大孔树脂吸附对城镇混合型废水的深度处理研究

（申请工学硕士学位论文）大孔树脂吸附对城镇混合型废水的深度处理研究培养单位：土木工程与建筑学院学科专业：市政工程研究生：李春标指导教师：李孟教授2017年3月大孔树脂吸附对城镇混合型废水的深度处理研究李春标武汉理工大学武汉理工大学硕士学位论文I摘要城镇污水处理厂收水成分上呈现出愈加明显的工业+市政混合型趋势，其中纺织印染废水占比之大以及对城镇污水处理厂处理效果的影响之大不容忽视。纺织印染工业作为我国传统优势工业支柱产业之一，其产生的废水水量大、成分复杂、难降解。城镇污水处理厂常规处理工艺往往难以应对，加之环保要求的不断提高，探究一种针对印染—市政混合废水的高效、节能的深度处理工艺迫在眉睫。本文以纺织印染大省山东省内一接收印染—市政混合废水处理厂处理现状为出发点，在参考相关研究资料后，提出在其常规处理工艺基础上，加入大孔树脂对混合废水进行深度处理，对其吸附过程、影响因素、吸附机理等进行分析探究，为实践提供一定借鉴。通过实验探究综合分析表明：1.在所选六种大孔树脂（D280、DA201、DA-201、AB-8、D3520和XAD-2）中，D3520对混合废水中难处理的PVA等污染物呈现出最为接近对照吸附材料粉末活性炭的吸附效果，且色度去除效果好，出水清澈，CODcr吸附能力可达15.6mg/g。2.D3520树脂静态吸附过程呈现较明显的两步，吸附前期吸附速率较快，随后逐渐减慢直至240min左右时达到吸附平衡状态，混合废水中CODcr浓度由最初的95.31mg/L降低至35.54mg/L，CODcr去除率达到62.7%，色度去除率高达95%以上。3.混合废水初始浓度的提高对D3520树脂的吸附能力有促进作用；D3520树脂吸附效果随pH值的增加而提高，当混合废水pH值达弱碱性后，继续提升pH值，树脂吸附能力提升幅度小；且在选定温度范围内，其吸附效果呈现类似趋势，结合相关排放标准和实际操作要求，选定初始浓度100mg/L、pH值8.0、温度25℃为后续吸附条件。4.吸附等温实验分析表明，Langmuir等温方程可以更好的描述D3520树脂对混合废水中PVA等污染物的吸附过程，其吸附过程属于单分子层的物理吸附，且吸附为优惠吸附，易于发生。5.D3520树脂对印染混合废水中PVA等污染物的吸附是可以自发进行的过程，即自由能变均为负值（0G）；其吸附焓变H为介于3~6kJ/mol（小于40kJ/mol）的正值，表明D3520树脂的吸附过程具有明显的物理吸附特性；吸附熵值0S，整个树脂吸附过程是熵增加的过程。6.动力学分析表明：树脂的整个吸附过程受到了树脂表面液膜扩散和内部孔道扩散的共同控制，其中成为D3520树脂整个吸附过程限速过程的就是吸附速度较慢的孔道扩散吸附过程。武汉理工大学硕士学位论文II7.采用50%乙醇浓度+蒸馏水、5%盐酸浓度+蒸馏水、以及5%氢氧化钠浓度+蒸馏水组合对D3520树脂进行静态再生效果最佳。8.在树脂动态固定床吸附中控制上样流速0.24m/h，树脂床高径比为2:1，吸附温度为25℃时D3520树脂对混合废水中CODcr吸附效果较佳；而在采用静态吸附所选脱附工艺进行脱附时，控制脱附流速为4.8cm/h，脱附温度为25℃时，脱附效果最佳；且在经过5次重复吸附-脱附再生实验后，D3520树脂依然可以保持最低平均79.5%的CODcr吸附率和95%以上的色度去除效果，说明D3520树脂在对印染混合废水进行深度吸附处理时拥有良好的稳定性。关键词：市政-印染混合废水，大孔树脂，深度处理，吸附机理武汉理工大学硕士学位论文IIIAbstractThecomponentsofwastewaterwhichflowintourbansewagetreatmentplantsincreasinglypresentthetrendofindustrial+municipalfeatures.Thereinto,thelargeproportionoftextileprintinganddyeingwastewateranditsimpactonthetreatmentefficienciesofurbansewageplantscannotbeignored.Asoneofthetraditionaladvantageindustriesofourcountry,theprintinganddyeingsewageisofgreatquantity,highcolorityandpoorbiochemicalpurificationability.Theconventionalprocessesareoftenunabletocopewithit,combinedwithenvironmentalprotectionrequirementdeepening,sotiisimminenttoexploreahighefficiencyandenergy-efficientadvancedtreatmentprocesstosolvethisproblem.Inthispaper,macroporousresinisappliedinsewageadvancedtreatmentaccordingtothetreatmentstatusofasewageplantwhichdealwithindustrial+municipalwastewaterinShandongprovinceandalotofrelevantresearch.Theadsorptionprocess,influencingfactors,adsorptionmechanism,etcareanalyzedsoastoprovidereferenceinpractice.Theexperimenttoexplorethecomprehensiveanalysisshowsthat:1.TheadsorptioneffectofPVAandotherpollutantswithD3520showedthemostclosetopowderedactivatedcarbonamongtheselectedsixkindsofmacroporousresins(D280,DA201,DA-201,AB-8,D3520,D3520andXAD-2),andthecolorremovaleffectisgood,theCODcradsorptioncapacityofupto15.6mg/g.2.D3520resinadsorptionprocessshowedamorepronouncedtwostepadsorption.Itsadsorptionratewasfastinthebeginningandthenslowdownuntilreachtheadsorptionequilibriumstatein240min.TheconcentrationofCODcrinmixedwastewaterdecreasedfrom95.31mg/Lto35.54mg/L,theremovalrateofCODcrreached62.7%,thechromaremovalrateisashighas95%.3.IncreasingtheinitialconcentrationofmixedwastewatercouldPromotetheadsorptioncapacityofD3520.D3520resinadsorptioneffectincreasedwiththepHvalueincreased,whenthemixedwastewaterpHvalueisweaklyalkaline,resinadsorptioncapacityincreaseslittlecontinuetoenhancethepHvalue,andtheadsorptioneffectshowedasimilartrendattheselectedtemperaturerange.Combinedwiththerelevantemissionstandardsandtheactualoperationrequirements,selectedinitialconcentration100mg/L,pHvalue8,thetemperatureof25℃forsubsequentadsorptionconditions.4.TheisothermaladsorptionexperimentsshowedthattheLangmuirisotherm武汉理工大学硕士学位论文IVequationcanbetterdescribetheadsorptionprocessofD3520resinforpollutantsofPVAinmixturewastewater.Theadsorptionprocessbelongstoasinglemolecularlayerphysicaladsorption,andtheadsorptionispreferentialadsorption,easytooccur.5.TheadsorptionprocessofPVAindyeingmixedwastewaterwithD3520resincanbespontaneous,anditsfreeenergychangesarenegative(0G).Theadsorptionenthalpychangebetween3~6kJ/mol(lessthan40kJ/mol),suggestingthattheadsorptionprocessofD3520resinhastheobviouscharacteristicsofthephysicaladsorption.0Sindicatestheresinadsorptionprocesswasofentropyincrease.6.Thekineticanalysisindicatedthattheadsorptionprocessofresiniscontrolledbysurfacefilmdiffusionoftheresinandinternaldiffusionchannels.TheslowporediffusionadsorptionprocessofD3520resinbecomestheratelimitingprocess.7.Ithasoptimumregenerationeffectusing50%ethanol+distilledwaterand5%hydrochloricacid+distilledwater,distilledwaterand5%sodiumhydroxideasregenerationprocess.8.Controllingsampleflowrate0.24m/h,theresinbedheighttodiameterratio2:1,adsorptiontemperature25degreescentigradeinthefixedbeddynamicadsorptionprocess,theadsorptioneffectofCODcrinwastewaterisbetter.Andcontrollingdesorptioncontrolrate4.8cm/h,desorptiontemperature25degreescanrecievetheoptimumdesorptioneffect.Andafter5timesofrepeatedadsorption-desorptionexperiments,theremovaleffectofCODcrcanstillmaintaintheminimumaverage79.5%andmorethan95%chromaremova