Membranetreatment

Differenttreatmentssuchaschemicalandbiologicalmethodshavebeendevelopedtotreat
wastewater.Thefollowingreasonshamperwiderapplicationofthesemethods:
Highcostoftreatment,Usingtoxicchemicals,Spaceforinstallation,Secondarypollution.
Asaresult,physical,membranebasedseparationbecamethepromisingtechnologyforthe21st
century.Themembranepressuredrivenprocessreliesontheporesizeofthemembranetoseparate
thefeedstreamcomponentsaccordingtotheirporesizes[97].
2.4.1.Microfiltration(MF),ultrafiltration(UF),nanofiltration(NF),andreverseosmosis(RO)
membranes
Membranesarethinfilmsofsyntheticorganicorinorganicmaterials,whichselectivelyseparatea
fluidfromitscomponents.MembraneseparationprocessessuchasMF,UF,NF,andROcanbe
usedtoseparatedifferentsizedmaterials.MFisseparationofsuspendedparticles,UFisthe
separationofmacromolecules,andROistheseparationofdissolvedandioniccomponents[98].NF
membranesaregenerallydesignedtobeselectiveformultivalentionsratherthanforunivalentions.
ROmembranesaredesignedtorejectallspeciesotherthanwater.Theyareunabletoofferasignif
icantbarriertodissolvedgasesandcertainlowmolecularweightorganicmolecules[99].
Membranesystemscancompetewithmorecomplextreatmenttechnologiesfortreatingwaterwith
highoilcontent;lowmeanparticlesize,andflowratesgreaterthan150m 3/handis,
consequently,suitableformediumandlargeoffshoreplatforms[100].
UFisoneofthemosteffectivemethodsforoilywastewatertreatment,especiallyforproduced
water,incomparisonwiththetraditionalseparationmethodsbecauseofitshighoilremovaleffi
ciency,thereisnonecessityforchemicaladditives,energycostsarelow,andspacerequirements
small[101].Inastudy,Liaetal.[102]studiedatubularUFmodelequippedwithpolyvinylidene
fluoridemembranesmodifiedbyinorganicnanosizedaluminumparticlestotreatoilfieldproduced
water.Nanosizedaluminaparticlescanimproveantifoulingperformanceofmembranes.Resultsof
theirexperimentsshowedthatCODandTOCremovalefficienciesofthesystemwere90%and
98%,respectively,andoilresiduewaslessthan1%.
BilstadandEspedal[103]comparedMFandUFmembranesinpilottrialtotreattheNorthSea
oilfieldproducedwater.ResultsshowedthatUF,butnotMF,couldmeeteffluentstandardsfor
totalhydrocarbons,SS,anddissolvedconstituents.ByUFmembranetreatmentwithmolecular
weightcutoff(MWCO)wasbetween100,000and200,000Da,totalhydrocarbonconcentration
couldbereducedto2mg/Lfrom50mg/L(96%removal).Benzene,toluene,andxylene(BTX)
werereducedby54%,andsomeheavymetalslikeCu,andZnwereremovedtotheextentof95%.
LeeandFrankiewicz[104]testedahydrophilicUFmembraneof0.01?mporesize,incrossflow
modetotreatoilfieldproducedwater.Ahydrocyclonewasfirstusedtodesandanddeoilthe
wastewater.Thehydrocyclonepretreatedtherawproducedwaterremovingsolidsandoilcontent
by73%and54%,respectively.O&GconcentrationafterUFcouldbereducedtolessthan2mg/L.
ThepreferredfeedwaterspecificationforidealperformanceofUFwasoilandsolidslessthan50
and15ppm,respectively.

LowpressuredrivenmembranesforMFofmembraneporesizebetween0.1and5?morUFwith
membraneporesizelessthan0.1?moracombinationofMF/UFpolymericorceramicmembranes
aresuitableforremovingoilcontentofoilfieldproducedwater.However,ceramicmembranesare
preferredoverdelicatepolymericmembranesbecausetheformerhaveabettertolerancetohigh
temperature,highoilcontent,foulants,andstrongcleaningagents[105].CeramicultraandNF
membranesarearelativelynewclassofmaterialsforthetreatmentofproducedwater[106].
Chenetal.[107]testedperformanceofceramiccrossflowMFstoseparateoil,grease,andSSfrom
producedwater.PermeatequalityofdispersedO&Gwas5mg/LandofSSwaslessthan1mg/L.
CombinedmembranepretreatmentandROtechnologyareeffectivemethodsforproducedwater
treatment[108].Xuetal.[109]investigatedatwostagelaboratoryscalemembranetotreatgas
fieldproducedwatergeneratedfromsandstoneaquifersasshowninFig.5.
TheystudiedultralowpressureROandNFmembranestomeetqualitystandardsforpotableand
irrigationwater,andiodideconcentrationinbrine.

Bentoniteclayandzeolitemembrane
Researcheshaveproposeddifferentmaterialsforconstructionofmembraneinvariousoperational
conditions.Keytechnicalobstaclestocosteffectiveapplicationofmembranesinproducedwater
treatmentincludelowaveragefluxrate,fluxdegradation,anduncertainmembranelife.Besides,
concernsregardingusingmembranesinoilfieldproducedwatertreatmentincludesensitivityto
variationinflowandpretreatmentandpurification[110].
Zeolitemembranespossessstablechemical,mechanical,andthermalproperties.Theycanbeused
instrongsolventenvironments,andathightemperaturesandpressures.ROzeolitemembranesare
suitablefortreatingoilfieldproducedwatertoseparatedifferentions(Na +,K+,Ca2+,andMg2+)
[111].Lietal.[112]studieddesalinationofoilfieldbrineusingapuresilicatezeolite
membrane.Inthisstudy,theyfoundthationfluxwasindependentoftheoperatingpressureandit
increasedasfeedconcentrationwasraisedfrom0.001to0.3M.
Abenchscalecellwasusedtopurifyoilfieldproducedwaterwithbentoniteclaymembranes.
ResultsoffeedingitwithdifferentTDSshowedthatclaymembraneswerenotsuitablefortreating
producedwaterwithhighTDS[113].
2.4.3.Combinedsystems
Incombinedsystems,differentphysical,chemical,andbiologicalmethodsareusedfor
pretreatmentofmembraneunits.
Barrufetetal.[114]proposedadsorptionasaphysicalpretreatmentprocesstoprecedeMFand
ROtoconvertbrinetoirrigationqualitywater.Thesystemincluded:
Sorptionpelletsmadeofmodifiedclaymaterial, MF,RO.
Resultsofastudyofthesystemshowedthatmodifiedclaycouldremoveoilbetterthanactivated

carbonandROcouldremovemorethan95%ofTDS.
Inastudytotreatoilfieldproducedwaterscontainingboronandsolubilizedhydrocarbon
compounds,amethodcomprisingwatersofteningtoremovesubstantiallyalldivalentcations
combinedwithROmembranewasused[115].Inaprocesstomeetdrinkingwaterquality
standardsfromoilfieldproducedwater,differentphysical,andchemicalpretreatmentsforROwere
proposedasfollows[116]:
Airfloatation,Clarification,Softening,Filtration,
RO.
Optimizedpretreatmentanduniqueseparation(OPUS)isacombinedphysical,andchemical,
treatmentsystemwhichwasusedforproducingboilerfeedwaster.OPUStechnology,which
consistsofmultipletreatmentprocesses,includingdegasification,chemicalsoftening,media
filtration,ionexchangesoftening,cartridgefiltration,wasusedasapretreatmentforRO.The
softenedwaterwasusedinChevronsoncethroughsteamgenerators,whichproducedthisgas
steamforoilextraction[117].Inasimilarmethod,Qiaoetal.[118]proposedacombinedsystem
pilotscaleplanttotreatoilfieldproducedwaterasshowninFig.6.Theeffluentsofthetreatment
systemcouldreduceoilandSSofoilywastewatertolessthan0.5and1mg/L,respectively.
Cakmakceetal.[119]investigateddifferentpretreatmentalternativestoROandNFmembraneto
findthemostappropriatetreatmentcombination.Finally,theyproposedasystemconsistingofthe
followingtreatmentasshowninFig.7.TheeffluentofthecombinedsystemcouldreduceCODtoo
lessthan250mg/L.
Becauseoftheneedforfrequentregenerationofphysicaladsorbersandhighrunningcostand
sludgeproductionfromchemicaltreatment,someresearchershaveproposedbiologicalpretreat
menttoprecedemembranetreatment.Nevertheless,theoptimaltreatmentofhighlysaline
wastewaterinvolvesabiologicaltreatmentofwastewaterwithacclimatedmicroorganisminsaline
environmentpriortomembranetreatmentespeciallywithRO[56].
Inapilotstudytoreuseoilfieldproducedwaterforirrigationandpotablewater,aseriesof
processeswereproposedasshowninFig.8.Thewarmsofteningprocessremoved95%hardness
(frominitialhardnessof1000mg/L)andROremoved95%ofTDS[120].Ontheotherhand,Tsang
andMartin[121]investigatedadifferentarrangementofacombinedsystemtotreatproduced
waterasfollows:
Dissolvedgasfloatation,Walnutshellfiltration,Warmsoftening,
Membranebioreactor,RO.
Doranetal.[122]proposedapilotprocesstotreatproducedwater.Theprocessincludedthe
following:
PrecipitativesofteningatpH9.510.0toremovesomehardnessandboron,andmostofthesilica,
HeatexchangecoolingandpHreduction,Fixedfilmbiologicaloxidationoforganicsand
ammoniaremoval

usingatricklingfilter,Filtration,Ionexchangesofteningtoremoveresidualhardness, RO.
Thetreatedproducedwatercouldmeetindustrialandirrigationrequirements.
Kwonetal.[123]concentratedonremovingvolatilehydrocarbonbeforebiologicaltreatment.
Theyusedsurfactantmodifiedzeolite(SMZ)adsorbentbedsandamembranebioreactor(MBR)in
combinationtoreducetheorganiccarboncontentofproducedwaterpriortoRO.Inthepilotplant,
syntheticandrealproducedwaterwerecycledthroughSMZadsorbentunitstoremovevolatile
organiccompounds(BTEX,acetone)andsemivolatileorganiccompounds(e.g.,napthalene).The
effluentfromtheSMZunitswasfedtotheMBRforremovaloftheorganicacidcomponentof
TOC.IntheMBR,acclimatedactivatedsludgewasseededandsubmergedmembraneswereusedto
filterbiologicaltreatedwastewater.Resultsofcontinuousrunwiththecombinedsystemshowed
thatremovalefficiencyofSMZwas40%oftheinfluentTOC(600mg/L).BTEXconcentrations
werereducedfromtheinitialinputlevelof705mg/LbytheSMZunitsandtoanaverageof2
mg/LaftertheMBR.
MurrayGuldeetal.[124]proposedacombinedonshoresystemforproducedwatertreatment.They
usedahybridROconstructedwetlandtotreatproducedwaterforuseinirrigation.Thetreatment
systemconsistedofdifferentsizeoffilters,acationexchanger,andRO.Thefirststagecould
remove95%and94%ofconductivityandTDS,respectively(Fig.9).TheROpermeateflowtoa
pilotscaleconstructedwetland.Thewetlandconsistedoffourcellsinserieswithvegetation
collectedfromtheoilfieldsite.
AlthoughROcanproducelowconcentrationpermeates,itrequireschemical,and/orbiological
pretreatment.Highinitialcostofmembranes,chemicalcleaningafterfouling,generationofchem
icalcleanerwaste,andproducingconcentratesasanewsourceofwastethatshouldbedischarged
orfurthertreated,arecommonproblemsofoilandgasindustriesoperators.
2.4.4.Modifiedmembranesystemstoreducefouling
Foulingisadsorptionoraccumulationofcertaincomponentsofproducedwateronthemembrane
surfaceorinthemembraneporesthateventuallycausesfluxefficiencytodecline.Foulingisa
fundamentallimitationtoeconomicviabilityofmembraneinproducedwatertreatment[125].
NewLogicInc.[126]usedavibrationshearenhancedprocess(VSEP)systemthatemployed
torsionalvibrationofthemembranesurface.Thesystemcreatedveryhighshearingenergyatthe
surfaceandthepores.Theresultwasareductionofcolloidalfoulingand
polarizationofmembraneduetoconcentrationofrejectedmaterials.Fig.10showscomparisonof
crossflowandVSEPseparationprocesses.Table4showseffluentcharacteristicsofproducedwater
byVSEP.
Ontheotherhand,EXTRANsuper(TM)whichiscomposedofnaturalcelluloseisresistanttoall
hydrocarbonsandorganicsolventsandisnotfouledbyoilmoleculesandcalciumscaling.In
membranesthatwereformulatedwiththischemical,waterpassedthroughthemembranesurfaceby
thediffusionprocess,whilehydrophobichydrocarbonswererejected[127].
Table5summarizesdifferentoperationalconditionsandresultsforproducedwatertreatmentwith
membranes.