高浓度有机废水发酵法制取氢气技术李永峰

李永峰,任南琪,胡立杰(哈尔滨工业大学市政环境工程学院,黑龙江哈尔滨150090):3,(Enterobacter)(Clostridium)(Citrobacter),,(),:;;;;:X172;X703.1:A:0253-4320(2005)03-0010-04FermentativebiologicalproductionofhydrogenbydigestinghighstrengthorganicwastewaterLIYong-feng,RENNan-qi,HULi-jie(SchoolofMunicipalandEnvironmentalEngineering,HarbinInstituteofTechnology,Harbin150090,China)Abstract:Itisahotresearchfieldthatbiologicalhydrogencanbeproducedbydigestinghigh-strengthorganicwastewaterintheacidogenicphaseoftwo-phaseanerobesintheworld.Theresearchforhydrogen-producingmechanism,processschemeanddesign,engineeringcontrolinpracticeonfermentativebiologicalhydrogenproductionisreviewed.Therearethreetypesoffermentaivehydrogen-producingmetabolicpathwayswhicharebutyricacidfermentation,ethanolfermentationandformicacidscissionreactioninfermentativehydrogen-producingmicroorganism.Themainprocessismixedculturebyactivatedsludge.Theprocessesofpurecultureandimmobilizedcellaredeveloped.ThebacteriaofgenusesofEnterobacter,Clostridium,Citrobacterandthenewtypeoffermentativehydrogen-producingbacteriawiththeethano-lfermentationareisolatedintheworld.Thegermplasmcanbeusedsuchasinpureculture,cellimmobilizationandbioaugmentation.Themixedcultureforfermentativehydrogenproductionundertheguidanceoftheethano-ltypefermentativebiohydrogen-producingtheoryhasbeenestablishedandwillbeappliedinthedemonstrationfactory.Keywords:hydrogenproduction;fermentation;hydrogen-producingmechanism;processdesign;engineeringcontrol:2004-10-08;:2005-01-17:(863)(2002AA001034):(1961-),,,,;(1959-),,,,,,,0451-86282110,[e-mail],,,[1-2],,,(),H2CO22090[3],[4]()111[5]H2CO2(Clostridium),10Mar.2005现代化工253ModernChemicalIndustry20053(C.butyricum)(C.tyrobu-tyricum),21,:5C6H12O6+12H2O+2NAD++16ADP+16Pi4CH3CH2CH2COO-+2CH3COO-+10HCO-3+2NADH+8H++10H2+16ATP12[5-6]H2,,,H2CO2,1,,[7],[8]ATP;ADP;NAD;NADH图1细菌乙醇型发酵产氢途径13,[9],12%,14,CoA,H2H2,,,,,,[10],221-,,,,,[3,11-13]RhodobactorsphaeroidesEnterobacteraerogenesEnter-obactercloacae[14-16],[17],B49,(上接第9页),,,,,,,,,,(2),,;,,,;,,,,,,,,,,,1120053:,,22,,,pH[11]35~38,,[11,13]pH40~50,,44pH50,,,40pH45,,pH40,,,,pH40~45[18]CH2S(),,,,,4~6h[11],,(CaCO3)300mg/L,pH4~45;300mg/L,pH40,,NaHCO3NaOHNa2CO3,[3,11,13]331,16srDNA[19],,,11/mLh-1EnterobacteraerogenesE.82005291222~35mol/mol()[20-21]850073mol/mol()EnterobacteraerogenesHO-39189mol/mol()[22-23]27mL/L()6mL/L()EnterobacteraerogenesHU-1016944050~065mol/mol()[24]ClostridiumbeijerinckiiAM21B3440mL/g(COD)[25]3794mL/g(COD)2303mL/g(COD)ClostridiumbutyricumIFO3847703[26]ClostridiumbutyricumIFO13949115019mol/mol()ClostridiumbutyricumLMG77-111896mL/g(COD)ClostridiumpasteurianumDSM52522166mL/g(COD)[26]Clostridiumsp.NO.2145mol/mol()[27]ClostridiumthermocellumYS567mL/g(COD)[26]EnterobactercloacaeT-BT0813888[16]:Kumar[16](EnterobactercloacaeT-BT08),2963mmol/h[28]B49,2500mmol/h,[29]Rennanq-ilyf3,3180mmol/h12现代化工253[29]Oh[30](Citrobactersp.Y19),271mmol/h32,,[8,12-13,17,19]Yokoi[20,25]HO-39,120mL/(Lh);,240mL/(Lh);,850mL/(Lh),7,,,,,[3],,,,,,,,,,,[12]4,,:,,,;35~38,pH40~60,4~6h,,,;,,[6],[1]LopesPintoFA,TroshinaO,LindbladP.[J].InternationalJournalofHydrogenEnergy,2002,27(11-12):1209-1215.[2]LevinDB,PittL,LoveM.[J].InternationalJournalofHydrogenEner-gy,2004,29(2):173-185.[3].[D].:,1993.[4]HawkesFR,DinsdaleR,HawkesDL,etal.[J].InternationalJournalofHydrogenEnergy,2002,27(11-12):1339-1347.[5],.[M].:,1994.[6]RenNQ,WangBZ,HuangJL.[J].BiotechnologyandBioengineer-ing,1997,54(5):428-433.[7],,,.[J].,2004,19():537-541.[8]LiYF,RenNQ,YangCP,etal.Biohydrogenproductionbehaviourandmolecularcharacterizationofanewspeciesofanaerobicbacterium[A].In:GuiotSR.AnaerobicDigestion2004:Proceedingsofthe10thWorldAnaerobicConfernce[C].Montreal,Canada,2004,Volume2:648-653.[9]SodeK,WatanabeM,MakimotoH,etal.[J].AppliedBiochemistryandBiotechnology,1999,77-79:317-323.[10],.[M].:,2004.212-275.[11],,,.[J].,2002,23(2):252-256.[12].[D].:,2003.[13].-[D].:,2004.[14]ZhuH,SuzukiT,TsygankovAA,etal.[J].InternationalJournalofHydrogenEnergy,1999,24(4):305-310.[15]YokoiH,OhkawaraT,HiroseJ,etal.[J].JournalofFermentationandBioengineering,1997,83(5):481-484.[16]KumarN,DasD.Biologicalhydrogenproductioninapackedbedreac-torusingagroresiduesassolidmatrices[A].In:Proceedingsofthe13thWorldHydrogenEnergyConference[C].Beijing:SciencePress,2000.364-369.[17].B49[D].:,2003.[18],,,.[A].:,,.[C].:,2004.830-833.(下转第15页)1320053:nA+n/2H2=nAH(1)AH():yAyA+yAH=11+Ka(pH2)n(2),yAyAH,Ka,pH2,AAH,,1,,,,Ka,,,,[5],,[6]1[4]1Ni-W/-Al2O3/min-1340360380A/kJmol-1ln(A/kJmol-1)03300105400506600957131012503100304501005300944975160250050340140390093910621903000604400905001144117512:13C:+3H2(1)+nH2(2)(3)m+nH22mC+mC4H6+2n/m(4)(2);(3),;(4),,,2,:,PtPd,,,,;Ni,10%,,,,,k(Pt)k(Ni)k(Pd)=1871(k),PtNi26,21(上接第13页)[19],,,.[A].:,.21[C].:,2003.814-818.[20]TanishoS,IshiwataY.[J].InternationalJournalofHydrogenEnergy,1994,19(10):807-812.[21]TanishoS,IshiwataY.[J].InternationalJournalofHydrogenEnergy,1995,20(7):541-545.[22]YokoiH,OhkawaraT,HiroseJ,etal.[J].JournalofFermentationandBioengineering,1995,80(6):571-574.[23]YokoiH,TokushigeT,HiroseJ,etal.[J].Jo