!

WE
SPE 10067
Evaluating Constant Volume Depletion Data
by Curti s Hays WhHson, Roga/and Dktrlct Co//ege and Stei n BarreTorp, Norwegian
Institute of Technology
@Copyright 1981, Society of Petroleum Englneere of /IIME
This paper was presented at the 56th Annual Fall Technicel Conference and Exhlbltlon of the Society of Petroleum Engineers of Al ME, held in
San Antonio, Texas, October 5-7,1981. The material Is subject to correction by the author. Permieslon to copy is restricted to en abstract of
not more than 300 words. Write! 6200 N. Central Expressway, Dallas, Texae 75206.
ABSTRACT Few engineersare aware of potentially-useful data
This paperpresentsreeultaof analyzingconstant
which can be derivedfromCVD data, someof themost
volume depletiondata obtainedfrom experimental
importantbeing&q& composition(and therefrom
analysesof gas condensatesand volatileoils.
K-values),density,molecularmass (andspecifically
Theoreticaland practicaldevelopmentsare supported
C7+ molecularmass); WUpOit density(usingtwo indep-
by analysesof experimentaldata from twoNorth Sea
endentmethods);and &L72&4g4@n molecularmass.
condensatereservoirs.
No assumptionscirempiricalreIationsare used to
calculatethesedata - only experimentalCVD data
The threemajor contributionsof thiswork are:
and simlllematerialbalanceequations.
(1) presentationof materialbalanceequationsused
A procedureoutliningthesecalculationswas first
to calculatefluid (particularlyliquid)properties
presentedby Reudelhuberand Hinds? Their descrip-
frommeasuredconetantvolumedepletiondata,
tion,however,is somewhatdifficultto followand
(2) a simplemethod for calculatingblackoil
not extensivelyknown or used by the industry. We
formationvolumefactorsand solutiongas-oilratios
thereforedecidedto presentthematerialbalances
for volatilesystemsusingmaterialbalanceresults
in equation-formusing currentSPE nomenclature.
and a separatorflashprogram,and (3) investigation
of the Peng-Robinsonequationof stateas a tool for
Using the materialbalance-derivedproperties,
matchingmeasuredPVT data and studyingvapor-liquid
a method is proposedfor calculatingblackoil
equilibriaphenomenaduringconstantvolumedepletion.
PVT properties- i.e.,formationvolumefactorsand
solutiongas-oilratiosused in two-phaseflow
The main examplepresentedis a rich ga~
equationsand reservoirmaterialbalances. The
condensatewhosemeasured,calculatedand simulated
method is not new in principle,as it was first
phasebehaviorare fullydocumentedin tablesand
suggestedby Dodson,Goodwilland Mayer2 in 1953 for
figures. Completedescriptionof the heptanes-plus
solutiongas/crudeoil systems. Theirmethod,
fractionis also includedao that other engineerscan
however,requiresexpensiveand time-consumingliquid
check,modifyand hopefullyimprovefluidcharacter-
sampleremovalsand experimentalflashseparations.
izationusing the Peng-Robinson(or.any other)
The proposedmethod followsthe same procedurebut
equationof state.
uses experimentally-determined vapor compositions
and materialbalance-derivedliquidcompositions
togetherwith a routinemulti-stageseparatorflaeh
INTRODUCTION
program(usinglow pressureK-valuesindependentof
systemcomposition).PVT propertiescalc~latedusing
Constantvolumedepletion(CVD)experimentsare
thismethodare comparedwith thosecalculatedusing
performedon gas condensateand volatileoil fluids
the Peng-Robinson3equationof state.
to simulatereservoirdepletionperformanceand comp-
ositionalvariation. Resultingdata can be used in
Thoughmore complicated,empiricalequationsof
a varietyof reservoirengineeringcalculation,
statecan alsobe used to evaluateCVD data. Several
among the most usefulbeingmaterialbalancecalcula-
investigators 51shave used the Peng-RobinsonEOS to
tiOnsjgeneratingblackoil PVT propertiesand more
simulatePVT studiesof lightgas condensatesand
recex,tly, the tuningof empiricalequationeof state.
All of theseapplicationsare addreasedin the
crudeoils,needleesto say avoidingsystemsoperat-
ing near the criticalpoint. Resultshave ranged
presentwork.
from excellentto poor, dependingon which properties
were compared. Conradand Gravier16proposeda
method to improveliquiddensityestimationsby
adjuetingpropertiesof the heaviestplus fraction
Referencesand illustrationsat end of paper
(boilingpointand Cl interactioncoefficient).
Firoozabadi,Hekimand Ketzs studiedanotherlean Mercuryis reinfectedinto the cell at constant
gas condensateand found thatby only adjuatingthe pressurewhile simultaneouslywithdrawingan equiv-
methane-plusfractioninteractioncoefficient,the alentvolumeof vapor. When initialcellvolumeis
Peng-RobinsonEOS overestimatedliquiddrop-outby reached,mercuryinjectionis ceased. Withdrawn
nearly100%. [As discussedlaterin thiswork, vapor is analyzedusinggas chromatographyto deter-
materialbalancecalculationsof CVD data for this mine composition,Yj. Moles of vaporproducedare
systemindicatethatmeasuredliquidvolumesare calculatedusing the real gas law and are reportedas
approximately100% low - i.e.calculatedliquid a cumulativepercentof initialmoles,np.
Compres-
densitieswere much too high.] sibilityfactor,Z, is also calculatedby noting
producedvapor surfacevolumeand equivilantcell
Over 30 constantvolumedepletionstudies volume (at pressureand temperature).Frommeasured
parformedby commercialand privatelaboratories vapor gravityand composition,heptanes-plus
were analyzedusing the materialbalanceapproach. wlecular mass is back-calculated.Liquidvolume
Three of these(NorthSea fluids)were chosento is measuredvisuallyand reportedas a percentor
be analyzedusing the Peng-Robinsonequationof state. fractionof cellvolume,which in essenceis a type
Their choicewas based on (1) internalconsistency of hydrocarbonliquidsaturation,SL.
of measuredCVD data,as indicatedby material
balancecalculations,and (2) availabilityof The experimentalprocedureis repeatedseveral
extendedcompositionaldata for the heptanes-plus times (6-7)until a low pressureis reached,say
fraction. All three fluidshave similarparaffin- 700 psig (4828kPa). The remainingliquidis removed
nephthene-aromstic content,with Watsonkcharacter- separated(i.e.distilled)and analyzedusinggas
izationfactorsrangingfrom 11.95 to 12.05for the chromatography.Measuredliquidcompositionshould
C7+ fraction. checkwith materialbalance-derivedcomposition.
[ Some muj okkboti ti ti &noo- t hand adj wt meauzed
The firstfluid (NS-1)is a rich gas condensate vapo~ compo. 6&on4 W &ema@f.iaZ Wanw chech.
and was chosento illustrateproposedtechniquesfor lti pmoceduu. d tieouzagedingenti. I$h good
analyzingconstantvolumedepletiondata. Extensive pzat i cet o Lnquhewht i t i a. t abomt omj f i epot i
data for this sampleand its heptanes-plusfraction mt xw, t kedok ~moo.thd data, and t o t oha. text ent
have been includedin tabularform so that other mat- bathtce-dtived da.t atwe tied .& @wJ!CWQ
engineerscan duplicate,mdify and hopefullyimprove kepot i . 1
our analyses.
The secondfluid (NS-2)is a lean gas condensate MATERIALBALANCEEQUATIONS
similarto thesystemsanalyzedin References5 and 16.
Our discussionof NS-2 is limitedto behavioror
LiquidCompositionand K-valueCalculations
observationswhich differfrom thosepresentedfor
the rich gas condensate. The last fluid (NS-3)is a Perhapsthe most usefulapplicationof constant
volatileoil operatingnear its criticalpoint. We volumedepletiondata is for calculatingliquid
had not completedour analysisof NS-3 using the compositionswhich, togetherwith measuredvapor
Peng-RobinsonEOS when this paperwas written;
compositions,yieldhigh pressureK-valueshaving
convergenceproblemswere encounteredwhen tryingto many importantreservoirand processengineering
simulatethe CVD process. NS-3 is thereforeonly applications.To arriveat the finalexpressionfor
mentionedwith regardto materialbalancecalculations
liquidcompositionin termsof measuredCVD data,we
and K-valuebehavior. More informationon any or all firststatemolal a~:dcomponentmaterialbalances,
of thesefluidscan be obtainedfrom the authors!
respectively,
DESCRIPTIONOF THE CONSTANTVOLUNEDEPLETIONPROCESS
& = Lb+ vk
. G . . . . . G . . . . . . . G . G * . . G . G . (1)
A constantvolumedepletionexperimentis
conductedat reservoirtemperatureand beginsat
& jk = Liz .jk+ vk gjk
. ..*..***.*.. (2)
saturation pressure. Cell volume,Vcell,or the
volumecontainedby the fluid,is initiallynoted
and used as a referencevolume. whera nL = moles of liquidwith compositionXj$
Mercuryis thenwithdrawnfrom the bottomof the
~ = moles of vaporwith compositionyjand nt =
totalmoles in the systemwith compositionz, each
cell, therebyloweringthe pressureas fluid expands.
quantitybeing determinedat pressurestagei.
During thisprocess,a secondphasedevelops- Subscriptj designatescomponentnumbersmakingup
eitherretrogradeliquid(for gas condensates)or
eachphase.
solutiongas (forvolatileoils). Mercurywithdrawl
is ceasedwhen a predeterminedpressureis reached. Eq. 1 statesthat totalmoles of the two phase
Some laboratoriesmeasureliquidvolumesduringthe
systemequalsthe sum of liquidand vapormoles,whil
firstpressurereduction,beforeany vapor has been Eq. 2 statesthat totalmoles of componentj in the
removed;thesevolumes,reportedrelativeto Vcell,
two phase systemequalsmoles of j in the liquidplus
representconstantcompositiondepletion. They moles of j in the vapor. The only data measured
closelyapproximate,however,volumeswhich would directlyand appearingin eitherof the equationsis
have been meesuredif the processhad been constant
volumedepletion. [Thiswas checkedusing the Peng-
vapor composition.The remainingunknownscan be
determinedfrom reportedCVD data and modifiedforms
RobinsonEOS simulatorfor lean and rich condensates. 1 of thematerialbalancerelations.
* RogalandDistrictCollege,Ullandhaug,4000
Stavanger,Norway
cmn 7nnc7 t!. H. WWTTSC)N AND S. B. TORP
3
,JrlaAvuufl
- . . . . --------- ---- -- - ---
?irstwe note that totalmoles at stagek equals All unknownsinEq. 1 have now been definedin
initialmolesminus cumulativemoles of vapor termsof measuredCVD data exceptliquidcomposition,
?roduced. We assumea basis of one mole initial whichwhen writtenin termsof the othervariables,
Eluid,that is n&l = 1, yielding becomes
k
% jk
- nvh.g.k
(3)
%k= 1 i:2&pi * ** ** ** * G
(9)
jk =
(n~- nvk)
G G G G o. . . . .* . . G . G .
rhe samematerialbalancecan be appliedon a
componentbasis,resultingin Equilibriumconstantsor K-valuesare definedas the
k
ratiobf equilibriumvapor to liquidcomposition,or
%kzjk=zjl - ~~ttipkgjk b-4)
jk
= yjkf~jk G *..*,.***.* G , . . ...*.*.* ., (10)
. = the incrementalmoles of vapor produced
whereAnpl
from the cell duringstage i, and zjl = the initial An effectivemeans of correlatingand checkingthe
fluidcompositionat stage ? (saturatedconditions). consistencyof calculatedK-values(i.e.liquid
compositions)is to plot log Kp vs the component
Moles of vapor remainingin the cell can be characterizationfactorF$ as suggestedby Hoffman,
calculatedusinga volumetricbalanceand the real Crump and Hocott! It has been our experiencethat
gas law (pV=nZRT). Recallingthe basis of one mole such a plot,when exhibitinglineartrendsapproach-
initialfluid,cell volumecan be calculatedfrom ing a commonconvergencepoint,indicateshigh
initialfluidproperties,which for gas condensatesis qualityvapor compositiondata, and to a lesser
Zd*R.T
extent,goodnessof liquidvolumemeasurements.
A more completediscussionof thismethodis present-
V
cau
. . . ...0.... . . . . . . . . . . . ,...0.
Pd
( Sa ) ed in a latersection,
and for volatileoils (existingas a liquidat bubble PhysicalPropertyCalculations
point pressure),
Constantvolumedepletiondatn can alsobe used
Vca M@b
to calculatephysicalpropertiesof equilibriumvapol
......G .G G *G .+G G G G G .....*.G G . (5b ] and liquid. A mass balanceis employedto carryout
the necessarycalculations,
where R = 8.3143J/mol-Kfor preferredS1 units,and I
R = 10.732 sia-ft3/mol-oRfor field units.[T(K),
f
Xk
p(kpa), V(m ) and T(R),p(psia),V(ft3),respective-
mLk+muk ** * * ** * 17]
lyl *
At each depletionpressure,liquidvolume is
wheremt = totalmass of the system,w = liquidmas:
and ~ = vapormass at stagek. Anotherway of
measuredvisuallyand reportedas a fractionof the statingthe mass balanceis that totalmass at stage
cellvolume,SLk. Actual liquidV01UK02vLk Can then k equalsinitialmass minus cumulativevapormass
be calculatedfrom producedfrom the cell. Recallingthe basisof one
mole initialfluid,and therebyequatinginitialmas!
with initial(saturation)nmlecular~ss~ Ms> gives
Lk Lk vcUf3
. G G G G . . .* G G G G . . , ,* G G G , G . . . . (6)
k
a% = h - & np.i%i
. . . G * .* G G G G , G . . (72)
and from a volumebalance,vaporvolumeVvk is
w~i~~e~~i is the vapor phasemolecularmass at
Vvk= (~ S~k)VC~ .G ....G G G .G .**G *G *G G G (7) stage I.
Both Ms and Mv can be easilycalculated
usingKays pseudocriticalmixingrule and approprial
componentmolecularmasses.
Using the real gas law, the correspondingmoles of
vapor nvk are calculatedfrom Vapor mass can now be calculatedby noting that
mass equalsmolecularmass timesmoles,or
PkVk
(81
vk
~
*******...*. G *****.***** G ****
= vk*vk
( 131
vk
. G . . . . G * . . * G $, . $. . G . . . . . . G
where pressurepk correspondsto vapor compressibility y
factorZk. * F = b(l/Tb- l/T)where b=[lOg(pc/pa)]/(l/Tb-l/Tc
and: Tb = boilingpointat atmosphericpressurePas
fMb and pb are buble pointmolecularmass and Tc and PC are criticaltemperatureand pressure,
density,respectively.Zd and pd are dew point respectively,and T is the systemtemperature.
compressibilityand pressure,respectively.
4 EVALUATINGCONSTAWTVOLUMEDEPLETIONDATA
SPE 10067
Liquidmass is calculatedas the differencebetween
BLACKOIL PVT PROPERTIES
totalmass and vapormass,
Dodson,ti.d~ suggestedan experimental
procadurefor determiningso-calledblack oil PVT
lb = %2 - vk
, . . . G . G . G G G . G . . G G . . .* G . G . + (14)
propertiesused in two-phaseflow equationsand
solution-gasdrivematerialbalancerelations.
Currentlaboratoryproceduresfor estimatingoil
Havingcalculatedmassesand volumesof equilibrium
formationvolume factorB. and solutiongas-oilratic
liquidand vapor,respective densitiescan be
Rso only approximatethe Dodson,@d. method-
calculateddirectlyfrom the ratioof m to V, i.e.
withoutflashingthe liquidphaseat each stageof
p = m/V (wherevolumescome fromEqs. 6 and 7).
the differentialvaporizationprocess, For medium
to low volatilecrudesthisprocedureappearsvalid
An independentcheckof vapor densitycan be
for most engineeringcalculations.The vapor
used to check the consistencyof measuredZ factors.
solutiongas-oilratioRsg is also assumedequal to
The relationis deriveddirectlyfrom the real gas
infinity- i.e. liquidcondensationis neglected.
law and can be statedas
Highlyvolatileoils and gas condensatefluids
VkP~
cannot,however,be analyzedor describedby the same
vk ~
.,**...........0.0.....*..**.(15)
differentialprocess, The basic problemposedby
thesemore volatilefluidsis thatduring two phase
flow there existboth two phasesand two components.
That is, flowingoil containssolutiongas which,
We can also calculatemolecularmass of the
when undergoingpressurereduction,evolvesand mixef
equilibriumliquid,and specificallyits heptanes-
with the existingvapor phase. Likewise,flowinggas
plus fraction. Rewritingthe mass balanceas
containsretrogradeliquidwhich also evolvesand
mixeswith the existingliquidwhen pressuredeclines
This complexthermodynamicphenomenonis, for all
.tk MLknLk%knvk
.0..G .....G *G .G G G . (~6)
practicalpurposes,impossibleto simulatein the
laboratory.
we can solvefor liquidmolecularmass ~k,
An alternativemethod is suggestedwhich,by
makingcertainsimplifyingassumptions,approximates
Zk - vk-nvk
the truemodel describedabove. Basically,
Lk =
G *.**. *.. **., ****...,. (17]
individualphase compositionsdeterminedfrom CVD
Lk
analysis(measuredor calculated)are flashedthrougl
a multi-stageseparatorsimulatorrepresentingfield
UsingKsysmixing rule, the heptanes-plusmolecular
conditions. Fig. 1 describesthe processdiagrsm-
mass can be back-calculatedto yield
atically.
N-l
Beforewe begin our discussionof the proposed
MLk -
~~1 j jki
method,let us define the fourbasicPVT properties
M
LkC7+ =
.*. *,*,**. (18)
used in two-phaseflow and reservoirmaterial
balanceequations:
kC?+
. Li . quLd vo. t umeof fx. a. t kuwi vo4L contioti
whereMj are molecularmassesof purecomponents.
%0 =
~.todz.tunko.il volumefiuu&&g @om dttih od x
The averageCT+ molecularmass ofthe two phase
:
systemshouldbe calculatedusing the relation
Ao.td g~ volumektiting @om tie ~ltihod x,
Lk*XkC7+~hLkC7+
R=
m
+ vkykC7+MvkCT+
(!7+
(?9)
40 htick &nk oi l vo&nemw&t Ag @om &!atJt od x
Lk xkC7+
+ vk*ykCT+
vapok vo&me od y, & atiehvoh cotiti
8=
9
.totig~ vo&unewwWng &om tie ~tih od g
i
Xotiga4 vohmemut i ng d~om tie f@h od y,
hg= ~tiektinko~ volwemwl$ing ~kom i~h od Y.
where x- are liquidcompositionsdeterminedfrom
1 msterla balanceequations. Yj are vapor composition
measuredexperimentally.
SPE 10067 C. H. WHITSONAND S. B. TORP 5
.
First, liquidcompositionx is flashedusinga
~asicvapor-liquid
APPLICATIONOF THE PENG-ROBINSONEQUATIONOF STATE
set of appropriateK-valuesand
equilibriaequations. [GlasOand Whitsonghave MeasuredCVD data and materialbalance-derived
1 low pressure documentedthat Standings blackoil propertieswere controlledusinga fluid properties
K-valuesare quiteaccuratefor flashcalculationsof packagebased on the Peng-Robinsonequationof state
blackoils. We have sincefound that they are also and developedby RogalandResearchInstitute. A
accuratefor flashcalculationsof mediumto highly completedescriptionof the computerprogramscan be
volatilegas condensates- i.e. systemswith gas-oil obtainedfrom the authors. The PVT packagenot only
ratiosless than about 50 000 SCF/STB(9000Sm3/Sm3).] includesgeneralvapor-liquidequilibriumoptions,
The sum of surfacegas volumesdividedby stock but it also includestwo optionsfor characterizing
tankoil volume is definedas the liquidgas-oil the heptan>s-plusfraction- me~hodspresentedby
ratioRso. Whitson or Robinsonand Peng.
Oil formationvolumefactorB. is calculated The numericalsolutiontechniqueused includes
from the relation a pre-iterativesucessivesubstitutionsmethod
btigti
followedby Newtonsmethodusinganalytical
z.m . + m~To
derivatives. Convergenceproblemswere encountered
g4 for the NS-1 fluidat temperaturesapproachingthe
B* = L
G G G *G .G G G *G *G G G *G G ,G , (20) criticalpoint - i.e.below reservoirtemperature.
v
STOL
Severalalternativenumericalmethodswere tried
(Powellsmethod and a newly-developedaccelerated
whereVSTO is stock tank oil volume (e.g.1 STB) and sucessivesubstitutionmethod) withoutsuccess
wheremg and mSTO are masses of totalsurfacegases Similarproblemswere notedwith the volatileoil
and stock tankoil, respectively.Liquiddensity,PL, system (NS-3)which, from all indications,liesvery
can be determinedfrom eithermaterialbalance near the criticalpoint at reservoirtemperature.
calculations(~ from Eq. 14 and VL from Eq. 6), or The lean gas condensate(NS-2)was solvedproblem-
from one of severalcompositionaldensitycorrelations free over a wide rangeof temperatures.
available6Jusingmaterialbalance-derivedliquid
compositions.We cautionthe use of PL calculated Pure componentproperties(criticalpressure,
frommaterialbalanceequationssinceonly a slight criticaltemperature,acentricfactorand molecular
error in retrogradeliquidvolumecan resultin a
mass) were used for non-hydrocarbons and hydrocarbon
substantialerror in liquiddensity- and therefore frommethane to n-pentane, Only n-hexanewas
Bo. The same errorwill.notaffectliquidcomposition consideredfor the CG fraction. Heptanesand
to the same degree. heavierpropertieswere estimatedusing the procedure
and equationssuggestedby Whitson~lwith several
At the same depletionsta~ek, vapor phasewith modificationsgiven in AppendixB.
compositionYj is separatedthroughthe flash
simulatorusing identicalK-values. The resulting To manipulatethe retrogradeliquidvolumecurve
surfacegas volumesdividedby stocktankoil volume the Watson characterizationfactorof the heaviest
definesthe vapor!solutiongas-oilratioRs .
%
componentwas adjusted,makingsure thatadjusted
Gas formationvolumefactor,on the otherhan , can propertieswere physicallyrealistic,
be accuratelyestimatedfrom the CVD compressibility
factorZ using the real gas law, Binaryinteractioncoefficientswere set equal
to zero except*3: Nz- Nz = -0.02,COZ - hydrocarbons
pbe*Z*T
s70 p
=0.15, N2 - hydrocarbons= 0.12,and Cl - ~n,
B
9
=*(1- .*. *,**.. *,..** (21) n
P TAe n@d
= 6~7*...*whichware esti~ted using a llnear
fit of the Katz and Firoozabadi13 data (theirTable 2)
where nSTO = 33301eS of stock tankoil resultingfrom
the flashof nfeedmoles of reservoirvapor.
~cl - cn
= o*14*yn - 0.0668 G .***,.....***. [22]
The me.jorassumptionimplicitin the proposed
method,assumingmeasuredCVD data are good:is that Theinteractioncoefficientbetweenmethaneand the
liquidand vapor compositionsare solelydependent heaviestcomponentwas then adjusteduntil a match
on pressure. That is, the composition-pressure of the measureddew point pressurewas obtained.
relationis uniqueand not alteredby physicalflow.
Examplesof PVT propertiesfor the rich gas
FluidDescription:Rich Gas CondensateNS-1
condensate(NS-1)are presentedin Figs. 2-5.
Here we have comparedpropertiescalculatedusing
NS-1 is a rich gas condensatefirst testedat a
materialbalanceresultswith thosecalculatedusing
Peng-RobinsonEOS simulateddata. Identicallow
gas-oilratio of 5500 SCF/STB(980Sm3/Sm3)from an
pressureK-valueswere used for both sets of data.
initialreservoirpressureof 7300 psia (50340kPa)
and temperatureof 280 oF (138oC). Stock tankoil
Vaporsolutiongas-oilratio is nearlythe
gravitywas 44 oAPI (0,8055gin/cc).Separatorsamplf
were takenwhile flowingthewell at 16.3MMSCF/D
same for both methodsof calculation. Liquid
(460*103Sm3) and a flowingbottomltole pressureof
solutiongas-oilratioand oil formationvolume
factorare both low for materialbalance-derived
7260 psia (50070kPa).
properties. The differenceis clearlya resultof
the lower liquiddensitiesestimatedby the Peng-
Robinsonequation.
6 EVALUATINGCONSTANTVOLUMEDEPLETIONDATA SPE 10067
Heptanes-PlusCharacterization MCN specificgravitiesand Eq. 22, as was the C1-CG
coefficient. Using thesedata in the Peng-Robinson
Extendedcompositionaldataof the C7+ fraction EOS yieldeda dew pointpressuremuch lower than
was not availablefor the NS-1 fluid,only molecular measured. The C1-CZS+interactioncoefficientwas
mass and specificgravity. Completetrueboiling then increaseduntil dew point pressurematched.
point (TBP)data were, however,availablefrom an
offsettingwell, NS-lb. These data were adaptedto The CVD simulatorwas run using the MCN
the NS-1 fluidusing the methodpresentedin Ref. 11, properties,as given in Table 3. The overallmatch
slightlymodifiedas discussedin AppendixB, was good to excellent,exceptfor liquidvolumes
which were much too high (32%simulatedmximum vs
Molal distribution(molefractionvs molecular 22% measuredmaximum). To check if measuredvolumes
mess) of the NS-lb fluidwas fit using the ganma were low we comparedmaterialbalanceliquiddensitie
distributionparameteralphaand variableupper with Alani-Kennedy7densities(usingmaterialbalance
boundrymolecularmasses. The optimalalphawas 0.712 compositionsand molecularmasses). Table 4 shows
for eta (minimummolecularmass in the C7+ fraction) resultsof the comparison,indicatingthatmeasured
of 92. Table 2 gives resultsof thematch, volumesare consistentexceptfor perhapssmell
errorsin the firsttwo volumemeasurements.
Molal distributionof the NS-1 C7+ fractionwas
then calculatedusinga = 0.712,q = 92 and l&7+ = Basedon theseresults,it was decidedto lower
184 (as comparedto 177 for the NS-lb fluid). We also the Peng-Robinsonliquidvolumesby adjustingthe
chose to hold upperboundrymolecularmassesconstant characterizationfactorof the CZ5+ fraction.
(equivalentto paraffinvalues),givingthe rasults By loweringthe factorfrom 12.42 to 11.80 resulted
presentedin Table 3. in a decreaseof the liquidvolumes- 8% for the
maximumdrop-out(from32% to 26%). The adjustment
Propertiesof the singlecarbonnumber (SCN) had littleor no effecton other estimateddata.To
groupswere estimeted*~by definingthe Kuop factors have loweredthe %Qp factorrmre wouldhave created
fromNS-lb SCN molecularmassesand specificgravities a physicallyunrealisticsystem. Adjustedphysical
using the relational propertiesfor the CZE.+fractionare found in
Table 3, as is the methaneinteractioncoefficient
K =4. S579.M0*]5J7g.#g4573 ........ (23)
used to adjustdew pointpressure. Completeresults
Uop
of the CVD simulationare presentedin Table 5.
Peng-Robinsonliquiddensitiesare comparedwith
Alani-Kennedyestimatesin Table 4.
Eq. 23 was then invertedand combinedwith NS-1 SCN
molecularmasses to yield SCN specificgravitiesand Over twentyother adjustmentsof the C7+ char-
normalboilingpoints,Tb, for the NS-1 fluid, acterizationprocedurewere attemptedfor improving
liquidvolumepredictions.None of thesewere part-
icularlyhelpful,thoughsome are worthmentioning:
Y
=6.010770K-1 1$24 GM0 17q47 . . . . . . . . . . . (24]
Uop
(1) extendingthe CT+ split to Cqo+ such that the
last componentwas very heavy, (2) increasingthe
numberof MCN groupsused to nine,CZ5+ inclusive,
where Tb = (y*~ )3, per definition. SCN data for
(3) splittingthe C7+ fractioninto eightSCN groups
NS-1 calculated;~ingEq. 24 are given in Table 3, and a Cls+ fraction,(4) using TBP
%3
p factors**
togetherwith criticalpropertiesestimatedusing the insteadof thoseestimatedfrom Eq.
Riazi-Daubert15 correlations(exceptfor Tb > 850 oF,
(5) using the Lee-Kesslerzpropertyco~r~~tions.~**
when modifiedcorrelationswere usedll).
Tuning the Peng-RobinsonEquationof State ** ActuallyKuo
E
is definedas T~13 /Y and could,
therefore,have een calculateddirectlyusing normal
Singlecarbonnumbergroupswere combinedinto boilingpointsdeterminedfromTBP analysis. Using
fivemultiplecarbonnumber (MCN)groups- CVC9, Kuop estimatedfrom Eq. 23 and measuredmolecular
C10-C13,C14-C17,C18-C24and C2S+ - as suggestedin massesand specificgravities,estimatednormal
Ref. 11. Group propertieswere calculatedusing boilingpointswere calculatedfrom Tb = (y*Kuo)3
Kays pseudocriticalmixingrule,exceptfor specific and are presentedin Table 2. f Some of theseva ues
gravitieswhich used a volume-weightedmixing rule. were higher thanupperboilingpointboundriesdefine
Methane interactioncoefficientswere estimatedusing for the specificSCN group. mo possibleexplanation
are provided:(1)due to distillationundervacuum it
was not possibleto duplicateexactboilir.gpoint
* The TBP analysiswas performedaccordingto the boundriesas definedin Ref. 14, or (2)measured
procedureoutlinedinRef. 14 and discussedbyKatz, uolecularmassesof the heavierfractionswere in
ti.d.~s The laboratoryonly reported,however, error. It was found,however,thatusingestimated
singlecarbonnumbermolecularmasses,mole fractions
%op factorsfromEq, 23-
when used for critical
and specificgravities. Cumulativevolumepercents propertyestimationsin the Peng-RobinsonEOS - gave
were then calculatedby notingthat incremental bettermatch of measuredconstantvolumedepletion
volume (permole) = mole fractionx molecularmess + data; the differencewas only minor.
specificgravity. Littlecurvaturewas exhibitedby
the TBP curve and normalboilingpointswere, there- *** Info~tion on theseor other simulationruns can
fore,merelyaveragesof the boilingpointrange for be obtainedfrom the authors. We would also apprec-
a given SCN group. iate suggestionsas to how one might improvethe
liquidvolumeprediction.
SPE 10067 C. H. WHITSONAND S. B. TORP 7
RESULTSANO DISCUSSION Temperatureeffectson the &g Kp vs F plotsof
NS-1 were investigatedby runningthe Peng-Robinson
Most resultspresentedin this paperare taken EOS airnulator at 340 F (171.1oc], some 60 F higher
from the threeNorth Sea systemsNS-1,NS-2 and NS-3. than reservoirtemperature.Fig. 10 presentsthe
It has been our experience,however,that some results,indicatingthat temperatureinfluenceis
featuresof CUD analysisare commonto all systems. (1) largestfor heavy componentsat largepressures,
We have triedto differentiatebetweenobsemations (2) negligibleat low pressures(aswas found in
which are specificto a givensyetem,and thosewhich Ref. 10), (3) relativelysmall comparedto the
are more generalin nature. We note in particular influenceof pressure,and (4) not significantin
that the K-valuecorrelationdevelopedin AppendixA changingthe apparentconvergencepressureof the
was developedfromour analysisof many fluids, system. These observationsare also illustratedin
rangingfromvolatileoils to lightgas condensates, Fig. 11.
Fig. 6 comparesmeasured(or more correctly, For lightereyatemssuch aa NS-2, theredoesnot
emoothed)vapor compositionswith thosesimulated alwaysappearsuch a uniqueconvergencepoint for
using the Peng-RobinsonEOS. The match is excellent, @ Kp VS F plots. We thoughtthat this perhaps
showingonly slightdeviationfor the C7+ and C6 resultedfrom a changein the totalcompositionof
components. Deviationof the hexanecomponentis the system,or from alterationin the heptanes-plus
probablydue to its incorrectcharacterization as properties. We investigatedthesepossibilitiesby
n-hexane. runninga constantcompositionsimulationof NS-1
(at 280 and 340 oF) andNS-2 (at 241 F). Resulting
Fig. 7 presentsheptanes-plusmolecularmassesof K-valueswere comparedwith CUD K-valuesand are
liquidand vapor phasesand the totalsystem.
Simulatedand materialbalance-derivedvaluesmatch
presentedas bg Kvs &lg p plots in Figs. 12, 13 and
14. All threesystemsclearlyindicatethat compsi-
well. Our experiencehas ahownthata good matchof tionalchangeduringconstantvolumedepletionis ?zo.4
C7+ molecularmaas using the Peng-RobinsonEOS is
significantenoughto influenceK-valuesor conver-
usuallydifficult,and very dependenton proper gencepressure,if in fact thereexistsa true
characterizationof the plus fraction. convergenceof K-valuesto unity. As seen in Fig. 14
the lean gas condensate(NS-2)does not appearto
Calculatedequilibriumconstantswere correlated have a convergencepressurefor componentsheavier
using the Hoffman,ti.t@.8method. Threemain reasons thanhexane.
are givenfor this choice:(1) the@ Kp vs T plot
providesa simplemeans of definingthe approximate
pressure-and temperature-dependence of K-values, CONCLUSIONS
(2) materialbalance-derivedK-valuescanbe evaluated
for consistencyby checkingthat~Og Kp vs F plotsare 1. Measuredconstantvolumedepletiondata for two
linearand converge,more or less, to a singlepoint gas condensatesand a volatileoil were analyzedusin
and (3)an approximateestimateof con~ergence simplematerialbalancesand the Peng-Robinson
pressurecan be determinedby extrapolatingthe slope
(of~og Kp vs F plots)vs pressurecurve to zero,
equationof state (EOS).
which can in turnbe used to improveinitialK-value 2. A simplemethod is proposedfor calculating
estimatesfor the Peng-Robinson(or any other) tblackoil pw properties(formationvolume factors
equationof state.SeeAppendixA. and solutiongaa-oilratios)of gas condensatesand
volatileoils.
Fig. 8 presentsNS-1 K-valuescalculatedusing
materialbalancerelations. The hg Kp vs F plots
3. Materialbalance-derivedK-valuescan be correlate
are linearand appearto approacha commn point. to yield an estimateof the apparentconvergence
As discussedin AppendixA, the convergencepointcan pressurewhich,when used in a newly-developedK-valt
give an estimateof the apparentconvergencepressure. correlation,helps calculatehigh pressureK-values
Actually,the most accuratevalue is obtainedby used as initialeatimateain equationsof state.
extrapolatingthe elopevs pressurecurve to zero,
as done in Fig. 11. The resultingestimateof pK# 4. Simulatedconstantcompositionand constantvolume
8000 psia (55170IcPa). depletionstudiesof lean and rich gas condensates
using the Peng-RobinsonEOS indicatethatK-values
Fig. 9 presentsNS-1 K-valuescalculatedfrom are &depf 2nde& of the depletionprocess.
the Peng-RobinsonEOS. Once againlinearplotsof
tog Kp vs F convergeto a point. From the extrapola- 5. Temperatureeffectson the Hoffman,&&c&.8 K-valu
tionof slope to zero in Fig. 11,
(51720kpa).
~*7500 psia correlatingtechnique(logKp vs F) were studied
Experiencewith the Peng-RobinsonEOS using the Peng-RobinsonEOS.
and materialbalanceevaluationof CUD data has shown
that rich gas condensatesand volatileoils exhibit 6. The Peng-Robinsonequationof atateusuallyover-
a more well-definedconvergencepoint than leaner estimatedliquiddrop-outfor gas condensatesduring
systems.
constantvolumedepletion. The problemwas normally
correctedor improvedby reducingtheWatson
Anotherinterestingfeatureshown in Fig. 9 is characterizationfactorof the heaviestcomponent.
thatheavycomponentsare bettercorrelatedusing the
log Kp vs F methodat higherpressurea. This ~~
suggestthatmethaneinteractioncoefficientsof the
plus fractionshave most influenceon K-valuesat
low pressures.
NOMENCLATURE K = convergence
A or A(p) = slopeof @ Kp vs F plot
L = liquidphase
b = elopeof the strai~htline connectingthe n
= carbonnumber
criticalpointand atmosphericboiling
o = oil
point on a @ vapor pressurevs l/T
plot,cycle-oR; cycle-K
P
= produced
B = formationvolumefactor,Bbl/STB; m3/Sm3 R
= reduced
CT+
= heptanes-pluscomponent
s = saturated(bubbleor dew point)
CVD E constantvolumedepletion
Sc = standardcondition
exp(x) = ex ; e = 2.71828...
STO = stock tank oil
EOS = equationof state
t = total (twophase]
F or F(T) = componentcharacterization factor,cycle v
= vapor phase
K = equilibriumconstant(K-value)
K = Wataon characterizationfactor
GreekLetters
Uop
&t = naturallogarithmto base e a = parameterin gammadistribution
log = logarithmto base 10
@
= parameterin gammadistribution
m = UISSS, lbm ; kg
r = gamma :Eunction
M = moleuclarmass, ibm/lb-mole; kg/kg-mole
Y
= specificgravityrelativeto air or
E = molecularmass of the totalsystem
water (60/60)
n = (1)moles, ibm-mole; kg-mole
A = incremental
(2) exponentin K-valuecorrelation
(s = interactioncoefficient
NS = North Sea sample
n
= parameterin ganmadistribution
(minimummolecularmass)
P
= pressure,psia ; kpa
P
= density,lbm/ft3;kg/m3 (gin/cc)
p(x) = probabilitydensityfunction
Pr
w = acentricfactor
= cumulativeprobabilityfunction
R = universalgas constant,10.732psia-ft3/
mole-oR; 8.3143J/mole-K
R = vaporsolutiongas-oilratio,SCF/STB;
ACKNOWLEDGMENTS
Sg
Sm3/Sm3
The authorswish to thankH. Xorvik,H. Asheim,
R = liquidsolutiongas-oilratio (same)
D. Murphy,V. Dalen and G. Nielsenfor usefulcomment
so
s = saturation,fractionor percent
concerni ng thiepaper. We also acknowledgecomputer
time and facilitiesdonatedby RogalandDistrict
T = absolutetemperature,R;K College,NorwegianInstituteof Technology(NTH)and
v =volume, ft3;m3
ContinentalShelf Institute(IKU). PhillipsPetro-
leumNorwayand Statoilshouldbe thankedfor contri-
X = liquidcomposition,fractionor percent butingwell-neededfluiddata to the petroleumliter-
= vapor composition,fractionor percent
ature. Economicalsupportfrom fryingpan publica-
Y
tions,Inc. is, as usual,appreciated.
Y or Y(p) = interceptof . bg Kp vs F plot
z = totalsystemcomposition
z = vapor compressibilityfactor
REFERENCES
1. Reudelhuber,F.O. and Hinds,R.F.: A Composition
Subscripts
al MaterialBalanceMethod for Predictionof
RecoveryfromVolatileOil DepletionDrive Reser-
a = atmospheric
voirs,TMW.,AIME(1957)2?0,19-26
b = bubblepoint (pb)or boiling(Tb) 2. Dodson~C.R., Goodwill,D. and Mayer,E.H.:
c = critical
Applicationof LaboratoryPVT Data to Reservoir
EngineeringProblems;T&zM.,AIMB(1953)198,
cell = cell,pertainingto PVT cellvolume 287-298
d = dew point
3. Peng,D.-Y. and Robinson,D.B.: A New ho-
g
= gas ConstantEquationof State,l nd. Eng, Ckm. Fund.
i = indexfor sumatian
(1976)IS,N0.1,59-64
j
= componentidentifier
k = depletionstage
SPE 10067 C. H. WHITSONAND S. B. TORP 9
4,
5.
6.
7,
8.
9*
10*
Watson,K.M.,Nelson,E.F. and Murphy,G.B.:
Characterization of PetroleumFractions,Znd.
Eng.Chn.(1935)27,1460-1464
Firoozabadi,A., Hekim,Y. and Katz,D.L.:
ReservoirDepletionCalculationsfor Gas Conden-
satesUsing ExtendedAnalysesin the Peng-
RobinsonEquationof State,Can.J . Chsm. Eng.
(Oct.,1978)56,610-615
Standing,M.B. and Katz,D.L.: Vapor-Liquid
Equilibriaof NaturalGas-CrudeOil Systems,
Th.uti. ,AIME(1944) 755,232
Alani,G.H. and Kennedy,H.T.:Volumesof Liquid
Hydrocarbonsat High Temperaturesand Pressures,
Tkut i .,,AIME(1960)219,288-292
Hoffman,A.E., Crump,J.S. and Hocott,C.R.:
EquilibriumConstantsfor a Gas-Condensate
System,Tfiati.,AIME(1953)198,1-10
Glas@,0. and Whitson,C.H.: TheAccuracy of PVT
ParametersCalculatedfrom ComputerFlash Separa-
tionat PressuresLess Than 1000 psia,SPE Paper
8033 (1979)
Standing,M.B.: A Set of Equationsfor Computing
EquilibriumRatiosof a CrudeOil/NaturalGas
Systemat PressuresBelow 1,000psia,J.Pti.
Tech.(Sept. ,1979)1193-1195
110
12*
13*
14.
15,
16.
17.
180
19.
Whitson,C.H.:CharacterizingHydrocarbonPlus
Fractions,EUR Paper 183 Presentedat the EUROPE
Meetingheld in London,England,Oct. 21-24,1980
Risnes,R,, Dalen,V. and Jensen,J.I.:Phase
EquilibriumCalculationsin theNear-Critical
Region,PaperPresentedat the 1981 European
Symposiumon EnhancedOil Recovery,Sept. 21-23,
1981
Katz,D.L. and Firoozabadi,A.: PredictingPhase
Behaviorof Condensate/Crude-Oil SystemsUsing
MethaneInteractionCoefficients,T~ti.,AIME
(1978)f6~,1649-1655
SelectedValuesof Propertiesof Hydrocarbonsan
RelatedCompounds,API Project44, TexasA&M
Univ.,CollegeStation(1969)
Riazi,M.R, and Daubert,T.E.:SimplifyProperty
Predictions,ff@o.Pkoc.(March,1980)l15-116
Conrad,P.G. and Gravier,J.F.:Peng-Robinson
Equationof StateChecksValidityof PVT Exper-
iments,0ti4GaAJ.(April21,1980)77-86
Yarborough,L.: Applicationof a Generalized
Equationof State to PetroleumReservoirFluids,
from Eqt ut t t ot iO{ $&W by Chao and Robinson
Wilson,G.M.:A ModifiedRedlich-KwongEquation
of State,Applicationto GeneralPhysicalData
Calculations,paper presentedat the 65th
NationalAIChEMeeting,Cleveland$1969
Brinkman,F.H. and Sickling,J.N.:Equilibrium
Ratiosfor ReservoirStudies,Tuw.,AIME(1960)
219,313-319
20. Standing,M.B.: Vo&una.t&ic and Pt i e 8ehavi o&o{
Oi l F.i&d ffyhoumbon Sy&tem, 8th printing,
Societyof PetroleumEngineersof AIME,Dallas
(1977)
21. Robinson,D.B. and Peng,D.-Y.:The Characteri-
zationof the Heptanesand HeavierFractions,
ResearchReport 28, GPA Tulsa,Oklahoma(1978)
22. Kessler,M.G. and Lee, B.I.:ImprovePrediction
of Enthalapyof Fractions,~@RO.phOC. (March,
1978)153-158
I
APPENDIXA
I
IMPROVEDK-VALUEESTIMATIONAT HIGH PRESSURES
Solutionof the Peng-Robinson(or any other)
cubic equationof staterequiresinitialestimates
of K-values. At higherpressures(> 500 psia)and
particularlynear phaseboundriesor the critical
point,theseestimatesare very importantfor deter-
mining the correctsolItionto the equation.
AccurateK-valueestimatescan also reducenumerical
divergencewhen searchingfor the solution.
WilsonDproposedthe followingthermodynamic
relationfor estimatingK-valueswhich should,in
pra~tice,only be used at low pressures,
c
{ }
~j =~xp 5*37(~+~j)(~-J/TRj) /pRj ..*** ( A- f )
where
Rj
E T/T
cj
I
pRj = plp~j
Tb ./Tc .
j+~.=?
10g (pcj/pa)
J
71-
Tbj / __f cj
d
5. 37 =$.W1O)
T and p define the systemstemperatureand pressure,
Tb is the atmosphericboilingpoint at pa, and Tc and
pc are criticaltemperatureand pressure,respectively
Actually,Eq. A-1 appearedin the petroleumliterature
some 10 yeara beforeWilsonproposedhis relation.
Hoffman,ti,ti.apreeentedEq. A-1 graphically(their
Fig. 4) and suggestedthe followinggeneralization
(albeitgraphically),
log KjP = A(~)* Fj(T) + y(p) . . . . . . . . . . . . . . (A-2)
I
where
1/Tb . - l /T
Fj(T) E log (P~j/PU) . . . . . . . (A-3)
7Tbj
- 1lTcj
10 EVALUATINGCONSTANTVOLUMEDEPLETIONDATA SPE 10067
A(p) = ~a~t i e- dependet i ht ope
I
pK (P4ti]=60*MC7+ - 4200 ............. (A-6)
It is easilyshownthat Eqs.A-l&A-2 are identical
for A(p=pa)= 1 and Y(p=pa)=.&?gpa - i.e.at
atmosphericpressure.
Engineersfamiliarwith Eq. A-1 are aware that
its accuracyis usuallylimitedto low pressures.
An investigationof the pressure-dependent slopein
Eq. A-2 showed,however,thatEq. A-1 couldbe
reformulatedto yield equally-accurateresultsat
higherpressures.
The quasi-thermodynamical model used to extend
Eq. A-1 is basedon the suggestionby Brinkmenand
Sicklinglg that plotsof tog Kp vs F(T) at several
pressuresintersectat a commonpoint definingthe
apparentconvergencepressureof the system. Their
relation,afterdroppingpressure-and temperature-
dependentnotation,is
PK
A(Fj - FK]
K. = 10
Jp
.,.*G G .,.*......G O. (A-3)
where ~ = convergencepressureand FK = the F-value
correspondingto pK at the comnonpoint of intersec-
tion. Eq. A-3 is es{]ilyderivedby noting thatKj=l
at convergencepressurepK. We can also show from
Eq. A-1 thatFK = ~og(pK/pa),or in termsof the
interceptin Eq. A-2,
and that exponentn = 0.6 for all systems.
We can now reformulateEq. 1 (theWilson-type
equation)to giveK-valuesat all pressuresand
temperatures,
Pc A-j
Ki. ( d)
{ }<
.exp 5,37* At(?-ui)(l-l/TRj) /pR
PK
. . . . . . . (A-7)
Note thatA=l for p=pa, reducingEq. A-7 to Eq. A-1.
For p=pK,K.=1, thusmakingEq. A-7 consistentat
i both pressue boundries. UsingEqs.A-5 (n=O.6),
A-6 and A-7, K-valuescan be estimateddirectlyfrom
inputdata used by equationsof state.
APPENDIXB
MODIFIEDC7+ SPLITTINGMETHOD
Methodspresentedin Ref. 11 were used to
determinethe molal distributionof the C7+ fraction
with the followingmodifications:
Y = Y(pl
I
(1)Minimummolecularmass (eta)was set equal to 92
=@PK-&hg(PK/Pa) ......... (A-d)
The pressure-dependence of slopeA was investi-
gated and foundto have the followingtwo properties:
(1) it rangedfrom O~A~l for pK<p<Pa and
(2) its formvaried from sligtlyconcaveup to
linear(seeFig. 11). From theseobservations,a
generalequetion-formwas found to fit A(p),
P - Pa, n
A=A(p)=l -( . . . . . . . . . . . . . . . . . (A-5)
pK- Pa
where exponentn variedfrom 0.5 to 0.8 for various
condensateand volatileoil systems. We found,
however,that n = 0.6 gave reasonableK-value
estimatesfor all fluid systemsatmostpressuresand
temperatures.In practice,exponentn and pK for a
particularsystemcanbe determinedexactly.by
plotting@(l-A) vs ~Og(p-~) where n is the slope
1 and the interceptequalsn. Og(pK-pa). SlopeA is
usuallydeterminedby drawinga best straightlineor
using linearregressionthroughdata for components
ethanethroughhexane,where our experiencehas shown
thatmethaneand carbondioxidealso lie on the line.
For more generaluse of Eq. A-5 (for example,
initialK-valueestimatesfor an equationof state),
we have found that a good estimateof apparent
convergencepressurecan be obtainedfrom the
heptanes-plusmolecularmassm
(2) The errorftinction used to determinethe optimal
alpha ($)was
E( Q) =2(2-2)2 . , 0. . , , , . , . . . . . . . . . . . . . . (B-l )
and was minimizedusing the half-intervalmethod.
(3) The uppermolecularmass boundrywas allowedto
vary between14*i - 12 and 14.i + 12, exceptfor C7
which had a rangeof 93 to 14*i + 12. Measuredmole
fractionwas matchedby varyingthe upperboundry.
Only two iterationsare requiredsince the relation
betweenboundrymolecularmassesand mole fractions
is nearlylinear.~That is, if upperboundryMi yield
zl, and M! yields22, and z = measuredmole fraction,
then the optimaluppermolecularmess boundryis very
nearly
M; -M;
M:pk =
M;+ (z-~2)~
......... (B-2)
22
- $
In some cases,Eq. 2 was used twicein order to
increasethe accuracyof the estimatedmole fraction
SPE 10067 C. H. WHITSONAND S. B. TORP
11
(4) In the originalmethodpresentedinRef. 11,
sin Ie carbonnumbermolecularmassescorresponding
R
to z. with molecularmass boundriesM: and M!+l w~s
i mere y the arithmeticaverage. Dale Embry (~hllllps
PetroleumCompany,Bartlesville)noted in a
personalcommunicationthat this approximationwas
not necessaryand that the exactanalyticalexpres-
sion is givenby
where G ** (%-3)
I
%,+- Q
i3= G .**** o*@** .*e** *e***..* (B-4)
a
Pk( X: x, a,b, c) = e- g ; [gU+j / r(u+j+l ) 1 ( B- 5)
j =o
g= ( x- c) / b G *+********.G *. *. **, *, *,. , , ( B- 6)
and, as previouslymentioned,q = 92. Concerning
Eq, B-4, @ is the samewhethera or a+l is used in
the cumulative.probability functionPr.
TABLE 1 - MEASURSDCONSTANTVOLUMSDEPLETXONDATA FOR THE NS-1 FLUID AT 280 %+
Coolpos i tions
Equilibrium Equilibrium
Vauor Liauid
Pressure - Psia Exp , Calc .
CO~ponent 6764.7 5514.7 4314.7 3114.7 2114,7 1214.7 714.7 714.7 714.7
. .
Carbon Dioxide 2.37 2.40 2,45 2.50 2.53 2.57
Nitrogen
2,60 0.59 0.535
0.31 0.32 0.33
Methane
0.34 t3.34 0.34 0.33 0.02
73.19 75.56
0.017
Ethane
77.89 79.33 79.62 78.90 77.80 12.42 10.704
7.80 7.s3 7.87 7.92 8.04 E.ho 8.70 3.36 3.220
Propane 3.55 3.47 3.40 3.41 3.53 ~., 74
iso-Butane
3,91 2.92
0.71 0.67
2.S96
0.65 0.64 0.66 0.72 0.78 0,91
normel-Butane 1.45
0.916
1.37 1.31 1.30 1.33 1.44 1.56 2.09 2.103
iao-PentaOe 0.64 0.59 0.55 0.53 0,54 0.59 0.64 1,40 1.417
normel-Pentana 0.68 0.62 0.58 0.56 0.57 0.61 0.66 1,60
Hexenea 1.09
1,624
0,97 0.S8 0.83 0,82 0.s5 0.90 3.68 3,755
Heptanes-plus 8.21 6,20 4,09 2,64 2.02 1.84 2,12 71,01 72, S15
,. .
Totala 100,00 100.00 100,00 100,00 100.00100.00100.00100,00100,000.
%,+
184,0 160,0 142.0 127,0 119.0 115,0 114.0 213,0 207.9
%,+
0.816 0.799 0.783 0.770 0,762 0.758 0,757 0,833 0,843
z 1,238 1,089 0,972 0.913 0,914 0.937 0.960
n -%
P
0.000 9.024 21,744 3S.674 55.686 72.146 81.301
-z
L
0.0 14.1 19.7 21.6 21,3 20,2 19.3
TABLE 2 - COMPOSITIONALAND PROPERTIES DATAOF FLUID NS-lB SAYPLEDFROM
A WSLL OFFSETTING NS-1 COMFARSDWITH CALCULATEDDATA
GENERATEDUSING THE METHODPFU%SENTEDIN RSF . 11
Measured
Single
Carbon Mole Molal Specific
Number Percent }Iaea Gravity
.
0.94 95 0,715s
: 0.s4 104 0.7365
9 0.74 118 0.7757
10 0,60 132 0,7639
11 0.41 144
12
0.7723
0.34 154 0.7s14
13 0.31 167 0.7939
14 0,26 180 0,8053
15 0.22 197 0.8096
Calculated
K
Boiling Upper
Uop Point Mole Molel Molal
Factor (%) Parcant Mass Maes
. .
12,05 641.7 0.935 95.1
11.93 678.3 0.83S 105,4
11,90 727.3 0.739 11s .9
11,99 768.4 0.600 134,2
12.04 S04 ,0 0.410 148,7
12.04 832,7 0,340 161,7
12.03 871,2 00310 175.0
12.02 907,0 0.260 188,7
12.13 947.1 0.220 202,1
12,30 1008,1 0.190 215,4
12.19 1019.0 0.170 228.9
12.20 1039.4 0.150 242.8
12.26 1069,4 0.130 256,8
12,28 1097.6 0.110 270,6
12,29 1130.8 0.080 283.0
12.32 1161,0 0.070 294,1
12.36 1191.4 0.060 304,8
12,38 1234,9 0.070 316,7
12.87 1465.6 0.508 439,1

12.25 6.190 177,0

(12.02)*
99.6
111.9
126.8
142.4
155.5
168,4
182.2
195.7
209.1
222.4
236,1
250.1
264.1
277.8
289.0
299,9
310.3
324.0
.
16 0.19
17 0,17
18 0.15
19 0.13
20 0.11
21 0.08
22 0.07
23 0.06
24 0,06
25+ 0.51
6,19
212 0,8152
226 0.8255
234 0.8303
250 0,8341
262 0.8400
277 0,8477
292 0,8531
308 0,8577
329 0,8666
471 0.8826

177 0,8061
* The higher average hop valua was calculated using a weisht-average
mixing rule, wharaas the lower value was estimated using the Whitson
correlation.
* The gamma distribution (Raf. 11) was usad where an optimal alpha of
0,712 wae found for eta (minimum molecular maas in the C7+ fraction)
of 92. Upper molecular maaaea wera found by fittins the meaeured
compositions,
TABLE 3- PHYSICAL PROPERTIES OF THE C?+ SINCLE ANDlNILTIPLE CARMN NUf4BSR
~ .OUPS USED ~ THE PENG-ROBINSON EQIJAT~N oF STATE ~ DEP,c21BE
L6SERV01R FLUID SEHAVIOROF THE NS-1 FLUID
Single
Carbon
Number
;
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
2s+
7- 9
10-13
14-17
18-24
25+
Boiling
Critical
Methene
Mole Molel Specific Point Temp. Prese, Acentric Interaction
Parcant Meae Gravity
(OR) (OR)
(peie) Factor Coefficient
..
1,2136 95,3 0,7177 646.8 971.6 457,5 0.2742
1,1730 106.5 0.7409 690,6 1021.4 423,4 0,3056
0,8600 120.7 0.7599 739.4 1073,2 383,2 0,3454
0,6872 134,7 0.76S2 781,4 1112.9 345,9 0,3861
0.5681 14s.7 0.7781 822.2 1152,1 316,8 0,4251
0.4783 162.7 0.7908 863.1 1192.3 294,0 0,4622
0,4074 176.7 0.8034 902.8 1231,2 2:4,9 0.4984
0.349s 190.7 0.8153 941.2 1268,3 258,4 0,5342
0,3021 204.7 0,8168 972.6 1294,2 240.4 0,5740
0.2621 218.7 0.8210 1029.8 1321.5 225.7 0.6127
0.2282 232,7 0.8310 1039,5 1354.0 214,6 0.6486
0.1992 246.6 0.8389 1072,0 1383,6 204,3 0.6855
0s1744 260,6 0,8432 1104.7 1408,7 194.0 0,7246
0.1529 274.6 0.8486 1131.6 1434.4 185,1 0,7634
0.1343 288.6 0.8554 1161.9 1461,0 177,4 0.8016
0.1182 302,6 0,8602 1190.2 1484.9 170,0 0.8416
0.1041 316.5 0.8639 1217.4 1507,0 162,9 0,8830
0.0918 330.5 0.8690 1245,1 1530,2 156.8 0.9241
0.7054 462,3 0,9192 1.488.0 1734,6 91.4 1,0590

S,21OO 184.0 0.8160
MULTIPLE CARBONNUMBERPROPERTIES USED IN THE FINAL CVO SIMULATION
3.2466 106.1 0.7385 688,3 1016.5 425.5 0.3044 0 .03659 ***
2,1410 152.7 0.7837 835,0 1163.6 313.1 0.4348 0,04292***
1.1421 209.2 0.8205 984,4 1304.5 237.4 0.5S56 0.04807***
0.9749 281,5 0.8524 1146.9 1446.0 182.7 0,7832
0,7054 462.3 0.9192
0 .05254 ***
1276.1* 1584,2* 168,8* 0.8819* 0.18400**
.
S,21OO 184.0 0.8160
* Adjusted valuea representing e Kuop factor of 11,80, The original veluee
correspond to a Kuop factor of 12,42 and ere given above (e.g. 1488 .0) ,
** Adjuetad valua ueed to match the maaeured daw POint Preeeur@.
*** Calculetcd ueing the Katz and Firoozabadi correlation, curve-fit tO yield
= o,14. y - 0.0668. Though not ehown in thie
~~~l&l~~i#~t~~~~n~Cl~n interect!on coefficient wae also calculated using
thie relation,
TABLE 4 - CALCULATEDLIQUID DENSITIES AS A FUNCTIONOF PRSSSURE FOR NS-l
Calculated Liquid Deneitiee (gin/cc)
Measured CVD Data Simulated CVD Data
Alani-l(ennedy Alani-Kennedy
Material Daneity Peng- Denaity
Pressure Balanca (M. B. Liquid Robinson (P-R Liquid
(pela) Deneity PrOpertiee)* Dcne i ty** Properties)*
5514.7 0.670 0, 60B 0,541 0.570
4314.7 0,680 0,649 0.554 0,596
3114,7 0.688 0.670 0,580 0.632
2114.7 0.700 0,682 0.608 0,664
1214.7 0.711 0.700 0,636 0,692
714,7 0,722 0,711 0,653 0,707
* The Alani-Kanncdy density cmralat ion requires 1iquid compoai t ions,
total liquid molecular mane, hcptanea-plue molecular mass ttnd specific
Sravity (ae well as preasurc and tempcraturo), Thase data were available
from either material balance calculations or P-R elmulntion reeulte,
** Tha Pcng-Robinson simulation uaad propertied giVenin Table 3 with an
adjuetcd KUOP G il,8 for the C25+ fraction, Using the original KUO factor
! of 12.42 gava evan lower liquid dcnnitlcs than thaac &ivcn ahovc, w th a
larser deviation from tho Alani-Kenady valuca,
TABLE 5 - SIMULATEDCONSTANTVOLUMEDEPLETIONDATA FOR THE NS-1 FLUIDAT 280 OF USING THE PENG-ROBINSON
EQUATIONOF STATE
Compositions
Equilibrium
Equilibrium
Vapor
L<quid
Component
Pressure- psia
Exp. Calc.
6764.7 5514.7 4314.7 3114.7 2114.7 1214.7 714G7 714.7 714.7
CarbonDioxide
Nitrogen
Methane
Ethane
Propane
iso-Butane
normal-Butane
iso-Pentane
normal-Pentane
Hexanes
Haptanes-Plus
Totals
M
c,+
c,+
z
- z
P
L-%
2.370 2.403 2.447 2.497 2.541 2.576 2.583 0.590
0.310 0.323 0.336 0.344 0.343 0.334 0.321 0.020
73.190 75.549 77.644 79.135 79.712 79.242 77.772 12.420
7.800 7.779 7.793 7,380 8.057 8.372 8.711 3.360
3.550 3.474 3.405 3.383 3.444 3.660 3.989 2.920
0.710 0.686 0.660 0.644 0.647 0.691 0.778 0.910
1.450 1.390 1.326 1.281 1.282 1.375 1.567 2.090
0.640 0.604 0.564 0.530 0.516 0.548 0.638 1.400
0.680 0.639 0.592 0.550 0.532 0.563 0.659 1.600
1.090 0.996 0.889 0.789 0.727 0.744 0.877 3.680
8.210 6.157 4.343 2.969 2.198 1.895 2.105 71.010
. . .
100.000 100.000 100,000 100.000 100.000 100.000100.000 100.000
184.0 161.0 142.7 129.1 121.2 116.4 114.5 213.0
0.816 0.799 0.783 0.770 0.762 0.758 0.757 0.833
1.203 1.037 0.937 0.890 0.886 0.911 0.936
0. 000 9.637 22.581 39.492 56.196 72.413 81.535
0. 00 19.55 26.11 26.65 25.11 23.00 21.58
0.595
0,029
11,939
3.623
3.133
0.967
2.314
1.509
1.770
4.223
69.897
100.000
209.1
0.843
IDENTICAL MULTI-STAGE SEPARATION
L
u
fA
\
.
Y-
ii!
3
g
z
0
H
1-
<
=
Ot
0
u.
gi ~92 g3
03 r
p*c. z. T
8
.
9 Tbc. p
% , -
. [ l -
deed
1
Lo
VAFOR
j
LIQUID
x.
B. =
mgl + %2 + %3 + ST
Vg 0 PL
PVT CELL
Fig. 1-Schematic description of the procedure for calculating black
oil PVT properties.
030 ~ (4 NS-I
0. 025 -
0. 020 -
0. 015 -
0. 010 -
0. 005 -
280 F
\
+ PENG-ROBINSON Z-FACTORS
+ MEASURED Z-FACTORS
0.000
I I I , , I , , I * 1 1 I , , I
{
o 1000 2000 3000 4000 5000 6000 7000
PRESSURE, psi a
Fig.2-Gaeformation volume factor vs pressure for NS.1 at280 F.
rnsoooo~~ 11111111111111
PENG-ROBINSON RESULTS
+fIIATERIAL BALANCE RESULTS
USI NG MEASURED DATA
NS-I
280 F
L
SEPARATOR CONDITIONS*
10000 -
PRESSURE TEMPERATURE
(psia) G ( F)
1014.7 155
264.7
*
5TANDING LOU PRESSURE
14.7 !%
(BLACK OIL K-VALUE
CORRELATION USED
O. l I l l
1000 2000 3000 4000 5000 6000 7000
PRESSURE, psia
Fig. 3-Vapor solution gas.oil ratio vs pressure for NS.1 at 280 F.
G
\
I
+PENG-ROBINSON RESULTS
-A-MATERIAL BALANCE RESULTS
g
~MATERIAL BALANCE RESULTS
USI NG P- R LI QUI D VOLUMES (SL)
~ 1.8
/
rn2. 0~, l , , , , , 1 I
I
I r , ,
I
, 1 t 1
I
, , I ,
I
1 I I t
I
I t 1 #
NS-I
280F
1. 6
,.Qo~AJ
4000 5000 6000 7000
PRESSURE, psia
Fig. 4-011 formation volume faotor vs pressure for NS.1 at 280 F.
+
-A-
-a-
PENG-ROBINSON RESULTS -
MATERIAL BALANCE RESULTS
MATERIAL BALANCE RESULTS
-1 , 1 I
I
I I I I
I
I 1 I I
I
I I I i
I
I , 1 ,
I
1 I 1 ,
I
1 1 , t
NS-I
280 F
USING P-R LIQUID VOLUMES
SEPARATOR CONDI TI ONS*
PRESSURE TEMPERATURE
(psia) ( F)
($L) p
1014. 7 155 ) A
264. 7 80
14. 7 60
* STANDING LOW PRESSURE
BLACK OIL K-VALUE
CORRELATION USECI
1
I
J
t 1 1 I 1 I 1 , I 1 , t 1 I I 1 I I I , 1 1 I I 1 , I # I 1 1 # I
1
1000 2000 3000 4000 5000 6000 7000
PRESSURE, psia
Fig.6- J1-lquldsolution gaa..oil ratio vs pressure for NS-I at 280 F,
K 240, 1 I I I
I
1 , 1
I
i 1 1 I
I
1 1 , I
I
I 1 1
I
I , 1 I
I
, I 1
I
w
to
W
[
+PENG-ROBINSON MATCH
e
k
aMATERIAL BALANCE RESULTS
=
USI NG MEASURED DATA
LIQUID
~ +MEASURED (+)
-i
280 F
l oo~
I #, , 1 , t , I
1000 2000 3000 4000 5000 6000 7000
PRESSURE, psia
I
Fig. 6-Calculated and measursd vapor compositions vs preesure for NS.1 at 280 F.
102
10
1
I
I
I
I , , 1
I
I
I
I ,
I
n , 8
I
, 1 1 ,
c1o
4
PENG-ROBINSON MATCH
o MEASURED (ACTUALLY THE DATA HAVE BEEN
SMOOTHED AND ADJUSTED ACCORDING
TO CORE LABORATORIES PROCEDURE)
C2
P=
N2 o
NS-I
280 F
10-
)
1 1 1 , I t I t t I 1 , 1 I , I I 1 ,
0 1000 2000 3000 4000 5000 6000 7000
PRESSURE, psia
Fig. 7-Calculated heptanes.plus molecular masses w pressure for NS.1 at 280 F.
w
XTRPWNSF LPESi I
F
d,
APPARENT CONVERGENCE
PRESSURE s 7500 psia
CO*
II
~ ICI-2
k
Z
n
lo~ ;
1 1 1 1
2.0 2.5 3.0 3.5 4.0 4.5
:
i
C25+ *ADJ USTED C7+F VI AL, UE, S
10- 3
1 I
- 4 - 2 0 2 4 6
COMPONENT CHARACTERI ZATI ON FACTOR, F=b( l / Tb - I / T>
Fig. 8- NS.1 K.vak!es at 280 F calculated using the material balance approach.
!
I I
, T
I
, , t
I
, *
I
, , , J
PRESSURE O MATERIAL BALANCE RESULTS
I NS-I
(psia>
USI NG MEASURED DATA
1-5514.7 LEAST SQUARES LINEAR
/:
.2 280*F
2- 4314. 7 REGRESSI ON
4
3- 3114. 7 ( N2ANDCF+ DATA EXCLUDED)
4- 2114. 7 . / ~
- 5- 1214. 7 A
6- 714. 7
COMPONENT CHARACTERIZATION FACTOR, F=b(l/Tb - I/T)
fo 105
I I I I I 1
.1-
In 280 F 1
Fig. 9- NS.1 K.values at 280 F calculated using ths PengRoblnson EOS,
PRESSURE
X 7500 psia-
NS-I
280 F
d
1 1 I 1 [
I
-2 -1 0 1 2 3 4 5
COMPONENT CHARACTERIZATION FACTOR, F=b ( 1/ Tb - I / T)
~lg. 10- Temperature effect on the Hoffman, et al. K.value corralatlon for NS.1.
u)
>
& 2. 0
1.0
0.0
PENG- ROBI NSON MATCH ( 280F)
- - PENG- ROBI NSON MATCH ( 340F)
o MATERI AL BALANCE RESULTS
1-
=j
/ I NTERCEPT Y ( p)
g
~
g
w
>
z
$:
+W
~g
%$
$:
. NS- I
<o.
0 2000 3000 6000 8000
PRESSURE, psia
Fig. 11- Slopes and Intercepts of log Kp vs F plots vs pressure for NS.1.
102
<
, 1 1 , , , , I , I * 1
>
COSTANT CO! l POSI TI ON NS- I
- - - - CONSTANT VOLUME DEPLETI ON 280 F
II
.?
= 10
+
z
$1
z
o
u
e
m
H
~
10-3 r
10-4 r
u
10-5 F C25+ ?.
~PRESSUREl
.?
10-6
(psia) 714.7
I , , , 1 1 ,
3X102 103 104
PRESSURE, psia
Fig. 12- Peng-Robinson K-values for NS.1 at 280 F representing two
depletlon processee.
102
10
1
10-
1o-i
10-2
10-
.
v I I , t *
I
, , , , ,
- - - - CONSTANT VOLUME DEPLETI ON NS- I
CONSTANT COMPOSI TI ON 340F
1
C14-C17
cI&cz4
10- 5
3X102 103 104
PRESSURE, psia
Fig. 13- PengRoblnson K.values for NS-1 at 340 F representing two
depletion processes.
x l o2k 1 1 , , , t I 1 1 1 t 1 t 1 1 - i
<
E CONSTANT COMPOSI TI ON
r
1
NS- 2
x
- - - - CONSTANT VOLUME DEPLETI ON z410F
1
10- 41
, I , 1 1 I
3X102 103 104
PRESSURE, psia
Fig, 14-Peng.Robinson Kwalues for NS.2 at 241 F representing two
depletion processes.
cl,+..--