电化学氧化与生物法联合降解木质素

29320163ＲesearchofEnvironmentalSciencesVol．29No．3Mar．2016．J．2016293434-441．CUIXiaominWANGYipingLIANGJidong．CombineddegradationofligninbyelectrochemicaloxidationandbiodegradationECO-BDJ．ＲesearchofEnvironmentalSciences20162[e-mail]．*[e-mail]*710049ECO-BDelectrochemicaloxidationandbiodegradationTiSn-SbO2Na2SO4ECO-BD8.64mAcm220.00kCcNa2SO40.15molL．ECO-BD1gLCODCr59.31%28.87kW·hkg．-ECO-BDECOCO2H2O0.20～0.250.31～0.37．ECOBDECO-BD．X703.51001-6929201603-0434-08ADOI10.13198j．issn．1001-6929．2016．03．16CombinedDegradationofLigninbyElectrochemicalOxidationandBiodegradationECO-BDCUIXiaominWANGYipingLIANGJidong*DepartmentofEnvironmentalEngineeringXi'anJiaotongUniversityXi'an710049ChinaAbstractLigninisacomplexthree-dimensionalaromaticpolymerwhichcontributestoasignificantvalueofCODchromaticityandPOPSinwastewaterofthepulpandpaper-makingindustry．InordertodevelopaneconomicallyeffectiveandenvironmentallyfriendlytechnologyforlignindegradationsynergeticlignindegradationcombiningelectrochemicaloxidationECOwithbiodegradationBDwasproposed．FirstlytheelectrochemicalpretreatmentofligninsolutionwasstudiedbygalvanostaticelectrolysisusingTiSb-SnO2astheanodeandsodiumsulphateastheelectrolyte．ＲesponseSurfaceMethodologyＲSMwasemployedtooptimizetheECO-BDprocessoflignindegradation．Currentintensityof8.64mAcm2electricquantityof20.00kCandconcentrationofNa2SO4of0.15molLweretakenastheoptimumconditions．UndertheoptimumconditionsaCODCrremovalrateof59.31%andspecificenergyconsumptionSECof28.87kW·hkgwereobtainedfor1gLligninsolution．SecondlyFTIＲandGC-MSanalysisshowedthatECOcaneffectivelydegradethestructuresofphenolichydroxylandchromophoricgroupsoflignin．Electro-oxidativeconversionofligninwasinitiatedwiththebreakingofligninpolymeronaccountofetherlinkagefloutingintomonomersandwasfollowedbytheiroxidationtoquinones．FinallyquinonesunderwentopeningofthearomaticringstoproducedicarboxylicacidsorwerefurthermineralizedtoCO2andH2O．AfterECOthebiodegradabilityofligninincreasedfrom0.20-0.25to0.31-0.37.Thereforethefollowingbio-degradationtimewassignificantlydecreased．InconclusionECOcandestroytherecalcitrantbondingstructureoflignintoproducebiodegradableintermediates．ECO-BDcouldbeaneconomicallyeffectiveandenvironmentallyfriendlymethodforlignindegradation．KeywordselectrochemicaloxidationbiodegradationligninresponsesurfacemethodologyＲSMCOD1．32．、、、3-5．．．6．ECOelectrochemicaloxidation7．ECO21．Pelegrini8DSAdimensionallystableanode．DSA〔IrO2、PbO29-10、TiTa2O5-IrO2、TiＲuO2-IrO2、TiSb-SnO2、TiPbO211-12、TiO2TiTiO2NTPbO213〕．β-O-414．ECO．ECO15．Ahmed716ECO．TiSb-SnO2TiPbO2BI〔ρBOD5ρCODCr〕0.19～0.260.29～0.350.36～0.4212．ECO-BDECOBD．11.1．．5Lρ200mgL800mgL．20d40%．100mLρlgL30℃、100rmin3d5mL100mL3．500rmin30min2OD600600nm2．ρ5.0gLρ10.0gLρNaCl5.0gLpH=7.0.ρKH2PO41.0gLρK2HPO41.0gLρNH4Cl0.2gLρMgSO4·7H2O0.2gLρCaCl20.015gLφ1.0mLL．ρFeSO4·7H2O2mgLρCuSO4·5H2O0.4mgLρMnSO4·H2O4mgLρCoCl2·6H2O1mgLρNiCl2·6H2O2mgLρB10.1mgLpH=7.0．1.21.2.1ECO-BDECO1、．31.5cm5cm．TiSb-SnO247.1cm2．200rmin25±1℃Na2SO4ρ1gL．BD500mL200mLpH7.0±0.2、．5%100rmin、30℃48hρDO2mgL3．534291ECOFig.1BatchreactorofelectrolyticsystemECOBD、ρCODCr、UV、、、．1.2.2ECO-BDX1、X2cNa2SO4X3ECO-BDCODCrY1SECspecificenergyconsumptionY2．1．1Table1Factorsandtheirlevelsofresponsesurfacetest－101X1mAcm22.506.2510.00X2kC101520X3cNa2SO4molL0.050.100.151.31.3.1400rmin30min0.22μm．ρCODCr．ρCODCrGB11914—1989《》ρBODWTWBODOxiTopIS6CPPA17．-Agilent8453UV-VisspectrophotometerAgilent．200～208268～287nm218．280nm．10280nm．BrukerTensor37FT-IＲBruker、．105℃1mg150mgKBr4cm－1400～4000cm－132．NicoletOmnicV8.0．GC-MS-Agilent68905973GC-MSAgilent．100mLpH2.0～3.00.22μm1mLGC-MS．HP-530.0m×320μm×0.50μm230℃250℃60℃5min10℃min280℃5min．He1mLmin1.0μL50∶1.EI70eV150℃．NIST2002．1.3.2、ρCODCrSEC．BDECO．ECOWECO=U×I×Δt1WECOECOkW·hUVIAΔth．1kgCODCr1.05kW·h．BDWBD=ΔCODBD×V×1.0510002WBDBDkW·hΔCODBDρCODCrmgLVL．SEC=WECO+WBD×1000ΔCODECO+ΔCODBD×V3ΔCODECOECOρCODCrmgL．22.1ECO-BD63432.1.1Design-Expert8.0.6295%〔45〕．2BBDTable2ExperimentalmatrixandresultsofBox-BehnkenDesignforlignindegradationX1mAcm2X2kCX3molLY1%Y2kW·hkg16.25150.1050.1729.18210.00200.1056.5422.5732.50150.1556.0022.58410.00150.0548.8136.4552.50200.1055.5931.53610.00150.1549.0931.2176.25150.1049.4831.1286.25150.1051.2127.1392.50150.0558.9022.79106.25150.1051.2128.38116.25100.0545.6123.28126.25200.0560.3535.24136.25200.1563.7022.14146.25150.1052.5027.94152.50100.1050.4717.47166.25100.1542.3921.521710.00100.1038.7329.79Y1=50.91－4.25X1+9.01X2－0.31X3+3.17X1X2+0.79X1X3+1.64X2X3－0.20X12－0.38X22+2.48X32－3.28X12X2+1.55X1X224Y2=28.75+5.57X1+2.43X2－3.72X3－5.32X1X2－1.26X1X3－2.84X2X3－0.35X12－3.06X22－0.14X32+2.35X12X3－4.74X1X225ＲSManalysisofvarianceANOVA19．453.P0.05．lackoffitP0.05．adequateprecision420Y1Y222.62514.356.Joglekar21Ｒ20.8．Y1Y2Ｒ20.99030.9699AdjＲ20.96900.9037Ｒ2AdjＲ20.219．Y1Y22．3CODCrY1SECY2Table3ANOVAresultsforthecubicmodelofCODCrremovalrateY1andSECY2oflignindegradationFP638.311158.0346.45＜0.000146.2551.250.9510.950.710.44595.3041.33429.631139.061