\

A Calculation Method for Carbonated ‘Water Flooding

CALIFORNIA RESEARCH CORP.
NOEL DE NEVERS*
LA HABRA, CAUF.

ABSTRACT REASONS FOR CARBONATED

WATER FLOODING
A calcdation method has been developed /or The calculation assumes that the addition of
carbonated water flooding. This me tbod takes into carbon dioxide to flood water increases the oil
account the e//ects of oil viscosity reduction and
recovery by two mechanisms:
oil swelling, due to carbon dioxide transjetred to
L Carbon dioxide transfers from the flood water
the reservoir oil from the carbonated flood water.
to the oil, thereby reducing the viscosity of the -
[t shows the e~ect of changes in ‘ carbonation
oil. At the lower viscosity, rhe oil flows more
pressure and carbonated water slug size.
readily and is more easily swept out by flood
The method is based on a Buckley-Leverett-
water. ,
type linear flow model. The nratbemat ical approach
2. The carbon dioxide which transfers to’ the
is similar to that developed by Welge,’ et al, /or
oil phase causes the. oil phase to swell. Assume
enriched gas drives. However, it contains a very
that the residual oil saturation (volume per cent
important advance over the previous papers in its
of pore space) is the same wheiher the oil is
solution to the problem of injection of a “slug” of
carbonated o’r not, Then the same volume will
carbonated water rather than continuous, injection
contain less stock tank oil if it is carbonated, due
O/ /l~id Of constant composition. The method also to oil swelling. The plain water driving the car.
shows the chromatograp bic tiature o/ the transport
bonated water slug forward will strip the C02 out
of CO 2 in a carbonated water flood.
of this residual oil., causing this oil to ahrink. This
Sample calculations indicate that viscosity re.
s wel Iing.followed-by-shrinking leaves behind a
duction is the most important source o/ incremental
lower residual oil saturation than would have been
oil recovery. Swelling contributes to a lesser extent,
left behind by a plain water f~ood. Since some oils
Raising the carbonation pressure increases refovery,
swell CO almost twice their original volume at
but this effect diminishes as pressure is iticreased,
reasonable C02 pressures, rhis effect may be
Increasing the slug ~ize also increases recovery,
large;
bzt again this effect dirhinishes as slug size, is
ITwo additional benefits sometimes claimed for
increased.
carbonated water flooding are:
INTRODUCTION 1. Adding C02 to flood water greatly increases
the water injectivity y in some cases. 1 (Injectivity
In recent years there has been considerable = BPD of water injected/ft of sand x differential
interest in carbonated water f100ding as a, secondary bottom-hole pressure, psi.) C02 forms a weak acid
recovery merhod. Several carbonated waterflood in’ water; injecting carbonated-water is, therefore,
field tests are now in progress. 1-3 Yet there is no somewhat like acid treating. If a formation responds ,
published method for predicting the r~sults of a to acid treating, it will probably have a higher
carbonated water flood. This paper presents a injectivity y for carbonated water than for plain
method for predicting the oil recovery for a carbonated water. Although the increased injectivity increases
water flood. che profitability of a carbonated water flood over a
In a carbonated water flood, a carbonated water plain water flood, it does not qhange the production
slug. is in je’cted into the, reservoir. Then this slug , Cwve based on total fluid injected. Therefore,
is driven forward by injecting plain water behind the method rmsented
. here does. not show any effect
it. The field opera~or must choose the carbonated of increased injectivity. -
water slug size and the C02:water ratio in the 2. It is claimed in one patentq that carbon dioxide
slug. The calculation rntkhod presented here shows will react with some constituents of the oil to
the effects of both sIug ..]ize and CO 2:water ratio form detergent s,’ These detergents are expected to
on o~l recovery, ,/ increase the oil recovery. There is little data
availabIe to support this idea. The calculation
Original manuscript received in society of Peholwn
Enginders office Mar?h 15, 1963, Reyised manuscript received method presented here takes no credit for extra
Nov. 4,’ 1963. Paper- Presented et U. of Oklahoma - $PE oil recovery “due” to the formation of any such
Production ,Researoh Symposium, held fn Norman, Old=., +,
April 29-30, 1963, detergents.
LReferendes given at end Of PaPet.
*Currently at the U, of Utah, Salt Lake City, Ut*.
1
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.,
9
MARCH,1964
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 CALCULATION METHOD recovered from this region flows forward and forms
the region of constant water saturation (or “oil
GENERAL FORM OF THE RESULTS bank”) shown from C to B, Note that the oil in
This method can best be understood by comparing this oil bank contains no C02; this is the extra
its prediction of the behavior of a carbonated water oil. driven ahead of the carbonated zone.
flood with the behavior of a plain water flood, as Now consider the production curve (Fig. ID).
predicted by the Buckley-Leverect method. This From O to B the carbonated water ,flood has the
comparison is shown on Figs. 1, A, B, C and D. same cutve aa the plain water flood. At time B,
Considet first Fig. lB. This shows the water the “oil bank” arrives at the producing well, and
saturation-distance profile for a plain water flood. the WOR remains constant utyil time C. At time C,
At A, the water saturation jumps from Swi to the the leading edge of the carbonated zone reaches the
breakthrough value. Thereafter (A to F) the water producing well. At this time the WOR begins to
saturation increases gradually. “ rise again and the first C02 comes out of the
This is reflected in the cumulative production producing well (Fig. lC).
curve, Fig. ID. For the plain water flood, the oil As the leading part of the carbonated zone is
product;.on rate is high and WOR is low or zero produced (C to E), the WOR increases and the ‘rate
unril water breakthrough (O to A). The oil produc- of C02 production from the producing well increase a.
tion rate declines (A to F) as the WOR steadily Finally,, at point E, the region of maximum carbon-
rises. ation reaches the producing well. Thereafter, the
Now consider rhe carbonated water flood. (For oil production rate falls almost to zero (E to G),
the moment consider steady injection of carbonated and the CO z production rate remains at a practically
water, Later a carbonated water sIug followed by constant, very high rate,
plain water will be discus seal.) As shown in Fig. The carbonated water flood curve above . is
‘IA, the carbonated water advances as a ‘{square constructed for an infinite C02 slug size, i.e.,
wave” (G to E) with a leading wedge (E to C). steady injection of C02 until the end of the project.
(The reason for this leading wedge will be dis- In a “slug” process, the oil production stops, for
cussed later. ) practical, purposes, when the last of the C02 comes
As shown on Fig. lB, this results in a somewhat out of the formatior+ If the total C02 in the carbonated
complicated water- saturat ion-di st &nce curv,~. At water slug is x (as shown in Fig. IC), then at time
the far right, ahead of point B, the result is the D the last C02 comes out of the formation. There-
same as for a plain water flood. To the extreme left after, no more, C02 comes out; you cans not get
. (G to E) in the region of high C02 concentration, more out than you put in. The cumulative-C02-
the water saturation is much greater than it would production curve becomes horizontal at x The
have been for a plain water flood, The extra dil oil production curve also becomes horizontal at
D.
As smaller and smaller csrbrnated warer slug
L E FIGURE1A 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 connect-
E II ‘a WA1E.QFLWD ing their cut-off points for various slug sizes,
s 61II----------------------L-----SW produces a plot of ~he type shown in Fig. 2, for
,one of the example problems to be discussed’ later. ~
OISTL+JCE FROM INJECTION WELL
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
ij!~::::..->’ recoveries; this will also be discussed later.
REQUIRED 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;
OP “ 3, The ‘solubiIity of C02 in reservoir oil as a-
PORE VOLUMES INJECTHJ
function of C02 pressure at reservoir temperature;
FIG. 1 - COMPARISON OF TYPICAL PLAIN AND 4. ‘The viscosity and density of solutions of
CARBONATED WATER FLOODS.

10 sOCIETY OF PETROLEUMENGINEERSJouRNAL

,, .. ---
.,
‘,,
;..,
., --- . .
 C02 in reservoir oil as a function of C02 concentra- in the oil phase at that same point.
tion, at reservoir temperature; 5. In the leading part of the C02-invaded-
5. The volubility of C02 in the flood water as a region, formation gas (mostly methane) is displaced
function of CO 2 pressure at reservbir temperature. from the oil by C02. It is asatrmed chat’the displace-
(For” fresh wat~r, these data are known from the ment of methane by C02 results in the oil viscosity-
literature. For brine, laboratory tests ‘ may be C02 concentration behavior shown in Fig, 3. In
needed~ and other words, displacing methane by C02 causes
6. The viscosity and density of solutions of -the viscosity to fall steadily until the C02 partial
CO z in flood water as a function of CO z pressure. pressure equals the original formation pressure,
(These may be estimated with satisfactory accu- at which point all the methane is assumed to be’
racy). expelled. If Iab data are available on the viscosity
of the crude oil-C02-CH4 system, this assumption
ASSUMPTIONS is unnecessary.
The basic assumptions of this calculation method 6. Molecular diffusion and convective diffusion
are as follows: (dispersion) of C02 in the flow direction are zero;
1. The assumptions of the Buckley -Leveretts i.e., C02 moves forward only by flow of the oil
method are applicable. These are: (a) the perme- and water phases, not by diffusion within them.
ability or porosity variations in the formation may
CHOOSING THE BEST
be neglected; (b) ths formation is a linear system; C02 :WATER RATIO
(c) the fhiids are incompressible; (d) only two phases
are flowing at any one point (i. e., there is no From the production curves for various C02: water
mobile gas phase); (e) the ,initial water and gas ratios, Fig. 2, it appears that higher C02:water
saturations are constant throughout the formation; ratios give higher oil recoveries. G,eneralIy, at
~wip w low ratios increasing this ratio makes a big change
(f) /w = kw/p ~+ ~. 1P. (i.e., capillary’ effects in recovery, at high ratios it makes a smaller
are ignored} and (g) gravity effects may be neglected. change.
2. The amount of oil dissolved in the water The C02 :water ratio for which this calculation
phase and the amount of water dissolved in the oil method works is limited by the formation pressure.
phase are negligible. At a given temperature and pressure the C02-
3. The totaI pressure is high enough that no solubi Iiry-in-water curveg sets a maximum on the

C02 gas phase is formed anywhere in the formation. C% :warer ratio for which no free C% gas is pre sent.
I 4. ,In those parts of the formation where C02 is If a higher ratio is chosen, free C02 gas will be
present, at any given point in the formation, the formed.
oil and water are in equilibrium; i.e., the partial From the ample calculations, it appears that
pressure of C02 in the water phase at any given increasing the C02 :water. ratio always increases
point is the same as the partial pressure of C02 the incremental oil production. Tliis is true up to

0
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:
0
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#
g
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l’ ‘ v’’’’’’’’:’’’’’’’’’’’’’’’’’”’’’”’’’”’’’
‘
0 10 to 30 w
WRC vOL”MES INJCCTEO

FIG. 2 — SAN JOAQUIN VALLEY COMPARISON OF PLAIN AND CARBONATED WATER FLCODS.

1-””.’..”. -’”’.-’””’.”-”””’ “’--””::

 -.

/’

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 BEST
CARBONATED 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 C02-
bubble-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 bubble-
point-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
I
OILv16COSIT
,Waruc
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 prop-
erties 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 C’02
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. C02-
bubble-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 I
and carbon dioxide requirement’ curves the incre-
mental oil recovery per ton Qf incremental
may be calculated for each sltig size.
C02 I
1
By applying appropriate prices to the oil and
C02 and an appropriate time factor, one may cal-
CUIat 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. .
LIMITATIONS OF THIS METHOD
+ ST c OF CALCULATION ! I

-H
This method of calculation makes no provision ,

+ I
— for unswept areaw In this regard it is sintilar to
the Buckley-Leverett methqd for water floods or ,,
CO* ST c gas drives. No@ally when the BuckIey-Leverett
L method is used, empirical correction factors are

II
C02-CH,-57U MIXTURES

~
.M--U
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
.10
0 200 400 600 00 Km m 1600 T to the carbonated water slug size. --
PRESSURE,
This method assumea that the pressure remains y
Fm. 3 — ~SCOSITY OF SAN JOAQUIN CRUDE AND constairt through the reservoir or at least the pres-
. CH4 OR C02. , ,
. ,,’.
la SOCIETY OF PETiiOLEUM ENGINEERS JOURNAL B
.’,

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sure remains high enoujzh so that no free -- gks phase
is firrmed. In practice, ‘this is unlikely. The reser-
voir 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
increased oil production or more rapid oil pro-
duction 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 water’s
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
C02 concentration. This makes the mathematics
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
high-viscosity crudes (9o ““ cp); Thus, for Idw-
viscosity etudes the predictions of the method
presented here do not appIy to the C02-foHowed-
by-water process. For high-viscosity crudes the
method presented here should give a fair approxi-
mation 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
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 solubi’lity of C02 in oil is two to ten times as
large as its volubility in water at the same con-
ditions.)
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
in 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 car-
bonated 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 con-
trolled 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 “car-
bonated 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.
‘

not include such phase behavior.

TABLE I - ANALOGY TO GAS CHROMATOGRAPH
As mentioned above, the calculated results for
very small slug si ze’s are not considered reliable. Gas Carbormtad
Chromatography Water Flood

‘;ixow solid su~:~t, e.g., .&shed fire Rorwvolr rock .

DISCUSSION OF THE CALCULATION
Fixed liquid Absorbent, e.g., asphait, or Reqldual IN
METHOD phase silicone 011
‘ BERAVIOR OF CAREON DIOXIDE” Nonabswb=d Helium or nitrogen water
carrier
IN A R&3ERVOIR
Transferred Sampl,e’being analyzed “ CO ~
Having seen the res&s of the calculation;’ con- component

MARCiit;1964 ,.
is, .

,’, ‘.

,.. . . ..>.
f . .
 From these and density data the concentration of shape as it moves through the reservoir, Fig. 6.
C02 in oil as a function of C02 concentration in The latrer shape of Fig. 6 is a physical impos-
water (Fig. 5) may be constructed, For regions sibility, for it showa two values of the concentra-
where no oil is moving, the rate of advance of a tion existing at the same point in ‘the reservoir.
given concentration is given by the simple formula The interpretation of this is that a discontinuity
(shock or front) forms to eliminate this multiple
Rate of advance of a concentration ft/day
value of the concentration, Two such di scontinuities
Rate of total fluid injection per unit area ft/day= form, one at the leading side of the carbonated
1 water slug and the other at the trailing side, When
Sw + (I - Sw) (slope of curve on Fig. 5) the se discontinuities are drawn in, the slug takes
on the shape shown in Fig. 7.
On Fig. 5 the slope increases from the origin to This is the general shape of a carbonated water
B, has its maximum value at B, and then decreases SI ug through a reservoir. If the maximum
moving

from B to higher concentrations. Therefore, for CO z concentration were chosen ac successively

concentrations from zero to B, the rate of advance lower value a, the shape of the carbonated water
decreases with increasing concentrarioq. For slug would be as shown in Fig. 8. In general, the
concentrations from B to C rhe rate of advance trailing edge of the slug moves faster than -the
increases with increasing concentration. (This leading edge. Seen another way, as che slug moves
srgumenr is exact for regions where no oil is through the reservoir, it spreads out so that the
moving. In regions where oil is moving, the general total amount of C02 in the slug comes to be con-
result is the same but some details are different. ) centrate ed in the leading (lower) concentrate ion S.
This relative speed concept shows how the The history of such a slug as it moves through a
s qusre wave of C02 concentration in water changes reservoir might be as shown in Fig. %

T = CONSTANT EFFECT 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 1
RE(JKJN ~REGJON\ RE~jON ~ REfK)N REGION
I
I
,.
i
-----
----- -.. ----,
SATURATION PRESSURE OF C02

FIG. 4 — SOLUEtILITY OF C02 IN WATER AND A

TYPICAL OIL.
3
J DISTANCE
o
~ FIG. 7 — SHAPE OF A CARBONATED *ATM? SLUG.
z
g
1--1
IF” MAXIMUM CONCdNTRATION
z_
g: =x
WA
fl:
IF MAXI M~h$ CONC~NTRATION
T , CONSTANT “’~:
w

HI(L .5
CO= CONCENTRATION

— C02 CONCENTRATION
IN WATER

IN OIL AS A FUNC-
LB/BBL

DISTANCE,
I
TION oF C02 CONCENTRATION IN WATER.
FIG. 8 — SHAPE Or, A CARBONATED WATER SLUG
FOR LOWER C02 CONCENTRATIONS.

ORIGINAL
SHAPE

FIG, 6 —
DISTANCE

CHANGE IN SHAPE OF A SQUARE WAVE OF

,C02 CONCENTRATION IN WATER.
FIG,” 9 —
SLUG
& HISTORY
AS XT MOVES mOUGH
D18TANCE

OF A cARBONATEi WATER
A RE9ERVOIR.

’14 SOCIETY OF PETROLEUM ENcxNEErt9 JouaNAL

,.

,,
-. .
,--- ..- ...
.,.
 -. . .._
slug size. Because of this trailing shock the lead- concentration regions at the rear di aappear. They
ing part of the C02 invaded zone does not know give up their C02 to the water flowing forward to
what happens behind it until the trailing shock the regions of low concentration.
catches up with it. These considerations all lead to one general
This point is very important. In the mathematical conclusion, namely that tile production curve for
treatment used, it ia assumed that the fractional continuous injection also spplies for all slug
flow of either phsse, at any point, depends only sizes; the production curve is followed until all
on conditions at that point, This means that chang- the C02 injected has co~e out “of the formation.
ing the composition of the injection fltiid cannot Then no more C% com&s out and the plain water
immediately change the flow anywhere except at, equations apply, However, the tesidual saturations
the injection point. The. effect of any such change will generally be so Iow that the oil flow is
wiIl be felt progressively further from the injection negligible.
wellbore at later times, as the changed composition Note that this procedure gives absurd results
propagates itself. One may consider the mathe- as the slug size approaches zero. This behavior
matical picture physically as follows: by Darcy’s and its explanation were discussed previously.
equation the flow in a porous medium is Note also that the effect of varying slug size is
much more complicated if a sharp trailing shock
*1OW - Pressure gradient x permeability
does not form. In that case the same production
== Viscosity
curve wilI not spply for all slug sizes up to the
If ihe injection rate is held constant while point where the last of ‘the C02 comes out of the
injeqtion fluid composition changes, then the formation. This situation for immiscible enriched
pressure gradient is practically constant. For any gas drives is entirely analogous. If the concentra-
one phase the permeability in the above equation is tion of enriching component forms a sharp trailing
a function of saturation, and the viscosity 1s a front, then the effect of slug size will be exactIy
function of fluid composition. Thus, the effeqt of as shown here for ubonated water flooding. From
a change in injection fluid composition is propagated . a few preliminary enriched gas drive calculations
only as fast as changed saturations and compo si- it appears that such a trailing shock does not
tions move from the injection well. always forni for enriched gas drives, whereas it
Now consider how a change in C02 concentration aIways forms for carbonated water floods.
from some finite value to zero propagates itself. Note that concentrations in the leading edge of
Because of the equilibrium relationship, Iow:. con- the C02 slug move with constant velocity, so
centrations move faster than high concentrations. that the leading edge obeys the stretching principle
This leads to a shock discontinuity in concen- of Buckley-Leverett theory The traiIing edge moves
trations., with a variable velocity (governed by the C02
Taking th~ viewpoint of a man riding with the material balance), ao that it does not obey this
shock, one observes the following:: As the !shock stretching principle. This is disctissed in the
advances the total amount of reservoir rock behind addendum. ,,
it increases, i.e.”, rock’ flows through it. .The toral
CONSTRUCTION OF SOLUTION
volume of residual oil behind the shock al’so
increases, so oil flows through the shock. The From ~his intuitive view of the progress of a
volume of water injected is greater than ~ rate csrbo~ared water slug through the reservoir, the
of volume- incr~ase behind the shock, so; water calculated solution is constructed, The C02-
. flows forw~:; through the shock: The oil flowing concentration-in- water vs di st snce diagram is
$ through the shock gives up its C02 to the water divided into five regions as shown on Fig. 7.
flowing through the shock. In’ Regions I and ~ there is no C% present, so
This transfer of C02 sets the speed of the shock; the solution must be the same as for a plain water
if the shock moves faster than the C02 t&nsfer ffood. The Buckley-Leverett equation is used for
allows, $he oil flowing through could not give up these regions. In Region III the C02 concentra-
all its C% to the water and-the region behind the
tion, is constant. Therefore, the solution’ is the
shock would become carbonated. If the shock same as for a plain water flood, except that the
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 ‘con-
FIG. 10 — CO ~ CONCENTRATION=DISTANCE DIA-
centration to regions of. low concentration, the high GRAM, .

M.4RC’H,,1964 1s

, .,, ,,
., ,. ..-
.. . . . . “.. ”.. .. .
‘../’
water and oil properties correspond to csrbimated the carbonated waterflood performance of both
oil and water at the msximum C02 concentration. crudes, so differences would be due only to oil
In Regions 11 and IV, C02 concentration is properties. The calculated performance for Loudon
changing with distance. Here differential material crude is Fig. .13.
balances for each component (water, oil and C02 ) DISCUSSION OF THE
are solved to give the saturation And concentration CALCULATED RESULTS
vs distance plot. The method is quite similar to Based on these and other sample calculations it
that developed by Welge, et al,b for enriched gas that:
appears
drives.
1. Viscosity reduction is the most important
At the boundaries between Regions II ‘and III
mechanism by which carbonated water recovers
and IV and V there are discontinuities in C02
more oil than plain water. For example, consider
concentration. The three material balance equations Table 2 for San Joaquin Valley crude and 1 ton/
(one each for water, oil and C02) for each of these
1,000 bbl slug size. Large increments in oil re-
discontinuities are solved to obtain the conditions covery accompany large changes in viscosity,
before and after each discontinuity.
2. Swelling of crude oil due to dissolved C02
Joining the solutions for the five regions yields
sat~ation-vs-distmce and C02- appears to be a minor factor in incremental oil
the complete
From this are recovery. Based on the few cases studied, it
concentration-vs-distsnce picture.
appears that. carbonated water flooding will not
constructed the C02 and oil production curves
be economical for crudes” which swell strong~y on
which are the final form of the calculated result.
carbonation but which do nor have a significant
The calculation method is discussed in more
viscosity reduction. For example, the Loudon
detail in Appendix, c~de at 850 psi CO z pressure swells tti 1,4 times
SAMPLE CALCULATIONS its original volume. Nonetheless, at r slug size
of 1 ton/1,000 bbl, its calculated incremental oiI
Sample calculations are included for two oils, a
recovery due to C02 is only 0.041 P.V.
viscous, low-gravity San Joaquin Valley crude and
3. Based on calculations not shown here, it
a mobile, high-gravi~ mid-continent crude.
appears that the shape of the high-Sw end of the
The C02 volubility, swelling and viscosity
kU/ko vs Sw curve is vety important. Assume that
reduction of the San Joaqu.in Valley crude are shown
a WOR of 100 represents the economic limit for
in Figs. 11 and 3. The permeability ratio curve is
a water flood. Then if oil viscosity/water viscosity
Fig. 12. The calculated wqter flood and carbonated
is 100, the terminal ‘Sw is that at which k.,V/k.o = 1.
waterflood performance for this field is, F“ig. 2.
If the oil viscosity is reduced by a factor of 10,
The mid-continent crude. chosen was the Loudon
Crude. Data. on its C02 volubility, swelling and 1000

1
1
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 m — — — — —

——
comparable saturation ~reqsure$. The same perme-
ability ratio curve (Fig. 12) was used to calculate
,’
— —
i I0

/
—
4
j ~.

I
i ~ ~, 1

j ~ 1(
— — — —
i
——
6 f
+x KW
G
!! ~ E!
~ b h; 0!
o “
If
‘q /
!j

E
~
~.
; “:
01 — -—
— — —
I
‘z;. i
~
]i
#
00! ——
—
~
f J
$ /
9AT”RAT ION =SSURC WI A
,
-., wrt— -
.. 0?! ‘..
% W*F ● I STNO$ N

FIG. 11 — SAN JOAQUIN VALLEY C~~E GOR AND “ FIG. 12 — PERkkABILITY RATIO CURVE FOR ‘
SWELLING FACTOR VS SATURA~ON PRESSURE, SAN JOAQUIN VALLEY CORE M@SERIAL.

16 ~ s’OCIETY OF PETROLEUM ENCXNSERS JOuRN.+L

,.
. .“
. ..’
. ..
 .

s ,.
P ‘“
s
.$ WFK VOLUMES OF Sm ❑ EcQvERtsO
 ,,

AFPENDIX For regions where C02 concentration is changing

with distance .(Regions U and IV on Fig. 7), there
DETAILS OF CALCULATION are thrqe simultaneous equations number 1, one
each for water, oil, and C%. The solution to
The calculated perf~rmance data are obtained
these equations is almost identical to that obtained
by using only two basic equations; one material
by Welge, et al, 6 for enriched gas drives.
balance equation for regions of continuous change
There are jump discontinuities in saturation at
of saturation and a different material balance
the Region V-IV boundary and the Region 111.11
equation for jump discontinuities in saturation
boundary (see Fig. 7). The solution for the Region
These equations are:
V-IV is easily obtained because there is no C02
L For ‘continuous saturation
present in Region V. Eq. 2 written for C02 becomes
,.
*

2. For jump discontinuities ... ,.. , .; . . . . . . .. . . . . ● .(3)

:$= For che Region 111~11boundary there are three

-() equations number 2 td satisfy,

BuckIey-Leverett
as weil as the
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 time-
consuming part of the problem.
The detailed derivation of the equations used
. . . . . . . .* *...@ .(2)
O.*.*,
and detailed calculations for one of the sample
For regions where there is no change in C02 problems are contained in an addendum to this
concentration (Regions I, III, and V on Fi& 7), paper. *
Eq. 1, written for water, reduces to *Materld supplementary to this paper has been deposited as
Document No. 77sS with the ADI Arufllary Publications Project,

(2LJ . _ :(:), Photcdupllcation Svc,, Library of Cmgreea, Weehington,

A copy may .be obtained by citing the Document number and by
remitting $ 16.2S for photoprlnts,
D. C.

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
the basic equation of the Buckley-Leverett theory. 5 C0ngresr4.

DISCUSSION

L, W. HOLM
v MEMBER AIME
~ ,1 THE
CRYSTAL
PURE OIL CO,
LAKE, ILL.

The anaIogy to gas chromatography used by the” direction ,of flow are negligible. I agree with this
author is art excellent way to describe the transport explansriim. He. states further that the lower slug-
of C02 in a carbonated water flood. Baaed upon this size limit ,to which the method applies is not known.
analogy, the author has developed a calculation This presents a problem in using the method. The
method which shows the effect. of carbonated water aurhor suBgests a procedure to determine the
slug size and C02 concentration on oil recovery. economic slug size and claims that this eliminates
However, I believe the practical use of the method the need for determining the lower Iimit.
is limited because the calculat~d fesults predict Such a procedure could gi<e @aleading results
‘that additional oil cah be obtained by carbonated because the suggested economic slug size. is
water flooding even though the carbonated water slug determined from the calctdated oif production and
size approaches zero. carbon dioxide curves, whiph admittedly are in error
The author has recognized that this is a paradoxi- at the low C02 requirements. Consequently, neither
cal %atalt obtained by the proposed calculation the econcimic slug size, nor the smallest slug size
method and attributes it ro two assumptions which for which, the method will predict the correct oil
are not valid for small slug “sizes, i.e.: (1) that at recoyery, can be determined by the method in its
any given point in the reservoir, the oil and water present’ ‘fo~~.
phases are always in C02 equilibrium, and (2) that We have conducted experimental, carbonated water
molecular and convective diffusion of CQ2, in the floods on cores up to 8. ft long and have’ found that
/“
la SOCIETY OF PET+ OLEUfd 13
NGINEEitS JOUftNAL
4
,“ ,
..
.— =..,... -, -..
.- .’- .
 7
only a smsll amount of additional high viscosity oil
(less than 15 per cent) was recovered over that m
obtained by a conventional water flood, when about %%%wmwl ---.-—.
2 tons of C% /1,000 bbl of pore volume was used.
~111 I &NUIW!UkL W& neck ~ I
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
n I 1 I I I I I I 1 I I I
oils (about 5 cp or less) our experin.sntal results w040b MLotk I*lhl*dot; ti* [*

agreed with de ‘Nevers’ ca~culaeed results only in 101AL PORE VOLLWS lNJSCIEO

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
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 car-
bonated 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.

, AUTHOR’S REPLY TO L. W. HOLM

,,

I would like to thank L. W. Hohn for his construc- combined-wirh-chromarographic-transport are beyond
tive discussion. He and I agree about the paradoxical our current knowiedge. Let us consider the problem
predictions ‘for small ‘slug sizes and their most of diffusion of a C02 slug in water in a reservoir
plausible explanation. I second his suggestion that ‘containing no oil.
a calculation method which included th+ effects of Perkins and JoIinson2 have shown that if two such
diffusion and non-equilibrium would be a significant diffusion experiments. are to have the same plot of
improvement over the method presented here. (concentration of diffuse~ materiaI in effluent) vs
Research work to provide - the necessary data for (pore volumes injected), both experiments “must have
that improvement is in the planning stage in the ‘ the same “value of (KI/UL) where KI is the longi-
Chemical Engineering Dept. of the U. of Utah. The tudinal diffusion (or dispersion) coefficient, U is
method presented here is, like most engineering the average interstitial velocity, and L. is the length
approximations, an interim method to use until we of the porous medium through which the &lffu’sIon is : ‘
know enough to make absolutely accurate predictions. taking place.
The laboratory carbonated waterflood data For the experiments to which HoIm refers,
presented by Helm are of great value. The the flood rates were about 5 to 10, ft/day. The
publication of more such ‘data, along with data on “particle size” of his cores was probably about ,
the concentration of C02 in the produced fluids vs 0.001 to 0.01 in. The molecular diffusion coefficient
pore volumes injected, would increase our under- for C02 in water at 18 C and low concentrations is
standing of carbonated water fIooding. given by Reid and Sherwood3 as about 1.7 x 10-5 sq
Helm’s 8-ft-core data with small carbonated cm/sec. If we combine these values in the dimension-
water-shag sizes reinforce the paper’s warning that !.ess group ( Ud /Do), we obtain values of 0.25 to 5.
caution is needed in applying the method at small Here + is t 1 e particle diameter and Do is the
slug sizes.. However, I question his conclusion that molecular diffusion coefficient.
~e calculation method gives incorrect predictions Perkins and Johnson2 show that for this range of
for field performance at slug sizes of about 2 tons/ values of (u4 /D.), K1 is roughly proportional to U,
1,000 bbl ~f pore volume. so that K1 /U f“, IS roughly proportional to I/L, This ,
Let us suppose that the mechanism by which a means that” to obtain the same ‘(concentration) vs
smaH carbonated water slug becomes ineffective for (poke volumes injected) curve, for a laboratory test
oil ● recove~ is diffusioh (including convective and a field flood, ~e laboratory core would have to
diffusion) f~om .a high C02 qoncentratipn to a low be as long as the iaverage fIow path in the field.
C02 concentration in ‘water. (Low concentrations of Furthermore, Perkitis:’and Johnson show that high
C02 in water will not affect oil, the way high values of K1 /UL (~.e~, short flow pathsj correspond
concentrations will. ) The mathematics of diffusion- to more severe or “here” rapid diffusion (on a pore
. . r
tiA’RCH, 19.64 19

f,

. . . . . . ‘\ ::. ”J ‘. . -.”.”’ -“:.*

 ,, .,

,--
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
reasonably correct for the 200 to 300-ft waterflood
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
uncertainty, the method for selecting slug size
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). Helm’s experi-
mental 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, Helm’s calculated production curve
does not show t~is straight-line portion. This may
explain the difference he notes between his experi-
mental 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’
10 Helm, L, W.: <tco~ Requirements in ~z Sk and
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

,.”

20 sOCIiZTY OF P~TROLSUM ENIXlkEWl JOURNAL

-.. ,,