T酸废母液蒸氨预处理的动力学研究张盛汉

2014,34(1)85~90ChinaEnvironmentalScienceT,*,(,201620)T,,TFenton,FentonpH.,FentonT,,.,pH,pH11,3000,95120min,99%,97%.,k=0.00883min1.:ln(k)=1.971611016.5026/RT,R2=0.9959,8451.20J/mol,0.139min1.T,.TX703A10006923(2014)01008506AmmoniaremovalkineticsofspentliquorofT-acidcrystallizationbyevaporation.ZHANGSheng-han,CHENQuan-yuan*,LIUHuan-huan(SchoolofEnvironmentalScienceandEngineering,DonghuaUniversity,Shanghai201620,China).ChinaEnvironmentalScience,2014,34(1)85~90AbstractForthepurposeofreducingtheconcentrationofammonianitrogenandtotalnitrogenofspentliquorofTacidcrystallization,whichwaspre-treatedbycomplexextractionprocess,Fentonoxidationandammoniaevaporationwastestedinordertocreatethefavourableconditionforthefollowingbiologicaltreatment.Theinfluenceoffentonoxidation,pH,gas-liquidvolumeratio,temperatureandreactiontimeontheremovalefficiencyofammonianitrogenandtotalnitrogenwasinvestigated.TheexperimentalresultsshowedthatconcentrationofammonianitrogenwasreducedbyFentonoxidation,whichenhancedtheremovalofammonianitrogenandtotalnitrogen.TheremovalofammonianitrogenandtotalnitrogenincreasedsignificantlyafterFentonoxidation.ItwasfoundthattheremovalofammonianitrogenandtotalnitrogenincreasedwithincreasingpH,temperatureandgas-liquidvolumeratio.Theremovalofammonianitrogenexceeded99%andtotalnitrogenexceeded97%atpH11,gas-liquidvolumeratioof3000,temperatureof95and120minofreactiontime.ItwasalsofoundthatammoniaremovalrateofspentliquorofT-acidcrystallizationbyevaporationfollowedthefirst-orderkineticequationandthereactionrateconstantkwas0.00883min1.TheArrheniusequationwasfittedasln(k)=1.971611016.5026/RT,R2=0.9959,wheretheactivationenergywas8451.20J/molandthepre-exponentialfactorwas0.139min1.ItwasconcludedthatammoniaevaporationwastheeffectivemethodoftreatingspentliquorofT-acidcrystallizationcontaininghighconcentrationofammonianitrogenandmaybeappliedinindustry.KeywordsT-acidcrystallizationliquorammoniaevaporationammonianitrogenkineticsactivationenergypre-exponentialfactorT(13,6,8)H(1),T,,,,,,,,.,[12].,[35],[6],[7],,[8][9].20130420(21277023)*,,[e-mail]8634[10][11],,.T,,,.,,.HO3SNH2HO3SSO3H1TFig.1MolecularstructureofTacidwastemotherliquor11.1T,HT,T,1200m3/d,65.37g/L,54.6g/L,COD20.91g/L,pH1.06.40%(NaOH),,1.1Table1TheequipmentofexperimentsTENSOR27BRUKEROPTICSHH4DIONEXICS90FA2004BPHSC3DACOLZB61.2FentonT,pH,pH.1LT,180mL30%H2O2,FeSO424.4g,3.0h,,(B).T(A)FentonT(B),40%NaOHpH,1L,CN1CTN1,.,,,,,,CN2CTN2,(1)(2),pH.N1N2NN1100%CCC(1)TN1TN2TNTN1100%CCC(2),HJ5362009[12].,HJ6362012[13].22.1pH2,pH,pH,,BA.(NH3)(NH4+).pH8,6%.pH9.25,.pH11,98%(NH3)[14].pH11,,,T((NH4)2SO4),,pH,NaOH370mL.pH11,A,B,FentonT,,OH,[1516].A,B,FentonT,BA,.1T87910111270758085909510060708090100ABpH(%)(%)AB2pHFig.2EffectofpHonammonianitrogenandtotalnitrogenremovalpH11,B99%,97%.pH,,,,,.,pH,,NH4++OH⇌NH3+H2O,,.,pH12NaOH80mL/L(T),,.pH12,,.,pH11.2,Fenton,SO42,4624.27mg/L.NO2NO3,NO3,[1719].2FentonTTable2IonconcentrationvariationsofspentliquorofTacidcrystallizationafterFentonoxidationbyionchromatogram(min)(μSmin)(mg/L)NO23.623.760.2370.572230.76563.18SO4210.0410.074.3056.6688680.8213305.09NO35.980.166147.25,TENSOR27FentonT,3.(cm-1)(%)120804009580655090508040100705570306020854000200016001200800abcde1800140010003Fig.3TheIRspectrosgram3a,T(NH2)(34003230),(OH)(35503450)(SO3H)(12101180);3b(OH)(NO2)(1350750)(SO3H),(NH2)(NO2),Fenton;3c(SO3H),(NO2).3d,(OH),(NH2)(NO2);FentonTCOD84.43%,TOC50.03%,,,3e.Fenton,T(NH2)(NO2),,4.Fenton,(SO3H)(OH),SO42,.,(OH)8834(NH2)(NO2),T.,,,CO2,H2O,NO2,NO3.HO3SNH2HO3SSO3HHO3SHO3SNO2SO3HOHNO2OHOHOHOHHOHOOHHOOHNO2H2O+CO2+NO2-+NO3-+SO42-4FentonTFig.4PathwayandproductofTacidbyFentonoxidation2.2pH11,95,,.5.,,,,,,.100020003000400050009092949698100708090100(G/L)(%)(%)ABAB5Fig.5Effectofgasliquidvolumeratioonammonianitrogenandtotalnitrogenremovals5,,.3000,,,,3000.,,,,,[2021],.3000,,,,.2.31LAB,pH11,708095,,3000,30min.6.6,,AB,,,BA.,B,A.95,.,,,,.Saracco[22]KpH,(3).53513/pH6054/1.44110e12.52810eTTK(3),K,,,,[23].,,.,95.6,95,AB.120min,,pH,,,.,,pH,1T89.120min,,,B99%.,.,120min.70306090120150180859095100708090100AB(%)(%)(min)AB803060901201501809092949698100667278849096AB(%)(%)(min)AB95306090120150180909294969810080859095100AB(%)(%)(min)AB6Fig.6Effectoftemperatureandreactiontimeonammonianitrogenandtotalnitrogenremoval2.470,8095[24],7,3.,(R20.95),,Wang[25],95:ln(C0/C)=0.00883t+3.56805,R2=0.9933.k0.007230.00883min1.,,,.03060901201501802102.83.23.64.04.44.85.2(min)y=0.00723x+2.91575R2=0.9828y=0.00777x+3.13572R2=0.9872y=0.00883x+3.56805R2=0.9933958070lnC0/C7ln(C0/C)(t)Fig.7Relationbetweenreactiontime(t)andln(C0/C)3Table3Kineticequationandcoefficientatdifferenttemperature()k(min1)R270ln(C0/C)=0.00723t+2.915750.007230.982880ln(C0/C)=0.00777t+3.135720.007770.987395ln(C0/C)=0.00883t+3.568050.008830.9933(k)(lnk)(1/T),,8.Ea,A.8,lnk1/T,Arrhenius,[19].ln(k)=1.971611016.5026/RT,R2=0.9959,(Ea)8451.20J/mol(A)0.139min1.AEak,A,k,Eak.,k,.,Ea,k.Ea8.451kJ/mol,,,pH.90340.002700.002750.002800.002850.002900.00295-4.95-4.90-4.85-4.80-4.75-4.70y=-1016.5026x-1.97161R2=0.9