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废水处理工艺设计的光解,除垢,管道与控制
废水处理工艺设计及计算第6章9-11节n目录『CONTENT』▷6-9PHOTOLYSIS光解▷6-10CHEMICALNEUTRALIZATIONSCALECONTROL&STABILIZATION化学中和水垢控制稳定性▷6-11CHEMICALSTORAGE,FEEDING,PIPING,&CONTROLSYSTEMS化学贮藏、供给、管道及控制系统n6-9PHOTOLYSISn6-91Photolysisisaprocessbywhichconstituentsarebrokendownbyexposureandabsorptionofphotonsfromalightsource.AswithAOPs,theprimaryuseofphotolysisisfortheremovaloftraceorganiccompoundsinwaterreuseapplications.Innaturalsystems,sunlightisthelightsourceforphotolysisreactions,however,inengineeredsystems,ultraviolet(UV)lampsareusedtoproducethephotonicenergy.Theeffectivenessofthephotolysisprocessdepends,inpart,onthecharacteristicsofthereclaimedwater,structureofthecompounds,designofthephotolysisreactor,anddoseandwavelengthoftheappliedlight.Thephotolysisratecanbeestimatedfromtherateatwhichthecompoundabsorbslightandthephotonicefficiencyofthereaction(quantumyield).定义n6-91光解工艺PhotolysisProcessesEngineeredphotolysisreactionsareconductedinspeciallydesignedreactorsoptimizedwithrespecttoUVdose.PhotolysisreactorsaretypicallycomprisedofastainlesssteelcolumnorpipecontainingUVlampsarrangedparalleltotheflow,perpendiculartotheflow,orinacrisscrossingpatternperpendiculartothedirectionofflow.原理Thephotonsthatareabsorbedcausetheelectronsintheouterorbitalofsomecompoundsformsanunstablecompoundthatsplitsapartorbecomesreactive.UV与O3、H2O2、Fenton联用。UV会促进H2O2产生OH·但加入H2O2会抑制某些有机物的分解n6-91FoulingthatmayoccurontheoutsideoftheUVlampprotectivequartzsleevemaybemanagedusinganautomaticcleaningsystemconsistingofacollarthatperiodicallymovesalongthelamptoremoveprecipitatesandinterceptedmatter.Whenusedinconjunctionwithreverseosmosispretreatment,thechemicalsaddedtoreducethepHforscalecontrolinthemembraneswillalsoreducethepotentialforprecipitationontheUVlamps.Photolysisreactionsarecausedbylightemissionintheultravioletrange(200to400nm).TherearethreetypesofUVlampsusedforphotolysisprocesses:(1)low-pressurelow-intensity,(2)low-pressurehigh-intensity,and(3)medium-pressurehigh-intensitylamps.Low-pressurelampsemitmuchoftheirenergyatawavelengthof254nmwhilemediumpressurelampsemitenergyatmultiple.Thetypeoflampusedandreactorconfigurationwilldependontheconstituenttoberemovedaswellasthewatermatrixandsite-specificconditions.n6-91光解所涉及基本概念:(1)紫外光吸收(2)入射能量(3)光解速率(4)电效率TheabsorptionoflightbyacompoundinwaterorotheraqueoussolutioncanbedescribedusingtheBeer-LambertLaw.Theabsorbanceofasolutionisameasureoftheamountoflightabsorbedbyconstituentsinthesolutionusingaspectrophotometerataspecifiedwavelengthandoverafixedpathlength.1紫外光吸收AbsorptionofUVLightA=absorbance,dimensionlessL=lightintensityafterpassingthroughsolutionL=lightintensityafterpassingthroughablanksoluteε=extinctioncoefficientC=concentrationoflightabsorbingsolutex=lengthoflightpathK=absorptivityTheextinctioncoefficientisafunctionofwavelengthbecauseasthewavelengthdecreasesmoreenergeticphotonsareabsorbedandtheabsorptivityofalightabsorbingcompoundincreases.n6-91不同物质的消光系数n6-91溶液中存在多种化合物的情形:使用多重波长光源的情形:canbedeterminedusingasimilarapproachsummingadsorptionofeachcompoundforeachwavelength.2入射能量EnergyInputforPhotolysisThelampoutputandreactorsizecanbeusedtoestimatetheenergyinputforthephotolysisreaction.存在问题:Theactualperformanceofaphotoreactorisexpectedtobelowerthancomputedduetolightbeingabsorbedbythereactorwallsorblockedbytheprecipitatethatformsonthelampsleeve.Whileasafetyfactorspecifictoaparticularsystemcouldbeappliedtocompensatefortheseinefficiencies,pilotstudiesareusedtoobtainmorereliabledesigncriteria.n6-913光解速率RateofPhotolysisTherateatwhichacompoundisphotolyzeddependsontherateandfrequencyofphotonabsorption.Thequantumyieldisaquantityusedtodescribethefrequencyatwhichphotonabsorptionresultsinaphotolysisreactionandisspecifictothetypeofcompoundandthewavelength.量子产率quantumyieldAsageneralrule,thequantumyieldincreasesaswavelengthdecreases(increasingphotonicenergy).n6-91伪一级动力学方程ThepseudofirstorderratelawTypically,thelightabsorptionbythecomponentthatistargetedforremovalisminorascomparedtothelightabsorptionbythebackgroundwatermatrix.(全局平均光解反应速率)4电效率ElectricalEfficiencyTheelectricalenergyrequirementforphotolyticreactionsissignificantduetotheprocessinefficiencies.Consequently,itisimportanttocompareprocessefficiencyonthebasisofelectricalusageperamountofcompounddestruction.Onesuchmeasureistheelectricalefficiencyperlogorder(EE/O)ofcompounddestruction.n6-91electricalefficiencyperlogorder(单位体积降低单位个数量级消耗的电能)通过测量EE/O可以对于特定反应可以计算流率。n6-91局限性PhotolysisProcessLimitationsTheefficiencyofthephotolysisprocessdepends,inpart,onthecharacteristicsofthewatermatrixandcompoundstargetedfordegradation.theextinctioncoefficientforresidualorganicmattervariesoverawiderangeandmayinterferewiththephotolysisofothercompounds.thelightenergyinputmaybeabsorbedbytheotherconstituents,theremaybephotonlossesuponreflectionoffthereactorwall,andtheprecipitatethatbuildsupontheexteriorsurfaceofsleevesthatcoverthelampsduetotheelevatedtemperaturewillblocklighttransmission.解决方案:ToovercomethelimitationsassociatedwithphotolysisprocessesrelatedtoabsorbanceofUVenergybynon-targetconstituentsinwaterreuse,pretreatmentusingreverseosmosisshouldbeusedtoremovemostoftheinterferingcompoundsandimprovetheoverallprocessperformance.Pilotstudiesshouldbeconductedtocharacterizetheexpectedefficiencyofphotolysisandtherateandcharacteristicsoffoulingofthelampsleeve.n6-10化学中和&水垢控制&稳定性』n6-102Theremovalofexcessacidityoralkalinitybytreatmentwithachemicaloftheoppositecompositionistermedneutralization.Ingeneral,alltreatedwastewaterswithexcessivelyloworhighpHwillrequireneutralizationbeforetheycanbedispersedtotheenvironment.Scalingcontrolisrequiredfornanofiltrationandreverseosmosistreatmenttocontroltheformationofscale,whichcanseverelyimpactperformance.Chemicalstabilizationisoftenrequiredforhighlytreatedwastewaterstocontroltheiraggressivenesswithrespecttocorrosion.定义与概念1PH调节Inavarietyofwastewatertreatmentoperationsandprocesses,thereisoftenaneedforpHadjustment.Becauseanumberofchemicalsareavailablethatcanbeused,thechoicewilldependonthesuitabilityofagivenchemicalforaparticularapplicationandprevailingeconomics.n6-102Wastewaterthatisacidiccanbeneutralizedwithanynumberofbasicchemicals.Sodiumhydroxideandsodiumcarbonate,althoughsomewhatexpensive,areconvenientandareusedwidelybysmallplantsorfortreatmentwheresmallquantitiesareadequate.Lime,whichischeaper,butsomewhatlessconvenient,isthemostwidelyusedchemical.Limecanbepurchasedasquicklimeorslakedhydratedlime,high-calciumordolomiticlime,andinseveralphysicalforms.Limestoneanddolomiticlimestonearecheaper,butlessconvenienttouseandslowerinreactionrate.Becausetheycanbecomecoatedincertainwastetreatmentapplications,theiruseislimited.Calciumchemicalsoftenformsludgesthatrequiredisposal.酸性废水调节物及其优缺点碱性废水的调节Ifacidicwastestreamsarenotavailableorarenotadequatetoneutralizealkalinewastes,sulfuricacidiscommonlyemployed.Insometreatmentplants,carbondioxideintheformoffluegashasbeenusedtoneutralizealkalinewastewaters.n6-102调节pH常用化合物n6-1022成垢可能性分析Withtheincreasingusethatisbeingmadeofnanofiltration,reverseosmosis,andelectrodialysisinwastewaterreuseapplications,adjustmentofthescalingcharacteristicsoftheeffluenttobetreatedisimportanttoavoidcalciumcarbonateandsulfatescaleformation.Theformationofscalewithinthetreatmentmodulewillcausedeteriorationintheperformance,ultimatelyleadingtothefailureofthemembranemodule.Manytheorieshaveresultedintheformationofrelativeindexesthatareusedtoassesswhetherawaterisundersaturated,balanced,orsupersaturatedwithrespecttocalciumcarbonate.Anundersaturatedwaterwilltendtodissolveanexistingcalciumcarbonatefilm;abalancedwaterwillneitherdissolveorformafilm;asupersaturedwaterwilltendtoformafilm.相关的理论包括:Langeliersaturationindex,Ryznerstabilityindex,MINTEQA2,MINEQL+等。n6-102LangelierSaturationIndexThetendencytodevelopcalciumcarbonate(CaCO3)scaleduringtheadvancedtreatmentoftreatedeffluentcanbeapproximatedbycalculatingtheLangelierSaturationIndex(LSI).判别标准:LSI>0:可能结垢LSI<0:不结垢,反而去除处理单元上的水垢LSI=0:不结垢也不除垢LSI只用于碳酸钙水垢总溶固系数n6-102RyznerStabilityIndexAnalternativeindexknownasthestabilityindexwasproposedbyRyzner(1944)andisusedinanumberofindustrialapplications.判别标准:RSI<5.5:形成重垢5.5查看更多