ELSEVIER Fluid Phase Equilibria 117 (1996) 265-272

A NEW ALGORITHM FOR ENHANCED OIL RECOVERY

CALCULATIONS

E. N e a u a , U Avaull6e a and J.N. Jaubert b

a Laboratoire de Chimie Physique - Facult6 des Sciences de Luminy - 163, Avenue de Luminy -
13288 Marseille Cedex 9 - FRANCE.
b
Laboratoire de Thermodynamique Chimique et Appliqu6e - Institut National Polytechmque de Lorraine -
Ecole Nationale Sup6rieure des Industries Chimiques - 1, rue Grandville - B.P. 451 - 54001 Nancy - FRANCE.

ABSTRACT

In order to test some algorithms currently available for enhanced oil recovery processes, the evolution of the
thermodynamic Minimum Miscibility Pressure (MMP) with respect to the enrichment level of the injection gas
by a solvent has been studied. Limitations of classical algorithms are evidenced and an alternative algorithm is
proposed.

1. INTRODUCTION

Nowadays, gas injection is a very important enhanced oil recovery (EOR) process and has become a
common practice even if a very complex technology is required. Although gas injection has been a subject of
important research and development for more than 40 years, much progress still needs to be made to
understand the mechanisms and to reduce the discrepancy between calculated and experimental values. In this
paper, a comparison between calculation methods commonly used in petroleum companies to estimate the
multiple contact minimum miscibility pressure (MMP) is made. An alternative algorithm to calculate the MMP
is described.

2. MMP DETERMINATION

2.1. Theoretical background

When a gas is injected into a reservoir crude oil, both fluids may be first contact miscible i.e. only one phase
is formed, no matter in what proportion the oil and the gas are mixed. Such a phenomenon usually takes place
at high pressures. However, at lower pressures miscibility may take place as a result of multiple contacts
between the oil and the gas. Such a process is often profitable because valuable heavy components will be at the
end contained in a phase with a fairly high mobility and will be recovered. The multiple contact miscibility is
commonly explained by the Condensing Gas Drive Mechanism (CGDM) or the Vaporizing Gas Drive
Mechanism (VGDM).

0378-3812/96/$15.00 1996 Elsevier Science B.V. All fights reserved

SSDI 0378-3812(95)02962-1
266 E. Neau et al. / Fluid Phase Equilibria 117 (1996) 265 - 2 72

LIGHT

/~ Dew curve The Vaporizing Gas Drive Mechanism

(Figure 1) takes place when a lean gas Go is
injected into a crude oil Lo containing a high
percentage of intermediate components. In this
process, the gas (at the front) is enriched in
intermediate components by repeated contacts
If,', \\ with the original oil (L0), moving its composition
on the dew curve of the phase envelope towards
~ ~ the critical point (CP). As illustrated in Figure 1,
the gas may become so enriched with
intermediate components that it may become
miscible (G3 in Figure 1) with the oil Lo.

HEAVY INTERMEDIATE

Figure 1. Vaporizing Gas Drive Mechanism.

LIGHT

The Condensing Gas Drive Mechanism

(Figure 2) occurs when a rich injection gas Go is
e.l contacted with an oil that is relatively lean in the
intermediate components. In this process, the oil
near the injection point (at the rear) is enriched
in intermediate components by repeated contacts
I tl with the injection gas (Go). The intermediate
// //
components of the gas condense into the oil
// // / moving its composition towards the critical point.
// // / As illustrated in Figure 2, the oil may become so
enriched with intermediate components that it
//// // / I
may become miscible with the gas.
/ // //

[ {
HEAVY INTERMEDIATE

Figure 2. Condensing Gas Drive Mechanism.

By definition the lowest pressure at which the oil and the gas phases resulting from a multiple contact
process (vaporizing or condensing) between a reservoir crude oil (Lo) and an injection gas (Go) are miscible in
any ratio is called the multiple contact minimum miscibility pressure (MMP).

2.2. Classical methods to calculate the MMP

To our knowledge, all the programs available in petroleum companies such as PVTsim (CALSEP MS and
DEWPOINT MS), PVT-X (PERA A/S) and the PVT-pack developed by the French Petroleum Company
TOTAL [1-2] are not able to determine whether the mechanism taking place is a VGDM or a CGDM. From the
user's point of view, both mechanisms have to be successively simulated and the "true" MMP is the lowest value
thus determined. From a practical point of view this procedure is time consuming and should be avoided.
Moreover, it is sometimes asked to the user to try different algorithms to calculate a given MMP. As a
consequence, in many cases, different values of the MMP may be obtained for a given mechanism and the user
must, once more, choose the smallest one.
 E. Neau et al. / Fluid Phase Equilibria 117 (1996) 2 6 5 - 2 72 267

The most currently available algorithms are either the negative flash [3-4] or a cell to cell simulation [5] or
one-cell simulation [3]. The accuracy of such methods was checked, using the PVTsim program, by plotting the
evolution of the MMP with respect to the enrichment level of an injection gas Go with a Solvent So. Results are
shown in Figure 3 where the enrichment level (Enr %) is the mole percent of solvent So mixed with Go in order
to define a new injection gas G; this gas is injected in the crude oil Lo at a constant temperature and the MMP
is calculated.

350.0 i I ~ I I I I I I I 350.0
i ....... NEGATIVE FLASH ~MMP/bar , , tMMP/bar
.: CALCL~ATION
300.0 300.0
.~ ........ 2................
i""'. .- ....... VGDM
250.0 ....'" SIMULATION 250.0

200.0 SIMULATION ~ 200.0

150.0 150.0
T = 369.25 K T = 369.25 K
(a) Enr% (b) Enr%
100.0 ~ , ~ ~ ~ , , D I00.0 , , , , , ,

0.0 50.0 100.0 0.0 50.0 100.0

Figure 3. Locus of the MMP with respect to the enrichment level at T/K = 369.25. (a) Results of the VGDM,
CGDM simulations and of the negative flash calculation. (b) Locus of the minima (true MMP).

Table 1. Table 2.
Composition of the different fluids used for MMP True Boiling Point (TBP) distillation of the reservoir
simulation (mole percent). crude oil.
Compounds Reservoir Gas Go Solvent Cut Mole percent Molecular Density
Crude Oil Lo So in reservoir Weight kg.m~
H2S 0.900 1.16 C5 2.546
N2 0.083 0.74 C6 3.488
CO2 3.463 4.57 C7 3.649 96.0 720.9
Methane 36.459 73.18 C8 3.377 112.0 753.3
Ethane 10.993 12.25 C9 2.869 124.0 766.6
Propane 6.822 4.77 60.0 C~o 2.211 134.0 777.1
Isobutane 1.215 0.54 Cu 1.996 147.0 788.6
n-Butane 3.716 1.49 40.0 C~2 1.662 160.0 799.0
Isopentane 1.576 0.39 C13 1.487 173.0 809.2
Pentanes 2.546 0.50 C~4 1.239 188.0 820.0
Hexanes 3.488 0.30 C~5 1.152 205.0 830.6
Heptanes 3.649 0.11 C~6 0.961 224.0 840.2
Octanes 3.377 C~7 0.821 235.0 845.4
Nonanes 2.869 Ct8 0.713 250.0 851.6
Decanes 2.211 C19 0.644 264.0 857.3
Cu+ 16.633 C20+ 5.958 435.0 927.7

Tables 1 and 2 show the composition of the different fluids and the results of the crude oil TBP distillation.
The PVTsim program was used with Pedersen's characterization of the plus fraction [6] coupled with the
Redlich-Kwong-Soave [7] equation of state (EOS) with standard binary interaction parameters [6].
268 E. Neau et al. / Fluid Phase Equilibria 117 (1996) 265-272

As shown in Figure 3a, the change of mechanism from condensing gas drive to vaporizing gas drive for an
enrichment level of 3 %, leads to a discontinuity of the true MMP from 255 to 280 bars. With the fluid
compositions given in Table 1, the PVTsim program was unable to calculate the MMP simulating a CGDM for
an enrichment level higher than 3 %. In the same way, the failure of the VGDM algorithm for enrichment
levels close to 75 %, or the surprisingly rapid increase of the calculated MMP at 36 % leads to choose the MMP
as the value of 277 bars given by the negative flash method (Figure 3a). Those results seem highly improbable
since it is well known that the enrichment of an injection gas by a LPG (Liquefied Petroleum Gas i.e. solvent
So) decreases the value of the MMP.

3. A N E W ALGORITHM FOR ENHANCED OIL RECOVERY CALCULATIONS

3.1. The proposed method

The algorithm proposed in this paper allows us to determine directly the MMP without simulating
successively a VGDM and a CGDM. It is based first, on the determination of the mechanism (CGDM or
VGDM) and then is followed by an accelerated successive contact simulation. In order to determine the proper
mechanism, the first step of the method consists in determining the FCMP (First Contact minimum Miscibility
Pressure) i.e. the lowest pressure where the injection gas Go and the crude oil Lo are first contact miscible. This
pressure may be determined by simulating a swelling test and locating the stationary point at the top of the P-X
diagram as shown in Figures 4a and b. In such a diagram, the amount of injected gas, noted as X~, is defined
by:
number of moles of gas (1)
Xga~ = number of moles of gas + number of moles of reservoir crude oil

At the FCMP, the segment [Lo-Go]joining the composition of the crude oil and of the gas is tangent to the
phase envelope. Consequently, the segment [Lo-Go] intercepts the P-X diagram either on the bubble curve or on
the dew point curve; it is then established that the mechanism taking place is thus respectively a CGDM (see
Figure 4a) or a VGDM (see Figure 4b).
1000. 1000.
P = FCMP /bar P = FCMP
L~ //'r-,\ ]GO

Pc . . . . . . . . . . . . . . . . cp - -
.....
bubble point curve
dew point curve
// "~I
bubble pointcurve/ I~
//
..... dew point curve / /i
500.0- / II 500.0 /
il
t
I Pc /~P
............................
I
J
Ca) / / ',
'
I
I
P
I
X$~ Xg~
0.0 , , , 0.0 ' 'X'c
0.00 0.50 XFc~X'c 0.0( ' XvCMVl.O0
Figure 4. P-X curves as obtained during a swelling test. (a) CGDM the stationary point (top of the curve) is
located on the bubble curve. 0a) VGDM : the stationary point is located on the dew point curve.

In a second step, at various pressures lower than the FCMP (in fact lower than the critical pressure, Pc, in
the P-X diagram), multiple contacts are performed between :
- the reservoir crude oil Lo and successively the injection gas Go and the equilibrium gases Gi, G2..... Gn in the
case ofa VGDM (see Figure 1).
- the injection gas Go and successively the reservoir crude oil Lo and the equilibrium oils L1, L2..... Ln in the
case of a CGDM (see Figure 2).
 E. Neau et al. / Fluid Phase Equilibria I 17 (I 996) 265- 272 269

3.2. Reduction of the contact number.

In order to accelerate the previous algorithm i e to reduce considerably the number of contacts, different
solutions are proposed :

a) Choice of the mixing proportions : LIGHT

In the case of a vaporizing gas drive
mechanism (see Figures 1 and 5), for each
contact k (k = 1, 2, ..., n), the equilibrium gas
Gk is determined as the gas phase in
equilibrium with the oil Ls.k (see Figure 5)
obtained by saturating the oil L0 with the
equilibrium gas Gk_~ obtained at the previous
contact.
After several contacts it is checked whether
the oil Lo and the gas Gk are miscible (the 1/I
pressure is greater than MMP) or the
equilibrium phases Ls.kand Gk are always the
same (the pressure is lower than MMP). MMP
is then determined by a simple dichotomy.
A similar procedure is applied in the case
//~ ~,~ ~;P criticaltieline~
of a condensing gas drive mechanism.
HEAVY INTERMEDIATE
Figure 5. Reduction of the contact number using optimal
mixing proportions (case of a VGDM).
b) Calculation of a criticit~ parameter 2e:
Even when the mixing proportions are optimal, it is sometimes difficult to know, when the contacts are
performed at a pressure close to the MMP, whether the composition of the fluids in equilibrium (Ls,n-G,) are
slowly converging towards a limiting tie line or miscibility can be finally achieved. In order to determine
rapidly whether the miscibility will be achieved or not, we propose to follow the evolution of the coefficients
K<i) = y(i)/xo), where y(i) and x<i)are respectively the mole fractions of component i in the vapor phase Gk and in
the liquid phase Lk in equilibrium at each contact k. When the pressure is equal to the MMP, after several
contacts, G~ and Lk will merge with the critical point, and all the K(i) values will be equal to one.
For convenience, we consider, at a given pressure P, the evolution of the function Lp with respect to the
contact number :

kp --=exp LnK(i) (C = number of components) ; ~.~tP = 1 (after several contacts) (2)

Li=l d
This criticity parameter ~,p indicates how far from the critical point the phases in equilibrium are. For instance
a value close to 1 indicates that the liquid and gas phases are quasi identical i.e. are located respectively on the
bubble and dew curve on each side of the critical point. For a critical fluid ~,p = 1.
Figure 6 shows an example of the evolution of the liquid and gas phase densities (Figure 6a) and of the
function ~,p (Figure 6b) with respect to the number of simulated contacts. When the pressure is higher than the
MMP the difference between the densities of the equilibrium phases decreases until a one-phase system is
obtained. At the MMP, after a few contacts, the monophasic system obtained is critical and the densities are
then identical. When the pressure is lower than the MMP, it was observed in many cases that the difference
between the densities of the liquid and gas phase decreases during the first contacts and then increases. This
evolution has already been put experimentally in evidence by Zick [g]. For the same reason, Lp (equation 2)
must be in these cases an increasing-decreasing function of the contact number for pressures lower than the
MMP and must increase and converge to a value equal to one if the pressure is equal to the MMP.
 270 E. Neau et al. / Fluid Phase Equilibria 117 (1996) 265-272

At a given pressure, when the function ~.v becomes decreasing, the successive contact simulation is stopped
and the corresponding pressure is declared lower than the MMP. This procedure allows one to considerably
decrease the number of contacts necessary to reach the limiting tie-line in the vicinity of the MMP. As shown
in Figure 6(b), less than ten contacts are usually necessary to determine whether the considered pressure is
higher or lower than the MMP. A personal computer needs less than one second to perform ten contacts with
optimal mixing proportions as described in the previous section.

" !. . . . Pi ' ...... "~Equilibrium 1.0 P3 _ - r MMP~.~--~

500.0 t " gas phase P4/ ..... _2--_--_-_\-~'_-_--_~-~[~[[. . . . . . . . . .

P2 liquid phase -
Liquid / densities
phase .. (kg.m -3)

ii i
i
o . . . . . . . . . . . . . . . . .
400.0
- , - . . .. . . . . . P2.
. .

G~
phase
. ..... ................. Vl . . . . . . . . . . . . . . -PJ ......................... t

,
T = 369.25 K
,
(a) |Contaot
~numberD 0.0
iT = 369.25 K , (b) 1number[>
CntaQt
300.0 '
6 11 16 6 11 16

Figure 6. Example of the evolution of the liquid and gas phase densities (a) and of 3.e (b) with respect to the
contact number. (---) pressures lower than the MMP (P~ -- 248 bars, P2 = 289 bars); (--) pressures
higher than the MMP (P3 = 320 bars, P4 = 318 bars). The MMP is equal to 317 bars.

c) Use of a negative [lash algorithm :

As illustrated in Figure 7, when the mechanism LIGHT
developed in the reservoir is a VGDM, most
commercial programs use a negative flash algorithm
to determine the limiting tie line passing through the
composition of Lo. The following equations are
solved:

X L o ( i ) = ~ . X L f ( i ) + (1 - o~) " Y G f ( i ) (3)

with i = 1 to c (number of components), and c > 1.

XLo(i) , X L f ( i ) a n d YGf(i) are respectively the mole
fractions of component i in the reservoir crude oil L0,
the final oil Lf (see Figure 7) and the final gas Gf
obtained after many contacts between Lo and Go.
When the pressure is equal to the MMP, the
limiting tie line is merged with the critical tie line,
whereas above the MMP (see Figure 1) no limiting tie HEAVY INTERMEDIATE
line passing through Lo exists. Equations 3 are solved Figure 7. Limiting tie line obtained at a pressure
for different pressures, and the lowest pressure for lower than the MMP for a VGDM.
which no solution is found is the MMP.
 E. Neau et al. / Fluid Phase Equilibria 117 (1996) 265- 272 271

The main problem with such an algorithm is that a tie line passing through the composition of Lo can be
found, even if the pressure is above the MMP. This occurs in many cases for real petroleum fluids described by
more than three components. As a consequence, it is impossible to define in a general way the MMP as the
lowest pressure for which equations 3 can not be solved. This definition is accurate only for real three
component mixtures or in very precise cases for real petroleum fluids. The negative flash must be used only in
theses special cases.
In ternary systems, the phases Lk and Gk in equilibrium (for instance [G1-L~] and [G2-L2] in Figure 7) are
converging towards the critical point respectively on the bubble and the dew curves when the contacts are
performed according to the appropriate mechanism. In this case, the function ~.~ defined by equation 2 is an
increasing function converging asymptotically to one. However, Figure 6b shows clearly that it is no more the
case when the fluid is described by more than three components. In such systems, for a pressure lower than the
MMP, during the first contacts the phases in equilibrium are converging towards a critical point i.e. the liquid
and gas phase compositions become more and more similar and the kp function is increasing. During the next
contacts, the phases in equilibrium are moving away from the critical point since the ~.p function is decreasing
(see Figure 6b). This effect can also be seen in Figure 6a where the difference between the densities of the
phases in equilibrium is increasing. It must be noted that this behavior is impossible for a real ternary system.
This fundamental difference between a ternary and a multi component system allows one to explain why the
negative flash can find a solution at a pressure higher than the MMP and sometimes higher than the FCMP.
More information concerning quaternary systems is given in the recent paper [9] by Johns et al. In Figure 6b, at
pressures lower than the MMP (dashed lines), after a few contacts the ~.p function remains constant indicating
that a limiting tie line has been reached (see for example pressure P2). This limiting tie line can be reached
either using a contact simulation as previously described or using a negative flash algorithm. When the
pressure is higher than the MMP, after a few contacts the equilibrium gas becomes miscible with the reservoir
crude oil L0. A one phase system is obtained and the contact simulation is not able to reach the decreasing part
of the ~.p function. However initializing the negative flash at the compositions corresponding to the limiting tie
line found at a pressure just below the MMP equations 3 can be solved explaining why the estimated value may
be much more higher than the one obtained using a contact simulation.
As a conclusion the use of the negative flash algorithm alone cannot be considered as a trustful method for
determining whether an oil and a gas are multiple contact miscible or not. However, in a few scarce cases, a
real multi component system may have the same behavior as a real three component system i.e. kp is an
increasing function of the contact number. In this case, and in this case only, the negative flash can be used to
find the MMP.

3.3. Comparison with usual methods to calculate the MMP

The proposed method was tested, to calculate the MMP with respect to the enrichment level of the injection
gas as previously made using PVTsim The results obtained are illustrated in Figure 8 and must be compared to
those of Figure 3. Nothing has been changed (same characterization procedure, same EOS), except the
algorithm.
Figure 3a shows that with classical methods, the true miscibility mechanism is a CGDM when the
enrichment level is lower than 3 %. Above 3 % the forward mechanism (VGDM) could only be simulated.
Such a result was surprising since the injection gas Go contains a very high percentage of methane and the
reservoir oil is rich in intermediate components. Moreover, when the enrichment level increases, the fraction of
butane in the injection gas G becomes higher and it could be expected to lead to a CGDM for high values of the
enrichment level.
Figure 8 shows clearly that the method developed in this work is in perfect agreement with the expected
behavior : the locus of the calculated MMP is a monotonous decreasing function of the enrichment level. The
mechanism taking place is first a VGDM (when the enrichment level is lower than 63 %) whereas for
significant values of the enrichment (Enr % > 63 %), the CGDM becomes more propitious.
The algorithm developed in this paper has been used with a complete success to simulate more than one
thousand MMP or MME (Minimum Miscibility Enrichmen0 with reservoir crude oils, gases and solvents very
different from those presented in this study.
272 E. Neau et al. / Fluid Phase Equilibria 117 (I 996) 265-272

350.0 I I I ~ I I I I I

VGDM CGDM ~MMP/bar

300.0

250.0

200.0

150.0
\
100.0
\
50.0
Enr %
0.0 I I I I I I

0.0 50.0 100.0

Figure 8. MMP calculation as a function of the enrichment using the method developed in this work.

4. CONCLUSION

A method was proposed to calculate accurately the MMP. The procedure consists in determining directly
the mechanism taking place (condensing or vaporizing), and then in performing successive contacts (backward
or forward) between a crude oil and an injection gas. Particular efforts were devoted to the decreasing of time
calculation using optimal mixing proportions and a function, noted gp, especially efficient at pressures close to
the MMP. Moreover, when gp is a strictly increasing function of the contact number a negative flash algorithm
is used. The continuous evolution of the estimated MMP in the case of the enrichment of an injection gas with a
solvent illustrates the efficiency of the proposed method.

ACKNOWLEDGMENT

The authors gratefully thank Professor A. P6neloux for helpful discussions and the French Petroleum
Company TOTAL for sponsoring this research.

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4. C.H. Whitson and M.L. Michelsen, Fifth International Conference on Fluid Properties & Phase Equilibria
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Geology & Engineering 5, (1989).
7. G Soave, Chem. Eng. Sci., 27 (1972) 1197.
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9. R.T. Johns, B. Dindoruk, F.M. Orr, SPE/DOE, 24112 (1992) 83.