. . .. * .-.

I-aa CL_
.-

Predicting Phase and ThermodynamicProperties of Natural Gases

Withthe Benedict-Webb-RubinEquation of State
J, F, WOLFE HUMELE
OIL & 4tEFfNlNG CO.
JUNIOR MEMBER AIME HOUS70N, TEX.

ABSTRACT development of their equation as eariy as 1940S The B-

W-R equation is a modification of the Beattie-Bridgeman

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The Benedict-Webb-Rubin equation o/ state was used equation of state and gives better PVT predictions than r’< , : .
.,
in digital computer programs to make rapid determina- the Beattie equation at densities above the critical density. J
tions of natural gas equilibrium phase compositions. Mix- Benedict et ai. made the equation applicable to mixtures / i

ture components were the nine hydrocarbons, methane
through heptane. Comparative tests were made with data
from field separators, plant exchangers and literature
sources. For most tests made, the B-W-R equations pre-
dicted component K-vaiues, mixture enthaipies and phase
densities within the accuracy of available correlations for
nine-component mixtures; significant deviations were noted
when mixtures contained components heavier than hep-
tane.
INTRODUCTION
Rapid, accurate methods for calculating the properties
of hydrocarbon mixtures are needed for predicting the be-
havior of natural gas processes. For example, because of
the common use of two-phase separation methods in gas
processing, calculations must be made for the density and
composition of equilibrium vapor and liquid phases. In
addition, predictions must often be made for the tempera-
ture and pressure changes associated with the flow of sin-
gle- and two-phase natural gas fluids through heat ex-
changers, chokes and turbines. The complex nature of
non-ideal mixtures makes rigorous calculations for these
natural gas properties ditllcult and time-consuming.
Natural gas properties” have conventionally been de-
termined with generalized’ data correlations. These corre-
by relating the mixture constants to composition and the
constants for pure compounds. Thepe authors, in a series
of articles in 1951: showed the accuracy of the B-W-R
equation when applied to light hydrocarbons and their
simple mixtures, and demonstrated the equation’s utility
for making vapor-liquid equilibria calculations.
since its inception, the B-W-R equation has been the
siubject of many papers. Numerous additions and modifi-
cations have been proposed,’+o1“-’*the purpose of most be-
ing to improve the equation’s ability to predict PVT pro-
perties of speeific mixture systems. In 1959, Opfell, Pings
and Sage summarized much of the work on “the B-W-R
equation in their book on equations of state?
Since naturai gases are primarily mixtures of light hy-
drocarbons, the B-W-R equation is a naturrd choice for
an equation of state to compute both phase equilibria and
thermodynamic properties of natural gases. Consequent-
Two.phase region
_ Reel behavior
/
I - ---Superimposed behovior of B-W-R
I
I
I
equotion

lations, such as the K-values presented in the NGAA Equi-

librium Ratio Data Book, are usually based on some aver-
I
I
I
g ,Critica.1

age property of the mixture and have proven to give

satisfactory estimates for the properties of most oil and gas I
“. SATURATED
systems. Digital computers, however, have not only in-
creased the utility of these mrrelations, but also have
made practicai the use of equations of state for calculat- .t P~
ing the properties of naturai gases, n
Potentially, if basic pure component data are availabl% \
.\
all the desired thermodynamic properties of mixtures can p,
be derived from a singie equation of state describing the
mixture. Currently, the best equation of state for describ-
ing the behavior of pure, light hydreearbons over single-
aud two-phase regions, both beiow and above criticai
@essure, is that of Benedict, Webb and Rubin.’ ‘SATURATED :. -:
.The equation contains eight constants which are deter- . . “. LWJIR
!.
‘ >.: ‘“;”
’.. ... ..””,” .’
:mptiMy.~~&Lwuaiim20.WWQmg9~-.. ._._ . —-
~. :;....

.5+-=%+.---L.-—-’L~
. .. . ... ,.

, .2:. --XL.. ________

,. f?..,,:>,,....: ... . . .
wit Pm data. Benedict and his co-workers presented the
B. - ...-

Patier %s rnwsented at SPE ‘Annual FaU Mectlnu held in benver.

v-
d
L—————
~m. 1—PURI+COWONWW 1’HASE ]hAfXLA.$f.

JOURNAL OF PETROLEUM TECHNOLOGY

 .
. -. . .. . .—. -..

Iy, the work reported here was undertaken to evaluate the
B-W-R equation, as a basis for predcting two-phase equi-
librium in natural gas systems, and to develop computer
programs for the B-W-R equation which will rapidly cal-
culate natural gas phase compositions. Details concerning
equations and derivations are in the Append!x,
SOLVING THE B-W-R EQUATION OF STATE!
“ The B-W-R equation expressing pressure as a function
of temperature and molar densfty is:
P = l?Td -i- (B.RT-A. -CJ~ # equation constants are positive, as are those of Benedict,
+ $[(1 -t y@ exp (–y&)] . . . ., .
Pure-component values for the eight constants appearing
shows that there is a range of pressures (P, to P,), at a
given temperature, for which the equation has more than
one density root. This pressure range is normaily un-
known, and the procedure used dor solving the equation
must be capable of detecting, multiple roots and, when
present, selecting the correct density for the mixture in
question.
The behavior of the B-W-R equation in Fig. 1 was for
a pure component. Mixtures behave in a similar manner;
the only differekcc is that for all pressures Were is only
one density root that has physical significance. If all the
there will normally be only one or three positive real
roots to the B-W-R equation (ignoring tangencies or dual
roots at a single point). It is possibie, nevertheless, to cre-
(1) ate a composition, temperature and pressure that will yield
five or more roots, qithough such a mixture may be un-
real. Consistent interpretation of the B-W-R equation when
multipIe roots are present requires that vapor phases use

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in Eq. 1 are listed in the Appendm. The B-W-R equation
can be used for mixtures by making the constants func- the smaiiest density root and liquid phases the iargest. Of
tions of composition. Benedict et al. proposed the foliow- course,” a single root “is always used, regardless of phase.
ing mixing rules This procedure was used in this work. Muitiple roots
were detected simply by scanning the function to a reason-
? 1’
B. =
[ I= 1
xiB,,, u = : x,u,’f’
[1i= 1
able density maximum of 2.0 lb-mole/cu ft.

EQUATIONS FOR COMPUTING

‘=[+A”I:
~=1::’’’’”1: THERMODYNAMIC PROPERTIES
When calculating thermodynamic properties from an

C<=lioc’”r
‘“=
[k’”]’ equation of state, it is convenient to use the mixture ther-
modynamic work function and then derive all other ther-
modynamic relations from the work function equation.

b=[iixh’’’r;’;
7=Ii:lxiy’”l”
‘2’ The work function can be expressed in terms of pressure,
temperature, density, composition and ideal properties in
the foliowing manne~
These mixing equations, which are largely empirical,
have been appiied with success for predicting the proper- A. = ~ x,[RT In (dRT”x,)+ U,”– TS,”]
ties of simple hydrocarbon mixtures, There have been <=1
modiilcations suggested to improve results with particular
mixtures,” and other forms of the ruies (such as the Lo- +,[d[~-:~d]tki. . .. . . . (3, ‘
rentz combination for B.) are probably more consistent
with solution theory. But these changes often improve the
accuracy of the equation of state oniy slightiy over the Eq. 3 is in tbe form presented by Behedict,’ and its
rules proposed by Benedict, and do so at the expense of derivation is included in the Appendix. Substituting an
more compiex equations for thermodynamic properties. equation of state for pressure in Eq. 3 allows the integra-
- The mixing rtde~ in Eq, 2 were used in this initial work tion to be performed. This integrated equation can then be
with natural gases. used to obtain equations for other thermodynamic pro-
perties.
PHASE BEHAVIOR NEAR VAPOR PRESS[JRE Entropy of a mixture is found by differentiating the
work function with respect to temperature:
The B-W-R equation of state requires a trial-and-error
solution for density when temperature, and pressure are
=-+,,=.....”.”..
specified. The trial-and-error method must account for the
behavior of the B-W-R equation near the vapor pressure
S,.
[.ll . . (4)

of a compound. This behavior is illustrated by Fig. 1, Enthalpy of a mixture can then be obtained from the
which shows how pressure and density are related for a following deihrition:
pure compound at constant temperature. At vapor pressure
P,,the ~ompound can exist in two phases, and the pressure- H., =AW-t TS~+ PV,. . , . . . . . (5)
density curve is discontinuous. The B-W-R equation is a Fugacity of a component in a mixture can aiso be ex-
continuous function and is unable to follow the disconti- pressed in terms of the mixture work function and ideal
nuity. Instead, density predicted from the B-W-R equation gas state propertied
oscillates about the vapor pressure (dashed line, Fig, 1).
The oscillation aflows the equation to predict yapor pres- aA,”
sure at both the equilibrium vaeor and liauid densities.
13eeause of the oscillation, at P,-three
. _—___ ——.—denskies—solve the “
B-W-R equaho~ one represents saturated vapor, one rep-
.RTln~=
._ __ ___
—
()
ax, *T,,,
-U, O+ TS,”-RT<
._L___
. . . (6)
,,._,u _______
The Appendix gives Eqs. 3 through 6 in terms of t=
..—.—
resents saturated liquid ‘and the other has no physical sig- B-W-R equation after the equation .of stite is substituted
niffcance. for pressure in Eq. 3. The ideal gas state properties for
Multi-valued solutions to the equation of state de not these. equations were obtained from API Research Proj-
, limited to the pure component’s vapor pressurej Fig, 1” ect 44:4
 .
-.

CALCULATION METHODS viere available to make a meaningful test. Enthalpy cal-

Two computer programs were written, for the B-W-R”
equation: one designed tosolve thephase behavior of mul-
ticomponent mixtures, the other to compute the (thermod-
ynamic and volumetric properties of a mixture of known
phase. Of primary interest was the adaptability of the
original B-W-R equation to field natural gas mixtures.
Original constants of Benedict’ for the methane-heptane
hydrocarbons were used; calculations were restricted to’
these nine components.
Thephase-behavior program tested the mixture in ques-
tion for single- or two-phase behavior in the following mann-
er.
1. Input data were, mixture composition, temperature
‘and pressure.
2. The mixture was flashed with arbitrary K-values to
prctduce a vapor and liquid phase (K-values were arbitrary
k,. ,il.e sense that’they needed only to force the input mix-
culations from the B-W-R equation were, however, corn- ,
pared with natural gas enthalpies computed from specific
heat data and with experimental temperature drops re-
sulting from the Joule-Thonlson expansion of a natural
gas.
PHASE BEHAVIOR OF NATURAL GASES
Calculated and experimentally-measured phase compo-
sitions, amounts and volume ratios are given in Tables 1
through 4 for four natural gases. Experimental results
were obtained by distillation and chromatographic analy-
ses of samples taken from field separators.
Phase compositions calculated with the B-W-R equa-
tion (and the associated equation. for component fugacit y)
were, with few exceptions, in agreement with experimental
results within tolerances normally associated with high
pressure, natural gas separator calculations. Computed

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LLL1~ into an initial two-phase condition which did not
produce unretdvapors oi liquids).
3. Density of each phase wtis computed from the B-
W-R ‘equation (Eq, 1) with a trial-and-error procedure
toa precision of 0.0001 lb-mole/cu ft.
4. The fugacity of each component in each phase was
calculated from Eq. 6,
5. Each component’s current K-value was multipled by
that component’s fugacity in the liquid phase and divided
bythecomponent’s fugacity in the vapor.
liquid/ vapor volume ratios, however, showed deviation
from the field data. The differences quite likely resrdt
from including all heavier-than-heptane components or
the natural gas in the heptane fraction. Pure-component
heptane B-W-R constants were used, and since heptane-
plus fractions were a major constituent of the liquid phase,
such differences were not unexpected. The most pro-
nounced disagreement is in Table 2 which represents the
TASLE I —EXPERIMENTAL AND COMPUTED NATURAL GAS PHASE BEHAVIOR

6. The new K-values were tested to see if the mixture Mole Per Cents Of r=86F P= 1,060 psia
was still within the two-phase region. If so, the input Wt4111d Separator vapor Separator Liquid
Euwrlnwnl B= Experiment S:W:R.
mixture was flashed with the new or corrected K-values. —.— —.

Steps 3 through 6 were repeated for 30 cycles, N? 0.42 0<44 0,44* 0.0 0.0”
C02 0,22 0.22 U.22* 0.33 0.33”
This procedure established two-phase equilibrium com- c1 89.05 91.24 91.200 26.91 28.325
positions by forcing each component’s vapor-liquid phase c: 4.55 4.54 4.525 4.68 5.137
fugacities to be equal within & 1 percent deviation. Out- CB 1.99 1 .ss 1.s6s 5.20 5.437
0,54 0.47 0.469 2.46 2.542
put results included phase compositions, component K- [C*
KL 0.67 0.49 0.s50 5.90 4.063
vahres, phase densities and amounts of each phase. The {(k 0.22 0.16 0.150 1,88 2.200
repetitive adjustment of y,/x, with computed fugacities I& 0.20 0.12 0.119 2.39 2.4S5
caused rapid convergence to equilibrium, The program cd+) 0.49 [0.44) [0.4591 8.11 9.437

always ran 30 iterations, but 3 to 10 cycles were usually C,”l. 1.65 -— ..—. -- ——42.14
—.. 40.044
100.00 100.00 100.000 100,00 m.olo
sufficient.
Calculations for mixture enthalpy and entropy required
Experimental .—B-W-R M W Ci 130
Vap.ar Mel Prqcticm = .97 .9667.s
that mixture composition, temperature, pressure and phase .03 .03428
liquid MoI Fraction =
be specified. Density was computed by trial-and-error from
Separator L/V (bbl/MMscf] .= 32,04 39,41
Eq, 1. Mixture enthalpy and entropy were then calculated
directly from Eqs. 5 and 4. *Sef toexwdmenfal volw<

COMPARISON OF R)%SULTS
TASLE 2—EXPERIMENTAL AND COMPUTED NATURAL GAS PHASE SEHAVIOR
WITH EXPERIMENTAL AND CALCULATED DATA
Mole Per CentS at T=8SF P= 1,070 psla
Experimental phase compositions ‘for 12 natural gases Wellhead Senarator vapor Separafer Liquid
were compared with B-W-R calculations, Samples of these GUS Expwlment
—. B.w-R
— Experiment
— .B-W-R
natural gases were obtained from field separators, The gases N, 0.16 0.18 O.IB* 0,0 0.0”
contained non-hydrocarbons as well as components heav- co: 1.42 1.4s 1 ,4S* 0.s6” 0.S6*
ier than heptane. Calculated and experimental agreement c, 83,45 S9.40 S9.105 25.41 2s.119
c; 5.49 5.26 S243 6.81 6.909
was relatively consistent for all 12 gases, and only four c, 2.66 2.26 2.244 6.54 6.53S
representative gases are presented here. These four illus- iG 0.69 0.52 0.493 2,33 2.630
trate the accuracy of B-W-R calculations for composition, ILC1 0.ss 0.48 0.557 4,81 4,037
IG 0.16 0.TS7 2,21 2.237
temperature, pressure and separator vapor/liquid ratio. 0.35
LIC5 0.2s 0.09 0.101 2.14 2.034
Phase and volumetric calculations were also made for cd+ ) 0.61 (0.!71 [0.420) S,63 5s34 ‘
simple, light hydrocarbon mixtures and the results com- c,’+ —..4.10 —. 43,26 41,11s

L-—---pared-with--experhnental-dat~epmkxi in the ii&fz..Mr.et 100.00 100.00 Io+loao. m 100.000

These data helped test the B-W-R equation at tempera- ---–-”----------------””------~”-----’--+ Experlrnental ~W-R MW C?= 1S2
tures and nressurea for which natural gas data were not Vapor Mol ,%ctlon = ,91 .
available, Accuracy of the B-WR equation for calculating Liquid MoI Fracflon = .09 .09279

the enthalpies and entropies of complex mixtures could $epwafor L/v [bbl/MMmf) = 98.05 - 83.5

not be directly verified; not enough experimental data *.Sot 10 eKperlmental value,
,,

S66 JO URh’AJ. OF PETROLEUM TECUNOLOCY

. “

.—

I
rABLE 3-EXPERIMENTAL AND COMPUTEti NATURAL GAS PHASE BEHAVIOR TABLE A-EXPERIMENTAL AND COMPUTED NATURAL GAS PHASE BEHAVIOR

Mole Per Cents at T=116F P= 995 Psla Mole Per CeMs at 7=156P P=2,521 psln
We:llwf Separator
Welllld Separator VOpOr Separator Llquld
Expurlment w% Ex&rlment B.’W.R
Experiment B.W-R Experiment B-W-R — .
—. — — —

Nz 0.69 [ .26 r.2d* 0.0 O.0* N? 0,24 0.25 0,25’ 0,0 O.0*

0.0 0.0 Coa 0.69 0,69 0.69* 0.46 0.46*

co, O.O 0.0 0.0
c1 90,25 91,27 91.260 40.54 40,721
c, 57.85 83.79 03,953 26.26 25.283
c: 4.11 4.10 4.11s 4.49 3.937
c, 4.89 4.94 4.924 4.83 4.848 . C* 1.5r t .49 1.492 2,SI 2.368
CY 7.41 4.49 4.704 10,96 10.783 ICI 0.34 0,33 0.332 0,84 0,741

iG 5,22 2.22 2.207 8.86 8,977 nc4 0.54 0,50 0.552 2.35 1.441
{C6 0.17 o.r6 o.hfo 0,71 0.673
nc4 4.33 r .59 1,502 7,67 7.856
ncz 0,12 0.12 0.1r9 0.70 0.661
Ic, 2.46 0,65 0.502 4.66 4,902 CO(+) 0.34 (1.091 [1.037} 2,9s 2.838
mcr, 1.36 0.36 0.218 2.38 2,783 c?+ 1.68 —.— —
8.67 8.865 100.00 100.00 I00.000
cd+ ) 4.12 [0.70] {0.730)
I
c,+ 11.67 25,51 25.703 Exparlmental S.W.R MW C?= 151
_—— _..— —— —---
100.00 I 00.00 100.000 100.00 Ioo.oeo Vomr Me{ I%acflon = .98 .97992

ExuertmenlaI
.—
B-W-R MW C;= 124
L1.auld Ma[ Fracllon =
Smnrator l/V [bbl/MMscf) =
,02
20.23
,02008
19,3
I
Vatmr MoI Fradf.an = .55 .55493
.44507 ●SOt 10 experlrnenlal value.

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Llquld Mo! Fraction = ,45

Sepamtor L/V (bbllMhkf) = 603. 658.

●Set to experimental value,

——— ..—. ——
natural gas having the heaviest heptane-plus molecular Literature data for simple hydrocarbon mixtures were
weight (152); the computed liquid/vapor volume ratio is used to check the B-W-R equation at temperatures and
15 per cent low and the predicted concentration of heavy pressures where natural gas data were not available. The
components in the vapor phase is more than twice the B-W-R eqwdtion has often been used with simple mixtures,<’
experimental value, although its use has frequently been restricted to calcu-
The inclusion of all heavy components with heptane did’ lating pressure from experimental density. Calculated and
not introduce serious error in the phase compositions of experimental dew point and bubble point curves for three
the lighter hydrocarbons for the gases in Tables 1 through mixtures are presented; the mixtures were chosen to illus-
3. Nevertheless, there are two conditions for which heavy trate results from the B-W-R equation over a range of
heptane-plus molecular weights can lead to large errors temperatures, pressures and compositions. The three sys-
when using the B-W-R equation of state for natural gas tems are: (1) methane-ethane binary” at – lOOF and pres-
calculations: mixtures having an abnormally high con- sures of 50 to 650’ psia; (2) ethane-n-butane binary” at
centration of hep~dne-phts components; and mixtures near 4G0 psia and temperatures of 50 to 250F; and (3) methane-
their bubble or dew points. propane-n-perrtane ternary” at 220F and 1.000 psia.
Table4 illustrates the effect of heavy heptane-plus mo-
4.0
lecular weight with a mixture. near its dew point. Initial I
calculations on this mixture with the methane-heptane B- & Experimmtall
W-R constants resulted in a prediction of a single vapor
phase. The resf.dts in Table 4 were computed with a
different set of B-W-R constants for heptane (plus). These
constants are more representative of the heavy mixture
fraction and were obtained from extrapolation of the
lighter B-W-R constants (constants are listed in the Ap-
pendix), Although this extrapolation was not sufficiently
accurate to predict K-values for individual heavy com-
ponents, the method can reduce the errors caused by
putting all heavy components with heptane,
The four natural gases contained nitrogen and carbon
dioxide in concentrations not exceeding 2 mole per cent.
B-W-R calculations were made with nitrogen and carbon
dioxide included with methane and ethane, respectively.
Presence of the nonhydrctcarbons in these small amounts .
did not seem to significantly affect results.
Experimental K-values, particularly- those for butane , -.
and pentane, tend to scatter because of difficulties asso-
ciated with analy~ing complex mixtures. These data are
conventionally smoothed by plotting the Iogarithm of the
K-value (or K-value-pressure product) vs a correlating
function.’6 Figs. 2 through 5 show experimental K-values,
smoothing lines and K-values calculated from the B-W-R
.--
_S~uation for_the natural gases in TabLes_l_t.hr@u@_4~.& —_.–_-o,s--_o– .4 5_._ -.Lll_- ._ L&_–_~&?._-.&i-._+
perimental and computed K-values showed general agree-
1
ment, but several kirge deviations did occur. A smoothing
line drawn through the computed K-values would not,
.’ b“ —-+-
Tb [1
however, show more than minor departure from the ex-
t% !&CokfPARrsoN OF ~XPERIMENTAf. AND (hrru’rm IVATURAL
perimental smoothing line. GAS K-VAI.IJI.X: 1,060 PSJ& 86F.
 “-

.— . --

Results for the three mixtures are presented in Figs. 6

through 8.’ In addition, calculated and experimental den- 2,0 - Tc,—
sities from the ethane-rr-butane binary are given in Table
5. The phase envelopes for all three mixtures were calcu-
A Experimental
lated within the accuracy of the graphs for the two bin-
ary systems; th8 calculated bubble point boundary of the O Computed

ternary was not as well defined, Data points were tested 1,0-“
inside and outside the two-phase regioru the B-W-R equa- I
-.—
tion program correctly predicted singie phases, Calculated .8
vapor and liquid densities for the ethane-n-butane bhrary
,6 -- _._—

x
Straight line represents

Y
3,0
,4 —— smoothed eiperimentol data -

2.0 O iC~

~ Experimental
!“I
O Computed
1.0 A —— .

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L
,8 .2 ~ “~’ ‘nC4 I -+
C2 I
.6 I

x
.4 —--— --—

!
~

I .1
o .5 1,0 1.5
-l_L 2.0 2.5 3.0
,2. i Straight line represents

“[i - +1
smoothed experimental data

.1
FIC, 5-COMPARISON OF EXWUM!XWAL AND Comtrrm NATURAL
.0 8 GAS K-VALUF-S: 2,521 PSXA,15617.
.06

—
Smoothedexpstimental two.phase
envelope
A Compositions and pressures used
?.5
-. 50 for computer input data
700 —
A Computer predicted correct
) single phase
“5 i -ii 20 o-a- + Cwnputer two-phase
predictims
Iw. 3—COMPARISON OF EXPEIWWINTAL AND COMPUTED NATURAL 600 —
GAS K.VALUES: 1,070 PSIA, 85F.
T = -lOO°F
4,0
5C0 —

2.0
o
A Esperitrwntal C2 ‘~
SATURATED
O‘ Computed p 400 — LIQUID
1.0 3
/
,8 tl
&.
A {
.6
C3 300 –-

.4
------- .
i C~
‘Straight Ilno represents
nc smoothed experiments I data
20o— A .,,:....-,“,---”-4-
~,,-...,.
, ,“
--
,. . .
. .2
nC IC5
y 7

.1 10o—
.08 L
.06- ------’
( I i I
1 I
:—.- . .. —- 0.—=5——,:0 ‘~;5-–—2;o—~:5- –— -–- —oJ-—–—;--.-+-–-” id-’--.+ ------ ————
-0 5 m
0

:[+-+1 Mtzls Per Cent Cl

FIG 4-COMPARISON OF EXPERIMENTAL AND COMPUTED NATUSSAL

FIG. 6-COMPARISON OF EXPERIMENTAL’a AND COMPUTEDPHASE
G s K-VALUES: 995 PSIA, 116F. BEHAVIOR OF THR BINARY SYSTEM MfiTHANfiETIiANE AT - 100F. I

l“...
----
s=
.. . .
f
.- . ..- . ...— .. ... . . . . —
- -
-.....— ... .
-
. .. . . ... ...-
-
””. . . .
JOu~NAL
-- ... . .
oF FET80LEUM
-- “
. ... .
TECHNOLOGY
-
. .. .
---
. . . .,.. ... .. .-—. 4
-.4\..,.
,-.,. ......,...=.. >............~-,. ... ...
=.,,~,,.,
.....—.. ..-.
..—.,.
_..
.,.
—,..
..
 .- .-. .

(Table 5) ditfered t’rom expcrimenttil data hy less than 1
per cent.
These mixtures, while not natural gases, are representa-
tive of compositions found in gas processing as absorber
residue gases, de-metbardm and de-ethanizer overheads,
etc. Results indicate the potential of the B-W-R equation
of state for predicting the performance of various unii
operations common to gas processing.
NATURAL GAS EXCHANGER
Enthalpy changes calculated with the B-W-R equation
changer that uses a cold oil streqm to chill liquid prop~nc
from 104 to 48F at ‘about 235 psia. The propane was nol
pure; small nmounts of ethane and butane were presenl.
This liquid was near its bubble point at 104F and 240
psia; the B-W-R equations correctly predicted a single
liquid phase at these umditions. Experimental density of
the propane liquid was 0,7185 lb-mole/cu ft at 48F and
230 psiw the B-W-R equation calculated a density, at
these. conditions, of 0.7171 lb-moIe/cu ft. Reported heat
HEAT LOADS
TABLE =OMPARISON OF EXPERIMENTALZ7 AND COMPUTED LIQUID
VAPOR DENSIYI ES FOR ETtfANE-n-BUTANE MIXTURES
AND

programs were compared with reported heat loads on op-

erational gas plant heat exchangers; The reported heat Mole ExPM#;td C;~p~;d
Parcent P~re&e Temyr;ture
loads are not a result of enthalpy data but are calculated (*) —— Phase
—— [lb/cu ft] (lb/cu St)

values based on plant test data, Two examples are pre- 17,49 400 246,2 4.53 4.49
sented. 45.10 400 205.4 2,69 3.67
6S.77 400 166.0 Wlpor 3.22 3.25
1. Table 6 gives the operating conditions for an ex- S2.lS 400 124,S Vapor 3,04 3.04
changer operating close to 870 psia. Inlet gas (composi-

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94.72 400 73.0 Vapor 3.12 3.13
tions and How rates are iri-”Table 6) is cooled from 71 to I 7.49 400 209.1 liquid 27.37 27.30

14F with a residue gas. The residue gas is warmed from 45.10 400 129,0 Uquld 2s,s1 2S.73
65.77 400 55.4 Llquld 28.26 2s.11
–8,5 to 66P. Reported heat load was 3,625,000 Btu/hr; S2.1 S 400 63.S Llquld 26.S0 26.75
calculations predicted an enthalphy change of 3,626,000 94.72 400 47.s llquld 25.23 25.13
Btu/hr on the inlet side and 3,600,350 13tu/hr on the
residue side,
2. Table 7 gives the operating conditions for an ex- TASLE 6-S-W-R CALCULATION FOR HEAT LOAO IN A GAS/GAS EXCHANGER
280
A CO~~j~~:::,~~:#;~$:;g 66F ~
-S.5F

I 240— A ~.m,u,e,,,c~,c,.~..,,,,, 1
+————— 10 I,3Z4 Mo1/D <
sin~leph.,e 865 PSi9 S70 psig

71 F : 4F
Absorber GaE
—----> —>

~~

k
160 — SATURATED
LIQUID ‘80”’9b!M.E-l 875’’’”
Gas Compositions, Mole Per Cent
120 — P =400 psia
Absorber GOS Residue Gas

80 — — Smoothed expe, ime”!. t Carbon Dioxide 0.200

h.ro-pho.e O.VG k+.
Met hone 92.348 96.136
r
& Ethane 4.069 3.491
40 ‘— 6-&o Cm,putm w..ph.se p,ed,,, ims Propane 1.67? 0.320

, . I. Butane 0.570 0,019

0 I 1 I I n-Sukme
f. POntane
0.440
0.140
0,015

o To 20 30 40 50 60 70 80 90 100
n-Pentane ,.
0.W5
0.0s0 0.005
Mole Per Cent Ethane Hexane 0.200 0.005
Heutane i- 0.154 0.004
.—
“FIG.7—COMPARISON OF EXPERIMENTAL’7 ANO COMPUTED PHASE 100.OQO 100.000
B~HAVIOR OF THE BINAaY SYSTEM 13THANE+Z-BUTANEAT 400 PSIA.
S.W.R~ head load On absorber sos -= 3,626,000 Stu/br
Q !0
S.W.R, head load on residue gas = 3,600,351 Stu/hr
~ ‘X.X*”’”’ ‘W”.pbw
AC.;gW;~;usa~~; >.-... ,S RopOrt5d head Iood = 3,625,2oO Btu/hr
A ‘t ‘. C:L’I

TABLE 7A-W.R HEAD 10AD CALCULATION FOR PROPANE CH I LIER

Cold
Warm
<——————
<— Rich 011

liquid near bubbl? , ~

Refrleemnt 4SF
point, 104P,
13,764 Mel/D
240 PdO
-n- Zm p$kl

Refrigerant Composition, Male Per Cmt

,, Ethane 2.281 “
PrOpanO 97,102
l-Sutane 0.421
n-wkme 0.196

..— . . ..—. — .—. -—-. .—— .—— — ..—. —.—.100.000 —.— —-

B. W-R Phase Program Predicted Lkiu:cl .Ph!$e fOr Wserofit ~l~tura

Mole Fraction n. Pantanm
Sxporinwntal mkw density at 48F, 230 psla = 0.7185 lb.mole/cu ft
B.W-R calculated density for same conditlom = 0.7171 Ib.mole/ca ft
FIG, 8-COMPARISON OF EXPZWIIMZNTAL=AND CONPUTED PHASE
MiAvIoR OF mm TSRNARY SYsmiiu METHAN~-PROPANi+n-PENTAN~ S.W.R rdrleeranthedf load = 954,189Stu/hr
AT 220F, 1,000 PSIA. Reported bad lead = 905,554 Btu/hr

MARCK,.Z966 .969 _
-1
 ‘-.--—-
.. 4
. .-, -’.

-. .

load of the exchanger was 90S,554 Btu/hr; enthalpy cal-

culati&rs from the E-W-R equation predicted a load of Bo-- I
Choke Inlet Conditions: ““
954,189 Btu/hr.
3995 psi., 8PF
These and other similar results indicate that enthalpy 60
Q
changes for natural gases in the vapor phase can be cal-
culated with the B-W-R equation of state with a reason-
40 .
able degree of reliability, B-W-R enthalpy calculations g.
for two-phase mixtures, or for liquid mixtures, are less \
\
reliable, and errors increase with the subcooling of liquids f 20
below their bubble points. Choke Inlet Conditions:
\
;
\
JOULE-THOMSON EXPANSIONS #o
u
,-6 \
The’ Joule-Thomson (or choke) expansion of a natural F \
K -20 .. \
gas is a common method used for cooling gas and separat- \ ,.
J
ing condensate liquid. Since choke expansions arc con-
I* I .- ‘~ \
stant enthalpy processes, predicting the outlet temperature ~-
requires mixture enthalpy calculations to be made at the { \
1
inlet and outlet temperatures and pressures. If two phases \
form as a result of the expansion, the amounts, composi- -60

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\
tions and enthalpies of each phase must be predicted. — Data by Buckley
\
Experimental data by Buckley’” for the Joule-Thomson -w
. --- Pure Methone \

expansion of a natural gas were used to check outlet Q Computed results for
, ‘\
expansion temperatures predicted with the B-W-R equa- 1 I I
Buckley’s Gas

tion and associated equations for enthalpy and fugacity. - 100I 1

4000 3200 2400 1600 eoo
Buckley used a natural gas of the following composition:
Final Expansion Pressure, psig
Mole
(per cent) [k 9—CkmrIIA1ilst}s OF IZXP13S[XII:NTAI.”” ASP (:{lXIIWITED k’t NAf,
7’KMIII:HA’IWRI:S FOII ‘rul: JOUI.S-TIIUIISUX khII~ XSIUY 01: A
,Methane 94,11 - N.4’ruwtt. CAS.
Ethane 2,67
Propane 0.89 natural gas mixtures. All calculations were made with dig-
i-But ane 0.21
ital computer programs using Benedict’s original equation
tz-,Butane 0.34 constants for the nine saturated hydrocarbons, methane
i-Pentane 0.20 , through heptane, Use of an equation of state permitted
n-Pentane 0.10
calculation of thermodynamically consistent, two-phase
— Hexane 0.29 equilibrium compositions. No assumptions or correlations
,“ Heptane+ 1.19.—— were involved other than those associated with “the equa-
100.00 tion of state itself. Comparisons of computed results with
This gas was expanded from 3,995 psia to pressures as available data shoiv that:
low as 1,000 psia, Inlet temperatures varied from 82 to 1. The B-W-R equation can be used to predict two-
OF. Most of the expansions resulted in the formation of a phase equilibrium compositions of many natural gas mix-
liquid phase; relatively large amounts of liquid were formed tures within the accuracies normally associated with con-
with outlet temperatures below –40F. Buckley presented ventional K-value correlation methods.
his results with smoothed curves that showed the outlet 2, Errors increase when the mixtures contain significant
temperature as a function of final expansion pressure. concentrations of components heavier than heptane. Accu-
Two of these curves, one for 82F inlet gas, the other for rate use of the B-W-R equation with rich rustural gases
OF iniet gas, are shown in Fig. 9. In addition, dashed or gas-oil mixtures will require equation constants for
curves showing the outlet temperatures that would be ob- these heavier components. Furthermore, the heavy com-
tained by expanding pure methane under the same condi- ponent coetllcients must. be compatible with the methane-
tions are plotted in Fig. 9. The methane curves illustrate heptane coefficients when applying B-W-R mixing equa-
the errors in final temperature that would result if natural tions.
&as calculations were made by assuming the gas to be pure 3, Solution of the B-W-R equation and associated com-
meth?ne. ponent fugacity equation with digital computers makes
Calculations based on the B-W-R equation were made at possible the rapid, therefore practical, prediction of two-
six outlet pressures for inlet temperatures of 82 and OF. ~- phase equilibrium compositions h’1,natural gases. Required
Computed outlet temperatures from the constant enthalpy ‘input data are feed composition, temperature and pres-
expansion are plotted on Fig. 9. Experimental and com- sure.
puted final temperatures were in good agreement; differ-
ences did not exceed 2F. Since these calculations involved NOM ENCLATURE
complex mixture$ in two phases, and required B-W-R
computation for phase density, enthalpy and component H = enthalpy, Btu/lb-mole ~
fugacity at many different tem~eratures and messures. the S = entropy, Btu/lb-mole-OR
u = internal energy, Btu/ lb-mole
L -SU=LIU1l U1 *LUIG
gun c.afi~lllvw tll~ WV. -.
.,—-..
.. —------- .. —-,,&=_w~c~n@rl~- Btu/lb-mole
—- —...: _._ ._. .
P = pressure, psia
CONCLUSIONS T = temperature, “R
.
d = density, lb-mole/cu ft
The B-W-R equation of state was used as a basis” for f, = fugacity of a component in a mixture, psia
calculating the phase and thermodynamic properties of f = functional notation
 >,.
● ✎✍

.- ..

V A volume, cu ft/ lb-mole 16.J3100mer, 0. T., Garui D. C, and Parent, J. D.: “Physioal
x = mole fraction Cbemieal Properties oi Methane.EtbrureMixtures”, Research
Brdletin 22, Institute of GrIs Technology (1953)
K = K-value = y,/x, = xl,/x{i 17.Kay, W. B,: ‘%fquid.Vnpor Equilibrium I{clatisms in Manry
In= natural logarithm Systnms”, ImL .@r, (Wm. (Mu IWII. 1940) 32, N(). 3, 363.
~~= number of mixture ccsp~ponents 18.Drtumon. R, H., Sage, B. 11. and J,wey, \V. N.: “l%ase Bc.
R =, gas constant, Btu/lb-mole-OR, or havior in the Metlta!Ie-1’roIJune-n.l’en@ne Syetem”, Trans,,
psia-eu ft/lb-mole-OR AIME (1943) 1S1. 206,
13,,,A,, C., b, a, c,a, y = constants for B-W-R equation 19,Buckley, S. E, and Lfgbtfoot, J. H,: “Effects of Pressure and
b’ = ‘(log P. -log 14,7)/(1 /T,- I/ T.) Tempera~ure on Cmrdenaatjon of DMillate fmm Natural Gas”.
Trans., AIME (1941) 142, 232.
8 = differential operator (to distinguish from den-
sity d)
APPENDIX
i? = partial differential operator
RELATING THE WORK FUNCTION OF A MIXTURE
SUPERSCRIPTS TO COMPOSITION, PVT BEHAVIOR AND
o = ideal gas state at unit pressure and system PURE COMPONENT IDEAL GAS PROPERTIES
temperature
* = ideal gas state at system density and tempera-
The work function of a mixture can be written in the
ture following manner

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SUBSCRIPTS
v = vapor phase A MT= Am~O+ (A.* -AmO), -1-(Am–AG*), . (A-1)
1 = liquid phase The 5rst term in Eq. A-1 is, by definition” (the superbar
i= “ith’” component of a mixture refers to partial thermodynamic properties):
m = mixture property
T = constant temperature
A.” = ~ @,0-2’~,”) . , . , . . . (A-2)
b = component normal boiling point i,=l
c = critical property
Since this is an ideal gas state, Eq. A-2 can be written:
REFERENCES
Am” = ~ x,( UJO-TSIO+RT lnx,). . . . (A-3)
1.Beneflct, M,, Wfebb,G. B. and Rubin, L. C.: “An Empirical i= 1
Equation for ThmvnodynamicProperties of Light Hydrocarbons
und Their MIxtnrea”, Chem. Eng. Prog. (Aug,, 1951) 47, No, The second term in Eq. A-1 is expressed as an isother-
8,419. mal integral:
Z,Benedict, M., Webb,, G. R and RubIn, L. C.: “An Empirical
Ilqaatimr for ThermodynamicPropertiedof Light Hydroeorbons
and Their Mixtures”, Jour. Clrerrz.H&. (April, 1940) 8, 334.
3, Benedict, M., Webb, C, B. and Rrrbin, L. C.: J’Reduction of
Equation to Charts for Prediction of Liquid.Va or Equilibria”,
Chern Eng. Prog, (Nov., 1951) 47, No. 11, 57!
4. Bloomer,0. T. and Rue, K, N.: “Thermodynamic Properties of
Nitrogen” Reserrrcls BuLfetin, Institute of (%s Technology
(1952) 1$.
5, Cullen, E. J. rural Kobe: K. A.: “Benedict Equation of State:
Application to Vapor-Liquid Eqrdlibria”, AI!7hE Jour. (Dee.,
1955) 1, No, 4,452.
6. Katz, D.: “Vapor.Liquid Equilibrinrn for Hydrogmr.Light Hy. The integration foiiows a path of ideal-gas densities and
droearbon Systems at Jaw Temperatures”, Ah%li Joar. the ideal gas law can be substituted for pressure:
(March, 1957) S, 1.
7. Opfell, ~, B. and Sage, B, H.\ “Benedict Equation of State: @
Ap Iicatlon to n.Hexane, a.Heptane, n.Nomme nmi jl.lkmm”, R T8d
Id EM. Chem. (1956) L No. 1,62.
8. Phr s, C, J, and Sage, ~. H.: ““Benedict Equation of State:
#aae-rr-Pentane System”’. htd, Eng. CherrL@956 ) U No.
(Am” -- A,.”),, =

J
,pt
~

= RT(lnr/*-ind”)
9. dpfell, J. B., Pings, C. J. and Sage, B. H.: Equations a/ Stute
jar Ifydrocarfrons,API, New York, N. Y, (1959), = RTlnd RT .
10.Opfell, J. B., Sage, B. H. and Pitzer, K S.: “Application of
Benedict Equation to Theorem of Corresponding States”, Irrd.
Eng. (Yrern. (1956) 48, IL = ~ .r,RTlnd RT . . . . . . (A-4)
j.-.1
11.0 fel~ J. B,, Schlinger, W._ G. and Sage, B. H.: “B&redict
-- E&tioriof State: A~limrtion to Methane, Ethmm, n~Butarm
and n-Pentane”, M. rzg. Chem, (1953) 46, No. 6, 1350. The third term in Eq. A-1 is written as the sum of two
12,Ifsieb, J. S, and Zimmerman, R H.: “Pre&ction of Compres- isotheritwd integrals: .
sibility of Natural Gas by Use of the Bene&ct-Webb-Rubin
Equation of State”, lad.’ Eng. Chem. (1958) 3, No. 2, 194. .,
13.Edmieter, W. and Canjar, L.: Applied Thernmdyrksw”cs,Gul[ A

-—
Publishing co,, Honeten, Tex. (1961),
14. Rossini, F, D.l Phzer, k, S,, Arnett,’ R. L,, B--”” , fi. M. and
Pimen~l,&.X.~Seleti&.Ya&s~.Phystim.&.Th& ti.--.–.
(A.--*)T)T =
.j—–—–--~.u–-–.
r 8A
—.. —-.–.---—-:—— ———
——.—--—-–
natrde Properties of Hydracarbarrs and Related Compaud,
APP3tesearch Projeot 44, Carnegie Press, Pittsburgh, Pa.
. =~Pw,n+J:Pwn, “
15,Hoffmrmn,A. E., Cnrmp, J. S. and Hocott, C. R.: “E ‘tibrium
constants for a GSS Condensate System”, Jour. %. Tech. ~. w>
(Jan., 1953) V, No, 1, L -
 ..
-. . “4

?4x, s,” )IX{RIn (dRT ‘

‘F’v”-r”v”
S,,, = – X,)
t=1
v V*
– (B.R+2CJT)d-bR@/2
d &
P8d P8d
=
H
0
—_
@
0
—,.
8
,., ,,(A.5)
-1-(2c&/ r)
.[
1-exp (-y&) _ exp (-y&)
ya 2’ 1
Substituting the ideal gas law in the second, term in 4. Fugacity of a component in a mixture:
Eq, A-5, and noting that by deflrdtion d = d*, Eq. A-5
reduces fw
RT In?, = RT ln(dRTx,)

(A:-Am*)r=~(P-:Td~8d . . . . . (A-6)
2(cocol)~
~
o
Sumrnhzg Eqs. A-2, A-4 and A-6 gives the desired re-
-i-(B,,
[
+B.,)RT–2(A:A”,Y
– .-p---
1
Sulti
i- (3/2)[RT (bzb,)’@–(aza,)’@]d*

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Am = S x, [RT In (d RTx,)+U,O-Z’S,O] -t- (3/5) [a(a’a,)’fl+ a(a’a,)’’’ld’
i=l
+ 3&(c’c,)’fi 1 -exp (– y~ _exp (–ye+
%~(p-:Td)8d .,..,., (A-7) T’ [ yd’ 2 1
n
This equatio~ is presented in the text as Eq. 3. -—2d’c — y, 4 1 –exp(-y@)
T=y()[ ys
These equations are for thermodynamic properties based
on the B-W-R equation of state. yti exp ( – y@
1. Work content of a mixture: - exp(–yd) –
2 1
AM = ~ x,V?T ln(dRTxJ+U,O-TS,O]
$-1
These are constants used for the B-W-R equation of

‘+’RT-A+’
state (units are consistent with R = 10.7335 psia-cu ft/lb-
mole-OR):
. .
Methane Ethnne . PrOpOne l-Bumne n.Butane
-1- (bRT-a)$+~+ ~ 6“ 0,6s2401 I ,W5540 1,558840 3.203290 1.992110
A. X104 0,699625 1.567070 2.591940 3. S58740 3. S02960
Coxlo.lo 0,027576 0.219427 0.620993** I .038740** 1.213050**
b 0.867325 3.8$3930 5.773550 10.8890il 10,26360
l–exp(-yO- -$exp(-y#) . axle+ 0.298412 2.085020 5,724S00 11,70470 11.37050
[ 1 Cx Iu-[@ 0.049s11 0,641314 2.624780 5.597770 6.192560
a 0.511172 1.000440 2,495770 4.414960 4.526920
2. 13nthalpy of a mixture: Y 1.539610 3.0279W 5,645240 8.724470 S.724470

Hw = ~ x,H,’’+(B.RT– 2A,, –4CJT’)d

[=1 I. Pentanm n-PentanO HOxene Heptane PIUS*
—— ——
.-t- (2hRT–3a)#/2+ 6aa@/5 B. 2,56385Q 2.510960 2, S48450 3.187820 3.932240
A.aX104 4.835360 4.592S30 S.443AOQ 6.607060 9.121130
~3cd,p) 1-exp (-y&) c. x ~o-1’l 2.1 33670** 2.591 720”* 4.055620** 5,79840il** 10.66080
+ b 17.14410 17. I441O 28.W320 38.99170 70.97230
[ yd= Ox lo-+ 22,69020 24,61480 42.99010 62.61060 95.12980
cxlo-~ 13,40250 16.13060 29.60770 48.34270 101 .S820
exp(-yd) + .yd’exP3(–:@ .
—
6 1 a
~ I
6.987770
11 .8s070
7~439920
12,1S840
11,55390
17.11150

●Hapkme constants used for results in Table 6 and Flu. 5,

17.90560
23.09420
39.71330
39.80000

3. Entropy of a mixtur- o*The~e ~on~<lent$ are lempe~ture dependent.t

—.- -_ .._ ._- —._—.

.. .. ... . ____ _________ . __ -_,_ —.—..— ...+..—...—.- —.—
— —._ .--——. ..&._ .4

..
I 9.78 , JOURNAL OF PETROLEUM TF,CiINOLOC~