Treatmentoptionsforwastewatereffluentsfrom

pharmaceuticalcompanies制藥公司廢水處理選項

A.M.Deegan,etal.Int.J.Environ.Sci.Tech.,8(3),649-666,Summer2011.ISSN

1735-1472

ABSTRACT摘要：

Inrecentyears,concernsabouttheoccurrenceandfateofactivepharmaceuticalingredients,

solvents,intermediatesandrawmaterialsthatcouldbepresentinwaterandwastewater

includingpharmaceuticalindustrywastewaterhasgainedincreasingattention.Traditional

wastewatertreatmentmethods,suchasactivatedsludge,arenotsufficientforthecomplete

removalofactivepharmaceuticalingredientsandotherwastewaterconstituentsfromthese

waters.Asaresult,complementarytreatmentmethodssuchasmembranefiltration,reverse

osmosisandactivatedcarbonareoftenusedinconjunctionwiththetraditionalmethodsfor

treatmentofindustrialwastewater.Mostoftheliteraturepublishedtodatehasbeenonthe

treatmentofmunicipalwastewater.However,thereisagrowingbodyofresearchthatlooksat

thepresenceofactivepharmaceuticalingredientsinindustrialwastewater,thetreatmentofthese

wastewatersandtheremovalrates.Thisarticle,reviewsthesetreatmentmethodsandincludes

bothtraditionalmethodsandadvancedoxidationprocesses.Thepaperconcludesbyshowing

thattheproblemofpharmaceuticalsinwastewaterscannotbesolvedmerelybyadoptingendof

pipemeasures.Atsourcemeasures,suchasreplacementofcriticalchemicals,reductioninraw

materialconsumptionshouldcontinuetobepursuedasthetoppriority.

近年來，更加關(guān)注出現(xiàn)水和廢水存在活性藥物成分、溶劑、中間體和原料及其歸宿，

包括制藥工業(yè)廢水。傳統(tǒng)的廢水處理方法，如活性污泥，不足以完全去除這些水中的活性

藥物成分和其他廢水成分。因此，通常與廢水處理的常規(guī)方法結(jié)合，采用補充處理方法，

如膜過濾、反滲透、活性碳。到目前為止，多數(shù)發(fā)表的文獻都是關(guān)于城市廢水處理。但是，

越來元多研究著眼于工業(yè)廢水中活性藥物成分的存在、這些廢水處理和去除率。本文綜述

這些處理方法，包括傳統(tǒng)方法和高級氧化工藝。文章最后表明廢水中的藥物問題不能只是

采用管末端措施節(jié)約。應(yīng)將繼續(xù)追求作為最優(yōu)先項的源頭措施，如替代關(guān)鍵化學(xué)品、減少

原料消耗。

Keywords:Advancedoxidation;Industrialwastewater;Pharmaticeuticaleffluent;Personal

careproducts

INTRODUCTION引言

ThepresenceofPharmaceuticalsandpersonalcareproducts(PPCPs)wasfirstidentifiedin

surfaceandwastewatersintheUnitedStatesandEuropein1960s(Stumm-ZollingerandFair,

1965).Concernsabouttheirpotentialriskwasraisedin1999(DaughtonandTernes,1999)with

theissueattractingconsiderableinterestafterthepresenceofpharmaceuticalsinriverwaterwas

linkedtofeminisationoffishlivingdownstreamofWastewatertreatmentplant(WWTP)outfalls

(Larssonetal.,1999).Furthermore,alinkbetweenanon-steroidalanti-inflammatorydrug,

diclofenacandtherenalfailureofvulturescontributingtothe>95%declineinitspopulationin

theIndiansubcontinentsincethe1990'shasbeenreported(Oaksetal.,2004).Publicawareness

wereraisedafterastudyshowedthatorganicwastewatercontaminants,includingPPCPs,were

presentin80%of139U.S.streams(Kolpinetal.,2002).Althoughtheconcentrationlevelsof

PPCPsfoundintheenvironmentareattraceconcentrations,theirchemicalpersistence,

microbialresistanceandsynergisticeffectsarestillunknown(Ankleyetal.,2007;Madukasiet

al.,2010),whichisacauseforconcern.Moreover,lowconcentrationscanelicitadverseeffects

on叫uaticlife(Miegeetal.,2008;2009).

I960年代，首先確定了美國和歐洲地表水和廢水中存在藥品和個人護理產(chǎn)品(PPCP)。

1999年，提出了其潛在風(fēng)險問題，將河水中藥物的的在與生活廢水處理廠(WWTP)排污口

下游魚類雌性化關(guān)聯(lián)起來之后，這一問題引起相當(dāng)大關(guān)注。另外，報告一種非-類固醇抗炎

藥物雙氯芬酸與禿鷲腎功能衰竭之間的關(guān)系，導(dǎo)致1990年代以來印度次大陸禿鷲數(shù)量下

降95%以上。一項研究表明，包括PPCP在內(nèi)的有機廢水污染物存在于80%的139條美國

河流中之后，公眾意識提高。盡管環(huán)境中發(fā)現(xiàn)的PPCP的濃度水平為痕量濃度，但是，依

然不清楚其化學(xué)持久性、微生物耐受性和協(xié)同效應(yīng)，這是關(guān)注的原因。另外，低濃度可能

引起不利水生生物影響。

Pharmaceuticalsentertheenvironmentfromamyriadofscatteredpoints.Themainsources

ofcontaminationincludepharmaceuticalproductionplants,WWTPs,hospitals,landfillsand

evengraveyards(KhetanandCollins,2007;Lillenbergetal.,2010).Themostinvestigatedroute

ofentryofpharmaceuticalsintotheenvironmentisthatfrommunicipalWWTPs.Human

excretionofunchangedorslightlytransformedActivepharmaceuticalingredients(APIs)

conjugatedtopolarmoleculessuchasglucoronideenterstheWWTPwheretheseconjugates

maythenbecleaved,releasingtheoriginalAPIintotheenvironment(Heberer,2002).Activated

sludgeWWTPshavereceivedparticularattention(Jonesetal.,2007;Watkinsonetal.,2007).A

limitednumberofstudiesalsofoundpharmaceuticalsindrinkingwater(Webbetal.,2003)and

hospitalwastewater(Suarezetal.,2009).MonitoringofAPIsbeingreleasedfrom

pharmaceuticalproductionfacilitiesisnotroutineandtheimportanceofsuchreleaseshasnot

yetbeenestablished(LarssonandFick,2009).Furthermore,pharmaceuticalindustry

wastewatersmaycontainorganicsolvents,catalysts,additants,reactants,intermediates,raw

materialsandAPIs(Sreekanthetal.,2009),whichmakesthemdifficulttotreat.Thepresenceof

toxicorrecalcitrantsubstancesinsuchwastewaterresultsinlowerChemicaloxygendemand

(COD)removalefficiencies(Chelliapanetal.,2006).Ithasbeenestimatedthatuptohalfofthe

pharmaceuticalwastewaterproducedworldwideisreleasedwithoutanytreatment(Enickand

Moore,2007).WhilesomeattentionhasbeenfocusedonEndocrinedisruptingchemicals(EDCs)

theremovalofotherspecificAPIsislargelyignored.Biologicaltreatmentofwastewateristhe

mostcommonandeconomicalwastewatertreatmentmethod(Kuliketal.,2008).However,

biologicalmethodshaveshowntobeinsufficientfortheremovalofallpotentiallyhazardous

constituentsofthewastewater(Claraetal.,2005;Jossetal.,2005;SumanRajandAnjaneyulu,

2005;Girietal,2008;2010).Recently,Membranebioreactor(MBR)technology,ozonationand

advancedoxidationprocesses(AOPs)haveshownvaryingdegreesofefficiencyforthe

treatmentofpharmaceuticalwastewaters(Andreozzietal.,2005;DollandFrimmel,2005a,

Perez-Estradaetal.,2005a;Andreozzietal.,2006;Helmigetal.,2007).Astheawarenessofthe

inefficienciesoftheindividualtreatmenttechnologiesfortheremovalofhazardoussubstancesin

pharmaceuticalwastewaterisincreasing,theintegrationandcombinationoftreatment

technologiesmayprovideamoreeffective,albeitexpensivesolutioninthefuture.Thisreview

aimstoprovideanoverviewofthecurrentknowledgeregardingtherangeoftreatmentmethods

availableforPPCPremovalfromindustrialwastewatersinordertogetbaselineknowledgeof

theeffectivenessofthevarioustreatmentoptions.Thisknowledgecouldhelppharmaceutical

productionfacilitiestobepreparedtotakepreventativemeasuresbeforerequiredtodosoby

legislation.ThisliteraturereviewwascarriedoutatDublinCityUniversityin2010.

藥物由無數(shù)分散點進入環(huán)境。主要污染源包括制藥廠、WWTP、醫(yī)院、垃圾填埋場，

甚至墓地。調(diào)查最多的藥物進入環(huán)境路徑是由市政WWTP。與葡萄糖等極性分子共拆的沒

有變化或略有變化活性藥物成分(API)的人類排泄物進入WWTP,之后這些共輾物可能分

解，將原始API釋放到環(huán)境中。活性污泥WWTP廠受到特別關(guān)注。有限的研究也在飲用

水和醫(yī)院廢水中發(fā)現(xiàn)了藥物。由藥品生產(chǎn)設(shè)施釋放AIP監(jiān)測并非例行，而且還沒有確定這

種釋放的重要性。另外，制藥工業(yè)廢水可能含有機溶劑、催化劑、添加劑、反應(yīng)物、中間

體、原料API,,使之難以處理。這類廢水中有毒或頑固性物質(zhì)的存在導(dǎo)致較低的化學(xué)需氧

量(COD)去除效率。估計多大一半的全世界產(chǎn)生的制藥廢水未經(jīng)任何處理排放。雖然一些

關(guān)注集中于內(nèi)分泌干擾物(EDC)上，但是，很大程度護忽視了其他特定API的去除。廢水

生物處理是最常見和最經(jīng)濟廢水處理方法)。但是，表明生物方法不足以去除廢水中的所有

潛危險成分。最近，膜生物反應(yīng)器(MBR)技術(shù)、臭氧氧化和高級氧化工藝(AOP)顯示處理

制藥廢水的不同程度效率。由于更加意識到單一處理技術(shù)去除制藥廢水有害物質(zhì)的效率低,

處理技術(shù)的集成和組合可能在未來提供更有效但更貴的解決方案。本綜述目的是概述目前

工業(yè)廢水中PPCP去除可用處理方法的知識，從而取得不同處理選項有效性的基準(zhǔn)知識。

這種知識有助于制藥生產(chǎn)設(shè)施在立法要求之前準(zhǔn)備好預(yù)防措施。這篇文獻綜述是2010年

在都柏林城市大學(xué)進行。

Conventionaltreatmentmethods常規(guī)處理方法

Biologicaltreatmentmethodshavetraditionallybeenusedforthemanagementof

pharmaceuticalwastewater(SumanRajandAnjaneyulu,2005).Theymaybesubdividedinto

aerobicandanaerobicprocesses.Aerobicapplicationsincludeactivatedsludge,membranebatch

reactorsandsequencebatchreactors(LaParaetal.,2002;SumanRajandAnjaneyulu,2005;

Noble,2006;Changetal.,2008andChenetal.,2008).Anaerobicmethodsincludeanaerobic

sludgereactors,anaerobicfilmreactorsandanaerobicfilters(Gangagnietal.,2005;Enrightet

al.,2005;Chelliapanetal.,2006;Oktemetal.,2007;Sreekanthetal.,2009).Thewastewater

characteristicsplayakeyroleintheselectionofbiologicaltreatments.Solvents,APIs,

intermediatesandrawmaterialsrepresentbiologicallyrecalcitrantsubstanceswhichaffectthe

efficiencyofbiologicaltreatmentsystems(Ozetal.,2004;Helmigetal.,2007).Activatedsludge

(AS)treatmentisunsuitableforthetreatmentofwastewaterwheretheCODlevelsaregreater

than4000mg/L(SumanRajandAnjaneyulu,2005).

傳統(tǒng)上制藥廢水管理采用生物處理方法。可用細分為好氧和厭氧工藝。好氧應(yīng)用包括

活性污泥、膜序批反應(yīng)器和序批反應(yīng)器。厭氧方法包括厭氧污泥反應(yīng)器、厭氧膜反應(yīng)器和

厭氧過濾器。廢水特性在生物處理選擇中起到關(guān)鍵作用。溶劑、API、中間體和原材料是

影響生物處理系統(tǒng)效率的生物頑固性物質(zhì)。活性污泥處理(AS)不適合處理COD水平大于

4000mg/L的廢水。

Conventionalactivatedsludgewithalonghydraulicretentiontime(HRT)hashistorically

beenthemethodofchoiceforthetreatmentofpharmaceuticalindustrywastewater(ElGohary

andAbou-Elea,1995;Ozetal.,2004).Ithasalowercapitalcostthanmoreadvancedtreatment

methodsandalimitedoperationalrequirement;itisgenerallymoreenvironmentallyfriendly

thanchlorination.However,highenergyconsumption,theproductionoflargeamountsofsludge

(Sreekanthetal.,2009)andoperationalproblemsincludingcolour,foamingandbulkingin

secondaryclarifiersareassociatedwithactivatedsludgeplants(Ozetal.,2004).Factorswhich

affecttheefficiencyofactivatedsludgefacilitiesforthetreatmentofpharmaceuticalwastewater

includeHRT,temperature,pH,dissolvedoxygen(DO),organicload,microbialcommunity,

presenceoftoxicorrecalcitrantsubstancesandthebatchoperationofpharmaceuticalproduction

facilities(LaParaetal.,2001a;LaParaetal.,2002;SumanRajandAnjaneyulu,2005).These

variablesrequiremodificationforadaptationtopharmaceuticalindustrywastewater.

長水力停留時間的傳統(tǒng)活性污泥歷史上一直是選擇的制藥工業(yè)廢水處理方法。投資成

本低于更先進的處理方法，運行要求有限；通常比氯化更環(huán)保。但是，與活性污泥相關(guān)的

是高能耗、產(chǎn)生大量污泥和運行問題，包括二沉池中顏色、起泡和膨脹。影響活性污泥設(shè)

施制藥廢水處理效率的因素包括HRT、溫度、pH、溶解氧(DO)、有機負荷、微生物群落、

有毒或頑固性物質(zhì)的存在，以及制藥生產(chǎn)設(shè)施的序批運行。需要調(diào)整這些變量，適應(yīng)制藥

工業(yè)廢水。

Temperatureisakeyfactorintheefficiencyofactivatedsludgefacilities.Ithasan

importantroleinselectingindividualmicrobialspeciesandoverallmicrobialdiversityinthe

activatedsludge.Thisiswhereindustrialwastewatercanbeverydifferentfrommunicipal

wastewater.CODremovalandexaminationof16srRNAofthebacterialcommunityinaerobic

biologicalsystemsat5℃intervalsbetween30and70℃showedthathightemperatureswere

limitingfactorstoCODremoval(LaParaetal.,2001b).Thenumberofbacterialspeciesdecline

withtemperaturebetween30-60℃,withtheactivatedsludgeprocessfailingattemperatures

above60-65℃(LaParaetal.,2001a).Atwostageoperationat55℃followedby30℃

producedalowerqualityeffluentthanoperationat30℃alone.Therefore,waterfromhigh

temperatureprocessesmustbecooledpriortotreatmentbyAS,whichincreasesthetimeand

costoftreatment.

溫度是影響活性污泥設(shè)施處理效率的關(guān)鍵因素。在選擇活性污泥中不同微生物種類和

整體微生物多樣性中起到重要作用。這正是工業(yè)廢水與城市廢水非常不同之處。30至70℃

之間5℃間隔的COD去除和好氧生物系統(tǒng)中細菌群落的16srRNA分析表明，高溫是COD

去除的限制因素。細菌種類數(shù)量在30-60C之間隨著溫度下降，活性污泥工藝在高于60~65℃

的溫度下失效。55℃和之后30℃下2級運行出水水質(zhì)低于只是30℃下運行。因此，高溫

工藝的水必須在AS處理之前冷卻，增加處理的時間和成本。

TheimpactofpharmaceuticalsontheASprocessappearstobenegligibleundernormal

operatingconditions(Stamatelatouetal.,2003).Howeverathigherconcentrations,whichmay

beexpectedinthewastewaterofpharmaceuticalmanufacturingfacilities,theymaybecome

inhibitory.WhilethereareanumberoflimitedstudiesontheremovalefficiencyofAPIsfrom

pharmaceuticalmanufacturingfacilities,itisknownthatremovalefficiencyofmunicipal

facilitiesisdependentontheAPIspresentinthewastewater(Uraseetal.,2005).ASisan

efficientmethodfortheremovalofsomeAPIs,butnotallfrommunicipalfacilities(Zwienerand

Frimmel,2003;Castiglionietal.,2006;Watkinsonetal.,2007).B-Lactamandquinlonedrugs

inparticularappeartobesusceptibletoaerobicoxidation.InaWWTPinBrisbaneAustralia,B

-Lactamantibioticsshowedhighbiodegradabilityduetohydroliccleavageofthe6-lactamring.

LincomycinandsulphonamidesweretheleastaffectedbyAStreatment(Jossetal.,2005).

Similarstudieshavealsofoundthattheefficiencyoftheprocessisdependentonthecompound

underinvestigation(Jossetal.,2005).Ibuprofen,naproxen,bezafibrateandestrogens(estrone,

estradiolandethinylestradiol)showedahighdegreeofremovalwhilesulfamethoxazole,

carbamezapineanddiclofenacshowedlimitedremoval(Claraetal.,2005;Jossetal.,2005;Xu

etal.,2008).Removalefficienciesarelikelytodecreaseduetothedevelopmentofmore

resistantAPIs(KhetanandCollins,2007).Anumberofpilotscalestudieswereconductedusing

Sequencebatchreactors(SBRs)andMembranebioreactors(MBRs)inanattempttoimprovethe

effectivenessofAStreatment(Claraetal.2005;Radjenovicetal.2007).SBRisanactivated

sludgemethodoftreatmentinwhichseparatetanksforaerationandsedimentationarenot

requiredandthereisnosludgereturn.Thistypeofprocessisidealforuseinsmallsystemsor

whenlandislimited(Ilerietal.,2003).Inonestudy,removalratesof82%Biochemicaloxygen

demand(BOD),88%COD,96%NH3and98%Suspendedsolids(SS)fromdomesticand

pharmaceuticalwastewaterwereachievedwithaSBRoperatedfora4haerationanda60min

sedimentationperiod(Ilerietal.,2003).Inanotherstudy,slightlylowerremovalefficienciesat

between63-69%ofCODlevelswereachievedusingSBRtechnology(Aguadoetal.,2008).

在正常運行條件下，藥物對AS工藝的影響似乎可以忽略不計。但是，在可能預(yù)計的

制藥廢水設(shè)施廢水中更高的濃度下，可能具有抑制作用。雖然制藥設(shè)施API去除效率的研

究數(shù)量有限，但是，中座周知，市政設(shè)施的去除效率與廢水中存在的API相關(guān)。AS是去

除一些API的有效方法，但是，并非都從市政設(shè)施去除。8-內(nèi)酰胺和quinline類藥物似乎

特別易于受好氧氧化。在一個WWTP,由于B-內(nèi)酰胺環(huán)水解裂解，6-內(nèi)酰胺抗生素顯示

高生物降解性。林可霉素和磺胺類藥物受AS處理影響最小。類似的研究也發(fā)現(xiàn)，這一過

程的效率取決于研究的化合物。布洛芬、蔡普生、苯扎貝特和雌激素(雌酮、雌二醇和雌二

醇)去除程度高，而磺胺甲惡理、氨基甲氮平和雙氯芬酸顯示去除有限。由于耐受性更強

API的發(fā)展，去除效率可能降低。采用序批反應(yīng)器(SBR)和膜生物反應(yīng)器(MBR),進行了一

些先導(dǎo)規(guī)模研究，嘗試改善AS處理效果。SBR是一種活性污泥處理方法，其中分離出曝

氣池，不需要沉淀池，沒有污泥回流。這種工藝非常適合小型系統(tǒng)或土地受限時。在一項

研究中，采用4h曝氣和60min沉淀時間暈的SBR,生活和制藥廢水達到82%生化需氧量

(BOD)、88%COD、96%NH3和98%懸浮固體(SS)的去除率。在另一項研究中，采用SBR

技術(shù)達到的去除效率略低，COD水平為63~69%之間。

MBRsareknowntobeeffectivefortheremovalofbulkorganicsandcanreplace

traditionalmethodsoroperateincombinationwithconventionalASsystemsorashybrid

systems(Noble,2006).ThemainadvantagesofMBRsoverASisthattheyrequirelessspacefor

operation(Yangetal.,2006),andcanalsotreatvariablewastewatercompositions(Changetal.,

2008).HighCODandBODremovalhavebeendemonstratedinpharmaceuticalproduction

facilities(DeWeveretal.,2007).Forexample,a10m3perdaycapacityMBRoperatedata

pharmaceuticalfacilityinTaiwan,removed95%ofCODand99%ofBOD(Changetal.,2008).

However,completeremovalofallAPIsisrare(Helmigetal.,2007).WhiletheMBRremoved

17-P-estradiol,17-B-estradiol,17-P-dihydroequilin,trimegestone,estriol,medrogestone,

norgestrel,andestradiolvaleratetonearandbelowthedetectionlimits,estrone,ethinylestradiol,

andvenlafaxine,aselectiveserotoninreuptakeinhibitor(SSRI),wereshowntobemoreresistant

totheMBRtreatment(Helmigetal.,2007).Oneexplanationforthisisthatpharmaceutical

compoundsaregenerallysmallerthanthemembraneporesandsoonlysubstancessorbedon

particlesareretained(Radjenovicetal.,2007).Inordertoremovethesmallercompounds,

membranessuchasthoseusedinreverseosmosisornanofiltrationareused,howevertheseare

expensive,whichhaslimitedtheirwidespreaduse(Claraetal.,2005).

認為MBR有效去除大量有機物，可提到傳統(tǒng)方法，或與傳統(tǒng)的AS系統(tǒng)或混合系統(tǒng)

組合運行。與AS相比，MBR的主要優(yōu)點是其要較少的運行空間，且可處理各種廢水成分。

驗證了制藥設(shè)施中高COD和BOD去除率。例如，在臺灣一個制藥設(shè)施運行的10m3/d規(guī)

模MBR去除了95%COD和99%BOD。但是，極少完全去除所有API。雖然MBR講17-

B-雌二醇、17-雌二醇、17-二氫馬奎林、曲美司酮、雌三醇、甲地孕酮、去甲孕酮

和雌二醇戊酸酯去除到接近或低于檢測限，但是，表明雌酮、雌二醇和一種選擇性5-羥色

胺攝取抑制劑(SSRI)文拉法辛更耐受MBR處理。對此的一種解釋是藥物化合物通常比膜

孔小，因此，只是截留吸附顆粒上的物質(zhì)。為了去除較小的化合物，采用反滲透或納濾所

用的膜，但是，這些很貴，限制其廣泛使用。

Theadvantagesofanaerobictreatmentoveraerobicprocessesisitsabilitytodealwithhigh

strengthwastewater,withlowerenergyinputs,sludgeyield,nutrientrequirements,operatingcost,

spacerequirementandimprovedbiogasrecovery.However,becauseawiderangeofnaturaland

xenobioticorganicchemicalsinpharmaceuticalwastewatersarerecalcitrantand

nonbiodegradabletothemicrobialmasswithintheconventionaltreatmentsystem,anaerobic

processesarenotalwayseffectiveinremovingthesesubstances.

與好氧工藝相比，厭氧處理的優(yōu)點是能夠處理高濃度廢水，能量輸入、污泥超濾、營

養(yǎng)物需求、運行成本、空間需求更低和提高沼氣回收率。但是，由于制藥廢水中大量天然

和異源有機對常規(guī)處理系統(tǒng)中微生物質(zhì)的頑固性和不可生物降解性，厭氧工藝并非總是有

效地去除這些物質(zhì)。

Onewayaroundthisistouseanaerobicmicroorganismssuchasmethanogenicarchaea,

whichcanadapttolevelsmanytimesthosethatinhibitunadaptedmethanogens(Fountoulakiset

al.,2008)aswellasincorporatingdifferentconfigurationsincludingbiomembranereactors,

stirredtankreactors,up-flowanaerobicfiltersandfluidisedbedreactors(GangagniRaoetal.,

2005;Chelliapanetal.,2006;Oktemetal.,2007).Up-flowanaerobicstagereactors(UASRs)

usedasapre-treatmenttoactivatedsludgeforindustrialeffluenthavebeenshowntobeefficient

fortheremovalofpharmaceuticalsevenathighconcentrations(Chelliapanetal.,2006;Oktem

etal.,2007).AUASRfedwithrealpharmaceuticalwastewatercontainingtheantibioticstylosin

andavilamycinshowedahighdegreeofCODanddrugremoval(Chelliapanetal.,2006).Fora

Hydraulicretentiontime(HRT)of4d,Organicloadingrate(OLR)of1.86kgCODm-3/d,COD

reductionwas70-75%,withanaverageof95%tylosinreduction;however,CODremoval

decreasedwithanincreaseintylosin(Chelliapanetal.,2006).AhybridUp-flowanaerobic

sludgeblanketreactor(USABR)whichcombinesaUASRandanaerobicfiltertechnology

showedsignificantremovalofCODatamuchhigherOLRfrompharmaceuticalwastewater

(Oktemetal.,2007).ForaHRTof2daysandanOLRof8kgCODm-3/dmaximumrateof

removalwasfoundtobe5.2kgCODm-3/d(Oktemetal.,2007).AUASRoperatingin

thermophillicmode(55℃)showedahighCOD(65-75%)andBODremoval(80-94%)even

athighOLRof9kgCODm-3/d(Sreekanthetal.,2009).Carbamazapine,however,wasnot

degradedusingaUASR.

一種方法是采用厭氧微生物，如產(chǎn)甲烷古生菌，可適應(yīng)抑制不適應(yīng)產(chǎn)甲烷菌數(shù)倍的水

平，且采用不同的配置，包括生物膜反應(yīng)器、攪拌池反應(yīng)器、上向流厭氧過濾器和流化床

床反應(yīng)器。上向流厭氧階段反應(yīng)器(UASR)用于工業(yè)廢水活性污泥的前處理，表明即使?jié)舛?/p>

高，也有效去除藥物。UASR進水為含抗生素泰樂菌素和阿維拉霉素的實際制藥廢水，顯

示COD和藥物高度去除。水力停留時間(HRT)為4d、有機負荷(OLR)1.86kgCODmWd,

COD降低70~75%,平均泰樂菌素降低95%；但是,COD去除率隨著泰樂菌素增加而降低。

混合上向流式厭氧污泥床反應(yīng)器(USABR)組合了UASR和厭氧濾池技術(shù)，表明更高OLR

下制藥廢水COD去除率高得多。HRT為2d,OLR為8kgeODm-3/d,發(fā)現(xiàn)最大去除速率

為5.2kgCODm-3/do高溫模式(55℃)下運行UASR,表明即使在9kgCODmWd的高OLR

下，COD(65?75%)和BOD(80?94%)去除率也很高。但是，采用UASR沒有降解卡馬西平。

Physio-chemicaltreatmentoptions物■化處理

Asseeninoxidationreactionssection,conventionalwastewatertreatmentsystemscanbe

effectiveinremovingsome,butnotallpharmaceuticalsfromwastewater.Therefore,other

treatmenttechnologieshavebeenexploredwiththeintentionoffindingsuitablepolishing

techniquestofurtherreducepharmaceuticalsconcentrations.Thesetechnologiesinclude

membraneseparation,chemicalremoval,activatedcarbon,chlorination,ultravioletirradiation

andothernovelapproaches.Theefficiencyofthesemethodsforthetreatmentofpharmaceutical

wastewatervariessignificantlyandisdescribedbelow.

如氧化反應(yīng)部分所見，常規(guī)廢水處理系統(tǒng)可有效地去除廢水中的一些但并非所有藥物。

因此，探索其他處理技術(shù)，目的是找到合適的深度處理技術(shù)，進一步降低藥物濃度。這些

技術(shù)包括膜分離、化學(xué)去除、活性碳、氯化、紫外線照射和其他新方法。這些方法處理制

藥廢水的效率差異很大，如下所述。

Membraneprocesses膜工藝

SeveralmembranetypesandapplicationswereevaluatedfortheremovalofAPIsatpilot

andfullscale,includingmicrofiltration,ultrafiltration,nanofiltration,reverseosmosis,electro

dialysisreversal,membranebioreactorsandcombinationsofmembranesinseries(Bellonaand

Drewes,2007;Snyderetal.,2007).Microfiltrationandultrafiltrationaregenerallynotfully

effectiveinremovingorganiccontaminantsasporesizesvaryfrom100-1000timeslargerthan

themicropollutantswhichcanslipthroughthemembranes.

評估了先導(dǎo)和全規(guī)模去除API的集中膜和應(yīng)用，包括微濾、超濾、納濾、反滲透、電

滲析逆轉(zhuǎn)、膜生物反應(yīng)器和膜串聯(lián)組合。由于孔徑比微污染物大100-1000倍不等，微污

染物可以通過膜，微濾和超濾并非完全有效去除有機污染物。

Thepressure-drivenmembraneprocessesNanofiltration(NF)andReverseosmosis(RO)

havebeenthefocusofattentionofmanyresearchersforthetreatmentofdrinkingwater

(Watkinsonetal.,2007).However,thestudiesontheuseofRO/NFforpharmaceuticalremoval

islimitedandmostofthestudiesemployedNFandROmembranesfortertiarytreatmentin

wastewaterrecyclingplantorfortreatingsalinegroundwater.(Nghiemetal.,2005;Yoonetal.,

2006;Snyderetal.,2007).ROindifferentconfigurationsshowedefficientremovalofthirty-six

personalcareproductsandendocrinedisruptingchemicalsincludingantibiotics,lipidregulators,

hormonesandoralcontraceptives,antiepilepticsandanalgesics(Snyderetal.,2007;Watkinson

etal.,2007).

壓力驅(qū)動膜工藝納濾(NF)和反滲透(RO)飲用水一直很多飲用水處理研究人員關(guān)注的

焦點。但是，采用RO/NF去除藥物的研究有限，大多數(shù)研究的NF和RO膜用于廢水循環(huán)

利用廠的三級處理或處理咸水地下水。不同配置的RO顯示有效去除36種個人護理產(chǎn)品和

內(nèi)分泌干擾化學(xué)物質(zhì)，包括抗生素、血脂調(diào)節(jié)劑、激素和口服避孕藥、抗癲癇藥和止痛藥。

ROmembranesremovedthemajorityofcompoundsinvestigatedtolevelsbelowthelimit

ofdetection.However,pentoxifylline,iodopromide,dimethyltoluamide(DEET),meprobamate,

phosphanetriyltripropanoicacid(TCEP),gemfibrozil,muskketoneandoxybenzonewere

detectedinthepermeateofavarietyoftheconfigurations(Snyderetal.,2007).Apossible

reasonforthisisshortcircuitingofthemembraneorthefailureofmembranesupportmedia.

(Bellonaetal.,2004).Radjenovicetal.(2007)investigatedtheremovalofarangeof

pharmaceuticalsincludinghydrochlorothiazide,ketoprofen,diclofenac,propyphenazoneand

carbamazepineusingNFandROtechnologiesforafullscaledrinkingwatertreatmentplant,

withhighrejectionpercentages(>85%)forallthepharmaceuticalsreported.Pharmaceuticals

canberejectedonNFandROmembranesbyoneoracombinationofthreebasicmechanisms:

sizeexclusion(sieving,stericeffect),chargeexclusion(electrical)andphysico-chemical

interactionsbetweensolute,solventandmembrane.Inlaboratory-scalecross-flowtestswith

NF-90membranesrejectionsofketoprofenanddiclofenacwerereportedtobegreaterthan90%

(Amyetal.,2005;Xuetal.,2005).InanotherstudywithROmembranestheretentionof

negativelychargeddiclofenacwas95%(Kimuraetal.,2003).Somestudiesreportedhigher

removalefficienciesofpolarandchargedcompoundsinNF/ROprocessesduetointeractions

withmembranesurfaces(OzakiandLi,2002;Bellonaetal.,2004;Amyetal.,2005;Braekenet

al.,2005).ThoughbothNFandROtreatmentshowspotentialasanefficientmethodfor

removingpharmaceuticalsfromthewastewater,thedisposalofthesludgewhichcouldcontain

thepollutantinamoreconcentratedformremains.

RO膜將研究的大多數(shù)化合物去除到低于檢測限水平。但是，在各種配置的滲透液中，

檢測到己酮可可堿、碘普羅胺、二甲基甲苯胺(DEET)、甲丙氨酯、三丙基磷酸(TCEP)、吉

非羅齊、鹿香酮和氧苯酮。可能的原因是膜短流或膜載體介質(zhì)失效。調(diào)查一個券規(guī)模飲用

水處理廠，采用NF和RO技術(shù)去除各種藥物，包括氫氯睡嗪、酮洛芬、雙氯芬酸、丙吩

酮和卡馬西平，報告的所有藥物截留率高(>85%)。NF和RO膜可通過三種基本機理之一

或其組合去除藥物：尺寸排除(篩分、空間效應(yīng))、電荷排斥(電)和溶質(zhì)、溶劑和膜之間物理

-化學(xué)作用。在采用NF-90膜的實驗室規(guī)模錯流實驗中，報告了酮洛芬和雙氯芬酸去除率超

過90%。在另一項采用RO膜的研究中，帶負電荷的雙氯芬酸截留率為95%。一些研究報

告了由于與膜表面的相互作用，極性和帶電化合物在NF/RO工藝中去除效率更高。盡管

NF和RO初始顯示出作為廢水中藥物去除高效方法的潛力，但是，依然需要處置可能含更

為濃縮刑庭污染物的污泥。

Activatedcarbon(AC)

ACisarecognisedconventionaltechnologyfortheremovalofbothnaturalandsynthetic

organiccontaminants(Hrubecetal.,1983;Annesinietal.,1987).Itismostcommonlyappliedas

apowderedfeedoringranularforminpackedbedfilters.Granularactivatedcarbon(GAC)can

beusedasareplacementforanthracitemediainconventionalfilters,providingbothadsorption

andfiltration.ItcanbeappliedfollowingconventionalAStreatmentasanadsorptionbed.

However,carbonregenerationanddisposalareenvironmentalconsiderations(Snyderetal.,

2007).

AC是公認的去除天然和合成有機污染物的傳統(tǒng)技術(shù)。最常作為粉末進料或填料床濾

器中顆粒形態(tài)應(yīng)用。顆粒活性碳(GAC)可替代傳統(tǒng)濾池中無煙煤濾料，起到吸附和過濾作

用。可在常規(guī)AS處理后作為吸附床使用。但是，碳再生和處置是環(huán)境考慮因素。

Ingeneral,sorptionisdescribedusingFreundlichisotherms,withsorptionbehaviour

quantifiedasthespecificsorptioncoefficient,KD(L/mg)(Nagaokaetal.,2002;Lietal.,2005).

Thiscoefficientistheratioofequilibriumconcentrationsofadissolvedcompoundinasystem

containingasorbent(ACorsludgeorsolids)andanaqueousphaseandexpressedas:

一般來說，吸附使用Freundlich等溫式描述，吸附特性量化比比吸附系數(shù)Kd(L/mg)。

這一系數(shù)是含吸附劑(AC或污泥或固體)和水相體系中溶解化合物平衡濃度之比，表示為：

WhereCsads(eq)istheamountofthecompoundsorbedonthesorbentatsorptionequilibrium

(mg/g),andCawads(eq)istheconcentrationofthecompoundintheaqueousphaseatsorption

equilibrium(mg/L).

式中Csads(Eq)是吸附平衡時吸附劑上化合物量(mg/g),CawHds(Eq)是吸附平衡時水相化

合物濃度(mg/L)。

SorptionisnegligibleforsubstanceswithlogKDvalueslessthan2,butislargewhenthe

logKDvalueisgreaterthan4(Claraetal.,2005).ThereportedLogKDvaluesofestrogenslike

Estrone,170-Estradioland17a-Ethinylestradiolrangedfrom2.2to2.8(Carballaetal.,2008)

and2.0to2.84(Ternesetal.,2004),respectively.SincetheselogKDvaluesarebetween2and4,

sorptioncanbesuitableasaremovalmechanism.Duttaetal.(1997)studiedtheadsorptionand

desorptionof6-aminopenicillanicacid(6-APA)inaqueoussolutionusingactivatedcarbon.They

foundthattheadsorptionprocesswashighlyreversible,theextentofreversiblyadsorbed6-APA

wasaround93%.

對于logKD值小于2的物質(zhì)，吸附作用可以忽略不計，當(dāng)logKD值大于4時，吸附作

用很大。報告雌激素的LogKD值。如雌酮17B-雌二醇和17a-乙烯基雌二醇分別在2.2h

至U2.8和2.0至U2.84之間。月餅與這些logKD值在2和4之間，吸附適合作為去除機理。

采用活性炭研究水相中6-氨基青霉烷酸(6-APA)吸附和解吸特性。發(fā)