分子筛催化剂亚硫酸盐体系降解水中对乙酰氨基苯酚权晓琪

1001-3[e-mail]1996－femaleMaster＇sdegreeＲese[e-mail]．*[e-mail]．-*071003．、SBA-15Co-SBA-15APAP．pH、、、．APAP．O643．32A．n-acetyl-p-aminophenolAPAP．APAP、、、1．．2000SO·－4SulfateＲadical-basedAdvancedOxidationProcessesSＲ-AOPs2－3．SO·－4pH2．5～3．1V4－6、、pH3～10．SO·－4、SO·－5—．7．．FeMnCo8－10．SBA-15．APAP、pH、、APAP．1APAP336Vol．33No．6201912JOUＲNALOFMOLECULAＲCATALYSISCHINADec．2019DOI:10.16084/j.cnki.issn1001-3555.2019.06.00891%2APAP30min3APAPpH4APAP50%5APAP55℃．11．1KSL-1200XBE-52AAGZX-9140MBEDF-101SFA2204BGWA-UN1-20PHS-3CpHJES-FA200．1Table1ChemicalsChemicalsPurityManufacturerH2SO4AＲTianjinchemicalreagentNo．3factoryHClAＲTianjinchemicalreagentNo．3factoryNaOHAＲTianjinchemicalreagentNo．3factoryNa2SO4GＲTianjinchemicalreagentNo．3factorySBA-15NanjingXianfengnanotechnologyco．LTDAPAPAＲMeOHTediaTianjinkermiouchemicalreagentco．LTDTBAAＲTianjinkermiouchemicalreagentco．LTDEthanolAＲTianjinkermiouchemicalreagentco．LTD1．21．2．12%Co/SBA-15Co1．2．1．100mL．2gSBA-155h．24h．SBA-1560℃2h．450℃5h．Coloading=mComSBA－15×100%=mcobaltnitratehexahydratemSBA－15×MCoMcobaitnitratehexahydrate×100%1．2．2APAPAPAP0．02mmol/L2mmol/L50mL200mL．pH．012．551030min1mL．100μL20μL．1．30．02mmol/LAPAP、1mmol/L2%Co/SBA-15．0．22μm、1mL、100μL．22．1APAPL5－256pH25．265332APAPTable2FactorleveltableoforthogonalexperimentofAPAPLevelsFactorApHFactorBT/℃FactorCCo∶SFactorDO21L·min－1%18350．51026651303725221410550．15059450．051003APAPTable3OrthogonaldesigntableanddataofAPAPNumberFactorsABCDDegradationrate/%18350．51019．78286513021．72382522183．5848550．15010．3858450．0510027．09663512157．69766525091．2886250．11001．1496550．05107．00106450．53054．0311735210029．46127650．11041．05137250．053012．17147550．52175．451574515074．121610350．13053．691710650．052131．351810250．55025．20191055110035．6520104521048．36219350．055022．45229650．510035．902392511042．082495523077．99259450．12122．47k132．51036．61442．07231．654k242．22844．26046．25243．920k346．45032．83466．13454．108k438．85041．29425．74644．686k540．17845．21420．01225．848Ｒ13．94012．38046．12228．2603656-pHpH．2．1．1FFIIv3．14．4APAPTable4AnovatableoforthogonalexperimentFactorsSSDOFFrateFcriticalvaluea=10%pH520．05740．2032．330T/℃549．07540．2142．330CoS6645．27042．5942．330O21L/min%2531．43140．9882．330Error10245．8316APAPF10%F2pH、、APAPpH=7、45℃、21%．2．1．2pH=745℃221%55．5Table5ThedegradationrateofacetaminopheninthefivegroupswasoptimizedNumbersDegradationrate/%193．06292．60392．89494．00593．270．223295APAP92．60%～94．00%93．18%0．22329．2．1．3．．Co/SBA-155pH=745℃221%30minAPAP1．1APAPFig．1EffectofcatalystcycletimesonthedegradationrateofAPAP15．30min93．18%APAP185．03%46533530min75．45%APAP．．Co．．2．2CoSBA-152211．2aSBA-15TEMbCo-SBA-15TEMFig．2aTEMofSBA-15bTEMofCo-SBA-153Co-SBA-15SEMFig．3SEMofCo-SBA-15780．7796．8eV．CoCoCo2+．2．32．3．1．MeOHTBAHO·SO·－4kMeOH/HO·=1．2－2．8×109m－1s－1kMeOH/=1．6－7．7×109m－1s－1kTBA/HO·=3．8－7．6×108m－1s－1kTBA/SO·－4=4－9．1×105m－1s－1．0．5mmol/LMeOHHO·SO·－40．5mmol/L5656-4Co-SBA-15XPSFig．4XPSofCo-SBA-15TBAHO·APAPSO·－4SO·－5．APAPAPAP5Fig．5Freeradicalquenchingexperiment．6．6Table6ContributionrateoffreeradicalsT/minAddTBAContributionrateofHO·AddMeOHContributionrateofSO·－4+SO·－5ContributionrateofSO·－4ContributionrateofSO·－500．000．000．000．000．000．00221．8713．2310．0586．7746．8939．88551．305．9920．5794．0156．3137．701062．5910．9336．5389．0737．0851．992066．0217．2247．0082．7823．8558．933067．8724．1255．6575．8813．6662．214068．7629．9862．0170．026．8763．165068．8430．2663．9169．745．0064．756068．9230．2864．8769．724．1165．626Fig．6ContributionrateoffreeradicalsSO·－5SO·－4HO·．2．3．2ElectronSpin-resonancespec-troscopyESＲ、DMPO100mmol/LJES-FA200ESＲ7．cwESＲg=2．00138DMPO11∶2∶2∶1αN=αf=1．493mTDMPO-OH·OH·12－15．665337ESＲFig．7ESＲspectrumDMPO1SO·－4DMPODMPO-SO·－4．2DMPO-OH·Na2SO4SO·－4DMPO-OH·DMPO-SO·－416．DMPO-SO·－4717．SO·－5．2．3．3SBA-15．CII－SO318SO·－319－20SO·－3SO·－4SO·－5．CoII+HO→CoII－OHalkalinepHCoII－OH+SO2－3→CoII－SO3+H2OCoII－SO3+O2→CoIII－SO+3CoIII－SO+3+SO2－3→CoII－SO3+SO·－3SO·－3+O2→SO·－5SO·－5+SO2－3→SO2－4+SO·－4SO·－5+HSO－3→HSO－4+SO·－4SO·－5+SO2－3→SO2－5+SO·－3SO·－5+HSO－3→HSO－5+SO·－3SO·－4+SO2－3→SO2－4+SO·－3SO·－4+HSO－3→HSO－4+SO·－3821－24．8APAPFig．8Possibledegradationprocesses33．1APAP2．3．2pH、、APAPpH=7、45℃、21%593．18%．CoO325－26pH7～8pH27．SO·－5、SO·－4HO·ESＲSO·－4HO·SO·－4HO·．APAP、．7656-PMS．．1SuarezSＲamillMOmilFetal．Ｒemovalofpharma-ceuticallyactivecompoundsinnitrifying-denitrifyingplantsJ．WaterSciTechnol20055289－14．2AnipsitakisGPDionysiouDD．ＲadicalgenerationbytheinteractionoftransitionmetalswithcommonoxidantsJ．EnvironSciTechnol2004383705－3712．3AnipsitakisGPDionysiouDDGonzalesM．Cobalt-me-diatedactivationofperoxymonosulfateandsulfateradicalattackonphenoliccompounds．Implicationsofchloridei-onsJ．EnvironSciTechnol2006401000－1007．4MatzekLWCarterKE．ActivatedpersulfatefororganicchemicaldegradationAreviewJ．Chemosphere2016151178－1885OhWDDongZLimTT．GenerationofsulfateradicalthroughheterogeneouscatalysisfororganiccontaminantsremovalCurrentdevelopmentchallengesandprospectsJ．ApplCatalBEnviron2016194169－201．6HuPLongM．Cobalt-catalyzedsulfateradical-basedad-