEBECAUSEOFTHELOWSOLUBILITYOFSULFUR,THECONVERSIONOFTHESULFURTOTHIOSULFATEWASFBIVERYHIGHPHENOLICCOMPOUNDSWEREALSOKNOWNASDUETOTHEOXIDATIONREACTIONBETWEENTHESULFITE/BISULFITEANDDISSOLVEDOXYGEN,SULFATECANBEPRODUCEDBOTHINTHELIMEANDLIMESTONEFLUEGASDESULFURIZATIONFGDSYSTEMINTHEPRESENTOFCALCIUMION,SULFATEINTHEABSORBENTLIQUIDWILLLEADTOTHEPRODUCTIONOFCALCIUMSULFATE,WHICHISTHEMAINCOMPONENTOFSCALINGANDFOULINGACCORDINGLY,THERELIABILITYOFTHEFGDSYSTEMWILLBELOWEREDDURINGREGENERATIONSTEPOFDUALALKALIFGDSYSTEM,SODIUMSULFATEWILLREACTWITHLIMEANDPRODUCECALCIUMSULFATEANDSODIUMHYDROXIDEANDBECAUSEOFTHEHIGHHARDNESSOFCALCIUMSULFATE,THEABSORBENTLIQUIDNEEDTOELIMINATETHEHARDNESSINASECONDSEDIMENTATIONTANKBYSODIUMCARBONATEONEREASONFORTHEPROBLEMISTHATTHEBOILERSTENDTOBEOPERATEDATHIGHERLEVELSOFEXCESSAIRANOTHERONEISTHATTHEHEAVYMETALSINABSORBENTSUCHASMANGANESE,COBALT,ANDCOPPERCATALYZETHEOXIDATIONRATESOOXIDATIONINHIBITIONISNECESSARYFORDUALALKALIFGDSYSTEMTOIMPROVETHERELIABILITYUNCATALYZEDOXIDATIONANDCATALYZEDOXIDATIONWEREINVESTIGATEDBOTHINHOMOGENOUSANDHETEROGENEOUSSYSTEMINAREVIEWLINEKANDVACEK,1981ITISFOUNDTHATTHEOXIDATIONRATEOFSULFITECANBEEXPRESSEDASRKC52CC公式有误WHERE,RISTHEOXIDATIONRATE,KISTHEREACTIONCONSTANT,PREOJECTSUPPORTEDBYTHEHITECHRESEARCHANDDEVELOPMENTPROGRAM863OFCHINANO2001AA642030L,THEKEYRESEARCHPROJECTOFZHEJIANGPROVINCENO2004C23028ANDNEWCENTURYEXCELLENTSCHOLARPROGRAMOFMINISTRYOFEDUCATIONOFTHEPEOPLESREPUBLICOFCHINANONCET040549CORRESPONDINGAUTHOREMAILZBWUZJUEDUCNFIGISKETCHOFTHEEXPERIMENTALAPPARATUSEFFECTIVEINHIBITORSFORTHEOXIDATIONINBOTHOFORGANICANDINORGANIC,BUTITISHARMFULTOHUMANHEALTHANDHOSTILETOTHEENVIRONMENTTHEYACTASCHAINBREAKERSBYRECEIVINGEXCESSENERGYFROMA“HOTCHAINMOLECULE”JEUANDALYEN,1933,ORBYSCAVENGINGFREERADICALS,TRANSIENTSINACHAINREACTIONHUIEANDNETA,1985WANDAETAT2003EXPLAINEDTHEINHIBITIONMECHANISMDURINGTHEPROCESSOFTHEREMOVALOFQUININEITWASKNOWNFROMTHEIRWORKTHATTHEREACTIONTRANSIENTACTEDASACATALYST,WHICHTRANSFORMEDSULFITEINTOSULFONATESINTHEREACTIONMOSTOFTHESEWORKSFOCUSEDONTHEOXIDATIONANDOXIDATIONINHIBITIONBYTHIOSULFATEINTHELIMEORLIMESTONESLURRYORINHIGHDILUTEDSULFITESOLUTIONSINTHISPAPER,WESTUDIEDTHEINFLUENCEOFCATALYSTCONCENTRATIONANDPHVALUEONSULFITEOXIDATION,SULFITEOXIDATIONINHIBITIONBYTHIOSULFATE,THEOPTIMALPARAMETERSANDTHECONSUMPTIONRATEOFTHEINHIBITORINCONCENTRATEDSOLUTIONSTHETEMPERATURETWASCONTROLLEDAT2555CACOMPLEXPHELECTRODECONNECTEDTOPHVALUEMEASUREMENTINSTRUMENTPHS25WASUSEDTHEEXPERIMENTSWERECARRIEDOUTBOTHINTHEABSENCEOFCATALYSTANDINTHEPRESENCEOFMANGANESESULFATETHECONCENTRATIONOFCATALYSTVARIEDINTHERANGEOFL0X1065X103MOL/LTHECONCENTRATIONOF5MMOL/LWASAHIGHLEVELFORCATALYST,ANDITWASMEASUREDINTHEWASTEWATEROFDESULFURIZATIONSYSTEMINHANGZHOUBANSHANPOWERPLANTTHEPHVALUEWASCONTROLLEDBELOW100ITWASFOUNDTHATWHENPHWASHIGHERTHAN102,THECATALYSISWILLCHANGEFROMACCELERATIONTODECELERATIONOFTHEOXIDATIONRATELIMANDHAMRICK,1984THECONCENTRATIONSOFSODIUMSULFITEANDSODIUMTHIOSULFATEINTHECONCENTRATEDSOLUTIONWEREMEASUREDANALYTICALLYBYMEANSOFANOXIDATIONREDUCTIONTITRATIONASTHEFOLLOWING1ACERTAINAMOUNTSOFSULFITESOLUTIONANDTHIOSULFATEWASADDEDTOANEXCESSOFIODINEIODIDESTANDARDSOLUTIONWHICHWASTHENBACKTITRATEDWITH001MOL/LOFSODIUMTHIOSULFATEINARSENOUSACIDSOLUTIONWITHSTARCHASANINDICATOR2THECONCENTRATIONOFTHIOSULFATEWASANALYZEDDIRECTLYBYFORMALDEHYDEFIXATIONOFSULFITEFOLLOWEDBYIODINEIODIDEOXIDATIONANDBACKTITRATIONOFEXCESSIODINEWITHARSENOUSACIDTHECONCENTRATIONOFSULFITEWASESTIMATEDASTHEDIFFERENCEBETWEENRESULTSOBTAINEDFROM1AND21MATERIALSANDMETHODSTHEOXIDATIONINHIBITIONRATEOFSODIUMSULFITEWASDETERMINEDWITHALABORATORYSCALEAPPARATUSINFIGLITCONSISTSOFATHERMOSTATICSTIRREDREACTORWITHFEEDINGANDDISCHARGINGOFGASPHASETHELIQUIDPHASEWASKEPTINTHEREACTORTHEREACTOR,MADEOFPYREXGLASS,ISAFIVENECKEDFLASK,THECENTERNECKFORSTIRRING,ONEPAIRNECKSFORGASINANDOUT,ONEFORPHVALUEMEASUREMENTANDTHELASTFORSAMPLINGTHEVOLUMEOFTHEREACTORIS1000CM3ANAIRCOMPRESSORBLASTSAIRINTOTHEREACTORCONTINUOUSLYSINCETHESULFITEOXIDATIONWASVERYSENSITIVETOTHEIMPURITIES,DISTILLEDWATERANDANALYTICALGRADEOFCHEMICALSWEREUSEDFORALLEXPERIMENTSEVENTHOUGHITWASTREATEDCAREFULLY,THEREWASSTILLALITTLEDIFFERENCEINTHEINITIALCONCENTRATIONOFSULFITESOLUTIONAPPROXIMATELY25MMOLFLTHESODIUMIONCONCENTRATIONWASABOUT50MMOLFL,WHICHWASVERYLITTLECOMPAREDWITHTHESODIUMIONCONCENTRATIONMORETHANIMOL/LOFTYPICALDUALALKALIFGDSYSTEMINUSWANGETAL,1983PIKE,1982DUALALKALIFGDSYSTEMINCHINAISDIFFERENTFROMOTHERCOUNTRIES,ITONLYHASSINGLELOOPWHILEOTHERSHAVETWOLOOPSYANETAL,1998LIANDTAN,1999WUETAT,2001THESODIUMSULFITESOLUTIONWITHSODIUMTHIOSULFATEINTHEFLASKWASRAPIDLYANDCONTINUOUSLYSTIRREDBYAMOTORANDBUBBLEAERATEDBYTHEAIRCOMPRESSORASSOONASTHESTIRANDAERATIONBEGAN,THEOXIDATIONSTARTEDANDTHEPHVALUEBEGANTODECREASETHEROTATINGSPEEDNWAS350R/MINANDTHEAIRCOMPRESSORBLASTVOLUMERATEGWAS180L/H,2RESULTSANDDISCUSSIONOXIDATIONINHIBITIONOFSULFITEWASINVESTIGATEDBYADUSTINGTHEPARAMETERSSUCHASPHVALUE,CATALYSTCONCENTRATION,ADDINGINHIBITORINTHEDUALALKALIFGDSYSTEMTHEMECHANISMOFTHEOXIDATIONINHIBITIONANDTHEOPERATINGPARAMETERSOFINHIBITIONPROCESSWEREFOCUSEDONFURTHERMORE,THEEXPERIMENTALCONSUMPTIONRATEOFINHIBITORWASALSOINVESTIGATEDANDCOMPAREDWITHTHERESULTOFPILOTTEST21EFFECTOFPHVALUEFIG2SHOWSTHEOXIDATIONPROCESSAT25CWITHOUTCATALYSTANDCONTROLLINGTHEPHVALUEINFIG2ITWASFOUNDTHATTHEPLOTOFTHESULFITECONCENTRATIONVSTIMEWASASTRAIGHTLINEWITHASLOPEOF1538MMOL/LHBETWEEN0MMTO80MILL,WHICHMEANTTHATTHEOXIDATIONRATEWASCONSTANTWITHAPHVALUERANGEFROM64TO89FIG3GIVESTHERESULTSOFAFURTHERSTUDYONTHEPHEFFECTWHENPHWASMAINTAINEDCONSTANTLYUSING01MOL/LNAOHOR01MOL/LHC1THERESULTSSHOWEDTHATTHEUNCATALYZEDOXIDATIONRATEINCREASEDFROM7956TO1790MMOL/LHWITHANINCREASEINPHVALUEFROM30TO60WHILEITREMAINEDNEARLYCONSTANTWITHPHVALUEKEPTWITHIN68,ONLYDECREASEDABOUT30FROM1790TO1736MMOL/LHCOMPAREDWITHTHEDATAINLITERATURE,THERESULTSATLOWPHVALUEARESIMILARTOTHOSEOFTHEFORMERRESEARCHERSWILKINSONETAT1993FOUNDTHATTHEREACTIONRATEDECREASEDABRUPTLYATLOWPHVALUE4559,WHILETHEOXIDATIONRATEBECAMECONSTANTWITHPHVALUEABOVE59VIDALANDOLLERO2003FOUNDTHATINTHERANGEOF2060OFPHVALUE,THEOXIDATIONRATEWASPROPORTIONALTOCH69符号错误）INSEAWATERHOWEVER,INTHERANGE60100THEOXIDATIONRATEBEGANTODECREASERAPIDLYWITHPHVALUEBECAUSEOFTHECONVERSIONOFACCELERATIONTODECELERATIONEFFECTOFTHECATALYSTLIMANDHANRNCK,1984BENGTSSONANDBJERLE1975FOUNDTHATTHECOBALTCATALYZEDOXIDATIONRATEWASAPPROXIMATELYPROPORTIONALTOC00符号错误）WITHINTHEPHVALUERANGEOF6085INDILUTESOLUTIONTHEDIFFERENCEOFTHERELATIONBETWEENTHEOXIDATIONRATEANDPHVALUEWASTHEPHVALUERANGETHEPOSSIBLEIMPACTFACTORSMIGHTBEINVOLVEDINSYSTEMTEMPERATURE,SULFITECONCENTRATION,CATALYSTSPECIES,ANDMASSTRANSFERCONDITIONSTHEOXIDATIONRATEINCREASEDWITHPHVALUECANBEEXPLAINEDBYTHERELATIONBETWEENTHESULFITEANDBISULFITEASFOLLOWSSO3HHS03符号错误）THEOXIDATIONRATEISINDEPENDENTOFTHEBISULFITECONCENTRATIONINHOMOGENEOUSSYSTEMATLOWPHVALUE,THEMAINSIVEXISTSASHS03符号错误）,THECONCENTRATIONOFS032符号错误）ISLOWANDTHEOXIDATIONRATEOFSULFITEBECOMESLOWINCREASINGTHEPHVALUEOFTHESOLUTIONSGIVESARISEOFTHECONCENTRATIONOFS032符号错误）ANDIMPROVESTHEOXIDATIONRATEOFSULFITEHOWEVER,WHENPHVALUEISHIGHERTHAN6,THESULFITECONCENTRATIONISSOHIGHTHATAFURTHERINCREASEINTHESULFITECONCENTRATIONCONTRIBUTESNOMOREEFFECTONTHEOXIDATIONRATEINORDERTOAVOIDTHEOXIDATIONANDIMPROVETHEDESULFURIZATIONRATE,THEPHVALUESHOULDBECONTROLLEDATALOWERVALUE少图22EFFECTOFCATALYSTTHECATALYZEDOXIDATIONREACTIONOFSULFITETOSULFATEWASREGARDEDASAFREERADICALCHAINMECHANISMBYSEVERALINVESTIGATORSINLINEKSREVIEWLINEKANDVACEK,19812S032MN2MNS03345S0302S0S032_,S052公式错误SO5S03S052_S0322S042STEP4ISRAPIDANDDOESNOTLIMITTHEOVERALLREACTIONRATEBECAUSEOFTHEZEROORDEROFTHEREACTIONWITHRESPECTTOOXYGENINHOMOGENEOUSSYSTEMSTHETERMINATIONOCCURSPRIMARILYBYTHECOMBINATION18SOSOPOLYTHIONATES公式错误THESULFITECONCENTRATIONINDUALALKALIFGDSYSTEMISRELATIVELYHIGHERCOMPAREDWITHTHATINTHEFORMERRESEARCH,ABOUT25MMOL/LTHERESULTSINFIG4SHOWTHATTHEOXIDATIONRATEISNEARLYCONSTANT,1628MINOL/LH,INTHERANGEFROM10TO25MMOL/LOFSU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EEXPERIMENTALRESULTS,THECONSUMPTIONRATEOFTHIOSULFATEIS400AND3000MMOLNA2S2O3/MOLNA2SO3INTHEABSENCEOFCATALYSTANDINTHEPRESENCEOFCATALYST,RESPECTIVELY130135140145150155160300305310315320325330335340IOFIG8TEMPERATUREDEPENDENCYOFTHEZEROORDERREACTIONRATECONSTANTATPH6OANDCJNJITORL27XLO2MOL/LINCONCENTRATEDSOLUTION16EA131V112IBIIA_OXIDATIONINHIBITIONOFSULFITEINDUALALKALIFLUEGASDESULFURIZATIONSYSTEM231NO2RSTSCRUBBERTESTSHOWSTHATTHESODIUMTHIOSULFATECANENHANCETHEDESULFURIZATIONEFFICIENCYINDUALALKALIFGDSYSTEMANDTHECONSUMPTIONRATEOFTHIOSULFATEISINWELLAGREEMENTWITHEXPERIMENTALRESULTSAPPROXIMATELY3000MMOLNA2S2O3/MOLSO2INTHEPRESENCEOFCATALYSTCESSJCHONGQINENVIRONMENTALSCIENCE,2154952LIMPK,HAMRICKGTH,1984P11DEPENDENTCATALYSTINHIBITORCONVERSIONOFMANGANESEIIINTHEAUTOXIDATIONOFSULFITEJJ,JPHYSCHEM,8811331136LINEKVVACEKV,1981CHEMICALENGINEERINGUSEOFCATALYZEDSULFITEOXIDATIONKINETICSFORTHEDETERMINATIONOFMASSTRANSFERCHARACTERISTICSOFGASLIQUIDCONTACTORSJLCHEMENGSCI,3617471768LINEKVMAYRHOFEROVAJ,1970THEKINETICSOFOXIDATIONOFAQUEOUSSODIUMSULPHITESOLUTIONJCHEMENGSCI,25787800OWENSDR,MAILERG,MOSERRETAL,1988ADDINGSULFURTOFGDABSORBERREDUCESSCALE,UPSPERFORMANCELJPOWER,51517PIKEDE,1982PROCESSFORREMOVALOFSULFURDIOXIDEFROMGASSTREAMSPLUNITEDSTATESPATENT,4,313,924ROLLAE,CHAKRABARTICL,1982KINETICSOFDECOMPOSITIONOFTETRATHIONATE,TRITHIONATE,ANDTHIOSULFATEINALKALINEMEDIAJENVIRONSCITECHNOL,16852857VIDALBF,OLLEROP,2003AKINETICSTUDYOFTHEOXIDATIONOFSIVINSEAWATERJJENVIRONSCITECHNOL,3527922796WANDAPB,TADEUSZB,MAREKU,2003SYNERGYINTHEAUTOXIDATIONOFSIVINHIBITEDBYPHENOLICCOMPOUNDSJJAMCHEMSOC,10717421748WANGKH,BIOCHINIRI,LEGATSKILK,1983SODIUMLIMESTONEDOUBLEALKALIFLUEGASDESULFURIZATIONMETHODPJUNITEDSTATESPATENT,4,410,500WILKINSONPM,DOLDERSUMB,CRAMERSPHETA,1993THEKINETICOFUNCATALYZEDSODIUMSULFITEOXIDATIONJLCHEMENGSCI,485933941WUZB,LIUY,TANTE,2001STUDYOFDUALALKALIFGDPROCESSJ1ACTASCIENTIAECIRCUMSTANTIAE,215534537YANNQ,SHIY,WUZBETA,1998PROCESSOFDUALALKALIFGDINAROTATINGSTREAMTRAYSCRUBBERJLENVIRONMENTALSCIENCE,1957274REFERENCESBENGTSSONS,BJERLEI,1975CATALYTICOXIDATIONOFSULFITEINDILUTEDAQUEOUSSOLUTIONSJ1CHEMENGSCI,3014291435CHANGJCS,KAPLANN,1983PILOTEVALUATIONOFLIMESTONEREGENERATEDDUALALKALIPROCESSCLINPROCEEDINGSOFEIGHTHSYMPOSIUMOFFLUEGASDESULFURIZATION,NEWORLEANS,LA,NOVEMBERCHANGJCS,BRNATG,1986PILOTTESTINGOFSODIUMTHIOSULFATEJENVIRONMENTALPROGRESS,54225233DANCKWERTSPV,1970GASLIQUIDREACTIONSMNEWYORKMCGRAWHILLDEWAALKJA,OKESONJC,1966THEOXIDATIONOFAQUEOUSSODIUMSULPHITESOLUTIONSIJLCHEMENGSCI,21559572DINEGARRH,SEMELLIERH,VICTORKLM,1991KINETICSOFTHEACIDDECOMPOSITIONOFSODIUMTHIOSULFATEINDILUTESOLUTIONSJJAMCHEMSOC7320502054HUIERE,NTAP,1985ONEELECTRONREDOXREACTIONSINAQUEOUSSOLUTIONSOFSULFITEWITHHYDROQUINONEANDOTHERHYDROXYPHENOLSJJPHYSCHEM,8939183921JEUKK,ALYENHN,1933ACOMPARISONOFORGANICINHIBITORSINCHAINREACTIONSJLJAMCHEMSOC55575588LANCIAA,MUSMARRAD,PRISCIANDAROMETAL,1999CATALYTICOXIDATIONOFCALCIUMBISULFITEINTHEWETLIMESTONEGYPSUMFLUEGASDESULFURIZATIONPROCESSJCHEMENGSCI,5430193026LIYP,TANTE,1999BASICSTUDYONDU