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AND A QUATERNARY AMMONIUM SALT 'ENAMIN #4!#  4HE MATERIALS OBTAINED WERE CHARACTERIZED BY 8 RAY
DIFFRACTION AND INFRARED SPECTROSCOPY4HE RESULTS SHOWED A GOOD GASOLINE TOLUENE DIESEL FUEL AND KEROSENE
ADSORBINGCAPACITY

+EYWORDSORGANOCLAYS NANOSTRUCTURED ADSORPTION

)NTRODUCTION /RGANOPHILICCLAYSnLITERATUREREVIEW

3MECTITICCLAYS ALSOKNOWNASBENTONITESANDUSEDINAVARIETY -OSTCLAY ORGANICCOMPOUNDSAREOBTAINEDTHROUGHBENTONITES


OF INDUSTRIAL APPLICATIONS ARE THE MOST WIDELY UTILIZED AND MOST ESPECIALLY THE!MERICAN7YOMING BENTONITE!CCORDING TO 3OUZA
INTERESTINGGROUPOFCLAYMINERALS(OWEVER THEIRREALPOTENTIALITIES 3ANTOS BENTONITESAREPREFERREDBECAUSEOFTHESMALLDIMENSIONSOF
CANONLYBEDEVELOPEDBYSUBJECTINGTHEMTOCHEMICALTREATMENTS THEIRCRYSTALSANDTHEIRHIGHIONEXCHANGECAPACITY4HESEFEATURES
!REASPOLLUTEDBYORGANICCOMPOUNDSAREOFGREATCONCERNINTERMS ALLOWFORFASTANDCOMPLETEINTERCHANGEREACTIONS-OREOVER
OF ENVIRONMENTAL CONTROL 3EVERAL TYPES OF SORBENT MATERIALS HAVE THEIRINTERPLANAREXPANSIONCANBEANALYZEDBY8 RAYDIFFRACTIONAND
BEENSTUDIEDTOREMEDIATETHESEAREAS!MONGTHESEMATERIALS OR INFRAREDSPECTROSCOPY
GANOCLAYSOBTAINEDFROMSMECTITICCLAYSANDQUATERNARYAMMONIUM /RGANOPHILICCLAYSHAVEBEENSYNTHESIZEDFROMTHESODIUMFORM
SALTS n CONTAINING AT LEAST A  CARBON CHAIN BETWEEN THEIR LAYERS OFBENTONITE WHICHISHIGHLYHYDROPHILIC BYADDINGQUATERNARYAM
nREPRESENTAPROMISINGMATERIAL MONIUMSALTSCONTAININGATLEASTTWELVECARBONATOMS TOAQUEOUS
!REASCONTAMINATEDBYPETROCHEMICALSREPRESENTACOMMONAND DISPERSIONS OF SODIUM BENTONITE 4HESE DISPERSIONS MUST HAVE A
SERIOUSENVIRONMENTALPROBLEM!CCORDINGTOTHE%0!%NVIRONMENTAL HIGHDELAMINATIONGRADE IE THELAMELLAEMUSTBESEPARATEANDNOT
0ROTECTION!GENCY DATABANKn"&33 "IOREMEDIATIONINTHE&IELD LAYEREDINORDERTOFACILITATETHEINTRODUCTIONOFORGANICCOMPOUNDS
3EARCH3YSTEM PETROCHEMICALPRODUCTSARERESPONSIBLEFOROF 5NDERSUCHCONDITIONS SALTORGANICCATIONSREPLACESODIUMBENTONITE
GROUNDWATERCONTAMINATIONINTHE53 CATIONS CAUSINGTHECLAYTOCHANGEFROMAHYDROPHILICTOANORGA
,EAKAGESFROMUNDERGROUNDORSUPERlCIALFUELRESERVOIRSOCCURDUE NOPHILICFORM 
TOPIPEFAILURESORCORROSION4HESEFUELLEAKAGESCANCAUSEENVIRONMEN 3OMEORGANOPHILICCLAYSSWELLINSPECIlCORGANICSOLVENTS!C
TALPOLLUTION GROUNDWATERCONTAMINATION DISEASESANDSAFETYPROBLEMS CORDINGTO,ABA THECATIONICMOLECULEPORTIONOFTHESESALTSOCCU
SINCETHEYCANREACHPLUVIALGALLERIESANDSANITARYSEWERS PIESTHESITESPREVIOUSLYOCCUPIEDBYSODIUMCATIONS WHILETHELONG
.ATURALCLAYSCONTAININGMETALSASTHEEXCHANGECATIONSARENOT ORGANICCHAINREMAINSINTERCALATEDINTHECLAYSLAMELLAE
GOOD ADSORBERS FOR REMOVING NEUTRAL ORGANIC MOLECULES BECAUSE 3EVERALORGANOPHILICCLAYSHAVEBEENPREPAREDANDCHARACTERIZED
THESETYPESOFCLAYHAVEAHYDROPHILICCHARACTERWHICHISINDUCED INTHE,-03OLLABORATORYOFTHE5NIVERSITYOF3O0AULOS0OLYTECHNIC
BYTHEMETALLICCATION/RGANICMOLECULESAREHYDROPHOBIC SOTHEY 3CHOOL USING"RAZILIANSMECTITICCLAYMINERALS 
DISPLAYNOAFlNITYWITHTHEHYDROPHILICSURFACESOFCLAY(OWEVER
THEHYDROPHILICITYOFCLAYSCANBETRANSFORMEDINTOHYDROPHOBICITY %XPERIMENTAL
WHENTHEEXCHANGEINORGANICCATIONSAREREPLACEDBYQUATERNARYAM !PALECHOCOLATE COLOREDPOLYCATIONICBENTONITEFROM0RIMAVERA
MONIUMCATIONSINTHEFORMOF;#( .2= OR;#( .22= 4HIS LOCATEDINTHEMUNICIPALITYOF"OA6ISTA STATEOF0ARAIBA "RAZIL WAS
REPLACEMENTRESULTSINORGANOPHILICCLAYS4HEORGANOPHILICPROPERTIES GROUNDTOAPARTICLESIZEOFLESSTHANMMTOPREVENTITFROMSWELLING
OFTHESEMODIlEDCLAYSREDUCETHEHYDRATIONOFORGANICCATIONSWHEN INWATER)TSINTERLAYERCATIONSWERETHENREPLACEDBYSODIUMACCORD
COMPAREDWITHEXCHANGEINORGANICCATIONS INGTOTHEFOLLOWINGPROCEDUREANAQUEOUSDISPERSIONWASPREPARED
3EVERAL ORGANOPHILIC CLAYS HAVE PROVED HIGHLY EFlCIENT IN RE BYSLOWLYADDINGGROUNDCLAYTODISTILLEDWATERUNDERMECHANICAL
MOVINGNEUTRALORGANICCONTAMINANTSFROMWATERANDCANBEUSED STIRRING4HEWEIGHTOFTHEDISPERSIONWASGANDTHEQUANTITY
FOREXAMPLE TOTREATCONTAMINATEDWATER LINEWASTERESERVOIRS TREAT OF CLAY ADDED WAS  G 4HE MIXTURE WAS STIRRED MECHANICALLY
INDUSTRIALWASTESANDADSORBOILANDFUELSPILLS  MINUTES!BEAKERWASTHENPLACEDONAHOTPLATEANDACONCEN

E MAILKLEBERSONPEREIRA POLIUSPBR FRRVDIAZ USPBR


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TRATEDAQUEOUSSOLUTIONOFSODIUMCARBONATEWASSLOWLYPOUREDINTOIT GREATERINTERLAYERSPACINGTHANTHECORRESPONDINGNATURALBENTONITE
MEQGOFDRIEDCLAY UNDERMECHANICALSTIRRINGANDHEATING 4HISBEHAVIORWASCONlRMEDBY6ALENZUELA$IAZ 
4HEDISPERSIONWASHEATEDTOTHEBOILINGPOINTANDTHENALLOWEDTO
COOLTOROOMTEMPERATUREFORHOURS4HEWEIGHTOFTHEDISPERSION )NFRAREDCURVES
WASCORRECTEDBYADDINGWWWATERTOTHECLAY4OTRANSFORM 4HEABSORPTIONOFINFRAREDRADIATIONBYCLAYSWASRECORDEDOVER
THE SAMPLE TO AN ORGANOPHILIC FORM A QUATERNARY AMMONIUM SALT ARANGEOFTOCM &IGURE 
'ENAMIN#4!#  INAAQUEOUSSOLUTIONWASSLOWLYADDED 4HE NATURAL CLAY SHOWED CHARACTERISTIC SMECTITIC CLAY MINERAL
MEQGOFDRIEDCLAY UNDERMECHANICALSTIRRING4HEMIXTURE PEAKSAT      ANDCM 4HE
WASSTIRREDFORMINUTESANDTHEDISPERSIONWASLEFTSTANDINGAT NATURALCLAYSHOWEDNOINTENSEPEAKSCORRESPONDINGTOORGANICMATTER
ROOMTEMPERATUREFORHOURS AFTERWHICHITWASlLTEREDTHROUGHA AT ANDCM "ALAASSIGNEDTHEANDCM 
"CHNERFUNNEL4HECAKEWASDRIEDAT#FORHOURSANDTHEN PEAKSTOTHE#(SCISSORVIBRATIONBANDANDTHESYMMETRICAL#(
GROUNDANDSIEVEDTHROUGHAMESHMM SIEVE STRETCHING ABSORPTION BAND RESPECTIVELY4HE  CM  PEAK WAS
4HE ORGANOPHILIC CLAY AND RAW CLAYS WERE ANALYZED BY 8 RAY ASSIGNEDTOTHE#(STRETCHINGBAND
$IFFRACTION 82$ AND )NFRARED 3PECTROSCOPY &4)2  4HE 82$ 4HEORGANOPHILICCLAYALSOSHOWEDTHECHARACTERISTICPEAKS OF
PERFORMED BY THE POWDER METHOD USING A 0HILIPS 80%24 -0$ CLAYMINERALS ALBEITOFLOWINTENSITY4HISISANINDICATIVEOFTHEOR
DIFFRACTOMETERWITH#U +ARADIATION K6 M! SCANSPEEDOF GANOPHILICCHARACTEROFTHECLAY4HEORGANICMATTERPEAKSAT
1SANDSECONDSPERSTEP&4)2WASPERFORMEDBYTHE+"R ANDCM WERESHARPERTHANTHOSEOFTHENATURALCLAY
METHODWITHA.ICOLET-!'.!%303SPECTROPHOTOMETER 4HE#( #(AND#(BANDSCONlRMEDTHEALKYLAMMONIUM
INTERCALATIONINTHEINTERLAYERGALLERIESOFTHECLAYMINERAL ANDTHE
3WELLINGTEST
LOWERINTENSITYOFTHECHARACTERISTICCLAYMINERALPEAKSINDICATEDTHE
4HE SWELLING OF THE ORGANOPHILIC CLAY IN ORGANIC LIQUIDS WAS ORGANOPHILICNATUREOFTHETREATEDCLAY
MEASUREDINTOLUENE DIESELFUEL KEROSENEANDGASOLINEGOF
POWDERWASGRADUALLYADDEDINSMALLPORTIONSTOM,OFORGANIC 3WELLINGTESTS
LIQUIDCONTAINEDINAM,GRADUATEDCYLINDER WITHOUTSTIRRING &IGURESHOWSTHESWELLINGOFTHEORGANOCLAYS
!FTERHOURSATROOMTEMPERATURE THEVOLUMEOFTHECOLUMNOF )NTERMEDIATEVALUESFROMTOM,G WEREOBSERVEDFORTHESWELL
CLAY WAS MEASURED AFTER WHICH THE DISPERSION WAS STIRRED WITH A INGINKEROSENEWITHMIXING GASOLINEWITHANDWITHOUTMIXING AND
GLASSRODANDALLOWEDTOSTANDFORANOTHERHOURS4HESWELLING DIESELWITHANDWITHOUTMIXING ATTESTINGTOTHEORGANOPHILICITYOFTHE
WASTHENRECORDED ORGANOCLAYS4HEORGANOCLAYSHOWEDHIGHSWELLINGVALUESINTOLUENE
WITHANDWITHOUTMIXING IE ANDM,G RESPECTIVELY ANDALOW
!DSORPTIONTEST
M,G SWELLINGVALUEINKEROSENEWITHOUTMIXING 
4HETOLUENE DIESELFUEL KEROSENEANDGASOLINESORPTIONCAPACITY !SCANBESEEN NOSIGNIlCANTINCREASEWASFOUNDWHENTHESWELL
WASMEASUREDFOLLOWINGAMETHODBASEDONTHEh3TANDARD-ETHODS INGWASRECORDEDAFTERHOURSANDAFTERMIXING
OF4ESTING3ORBENT0ERFORMANCEOF!DSORBENTS!34-& AND 4OLUENESHOWEDTHEHIGHESTSWELLINGVALUE WHICHWASCONGRUENT
!34-&  v4HISTESTGIVESIDEALIZEDLABORATORYDATAWHICH WITHTHEADSORPTIONTEST
CANBEUSEDTOCOMPARETHEOILADSORBINGCAPACITYOFONEADSORBENT
WITHANOTHER ANDALSOGIVESRELATIVECOSTEFFECTIVENESS)TSHOULDBE !DSORPTIONTESTS
KEPTINMINDTHAT UNDERNORMALSERVICECONDITIONS ANADSORBENTWILL 4HEADSORPTIONOFORGANICCOMPOUNDSWASSTUDIEDACCORDINGTO
NOTBEEXPOSEDTOASUFlCIENTLYTHICKOILLAYERTOBECOMECOMPLETELY !34-& 4ABLESHOWSTHERESULTSFORORGANOCLAY
ORRAPIDLYSATURATED4HISTESTWILLTHEREFOREGIVEMAXIMUMPOSSIBLE 4HE ORDER OF ORGANOCLAY ADSORPTION CAPACITY WAS TOLUENE 
CAPACITYDATAANDANIDEALIZEDTIMESATURATION4HEADSORBENTSAMPLE GASOLINEDIESELKEROSENE4HEDATAINDICATEDTHATTHEORGANOCLAY
ISWEIGHED MINIMUMWEIGHTOFG ANDTHEVALUEISRECORDED4HE ADSORBEDMOREGASOLINE ANDTOLUENE THANDIESEL
TESTCELLISlLLEDWITHANINITIALLAYEROFTESTLIQUID4HEADSORBENTIS ANDMOREGASOLINE ANDTOLUENE THANKEROSENE
PLACEDINABASKETAMESHSTAINLESSSTEELBASKET WHICHISTHEN 4HEADSORPTIONCAPACITYOFTHEORGANOCLAYWASHIGHERTHANTHAT
LOWEREDINTOTHETESTCELL4HEADSORBENTSHOULDBEALLOWEDTOmOAT OFTHENATURALCLAY4HEORDEROFNATURALCLAYADSORPTIONCAPACITYWAS
FREELYWITHINTHETESTCELL!FTERMINUTESMINUTESTHEBASKET KEROSENEDIESELGASOLINETOLUENE4HEADSORPTIONVALUESWERE
WITHTHEADSORBENTISREMOVEDMANUALLYINAVERTICALDIRECTIONAND BETWEENTOGHYDROCARBONGNATURALCLAY
ALLOWEDTODRAINFORSECONDSSECONDS!TAREDWEIGHINGSUPPORT 4HE DATA SHOWED THAT THE ORGANOCLAY ADSORBED MORE TOLUENE
ISPLACEDUNDERTHEADSORBENTSAMPLEMESHBASKETSETTOCATCHANY  GASOLINE DIESEL ANDKEROSENE
ADDITIONALDRIPSANDTHEENTIRESYSTEMISWEIGHED!LLTHETESTSARE THANDIDTHENATURALCLAY
CONDUCTEDINDUPLICATEWITHAMINIMUMOFTWORUNSUSEDFORCALCULA 4HE ORGANOCLAY ADSORBED TOLUENE AND GASOLINE EQUAL TO ABOUT
TIONS"ASEDONTHEDATAOBTAINED THEADSORBEDOILISCALCULATEDAS TIMESITSWEIGHT4HISORGANOCLAYMAYBEUSEDASADSORBENTMATE
THERATIOOFADSORBEDOILTODRYADSORBENTWEIGHT RIALFORHYDROCARBONS

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4ABLE2ESULTSOFADSORPTIONTESTING
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!DSORPTIONHYDROCARBONCLAY GG
&IGURESHOWSTHEINTERLAYERSPACINGSOFORGANOCLAYSANDNATURAL 3OLVENT .ATURALBENTONITE %XPERIMENTAL
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