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SPE 6050
of liquid and moles of vapor per mole of fluid which shows that Zi moles of component i, when
mixture are determined, equilibrated, will be distributed as Lx i moles of
Fluid mixtures considered areeither single-phase component i in the Iiquid phase and Vyi moles of
and saturated or two-phase (liquid md vapor) at component i in the vapor phase. From Eqs, 1 and 2,
the system temperature and pressure. Fig, I presents ~i, Yi ~ and Zi are mole fractions and, by definition,
,
a simplified phase diagram for a given fluid
mixture as a function of temperature and pressure.
The bubble-point and dew-point loci are shown and
their intersection is the critical region. The curve
() ;Z ~ , must be unity,
i=l
These equations also require a restrictive equation
on the liquid phase compositions of
described by these loci is called the saturation
envelope, The region encompassed by the srtturacion
envelope is the two-phase region, Phase equilibria
of fluid mixtures that are within the envelope ~cil
!Xi=l’” ”””””.””.’(sa)
are described by the equations for a single. stage
separation unit, The saturation pressure equations or a restrictive equation on the vapor phase
that are simplifications of the single-stage, compositions,
separation equations describe che phase equilibria
of fluid mixtures on the saturation envelope.
The single-stage, separation and saturation- ~yi=l . . . . . . . . . ..o(3b)
pressure equations are presented and then folIowed ia~
by pzeseneat~on of MVNR for calculation of phase Both Eqs. 3a and 3b cannot be used because, given
equilibria described by these equations. one, the second may be derived hy combining the
given equarion with Eqs. 1 and 2,
SINGLE-STAGE SEPARATION EQUATIONS The component fugacity in each phase is
introduced co develop a criterion for thermodynamic
The single-stage separation unit can be described
equilibria. Physically, the fugacity of a component
with four types of equations, an ouer.all material
in one, phase, with respect to the fugacity of that
balance, component material balances, a restrictive
component in a second phase, is a measure of the
equation on the phase compositions, and tbermody.
potential for transfer of that cc,mponent between
namic phase equilibria equations. The overall
phases. The phase with the lower component
material balance can be written as
fugacity accepts the component from the second
L+v= l, . . . . . . . . . . . ..(1) phase. Equal fugacic;es of a component in the two
phases results in a zero net transfer. A zero transfer
wht :e L is the moles of liquid per mole of fluid for all components implies a fluid system that is in
mixture and V is the moles of vapor per mole of thermodynamic equilib~ium. Therefore, the thermody-
fluid mixture. The component material balance for namic phase equilibria equation can be expressed
each component within the fluid mixture can be by
writren as
=f ~v;~~i:n..........(4
LXi + VYi = Zi ; l~i:n, . . . .“ . .(2) f iL
z~-z~+zL[~-BL(BL+l)l
JUNE, 1~ 175
.
Steps 5 and 6 of the V-Y iteration outline the Consider the V-Y iteration for a two-phase fluid
defining equations for these iterations. Fewer that is predominantly vapor. If ~ is defined as a
defining equations are required by these iterations
thpn required by the L-X and V-Y iterations because vector, (v, yz, y3t. ..s Yn ) T and ~ as the error
of the lesser total number of unknowns. vector, (+1, 42$ s.. ~ q5n)T, then a linear correction
algorithm can be written as
ERROR DETERMINATION
The error equations are the equations remaining Jq{*q+l -~qJ = -~,...... .(17)
after selection of the defining equations.
where the superscript q indicates the quantity is
LoX and V-Y Iterations evaluated using known values from iteration. q. This
set of simultaneous linear equations is solved for
A review of Paragraphs 1 and 2 in Section 3
(V-Y and L.X iteration~~, and Eqs. 1 through 8 the elements of ~q+l, which are the values of the
shows that Eq. 4 has not been included as a defining iteration variables used in ,the next iteration.
equation. There are n of these equations and there Qua&atic convergence of Eq, 17 near the solution
are n iteration variables. is obtained when 9 is the Jacobian matrix, defined
~~ error equations, which represent the residual as the matrix in which each element is the partial
ei the thermodynamic phase equilibria equation (Eq. derivative of one of the errors with respect to one
4) can be written as iteration variable when all other iteration variables
are constant,
-f ~V ; lc_i.~n . . . . .(14) The elements of $ for the V-Y integration are
q = ‘iL
defined by the following equations.
These equations are evaluated. If the Euclidean
norm of the @i’S, Ni
—;l<i<n, . . . . . . ..(l8)
Ji3. ‘w --
n.
wi
— * l<i<n, 2~:n . . . . “(I9)
Jij, “ay ~ ’--
is less than the error tolerance, the iterative
sequence ends. If not, the iteration variables are The analytical expressions for the derivatives in
corrected by the methods outlined in Section D. Eqs. 18 and 19 can be obtained by differentiating
the defining equations (Eqs. 1, 2, and 3) with
p-Y and p-X Iterations respect to the iteration variables (see Appendix B).
The resulting equations then are used during the
For the p-Y iteration, there are n + 1 iteration
implicit differentiation of the error equations. The
variables. Eq. 14 represents n error equations, and
elements of g are
the remaining error equation is the residual of Eq.
11, which :an be written as
jil.~.-~
w~ n afiL
‘x);
—(Yj-j
1
j=2 axj
(15)
‘n+l = ‘s -P’”””””
i=l ‘J’iv l<~<no.....a.(zfj)
——
JUNE. 1978 In
.
. ,
multiple-contact, miscible oil recovery methods TABLE 1- ‘WCLI DEAN NORMS FOR Ml XTURE A
with either CC)2 or rich-gas injection requires an USING MVNR
understandir. g of the transition zone that exists Iteration Numl ?! Euclidean Norm
/A’\
---EQUILIBRIUM TIE LINES C*2
—SUCCESSIVE
SUBSTITUTIONS
‘MVNR SATURATED VAPOR
-“-- TIE LINES
SATURATED VAPOR
Q
9
7S%c% C02
1s%co* 75%C*2 25%clD
2S%C10 25%C4 75 - :: C4
f
‘SATURATED LIQUID
FIG. 2 - CALCULATED PHASE EQUILIBRIA BY FIG, 3 - COMPARISON OF SOLUTION METHODS AND
SUCCESSIVE SUBSTITUTION, ccl ~ - n~, - c ~~ CALCULATED PHASE-EQUILIBRIA FOR CO~ - nC, -
FLUID SYSTEM AT 1,600 PSIA AND 160%. C ~o FLUID SYSTEM AT 1,600 PSIA AND 160%.
m SOCIETY OF PETSOLEUM ENGINEERS JOURNAL
.
iterations to calculate the saturation pressure. The MVNR Methods. ” For two-phase fluids, either the
Euclidean norm as a function of the iteration number L-X or V-Y iteration is used. The LoX iteration is
is presented in Table, 3. Quadratic convergence used for a fluid that is predominantly vapor (L < V),
was obtained near the soIuticm. Two-phase calcula- while the V-Y iteration is used for a fluid mixture
tions for the results presented in Fig. 4 each that is predominantly liquid (L > V). Therefore, the
required four or five iterations. The Euclidean norm V-Y iteration was used :s calculate the results in
as a function of iteration number for the calcular.ions Fig, 4. To demonstrate the effect of improper
at 4,950 psia is presented in Table 3, Quadratic selection of iteration variabIes, the phase equilibria
convergence was obtained near the solution. MV1-R in Fig. 4 was calculated using only the L ..Y iteration.
methods required a total of 52 iterations to calculate (The calculations began at 4,500 psia, not at the
the saturation pressure and the ph~se equilibria at saturation pressure.) The results were identical
10 pressures (Fig. 4). to those in Fig. 4, up to and including 4,850 psia.
The method of successive substitwions also was The L-X iteration required two additional iterations
used to calculate the phase equilibria presented in ac 4,900 psia, but did converge. At 4,950 psia, the
Fig. 4. The program allowed 100 iterations per L-X iteration diverged, The decision to switch
solution. At all pressures, the Euclidean norm iteration variables based on the “predominant
exceeded the sFecified tolerance of 10+ after 100 phase” is arbitrary as demonstrated by these
iterations. However, the calculated mole fraction of results because L was much larger than V before
liquid, L, as a function of pressure, agreed within convergence occurred. However, this method o:
0.001 of the values calculated by MVNR methods. selecting iteration variabIes is successful.
Table 3 presents the Euciidean norm for the first 10
iterations of the method of suc~.essive substitutions CONCLUSIONS
at 4,gs0 psia and the error nonm after 100 iterations.
Note that the norm was reduced to only 0,07. The Iteration sequences, referred to as minimum
method of successive substitutions required a total variable Newton-Raphson (MVNR) methods, were
of 1,000 iterations to calculate the phase equilibria deveIoped for calculating the phase e(,uilibria in
p~esented in Fig. 4, This did not include a the two-phase region and the saturation pressure of
saturation-pressure calculation. a multicomponenc fluid mixture. The phase-equilibria
For this example, MVNR methods required equations used for these calculations incorporate
approximately 10 ‘5 CPU second/component/iteration the RedIich-Kwong equation of state. This study
and the total CPU time, compared with the t;me presents results for a multicomponent fluid mixture
required by the method of successive substitutions, that demon strate the foIlowing conclusions.
was reduced by a factor of seven. MVNR methods 1. MVNR methods can be used to calculate phase
actually performed more calculations because the equilibria of C02 and rich-gas, multiple-contact,
saturation pressure and the two-phase calculations miscible oil recovery methods because these
were calculated. This clearly demonstrates the methods converge for near-critical fIuid mixtures.
computational advantage of MVNR methods. The method of successive substitutions diverges
The convergence of MVNR methods depends on for these mixtures.
the proper choice of iteration variables as 2. MVNR methods exhibit quadratic convergence
discussed in the section entitled,. c‘Description of for phase-equilibria calculations in the two-phase
region. The success of these calculations depends
on the proper selection of iteration variables, A
successful selection procedure is given.
3. MVNR methods converge quadratically for
49W-
TABLE 3- EUCLIDEAN NCRMS, RESERVOIR
OIL PHASE-EQUILIBRIA CALCULATIONS
= Method of SUCCeSelve
~ 4m — —. MVN R Methods substitutions
. Iteramtg Saturation Two-Phsse Two-Phase
a —. pressure at
— 4,950 psla
st 4,950 psla
2 o 240.6 3.28 3.3
~ 4700- .. *
1 4s.3 0,90 3.0s
& 2 5.67 0,13 2.91
3 1,71 0,0025 2,76
4 1.32 6. X 10-7 2.62
4600“ 5 0.81 2.48
6 0,43 2.36
7 0.136 2.24
8 0.0126 2,14
451Xl 1 9 9. x 10+’ 2,03
.5 .6 .7 .8 ,9 1.0 10 4. x 10-9 1.94
. .
L, MOU FRACTION LIQUID .
FIG. 4 — LIQUID MOLE FRACTION VS PRESSURE/ .
RESERVOIR-OIL SYSTEM. 100 0:07
;=
= error tolerance for the Euclidean norm
error equation for MVNR ~ =-- ! !
i-l j=l
Xpjuij’ “ “ “ “ “ “ “(A-3)
+= error vector for MVNR
$“ componint fugacit y coefficient
a= Pitzet acentric factor
~= ! !
ifsll j=l
yp’j~ij’ “ “ “ “ “ “ “(A-4)
la SOCIETY OF PETROLEUM ENGINEERS JOURNAL
and
aY~
=-l; 2~~n . . . . . . . .. (B-3)
F
j
Differentiating the component material balances
with respect to the independent liquid-phase
compositions gives
axi
‘Is ; zli,j~n . . . . (B-4)
~ --.1 ij
f3io, ., . . . . . . . .. (A-9)
biL = ~ APPENDIX C
ai j = aji Wi n afiv
1 — (Yj-xj ) ;
1/2 ~il”~=-ij=2aYj
= (1 -
. . . . . . . ..*.*
Cij)
{1‘aipri
~
.. ‘ri
““”””*
‘aj
~2.5
rj
‘rj
“ (A-n)
I<i<n
——. . .. ”””
.(C-l)
QP~
= —..
bir . . . . . . .. .(A-12)
‘i T
ri .
,,. ,
:. .,, .:
. !’
,. .81$*+1
~n+l,n+l = 3p
f
PY~ ‘iL afiv
— .8fiL + ~L.- .—
..9+ f ‘%vpx~ af~L
f iv
. . . . . . . . . . .
ap P ‘iv
. . . . . . . . .
8P
(c%)
‘j L
. . . .,.
II —-
. . . . . . . . .
f:L axj
● . .
●
‘
l~~n
. (c-9)
*
P-X, ITERATION
1’ a$ni-l
w~ afiL
‘n+l, ni-l = ~p
l~i,j~n, . . (C-7)
ji,j = q” 3X4
ji,n+l=~=~-
Wi afiL afiv
—
3P
; I<i<rl
. .
,
=1-
n
l—-—
i=l fiv
II
(
PXi
. . . . . . . . . . . . . . .
afiV
ap
+ ‘iv
P
✎
fiv
‘iL
afiL
T
. . . (c-lo)
“.
}
. . . . . . . . . . . . . . . . . . . . (C-8)
***