MAP法处理饲料级磷酸氢钙母液的研究邹宇

2　9环境工程学报Vol.2,No.920089ChineseJournalofEnvironmentalEngineeringSep.2008MAP邹　宇　伍　钧＊　杨　刚　唐　微(,625014)　　MAP(),。,pH=9.5,n(NH+4)∶n(PO3-4)=1∶1,10min,40℃。,40℃,PO3-4、Mg2+Ca2+98.46%、92.54%98.48%,15.91、70.252.94mg/L。P2O5、NH+4-N、CaOMgO29.08%、6.07%、2.83%15.91%,MAP。　MAP　　　　X703.1　　　A　　　1673-9108(2008)09-1169-04Researchontreatmentofmothersolutionoffeed-gradecalciumhydrophosphatebyMAPprocessZouYu　WuJun　YangGang　TangWei(FacultyofResourcesandEnvironment,SichuanAgricultureUniversity,Yaan625014)Abstract　Highlyconcentratedmothersolutionoffeed-gradecalciumhydrophosphatewastreatedbymagne-siumammoniumphosphate(MAP)process.Theoptimalreactionconditionswereinvestigatedandtheconstituentsofproductwereanalyzed.Theresultsindicatedthattheoptimalreactionconditionswereasfollows:pHof9.5,n(NH+4)∶n(PO3-4)ratioof1∶1,reactiontimeof10minutesandreactiontemperaturebelow40℃.Undertheseconditions,whenthetemperaturewas40℃inthemothersolution,theresultantremovalefficiencyofPO3-4,Mg2+andCa2+reachedto98.46%,92.54%and98.48%,andtheresidualconcentrationwas15.91mg/L,70.25mg/Land2.94mg/L,respectively.TheingredientcontentofP2O5,NH+4-N,CaOandMgOintheprecipitateswere29.08%,6.07%,2.83%and15.91%,respectively,andMAPinvolvedcanbereusedasafertilizer.Keywords　MAPprocess;mothersolutionofcalciumhydrophosphate;phosphorousrecovery;recycling:(02NY029-099):2008-01-22;:2008-05-19:(1982～),,,。E-mail:[e-mail]＊,E-mail:[e-mail]　　2。,,、,,、。:H3PO4+Ca(OH)2CaHPO3·2H2O(1),()。Mg2+、Ca2+、SiO2、K+、Na+,P2O50.2%～0.4%。,PO3-4,pH,,(),、[1,2]。PO3-4、Mg2+Ca2+,,,,。,MAP、,,、。(MgNH4PO4·6H2O),,,[3],MAP,P2O558%,,,,。:HPO2-4+Mg2++NH+4+6H2OMgNH4PO4·6H2O↑+H+(2)2Mg2+、NH+4PO3-4,Ksp(Ksp=7.08×10-14～3.89×10-10)[4],。,,,pH5～7,,。,,MAP,MAP,。Mg2+、PO3-4Ca2+,Mg2+PO3-4,MAP[5,6],NH+4-N,MAP,、,,MAP。1　1.1　,:PO3-41033.77mg/L,NH+4-N20.43mg/L,Ca2+193.67mg/L,Mg2+942mg/L,40℃,pH6.18,n(Mg2+)∶n(Ca2+)∶n(PO3-4)=1.1770∶0.1452∶11.2　:PHS-4C、、HHS-85、YXQG02、722、MKIIM6。1.3　10mol/LNaOHpH,NH4HCO3[7,8],、、,MAP,。:(1)pH;(2);(3);(4)。PO3-4、NH+4-N、Ca2+Mg2+,[9]。40℃48h[10],[11]。2　2.1　2.1.1　pH200mL250mL,,20℃,NH4HCO3,n(NH+4)∶n(PO3-4)=1∶1,100r/min,10mol/LNaOHpH7.5、8、8.5、9、9.5、10、10.5、1112,15min,20min,0.45μm,PO3-4、NH+4-N、Ca2+Mg2+。pHPO3-4、NH+4-N、Ca2+Mg2+1。1　pHPO3-4、NH+4-N、Ca2+Mg2+Fig.1　EffectofpHvalueonresidualconcentrationsofPO3-4,NH+4-N,Ca2+andMg2+1,pH,PO3-4、NH+4-N,Ca2+、Mg2+。pH,(2),,MAP,PO3-4、NH+4-NMg2+,pH9.5,NH+4-N,MAP,[12],NH+4-N,Mg3(PO4)2,pH10,Mg3(PO4)2,pH11,Mg(OH)2[13]。pH,Ca2+Ca5OH(PO4)3、CaHPO4·2H2O、Ca3(PO4)2Ca(OH)2[14,15]。,pH9.5,MAP。2.1.2　氮磷比200mL250mL,n(NH+4)∶n(PO3-4)0.6∶1、0.8∶1、1∶1、1.2∶11.4∶1,pH9.5,2.1.1。PO3-4、NH+4-N、Ca2+Mg2+2。2,PO3-4、Mg2+n(NH+4)∶n(PO3-4),n(NH+4)∶n(PO3-4)1,;NH+4-N、Ca2+,n(NH+4)∶n(PO3-4)1,NH+4-N。11709　:MAP2　N∶PPO3-4、NH+4-N、Ca2+Mg2+Fig.2　EffectofN∶PonresidualconcentrationsofPO3-4,NH+4-N,Ca2+andMg2+NH+4-N,,MAP,pH[16]。n(Mg2+)∶n(PO3-4)=1.18∶1,,NH+4-N,PO3-4、NH+4-N、Mg2+MAP,[17],Ca2+,Ca2+,NH+4-N。,n(NH+4)∶n(PO3-4)1。2.1.3　反应时间200mL250mL,n(NH+4)∶n(PO3-4)1∶1,pH9.5,5、10、15、2030min,2.1.1。PO3-4、NH+4-N、Ca2+Mg2+3。3　PO3-4、NH+4-N、Ca2+Mg2+Fig.3　EffectofreactiontimeonresidualconcentrationsofPO3-4,NH+4-N,Ca2+andMg2+3,PO3-4、NH+4-N、Ca2+Mg2+。5～30min,PO3-44.5mg/L,99.5%。,MAP。Stratful[16]1min,0.1mm,60min,0.8mm,3h3mm,,Mg2+PO3-44%,[4]。,,10min。2.1.4　反应温度200mL250mL,10℃、20℃、30℃、40℃50℃,n(NH+4)∶n(PO3-4)1∶1,pH9.5,10min,2.1.1。PO3-4、NH+4-N、Ca2+Mg2+4。4　PO3-4、NH+4-N、Ca2+Mg2+Fig.4　EffectofreactiontemperatureonresidualconcentrationsofPO3-4,NH+4-N,Ca2+andMg2+4,10℃40℃,PO3-4、NH+4-NMg2+,Ca2+。,PO3-4、NH+4-N,Mg2+,Ca2+。50℃,PO3-444.86mg/L,99.64%95.66%。,,[18];,[13],,,MAP,PO3-4、NH+4-NMg2+,、,Mg2+Ca2+。,40℃MAP。2.2　40℃,2.1,MAP(pH=9.5,n(NH+4)∶n(PO3-4)=1∶1,10min,1171240℃),PO3-4、NH+4-NMg2+。:P2O529.08%,NH+4-N6.07%,CaO2.83%,MgO15.91%。,n(Mg2+)∶n(NH+4)∶n(PO3-4)1∶1∶1,。,MAP。,29.08%P2O5,。2.3　,100,,MAPN、P,,,。,,,、。,,,。MAPPO3-4、Mg2+,,,,,,。,MAP,。MAP。3　　(1)MAPpH=9.5,n(NH+4)∶n(PO3-4)=1∶1,10min,40℃。40℃(),PO3-4、Mg2+Ca2+98.46%、92.54%98.48%,15.91、70.252.94mg/L。。(2)pH=9.5,n(NH+4)∶n(PO3-4)=1∶1,10min,40℃,P2O529.08%,N6.07%,CaO2.83%,MgO15.91%,,,。(3),NH+4-N,。40℃,,,。[1].30kt/a.,2002,17(2):40～41[2].P2O5.,2001,16(3):40～43[3]SimonParsons,JamesDoyle.StruviteRecoveryandRe-use.The2ndInternationalConferenceonPhosphateRe-coveryforRecyclingfromSewageandAnimalWastes.TheNetherlands:Noordwijkerhout,2001.125～133[4]OhlingerK.N.,YoungT.M.,SchroederE.D.Predic-tingstruviteformationindigestion.Wat.Res.,1998,32(12):3607～3614[5]BattistoniP.,PavanP.,PrisciandaroM.,etal.Struvitecrystallization:Afeasibleandreliablewaytofixphosphor-ousinanaerobicsupernatants.Wat.Res.,2000,34(11):3033～3041[6]MombergG.A.,OellermannR.A.Theremovalofphos-phatebyhydroxyapatiteandstruvitecrystallizationinSouthAfrica.Wat.Sci.Tech.,1992,26(5～6):987～996[7],,,..,2003,23(2):90～92[8]..,2003,18(4):16～17[9]《》.(4).:,2002.243～279[10],,..:,1986.89～94[11]..:,1976.173～175[12]SiegristH.Nitrogenremovalfromdigestersupernatant-comparisonofchemicalandbiologicalmethods.Wat.Sci.Tech.,1996,34(1～2):399～406[13],..,2004,22(1):7～10[14]SylviaRegy,DenisMangin,JeanPaulKlein,etal.PhosphateRecoverybyStruvitePrecipitationinaStirredReactor.UK:CEEP,2001.54～58[15]HansCarlss