磷化氢熏蒸尾气的清除以及安全排放技术研究

中国科学技术大学硕士学位论文磷化氢熏蒸尾气的清除以及安全排放技术研究姓名：沈淼申请学位级别：硕士专业：应用化学指导教师：程新胜20100501IPH3PH38-93()/C2-MSBET1119.26m2/gVt0.369cm3/gVmic0.470cm3/gC2SBET941.93m2/gVt0.336cm3/gVmic0.449cm3/gPH325%AbstractIIAbstractTheeconomiclosseswerecausedbystoragepests.Thesuccessfulfumigationistoreduceoravoidthisunnecessaryloss.Keyfindingsofsuccessfulfumigationareaffectedbydose,lengthofexposure,temperatureandmoistureandthesuitablefumigationmethods.Thisrequiresthatweclearthefumigantconcentrationchangeovertime,determinetheeffectivenessoffumigationaccordingtothechangeoffumigantconcentration,choosethebestmethodoffumigationwhichcouldachievethesuccessfulfumigationandusetheminimaldosage.Inaddition,afterfumigation,fumigationwarehousecontainshighconcentrationofphosphinegas.Theusualmethodisdischargingdirectlyintoatmosphere;suchactivitycanresultsingasconcentrationwhichexceedstheshort-termexposurelimitsof0.3ppmofphosphine.Highconcentrationofresidualphosphinenotonlypollutestheenvironmentandposeahazardtothehealthofmammals,italsoviolatesafetydischargelaw.Howtoeconomic,environmentallyfriendlyabatementresidualphosphineisnotable.Inthecaseofin-storefumigationandstackfumigation,theconcentrationofphosphineinsideandoutsideofthestripswhichpackedbycorrugatedboxwithplasticliningwasdeterminedinordertofindanoptimalfumigationmethod.Afterfumigation,theconcentrationofPH3wasdeterminedtomakesurethesafetyandeffectivefumigationtime.Theresultsindicatethattheeffectofstackfumigationisbetterthanin-storefumigation.However,thestackfumigationstillhasleakage.Inordertogivesuccessfulandsafetyfumigationtostripspackedbycorrugatedboxwithplasticlining,thewholeprocessoffumigationtimeshouldlastfor8-9days.Threecommercialactivatedcarbons(coal-based)whichweremodifiedbyferritesulfatewithoutcalcination,wereusedtoadsorb/oxidizephosphinedirectly.ThecharacteristicsofallthosetypesofcarbonswereevaluatedbymeansofBoehmtitration,thermalanalysis,nitrogenadsorptionandinductivelycoupledplasmaatomicemissionspectrometry.TheresultsshowthattheSBET(surfaceareacalculatedusingBrunauer-Emmett-Teller(BET)equation)1119.26m2/g,Vt(totalporevolume)0.369cm3/gandVmic(microporesvolume)0.470cm3/gofC2-MweremuchhigherthanSBET941.93m2/g,Vt0.336cm3/gandVmic0.449cm3/gofC2.Moreover,thephosphinebreakthroughcapacityofC2-Mwasextendedby25%thanbefore.TheresultsalsoindicatethatactivatedcarbonwithslightacidityandawelldevelopedAbstractIIIporousstructurehashigherPH3breakthroughcapacityandlongeroperationallife.BasedontheFouriertransformedinfraredspectroscopyandthermalanalysis,phosphoricacidwasthefinaloxidationproduct,thusexhaustedactivatedcarbonscanberegeneratedbywashingwithwater.Basedonthesmallscaletestinlab,apilotfixedbedreactorabatedphosphinethatcouldachievethelowofsafetydischargewasdesigned.Keyword:phosphine;fumigation;abatement;modifiedactivatedcarbon,__________________________________________________________________________________________111()1.11.1.16007035[1][2]12[3]1.1.2[4]19871992[5][6]20g/m3120[7][7,8]50[9]1975[10]131.1.3()()()()()()[11][12]14[13]1.21.11.1(mg/m3)24mg/m39.7mg/m3550830mg/m30.5-1.02798mg/m3[11,14][15]G()2000ppm24h2-3d151.30.3ppm8h5d(0.1ppm)[14]60min1ppm1998EPA0.03ppm[16]EPA500750[17]2010111mg/m3[18][19]1.41.4.1[19]Anderson[17]161.4.2[18]Bridges[19][16]1.4.3[16]200°C1.4.3.1Jurgen[20]1-25%PH3171.1PH31ppmPH3PH31.11.4.3.2AgNO3Cu(NO3)22%AgCuPMAgAgNO3[21,22]Ag322342PH4HOHPO4HO+→+Bridges[18]PMAg/CAgH2O2[21,22]MAg+AgAg+++22M(O)+2Ag+2HM(=O)+2Ag+HO→2222M(=O)+HOM(O)+HO→18PMV5+Ti4+Mo6+W5+-(peroxo-ligand)1.4.3.3800[23,24]PMvapure620(Norit)[19,20]vapure620[25]1.4.3.4Nishino[26]130PH3PH31.51.PH3192.PH3pH3.10[1]RajendranS.2002.Postharvestpestlosses[M],Ed.PimentelD,EncyclopediaofPestManagement,MarcelDekker.[2]WhiteNDG.1995.Insects,mitesandinsecticidesinstored-grainecosystems[M],Eds.JayasP,WhiteNDG,MuirWE,Stored-GrainEcosystems.Marcel-Dekker.[3]ReddyPV,RajashekarY,BegumK,LeelajaBC,RajendranS.2007.Therelationbetweenphosphinesorptionandterminalgasconcentrationsinsuccessfulfumigationoffoodcommodities[J].PestManagSci,63:96–103.[4],,,.2007.[J].,2:6-9.[5]PrabhakaranS.,2006.CommercialperformanceandglobaldevelopmentstatusofProfumesgasfumigant[C].2006.eds,LoriniI,BacaltchukB,BeckelH,DeckersD,SundfeldE,dosSantosJP,BiagiJD,CelaroJC,FaroniLRD’A,BartoliniLOF,SartoriMR,EliasMC,GuedesRNC,De-FonsecaRG,ScusselVM.ProceedingsoftheNinthInternationalWorkingConferenceonStoredProductProtection,15–18October2006,SaoPaulo,Brazil,BrazilianPost-harvestAssociation,Campinas,Brazil,pp.635–641.[6],,,,,,.2008.[J].,7:60-62.[7]RajendranS,SriranjiniV.2008.Plantproductsasfumigantsforstored-productinsectcontrol[J].JournalofStoredProductsResearch,44:26-135.[8],,,.2004.[J].,6:85-88.[9]SubramanyamB,HagstumDW.1996.IntegratedManagementofInsectsinStoredProducts[M],ed,MarcelDekker.[10]HallidayD,HarrisAH,TaylorRWD.1983.Recentdevelopmentintheuseofphosphineasafumigantforgrainsandotherdurableagriculturalproduce[J].Chem.Ind.,12:137-146.[11]WilliamsP,NicksonPJ,BrabyMF,HendersonAP.1996.Phosphinefumigationsofwheatin2500m3steelbinswithoutrecirculationfacilities[J].J.storedProd.Res