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Miscible Displacement in a Multiphase System GARY GENE R. THOMAS* COUNTRYMAN** H. JUNIOR MEMBERS AIME
Miscible Displacement in a Multiphase System GARY GENE R. THOMAS* COUNTRYMAN** H. JUNIOR MEMBERS AIME

Miscible Displacement in a Multiphase System

GARY

GENE

R.

THOMAS*

COUNTRYMAN**

H.

JUNIOR MEMBERS AIME

IRVING FATT

MEMBER AIME

ABSTRACT

Miscible displacement in both the wetting and non- wetting phase has been studied in two-phase systems. Experimental data show that dispersion is a function of saturation and cannot be predicted from dispersion theory developed for single-phase miscible displace- ment. Some of the effect of saturation on dispersion is a result of the development of dead-end pores or a dendritic pore structure in multiphase systems. The presence of dead-end pores or dendritic structure is confirmed by pressure transient studies.

INTRODUCTION

Displacement by flooding with a miscible liquid is a possible means for recovering the estimated two-thirds of the oil that remains behind after primary production. The immense economic importance of a process that can recover such large quantities of oil has led to extensive laboratory studies of miscible displacement. As usual in production research, most laboratory studies of miscible displacement have not attempted to reproduce all of the conditions existing in a petroleum reservoir. In the early stages of inves- tigation the need has been for information on the broad, basic principles of the phenomena involved in miscible displacement. The effects of overburden pressure, reservoir temperature, and wettability have been considered of secondary importance. However, one property of a petroleum reservoir which is expected to be of major importance and yet has been omitted from many laboratory studies is the presence of inter- stitial water. Two possible effects of interstitial water on the displacement mechanism in the hydrocarbon phase immediately come to mind. First, from the generally accepted theory that capillarity governs the distri- bution of oil and water in porous rock one would expect that for water-wet rock the water will be in the small pores and oil in the large pores. A miscible displacement of oil carried out in the presence of water is operating in a pore size distribution shown in Fig. lb, whereas if the same test had been performed with only one phase present the pore size distribution

Original manuscript received in Society of Petroleum Engineers office Dec. 4, 1962. Revised manuscript received March 21, 1963.

*Presently

associated

with

California

Research

Corp.

**Now

associated with Continental Oil Co., Ponca City,

Okla.

**Now associated with Continental Oil Co., Ponca City, Okla. U. OF CALIFORNIA BERKELEY, CALIF. is as

U. OF CALIFORNIA BERKELEY, CALIF.

is as shown in Fig. lao Although there is not yet a theory of miscible displacement which explains in detail the effect of pore size distribution, one would expect the differences between Figs. la and lb to influence the displacement efficiency. A second factor which may make a multiphase system different from a single-phase system is the presence in the multiphase system of dead-end pores or dendritic structure. Experiments of various kinds on reservoir rock have led to the belief that all pores in the network structure of a porous rock take part in conducting fluid during single phase fluid flow. 1 ,2 There are then no dead-end pores and no fingers or dendritic structures containing stagnant fluid. In a multiphase system, however, the second phase may

lReferences given at end of paper.

(/)

w

a:

o

Q.

l>

o

a:

w

m

;::!;

::J

Z

at end of paper. (/) w a: o Q. l> o a: w m ;::!; ::J

----------~------l

Oll

o

RADIUS-

A.

FIG.

FIG.

la

(/)

w

a:

0

Q.

l>

0

a:

w

m

;::!;

::J

Z

-

0

Ib -

PORE SIZE DISTRIBUTIONS FOR FLUID IN A SINGLE PHASE SYSTEM.

PORE SIZE DISTRIBUTIONS FOR FLUID IN A SINGLE PHASE SYSTEM. 0 RADIUS- B. PORE DISTRIBUTION OCCUPIED

0

RADIUS-

B.

PORE DISTRIBUTION OCCUPIED BY NON- WETTING PHASE IN SAME SYSTEM.

189

trap single pores of the other phase or may even isolate large fingers or dendrites containing the other phase. These dead-end pores or dendrites are stagnant peninsulas which communicate with the flowing fluid only by molecular diffusion. Reports of the effect of dead-end pores or dendritic structures on flow in multiphase systems are not frequent in the literature. Fatt 2 has used a network model to estimate the effects of dead-end pores on relative permeability. Orlob and Radhakrishna,3 and Biggar and Nielsen 4 have studied the effect of trapped air on the displacement of water by water in a sand pack. Raimondi, et aI,5 have studied the effect of water saturation on mixing during miscible displace- ment in both water and oil phases. Goddard, et aI,6 have concluded from electrical conductivity and dif- fusion studies that the nonwetting phase has a den- dritic structure and that a "considerable" fraction of the nonwetting phase volume contributes little or nothing to its fluid conductivity. We present in this paper results of miscible dis- placement studies on porous rock containing water and oil in which displacement efficiency was observed independently in the water and oil. The observed dependence of displacement efficiency on saturation is interpreted to indicate presence of dead-end pores or dendritic structure. Pressure build-up data for the nonwetting phase fluid confirm the presence of dead- end pores.

WETTING PHASE

EXPERIMENTAL

All displacement studies were carried out on Boise

sandstone. This is a relatively clean, uniform sand- stone quarried in Boise, Idaho. The samples used in this work had a permeability in the range 1 to 2 darcies and porosity 23 to 26 per cent. Capillary pressure and relative permeability curves are given in Refs. 7 and 8. The flow system was a bar of sandstone 5 ft long and 2 x 2 in. cross section. The bar was cast in epoxy resin to give a Yrin. thick covering on all sides. Details of the casting procedure and the ap- pearance of the finished flow system are given in Refs. 7 and 8. For displacements in the water phase a Penn State arrangement was used. Water and oil were flowed through the core simultaneously from a pair of con- stant flow rate piston pumps. The oil phase was a commercial mixed hexane. The tagged water was a solution of 156 gm sucrose and 165 gm methanol per liter of solution. This solution had a density of

room

Formaldehyde was added

as a bactericide to the sucrose-methanol solution and to the distilled water which displaced it in the flow tests. Formaldehyde concentration was about 0.5 per cent. The water solution and hexane were equilibrated before use by mixing each with a small quantity of the other. The sucrose-methanol solution acts as double tagged water, introduced by Handy,9 in which the methanol is a fast diffusing tracer to indicate both

temperature (about 72 F).

1.0364

gm/cc and a

viscosity of 2.23 cp

at

190

mixing and molecular diffusing while the slow diffusing sucrose shows only the effect of mixing. Refractive index and density of the effluent water were used as

a measure of sucrose and methanol concentration. From known solutions it was found that sucrose concentration in grams per liter was given by

S

1, BOd + 4.59R

-

1, 112.

(1)

=

.

.

and methanol concentration in gm per liter by

M

=

-3, 767d + 14.4R + 3,781

.

.

.•

(2)

All figures in the above coefficients are significant and must be used for acceptable accuracy. The error in concentration measurement using Eqs. 1 and 2 was estimated to be not greater than 3 or 4 per cent.

were adj usted to

The water and hexane flow rates

give a water-oil ratio that would give the desired water saturation as read from the kw1ko curve for the flow system. Flow rates and saturations are given in Table 1. When the effluent water-oil ratio was constant the water in the input flow lines and in the dead space at the input face of the sandstone bar was replaced by sucrose-methanol solution. The input water flow line was then switched to the pump con- taining the sucrose-methanol solution and collection

of the effluent was started. Samples collected ranged

from 3 to 10 cc depending upon the rate of change of concentration. According to the kw1ko curve given in Fig. 1 of Ref. 7 there will be a small change in water saturation

when water-hexane input is changed to a sucrose solution-hexane input. This is because of change in water-oil viscosity ratio from 3 for water-hexane to 6.7 for sucrose solution-hexane. This change in water saturation will be greatest for the system shown in Fig. 5, where Sw is 55 per cent, because the kw1ko curve is changing more rapidly with satu- ration than for the multiphase systems shown in Figs. 3 and 4. However, even this maximum change, at Sw = 55 per cent, is only about 2 percentage units. Water saturation may have been reduced to 53 per cent from 55 per cent when water-hexane was switched

to sucrose solution-hexane. This uncertainty in water

saturation probably does not affect the conclusions drawn from the experiment. The effect of the water picked up at the front and moved ahead would be to shift the curves of Fig. 5 to the right so that curves

"corrected" for this effect would be even further to the left, thereby making even more distinctive the differences between Figs. 4 and 5.

TABLE 1 -

WATER-OIL FLOW RATES AND SATURATIONS

FOR BOISE SANDSTONE DURING WATER-WATER MISCIBLE DISPLACEMENT TESTS

Water flow rate cc/sec

Oil flow rate cc/sec

Frontal advance

ft/day

Sw per cent

0.00342

0.06158

3.2

55

0.01539

0.01539

12.5

64

0.06158

o

40.0

80*

0.01539

8.0

100

*Water saturation at residual oil, established by water flooding after the tests at 55 and 64 per cent SIN" Order of tests was

64,

55, 80 per cent S .".

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NONWETTING PHASE

During the water-water displacement studies de-

scribed above, attempts were made to tag the hexane

so that displacement efficiency in the nonwetting

phase could be observed simultaneously. Oil soluble

dyes were tried but found to be unsuitable because

of excessive adsorption in the sandstone flow system.

A second hydrocarbon, such as octane, was also

tested as a tagging material but was found unsatis- factory. The analysis method, refractive index, was

100.------.-------.------.------,

40
40

z

~ 80r-------+-------+-----~6-------4

<l

a::

I-

Z

W

~ 60r-------~------~~----+-----~

o

u

J

<l

Z

(!)

a::

0

lL.

0

I-

z

w

u

a::

w

a

20

OL- ~~

0.800

0.900

EFFECTIVE

PORE

Sw= 100 PERCENT

+-+

SUCROSE

-0--0- METHANOL

L

1.000

~

1.100

~

1.200

VOLUMES

PRODUCED

FIG.

SUCROSE-METHANOL SOLUTION DISPLACING WATER

IN SANDSTONE AT Sw = 100 PER CENT.

2 - CONCENTRATION IN EFFLUENT FOR

.'

100.------.------~----~-----,-_~.--~

~

r-

c

~

/~

~~

0

~ 80~--~---+_-,,~L----4---~

~f

60r------r------~~--1-----~-------

j

J

~

~ 40~---4--~~---4-----+---~

;

§ 20r---~~~oL,~~-t----4~S~w-=-8~0~P~E=R~C~E~N=T~

5

a. OL-

~~

-L

+-+ SUCROSE

-0-0- METHANOL

~ ~L-

~

~

0.800

0.900

1.000

1.100

EFFECTIVE

PORE

VOLUMES

1.200

1.400

PRODUCED

- SUCROSE-METHANOL SOLUTION DISPLACING WATER

FIG.

CONCENTRATION IN EFFLUENT FOR

3

IN SANDSTONE AT S w =

80 PER CENT.

SEPTEMBER,

1963

not sensitive enough to measure accurately octane in hexane. F or studies in the nonwetting phase an entirely new scheme was devised. A Boise sandstone bar of

the same size as described above and similarly en- cased in plastic was placed in an oven and heated

to 160 F. Liquid parafiin, from tanks in the

oven, was then flowed through the bar at an input pressure of 65 psig. When air bubbles no longer ap- peared in the liquid paraffin effluent the bar was considered liquid saturated. Paraffin injection was then stopped and air at an input pressure of about 1 psig was injected until no more paraffin was displaced by air. The oven heaters were then turned off and the system allowed to cool for several days. The above procedure was repeated except for higher air injection pressures to obtain the different paraffin saturations reported below. There are several objections to the above procedure but they do not seem serious enough to invalidate the results obtained. First, flooding the dry sandstone bar with liquid paraffin until no further air was pro- duced may leave a small, about 5 per cent, residual gas saturation. This gas is trapped and presumably completely surrounded by paraffin. The gas bubble is then part of the wetting phase vol ume and is in- cluded as wetting phase in the nonwetting phase volume measurement. Second, displacing paraffin by air to establish a nonwetting phase saturation may give an end effect and therefore a nonuniform saturation. This was tested by using a center tap on the bar as the input point for permeability tests. Both halves of the bar had the same permeability within 5 to 10 per cent. When the flow system was at room temperature,

same

100 ,--------,-------,--------,--------, z o ~ 80r-----~------+_--~L+----~ a:: I- z W u z o
100 ,--------,-------,--------,--------,
z
o
~
80r-----~------+_--~L+----~
a::
I-
z
W
u
z
o
60r-----~----~~----+-----~
u
J
<l
Z
(!)
40r------r----~+_----_+------
a::
o
lL.
o
I-
20r-----or~~--+_-----L----~
Z
Sw = 64 PERCENT
W
U
a::
+-.
SUCROSE
w
a
~
METHANOL
OL-
-L
L-
_L
~

0.800

0.900

EFFECTIVE

PORE

1.000

VOLUMES

1.100

1.200

PRODUCED

FIG.

SUCROSE-METHANOL SOLUTION DISPLACING WATER

FOR

4 -- CONCENTRATION

IN

EFFLUENT

IN SANDSTONE AT Sw = 64 PER CENT.

191

air permeability and air volume were measured. The air permeability was obtained by applying a very small air pressure (0.15 to 0.30 psig) to the upstream end and then timing the travel of a slug of water moving through a calibrated tube at the downstream end. The air volume was measured by collecting the air produced by depleting the pressure in the bar from 7.5 to 0 psig. A Boyle's Law calculation based on the volume of air collected gives the total volume of the bar available to air. This volume includes dead-end pores and dendritic structures. After air permeability and volume were measured,

a pressure build-up curve in the air phase was ob- tained as follows. At the upstream end a constant- pressure air source was connected. At the downstream end a quick-closing toggle valve and Wiancko pressure transducer were installed so that after the system was flowing at steady state the valve could be closed and the pressure build-up recQrded from the Wiancko pick-up. The pressure build-up at the downstream end could also be recorded for the bar at uniform atmospheric pressure initially by applying the up- stream air pressure through a quick-opening toggle valve. The upstream air pressure was 0.30 psig. At this low pressure differential and near-atmospheric mean pressure the compressibility of air is almost independent of pressure. After the air flow measurements the upstream end

of the bar was connected to two stainless steel tanks,

one containing a solution of 1 gm/liter NaCI and 5 cc/liter formaldehyde in distilled water, and the other a similar solution except with 10 gm/liter NaC!. The 1 gm/liter NaC! solution was passed through the bar until five pore volumes were collected at the outlet. The input fittings were then drained and filled with the 10 gm/liter NaC! solution and injection of this solution was started. The effl uent was then collected in vials holding about 12 cc. The electrical conductivity of the effl uent in each vial was measured with a portable AC Wheatstone bridge. Upon completion of the water-water displacement test the bar was flushed with distilled water and then dried by flowing dry air for several days. The bar was then returned to the oven and heated to 160F

so that more paraffin could be displaced by the air

flow.

described above.

plot, Fig. 8, was constructed from this curve. The

semi-log plot was used in this way because of the absence of data points in the range 40 to 80 per cent gas saturation. No data could be obtained in this region because small changes in the air input pres- sure during liquid paraffin displacement caused a

large change in

sence of data in the center of the curve there appears

paraffin saturation. De spite the ab-

100r------,------.-----~----~

80

60

20 t-

O~--~

the ab- 100r------,------.-----~----~ 80 60 20 t- O~--~ 0.700 0.800 0.900 LOOO 1.100 EFFECTIVE

0.700

0.800

0.900

LOOO

1.100

EFFECTIVE

PORE

VOLUMES

PRODUCED

5

100.----.------.---,----.

z

0

l-

e::(

a::

I-

Z

W

(,)

Z

0

(,)

J

e::(

Z

l!)

a:: 40 t-~-----1If_-- +--- J.------l

o

I.L.

I-

o

z

w

(,)

a::

w

a

t-~-----1If_-- +--- J.------l o I.L. I- o z w (,) a:: w a , " -,''---t----+-----L---------l

,

"

-,''---t----+-----L---------l

Sw = 55

PERCENT

+-+

SUCROSE

METHANOL

_L

~

~

- SUCROSE-METHANOL SOLUTION DISPLACING WATER IN SANDSTONE AT Sw = 55 PER CENT.

CONCENTRATION IN EFFLUENT FOR

FIG.

z

o

a::

I-

z

W

(,)

Z

(,)

J

e::(

Z

I.L.

o

W (,) Z (,) J e::( Z I.L. o ~--1-----+--------j o 601----~--~~~--~--~ All other

~--1-----+--------j

(,) J e::( Z I.L. o ~--1-----+--------j o 601----~--~~~--~--~ All other operations were then

o 601----~--~~~--~--~

All

other

operations

were then repeated as

All other operations were then repeated as RESULTS l!)401-----+-----+---+r-"'u.t------i WETTING

RESULTS

l!)401-----+-----+---+r-"'u.t------i

WETTING PHASE

a::

o

Displacement curves for sucrose-methanol solution displacing water are shown for three water saturations in Figs. 2 through 5. In this system the viscosity ratio is favorable, that is, fingering is inhibited. In Fig. 6 is shown the effect of an unfavorable viscosity ratio when water displaces the sucrose-methanol solution.

~201------'-------+----+---"<-----:~

w Sw = 100 PERCENT

(,)

a::

+-+ SUCROSE

w

a

METHANOL

O~

~

_L

o

0
0

~

NONWETTING PHASE

The relative gas permeability curve is shown in Figs. 7 and 8. The semi-log plot in Fig. 7 has the form typical of the nonwetting phase. The arithmetic

0.800

0.900

EFFECTIVE

PORE

1.000

1.100

1.200

VOLUMES

PRODUCED

- DISPLACING SUCROSE-METHANOL SOLUTION IN SAND- STONE AT Sw = 100 PER CENT.

CONCENTRATION IN EFFLUENT FOR WATER

FIG. 6

192

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to be little doubt that the curve has the shape shown in Fig. 8. The miscible displacement curves for NaClsolution as the nonwetting phase are shown in Fig. 9. The double tracer sucrose-methanol solution could not be used in this system because it attacked the paraffin. The pressure build-up curves for the nonwetting phase are shown for two initial conditions in Figs. 10 and 11. On these plots the dimensionless time is given by

kt T = -- •••• • • • • • • • • •• (3)
kt
T
=
--
••••
••
(3)
cppcL2
where k is air permeability, t is time, cp is the total
100
- ~
~
'\
~ z
~
a::
«
\ \
10
0
I-
>-
!::
J
iii
«
IJ.J
::e
a::
IJ.J
1.0
a
\ '\
IJ.J
(.
~
~
1\
J
IJ.J
a::
0.1 0
20
40
60
80
100

Sp, % OF PORE VOLUME CONTAINING PARAFFIN

FIG. 7 - GAS RELATIVE PERMEABILITY FOR BOISE SANDSTONE. 100 .~ ~ ~ z r\
FIG.
7 -
GAS RELATIVE PERMEABILITY FOR BOISE
SANDSTONE.
100
.~
~
~
z
r\ \ \
~
a::
80
«
o
I-
>-
60
I-
J
In
<l
IJ.J
40
~
a::
IJ.J
a
1\
~
20
i=
<l
~
J
IJ.J
~
0::
20
40
60
80
100
Sp, % OF PORE
VOLUME
CONTAINING
PARAFFIN
FIG.
8
-
GAS RELATIVE PERMEABILITY FOR BOISE
SANDSTONE.
SEPTEMBER,
1963

air volume (including dead-end pores if any are pres-

f1 is air viscosity, c is air compressibility

(taken at the mean air pressure) and L is the length

of the bar. On Figs. 10 and 11, P is the variable

pressure

is the constant

upstream pressure.

ent),

at

the

closed end and Po

1.00 SNW, % ~ 0 ~ -dJ 0.90 I-- 0 36.9 A 27.9 ~ PJ
1.00
SNW, %
~
0
~
-dJ
0.90
I--
0
36.9
A
27.9
~
PJ
/
z
/J.
00.80
v::
!;t
V
/
:= 0.70
z
/
I
t
IJ.J
o z
0.60
o
o
J
I
~
<l 0.50
z
/
1/
/
~
ii: 0.40
o
T
/
/
15 0.30
1/
I-
I
/
Z
~
0.20
0::
~
II
IJ.J
a
0.10
V
V
o
0.40
0.60
0.80
1.00
1.20

PORE

VOLUMES THROUGHPUT" QrV NW

FIG. 9 - CONCENTRATION IN EFFLUENT FOR A SALINE SOLUTION DISPLACING A LESS SALINE SOLU- TION IN SANDSTONE AT SEVERAL NONWETTING PHASE SATURATIONS.

1.00 0.8 O~~ SNW,% 0.6 f--- o \~ \ , 100 -- --- 78.3 0.4
1.00
0.8
O~~
SNW,%
0.6
f---
o
\~
\
,
100
-- ---
78.3
0.4
I---
36.9
,,~
---
\
27.9
•.'\.
--
20.1
0.20
.•.•.•
\.
\,
0
~
a
\
~O.IO
.
~,
'.
-~,
a
0.0 8
I
~.,
",~,
006
"0
l'.
'~
,~
004
BOUNDARY CONDITIONS
"'\:;,
'~
1',
r
0
:~
I
ALL X
'.
.:,
~'
00
2
r
>0
P
I
X"O
\
~
l'
>0
.!L
O
X
L
".
1IX
'.'
~
I
I
I
0.0 0
0.20
0.40 0.60
0.80
1.00
1.20
1.40
1.60
DIMENSIONLESS TIME,
'(
FIG.
10 -
PRESSURE BUILD-UP IN NONWETTING

PHASE AT x = L FOR SANDSTONE AT VARIOUS NON-

WETTING PHASE SATURATIONS.

193

DISCUSSION OF RESULTS

WETTING PHASE

Tests in the wetting phase were designed primarily

to study the effect on dispersion at the displacement front of change in water saturation and the resulting change in pore size distribution. In addition, by using two tracers, the experiments also gave a measure of the difference between dispersion and diffusion in causing mixing at the displacement front. The results obtained in the wetting phase tests

are similar to

water system. The frontal advance for all displace- ments, except Sw = 80 per cent, is in the range used

by Handy. At Sw = 80 per cent, the rate here is 40.0 ft/day compared to Handy's high rate of 16.5 ft/day. However, since Handy reported no radical change in behavior in the range 0.5 ft/day to 16.5 ft/day, it is unlikely that behavior at 40 ft/day is greatly different. At water saturations of 100, 80, and 64 per cent the displacement in the water phase, as shown in Figs. 2 through 4, is not greatly affected by diffusion at the mixing front. The direction of the separation of the sucrose from the methanol curves is in the direction to be expected from the effect of diffusion into dead-end pores or dendritic branches, but the magnitude of separation is too small to be easily interpreted.

water saturation of 55 per cent, Fig. 5, there

is increased separation and a shift of both curves to

the left. Table 1 shows that this displacement was

those reported by Handy 9 for an all-

At

1.00 ~ I 0.80 ~ SNW. % ~ --- -- 0.60 100 f----- ~~ ---
1.00
~
I
0.80
~
SNW. %
~
---
--
0.60
100
f-----
~~
---
78.3
":\'
36.9
l-~
-
I----
0.40
27.9
--
.\
~~"\
20.1
1',
'\~
"\
.,
""
0.20
~
"
\
~
"
cf
\
"
""
~ 0.10
\
Q.
~,
'.
1'"
0.08
I
rx;
"\
"-
\'"
"-
0.06
\'"
.'.
\
\:
'"
,
0.04
BOUNDARY
CONDITIONS
\ •
7=0
P=O
ALL
X
7
>0
P = I
x=o
\.
0.02
7
>0
~~ = 0
X = L
'.
\.
~.
'. '.
\ \
I
0.20
0.40
0.60
0.80
1.00
1.20
1.40
DIMENSIONLESS TIME, '/
-
PHASE AT x
FIG.
11
PRESSURE BUILD-UP IN NONWETTING
= L FOR SANDSTONE AT VARIOUS NON-

WETTING PHASE SATURATIONS.

194

made at 3.2 ft/day, and is the lowest rate used. There is therefore the question of whether the change in behavior at Sw = 55 per cent is a result of the low water saturation or low rate. However, at Sw = 100 per cent Handy observed no change of behavior down to 0.5 ft/ day. We therefore conclude that the change in behavior 'we have noted at S w = 55 per cent is a result of the low water saturation. At low water saturation we expect an increased number of dead-end pores or dendrites which would cause dif- fusional effects and give the separation of curves shown in Fig. 5. The shift to the left of both sucrose and methanol curves so that they no longer cross the 50 per cent concentration line at 1.0 effective pore volumes produced is evidence for the existence of water volume that does not contribute to the water flow channels. Whether this water volume is in dead- end pores or in dendrites cannot be stated with cer- tainty at this point.

main method of theoretically describing the

dispersion due to mixing during miscible displace- ment is a statistical approach based on random walk theory. This statistical treatment assumes single component, single phase flow. Orlob and Radhakrishna 3 suggest that a second component merely changes the porosity. The data presented in Figs. 2 through 5 can be used to determine if a simple change in porosity will bring all displacement curves into agreement with displacement theory for single component, single phase flow. The most convenient displacement parameter to use in comparing displacements at different water saturations is the index of dispersion f3 given by

Day and Forsythe: 10

The

f3 =

2D

v

(4)

where v IS the frontal advance rate and D is Lvi41rVI s2, where L is the length of system, VI the pore vOolume, and So is the slope of the relative

concentration in the effluent vs volumetric output evaluated at relative concentration equal to one-half.

Inspection of Eq. 4 and the definition of D shows

that if So is calculated from Figs. 2 to 5 where vol-

umetric output is a dimensionless fraction of an ef-

fective pore volume then

f3

(5)

Eq. 5 shows that if changes in water saturation do not change the statistics of mixing at the displace- ment front but merely change the porosity, then f3 should be the same for displacements at all water saturations. However, if a change in water saturations causes a change in pore size distribution of effective pores and if pore size distribution is important in establishing the statistics of mixing then f3 will change with change in water saturation. Table 2 shows the indices of dispersion relative to the index at Sw = 100 per cent. For sucrose, the

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TABLE 2 -

RELATIVE INDEX OF DISPERSION

Sw

Per cent

----

(3Sj(3100

Sucrose

100

1.00

80

1.00

64

1.00

55

1.96

(3s ":(3100

Methanol

2.35

2.35

5.2

slow diffusing tracer, there is no change in (3 until S w is below 64 per cent and then there seems to be

a radical change. F or the fast diffusing tracer, meth-

anol, the index changes as soon as the water satura- tion is less than 100 per cent. These results indicate

that during displac.ement in multiphase systems dif- fusion effects are much different than in single phase systems. However, mixing at the displacement front is not changed radically until water saturation is about 50 per cent.

NONWETTING PHASE

The nonwetting phase displacement tests described in this paper are not the first to be carried out in a multiphase system. 5 However, they are unique in the use of a flow system in which the wetting phase is stationary within the porous medium at all saturations. Other advantages of the solidified wetting phase system are: (1) needs only one constant rate pump, (2) change in viscosity of the nonwetting phase at constant rate does not change saturation and(3) both rate and viscosity effects can be studied by controlling flow of the nonwetting fluid alone. The requirement in nonwetting phase displacement tests that the wetting phase remain motionless at all saturations is mentioned by Raimondi, et al. 5 In discussing the relation between wetting phase satur- ation and index of dispersion, they state that the increase in this index with increase in water content above interstitial saturation is probably a result of the water not being a "rigid phase". They also present a graph to show the effect of rate on index of dispersion. Their proposed explanation of this graph is that the index should be decreasing with decreasing rate at water saturation above interstitial saturation because the water becomes "more quies- cent" as the rate decreases. The effect of saturation on index of dispersion for the solidified wetting phase systems are given Table 3. Table 3 shows an increase in (3 with increasing wetting phase saturation; but this effect cannot be explained by simply postulating an increase in mixing of the nonwetting fluids because of motion in the wetting substance. The breakthrough curves of Fig. 9 may be used to explain qualitatively the effect of saturation on index of dispersion shown in Table 3. In Fig. 9 the relative concentration of tracer in the effluent is plotted against the number of pore volumes injected where a pore volume is taken as the total volume available to the nonwetting, tracer-bearing fluid. When there is no paraffin in the bar the break-through curve

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TABLE 3 -

RELATIVE INDEX OF DISPERSION FOR

DISPLACEMENT IN NONWETTING PHASE

Nonwetting phase saturation,

per cent

(3snj(3 100

100

1.00

36.9

6.13

27.9

9.35

follows the generally accepted theoretical curve for miscible displacement in single phase flow. That is, the curve is symmetrical and passes through CICo = 0.50 at one pore volume throughput. When paraffin was added to the flow system as a wetting phase, the displacement of water by an aque- ous solution gave the two break-through curves shown to the left in Fig. 9. These two curves are clearly unsymmetrical and do not pass through the "ideal" point of CIC o = 0.5 at one pore volume throughput. The translation to the left of these two curves is probably a result of the change in pore size distri- bution. When paraffin, as the wetting phase, is present in the flow system, then by the capillarity concept, the nonwetting fluid occupies only the larger pores. The paraffin may then cause the nonwetting fluid distribution to be dendritic or dead-ended. The curves in Fig. 9 suggest a distribution in which a portion of the nonwetting fluid contributes little to the conduc- tivity of that fluid. During miscible displacement, fluid in these nonconducting pores probably remains motionless so that displacement from these pores should be more dependent upon molecular diffusion than upon hydrodynamic dispersion. Further displace- ment tests in the nonwetting phase should be made at various floV'( rates to distinguish between the rela- tive importance of diffusion and dispersion on the total mixing process.

PRESSURE TRANSIENT TESTS

Several papers from this laboratory 8,11-14 have shown that pressure transient tests can detect the presence of dead-end pores or dendritic structure. The system in which paraffin was the wetting phase seemed ideal for applying these tests. Figs. 10 and 11 show a pressure parameter plotted against dimen- sionless time T where

kt

T=---

cpp.cL2

(6)

k is permeability, t is real time, cp is porosity, p. is viscosity, c is compressibility, and L is length of the system. The porosity term is based on the total volume available to the nonwetting phase as meas- ured by the Boyle's Law test described in the Pro- cedure section. Curve 1 in Figs. 10 and 11 is for the flow system at the single phase condition. This curve is in ex- cellent agreement with theory for pressure transient during nonsteady state flow of a slightly compressi- ble fluid. In the absence of dead-end pores or dendrites the other curves in Figs. 10 and 11 should be coin-

195

cident with Curve 1 if the effective permeability and porosity in the nonwetting phase are used to calculate T. The wide separation of the several curves in Figs. 10 and 11 is excellent evidence for the presence of dead-end pores or dendritic nonwetting phase structure.

CONCLUSIONS

The overall and most general conclusion from the study presented here is that the miscible displace- ment process in the multiphase system studied here is different and more complex than in a single phase system. The presence of a second phase probably caused some of the displacing and displaced fluid

to be trapped in dead-end pores or dendritic structure. Conclusions in detail for the system studied here are:

1. Dispersion in the wetting component of a two

immiscible liquid system increased with decreasing saturation of the wetting fluid.

2. Longitudinal diffusion phenomena in the wetting

component decreased with decreasing saturation of

that component.

3. The dispersion coefficient is not an adequate

measure of mixing for displacements in multiphase systems.

4. Dispersion phenomena are dependent upon

component distribution in a two immiscible fluid

system.

5. The use of paraffin as a wetting material makes

possible a convenient model for studying mixing between two miscible fluids acting as a nonwetting

phase.

efficiency of a miscible displacement

process performed in the nonwetting fluid is decreased as the wetting phase saturation increases. This is because all of the pore volume containing nonwetting fluid does not conttibute to the conductance for this

fluid.

6. The

ACKNOWLEDGMENT

Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for support of the re-

196

search which led to this paper.

REFERENCES

1. Fatt, I.: "Pore Structure of Sintered Glass", Jour. Phys. Chem. (1959) Vol. 63, 751.

2. Fatt,

I.:

"Influence of Dead-End Pores on Relative

Permeability of Porous Media", Science (1961) Vol. 134, 1750.

G. T. and Radhakrishna, G. N.: "The Effects

of Entrapped Gases on the Hydraulic Characteristics

of Porous Media", Trans. Am. Geophys. Union (1958)

Vol. 39, 648.

3. Orlob,

4. Biggar, L. W. and Nielsen, D. R.: "Miscible Displace-

5.

ment in Porous Media", Jour. Soil Sci. (1961) Vol. 12,

188.

Raimondi, P., Torcaso, M. A. and Henderson, J. H.:

"The Effect of Interstitial Water on the Mixing of Hydrocarbons during a Miscible Displacement Pro- cess", Mineral Industries Experiment Station Circular No. 61, Pennsylvania State University (1961).1. 6. Goddard, R. R., Gardner, G. F. H. and Wyllie, M. R. J.: "Some Aspects of Multiphase Distribution in Por- ous Bodies", Paper presented at Third Congress of the European Federation of Chemical Engineering, London (June, 1962).

7.

Countryman, G. R.: "Diffusion and Mixing in the Water Component During Miscible Displacement in a Porous Medium Containing Water and Oil", M.S. Thesis, U. of California, Berkeley (1960).

8.

Thomas,

G.

H.:

"Nonwetting

Phase

Fluid

Flow

through a Porous. Medium Containing

a

Solidified

Wetting

Phase",

M.S.

Thesis,

U.

of

California,

Berkeley (1962).

 

9.

Handy, L. L.: "An Evaluation of Diffusion Effects on Miscible Displacement", Trans., AIME (1959) Vol. 216, 382.

10.

Day, P. R. and Forsythe, W. M.: "Hydrodynamic Dispersion of Solutes in the Soil Moisture Stream", Proc., Soil Sci. Soc. America (1957) Vol. 21, 477.

11.

Goodknight, R. C., Klikoff, W. A., Jr. and Fatt, I.:

"Nonsteady State Fluid Flowand Diffusion in Porous Media Containing Dead-End Pore Volume", JOUT. Phys. Chem. (1960) Vol. 64, 1162.

12.

Goodknight, R. C. and Fatt, I.: "The Diffusion Time- Lag in Porous Media with Dead-End Pore Volume", Jour. Phys. Chern. (1961) Vol. 65, 1709.

13.

Fatt, I.: "A Modified Diffusion Time-Lag", Jour. Phys. Chem. (1962) Vol. 66, 760.

14.

Goodknight, R. C. and Fatt, I.: "Surface Concentration Build-Up during Diffusion in Porous Media with Dead- End Pore Volume", Jour. Phys. Chem. (April, 1963).

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