ACCURATEBS&WTESTING

IMPORTANTFORCRUDEOILCUSTODY
TRANSFER
11/12/1990

JaneWilliams
OryxEnergyCo.
Richardson,Tex.
Monitoringcrudeoilsedimentandwatercontentatthefieldproductionsiteisessentialinaccurate
crudeoilcustodytransferoperations.
Thisisaccomplishedbymanualmethods,oronlinedeviceslikecapacitance,density,orenergy
absorptionanalyzers.
Forcustodytransferpurposes,sedimentandwaterisdeterminedbyatestwhichfollowsoneofthe
APImanualsofpetroleummeasurementstandards(MPMS).
Typically,thistestisconductedinthefieldbythefieldcentrifugemethodwhich,ifperformedproperly,
yieldsveryaccurateresults.Laboratorytestscanbeperformed,butsamplehandlingbecomeseven
morecritical.

MONITORINGBS&W

Thequantityofsedimentandwaterincrudeoilmustbeestablishedaccuratelyaspartofthecustody
transferprocess.Purchaserspayonlyforthecrudeoilreceivedandwanttominimizethequantityof
sedimentandwatertheymusthandle.
Consequently,monitoringthesedimentandwatercontentisperformedattheproductionsitetoprevent
excessiveamountsenteringthepipelinesystem.

Howmuchapipelineiswillingtoacceptintoitssystemdependsongeographiclocation,market
competitiveness,anditsabilitytohandlethesedimentandwaterinthesystem.Eachpipelinepublishes
thequantityitwillaccept.
Mostpipelinesrequirethataleaseautomaticcustodytransfer(LACT)unitbeequippedwithabasic
sedimentandwater(bs&w)monitor,typicallyinaverticalriseofpipe.Mostofthebs&wmonitorsinuse
arecapacitancedevicesandgenerallydetectonlytheamountofwaterpresent(Fig.1).
Thecapacitanceprobeworksbymeasuringthecapacitanceofthefluidfilledprobeandcomparingthe
valueobtainedtothosevaluesobtainedwiththeprobefilledwitheitherallwateroralloil.The
capacitanceoutputfromtheprocessfluidfilledprobewillbeproportionaltothewatercontent.
Thistechniqueassumesthatthedielectricstrengthsoftheoilandthewaterwillremainrelatively
constant.
Thistypeprobecanbeaffectedbytheamountofwater,theemulsioncharacteristics,temperature,
variationinpropertiesofeitherthehydrocarbonorthewater,presenceoffreegas,andparaffin
deposition.Theanalyzershouldbecalibratedatthefactorybythemanufacturerwithoilandwater
similarincompositiontowhatthedevicewillencounterinthefield.
Theanalyzerisinstalledinverticalpipetoprovidethebestmixingwhich,ifthewatercontentisless
than3%,willensurethatanoilcontinuousemulsionwillexist(essentialforthistypeofdevice).The
analyzershouldbecalibratedatnormaloperatingtemperaturesbecausedielectricconstantisa
functionoftemperature.
Table1showsthedielectricconstantofwateratvarioustemperatures.Table2showsthedielectric
constantsofexamplehydrocarbons.Fig.2demonstratesthechangeindielectricconstantasa
functionofsalinity.Thesechangesrequirethattheanalyzersbezeroedandspannedinthefield
periodicallytorenderoptimumperformance.
Freegasinthestreamtypicallyresultsinundermeasurementofthewatercut,socareshouldbetaken
toreduceoreliminateanyfreegasinthesystem.
Similarly,thebuildupofparaffinintheprobecauseserroneousreadings.Thisbuildupcanbeminimized
bychemicaltreatments,heattracing,orfrequentcleaningwithasolvent.Careshouldbetakentoavoid
damagetotheprobe'scoatingduringcleaningtoavoiderrors.
Othertypesofanalyzerstomonitorwatercutarebecomingmorepopular.One,thedensitytype,
worksbecausethedensitiesofoilandwateraregenerallyverydifferent.Thus,measuringthedensity
oftheemulsioncanyieldthepercentagewater.
Thevibratingelement,differentialpressure,nuclear,andCoriolismetersaredensitymonitors.These
devicesareaffectedbytemperature,freegas,variationinthedensitiesbetweentheoilandwater,
vibration,andparaffindeposition.
Becausetemperatureaffectsfluiddensity,theseunitsmusteitherhavetemperaturecompensationor
beinstalledonasteadytemperaturestream.Theeffectoffreegasandparaffinonthesedevicesis
similartotheeffectonthecapacitancedevices.

Vibrationeffectsshouldbeminimizedoreliminated,especiallyonthevibratingelementdevicesand
Coriolismeters.
Theseunitsdonotworkwellonheavycrudesforwhichthedensitiesofthecrudeandwaterare
similar.
Anothertypeofunitinuseistheenergyabsorptionwatercontentmonitor.Thisdevicemeasuresthe
electromagneticenergyabsorptionrate.Thedifferenceintheenergyabsorptionratesbetweenwater
andhydrocarbonsisutilizedtodeterminethewatercontent.
Thesedevicesarenotaffectedbyvariationsinfluiddensitiesandarelessaffectedthantheother
devicesbyparaffindeposition.
Thesemonitorsshouldbeinstalledinverticalpipewithdownwardflowsothatanoilcontinuous
emulsionoccurs.
Freegashassignificantimpactonthesedevicesandthusmustbeeliminatedfromthestream.Thisis
accomplishedbyproperseparatordesignoruseofanaireliminator.
Variationsintemperatureofthestreamaffectthesedevicesanddictaterecalibrationwheneverlarge
variationsoccur.Fieldcalibrationshouldbeperformedperiodicallytoobtainoptimumperformance.The
frequencywithwhichthisisrequiredisafunctionofthefieldconditions.

FIELDTESTING

Whilemonitoringofsedimentandwatersetsupa"go/nogo"decisiononwhetherthepipelinewill
handleaparticularquantityofcrude,thesedimentandwatertestingisusedforthedeterminationofthe
custodytransferquantityforwhichtheproducerwillbepaid.
Typically,thismeasurementisperformedattheproductionfacility,utilizingAPIManualofPetroleum
MeasurementStandards(MPMS),Chapter10,Section4,DeterminationofSedimentandWaterin
CrudeOilbytheCentrifugeMethod(FieldProcedure)1986.
APIMPMSCh.10,Sec.4requiresthecentrifugetubes(Fig.3)usedbeeither6orBin.cones.The
standardspecifiesallowabletubedimensionsandtolerances.
Hereisthefieldprocedure:

1.Filltwocentrifugetubestothe50mlor100partmarkwiththehomogeneoussampleto
betested.Readthetopofthemeniscus.
2.Fillthetwotubeswith50mlofsolventwhichbringsthetotalcontentsofthetubestothe
100mlor200partmark.TheacceptablesolventsareStoddard,kerosine,toluene,and
xylene.Notethattolueneandxyleneshouldbewatersaturatedattesttemperature.

3.Invertthetubes10timestomixthesampleandsolvent.Thisshouldbedonebeloweye
levelforsafety,andsafetyglassesarerecommended.
4.Placethetubesinthepreheaterandheatto140F.5F.
5.Invertthetubesagain10timestomix.
6.Placethetubesonoppositesidesofthecentrifugetobalancetheloadandclosethelid.
7.Centrifugeforaminimumof5min.
8.Whenthecentrifugecomestoarest,testthetemperatureofthetubecontentswithout
disturbingtheoilwaterinterface.
9.Ifthetemperatureofthesampleis125F.orgreater,readandrecordthecombined
sedimentandwatercontentatthebottomofeachtube.Ifthetemperatureislessthan
125F.,thetubesmustbereheatedandthetestrepeatedwithoutfurtheragitationuntil
twoconsecutiveconsistentreadingsareobtained.
10.Ifanemulsionisvisible,addasolventcontainingademulsifiertothesampleandretest.
(ThisiscoveredintheappendixoftheStandard.)
11.Comparethereadingsfromthetwotubes.Iftheresultsvarybymorethanone
subdivisiononthecentrifugetube,thesamplewasnothomogeneous.Thus,thetest
shouldberepeatedwithtwofreshsamples.

Iftheprocedureisfollowedclosely,theresultsobtainedwillbereliableandaccurate.Inorderforthe
correctresultstobeobtained,specialattentionshouldbegiventotheobtainingofarepresentative
sample.
SamplingiscoveredinAPIMPMS,Chapter8,Sections1and2.Fig.4showstanklocationsfortaking
samples.

SAMPLESIZEREADING

Ifthecentrifugetubeisfilledwithanyproportionotherthan50:50sample/solvent,theresultscannotbe
readdirectlyfromthecentrifugetube.Thefollowingequationmustbeusedtoadjustfortheincorrect
mixture:

Sedimentandwater,%(S/V)x100

where:
S=Volumeofsedimentandwaterfound,ml
V=Volumeofoiltested,ml
Thisiswhytheprocedurerecommendsthatthesamplebeplacedinthecentrifugetubeinitially.Ifthis
isdone,adjustmentstothequantitycanbemadebyeitheraddingorremovingsampleuntilthe50ml
markisachieved.
Theproperreadingisatthetopofthemeniscus.Iftubesmarkedwith100mlatthetopareutilized,the
actualsedimentandwateristhesumofthereadingsfromthetwotubes.
Iftubesmarkedwith200partsareused,thecorrectsedimentandwaterresultistheaverageofthe
tworeadings.

SOLVENTS

Solventscanbehazardousandconsequentlyshouldbehandledwithcaution.Avoidbreathingthe
vapors.Useonlyinwellventilatedlocations.Rubberglovesshouldbeusedtoavoidrepeatedor
prolongedcontactwiththeskin.
Handlingprecautionsrecommendedbythemanufacturershouldbefollowed.Thesesolventsareeither
flammableorcombustibleandthusnecessaryprecautionsshouldbeobserved.
Stoddardsolventsaremostcommonlyusedinthefieldsincetheyarereadilyavailableandrequireno
watersaturation.Asphaltenicandparaffiniccrudesrequiretheuseofeithertolueneorxylenetoobtain
thecorrectresults.
Bothofthesesolvents,however,mustbewatersaturatedattesttemperature(140F.)andmaintained
atthistemperatureuntilused.ThepropertechniqueforwatersaturationiscoveredinAppendixofAPI
MPMS,Chapter10,Section4.
Onevendorhasstartedpackagingwatersaturatedtolueneinglassvialswhichareeasytouseinthe
fieldandminimizeanyexposuretothetoluene.Thesamevendorhasadeviceavailabletoheatthe
glassvialsto140F.priortouse.

LABORATORYTESTING

Sometimessamplesaretransportedtoalaboratoryforthedeterminationofsedimentandwaterfor
custodytransferpurposes.Inalabenvironment,theactualtestsperformedcanbemoreaccurate
however,propersamplehandlingbecomescritical.
Duringtransportationtothelab,thesamplemaystratifyorseparateintolayers.Beforetheanalysisis
performed,thesamplemustbebroughtbacktoitsoriginalstatebymixing.

Howoftenthesampleistransferredaffectshowrepresentativeistheactualfieldfluid.Withouta
representativesample,itisimpossibletoobtainthecorrectresults.
RepresentativesamplescanbeanalyzedforwatercontentbyuseofAPIMPMS,Chapter10,Section
3,"DeterminationofWater&SedimentinCrudeOilbytheCentrifugeMethod"(LaboratoryProcedure).
Thismethodisverysimilartothefieldcentrifugemethod,exceptthatonly8in.centrifugetubesand
watersaturatedtoluenearepermitted.
ThewatercontentmayalsobedeterminedbyAPIMPMS,Chapter10,Section9,"Determinationof
WaterinCrudeOilsbyCoulometricKarlFischerTitration."Thismethodologyprovidesaccurateresults
inthe0.025.0%waterincrudeoils.Mercaptanandsulfideinthecrudeinterferewiththistest.
ThemethodologyinAPIMPMS,Chapter10,Section9,requiresthatanaliquotbeinjectedintothe
titrationvesselofaKarlFischerapparatus.IodinefortheKarlFischerreactioniscoulometrically
generatedattheanode.
Excessiodineisdetectedbyanelectrometricendpointdetectorandtheprocessterminatedwhenall
thewaterhasbeentitrated.Onemoleofiodinereactswithonemoleofwater.Therefore,thequantityof
waterisproportionaltothetotalintegratedcurrentaccordingtoFaraday'sLaw.
Mixingiscriticaltothismethodologybecausethelargestaliquotinjectedisonly1g.Inthehigherwater
contentranges(0.55.0%),only0.25galiquotsarerecommended.Thustheabilitytogeta
representativesampleiscritical.Thequalityofthereagentsandsolventsusedinthistestisalso
important.

LABORATORYPROCEDURE

1.Addfreshsolventstotheanodeandcathodecompartmentsofthetitrationvesseland
bringthesolventtoendpointconditions.
2.Mixthesamplesothatarepresentativealiquotcanbeobtained.
3.Startingwithaclean,drysyringe(highqualityofsuitablecapacity),withdrawatleast
threeportionsofthesampleanddiscardtowaste.
4.Withdrawthealiquottobetestedintothesyringe.
5.Cleantheneedlewithapapertissue.
6.Weighthesyringeandcontentstothenearest0.1mg.
7.Inserttheneedlethroughtheinletportseptum,startthetitrationand,withthetipofthe
needlejustbelowtheliquidsurface,injectthesample.

8.Withdrawthesyringe.
9.Weighthesyringetothenearest0.1mg.
10.Aftertheendpointisreached,recordthetitratedwaterregisteredontheinstrument
display.

Thecalculationisasfollows:

Water,mass%=W1/(10,000XW2)

where:
W1=Massofwatertitrated,mg
W2=Massofsampleused,g
Water,vol%=AR

and:
A=Water,mass%
R=Relativedensityofcrudeoil

Additionally,theappendixcoversamethodologywhichutilizesvolumetricdeterminationofsamplesize.
Resultsofroundrobintestingindicatethatthevolumetricmethodologycanbejustasaccurateasthe
methodologydescribedherepreviously.
Thevolumetricmethodologycanbeperformedinalaboratoryenvironmentorinthefield.This
techniquerequireshighqualitysyringes.Tenmlgraduatedforreadingsto0.01mlispreferred,butthe
resolutionmustbeatleast0.01ml.
Thepresenceofgasbubblesinthesyringeisasourceofuncertainty.Anygasbubblesshould
thereforeberemovedbeforethetestisperformed.Theprocedureisthesameasjustdescribed,but
insteadofweighingthesample,notethesamplevolume.
Thecalculationisasfollows:

Water,volume%=

V1/(10,000XV2)

where:
V1=Volumeofwatertitrated,ml
V2=Volumeofsample,ml

"WaterbyDistillation"iscoveredinAPIMPMS,Chapter10,Section2.Itisconsideredthemost
accuratemethodologyavailable.
However,thistechniqueisverytimeconsumingandthusisrarelyperformedfornormalcustody
transfersofcrudeoil.
Alloftheselaboratorymethods,exceptthecentrifugemethod,testonlyforthewatercontent.Thusa
secondtestmethodmustbeperformedtodeterminethesedimentcontent.
Occasionally,theCoulometricKarlFischermethodologyisutilizedtoobtainthewatercontent,andthe
sedimentcontentisobtainedbycentrifuge.Generally,iflaboratorytestsareperformedtoobtainthe
watercontent,thesedimentcontentisobtainedbyeithersedimentbyextractionorsedimentby
filtration.
SedimentbyextractioniscoveredinAPIMPMS,Chapter10,Section1.Sedimentbyfiltrationhasnot
yetbeenfinalizedasanAPIstandard.Bothofthesetechniquesarestrictlylaboratorytechniquesand
arenotcoveredherebecausetheyarerelativelytimeconsuming.

Copyright1990Oil&GasJournal.AllRightsReserved.

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