光催化去除焦化废水中氰化物的影响因素研究成泽伟

《》2009151成泽伟,苍大强,全　魁(北京科技大学冶金与生态工程学院,北京100083):氰化物对生物体具有剧毒作用。利用纳米TiO2粉体,以紫外光为光源,进行了光催化降解去除焦化废水中氰化物的实验研究,系统考察了焦化废水的pH值、CN-初始浓度、TiO2用量、温度、曝气量等因素对去除焦化废水中CN-的影响。结果表明,当废水pH值为2.0～3.0,TiO2用量为0.3g/L,温度为30℃时,总CN-去除率可达43.6%。光催化去除CN-过程符合一级动力学反应规律。当曝空气量为0.8L/min时,总CN-去除率提高到58.2%;当曝氧气量为1.0L/min时,总CN-去除率提高到68.2%。并且TiO2可以多次循环使用。:焦化废水;TiO2;光催化;CN-:X756　　　:B　　　:1006-6772(2009)01-0110-05　　:2008-07-29　　:(1975-),,,,。　　(Cya-nide),(CN-),(HCN)。,,[1]。《(GB13456-92)》0.5mg/L。2070。,。,,,。TiO2,,,,。1　TiO2(387.5nm),,(e-/h+),TiO2。TiO2-H2O,h+OH-H2O·OH。·OH,,。e-O2·O-2·OOH,。CN-[2]:2·OH+CN-※OCN-+H2O2·OOH+2CN-※2OCN-+H2O2CN-OCN-,:OCN-+2H2O※HCO-3+NH3NH3·OH·OOHN2NO-3[3-4],HCO-3CO2。2　2.1　实验原料和仪器TiO2。110DOI:10.13226/j.issn.1006-6772.2009.01.008　　　　　　　　　　　　　　　　　　《CAJ-CD》20～30nm,98%。,1。1　CODCr/(mg·L-1)NH3-N/(mg·L-1)CN-/(mg·L-1)pH3000～400060～1001.10～1.507.0～9.0:;;;TG16-WS;DHG-9140A;EMS-13;250W,350nm～450nm,365nm。MERCKNOVA60。LZB-2;PHSJ-3FpH。1。1　1———;2———;3———;4———;5———;6———;7———2.2　实验方案15min。600mL,TiO2,NaOH、H2SO4pH。15min,。,,,,。,、,CN-,CN-。3　3.1　光催化剂用量对总CN-去除率的影响:30℃,120min,H2SO4NaOHpH3.0、6.09.0,TiO2。2:pH3.0、6.09.0,TiO2,CN-;0.3g/L,CN-;,CN-。2　TiO2CN-。,。,·OH,,,,,,。,CN-,,0.3g/L。3.2　pH值对总CN-去除率的影响:30℃,TiO20.3g/L,120min,H2SO4NaOHpH1.0～12.0,pH。3:pH3.0～8.0,CN-pH;pH2.0～3.0,CN-;pH1.0,CN-,。3　pHCN-TiO2,[5]:-Ti-OH+2※-Ti-OH+H+-Ti-OH※-Ti-O-+H+,TiO2,111《》2009151,CN-,CN-,;(pH2.0),,,,。pH8.0,CN-pH;pH8.0,CN-。,,OH-,·OH,[6]。,pH2.0～3.0,CN-;pH8.0,CN-。3.3　温度对总CN-去除率的影响:pH3.0,TiO20.3g/L,120min,,CN-。4:,,30℃,。OCN-,。,[7—8]。4　CN-3.4　,Langmuir-Hinshelwood[9]。CN-,TiO2,CN-。:30℃,pH3.0,TiO20.3g/L。2。2　CN-CN-(mg/L)k(min-1)R20.37-ln(Ct/C0)=0.0067t+0.02330.00670.98810.73-ln(Ct/C0)=0.0057t+0.01750.00570.98961.10-ln(Ct/C0)=0.0045t+0.01640.00450.9819　　2,-ln(Ct/C0)t,TiO2CN-,CN-,。3.5　曝气对总CN-去除率的影响,:30℃,pH3.0,TiO20.3g/L,120min,CN-。5:0.8L/min,CN-58.2%;0.8L/min,CN-;0.8L/min,CN-。O2,,,O-2·,O-2·,O2-2、·OOH、H2O2·OH。,,[10]。O2:O-2·+H2O※·OOH+OH-2OOH·※H2O2+O2·OOH+H2O+e-※H2O2+OH-H2O2+e-※OH-+·OH,,,,-,,。50.8L/min。5　CN-112　　　　　　　　　　　　　　　　　　《CAJ-CD》,5:1.0L/min,CN-68.2%;5,,,,CN-10%。3.6　催化剂重复利用,、、、。TiO26,,CN-,33.2%。TiO2,CN-。TiO2。,TiO2,。4　　　TiO2,,Langmuir-Hinshelwood,。CN-,。,、pH、、CN-,。CN-:0.3g/L、pH2.0～3.0、30℃,CN-43.6%;CN-,。0.8L/min,CN-58.2%;1.0L/min,CN-68.2%。TiO2,,。:[1]　,,.[J].,2004,12(22):13-17.[2]　.[J].,2006,4(5):1-5.[3]　LeeJaesang,Park,Hyunwoong,Choi,Wonyong.SelectivephotocatalyticoxidationofNH3toN2onplatinizedTiO2inwater[J].EnvironmentalScienceandTechnology,2002,36(24):5462-5468.[4]　ZhuXin-dong,SunnyrC.EffectsofpHandCatalystConcentrationonPhotocatalyticOxidationofAqueousAm-moniaandNitriteinTitaniumDioxideSuspensions[J]　.EnvironmentalScienceandTechnology,2005,39(10):3784-3791.[5]　,,,.TiO2-SBR.,2007,27(9):1445-1449.[6]　,,,.TiO2B[J].,2006,29(6):16-17.[7]　DaneshvarN,RabbaniM,ModirshahlaN,etal.KineticModelingofPhotocatalyticDegradationofAcidRed27inUV/TiO2Process[J].JPhotochPhotobioA,2004,168:39-45.[8]　,,.ZnOX-BR[J].,2008,8(1):55-59[9]　WangShinpon,Shiraishishinpon,NakanoKatsuyuki.Asynergisticeffectofphotocatalysisandozonationonde-compositionofformicacidinanaqueoussolution[J].ChemicalEngineeringJournal,2002,87(2):261-271.[10],,,.TiO2[J].,2007,33(9):34-38.Studyoninfluencingfactorsforphoto-catalyticremovalofcyanideincokingwastewaterCHENGZe-wei,CANGDa-qiang,QUANKui(SchoolofMetallurgicalandEcologicalEngineering,UniversityofScienceTechnologyBeijing,Beijing100083,China)Abstract:Cyanideisseriouslyharmfultoorganisms.Photo-catalyticdegradationandremovalofcyanideincokingwastewaterwasexaminedbynano-TiO2underUltraviolet.EffectofpHofcokingwastewater,theinitialconcentra-tionoftotalCN-,amountofTiO2,temperatureandaerationrateonremovalofCN-incokingwastewaterwerein-vestigatedsystematically.ExperimentalresultsshowthatremovalrateoftotalCN-is43.6%underthecondition113《》2009151thatpHisat2.0～3.0,TiO2amountis0.3g/L,temperatureis30℃.Photo-catalyticremovalofCN-accordswiththefirstgradedynamicequation.Whenthevolumeofairis0.8L/min,removalrateoftotalCN-canreach58.2%.Whenthevolumeofoxygenis1.0L/min,removalrateoftotalCN-canbeupto68.2%.AndTiO2canberecycledseveraltimestoreuse.Keywords:cokingwastewater;TiO2;photo-catalysis;CN-(99)DerivationandexperimentstudyoftheformulaforcalculatinghardgrovegrindabilityindexofcoalSUNGang(CoalTestResearchInstitueBranch,ChinaCoalResearchInstitue,Beijing100013,China)Abstract:ThepaperhasderivedtheChina'sformulaeforcalculatingHardgrovegrindabilityindexofcoal,andex-perimentstudyshowsthatlinearregressionformulaisbestinthewholevaluescale,andthatnear“regressionpoint”,“singlepoint”regressionformulaeofferbettervalueaccuracy,butnotasgoodas“singlepoint”regressionweightedformulainthewholevlauescale.Keywords:Hardgrovegrindabilityindex;formula;coal(109)ResearchondisposaltechniquesforcoalminesludgeLIUZhen-rong1,SONGZheng-chang1,LVQiao-ling2,LIUFang1,LiJian1(1.SchoolofMechatronicEngineering,ChinaUniversityofMiningandTechnology,Xuzhou221008,China2.SchoolofChemicalEngineeringandTechnology,ChinaUniversityofMiningandTechnology,Xuzhou221008,China)Abstract:Minedrainagesludgeisaresourceofgreatpotentialvalue.Thesourcesandcompositionofminesludgearean