Waxprecipitation

Waxcomponentscanprecipitatefrompetroleumfluidswhentheoriginalequilibriumconditionsofthereservoirarechangedsothatthesolubilityofthewaxesisreducedhowever,wax
precipitationdoesnotnecessarilyleadtodeposition.Thispagediscusseswaxprecipitationbehaviorandexperimentalmeasurementstopredictthetendencyofacrudeoiltoprecipitate
wax.

Contents
1Waxprecipitationbehavior
2Analyzingpotentialforwaxprecipitation
2.1Compositionalanalysisofpetroleumfluids
2.2Measurementofwaxprecipitationdata
2.2.1Waxappearancetemperatureorcloudpoint
2.2.2Waxdissolutiontemperature
2.2.3Pourpointtemperature
2.3Quantificationofwaxprecipitation
2.3.1Bulkfiltrationapparatus
2.3.2Pulsednuclearmagneticresonance(NMR)
3References
4NoteworthypapersinOnePetro
5Externallinks
6Seealso

Waxprecipitationbehavior
Thereasonthatwaxprecipitationdoesn'tnecessarilyleadtodepositionisthatindividualwaxcrystalstendtodisperseinthefluidinsteadofdepositingonasurface.Ifthenumberofwax
crystalsbecomeslargeenoughorifothernucleatingmaterialssuchasasphaltenes,formationfines,clay,orcorrosionproductsarepresent,thecrystalsmayagglomerateintolargerparticles.
Theselargerparticlesthenmayseparateoutofthefluidandformsoliddeposits.
Fig.1[1]showsatypicalwaxprecipitationenvelopeonapressuretemperaturediagram.Incontrasttotheasphalteneprecipitation(/Asphaltene_precipitation)envelope(APE),the
solid/liquidphaseboundaryisnearlyverticalforwaxes,illustratingwaxprecipitationsstrongdependenceontemperatureandweakdependenceonpressure.

(/File%3AVol1_Page_399_Image_0002.png)
Fig.1Pressuretemperaturewaxprecipitation
envelopes(afterLeontaritis [1]).

Temperaturereductionisthemostcommoncauseofwaxdepositionbecausewaxsolubilityinhydrocarbonfluidsdecreasesasthetemperatureislowered.[2]Reservoirfluidcoolingoccurs
throughouttheproducingfluidsystem.Coolingcanbecausedbyoilandgasexpansionattheformationface:
Throughcasingperforations,orthroughotherorificesorrestrictions
Bydissolvedgasbeingliberatedfromsolution
Byradiationofheatfromthefluidtothesurroundingformationasitflowsupthewellbore
Bytransferofthefluidthroughlowtemperaturesurfacefacilities
Byinjectionofwaterorotherfluidsattemperaturesbelowthereservoirtemperature
Pressurechangesusuallyhaveaverysmalleffectonwaxprecipitationtemperaturesandamountshowever,changesintheoriginalequilibriumcompositionofthefluidscanresultinalossof
waxsolubility.Afairlyconsistenttrendisthatthelightestcomponentsinacrudeoilactasgoodsolventsforwaxes.Liberationofsolutiongasfromacrudeoilaspressuredecreasesbelow
thebubblepoint(/Glossary%3ABubblepoint)ofthefluidhasbeenshowntoincreasethecloudpointtemperatureoftheoil.[3]Thiseffectalsohasbeenobservedinsyntheticmixturesof
methane,decane,andheavynalkaneswithcarbonnumbersfrom18to30[4]andforstocktankoilsmixedwithmethaneandcarbondioxide.[5]Thistrendhasbeenshowntobereversed
inastudyoftwogascondensatefluidsinwhichthecloudpointtemperaturedecreasesaspressureisreducedbelowthevapor/liquidphaseboundaryandmayincreaseonlyatverylow
pressures.[6]Theadditionofintermediateparaffinic,naphthenic,andaromaticcomponentswithcarbonnumbersfrom5to10hasbeenshownexperimentallytodecreasethecloudpoint
temperaturefortwocrudeoils.[7]Somemodelpredictionscontradicttheseresults,indicatinganincreaseincloudpointtemperaturewhenpentane,hexane,ornonaneweremixedwith
stocktankoils.[5]

Analyzingpotentialforwaxprecipitation

Thereareanumberofexperimentalmeasurementsperformedonpetroleumfluidstodefinetheirtendencytoprecipitatewax.Measurementsofthetemperatureatwhichwaxprecipitation
occursandtheamountofwaxprecipitatedaredonewithstabilized(stocktank)oilsandlivereservoirfluids.Compositionalanalysisofthefluidsisperformedtodeterminethe
concentrationsofchemicalspeciesthatcanprecipitateaswaxes.Thispagedescribesthesetypesofanalyses.

Compositionalanalysisofpetroleumfluids
PetroleumconstituentsmaybebroadlyclassifiedasbelongingtotheC6ortheC6+fraction.TheheavyendmaybefurtherclassifiedwithSARA(saturates,aromatics,resins,and
asphaltenes)analysis.Variouschromatographymethodsallowthedeterminationofthemassfractionsofsinglecarbonnumber(SCN)fractionsofafluid.OneSCNiscomposedofallthe
componentswithboilingpointsbetweenconsecutivenalkaneboilingpoints.Forexample,theC7SCNiscomposedofallthecomponentswithboilingpointsbetweentheboilingpointofn
C7andnC8.Theseanalysesroutinelyextenduptocarbonnumber30andmaybedoneuptoacarbonnumberof45ormore.
DetailedPNA[paraffinic(P),naphthenic(N),andaromatic(A)fraction]analysesalsocanbeperformed.Dependingonthedetailsoftheanalysis,thearomaticfractionmayormaynot
includetheresinsandasphaltenes(/Asphaltenes_and_waxes).Itisalsopossibletodeterminetheamountsofindividualnalkanes.Thesetypesofanalyses,althoughexpensive,are
especiallyvaluableforwaxprecipitationmodelingbecausetheyveryaccuratelydefinethecomponentsofafluidthatwillprecipitateaswax.

Measurementofwaxprecipitationdata
Thereareafewbasicmeasurementsthatcharacterizeafluidstendencytoprecipitatewax.LiraGaleanaandHammami[8]reviewedtheexperimentaltechniquesusedtoobtainthese
measurements.
Waxappearancetemperatureorcloudpoint
Whenaliquidsolutionormeltisloweredtothewaxappearancetemperature(WAT),thewaxmoleculesformclustersofalignedchains.Oncethesenucleireachacriticalsize,theybecome
stableandfurtherattachmentofmoleculesleadstogrowthofthecrystal.Formationofthesenucleicausesthefluidtotakeonacloudyappearance,hencethenamecloudpoint.Thisalsois
referredtoasthewaxcrystallizationtemperatureorwaxappearancepoint.DeterminationofaWATsignificantlyhigherthanthetemperaturesexpectedtobeencounteredduringproduction
indicatesthepotentialforwaxdepositionproblems.
TheWATdependsonwhichtechniqueisusedfortheanalysis.Forexample,amicroscopymethodallowsforobservationofmuchsmallerwaxcrystalsthanavisualtechniquewiththe
unaidedeye.ThefollowingtechniquesareusedtodeterminetheWAT.
AmericanSocietyforTestingandMaterials(ASTM)visualmethods.Oilinaglassjarissubmergedinacoolingbath.Asthetemperatureofthebathislowered,thetemperature
atwhichthefluidscloudinessisfirstobservedisdeterminedtobethecloudpoint.
Coldfinger.Atemperaturecontrolledrodisinsertedinagentlyheatedoilsample.TheWATisdeterminedasthetemperatureatwhichwaxbeginstoadheretotherod.
Viscometrymethods.Viscometrictechniquesrelyondetectionofchangesinrheologicalpropertiesofanoilaswaxprecipitates.Abreakinthecurveofviscosityplottedvs.
temperatureistakenastheWAT.
Differentialscanningcalorimetry.Thismethoddetectsthelatentheatoffusionreleasedoncrystallization.Althoughtherecanbesomeuncertaintyininterpretationoftheresults,
differentialscanningcalorimetryhasbeenwidelyusedforWATdeterminationandalsocanprovidedataontheheatcapacitiesandheatsoffusionortransitionassociatedwith
liquid/solidandsolid/solidphasetransitions.
Crosspolarizedmicroscopy.Inthistechnique,amicroscopewithatemperaturecontrolled"hotstage"isusedtoviewanoilsamplethatisbeingcooledataconstantrate.Theuse
ofapolarizedlightsourceandpolarizedobjectivesonthemicroscopeallowthewaxcrystalstoshowupasbrightspotsonablackbackground.Thistechniqueusuallyprovidesthe
highestWATvaluefordeadoils.
Lighttransmittance.TheexperimentalapparatusforthismethodconsistsofaPVTcellwithalightsourceandalightpowerreceivermountedonoppositesidesofthecell.When
waxcrystalsappearinthefluid,theamountoflighttransmittedisreduceddramatically,andtheWATcanbeseenasasharpdropinaplotoflightpowerreceivedvs.temperature.
Thismethodcanbeusedathighpressureand,therefore,canbeappliedtolivereservoirfluidsaswellasstocktankoils.
Ultrasonics.Similartothelighttransmittancetechnique,anultrasonicsignalissentthroughthefluidsampleandreceivedatatransducer.Thevelocityoftheultrasonicwavedepends
onthedensityofthemediumthus,thetransittimeforthewavewillchangeattheWAT.
Waxdissolutiontemperature
Thewaxdissolutiontemperatureisdefinedasthetemperatureatwhichallprecipitatedwaxhasbeendissolvedonheatingtheoil.Theexperimentaltechniquesmostoftenusedfor
determiningwaxdissolutiontemperaturearedifferentialscanningcalorimetryandcrosspolarmicroscopy.
Pourpointtemperature
Thepourpointtemperatureisthelowesttemperatureatwhichtheoilismobile.Thisisusuallyidentifiedasthestocktankoilgelationtemperature.TheASTMpourpointtest,similartothe
ASTMcloudpointtests,involvesplacingasampleofthefluidinajarandcoolingitinatemperaturecontrolledbath.Ateach3Ctemperaturestep,thesampleistestedbytippingthejar
todetermineiftheoilisstillmobile.

Quantificationofwaxprecipitation
NoneofthetestsusedtodeterminetheWATprovidedataontheamountofsolidprecipitatedatatemperaturebelowtheWAT.Experimentaltechniquestodeterminetheamountof
precipitatedwaxaredescribednext.
Bulkfiltrationapparatus
Inthissimpleexperiment,oilinacylinderisequilibratedatthedesiredconditionsofpressure,temperature,andpossibly,solventconcentration.
Theentirecontentsofthecylinder,includingoilandanysolidsthatmayhaveprecipitated,areejectedthroughafilter.Thesolidscollectedinthefilterthenmaybeanalyzedforamountand
chemicalcomposition.Thistechniqueistimeconsumingandexpensivebuthastheadvantageofprovidingsamplesoftheprecipitatedsolidforanalysis.
Pulsednuclearmagneticresonance(NMR)

Pedersenetal.[9]usedanNMRapparatustodeterminetheamountofprecipitatedsolidsasafunctionoftemperaturefor17crudeoils.TheexperimentalNMRsignalsforeachoilwere
comparedwithcalibratedsamplesofpolyethyleneinwaxfreeoil.Althoughthistechniquedoesnotallowforchemicalanalysisofthedepositedsolids,resultsareobtainedmuchmore
quicklythanwiththebulkfiltrationapparatus.

References
1.1.01.1Leontaritis,K.J.1996.TheAsphalteneandWaxDepositionEnvelopes.FuelSci.Technol.Int.14(12):1339.http://dx.doi.org/10.1080/08843759608947560
(http://dx.doi.org/10.1080/08843759608947560)
2.Allen,T.O.andRoberts,A.P.1982.ProductionOperations,secondedition,Vol.2.Tulsa,Oklahoma:OilandGasConsultantsInternational.
3.Allen,T.O.andRoberts,A.P.1982.ProductionOperations,secondedition,Vol.2.Tulsa,Oklahoma:OilandGasConsultantsInternational.
4.Daridon,J.L.,Xans,P.,andMontel,F.1996.Phaseboundarymeasurementonamethane+decane+multiparaffinssystem.FluidPhaseEquilib.117(12):241248.
http://dx.doi.org/http://dx.doi.org/10.1016/03783812(95)029591(http://dx.doi.org/http://dx.doi.org/10.1016/03783812(95)029591)
5.5.05.1Pan,H.,Firoozabadi,A.,andFotland,P.1997.PressureandCompositionEffectonWaxPrecipitation:ExperimentalDataandModelResults.SPEProd&Oper12(4):
250258.SPE36740PA.http://dx.doi.org/10.2118/36740PA(http://dx.doi.org/10.2118/36740PA)
6.Daridon,J.L.,Pauly,J.,Coutinho,J.A.P.etal.2001.SolidLiquidVaporPhaseBoundaryofaNorthSeaWaxyCrude:MeasurementandModeling.EnergyFuels15(3):730
735.http://dx.doi.org/10.1021/ef000263e(http://dx.doi.org/10.1021/ef000263e)
7.Meray,V.R.,Volle,J.L.,Schranz,C.J.P.etal.1993.InfluenceofLightEndsontheOnsetCrystallizationTemperatureofWaxyCrudesWithintheFrameofMultiphaseTransport.
PresentedattheSPEAnnualTechnicalConferenceandExhibition,Houston,36October.SPE26549MS.http://dx.doi.org/10.2118/26549MS
(http://dx.doi.org/10.2118/26549MS)
8.LiraGaleana,C.andHammami,A.2000.WaxPrecipitationfromPetroleumFluids:AReview.InAsphaltenesandAsphalts,ed.T.F.YenandG.V.Chilingarian,Vol.2,No.40B,
Chap.21,557608.Amsterdam,TheNetherlands:DevelopmentsinPetroleumScience,ElsevierScienceB.V.
9.Pedersen,W.B.,Hansen,A.B.,Larsen,E.etal.1991.WaxprecipitationfromNorthSeacrudeoils.2.Solidphasecontentasfunctionoftemperaturedeterminedbypulsed
NMR.EnergyFuels5(6):908913.http://dx.doi.org/10.1021/ef00030a020(http://dx.doi.org/10.1021/ef00030a020)

NoteworthypapersinOnePetro
UsethissectiontolistpapersinOnePetrothatareaderwhowantstolearnmoreshoulddefinitelyread

Externallinks
UsethissectiontoprovidelinkstorelevantmaterialonwebsitesotherthanPetroWikiandOnePetro

Seealso
Asphaltenesandwaxes(/Asphaltenes_and_waxes)
Thermodynamicmodelsforwaxprecipitation(/Thermodynamic_models_for_wax_precipitation)
Formationdamagefromparaffinsandasphaltenes(/Formation_damage_from_paraffins_and_asphaltenes)
Waxproblemsinproduction(/Wax_problems_in_production)
Modelsforwaxdepositioninpipelines(/Models_for_wax_deposition_in_pipelines)
Remediatingwaxdeposition(/Remediating_wax_deposition)
PEH:Asphaltenes_and_Waxes(/PEH%3AAsphaltenes_and_Waxes)
Categories(/Special%3ACategories):
3.4.1Inhibitionandremediationofhydrates,scale,paraffinorwax,andasphaltene
(/Category%3A3.4.1_Inhibition_and_remediation_of_hydrates,_scale,_paraffin_or_wax,_and_asphaltene)
YR(/Category%3AYR)

(https://www.onepetro.org/search?q=Waxprecipitation)

(http://scholar.google.ca/scholar?q=Waxprecipitation)

(http://www.worldcat.org/search?q=Wax

precipitation)

(http://wiki.seg.org/index.php?

title=Special%3ASearch&redirs=1&fulltext=Search&ns0=1&ns4=1&ns500=1&redirs=1&title=Special%3ASearch&advanced=1&fulltext=Advanced+search&search=Waxprecipitation)
(http://wiki.aapg.org/index.php?
title=Special%3ASearch&profile=advanced&fulltext=Search&ns0=1&ns4=1&ns102=1&ns104=1&ns106=1&ns108=1&ns420=1&ns828=1&redirs=1&profile=advanced&search=Wax
precipitation)