-..

NECMETTIN
MUNGAN
JUNIOR MEMBER AIME
,.

ABSTRACT
Laboratory water floods we,re performed in oilwet and water-wet alrmdum and Torpedo cores,
a refined oil with n-i)exylarnine or
displacing
Triton X-100 solution.
Also, some floods were
performed in. which a sucrose solution was displaced with rt-butyl alcohol. The purpose 01 the
tests
was to see if the oil recovery could be
increased
and to examine what role the inter.
facial tension reductiorr and nettability
change
play in the recovery mechanism.
lt was found that the cbromatograpbic transport
of amine was influenced
by core wettab;lity.
In
oil-wet cores, the rate of advance of the amine
band could be predicted from equilibrium cbiomatoband
grapby, while irt water-wet cores the ami
moved
faster
than
predicted,
indicating
a
non,
,.
f.
eqraltbrium process,
By reducing the ihterfacial
tension to 1,1 dyrze/
cm, oil recovery was irrcreased. More oil was
recovered from Dri- f ilmed cores t ban from waterwet cores, Reversing the nettability
of the porous
media from oil- wet condition ako resulted in sotie
adiitiorral oil recovery. Neutral nettability
floods
did not increase oil recovery.

INTRODUCTION

Interracial
forces in petroleum reservoirs
are
responsible
for retention of large quantities
of
residual
oil. Increasing
exploration
costs have
created an incentive to attei-npt recovery of this
residual
oil by new and novel processes.
One
novel process involves changing the mterfacial
forces by introducing a chemical into the reservoir
during water flooding.
Recently, several investigators
have carried out
laboratory
displacement
tests using aminee. l~s~q
T&e amines adsorbed. onto, in,iti ally water-wet core
stirfacesj chtingirig tiiern to oil wet, -AdditionZd oilin Saclety of pe~oleum
Original manuscript received
Engineers office July 27, 1963. Revleed manuscript received
Jan. 29, 1964, Paper preeented at SP E Annual Fall Meeting.
held in New Orleans, Oct. 69, 1963.
1References giveti at end of paper.

JUNE,

,..
=----

SINCLAIR
RESEARtd,
TULSA, OK1.A.

-----

1964

INC.

WIXS recovered
when the cores were flooded in a
the. wearability
from ail-wet
man ne r reversing
conditions.
In all these studies, the nettability
reversal was considered responsil .. or increased
oil recoveries although it was noted that amines
also reduced oil- water interfaci al ten sion.
h-t the present study, displacement
experiments
were performed in water-wet- and Dri- filmed cores.
The purpoee was to separate the effects of lowering
the interracial tension from changing the nettability.

LABORATORY

STUDY

All experimental gk:a- given in this paper have

been obtained at- a temperature of 70F k 1 and
prevailing
atmo epheric pressure.
FLUIDS

AND

MATERIALS

The oil used in these experiments* was washed

with H @04 anr! passed through ~wo 100-2110 mesh
sil ic a-gel beds to remove unsaturates and surface
active impurities. Normal hexyIamine* * of praccica~
purity was used, and the alundum cores*** were
composed of nearlv,pure A 1203. Fused quartz (Si OJ
and Lucalox (A12 Q )7 pIates were used in the
contacr angle measurements,
DISPLACEMENT

>

s.

,-

TESTS

Displacement
tests were performed in aiundum
and Torpedo cores. Before displacement
runs,
cores were acidized with 0.1 normal HC1, flushed
with distiiled water- and fired at 1,200F to make
them water wet. This procedure also reduced water
sensitivity
of the Torpedo. cores. Oil-wet cores
were prepared from water-wet cores by flowing
several pore volumes of 1 per cent by weight Drifilm SC;87t t solution in heptane through che cores,
and
flushing the cores with nitrogen, evacuating,
finally heating che cores at 300F for 4 or 5 hours.
Between fioods, cores were cletwed by conventional
-prifcedties and t~eated-again-- asabovei:- --he
011 used was Xteerol, manu!act~=f W the ~ite
Division of ~nneborn ~heml~=l -A Refining CO.
**obtained from Kodak CO.
smcobtained from Retiactmies Division
tObtained Prom General Eleetrlc Co.
t tObtalned from Generel Electric CO.

of Norton CO.

oil

--;

--

\,

-,

RESULTS AND DISCUSSION

INTERFACIAL

STUDIES

The effect of n-hexylamine on water-oil interracial .tgmsion is- shown .in Fjg:. 1. The. imetfacial
tension
decreased
continuous y from 47 to 1.1
dynes/cm as aqueous amine concentration changed
from zero co 0.1 mole amine/liter of water.
Fig.
1 SLSO shows water-advancing
contact
angles as measured in water. When no amine was
present in the fluids, the contact angle was 64

----

-.

To prepare a core for flooding, the core was

svacuated,
weighed and saturated with distilled
vater. In Torpedo cores, the aqueous phase was
30,000 ppm brine. After saturation, the core was
eweighed to derermine the pore volume. Moxe
water was put through the core to obtsin specific
permeability. Oil was then flowed through the core
.tntil residual water saturation was obtained and
:he core was. allowed to stand a day. Before
starting the water flood, 1 to 2 pore volumes of
>il were flowed through the core to determine the
sffective
permeability
to oil at residuaf
water
saturation. In all floods,, the fluids were mutually
saturated with each other.
To compare oil recovery efficiency from any of
the, low inter,facial tension or nettability
reversal
floods to that of a conventional water flood in the
same core, a control water flood was run, The oil
and the water contained no chemical during the
control flood.
Interracial
ce~sion was measured by a pendant
drop apparatus similar to the one described
by
Hough and Heathington.5 Nettability was measured
by contact angle formed between the fluid interface
and the solid surface. A simple modification was
made to incorporate a protractor into the pendant
drop equipment to read contact angles directly by
rotating the cro ss-haira on the image of three-phase
contact. Also, imbibition rests were run to determine
wettabilit y of cores before and after coming into
contact with O.1 normal amine solution.
To calculate chromatographic transport of amine,
one must know the adsorption isotherm of amine,
distribution
coefficient of amine, surface area of
cores and fIuid saturations. The adsorption isotherm
was determined by technique .simil}ar to Taber$s, 6
A short core, sealed in a Lucite sheath; was
mounted bet ween two small-volume containers and a
small amount of amine solution of known concentration was cycled throu~h the core until adsorption
equilibrium-was reached. The discribucion coefficient
of amine was found by adding amine to flasks
containing
known amounts of oil and water and
shaking the mixture for one day. Amine concentration in the aqueous phase was deterh-tined by
titration with HC1 solutions, Surface areas of $ores
were determined by the nitrogen adsorption technl que.
To determine the arrival and the shape of the
amine band during displacement tests, samples of
the effluent wat:r were titrated with HC1.

... ...-

. -.

.
..

._.
-..---

,--

silica
and 63 on alundum surface,
indicating
water-wet
surfaces,
As amine ~:sncentration
is
?ncreased to 0,1 mole/liter, contac, angles increase
to 116 knd 123 on alundum and silica, respectively,
indicating
tii~t the surfaces
sre becoming progressively
oil w+
On Dri-filmed alundum and
silica surfaces, contact anglea were 12b and 130,
respectively,
and did not change for the entire
amine concentration
range between . ze}o to 0.1
mole/liter.
Therefore, Dri-filmed surfaces remain
oil wet during both water and amine floods. Imbibition tests which are summarized in Table 5 show,
< that water-wet cores become oil wet upan amine
adsorption, while Dri-filmed cores remain oil w~t.
,
on

CHROMATOGRAPHY

OF AMINE

Adsorption
isotherms
of amine on water-wet
silica and alundum are shown in Fig. 2. On Drifilmed alundtim and silica surfaces, the amine
adsorption was found to be nil. Fig. 3 shows the
distribution
coefficients
of amine. Under ihe
160 ~

[00

AQUEOUS AMINE

CONCENTRATION, (MOIWLlf.l)Xl@,

TENSION
AND CONTACT
1 INTERFACIAL
ANGLE FOR KLEAROL-WATER-SOLID
SY STEMS.

FIG.

10

,,

6
-.

l~;

o.

s Wcff
mm

Sranw?)

OA/unUum

-i

2 -.
_. .._

1!

...

.-

. . .2:

,.

------!
1

100

00

EOUILISRiUM A&ous

4%NE :cot%ENTsm%

ADSORPTION
ON
FIG. 2 AMINE
SILICA AND ALUND~:
SOCIETY

116

*.

, -.

lMOWLftfklo4

WATER-WET

OF PETROLEUM =NSINEERS
.

JOU8N.L

,.
.

.-.

; _->
...
~.-:.

,. .

..

#..

TABLE

1-

SUMMARY OF CORE PROPERTIES

Lmw#h
Number

A-1

,o~,z
AQUEOUS AMINI? CONCENTRATION, Mol@s/Lltsr

C+EFFICXENT
OF AMINE IN
FIG. 3 DISTRIBUTION
OIL-WATER AND OIL-BRINE SYSTEMS+

of equilibrium
chromatography,
assumption
rate of movement of amine is given by: 1,3

the

where: R = Rate of movement of amine relative to

rate of movement of water,
so, sti, = Oil
and water saturations,
in fraction
of pore volume,
a = Distribution coefficient of amine,
A+= W~~~ce~JJ
$~c~t
O1urne of Pore
/(ci) = Amine adsorption per unit area, gm/sq cm,
ci = Injected amine concentration, gin/cc
The total injection V, in pore volumes, necessary
to move the amine to the outlet face of a core can
by:
be obtained

v=+

e.

.. .

Irr Fig. 4, concentrations of amine jn the effIuent

water, expressed as per cent of the injected amine
concentration,
are shown for water-wet core D+25
and Dri-filmed core D-27. The shapes and the
general features of these profiles are typical for
all eight floods in which effluent amine concentration was monitored. These floods are reported in
Table 2.
. . .Fgr. cpre D:27, at the ti_rne of -amine_ injection,
s-w = 0.73-- and So = 0.27. The distribution
coefficient, shown in Fig. 3, is 5.1. Using these data
in Eqs, 1 and 2, chromatographic trsnspozt rate of
0.365 and V = 2 PV are calculated.
As shown in
Fig. 4, the first appearance of amine in the effluent
was after 2 pore volumes of injection. This indi-

Nature

Dlamoter

Absolute
Pwosit y Permsuhl Ilty

sa%~.
WW
WW
OW
OW

3.81
3.81
3.81
3.81

2b54
%54
3854
2,54

27,3

k2
A-3
A-4

Alunkm
Alundum
Alundum
Alundum

27.4
27,2
27.2

4s0
$455
460
-465

2!

Alundum WW
Alundum$OW

7.55
7.55

3.18
3.18

28,6
28,3

85
8S

C-9
G 10
C-II

Alundum WW
Alundum WW
AlundumO W

7.46
7.46
7.46

3,18
3.18
3.18

29,4
29.2
29,0

135
131
116

0.25
Eh26
D.27
0.2B

Alundum
Aluhdum
Alundum
Alundum

3.18
3.18
3.18
3.18

26,1
26,0
25,0
25,2

245
250
233
230

F. 17
F. 18
F-19

Alundum WW
Alundum OW
Alundum OW

3.18
3.18
3.18

26.3
25,4
25,9

144
163
166

G29
G-31

A1.ndum WW 10.0
Alundum OW 10.0

3.18
3.18

27,2
27,0

T. 33
T-34
7.36
T-37

Torpedo
Torpedo
Torpedo
Torpedo

WW, 3 LO
WW 31.0
O W 31.0
OW 31.0
7.50
7.50
.7.50

3,

7.6
WW
7,6
OW
WW 31.0
OW 31.0

1s

3.]8
3.18
3.18

240
230

100
75 ,
105
85

20,0
19,2
21.0
1907

cates
that equilibrium
transfer
of amine from
injection water to rhe fluids in the core was taking
place.
: FOJ die water-wet core D-25, on the other hand,
the amine appezmed in the effluent after only &7
PV of amine had been injected.
Using the data
so = 0.3, Sw = 0.7 from Table
2; distribution coefficient of 5.1 from Fig. 3; surface ar&a per unit
volume of pore space of A ~ = 4,870, and amine
~4
adsorption from F-, :2 in Eqs. 1 and 2, the chromato~
graphic transport ,iite is R = 0.31 and,total injection
to amine breakthrough is V = 2.26 PV, If equilibrium
chromatography were to take place, the amine should
not appear in the effluent until 2.26 pore volumes
had been injected.
Ch-re,explanation for equilibrium transport of amine
in Dri-filmed cores, as contrasted to non-equilibrium
transport in water-wet cores, comes from consideration of residual oil distribution in the two nettability
systems,
In Dri-filmed cores, the residual oil ~is
in the pendular structures connected to each other
by a film of oil spreading over the grain s~faces,
In such systpms, amine solution contacts the oil
through a large interf acial area, facilitating rapid
transfer of amine into the oil.
cores,
the residual oil is in the
In water-wet
form of discontinuous
structures,
exrending over
several
pore spaces
and occupying the insular
region of the porous matrix. The amine must
diffuse
into these oil masses and be stripped
_.-out .o~_the- in jeqtctd, water?.. Since. .a.miite diffus~on.
within the oil, phase is slow, not enough contact
time is available for equilibrium transfer of amine
into the oil masses. It appears Iikel y that if longer
cores or lower displacement rates are used, movement of amine in water-wet cores will foHow
predictions
from chromatography,
._
al?

.,.
-,

.
,.

.
.

. .

. . . . .. ..

DISPLACEMENT

A summary of core properties is given in 1abl,e 1,

For the sake of brevity, the abbreviations
WWand
OW ate used to indicate water-wet and Dri-filmed
cores.
Amine Floods Subsequent
To Water Floods
Out first concern in displacement tests was how
reproducible rhe interstitial
water and the residual
oil saturations
would be for a given c,ore and a
r.:.,-- flmm~-,--J,,.T-!-.1-e ? -*2 ~ ek,-.... .-.. -..-2

Flood
Number
Cantrd

28+3

Cantrol

Displacement
Rate (ft/D)

.;

runs in alundum and Torpedo cores, Floods were

performed at displacement rate of 1.4 ft/day until
the flow of oil had ceased. The rate was then
increased to 21 ft/driy. The higher rate was used
primarily to minimize capillary end effects. The ,
21 ft/day rate removed less than 1 per cent pore
volume additional oil from water-wet cores, and
10 to 12 per cent pore volume additional oil from
Dri-filmed cores. Water flooding at higher rates,
up to 60 ft/day, recovered no more oil. The re suhs
given in Tables 2 and 4 indicate that for a given
core, water and amine ~flood performances
were
remoducible
if flood conditions were not varied.

TESTS

TABLE

... .

2 SUMMARY OF AMINE FLOODS IN ALUNDUM CORES

Cumulative
Inlection (PV)

1,4 W*

*
B-5, WW

21.0 w

104 w
21.0 w

14

First
Interstitial
Phase. %PV
17.6

Run
Residual
oil, %Pv
31.0

29.9

17
21

1.4 w
21.0 w

5
9

1.4 A*
21.0 A

14
17

25.0
23,5

21.0 w

21

20,5

1*4 w
2100 w

5
9

1*4 w

14
17

woo
29,8

21

29,8

21.0 w

..

29.9
29,9

21*O w

2100 w

Second Run
Intorstltial ~d~

29,9

17*!i

B-5, WW

0.35,

Ww

20,0

29.8
29.4

16.8

31,5
31,2
25.5
24.0

21.0

31.0

31.2
30,0

,
5&6

=.,

1.4 w

21.0 w
1.4 A

9
17

25,0

24.5

21

22,3

2109

,,

1*4 w

21.0 w

26,5

1,4 w
21,0 w

14
17

26,5

21

26,3

0.7, OW

1.4 w

s-7, Ow

22.9

37.5
26.3
20.0

17

18.0
17.6

17.2

D-27, OW

19.0

26.8
26.7

21

26.7
-

1900

39.1-27,0

- -- 19.1

38;7-

1,4 A

23.0

23*5

21,0 A

17

20.0

21,0 w

21

20,0

21,0
21,0

.,

--

-.

. ..

.-__j

27.7

9
14

..

39*O
26,S

17

:,2

37.3
20.3

*W and A ipdlcate displacing phases are either watmr or amine.

,.

23,6

26.9

5
9
14

-L4 w
21.0 w

37,0

9
14
21

21,0 w
21*O w

23.4

30,0
25,5

26,4

21,0 w
1.4 w

..,,.&

21.0 w

2100 A
21,0 w

-. . .

21.1

14

1,4 A

Control

3 Lo

21.0 A

1.4 w
21,0 w

--

20.4

3005
26,5

21*O w
8&9

D.25, Ww

I
,. ,---

. .I

,,

,,

1 -----

TABLE

3-

SUMMARY OF AMINE FLOODS IN ALUNDUM

cumulative

Number

Rate (ft/0)

13

L4 w
, 21*OW

5
9

1,4 A*

14

14

17

1.4 w

5
9

21.0 w

,
8

21,0 A

21,0 A

14
17

1*4 w
21.0 w

5.
9

1,4 A

14
17

1,4 A

21.0 A

21.0 w

LA
..- A

1,4 w
.21.OW

c-l

27.0
23.5
21,5

-,
26,0
24,5

23.5
21.3
or amine.

-L
.

h!r,-/--4
z-------

..

1?
9
INJEOTION, PORE VOLUMES

!
. .. ,.,
<;

. ..-

-.
.
,.

{,

,,

----

ORI-FILMED
CORE, No. G-31
b Ahf/NE F~D

o WirER IVCWU
-. cV$r~OL WAWi

i?o

16

16

-.

~.+.-+-.-~o

i
-.--!-

200

?10

FIG. 4 TYPICAL PERFORMANCE

FOR DRBFILMED
(OW) AND WATER-WET (WW) ALUNDUM CORES.
JUNE, 1964

--,

.40. -

----

tf

I q.
&?60

Cores

To compare the effect of low interracial tension

. ~.._ -.
m~
~~--1

Olf

R?

-.

Floods lY Amine Equilibrated

!
00k

45

!.

facial tension as the core became oil wet. The

final ~ater flood recovered 2.6 to 3 per cent pore
volume of oil by reversal of nettability
from oilwet conditions.

.@

.Jc

. .

36.0
28,1

12,5

F. 19, OW

. .-..

22,0
19,9

phases are either water

,,

37.0
29.3

12,9

F.18, Ow

1[

31.3
310.1

14*9

F-17, WW

Fig. 4 shows typical oil recovery histrxy for the

18 floods given inlables
2, 3 and4. InDii+Umed
cores, flooding with amine recovered an average
of 8.2 per cent pore volume additional oil. The
increased
recovery is due to lowering the interracial
tension,. since nettability
of Dri-filmed
cores- does not change dtiring amine-floods. Little
or no additional oil was recovered when the amine
flood. From
flood was followed by a final water
water-wet
cores;
amine fJoods recovSred an average
of 5.7 per cent pore volume additional oil. This
additional recovery is due to lowering the inter-

.,

ii.o

15.5

1,Ow

14
17

1,4 A
2L0 A
*W and A indicate displacing

31.1

14,2

2s,8

5
9

30.8
26.9

17

21.0 &
18

30.1
29,9
96.6]
25.7

13.6

C.lo,.ww

5
9
1A

L4 w

17

c-9, Ww

5
9

1.4 w
21,0 w

16

-x?.!lQ

14
17

1,4 A

15

Coro

-.

21.0 A

oil

Water

-@!!__-

Residual

,Interstitiel

Inloct[on

Displacement

Flood

CORES

INJECTION
FIG.

, PORE VOLUMES

FLOOD PERFORMANCE
OF CORE EQUILIBRATED WITH 0.1 NORMAL AMIN~,
119

.
,,.
., -..

.
79

TABLE

5 z

SUMMARY OF IMBIBITION

core
A. 1, WW Inltlal
A.3, OW Initial
A.2, WW Inlt id
A-h, OW Irritiol
k 1,
A-3,
A-z
A-4,

WW
OW
WW
OW

.C.andltfon,
Condltlon,
Condition,
Condition,

Equilibrated
Equilibrated
Equillbratad
Equilibrated

CantrOl
Control
Control
Control

?.s~

.
=-:.

24
IN,IECTION , PORE

FIG, 6 FLCOD
RATED

with ,0. IN
withO. IN
with.O.lN
with O.IN

Amine
Amine
Amine
Amine

45
o

Amine
AmIns
011
011

5
d
25

10

PERFORMANCE
OF CORE EQUILIBWITH 0.1 NORMAL AMINE.

to transient nettability
change. in identical cores,
the floods shown in Table 6 and Figs. 5 and ~
were perfotmed. In, these floods, the cores had

Flaod
Number
Cantrol

4 SUMMARY OF AMINi

Dispkrcement
Rate (ft/D)
1.4 B*
1,4 B
21.0 B

5
9
14
17

21.00

21

1.4 B
21,0 B

21

37

phase.

CORES
lntOrstltlal
Water
(% Pv)

Core

21,0 B

20

FLOODS IN TORPEDO

Cumulative
Inlp;ien

9
36

been equilibrated by using water *ird oil containing ~

amine during saturation of the cores and flowing
each fluid. until effl sent amine concentration, was
equaI to. that being injected.
Fig. 5 shows that flooding with ,0,1 normal amine
solution recovered 11 per cent pore volume additional
oil as compared to control flood. l%is increa~e in
recover y is due to lower interracial
tension since
nettability
did not change. When the same core
was prepared again, but flooded with water instead,
the recovery was only 4 per cent pore volume: higher

VOLUMES

TABLE

Imbibition

Water
water
011
oil

The imbibing fluld is alsci the Interstltlal

-,

TESTS

Imbibing
.~ FluId*

T-33, Ww

Residuol

oil

-@N_

21.7

37.0
36,8
36,8
36.8

T.33,

WW

37,2

22.0

1.4 A*
21,0 A

9
14

36.5
28,9

17

21.0 B

21

28,9
27.0

1,4 B
21.0 B

5
9

1.4 A

14

27.8

21.0 A

27.8

21,0 B

17
21.

1,4 B

21.0 B
1.4 B

9
14

21.0 B

17

24.3
24.3

21,0 B

21

24.3

T-36,

WW

36.8

35,0

20,8

34.B

26.0

.,
Control

23

s.-=

. . . . .. .

.
24

. - . ... ..-

1,4 B

21,0 B

1,4 A

14

21,0 A

17

2.1,0S

___

?1

1--34, Ow

31.5

26.8

24.3

1--34, Ow

27.0

33.0
25.0

14.9
14,0
.

..

14*O

1.4 B
21.0 B

1.4 A

14

15.O

21,0 A

17

14,0

21

14,0

21.0 B
*B and A indicate displacing

T.37, Ow

26,0

31,5
23.5

phases me either brine or amine.

-- . .

1.. .

-.

.
than the control flood and 7 per cent pore volume
less than the amine flood.
This lower recovery is due to rise of interracial
tension value because of depletion to amine from
the core fluids. However, ac Spore volumes, injection was changed to amine and additional
5
per cent pore volume oil was recovered over a
span of 5 pore volumes of injection. This recovery
is dgain due to lowering of interracial tension. It is
concluded
that in an oil wet core, lowering of
interracial
tens ion will recover additional
oil,
and as Fig. 5 indicates, the total injection necessary
to recover the additional oil is lower if the incerfacial tension is reduced early in the life of the
flood.
Fig. 6 shows similar floods performed in an
initially water-wet core. When the core had been
and was flooded with amine, the
equilibrated
recovery was 8.5 per cent higher than the control.
This was because the core had become oil wet and
the iixerf acial ten sion was low. Following the
amine flood with a plain water flood recovered an
additional 1.5 per cent pore volume of oil, due to
When the core was flooded
nettability
reversal.
with water first, the nettability
reversal oil was
5.5 per cent pore volume. Following the plain
water fiood with an amine flood yielded an additional

-_.

TABLE

6-

SUMMARY O P FLOODS IN CORES

Interstitial
Phase

,=.

Flood
Number
C6ntrel

23

&

G29,

EQUILIBRATED

10,2

G.29, WW

C8ntrol

Residual

011
J?i!3L

34*O
34.0

5
5

..+

.21

29*O

21

22.5

Water

21
21

5
5

26,0
24,5

water

21

Water

21

30,6

12.1

Wafer
Amine

21
21

5
5

27,0
22,4

27

G.31, OW

11.9

Amine

21

21.0

Water

21

20.5

7-

SUMMARY OF TRITON
..

X-1OO AND n. BUTYL

Phase

Displacing

Iniectlon

011

(% Pv)

Phase

(ft/D)

(Pv)

_!!@!!-

Control

D-26, W W

18,0

Water

21,0

5.0

32,5

D-26, WW

1907

.- ..-

...

. -----

T;lton X=lUO
Trlten X*1OO ,.
. . . . . ..
. . .. .

S*O

1.4
._

?!*O

.. .

-_..._

5.Q . .

26*7

34

D-26, WW

18,9

TritOn X- 100

21,0

5.0

26,9

Control

D-28, OW

20,5

Water

21.0

5.0

3005

21.1

Alcohol
Alcohcd

1*4

5,0

24,5

21.0

5.0

24,5

Alcohol

21.0

5.0

24,6

D-28, OW

36

0-28, OW

37

21,7

Jutia@96a

..
,,

. . .._.

. ...

... --,

..

-..,

.,. -

Residual

Inlectlwr
Rate

Core

.-.... -= -..

ALCOHOL. FLOODS

Number

. . ..-

30,6

,5

0-31, Ow

33

.._.

AMIN~

In[ecilan

21
21

Interstitial

....

FLOODS

26

Flood

WITH 0,1 NORMAL

Amine

12.9

TABLE

..

ALCOHOL

-f!!.@-

Water

10*3

G.31, OW

AND

Rate

Amine
24

X- 100

The results presented so far show that the use

of amine in Dri-filmed cores did not interfere with,
the wetting conditions, but rather recovered more
oil by lowering the interfacird tension. In waterwet cores, use of amine resulted in two simultaneous.
effect a: the core became oil wet and the interracial
tension
was lowered, To reduce the interracial
tension without interfering. with the wetting conditions in systems where ,,rhe displacing fluid is
the wetting phase, two flood systems were selected.
In one system, rhe displacing phase was 6,000 ppm
aqueous solution of Triton X-100, the displaced
phase was oil, and the core was muffled aIurtdum.
The contact angle was 65, oil the non-wetting
phase, and interracial ten:sion was i, 1 dyne/cm.
In a second system, a 49 per cent by weight
sucrose solution was disp!aced by n-butyl alcohol
from a Dri-filmed alundum core. The contact angle
wa5 135, sucrose the non-wettin~ phase, and
interracial tension was L 1 dyne/cm~ Ii should be
noted that this particular sucr6se-alcohol
system
had a viscosity ratio of 10,3 cp, which was close
to the 10.5 for the oil-water and the ,oil-Triton

Inlectlan

11.0

WW

TRITON

Di splaclng
Phase
.
Water
Water

(% Pv)

6.29, WY

6.5 per cent pore volume oil, due to rendering the

core oil wet and lowering the interracial tension.

..

t
..=

. ..

..

-.

..-_

..

,-

----

. .. .

. . . ..

~-.

L;

L.+-__&.

lNJECTlttN, PORti VOLUMES

-i

VOLUMES

OF TRITON
X-1OO AND
FiG. 7 PERFORMANCE
0.01
NORMAL AMINE FLOODS.

FIG, 8 PERFORMANCE
OP ALCOHOL AND
NORMAL AMINE FLOODS.
:

,sys,tdms. The control flood in each case

was water displacing oil. Thus, the only difference
between the control and the Triton X- 100 or ~cohol
flood was the interracial tension.
The results of these floods are given in Table 7
and are shown @ Figs. 7 and 8. Recovery for che
Triton X;1OO fldod was 5.7 per cenc pbre volume
more than the controL Recovery for the alcohol
flood was 6 per cent pore volume more than the
control. The additional recovery is less than the
11 per &ent recovery obtained with similar interfaciai
tension reduction in amine displacing oil from Drifilmed core. The reason is that, in the latter case,
the displaced phase is the wett; ng phase.
,
Moore and Blum7 have shown that a wetting
phase remains continuous behind the displacement
front, while non-wetting phase residuals are discontinuous, Consequently, wetting phase residuals
can be mobilized
with a sm.aller reduction
in
interracial
tension, because . longer Iengths
of
,.residuals result in greater hydrodynamic pressure
drop across them.

oil recovery from water-wet cores did not increase

over that of contr& The core was water wet during
the control but had neutral nettability,
as indicated
by a contact angle of 900, during 0,0 l-normal amine
flood. The results are given in Table s and are
shown in Figs. 7 and 8. A small amount ?f additional
recovery waa obtained from Dri-filmed cores, due
perhaps to, the reduction of interracial tension from
47 to 29 dynes/cm. Thus, neutral nettability floods
recovered less than the wettabilitv reversal and the
low interracial tension floods.

-t
CONC&ONS

NEUTRAL

NETTABILITY

FLOODS

TABLE
Flood

Number
. . .

~,
122
~.
,
;-.
,=. .... ....

Core

COintrOl

---- D-26;
WW:- -

8 &

0.01

1, Reducing interracial
tension born 47 to L 1
dynes/cm
resulted
in increased
recovery.
The
increaae in recovery= was greater, if the displaced
phase was the wetting phase.
2. Nettability
reversal
from oil-wet to waterwec conditions
resulted
in some additional oil
recovery.
3. NeutraI
wetcabilicy
did not increase
oil
...
recov erv.
4. A~ink
transport
in Dri-filmed cores was
predictable
by equilibrium. chromatography y. In
water- wet cores, the amine band moved faster than
predicted by theory.
,

Wberr a 0,0 l-normal amine solution was used. to

flood water-wet and Dri-filmed alundum cores which
had been equilibrated with 0;0 l-normal solution, the

l-

INJECTION , PORE

X:100

,..
,,.. ..-.

J.

.+

SUMMARY OF FLOODS WITH 0,01 NORMAL AMINE

Equll Ibrlum

Interstltlal
Phase

Wettabilit y

NEutraI

29

D. 26, V/W

Neutrsl

30

0-26, WW

&trol
32

Inlectlon
Rote

(ft/o)
18,0 --

.2,

Residual

011

Iniection

. . ----

... _ -. ;.

-..

. ..-.-32.5..

18,5

21

32,1

Neutral

19;0

21

32,3

D-28, Ow

Oil Wet

20,5

21

30,5

D-28, OW

Oil Wet

21,3

21

27.0

..

.-

i
#....

...... . .

..
-

..

-- .,,.

.-

.,.

. sOCIETY

OF PFTROLItUM

ENGINEERS

JOURNAL

. ...

..-.
: -:

::::-

----

-.

,---

-----

,+
,

4. Lesch,

REFERENCES

c,

& 1% and limrnins, R, S.: WtwomatograPMo Tranaport of Reverse-Wettin~ Agents snd

Its Effect on 011 Displacement in Porous Medla$~,

L Mictmels,

R. O., Wagner, 0. R., Wood, H, W, and Harpke,

F,: UA Laboratory and Field Study of weftability

A4 ustment In Water Flooding, Trans., AIME (1962)

vol.

225,

206,

Trarie., AIME ( 1960) Vol. 219, 1S0.

R O.: (Improving Oil.
2. Wagnek, 0, R and Leach,
Displacement
Efficiency
by Wettsbllity Adjustment>r,
Tram%, AIME ( 19S9) Vol. %6, 65.

5! Hough, E. W. and Heathington, K.: 4~A Simplified

Pendsnt
Drop Apparatus for Uae at Atmospheric
Pressure}), Prod, Monthly (1961) Vol. 25, No, 5, 21,
6. Taber, J. J,: +l%e Injection Of Detergent slugs fn
Water Floods~, Trans., AXME (1959) Vol. 213, 1S6,

A.: g~ffect of Chromatographlc

Tranaport
3. Stancell,
of Reverse-Wetting
Agents on Oil Displacement
from
Porous Media$$, SC. D. Tbesfs, M,I;T. (1962).
.,

7, Mo&e,
billty

T. F, and Blum, H, &: UrnpOrtance of WettaAgent Water Flooding}r,

in Surface-Active

***

Oil & Gas Jour. (1952) Vol. 51, No, 31, 108.

,1-

,.

.?

,,

..

.-

--

-.

_.-_..-:

-.

JUM!.

1964.

._ -_=

:_, 1