· .... ~ .

•
Importance Of The C7 +

Fraction In Phase

Behavior Calculations

Fourth in a series, this article presents numerical examples of the magnitude

of the physical property changes obtained by perturbing the molecular weight
of C 7 +. A hypothetical volatile/condensate fluid and a black oil are considered.

hysical properties of pure components essen­ identified by assigning "virtual" critical properties and
ti;!l for .!;~tion of state (EOS) calculatio;:;sa;=e­ an acentric factor to it. However, by using the plus frac­
the critical pressure (Pc)' the critical tempera­ tion as a single component, fluid property predictions
ture (Tel, an~ the acentric factor (w). Many of " using an EOS can be erroneous, and invalid conclusions
these prop.:nics have been measured and compiled maY result. In these case s, correct results can be
throughout the years. Petroleum engineers are usually obt;ined when the heavy fraction is subsequently bro­
interested in the behavior of hydrocarbon mi:<:tures ken clown mto a manageable number of seudocom 0­
l"ther than in the pure components. However, a s seen in nents or computatlOns. T e number of pseudo­
Anide 1 of this s eri es, to predict the behavior of fluid components may range bet,VC"en two and an upper limit
mixtures, EOS calcul<ltions require critical propenies often constr;:lined by computational load and degree of
anel <lcentric factors of pure ,components, which arc used accuracy required. An apparent constraint in defining
with appropriate mixing rules . l these groups is to ensure that the molecular weight and
Problems arise when working w ith any type of reser· specific gravity of the mixtut'e must be equal to the mea­
voir oil that may consist of thousands of different molec­ sured properties for the C7 + fr.J.ction.
ular species, most of them nea rly impossible to quantify There a re numerous correlations for estimating criti­
accurately u sing any an::dytical lec h n ique. A common cal properties and acentric factors of a heavy fraction.
appro<lch is to charac ter ize th is o il m ixtu re as being Most of these use specific gravity and normal boiling
made up of well-defined components (C 1' CO" C" etc.), point as.~orrelatin&..Rii-amii:e·i-s; others use the molecu­
plus a hea\":; fraction. Defined compon en is ~ay be \~r weight ::~he specific gravity. Frequently, these are
quantitativ"ly identified using a gas chromatogrnphic the only measurectprop-enlesofihe fraction.
analysis . The unddined fraction, usu<lllv kno w n as the The objective of this article is not to discuss the
C7• frac l ion, conta ins hydrocat:bon com-pou nds heavie r advantages or disadvantages of the different ways to
than hep t<l ne. Dependi ng upon the cases studied , th is handle the C; fraction by splitting or nOt, or to dis­
fi-action may be extended to C 10 • or C~O· or split into a cuss the different correlations to allocate critical prop- "
larger nu m ber o f fractions. "" erties and acentric factors. These are case-dependent
To be able to use the EOS for any physica l properLy decisions, which will depend upon the Iype of reser­
prediction of reservoir fluids. the C 7 " fraction must be voir fluid, degree of accuracy required, time and eeo­

by Maria A. Barrufet, Assistant Professor, Texas A&M University

OCTOBER 1998 Hart's Petroleum Engineer International 47

 • ,l.:!~ :1-1.'1 i =' ~A C I tU,"" C~::.:-.-,c::=.!{rS ~=- i W:: =-_"'t M~ ir:).. ..... .s ':"...,0 LAS7
Fii A:::-TlOH OF CRUD "-·OlL SYS,::/,{S

las: Fr2c:'cf"l
Us: =
1111 ra c: ion 0=.05 :-:y. a: IS.S·C . ,1.~cl~:.:I2.:
C:c:C~ Oil Frac:cn C09lticien: (g/ml) We;;~
~o;:,.,an ~{ eJ. • c." ­ 0.17 0.902 351
:10ia01C'" c.,. - 0.17 0.923 1!92
Slancing ar.d Kat2" C-..: - I.coa
....
0.25 :322
Kac 2nd r.ac,'1r.1u: h" C-- 0.20 0.939 SC3
:Ovans ar.<l Ha~ris' C- ­ 0.25 0.91.! J-!2

IC:1C:::::i h~;:;an:: alus ics arooc:ci::s. Tne :cfo, ~, 2nycorr::la­ 3. Ha(""'~'n. A. ~ .. Cr"",? 1. S., >..od ;:CC~(;. C. :Z.: "~uil:oric;;1
lio<l of me(h2.,:~ WiL": ~e i2.Sl g:vU? 's i:;:e:-aclion coeffi­ . Cons,-,-ot:; (or, Gas·CanccS-J,c: S;'>::=." Jr:: .--" .. AJ:-'C::: (195:3)
198, 1·10.
ci:::1t should wail {a, '<lore C2l.1 WiL'J sys:crAs, iilcluding
9. CVJJ\s. R. 3. ~~e r.J.:-;;J. D. : "="::d j~:: ":7\ Vl:xJ(i::.>tion :l..: ll:OS.
cru:: baiJins-point ar,2Iyses. r-yd.-uc:u:,on Mi ~ ;ur:: Cor.'-lini"3· T'~'o Canc:~::-:>"or.s oi P.o.
L.l./\C,:>:;G r.c",ic ~ 2Jc:ia,-" "{.ce. C"'3. Ciw::. (\956) I, 00. '1,
Recommendation .t5-50.
10. "Sdcc;::::! VJ/u= o( ?':o~i::s oi :-: '.~=y,~-, L,e! ?l.:!,co:!
Vir.~:1 obui.nins cOr.!i=osilion caw for c;ud~-oil r~c,­
Compococ<:' A?I ?':ojco~ -!...! , Tc~ ~ .~~\'I U.. C.~II:!: S:>:;on
voi..--s, bebale-poUl! pr:.5sur:: C~s{or.l2.Iily is obu:ncd 2! (1%9).
the ~:S::r-/Oi.;- t::7lpC2.;t;~ on 2. bOClO~-:1Olc or r::com· II. ZccC<:: ... i:.:~. D. lnd h{:: . L : ··C:::-:--=~:::O;'l l..~~ ?:-~ic::c" ct
bi~d S2.r.l91::. T.le c::r<l~siticn with :;;::~ded 2r12Iys::s Vlpor-CG:;;!1 ~:.;ilibr.l ..... i{~ L';-:; ~~c;;-;( ...... c::~ ~I..:.l::o,~ o(
S"c=.",lICi.EJour.(19'O)lci,:-;o.I.I!2.
(Q C,~ ~ or mor::, us~,; a {n.::: boiling c!s{ii(~tion a10,'g
I:'. SJgc. B. S. ,,,:l uC:J. \'I. 1'1.: .\(or-"Fc?n O~ ,J,PI ,~<sc=ro.'
wit!l QUDck ~ir.(. P'::1g.Rob!r.son-:\G,l.. p,oc:::i~r:, and frojecl 17 - Tr.a.710c.,r..::r.;ic .;J.-o.y-.~;·c; 0/ ri-..( !-:rr.: ?::..-~/j..,
0:"::- ?~FOS~d ~:::~h;1!SU~ (1!1c!l.!cing pr~~c~ies of Ul'! nycroc=r:'orJ ;.-.c Ni.703"" A?:.;:;':;'" «950) .
groL::'s, If ne::::sS2ry) c~n be u-s:::: 1O 2.55::55 :he in(::-ac{ion I). Soim.1.1r.d :<0"-'.1. ?: " ;-" I:.;I::?~,-,=!C:c Vol'"C::c~-:c ::':;"iliC.--i,
ccdiic:e:ll [or r.,::th2:;~ ~i1d (r::: !2.S; fr:!c:io n . The inr=:-ac· or ~(:::~~nc.n~r.::':':l:-'':: 3i:l~1 S~1c..::~ l: T=::".?c:.-:I~':"-::::: 3<.:"""'::::.,
-IIO"l..~c 150"::::. "i. G<.-r.. =:.,!.Dc.:..;; (h, . 1961) 7, No. I. J·3.
lion cc-:iiiclei1! the " ",.,:1 1 g: '1;: th:: in{oD.~tion r=quird I~. Rc..:tr.-.:::.:-i. h .• $1,:. a.;-; ... :1C bc:::·.~. N .: " f'::= ::':;uiGonl
for ?r::::l:c:i..,g ~h as ~ b~!l::t vio •.~( o(h::~ cClr.di(icr.s. in !-iyC:;-JCl~" Srs:c;";".5.VoI~::-:::::-:c .J....=. .:! ?':1l~ 3<:-:l"ie< of :"'1.::
:--'Ic'-~J.,c.o.l-i=;:,-,"= Sy':=",:' (nC. £"!' C;-'c.",. (!956) I, :-;0. I.
Conclusions 29-!:2.
\5. Ko~n. 1. ? J..-:C 3,-::ld:s;'. ';.J. ::.: "~:~:::pi\~~ l:::~ VO!'J;-;'.c::-:!:
: P;-OfJ"::i" c.s~~Ll~cioiL of ::::::~":2L1::: .\ v21:...:::s i;"i bo!...!l cl"'...Id~-oi!
~l1ilio:-:l 01 ~~:: ;\'~c:":;::1.'::·n-C c-:~'";..::: S~'';;::;'':1 J: :::71p::~::'::::':
12r.d'cor:d-:: n.s:(= sys.~:~ is =5s::1(i2..l for:~ :c::~--.:?::: esC· 3<:",<.:., - I 10- lOC ISO·C." J . Cr..<." ,. '::'"1, Dc:; OJ.,. IY'--!) 9,
r71J~::or :JL! o c l~ ?OL"",:, C-;:')..I !=']lfH, J.;:~ ~:JSllti1g 0; L~!~-: :-;". I. 5. .1.
10. Shi?fr..lo. l. ,'.(, ,ed :(ot-.n. ? 1.: "":=:=:-:J!:cc:>,,, ?~.l:= ,,-,e!
\! sys;:o.:s. uSLng our ?ropos::d p[';Jcedcr::, pr:::dic\::d me(;"
2~::'\ v2.1 u::s ag r:::: ""'::11 ",i:..'1 r..::2sur::d '.':!Il:::5. Volu~c~c ~'.!i!ioril!::l i:; ,~c \{::~:;:: ·.1·~Cr.1..~-: S1s::::::'.. ··
i. Ci.cr.; . .::~!. D:::= (A?r'i 1~,,6) 11. )'".2. 176-I:i8.
?'cr g2.S--:onC::,ls2;= sy,t'::-:1S, t!:.: ?::ng·2o'uinsJn-AG.~ Ii. A: " . S. Jr.C :<:>~" . 1. ?: "So~c.Gq0<! ...' '"or ::~'":;io:'~::: i" C~:
proc::d:.!..r:: \,:.lith C~(~;-;G:::d ~,:!!/SlS 2:'C ~~~~r2C,!O~ .:::>cffi­ :"fc:Jll~<·r.·~C:HJ.~'::' lr.C =-:'~J;-:::.I'·'=;~~-.::: 3i::.l..-.' Sy~:"::::t,'·
Ct~~~ (er i11C~Jnc ~:-:d C)- CQr.S~lt:~;F..s C0:'C~']\::~ wi~!-l i . Gcr.,. ::,'1. Dc:= (19,0) 15 . .' -:0. J. j~2·j'".
c::~si(i' S::::;':;5 W g:": r:::I!~~!:: ,::s~iG. ror c:-~dc·oi1f 13. S':s:. 3 . C' .. \':;=:lS:::. D. c.. lce L:::-::... \'I. ,':.: "~'I: ~:.,:.
libr.J i:-: ;'::(~:-::-..::.:.-::'o., S:(~:::-:-t~." {.-:.:;'. 3:.-: j ' C.~: ,":":. (~?~.;)J ·1S.
r..:!:,,,::-!t·gJ.s s:.·S~::IilS, ~1: ii'i(:~:-J::::C:1 cc~~'fici:::t~ for l7".:: ­ Ie...: 5. Ie..: ;.
I? s...::-'cx~. ::. ?. :-:o;,r.-:-:~;::'.. A. ~ ...,~~ ~.< ...1... S .. L~~::·:>r::(.
2 o'' : :JI:: c".)ir.: . Q~ i::::::~~: :-:-2~ T:;2i~ 3. C.:!:"l:::-ing 1. :; .. l~C ~'!l}:-::::~,::. D.: ··S.::j~2:':;=-:.· :::,..\I::."'..l.-:::~ 3.:.-"':::-:::"·
C:!:J. ·.:-·i:h t~-!: ::v~!i:.;-;·)~-:·: 2--:2];·5::5 cr L.''':~::: cils s:~CL:!d lr.c·. ~·--:t. C;.. t:,--:-:. (!-.: .... = I ~O) j ~. 13·).. j';;
~ 'J. ::;. :";'-:-":(. :-i. :-: .. 5.1 s:. 3. :-: .. J;'.~ ~-::::,' ':.:. ,'1.: .. ~~c =:~l.:;:'; ·:;-:l
~-;:.:~ :.' :~ :7:: : 2\: ~~~ :::::::-'!::~I).'" c,)::~-:=!c:::~:s fo;- ::-::: ]2..3:
i:-. :-!:,-C:-::..:.1;:0.-: S~:~;:::: •. 'ia!:.::-:-::':-;:: .1..-:': ;,,:"-,.!.;: 3-:::'J·"::H :;" :.~.:
;\.f:::".l:-:::·C:(:!o;-::;.~::.: S:J~:::71.·' i.-":::. ':.":~. ~_.~~.7: . (:95':;j 3 ..~;::,
2, ::,..:0· ~~;.
~i. ?~H!Or,. ?. 5. J::C .'.1::-:"::::::.1. I . ••• ··\·::",::-·~:c'';:·: ~::i~::-:'':~ :.,,:
R~!-~;~:1C~ :"~':.'.:-:':':J~: .•';;:-Jg::., 5:q::::::. J. C.:~. ~.":~" :.:.;; !:-..:i;; !~j)
(t, ~J. i. J':-=--;~5.
I. S:';"~::-:$. :<. ~.: ....; .'·:·':"·"'\";::?:-::lC:... :.'J:- C-::::~:·"'S·i.:,".s. ::....::~ .~.'~.~.~ ...)J:•.•
S:.::..: .)~~.'7'.::::-:' U~::-.~ ?;:J:': ~."::;::"':J J':l:':. ~ • _ .. .':::-::~:,: ..' - ~ __ .. . 5:...... .
;.~ ~:-:.: 7 ·,,:,·').~~: ?:sio::.··" :::-'~.7;. ~'-:j'. :.,:;.:: :C·:: :9 .j:;~ J,
(C'-:::. ;~51 J .~J.j71. -:-.':;.-:: . .!'.:~.~=.. :3.]/.
~-::;!"::. G.: .. ~:!;::.;'-:'''::-:-' C~:-:S:~.-::1 .: ::-:;:7: J \!~cjr:::::: ?:::!:';c:~·
;-";0 . .!, .::;...:.....:.;j,
~~ '-'.:;:-. ~ ~:;:.: l::):"l ::' 3 :~~: .. c:~:.-:-; . 5:;.
: :'1:. ~ :I~; .
). '':..'=::. =.;-: l::..! =::-..!:. - ..~.,-: .:: ... ~::.:!::::':: ~:' ::3''':'': :.;::...",:O~ ');. ... S:J:-:::: .~~. :.~. =. J':'~ :"':'1:..:. : ..
:--;.1:-:.:21 ::~·C:·,,:~: C:i 5:.·'j
?:: -:.:::: .",:) :"'1: 1 :1::;:-:-: _'\.::•. ::.~;;-~': ?:)~~:~ .:.:' :...:;:-:; :-::.. c;-:;...:~:..:::
:::,~:,::7',." ?-.:..-. . :'=C?!.. 5~::~ ..!.••-::-.:.:..:.: C~:-.·.. -::.-::;'J:-:. S~:~~ ~ !S7J)
;.;.,) !
=::~:7:l ;: . ;:' . ? : .. ?::~;::: . . . ~ __'-.: ~.:.s.:: 3-::':-'.1.·;; ·)r:: ;-:J.;-":;-!:':;!,;::-\ Cc,~~~;-:.; : .~. J =:--..:~ v·1·.':! :-..:;-:; .=.~ S~-::::-:-.. · ' •. .:.-:)' ~.'~:.";'";,
{S.:?;, t~;:):-'~. !.j;:.:'J;;
?:~-::I:-. ::~.··?:: J ..:i~;~:-;l::.::r:, G ..:;;' .\~:.:~:~:., ...l.•.-;,-: .;...:-:::-:: (:,;;-;.:)).
S: J ,-:,:;., ; , ,'.~ . 3 :--:.1. :;. '.: -_:-:J,' :..:.;. ::-.::':
?.::;~. C> . •~. l.-:C ::\.:-::;::\..:::. 0.3.· ··A :',':;.·).·7""'·v·CJ::;·-.l::: :=..::.~. Oi! Sy~::.-;-.~, · .J..:-:.:' .:''::--J:
;:: ., : 5:..1:=,'· -" ,,:.:;!, ; ';j'" . C.~(.7: . .~:::::.., (!.~;~~ ~~ .."~o. ;. :5~ ..:..:.
~;.
i. 3':: S;:-;l.', D. := .• 7:·,. ~.! ..=... J.... ::: :<l::. C)-. ~.: .=:.::.-::;j.-::;:': C,:-.>
~! s.: I ). ....'7T
=.·:·-,,;=:;·o,"'t :'."': ;·.'.;:!..: ... .;!C·.:; .:;)::::','- -' \.·,J~o-·-":I S--:rJ -\-~~::l'"
C~ .';1,;...)C:!:":~."!,. :"': .,:., .:.;~~<' c:·: ·:~~t;;:-'5;.· ~,-.",. _.. _......._...,
c,·; "'.11 r:-.l .~'-' :"::'•.-;:
::IJ;--'
j -::>: .--:-: ;.1
.!-::::{:; : .... : ::' : ... :"·,:'.L.cn ;..1.1
::."'-: "", -::-:. ::."":c::: y. ::;1. ~~ . :;:-7 .
3..x:: -: ':( 0 1 =>-: ;-:;I-:-.f"".
:"i. ;l;-~ ..:::--.-,: :-;-'."'~::·;-l:-::'::r:"' -=-; :I,,''! ;7.
C..:.·,-::: . .:>~. :-:.: ··P:-.·,,:,:,:-!! C:l:J :':-~ :J:~: :~):;':J:": C:::'::":~J:;:'.-'; :-:-~~. ;>~""'IS:-~ :.-::: \ ~.r;1 ;r":Yor.:-:: l::"'.~ S?::·.J,.L.:= 5:-;-.: ..... ,.. .....1: .=1.1 ~-:-: .-nCJ :
- \·!;".::: ·L~·,::..! S;:': ::: J:--:! .:J,~=-: . .-\?: ~':~. >r·~··: __ ~.!:~.:.-.~
:,~j:) S:. jj: . ,j6
 = • • - . • ..
Mole %
0.121
0.605
74.864
3.885
2.416
0.971
0.966
0.503
1.208
'1
1.505 I
12.955 0.84

nomic constraints. analysis.~ Densities for higher molecular weights have

The objectives of this article are to present some been smoothed.
numerical examples that i ndicate the magnitude of Fig. 2 illustrates th~ effect of the C7 ~ in the evaluation
changes in the physical properties obtained by p er­ of phase envelopes for fluid A. rl can be seen that, at a
turbing the molecular weight of the C 7 " and by split ­ reservoir temperature of 250°F. the fluid classifies as 11
ting this fraction. A hypothetical volatile/condensate gas condensate for the lower molecular weight and as a
fluid. A. and a black oil fluid. B. are considered in this volatile oil for higher molecular weights.
analysis. fig. 3 indicates [he effect of splitting the C/' fraction .
Among the properties analyzed are the effect of the All envelopes correspond to Fluid A with composition
C7 ' fTactio n molecular weight in the evaluation o f for­ and molecular weight for the C7 ' fraction as indicat~d in
mation volume factors (8 0 ) and of solution gas oil. [LItios Table I. The difference among the predictions is due to
1) for a black oil. The effect of splitting upon s atura­ the splitting. The c;J.ses included are:
,m pressures and the prediction of wax deposi tion will t! No plus fraction-indicated bv considerin~ that C - is
.'>0 be briefly presented , The Suave-Redlich-Kwong only one component with the -critical prop~rties e,,'11lu ­
(<:'RK) EOS is used for all co m putations. ated from Pedersen et a1. correlations using the pro­
vided density and molecular weightS
_,atile/Condensate Fluid A II One plus fraction-indicated by the molecubr weighl
.A synthetic fluid. which may cla ssiry as 11 volatile oil or and density provided. which are assumed to belong to
a gas condensate . was selected for the first example. 2.) n mixture of componen ts from C7 to Cao '
This hypoth e tical oil cont::Jins about 75% methane and .. Two or more plu~ fractions-indicated by sever;)1 cuts
13% C,- (composition indicated in Table 1). The defined according to the Pede rsen et al. schcme 6
molecular weight of this fr:J.ction was al lowe d to
ch:lflge betwet!n 107 and 25 I. Fig . I shows the pairs Increas ing the number of splits in Fluid A causes th e
used for molecular wci~ltts and densities for the C-' EOS to predi ct lower critical temper'a turcs and higher
fraction as obtained fr;m a typical chromZ1tographic critical press ures. Therefore. by proper selection of the

~< ~'~.·';::~'~·.~ 7'oob ····7,·; -. <~ . ~'/ '~:: :' :~',,: ·-·:/.,:';;,::/.~.~~.:~i;}j ~:~-::..:;:: .~ .':.:" ~":; '; "
", '," .
:. :< ... ;,: .:.~ ..~ ... ." • Criti cal poi nts
.;,:j,:: ? :'; 6000 ~:::=:==+:::::-~ Increasing MW C, ' , ~. ' ,

::. 0.90 ..... '

ME 0 .80
~ . "

en 0.J)6
} .o.e.
~ A." ' "

.. 0. 0.82

" ' ~~~

'. 0.76

0.76 '-'--:-:-C-~---;------:-:--;---c----.,---,J
, .......100 ·· 200 .. JOO
..·· .. ~OO·

" . Mol.CuI.r ,,:~Ightof c,' ..

1. Thi, curve shows the relationship between molecular
Fig . 2. phase envelopes for Fluid B, with composhion indicated in
ht of the hydrocarbon fraction and density at stan dard
Table 1. move toward the right as the molecular weight of the c..;.
fraction changes from 107 to 251.

Hart's Petroleum Enginee r International OCTOBER 1998

 R E S E RV O I R E NGIN EERI N G

'-.345
- 305
- 2i8
- 2J7

:';.< -" . .';., "

).000 .• t,:',

o L - -_ _- , - , - - , - J _ _-=::::=:::::-::===~~~ " ';:.::):, ~.; ~'.:. .:". ·.~1:0. ., . ..

o,,::-g~¥6;~~~el:~r~':~~e~~00 '60:700
.. '"." -, , 'Q ,:c ;; ,,'1,000' " 2J)OO ', ;-'.:>,3D?O :.":.;" "'1000';' :,, - ' 5/loo :,
.100 , ,SOO
!:. ' ·:<'L~,; ,,::'_':),:,~.,~~U~"!PSI~· " , ?,, " 'C): ,',',
Fig. 3. The phase envelope shifts are the result of splitting the c,' Fig_ 5, A5 the molecular weight of the C/ fraction increases, the
fraction in R~id B, with '~;'mposjtion indicated in Table 1, formation volume factor of Black O~ B also increases, Fluid B has
38 mole % of ~-,
Ct' ~plitling,;J fluid can be: modelc:d eith<! r~~ a gas con~
densate, exhibiting a dew point at reservoir {e:mp<!,r;:llure Black Oil
or a~ a \'olatilc: oil, exhibiting a bubbl<! po in l. The: pre­ Fluid pl'Opc l'lks. slich ;:IS R.; anJ B", Gin be s,,'stclll:ltic:1.l­
dicted physical propenies u<!p<!nd upon lh.: numbc:r of Iy and C::lsil," ~\'alllat<!J rrom :In EOS :\s a function or
splits a~ indicated in the: pre,'ious l"igun:, bu t :trta a cer· pressure, tenlperatlll'e and compositions a s i n JiGIl~J in
t:tin numbc:t- which is case-de:pc:ndc:nt-t h~ pre:diLtcd Articl\? 2 of thi s s~I'i~~ , ; The: mok:cubl- "'ciglll o( the C-­
physical properties eithc:r reach a plak~\ll or CC;\SC fl~\cti()n ;.Iso :-.rf\!Cls th~ ,'allle:s 01' thes\! p'-;)r~ni<:s 1'01' '"
changing with the numbc:r of splits. black oil. Fig, 3 sho,,'s the changes in B", rcs ulting: I'rom
Fig. 4 illustrates th<! ,'ariation in Ih., pr~d it:k'd ';:'(lW:.I­ chan!!cs in thL 'TlIlk'cul:ll' \\' ~i!.dll,)r lit~ C-- rr-:lction rUI':I
tion pressure at T = 250'F ror Fluid .-\ w ith cc)lllpositi()n~ typic;1 \Vest Tex:ls bbd; oil (F-Iuid B) "'itl~ ahout 3$'}0 c­
give n in Table I anJ with ,'arying 11l 0kcul al' \\'c: igills 1'01' and SW'" C I ' TII~' Il1llkc\1I~'r wt::ights h~re "'~I'\! citang,:J
(he: C;-Il'action, Thn:.: tiirr":l'<!nt ca ::~ s ;11''': prcs':I1LL'd : b~lwecn 237 tcqlli\':ti.:nt to C,~) ~1I1d 3-15 kqui\':dcnl tu
• 'vV ithout considering a plus fraction,
C,,). It GIn be 011SL'IY l'd titat hi!!itcl' III Ilkc \1];\1' \\'cilIhts
.. With t\\'O pS~lI(locomponcnl gmllps,
ill'~['e;l:;" tilL' bubbk'-p'Ji III pl'essu~'t:s, ,,'hcreas tite." I,;\\'er
a \\,ith fOllr psc:udocomponent gmups,
Ihe 8", ,\II C:liclllati{)lls ,,'~re don~' a( 120"F,
Fig, 6 illustr:Hcs the ~Ilect of changcs ill th.: nlOkell­
It i~ apparc:nt th;,t th-: two :lnci rOllr psclItil1L'Om[ll)­ 1:11' \Veight lIron n" As c.\pcctcd, the ,; (\I~lli\l1l ga,;/oi!
n~nt schenH:s gi"~ nearly identical rcsults, b ut the c()ni­ r<ltil) d~cl'e;,scs :IS th L' 1lllllcCltl"I' "'L'ighl or the b e;I\'\'
put:1!ional 10:'ll is l11l1ch bigg ~r I'DI' the I~,t tel' G\SL', r, 'aClio n i ner':;ls,:".
Ho\\'e\'er, thi s l':lnnot be g~ner:llizl'd b\?'::llI s e , :1l ;mothe.- ' H <1 \\'C "LI', t IIL'St:: ch:\ll~LS arc nllt as i III pOl'lallt ~lS 1'0 I'
kmDer"tul'l~. S:ltlll';l\iOIl pressurcs change s ub;t:tlltialk \'uI:ttik oils, LIh:cl't;,inli~s in thc t: ,,,pt:ril1l~llt:l1 determi­
' \\'ith the nLlmb ~ro l' splittings, <IS ,"cn in Fig, 3, nation of this ,1/ can Ill:' "boLit +IO~~" , alltl a 10 17,,, chan'!e
is tr;\Ilsl:lkd int;;' abuut a se,;, change ill til.! bubble pl)i~lt '

, .
....a.
!!
9.000

8.000

7,000
.• No plus

" 2
~

9
\!) ,g
,~
,!
600

500

'400
Mol"culat weigh I of C,­
--'-
-
-
J~S
305
27a
~
~ e - 23;
'"0..
c
6,000
'~
i9 f) • • 0:­
300

•
@

~.i!
5,000 .~
• 200
!J e CI
,
••
I '"

VI
4,000
(j)
j 100
~
I 3.000
Tg2S0·1'
J O L­ - ­ -----­ ---­ -----­ ---­ __________~
100 120 140 160 180 200 220 240 260 o 1.000 '2000 '3J)OO

I Molecular weight of c,.

Fig, 4, Splitting the C/ fraction has the above effect on the Fig, 6 , These lines show the effect of the moleculu weight of the
saturation pressure a t 2SQoF, Fluid B compositio n is indicated i'n C, + fraction on the solution gas/oil ratio of Black Oil B, Fluid B has
Table 1. J8 mole % of c,',
OCTOBER 1998 Hart's P2,roleum Engineer InternalionC\1 49
 R ES E R VOl r.::. ' c..I"< '-" ...... L- "-- ., , , , _

. /i
I
I

and in R J , and less tha n 2% c hange in Bo' Splitting the

C
7
· ' in Black Oil B di d not i ntroduce any signific:lnt
changes in the prediction of these properties .

·Wax Dep ositi on Problem

I~f . MO::,",,, ~r' 0' c,
. ; , . ~ .. '

~jl~:l~
A major problem confronting the petroleum industry. is
th e u ntimely deposition of heavy orga n ic compounds
prese nt in the oil. The production, transportution and
processing of petroleum , bitumen a nd other he:lvy­
organic-containing hydrocarbons could be affected sig­
';'1\1~~~ :".'. ::~'~ ~:.~.
nificamly by deposition of solids (as ph,lItenes, paraf­ '-; ":: . :.: , ,~.~ 02
fin/wax, diamondoid, org:lno - metallic~, etc,) in the .-; ' .- : ~-:

res ervoir rock, oil well, pumps, storage vessds :lnd :_;"; .:' .:";:"!::;!:~;}:O, Q." _ tMO " 2000; :lil00 ' WOO - .6000
•• 6POO , 7.000 8POO
transportation pipelines with de":lstating economic con ­ ,": Pressuro/p<l.
sequences. Par:lffiniwa.\ deposition around the \\"ellbore
cause~ plugging of the pore space and permeability Fig. 7. These phase diagrams show the effect of the molecular
reduction. This le:lds to higher production costs, low weight of the C/ fraction on the precipitation of waxes at
pl-oduction, :lnd premature abandonment of wells _ constant temperature for Black Oil B. Fluid B has 38 mole % of S +.
As the crud<! oil flows through a cold pipe 01' conduit
(w ith a wall temper:llure below the! cloud point of the c:ln be expressed in terms of the [Ug<lCiIY coemeient of
component i in the liquid ph:-tse a s follo,,'s:
1 crude oil), cryst:lls of W:l."<: fonn and grow on the inner
wall. As the \Vax thickne!ss increases, the pressure drop
a c ross the pipe needs to be incre:-tsed to m:-tint:-tin :l con­ (3)

j
st:lnt flow r:lte. As a resu lt . the power requirement to
transport th e crude! oil will incre::!se. The blockage pl'oh­
lems in these crudes C:l n be controll<!d efficiently by
J/
" I ' [ - Ml f
-::::.x;¢,Pexp RT' ( T ]]­
1- T/

.J insula lion :lnd heating of the pipe to a temperature ,,-here .\is t he solid-phase mole fr.Iction of comronent i,

"bove th<!ir cloud point. Th~ kind and amount of deposi­

tiuns 01' heavy organics from petroleum lIuid s "ar;: anJ J.H; is lhe enthalp.'· of (usion or compunent i at the

depending on the hydrocarbon,; pn~sent in oil and on the

relative amounts of eacll bmik 01" ht:a\'y organics_ nOlm ~d melting ,point 0-
Tlt<! liquid fugacity cOL'flkienl

On~ question of interest in (he oi l industl,," is '\vb..:n" ot" flllr~ i i~ round fr om the EOS at the temp..:r:J.tur~ and

and hho\\' much" he;:Ivy organics wi ll precipitate out p,-esslIre 01' the system. COITclations or d~lla may be us cd

und~r certain conditions. Here . the EOS again helps in fo,' the ~nthalpy of hlsion and the melting tc!mpaatun.~.

pt'edicting the solubilitv of waxe:; in o il and th~ onset 01' Herc, the corn~lations propos<!d b.'· Wong were used_"

s olid de[1o,;ition as a runction oC temperature. prcssllre

:lnd oil comrosition. Wax Deposition As A Functicn Of Molecular

Weight Of Th e C7 + Fraction

Vapor-liquid-Wax Phase Equili b ria

Rt'selvoir Fluid B was used to predict diffel-ent wa.\­

At thel"modyn:llnic equilibrium :Imong a V~\POI' (gasl. liq ­

forming co nditions as ;1 function of tc:mpc:r;:ItLII"C, pres­

uid (oil) and:l solid (w;:n) phase. th..: fugacity urcompo ­

SlllT a nJ molecular \\:ei~h
-
t of the C-I - [raet 10 n. Tit"

nent i in tht' liquid phaSe! equals the! I'l.Ig:lcity or compo ­

nent i in the solid phas<!, and the rl.lg:\city (lr comjlon..:nt

Molecular weight of C,'

i in the gas phase.
- - 345
--305
--270
(I)
-J'. 2
- - 237

As indic:-ttc'd in .- \nick 2 of this series. "'hen " cubic EOS

.
.i:
01

~
><
isu:c:cI fa,' the liquid p hase ;md the g<lS phas.... it is prac­ ~
tical lL) express the hlg:lcities in krms oC fug-acity codFi­ PreSSlJre=
2:000p'ia
cit'n(:;, TIlliS Eq. I ma,- bc" e!xpr~sst!d :IS :
~
(2) 0
60 70 eo 90 lOa t to 120
Temperature/F
[n this expression . .t' j and _\ ace tlIe g<lS and the: liquid Fig. 8_ The molecular weight of the C,' fraction has a significant
pha:; \! mole fr<lction of component i. For all ideal solid effect on the precipitation of waxes at constant pressure for Black
ph;t~t' ll1i.\tl\,·e. the solid phase Ii.lgacity or COl\1ponc'nt i Oil B. Fluid B has 38 mole% of C 7 ••
Ii
I
I!
'l
I S2 OCTOBER 1998

~.- -' ~ - -~
 L:.. , " L:l 1 1'-1 c.. c.. K J N G

..

a. V,Jon .K. .'I'I.. -Ti-~(~ cCi'f\ afT.ICi :c )c,:d So'l.:::co-\...,cu,c-V.:.por i:.~...::J;Qfla: \.

r:ln !!c in the molecular weighls ::tn ::tlyzed was From 237 Pha'Se ~J(mahC" :'rc~ Hea ... y r.ycrccar:::..ol" N\'}\ [U res . " F;u :c Pt-:as~ tQu;'-i=­
10 3~5. ~till not ::tn ex tremely heavy oil. The composition vol . )C ;19861. fO~ . 205-279.
of mo~t par<lffin solid", usu::tll y consists of " mixture of
hydrocarbons ranging from CI~ to e;o with molecular ABOUT THE AUTHOR
wei~hts to 7,007.
Fig. 7 indicat<!s the percent of \\'a.x deposited ::tt a • Dr. Mana A. Barrufet is Associa te pror~s so r in th,
fi .'\ed temperature of 90°F and differen t pressures. This Dept. of P<orroieum Eng:in~ering :1l Texas A&.vl l'ni\'t~rsil\
shape. similar to the shape of viscosity. shows a mini - She ma\' b~ re::lched via ~-m:1il atllliJid@cilt!1'J'o/I. CO IlI. .
mum weight percent of wa.'\ depositioJ~n~a~r.:o~u~n~d':...:t~h:.'e~b~u:.'b~-~-,=========================
ble-point pressure. The higher per­
centages below the bubble point are
because the solubility of waxes
d~cre<lses as gas is lost from the Now You Can Upgrade Your
~o llltion. Fig . 3 shows the "'eight
p~I'c<!nt deposition of \\'ax as a func­
Downhole Pumps At No Extra Cost
tion of temperature for a fixed pres­ Wrth.~~ ' .' '. .
sure. The circle in the Clll've for.\.I

~ALLTM
= 305 indicates a transition fro~~
liquid-solid equilibrium to
\'apor-Iiquid-solid ~4uilibrium. As
cxpect<!d, wax deposition increases
as the molecul<lr \\'ei2ht of t he C."
increases. The deposi~ion tempel~­
ture also increases with the molecll­
1:11' \\'eight of the C 7 '. Fo r e xamp l~.
:Il 100°F. no \Vii;>.: \\'ill precipil..,(e a t
2.000 psia for molecular weights or
237 to 278; whereas. pt'edpitat~s
will form for high.::r mol<! LlI l~II'
weights.
Article 5 in this s~'I'ie~ \\' ill dis­ .,'
cuss another solid-\'ilpol' equilibri­
um probkm prt!s<ollled b \' gas
hyd r~lles . • i· 'Seats· 'Alloy

References
:-. 'in -Wear arid
I. aar~ v:·e(. M .A.. ~ A 911~i !n:r;,Quc::un 10 !.:=:...t.Jtlon~
or S tai(! i e, p(!uOI.?um = .~c::·nf!<;!rrr.c ;l,poziC.J(~ons..­
.· C~;rosion!'·.·:'-."·<
Pl!lfO,e".lm £.,s:ir:ee( If': :e~n.J{lor);i. ~";..Ifc;-' 19?8. " • '· 1 : ..... ... .

90. S 1-82.
2. ~A'Cal:1, \N.D., J ~ .• "C ;,~ m'c,)1 C()r.'co~r:;on
i)~I~~minel a~na'liu( 0: NO;;!SQrvOH =i v '-::: S .­
·= ,c6~~t~c{ '=:--:..:,
?~~,~o i eum Er. :;:neer 1('r~.?'nil:icn.Jt. Oc:OC~(
18-25 . ­
1'993.
; .~ yoU.·i.·'b~,~:L~~: : ·
.1. l\iCL.lin. \'1. 0 .. Jr .. "Re''1I~eo i'jJ,s-O,i
(n;\?r!J ~ey IrclC.llor:> 0: Res~r.-o ; ~
MJ[IO
F:IUC :vo":?~ '-:.distrfb utdr'.·
·.. .·d.. ·· 'r -~" .
P O; '.:;J:r!um
57-<'>0.
£-:~inf!~' Inrefl1a( ;o .... di. ~~(I; i '? 9.l.
:.:." to· ay.....·· ·
;);!:)~.c. E.H .. ~on:1ig!~!1. ~ r. ,""Ird :.1": , i.... . I .• ~ ..~::~.:~ ': . '~:.-.
-D, ... ;r:~utio" 0; ·N~'9nt. D ensity, Jna Mc;ec.JI.)(
Weic~ ; ,n Crt.:c~ Oil Oe;ived from C()rnout~("lled
Cao:l1.3 ry GC .-\Ilaly~'s.. - JOtJrt1~1 C' H,c.,- Res.
CII"rc'7l. & C.~(0m. C017l17l., 110;. ;3' \ 1935;, P .:)'
093-0:;0.
5 ?"!oersen, K. S., !=r'?O .e-nslunc.
Th o'7lJHen. ?. Pro,Oerilcs of 0;'$ Jnc NJi.vr,J1
G.1Sc"S. '101. 5, G\.. ; ~ P~:,I;~-:tf\g Co .. HOUHO .... , TX.
i 1?8S'.
-::. 5~1(~U;e:. ~.rI.,..l .. "E'lJluatton 0: 5 :.1nO.lfd r\iT
P r cC~'-'es ~o.-:-: fqua:,oflS 0: StJt~." P~~~Clel;I '1
::r:~lf ~ ~~r h~,,:( r ~ :: 0I1,,;. tl1.ly 1999..00 . .l?-So .
;, ? ~\::~rs~(t , K. 5.. '"fnom,)ss.~n . P.• "n'd != recers.t,; nd ,
..1.,1 .. --:'e rl1"oc 't'<'lamICS of P~lr o lC'tlm ;\Il;:,,:~(c!.
c'0 r :J :',.' ? ~~.1 \,! i1yC(CC.l(:)or.s: ?3 .-: .f ~~. C:-?., :
;:iJs:-: Col lculJ::vn p(oceou(es US Ir.g [;1~ 5KK
·L tC;l.:J ~.C tl 0; S ; a~.?N Inc t.--:s:.
CnefT'!. P~oce!aS 0~s .
Ch.'·:.. ·;oi. 2.l {I°SSl. pp . .yJ8-9SJ

Circle 122
OCTOi3ER 19 c 9 H;:!r,'s P-"troleum engineer Inter,-,atianal 53
Gas Condensate PVT - W hat's Really Important and Why? 28
C.H. Whitson, 0. Fevang. and T. Yang

C o mpon~nt EOS22 !;OS1 9 EOS12 EOS10 EOS9 fOS6 EOs.< EOSl

'}
N2 C1N2 C1N2 C1N2 C1N2 C1N2

CO2 CO2 CO2 CO2 CO2

Cl

C2
Cl

C2 C2 C2 C2
} C02C2 C02C2

>­ C1N2C02C2·C6 C1N2C02C2-GS

C3 C3 C3 C) CJ CJ

IC4
IC4 }
rC4NC4 rC4NC4 IC4NC4 IC4NC4
"
NC4 NC4
c::l-C6
IC5
rCS}
IC5NC5 IC5NC5 rCSNC5 ICSNCS
NC5 NCS

C6' C6 C6 C6 C6 C6

C7 C7 C7

ca C8 C8
} cr~ }
C9 C9 C9 C7C8C9F1F2 C7C8C9F1F2 C7C8C9F1F2 C7C8C9F1F2

Ci0. Fl

F2
F1

f2
} C9F1F2

C7C8C9F1·F8
F3 FJ

}
""}
F4 F4

FS FS
F:l-Fa F)·F8 FJ-F8 F)· Fa
...,
F6 F6

F7 F7 F&-F8

Fa Fa

F9 F9 F9 F9 F9 F9 F9 F9

Fig. 5 - Example pseudoization procedure reducing an ori gina l EOS

ch aracteri zation with 22 com ponents to mu ltiple pseudoized ch aracte rizati ons.