\

A Calculation Method for Carbonated Water Flooding

NOEL

DE NEVERS*

ABSTRACT
A calcdation
method has been developed
/or
carbonated
water flooding.
This me tbod takes into
account the e//ects
of oil viscosity
reduction and
to
oil swelling,
due to carbon dioxide transjetred
flood water.
the reservoir oil from the carbonated
[t shows
the e~ect
of changes
in carbonation
pressure
and carbonated water slug size.
The method is based on a Buckley-Leveretttype linear flow model. The nratbemat ical approach
is similar to that developed
by Welge, et al, /or
enriched
gas drives.
However, it contains
a very
important advance over the previous
papers in its
solution to the problem of injection of a slug of
carbonated
water rather than continuous, injection
O/
/l~id
Of constant
composition.
The method also
shows the chromatograp bic tiature o/ the transport
of CO 2 in a carbonated water flood.
Sample calculations
indicate
that viscosity
re.
duction is the most important source o/ incremental
oil recovery. Swelling contributes
to a lesser extent,
Raising the carbonation pressure increases refovery,
but this effect diminishes
as pressure is iticreased,
Increasing
the slug ~ize also increases
recovery,
bzt again this effect dirhinishes
as slug size, is
increased.

INTRODUCTION
In recent years there has been considerable
interest in carbonated water f100ding as a, secondary
recovery
merhod. Several carbonated
waterflood
field tests are now in progress. 1-3 Yet there is no
published
method for predicting the r~sults of a
carbonated
water flood. This paper presents
a
method for predicting the oil recovery for a carbonated
water flood.
In a carbonated water flood, a carbonated water
slug. is in jected into the, reservoir. Then this slug
is driven forward by injecting plain water behind
it. The field opera~or must choose the carbonated
water slug size and the C02:water ratio in the
slug. The calculation rntkhod presented here shows
the effects of both sIug ..]ize and CO 2:water ratio
,/
on o~l recovery,
received in society
of
Peholwn
manuscript
Original
Enginders office Mar?h 15, 1963, Reyised manuscript received
Nov. 4, 1963. Paper- Presented et U. of Oklahoma $PE
Production
,Researoh
Symposium, held fn Norman, Old=.,
April 29-30,
1963,
LReferendes given at end Of PaPet.
*Currently at the U, of Utah, Salt Lake City, Ut*.

CALIFORNIA
LA

HABRA,

RESEARCH

CORP.

CAUF.

REASONS
FOR CARBONATED
WATER FLOODING

The calculation
assumes that the addition of
carbon dioxide to flood water increases
the oil
recovery by two mechanisms:
L Carbon dioxide transfers from the flood water
to the oil, thereby reducing the viscosity of the
oil. At the lower viscosity,
rhe oil flows more
readily
and is more easily swept out by flood
water. ,
2. The carbon dioxide which transfers
to the
oil phase causes the. oil phase to swell. Assume
that the residual oil saturation (volume per cent
of pore space) is the same wheiher the oil is
carbonated
or not, Then the same volume will
contain less stock tank oil if it is carbonated, due
to oil swelling. The plain water driving the car.
bonated water slug forward will strip the C02 out
of this residual oil., causing this oil to ahrink. This
leaves
behind
a
s wel Iing.followed-by-shrinking
lower residual oil saturation than would have been
left behind by a plain water f~ood. Since some oils
swell CO almost twice their original volume at
reasonable
C02 pressures,
rhis effect may be
large;
ITwo additional benefits sometimes claimed for
carbonated
water flooding are:
1. Adding C02 to flood water greatly increases
the water injectivity y in some cases. 1 (Injectivity
= BPD of water injected/ft
of sand x differential
bottom-hole pressure, psi.) C02 forms a weak acid
in water; injecting carbonated-water
is, therefore,
somewhat like acid treating. If a formation responds
to acid treating, it will probably have a higher
injectivity y for carbonated
water than for plain
water. Although the increased injectivity increases
che profitability of a carbonated water flood over a
plain water flood, it does not qhange the production
, Cwve based on total fluid injected.
Therefore,
the method rmsented
here does. not show any effect
.
of increased injectivity.
2. It is claimed in one patentq that carbon dioxide
will react with some constituents
of the oil to
form detergent s, These detergents are expected to
increase
the oil recovery.
There is little data
availabIe
to support this idea. The calculation
method presented here takes no credit for extra
oil recovery due to the formation of any such
+,
detergents.
1
.,

MARCH,1964

.,

1,
.

,.

..

.):,

/,

CALCULATION
GENERAL

METHOD

FORM OF THE RESULTS

This method can best be understood by comparing

its prediction of the behavior of a carbonated water
flood with the behavior of a plain water flood, as
predicted
by the Buckley-Leverect
method. This
comparison is shown on Figs. 1, A, B, C and D.
Considet
first Fig. lB. This shows the water
saturation-distance
profile for a plain water flood.
At A, the water saturation jumps from Swi to the
breakthrough value. Thereafter (A to F) the water
saturation
increases
gradually.

This is reflected in the cumulative production

curve, Fig. ID. For the plain water flood, the oil
product;.on rate is high and WOR is low or zero
unril water breakthrough (O to A). The oil production rate declines (A to F) as the WOR steadily
rises.
Now consider rhe carbonated water flood. (For
the moment consider steady injection of carbonated
water, Later a carbonated water sIug followed by
plain water will be discus seal.) As shown in Fig.
IA, the carbonated water advances as a {square
wave (G to E) with a leading wedge (E to C).
(The reason for this leading wedge will be discussed later. )
As shown on Fig. lB, this results in a somewhat
complicated
water- saturat ion-di st &nce curv,~. At
the far right, ahead of point B, the result is the
same as for a plain water flood. To the extreme left
. (G to E) in the region of high C02 concentration,
the water saturation is much greater than it would
have been for a plain water flood, The extra dil

recovered from this region flows forward and forms

the region of constant water saturation
(or oil
bank) shown from C to B, Note that the oil in
this oil bank contains no C02; this is the extra
oil. driven ahead of the carbonated zone.
Now consider the production curve (Fig. ID).
From O to B the carbonated water ,flood has the
same cutve aa the plain water flood. At time B,
the oil bank arrives at the producing well, and
the WOR remains constant utyil time C. At time C,
the leading edge of the carbonated zone reaches the
producing well. At this time the WOR begins to
rise again and the first C02 comes out of the
producing well (Fig. lC).
As the leading part of the carbonated zone is
produced (C to E), the WOR increases and the rate
of C02 production from the producing well increase a.
Finally,, at point E, the region of maximum carbonation reaches the producing well. Thereafter,
the
oil production rate falls almost to zero (E to G),
and the CO z production rate remains at a practically
constant, very high rate,
The carbonated
water flood curve
above . is
constructed
for an infinite C02 slug size, i.e.,
steady injection of C02 until the end of the project.
In a slug process, the oil production stops, for
practical, purposes, when the last of the C02 comes
out of the formatior+ If the total C02 in the carbonated
water slug is x (as shown in Fig. IC), then at time
D the last C02 comes out of the formation. Thereafter, no more, C02 comes out; you cans not get
more out than you put in. The cumulative-C02production
curve becomes horizontal
at x The
oil production curve also becomes horizontal
at
D.

FIGURE1A

E II

WA1E.QFLWD

s 61II----------------------L-----SW
OISTL+JCE

FROM

INJECTION

WELL

ij!~::::..->

As smaller and smaller csrbrnated

warer slug
sizes
are chosen, thb cut-off point on the oil
production curve moves from D to C, This leads to .
~he paradoxical conclusion that as the carbonated
water slug size is reduced to zero, the incremental
oil recovery due to C02 does not go to. zero. This
will be discussed later.
The above production curve was construc~ed for
one C02 :wat r. ratio in the carbonated water slug.
For other CO ?~ water ratios, the cqrves are different,
Drawing several of these on one plot; and connecting their cut-off points for various slug sizes,
produces a plot of ~he type shown in Fig. 2, for
,one of the example problems to be discussed later. ~
This is the complete form of the results; a plot
of cumulative oil produced vs pore volumes injected
for various C02 :water injection ratios and various
slug sizes. Higher C02 :water ratios give higher oil
recoveries;
this will also be discussed later.
REQUIRED

OP
PORE

FIG.

1 -

VOLUMES

COMPARISON
CARBONATED

INJECTHJ

OF TYPICAL
PLAIN
WATER FLOODS.

AND

INPUT

DATA

,The required input data for this calculation are:

1. The formation pressure and temperature;
2. The water-oil permeability
ratio vs water
satriration curve for the formation;
3, The solubiIity of C02 in reservoir oil as afunction of C02 pressure at reservoir temperature;
4. The viscosity
and density
of solutions of

10

sOCIETY OF PETROLEUMENGINEERSJouRNAL

,,

,,
..

---

.,

;..,

.,

---

C02 in reservoir oil as a function of C02 concentration, at reservoir temperature;

5. The volubility of C02 in the flood water as a
function of CO 2 pressure at reservbir temperature.
(For fresh wat~r, these data are known from the
tests may be
literature.
For brine, laboratory
needed~
and
6. The viscosity
and density of solutions
of
CO z in flood water as a function of CO z pressure.
(These may be estimated with satisfactory
accuracy).
ASSUMPTIONS

The basic assumptions of this calculation method

are as follows:
1. The assumptions
of the Buckley -Leveretts
method are applicable. These are: (a) the permeability or porosity variations in the formation may
be neglected; (b) ths formation is a linear system;
(c) the fhiids are incompressible; (d) only two phases
are flowing at any one point (i. e., there is no
mobile gas phase); (e) the ,initial water and gas
saturations
are constant throughout the formation;
(f)

/w =

~wip w

kw/p ~+ ~.

1P.

(i.e.,

capillary effects

are ignored} and (g) gravity effects may be neglected.

2. The amount of oil dissolved
in the water
phase and the amount of water dissolved in the oil
phase are negligible.
3. The totaI pressure
is high enough that no
C02 gas phase is formed anywhere in the formation.
I 4. ,In those parts of the formation where C02 is
present,
at any given point in the formation, the
oil and water are in equilibrium;
i.e., the partial
pressure of C02 in the water phase at any given
point is the same as the partial pressure of C02

in the oil phase at that same point.

5. In the leading part of the C02-invadedregion, formation gas (mostly methane) is displaced
from the oil by C02. It is asatrmed chatthe displacement of methane by C02 results in the oil viscosityC02 concentration
behavior shown in Fig, 3. In
other words, displacing
methane by C02 causes
-the viscosity to fall steadily until the C02 partial
pressure
equals the original formation pressure,
at which point all the methane is assumed to be
expelled. If Iab data are available on the viscosity
of the crude oil-C02-CH4 system, this assumption
is unnecessary.
6. Molecular diffusion and convective diffusion
(dispersion) of C02 in the flow direction are zero;
i.e., C02 moves forward only by flow of the oil
and water phases, not by diffusion within them.
CHOOSING THE BEST
C02 :WATER RATIO

From the production curves for various C02: water

ratios,
Fig. 2, it appears that higher C02:water
ratios
give higher oil recoveries.
G,eneralIy, at
low ratios increasing this ratio makes a big change
in recovery,
at high ratios it makes a smaller
change.
The C02 :water ratio for which this calculation
method works is limited by the formation pressure.
At a given temperature
and pressure
the C02on
the
solubi Iiry-in-water
curveg sets a maximum
C% :warer ratio for which no free C% gas is pre sent.
If a higher ratio is chosen, free C02 gas will be
formed.
From the ample
calculations,
it appears that
increasing
the C02 :water. ratio always increases
the incremental oil production. Tliis is true up to

0
~
:
0

u
#
g
*

?
.4
:
.
.:

,.
l v:

to

10

WRC

FIG. 2 SAN JOAQUIN VALLEY

1-....

vOLMES

COMPARISON OF PLAIN AND CARBONATED

-.-.-

30

INJCCTEO

WATER FLCODS.

--::

-.

the C02 :water ratio at which free C02 gas is

formed. The calculation method will not predicc the
reservoir performance if free C02 gas is present.
This wifI be discussed later.
Thus it appesta that the C02 :water ratio should
be chosen as high as pri&ible. It should alwaya
be high enough that the bubble point pressure of
the. C02-water
solution is at or near formation
pressure.
In some cases it may be economical to
raise the formation pressure in order to obtain a
greater
recovery.
CHOOSING THE
CARBONATED

BEST
WATER SLUG

SIZE

The paradoxical
result was previously
shown
that as the carbonated water slug size is reduced
to zero, the calculated incremental recovery does
not go to zero. This is due to the inaccuracy of
two of the basic assumptions
as the slug size
becomes smsfI. The first is chat ac any gives point
in the reservoir, at every instant of time, the oil
and water phases ate in C02 equilibrium.
As the slug size gets smaller and smaller, the
time rate of concentration
change becomes larger
and larger. Suppose that the flood water C02bubble-point
pressure
vs time curve (f?r, some
point in the reservoir) is, for example, -d square
,wave. According to the fourth aasumpt ion, the oif
and water phases at a given point are always in
C02 equilibrium. This means that if the bubblepoint-vs-time curve for the water phase is a square
watie, the bubble.-point-vs:time
curve for the oil.
phase is, aLso a square wave and is in phase with
the water :curve.
If the #lapsed time for the square wave of bubble
point of water phase to pass a given point in the

Iu

,RESSURE

OILv16COSIT

,Waruc

CO*

,..

ST c

II
~
.M--U
C02-CH,-57U

.10
0

Fm.
.

MIXTURES

200 400 600 00 Km

LIMITATIONS OF THIS METHOD

OF CALCULATION
!

ST c

-H
+
1600

reservoir is one year, this equilibrium assumption

should be satisfactory.
CO z will diffuse into and
back out of the oil phase to keep the bubble point
pressures
almost equal. On the other hand, if the
~
elapsed time for thd kquare wave of bubble point
,pressure
in water to pass a given point in the
reservoir is one second, there will not be enough
time for the C02 to diffuse into the oil phase, The
CO z slug will pass by without affecting the properties of the oil phaae. As the C02 slug size is
made smaller the elapsed time becomes smaller
attd the equilibrium assumption less reliable.
:

The second assumption which fails as the slug

size i a reduced to zero is that molecular and

convective diffusion of CO z in (he flow direction
are zero. For large slug sizes this mode of C02
movement is negligible compared to-the moveroent
of CO z in the flowing fluids. For small C02 slug
sizes
the diffusion
effects become significant.
Consider
the previous example where the. C02bubble-point-pres sure-v s-time curve was a square
wave. If this wave has a? length of 1,000 ft, its
shape will not be significantly
altered by diffusion
as it moves through the reservoir, If, on the other
hand, its length is I ft, diffusion wou!d quickly
change it to a tbell- shaped curve with a much
lower peak vaIue. As such it would have much
Iesa effect on the properties of the oil phase, and
therefore much less effect on oil recovery.
The slug size at which these effects become
important is not known. Thus the lower slug size
limit to which the method applie; is not known,
However,
the following procedu~e to determine
the economic slug sizes eliminates the need for
determining this lower limit. FroW the oil production
and carbon dioxide requirement curves the incremental oil recovery per ton Qf incremental
C02
may be calculated for each sltig size.
By applying appropriate
prices to the oil and
C02 and an appropriate time factor, one may calCUIat e the rate of return fqr each incremental ton
of C02 injected. The first ion of C02 injected will
have a large rate of ret#n.
As the slug size is
increased,
the incrementtil rate of return will fall
and eventuality reach negative values. The slug
size should be chosen so thar the 1ast ton of C02
injected
earns the minimum acceptable
rate of
,return, for secondary recovery projects. .

PRESSURE,

~SCOSITY
OF SAN JOAQUIN CRUDE AND
CH4 OR C02. ,
,
.

,
,,

.,.

~ .

...

,. -.

,.

<

,..

.,

$,
....

This method of calculation

makes no provision
for unswept areaw In this regard it is sintilar to
the Buckley-Leverett
methqd for water floods or
gas drives. No@ally when the BuckIey-Leverett
method is used, empirical correction factors are
applied, to ir~co correct for areal and vertical
coverage. l%? same factors should be applicable
to C% flooding. The same coverage factor which
is a?p[ied t{ the oiI production shouId also apply
to the carbonated water slug size.
-This method assumea that the pressure remains
constairt through the reservoir or at least the pres,,.
SOCIETY OF PETiiOLEUM ENGINEERS JOURNAL

la

.. .

..i

sure remains high enoujzh so that no free -gks phase

is firrmed. In practice, this is unlikely. The reservoir will originally be at or neat its bubble point,
and the dissolution of carbon dioxide in the reservoit
oil will cause methane or other gases to be evolved.
Furthermore, if a pressure gradient exists through
the reservoir,
then a bubble point fluid ac the
injection WC?llwill give off gas as it pakses through
the reservoir. However, this assumption is psdy
covered by the nature of the calculated
reauIt
which indicates that the prtrtial pressure of C02
decreaaes
in the direction of flow through most of
the reservoir.
Hence, during most of the water
flood the total pressure may be high enough to
prevent the formation of a free gas. In any event,
formation of a free gas most likely results
in
increased
oil production or more rapid oil production
thsn this method predicts,
so that the
method is inherently conservative
on this point.
The calculation
method does not consider the
possibility
of using brine as a displacing
fluid.
It is known that dissolved
salts lower waters
ability to dissolve C02. If there is a change in
salinity in the formation, e.g., when the injected
fluid has a different salinity
from the connate
watert then the calculation would be more complex.
This effect will probably be very small.
The calculation
assumes that sII the C02 is
injected as a carbonated water solurion of constant
This makes the mathematics
C02 concentration.
simple and may indeed be the most economic way
to inject the C02.
An alternative procedure would be to inject all
the CO z as a pure component (liquid or dense gas)
and to follow it with water. The method does not
calculate
the behavior of the reservoir for such
a process.
Helm g shows that this latter process gives more
oil recovery than the carbonated waterflood process.
His data indicate that this difference is very large
for Iow-viscosity
crudes (e.g: 1 cp) and small-for
cp);
Thus, for Idwhigh-viscosity
crudes (9o
viscosity
etudes the predictions
of the method
presented here do not appIy to the C02-foHowedby-water process.
For high-viscosity
crudes the
method presented here should give a fair approximation of the results of a C02-followed-by-water
flood:
For some oils h third liquid phase can form when
the oil is contacted with c ttrbonated water. Under
these circumstances,
the reservoir would contain
three mobiIe phases oil, C02-rich phase, and
ctibonated
water. This method of calculation does
not include such phase behavior.
As mentioned above, the calculated
results for
very small slug si zes are not considered reliable.
DISCUSSION OF THE CALCULATION
METHOD
BERAVIOR OF CAREON
IN A R&3ERVOIR

Having

DIOXIDE

seen the res&s

of the calculation;

MARCiit;1964

TABLE

I -

ANALOGY

TO

GAS

CHROMATOGRAPH

Gas
Chromatography
;ixow

solid

su~:~t,

e.g.,

Fixed
phase

liquid

Absorbent,
e.g.,
011
silicone

Nonabswb=d
carrier

Helium

Transferred
component

Sampl,ebeing

.&shed

Carbormtad
Water Flood
fire

asphait,

Rorwvolr
or

Reqldual

analyzed

.
.

..>.
f

rock

IN

water

or nitrogen

CO ~

,.

,,

,..

con-

aider how these results are obtained. To do this,

first consider the general behavior of C02 in a
teservoir which is being water flooded.
When carbonated water contacts oil in a porous
medium, much of the C02 is transferred to the oil.
(For moat oils, at most pressures and temperatures,
the solubility of C02 in oil is two to ten times as
large as its volubility in water at the same conditions.)
The leading part of the carbonated water slug
repeatedly comes in contact with oil which conmins
no C02. If the first bit of oil removes one-half the
C02 from a ,segment of water, and the next bit
removes one-half of the remaining C02, etc., then
the C02 concentration
in this segment of water
becomes too sm~l to find (i.e., zero) very rapidIy.
This
me ttns that the initial
carbonated
water
injected gives up all its C02 to the oil it contacts.
This water then ptoceeds through the reservoir as
plain water. Thus, the C02 moves through the
reservoir more S1OWIy than the flood water. f~ the
oil does not Wove, then in this behavior the carbonated water fIood is an exact analog of the gas
chron-ratograph. This analogy is shown in Table 1.
A gas chromatography analyzes mixtures by noting
the time required for various components to pass
through a fixed chromatographic COIumn. The delay
times for given components are controlled by the
equilibrium relationship
for that component in the
carrier and the fixed liquid phase. Similarly for
carbonated water flooding the time required for a
slug of C02 to pass through the reservoir is controlled by the equilibrium relation for C02 in water
and residiaal oil.
The carbonated water process discussed
in this
cakulation
method is a slug process. Carbonated
water (or a mixture of C02 and water) is injected
into the reservoir until the planned amount, has
been injected. Then the carbonated water slug is
driven forward with plain water. The recovery ..of
oil. is depend&t
upon the behavior of this carbonated water slyg as it moves through the reservoir.
If carbonated w&er of constant composition is in-,
jetted for a fixed period of time and then followed
by plain water, containing no C02, then the slug
wouId enter the formation as a square wave.
As this square wave advances, it changes its
shape. The reason for the change of shape is that
aIl CO z concentrations
do not move at the same
speed. This is due to the kolubility relations of
C02 in oil and water, The volubility curves for a
typical oil and water are shown in Fig. 4.

is,

From these and density data the concentration of

C02 in oil as a function of C02 concentration
in
water (Fig. 5) may be constructed,
For regions
where no oil is moving, the rate of advance of a
given concentration is given by the simple formula
Rate of advance of a concentration
ft/day
Rate of total fluid injection per unit area ft/day=
1

Sw + (I - Sw) (slope of curve on Fig. 5)

On Fig. 5 the slope increases from the origin to
has its maximum value at B, and then decreases
from B to higher concentrations.
Therefore,
for
concentrations
from zero to B, the rate of advance
concentrarioq.
For
decreases
with
increasing
concentrations
from B to C rhe rate of advance
(This
increases
with increasing
concentration.
srgumenr is exact for regions where no oil is
moving. In regions where oil is moving, the general
result is the same but some details are different. )
This
relative
speed concept shows how the
s qusre wave of C02 concentration in water changes

B,

shape as it moves through the reservoir, Fig. 6.

The latrer shape of Fig. 6 is a physical impossibility, for it showa two values of the concentration existing at the same point in the reservoir.
The interpretation
of this is that a discontinuity
(shock or front) forms to eliminate this multiple
value of the concentration, Two such di scontinuities
form, one at the leading side of the carbonated
water slug and the other at the trailing side, When
the se discontinuities
are drawn in, the slug takes
on the shape shown in Fig. 7.
This is the general shape of a carbonated water
through a reservoir. If the maximum
were chosen
ac successively
CO z concentration
lower value a, the shape of the carbonated water
slug would be as shown in Fig. 8. In general, the
trailing edge of the slug moves faster than -the
leading edge. Seen another way, as che slug moves
through the reservoir,
it spreads out so that the
total amount of C02 in the slug comes to be concentrate ed in the leading (lower) concentrate ion S.
The history of such a slug as it moves through a
reservoir might be as shown in Fig. %
SI

ug

moving

EFFECT

T = CONSTANT

OF VARYXNG SLUG SIZES

From the problems studied to date, it appears

that a trailing
shock always forms. This fact
greatly simplifies the computation of the effect of
I
RE(JKJN

~REGJON\ RE~jON

REGION
I

~ REfK)N

,.

i
---------

SATURATION

FIG. 4

PRESSURE

SOLUEtILITY OF
TYPICAL

OF

-..

----,

C02

C02 IN WATER
OIL.

AND

A
3

DISTANCE

o
~

FIG. 7

z
g
1--1

SHAPE OF A CARBONATED

IF MAXIMUM
z_

g:
WA

T , CONSTANT

*ATM?

SLUG.

CONCdNTRATION

=x

fl:
~:

IF

MAXI

M~h$

CONC~NTRATION

CO=

CONCENTRATION

IN WATER

LB/BBL

IN OIL AS A FUNC C02 CONCENTRATION

TION oF C02 CONCENTRATION
IN WATER.

HI(L

.5

DISTANCE,

FIG. 8 SHAPE Or, A CARBONATED WATER SLUG

FOR LOWER C02 CONCENTRATIONS.

ORIGINAL
SHAPE

&

DISTANCE

FIG, 6

CHANGE IN SHAPE OF A SQUARE WAVE OF

,C02 CONCENTRATION
IN WATER.

FIG, 9
SLUG

HISTORY

D18TANCE

OF

cARBONATEi
WATER
A RE9ERVOIR.

AS XT MOVES mOUGH

SOCIETY OF PETROLEUM ENcxNEErt9 JouaNAL

14
,.

,,
-.

.,.

.
,---

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. .._

-.
slug size. Because of this trailing shock the leading part of the C02 invaded zone does not know
what happens behind it until the trailing shock
catches up with it.
This point is very important. In the mathematical
treatment used, it ia assumed that the fractional
flow of either phsse, at any point, depends only
on conditions at that point, This means that changing the composition of the injection fltiid cannot
immediately
change the flow anywhere except at,
the injection point. The. effect of any such change
wiIl be felt progressively
further from the injection
wellbore at later times, as the changed composition
propagates
itself.
One may consider the mathematical picture physically
as follows: by Darcys
equation the flow in a porous medium is

*1OW
==

- Pressure

gradient x permeability
Viscosity

If ihe injection
rate is held constant
while
injeqtion
fluid composition
changes,
then the
pressure gradient is practically
constant. For any
one phase the permeability in the above equation is
a function of saturation,
and the viscosity
1s a
function of fluid composition. Thus, the effeqt of
a change in injection fluid composition is propagated
only as fast as changed saturations
and compo sitions move from the injection well.
Now consider how a change in C02 concentration
from some finite value to zero propagates
itself.
Because of the equilibrium relationship,
Iow:. concentrations
move faster than high concentrations.
This leads to a shock discontinuity
in concentrations.,
Taking th~ viewpoint of a man riding with the
shock, one observes the following:: As the !shock
advances the total amount of reservoir rock behind
it increases,
i.e., rock flows through it. .The toral
volume of residual
oil behind the shock also
so oil flows through the shock. The
increases,
volume of water injected is greater than ~ rate
of volume- incr~ase behind the shock,
so; water
. flows forw~:; through the shock: The oil flowing
$ through the shock gives up its C02 to the water
flowing through the shock.
This transfer of C02 sets the speed of the shock;
if the shock moves faster than the C02 t&nsfer
allows, $he oil flowing through could not give up
all its C% to the water and-the region behind the
shock
would become carbonated.
If the shock
moved slower, the reverse -would happen.
The exact same phenomenon may be viewed
another way consider a C02-invaded region with a
C02 concentration-distance
diagram as shown in
Fig. 10. As this region moves through the fo~mation
it grows in length. This must happen,
because
low coricentrations
mov~ faster than hizh ones.
However, if it grew in ~ength without, a~y &her:
chsnge, the total amount of C02 in it would have
to increase. This is im~ossible, For the region to
grow in leiigth some concentrations must disappear.
Since C02 flows forward from regions of high concentration to regions of. low concentration,
the high

concentration
regions at the rear di aappear. They
give up their C02 to the water flowing forward to
the regions of low concentration.
These
considerations
all lead to one general
conclusion,
namely that tile production curve for
continuous
injection
also spplies
for all slug
sizes;
the production curve is followed until all
the C02 injected has co~e out of the formation.
Then no more C% com&s out and the plain water
equations apply, However, the tesidual saturations
will generally
be so Iow that the oil flow is
negligible.
Note that this procedure gives absurd results
as the slug size approaches zero. This behavior
and its explanation were discussed previously.
Note also that the effect of varying slug size is
much more complicated if a sharp trailing shock
does not form. In that case the same production
curve wilI not spply for all slug sizes up to the
point where the last of the C02 comes out of the
formation. This situation for immiscible enriched
gas drives is entirely analogous. If the concentration of enriching component forms a sharp trailing
front, then the effect of slug size will be exactIy
as shown here for ubonated water flooding. From
. a few preliminary enriched gas drive calculations
it appears that such a trailing shock does not
always forni for enriched gas drives, whereas it
aIways forms for carbonated water floods.
Note that concentrations
in the leading edge of
so
the C02 slug move with constant velocity,
that the leading edge obeys the stretching principle
of Buckley-Leverett
theory The traiIing edge moves
with a variable velocity (governed by the C02
material balance),
ao that it does not obey this
stretching
principle.
This is disctissed
in the
addendum.
,,
CONSTRUCTION

OF SOLUTION

From ~his intuitive view of the progress of a

csrbo~ared
water slug through the reservoir, the
calculated
solution
is constructed,
The C02concentration-in- water
vs di st snce diagram
is
divided into five regions as shown on Fig. 7.
In Regions I and ~ there is no C% present, so
the solution must be the same as for a plain water
ffood. The Buckley-Leverett
equation is used for
these regions. In Region III the C02 concentration, is constant.
Therefore, the solution is the
same as for a plain water flood, except that the

FIG. 10

CO ~

M.4RCH,,1964
,
.,

CONCENTRATION=DISTANCE
GRAM,
.

DIA-

1s

.,,

,.

,,
.. .

. . .

..

..

....

../

the carbonated
waterflood performance
of both
crudes, so differences
would be due only to oil
properties.
The calculated performance for Loudon
crude is Fig. .13.

water and oil properties

correspond to csrbimated
oil and water at the msximum C02 concentration.
In Regions
11 and IV, C02 concentration
is
Here differential
material
changing with distance.
balances for each component (water, oil and C02 )
are solved to give the saturation And concentration
vs distance plot. The method is quite similar to
that developed by Welge, et al,b for enriched gas
drives.
At the boundaries
between Regions II and III
in C02
and IV and V there are discontinuities
concentration.
The three material balance equations
(one each for water, oil and C02) for each of these
discontinuities
are solved to obtain the conditions
before and after each discontinuity.
Joining the solutions for the five regions yields
sat~ation-vs-distmce
and C02the
complete
From this are
concentration-vs-distsnce
picture.
constructed
the C02 and oil production
curves
which are the final form of the calculated result.
The calculation
method is discussed
in more
detail in Appendix,

DISCUSSION OF THE
CALCULATED
RESULTS

Based on these and other sample calculations

it
that:
appears
1. Viscosity
reduction is the most important
mechanism
by which carbonated
water recovers
more oil than plain water. For example, consider
Table 2 for San Joaquin Valley crude and 1 ton/
1,000 bbl slug size. Large increments in oil recovery accompany large changes in viscosity,
2. Swelling of crude oil due to dissolved C02
appears to be a minor factor in incremental oil
recovery.
Based on the few cases studied,
it
appears
that. carbonated
water flooding will not
be economical for crudes which swell strong~y on
carbonation
but which do nor have a significant
viscosity
reduction.
For example, the Loudon
c~de at 850 psi CO z pressure swells tti 1,4 times
its original volume. Nonetheless,
at r slug size
of 1 ton/1,000 bbl, its calculated incremental oiI
recovery due to C02 is only 0.041 P.V.
3. Based
on calculations
not shown here, it
appears that the shape of the high-Sw end of the
kU/ko vs Sw curve is vety important. Assume that
a WOR of 100 represents
the economic limit for
a water flood. Then if oil viscosity/water
viscosity
is 100, the terminal Sw is that at which k.,V/k.o = 1.
If the oil viscosity is reduced by a factor of 10,

SAMPLE CALCULATIONS

Sample calculations
are included for two oils, a
viscous, low-gravity San Joaquin Valley crude and
a mobile, high-gravi~ mid-continent crude.
The C02 volubility,
swelling
and viscosity
reduction of the San Joaqu.in Valley crude are shown
in Figs. 11 and 3. The permeability ratio curve is
Fig. 12. The calculated wqter flood and carbonated
waterflood performance for this field is, Fig. 2.
The mid-continent crude. chosen was the Loudon
Crude. Data. on its C02 volubility, swelling and
visco sit reduction were presented by Beesom and
Ortloff. 7 This crtide has a much higher C% volubility
and swelling
than the San Joaquin Valley crude,
and a 10wer percentage
viscosity
reduction,
for
comparable saturation ~reqsure$. The same permeability ratio curve (Fig. 12) was used to calculate

1000

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9ATRAT

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GOR AND
FIG. 11 SAN JOAQUIN VALLEY C~~E
PRESSURE,
SWELLING FACTOR VS SATURA~ON

FIG.

12 PERkkABILITY
SAN JOAQUIN VALLEY
sOCIETY

16 ~

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RATIO
CURVE
CORE M@SERIAL.

FOR

OF PETROLEUM ENCXNSERS JOuRN.+L

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WFK

VOLUMES

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For regions where C02 concentration
is changing
with distance .(Regions U and IV on Fig. 7), there
are thrqe simultaneous
equations number 1, one
each for water, oil, and C%. The solution to
these equations is almost identical to that obtained
by Welge, et al, 6 for enriched gas drives.
There are jump discontinuities
in saturation at
the Region V-IV boundary and the Region 111.11
boundary (see Fig. 7). The solution for the Region
V-IV is easily obtained because there is no C02
present in Region V. Eq. 2 written for C02 becomes

AFPENDIX
DETAILS OF CALCULATION

perf~rmance data are obtained

The calculated
by using only two basic equations; one material
balance equation for regions of continuous change
of saturation
and a different material balance
equation
for jump discontinuities
in saturation
These equations are:
L For continuous saturation
,.

...

2. For jump discontinuities

:$=

-()

. . . . . . . .*

*...@

.(2)

O.*.*,

For regions where there is no change in C02

concentration
(Regions I, III, and V on Fi& 7),
Eq. 1, written for water, reduces to

, .;

. . . . . . .. . . . .

.(3)

*Materld supplementary
to this paper has been deposited as
Document No. 77sS with the ADI Arufllary Publications
Project,
Photcdupllcation
Svc,, Library of Cmgreea,
Weehington,
D. C.
A copy may .be obtained by citing the Document number and by
remitting $ 16.2S for photoprlnts,
or $5.00 for 35mm microfilm.
Advance payment IS re qufred. Make checks or money orders
payable
tot
Chief,
Photodqrlic.stban
service,
Libr8?Y
of
C0ngresr4.

(2LJ . _ :(:),
the basic equation of the Buckley-Leverett

,..

For che Region 111~11boundary there are three

equations
number 2 td satisfy,
as weil as the
BuckIey-Leverett
equation on the Region III side,
and the corresponding
equation on the Region H
side. This leads to five nonlinear equations in
five unknowns. Their solution is the most timeconsuming part of the problem.
The detailed derivation of the equations used
and detailed calculations
for one of the sample
problems are contained in an addendum to this
paper. *

theory. 5

DISCUSSION
L, W. HOLM
v MEMBER

AIME
~

,1

THE

The anaIogy to gas chromatography used by the

author is art excellent way to describe the transport
of C02 in a carbonated water flood. Baaed upon this
analogy,
the author has developed a calculation
method which shows the effect. of carbonated water
slug size and C02 concentration
on oil recovery.
However, I believe the practical use of the method
is limited because the calculat~d fesults predict
that additional oil cah be obtained by carbonated
water flooding even though the carbonated water slug
size approaches zero.
The author has recognized that this is a paradoxical %atalt
obtained by the proposed calculation
method and attributes it ro two assumptions which
are not valid for small slug sizes, i.e.: (1) that at
any given point in the reservoir, the oil and water
phases are always in C02 equilibrium, and (2) that
molecular and convective diffusion of CQ2, in the
/
la

OIL CO,
LAKE,

ILL.

direction ,of flow are negligible.

I agree with this
explansriim.
He. states further that the lower slugsize limit ,to which the method applies is not known.
This presents a problem in using the method. The
aurhor
suBgests
a procedure
to determine the
economic slug size and claims that this eliminates
the need for determining the lower Iimit.
Such a procedure could gi<e @aleading results
economic
slug
size. is
because
the suggested
determined from the calctdated
oif production and
carbon dioxide curves, whiph admittedly are in error
Consequently, neither
at the low C02 requirements.
the econcimic slug size, nor the smallest slug size
for which, the method will predict the correct oil
recoyery, can be determined by the method in its
present fo~~.
We have conducted experimental, carbonated water
floods on cores up to 8. ft long and have found that
SOCIETY OF PET+ OLEUfd 13
NGINEEitS JOUftNAL

.-

PURE

CRYSTAL

.
.-

..
=..,...

-,

-..

only a smsll amount of additional high viscosity oil

(less than 15 per cent) was recovered over that
obtained by a conventional water flood, when about
2 tons of C% /1,000 bbl of pore volume was used.
This corresponds to a carbonated water slug size of
at least 20 per cent PV. By contrast, the proposed
calculation
method predicts that about 40 per cent
additional
high viscosity
oil would be recovered
over a conventional water flood by using only 1 ton
of C02 /1,000 bbl of pore volume. With low viscosity
oils (about 5 cp or less) our experin.sntal results
agreed with de Nevers ca~culaeed results
only in
the range of carbonated water slug sizes above
abbut 50 per cent W [about 4 tons of C02/1,000
bbl of pore volume). With the larger slug sizes, we
obtained ultimate recoveries of both low and high
viscosity
oils which corresponded very closely to
those predicted by the calculation method. However,
in that portion of the curves representing the esrty
stages of the floods, the shape of our experimental
oil recovery curves differed from the calculated
curve (aee Fig. D4).
In order to obtain a significant improvement in oil

,,

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%%%wmwl
~111

w040b

MLotk
101AL

PORE

&NUIW!UkL

I*lhl*dot;
VOLLWS

W&

neck ~

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ti*

[*

lNJSCIEO

FIG. D-1 EXPERIMENTAL AND CALCULATED OIL

RECOVERY CURVES
recovery we have found that the amount of C02 used

must exceed a certain minimum; this is true for

, liquid or dense-gas C02 slugs as well as for carbonated water floods. It appears then, that either the
effects
of diffusion or non-equi Iibrium must be
included in thip calculation method for it to be valid
for all carbonated
water slug sizes,
or else
experimental
work must be conducted to determine
the minimum slug size at which this method applies.

, AUTHORS REPLY TO L. W. HOLM

I would like to thank L. W. Hohn for his constructive discussion. He and I agree about the paradoxical
predictions
for small slug sizes and their most
plausible explanation. I second his suggestion that
a calculation method which included th+ effects of
diffusion and non-equilibrium would be a significant
over the method presented
here.
improvement
Research
work to provide - the necessary
data for
that improvement is in the planning stage in the
Chemical Engineering Dept. of the U. of Utah. The
method presented here is, like most engineering
approximations,
an interim method to use until we
know enough to make absolutely accurate predictions.
carbonated
waterflood
data
The
laboratory
presented
by Helm are of great value.
The
publication
of more such data, along with data on
the concentration of C02 in the produced fluids vs
pore volumes injected, would increase our understanding of carbonated water fIooding.
Helms
8-ft-core data with small carbonated
water-shag sizes reinforce the papers warning that
caution is needed in applying the method at small
slug sizes.. However, I question his conclusion that
~e calculation
method gives incorrect predictions
for field performance at slug sizes of about 2 tons/
1,000 bbl ~f pore volume.
Let us suppose that the mechanism by which a
smaH carbonated water slug becomes ineffective for
recove~
is diffusioh
(including
convective
oil
diffusion) f~om .a high C02 qoncentratipn
to a low
in water. (Low concentrations of
C02 concentration
C02
in water will
not affect oil, the way high
concentrations will. ) The mathematics of diffusion-

combined-wirh-chromarographic-transport
are beyond
our current knowiedge. Let us consider the problem
of diffusion of a C02 slug in water in a reservoir
containing no oil.
Perkins and JoIinson2 have shown that if two such
diffusion experiments. are to have the same plot of
(concentration
of diffuse~ materiaI in effluent) vs
(pore volumes injected), both experiments must have
where KI is the longithe same value of (KI/UL)
U is
tudinal diffusion (or dispersion)
coefficient,
velocity, and L. is the length
the average interstitial
of the porous medium through which the &lffusIon is :
taking place.
For the experiments
to which HoIm refers,
the flood rates were about 5 to 10, ft/day. The
particle
size of his cores was probably about ,
0.001 to 0.01 in. The molecular diffusion coefficient
for C02 in water at 18 C and low concentrations
is
given by Reid and Sherwood3 as about 1.7 x 10-5 sq
cm/sec. If we combine these values in the dimension!.ess group ( Ud /Do), we obtain values of 0.25 to 5.
Here + is t 1 e particle diameter and Do is the
molecular diffusion coefficient.
Perkins and Johnson2 show that for this range of
values of (u4 /D.), K1 is roughly proportional to U,
,
so that K1 /U f, IS roughly proportional to I/L, This
means that to obtain the same (concentration)
vs
(poke volumes injected) curve, for a laboratory test
and a field flood, ~e laboratory core would have to
be as long as the iaverage fIow path in the field.
Furthermore,
Perkitis:and Johnson show that high
values of K1 /UL (~.e~, short flow pathsj correspond
to more severe or here rapid diffusion (on a pore
. .
r
19

tiARCH, 19.64
f,

. .

. . .

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. .

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.,

,,
,-volume basis) than long paths. Thus it appears that
the slug size (based on pore volumes) which is
rapidly diffused to a low concentration
in an 8 h
long core may remain quite concentrated in a 200 to
300 ft long waterflood pattern. If this is true, the
predictions

of the calculation

could be quite wrong

for the 8-ft core flood, as Helm shows, and

correct for the 200 to 300-ft waterflood
reasonably
pattern.
Because of the effect described above, we simply
do not know whether a laboratory carbonated water
flood with a small slug size correctly represents a
field flood. This uncertainty will remain until we:
(1) solve the mathematical problem of chromatographic
transport coupled with diffusion and non-equilibrium,
or (2) obtain adequate laboratory. data on matched
carbonated water floods in which flood path length
is the only variable.
Hopefully,
both of. these
results
will be published soon. Faced with this
the method for selecting
slug size
uncertainty,
proposed in the paper appears more reasonable than
short - core floods to determine
small slug - size
behavior.
For all the, examples calculated
to date by this
method, there is predicted an oil bank which
corresponds to a straight line on a (pore volumes of
oil produced) vs (pore volumes of fluid injected)

plot, from about a PVI of 0.3 to 0.4 to a PVI of 1.1

CO 1.2 (see Figs.
1, 2 and 11). Helms experimental curve for 4.5 tons of C02 /1,000 bbl shows
this behavior, with a downward dip in the production
curve. This dip may be due to capillary end effects.
Surprisingly,
Helms calculated
production curve
does not show t~is straight-line
portion. This may
explain the difference he notes between his experimental and calculated curves.
NOMENCLATURE
DO = molecular diffusion coefficient, sq ft/see,
d; = particle diameter, ft,
K1 = longitudinal dispersion co~fficient, sq ft/see,
L = length of flow path, ft,
U = average interstitial velocity, ft/sec.
REFERENCES
1
<tco~
Requirements in ~z
Sk
and
10 Helm, L, W.:
Carbonated Water Oil Recovery Processes,
Prod.
Mm, (Sept., 1963) 6.
2. Perkins, T. K, and Johnson, O. C. i A Review of
Diffusion and Dispersion in Porous Media, Sot. Pet.
Engt Jora. (March, 1963) 70.
3. Reid, R. C. and Sherwood, T. IL: The Properties of
Gases and LiquideY, McGraw-Hill (195S) 288,
***

.f
8

,.

sOCIiZTY OF P~TROLSUM

20

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ENIXlkEWl

JOURNAL

,,