American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc

Download as pdf or txt
Download as pdf or txt
You are on page 1of 18

SOCIETY OF PETROLEUM ENGINEERS OF AIME PAPER

NUMBE:R
spE ~ 838
\.._) \ '"

Observation of 0 i I -Bank Formation Our i ng


Micellar Flooding
By
K. D. Dreher, Member SPE-AIME, and R. D. Sydansk, Marathon Oil Co.

@Copyright 1976
American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc.
THIS PAPER IS SUBJECT TO CORRECTION
This paper was prepared for the Improved Oil Recovery Symposium of the Society
of Petroleum Engineers of AIME, to be held in Tulsa, Okla., March 22-24, 1976.
Permission to copy is restricted to an abstract of not more than 300 words. Illu·
strations may not be copied. The abstract should contain conspicuous acknowledg-
ment of where and by whom the paper is presented. Publicat~on elsewhere after
publication in the JOURNAL OF PETROLEUM TECHNOLOGY or the SOCIETY OF PETROLEUM
ENGINEERS JOURNAL is usually granted upon request to the Editor of the appropri-
ate journal provided agreement to give proper credit is made.
Discussion of this paper is invited. Three copies of any discussion should be
sent to the Society of Petroleum Engineers office. Such discussion may be presen-
ted at the above meeting and with the paper, may be considered for publication in
one of the two SPE magazines.

ABSTRACT micellar systems was superior in the sandstone


core suggesting that the porous material has an
Observation of micellar systems within po- important influence on tertiary recovery. Reduc-
rous media is important to determine the fate of tion of reservoir water-pore surface interaction
each component (surfactant, cosurfactant, aqueous for a fraction of the in-place water was suggest-
phase, and hydrocarbon) during the displacement ed by the results obtained with the high water
of tertiary oil. It is possible to obtain such content micellar system.
information with the pulsed nuclear magnetic
resonance spectrometer and appropriate experi- Other results show the effect of CaCl 2 and
mental design. Various micellar systems were cosurfactant concentration on the formation of an
observed displacing tertiary decane and water oil-bank during displacement. For a particular
from small sandstone and porcelain cores. micellar system composition high concentrations
of CaCl 2 in reservoir brines need not be detri-
From an analysis of spin-lattice relaxation mental for initial mobilization of tertiary oil.
curves it was found that micellar system water
and cosurfactant are influenced by pore surfaces INTRODUCTION
when an oil-external microemulsion is introduced
into a sandstone or porcelain core. This result Examination of micellar solutions in porous
implies that interaction of the micellar system materials is important to determine the fate of
with the porous material may be more important each component during the displacement of terti-
than the nature (oil or water) of the external ary oil. Also, different kinds of reservoir rock
phase for efficient tertiary oil displacement. may alter the displacement efficiency of these
types of fluids. It is possible to trace certain
High (water-external microemulsion) and low components of micellar solution within core mate-
(oil-external microemulsion) water content mi- rial by appropriate experimental design and use
cellar systems were observed during displacement of the pulsed nuclear magnetic resonance (NMR)
of decane from both types of porous material. technique. This technique has been used to in-
It was noted that the high water content system vestigate fluids associated with a variety of
banked oil (based on a comparison to a piston- different porous solids. Relating the response
like displacement model) better than the low of water confined in porous media to permeability
water content system. Also, it was found that (1,2) and/or pore size distribution (3) has been
behavior (oil-bank formation) of both types of the subject of recent papers. In this paper
References and i 11 ustrati ons at end o.f nr~nflr
522 OBSERVATION OF OIL-BANK FORMATION DURING MICELLAR FLOODING SPE 5838
.-
spin-lattice relaxation data obtained for micel- All chemicals were reagent grade quality.
lar solutions in porous materials and during the The deuterium oxide was 99.8% isotopically pure.
displacement of tertiary decane will be present- The chlorocarbon was hexachloro-1,3-butadiene.
ed. The slug cosurfactants in all cases were alco-
hols: isopropyl (IPA), normal amyl (NAA), pri-
The goals of this work have been to develop mary amyl (PAA), or normal hexyl (NHA). The 320
information concerning the effect of porous mate- and 470 equivalent weight (eq wt) sulfonates were
rial (particularly sandstones) on the behavior 100% active sodium salt petroleum sulfonates ex-
of the surfactant and cosurfactant used in micel- tracted from commercial products. The 410 eq wt
lar solutions and to observe oil-bank formation sulfonate was a composite sample of 100% active
during displacement by different micellar solu- ammonium salt gas-oil sulfonates of our own manu-
tions. This was accomplished by tuning the puls- facture. The high water content micellar solu-
ed NMR spectrometer to respond to protons only. tions utilizing 440 eq wt ammonium salt petroleum
The micellar solutions were composed of differen1 sulfonates were of our own manufacture.
materials so that the component under investiga-
tion was the only material in the system that Two types of porous core rna teri a1 were used
would respond. For example, to observe the sul- in this study: a ceramic and a sandstone mate-
fonate, hydrocarbon was replaced by chlorocarbon, rial. In both cases, the core plugs were 0.89 em
water by heavy water, and isopropyl alcohol by in diameter by 2.0 em long. The ceramic cores
deuterated isopropyl alcohol. A change in the are commercially avail ab 1e from the Coors Porce-
spin-lattice relaxation rate of the sulfonate lain Company coded as P-12-C Porous Ceramic
(in porous material versus bulk solution) could Plugs. This material had a permeability of 210
then be attributed to the effect of the porous md, a porosity of 0. 40 and a surface area to pore
material on the sulfonate. volume ratio of 0.95 x 10 4 cm- 1 • The surface
area to pore volume ratio was determined from a
Decane was selected as the material to be standard nitrogen adsorption isotherm and the
displaced as tertiary oil since it has a spin- porosity. The sandstone core material from a
lattice relaxation rate very much different from producing Wyoming reservoir was characterized as
a micellar solution or water in core material. clean with respect to clays and well consolidat-
Also, the decane relaxation time is not a func- ed. The virgin sandstone was treated in a Soxh-
tion of saturation for cores initially contacted let extractor· in excess of 72 hours with toluene.
with water. The cores were then fired for 4 hours at 450°C
since this core material could not be completely
Certain conclusions have been made concern- cleaned of high molecular weight residual hydro-
ing the displacement of tertiary oil by micellar carbon by treatment in a Soxhlet extractor alone.
solutions. However, these notions must be re- These core plugs had a permeability of 120 md,
stricted to the compositions presented in this porosity of 0.20 and a surface area to pore vol-
report. ume ratio of 11 x 10 4 cm- 1 • The cylinder surface
and an approximate 1 mm concentric ring on the
EXPERIMENTAL outer core ends of the core plugs used in the
fluid displacement experiments were painted with
MATERIALS AND METHODS three coats of a viscous epoxy-based paint to
maintain pressure integrity during the floods.
The NMR instrumentation centered around a Cores to be saturated with fluids were placed
Bruker Model B-KR-322s variable frequency pulsed under a vacuum of < 5 x lo-s mm Hg for an excess
NMR spectrometer. The magnet employed was a of 4 hours. The cores were quickly immersed in
Bruker BE-30-B-9 research magnet with a 30 mm the saturating fluid and left thus for an excess
air gap and having a field inhomogeneity (6Ho) of 6 hours.
of approximately 1 part in 10 6 • A 10 mm temper-
ature control probe was used, which for protons In the fluid displacement experiments using
at 60 MHz, required a rf pulse of approximately the described core material, the micro core hold-
4 microseconds for 90° rotation. A Bruker B-ST- er shown in Figure 1 proved very satisfactory.
100/700 temperature control unit was employed to In the flooding experiments to ascertain recovery
regulate the sample temperature. All reported factors for tertiary decane, core plugs were sat-
NMR data are for protons at 25°C and 60 MHz. urated with brine, flooded with 5 PV n-decane to
Fluids were not degassed with respect to oxygen Swi, flooded with 5 PV brine to Sor and then
since standard vacuum and nitrogen purge degas- flooded with the first increment of micellar so-
sing techniques tend to alter slug compositions lution. The core was then immediately taken out
and are difficult to apply to fluids in porrius of the micro core holder, placed in a NMR sample
media. Diode detection was used for all the tube and pulsed NMR data obtained. Then without
work reported. The 90°-90° pulsed sequence was delay the core was placed back in the micro core
used to generate the spin lattice (TI) relaxation holder and flooded with the second increment of
data. · micellar solution and so on. No attempt was made
523
SPE 5838 K. D. Dreher and R. D. Sydansk
to monitor the produced oil cut directly as a Values of fc1 0 so obtained were compared to s1m1-
function of the pore volume mi~ellar solution lar values for a miscible-piston like displace-
injected since the total volume of residual n- ment based on material balance. This was done to
decane in the sandstone core was about 0.08 cc. conveniently visualize the NMR data. Oil-bank
formation, as presented here, is implied by no
DATA ANALYSIS movement of decane during the first 25% PV of
micellar solution injection. If fc1 0 exceeded or
Spin-lattice relaxation (TI) curves of all was less than the expected value, oil-bank forma-
micellar solutions were nonlinear regardless of tion did not occur in accordance with the model
whether data were obtained for the bulk system, presented in Figure 10.
in a ceramic core, or in a sandstone core. In
order to determine relaxation times and fractions RESULTS AND DISCUSSION
with a particular relaxation time, spin-lattice
decays were fit with a two component slow ex- OIL RECOVERY FLUIDS IN POROUS MEDIA
change model by the nonlinear least squares meth-
od. The equation is: Micellar fluids of varying compositions were
examined in ceramic and sandstone cores. These
micellar solutions were composed of different
materials so that information about various com-
ponents could be obtained with the NMR. Relaxa-
tion data were determined at 100% saturation of
the micellar solution in the core material. T1
where M is the equilibrium magnetization,
00
decays were obtained and data fit with the two
component slow exchange model. Figure 2 shows
M is the magnetization at time t, relaxation curves for a water-external micellar
solution in bulk, in a ceramic core, and in a
fa is the fraction of spins with sandstone core. This system had composition I
relaxation time Ta, and (shown in Table I) and had all the characteris-
tics of a water-external micellar solution. In
fb is the fraction of spins with bulk, the T1 relaxation was nonlinear with a
relaxation time Tb· short time of 40 msec and a long time of 1800
msec. The short component equaled 7% of the
Although relaxation times and fractions are pres- total relaxing species in the micellar solution.
ented for the curves obtained for micellar solu- These times and fractions must be considered
tions, this is done only for convenience of com- representative of the system as a whole since the
parison of different systems. When Ta and Tb are fractions do not correspond to any one component
close in value any one data fit by the least within the micellar solution. As can be seen in
squares method may not give a unique solution. Figure 2, at 100% saturation in ceramic and sand-
stone cores, the relaxation rates were enhanced.
To determine the fraction of decane (fc 10 ) In the ceramic core, the short relaxation time
in a core during a displacement, the thermal was 220 msec; the long relaxation time, 610 msec.
relaxation curves were fit with a three component The short fraction amounted to 44% of the total
model of similar form. However, further restric- relaxing species in the micellar solution. It is
tion was placed on the generation of fc1o by interesting to compare this relaxation curve with
imposing· known relaxation times of each component that of 100% water saturation which is linear in
on the data fit. The times used were determined this particular core with a relaxation time of
for micellar solutions, water, and water and 700 msec. In the sandstone core, the short re-
decane in the appropriate core material. At each laxation time was 20 msec and the long time 180
saturation, i.e., point of micellar solution in- msec. The short component made up 24% of the
jection, these times would correspond to the total relaxing species in this core.
times one would expect for the miscible-piston
like displacement shown in Figure 10. Since Figure 3 shows the relaxation curves for a
fa+ fb + fc1o = 1, there are only two parameters micellar solution of identical composition with
that can vary (fb and fc1o), and the data fit respect to moles of each constituent; however,
will be unique. in this case the H20 was replaced with deuterium
oxide (D 20) so that the only responding species
Only fc1o data are presented here. Through were the sulfonate and IPA. This micellar solu-
experimentation it was found that the relaxation tion had composition II. In bulk, this micellar
time of decane did not vary with saturation in a system had a short relaxation time of 34 msec and
core initially contacted with water. Therefore, a long relaxation time of 560 msec. The short
fc1o is that fraction of spins with a relaxation component amounts to 50% of the relaxing species.
time of 1700 msec. This time is much longer than Again, these times do not correspond to either
the micellar solution and water relaxation times the total IPA or the total sulfonate in the sys-
in porous media and, for this reason, fc1o is tern. A comparison of the long relaxation times
easily determined. for the data shown in Figure 3 with that shown in
524
OBSERVATION OF OIL-BANK FORMATION DURING MICELLAR FLOODING SPE 5838
Figure 2 indicates th-at the 1800 msec relaxation. Also, data i.n figures 2, 3, 4, and 5 indicate
time for the composition that contained water was that the IPA in both the water-external and oil-
due to the water. In the ceramic core, the mi- external micellar solutions was influenced by
cellar solution containing 020 had a short relax- pore surfaces. The bulk relaxation time for IPA
ation time of 130 msec and a long relaxation time is on the order of 1600 msec. In all cases, the
of 830 msec. The short relaxing component longest time observed for these micellar solu-
amounted to 49% of the relaxing species. Al- tions in a core was much less than this value.
though these times are somewhat longer than the
times obtained for the micellar solution in bulk, To determine what effect core material may
the general shape of the curves is very similar have on the relaxation characteristics of sulfo-
and the fractions remain the same suggesting nate alone, micellar solutions were prepared with
little or no interaction of either the sulfonate deuterated-IPA (D-IPA), 020, and chlorocarbon.
or the IPA with the ceramic core surfaces. In The results for an oil-external micellar solution
the sandstone core, the short relaxation time are shown in Figure 6. This system had the com-
was 47 msec and the long relaxation time, 260 position shown under V in Table I. Thus, the
msec. The short fraction amounted to 33% of the only responding species was the sulfonate. The
relaxing species. This suggests that the sulfo- relaxation was nonlinear for the bulk micellar
nate and IPA are being influenced by the pore solution . .The fast component (38 msec) accounted
surfaces when in a sandstone core. for 25% of the total protons. The long time was
170 msec. In the ceramic core, the T1 relaxation
Figure 4 shows the T1 relaxation curves for curve was almost identical. In the sandstone
an oil-external micellar solution in bulk, a core the fast component (34 msec) accounted for
ceramic core and a sandstone core. This system 31% of the protons. The long time was 140 msec.
had composition III. The fast relaxation time As can be seen the ceramic and sandstone cores
for this system equaled 75 msec; the long relax- had only a minor effect on the relaxation char-
ation time, 1600 msec. The fast component acteristics of this micellar solution.
amounted to 20% of the relaxing species. In the
ceramic core, the short component relaxed in 62 A comparison of the data shown in Figure 5
msec and the long component. in 340 msec. The with that shown in Figure 6 indicates that the
short fraction amounted to 38% of the relaxing long time associated with composition IV is due
species. In the sandstone core the short relax- to the presence of IPA. This result confirms the
ation time was equal to 11 msec and the long notion that IPA is influenced by pore surfaces.
relaxation time 89 msec. Again, the short frac-
tion amounted to 38% of the relaxing species. Figure 7 shows similar data for a micellar
solution composed of composition VI. The fast
Figure 5 shows comparable data for an iden~ relaxation rate (140 msec) accounted for 80% of
tical oil-external micellar solution as in Figure the relaxing species. The long time was 1400
4 except that D20 is substituted for H20. This· ms~c. In the ceramic core 67% of the protons
micellar system contained composition IV. This relaxed in 120 msec and the remainder in 510
new composition had a short relaxation time of msec. In the sandstone core the times were 88
90 msec and a long relaxation time of 770 msec. msec (71% of the protons) and 540 msec. These
The short fraction amounted to 60% of the total data again suggest little influence of pore sur-
relaxing species. Because of the difference faces on the relaxation rate for the sulfonate,
between the long component for the micellar solu- in this case a water-external system.
tion that contained water and the system that did
not contain water, i.e., 1600 vs 770 msec, the The curves shown in Figure 7 can be compared
long relaxation time of the slug containing water to those shown in Figure 3 (composition II).
must be attributed to the water. Although the With the exception of the data obtained in the
only relaxing species in this micellar solution sandstone core, the relaxation rates are similar.
are the sulfonate and IPA, the times and frac- There was significant enhancement of the rate for
tions do not correspond to either the sulfonate the system that contained IPA in the sandstone
or IPA. In the ceramic core this composition had core. Thus, for the water-external system sulfo-
a short relaxation time of 66 msec and a long nate and IPA cannot be easily separated.
relaxation time of 300 msec. The fraction relax-
ing at the faster rate amounted to 46% of the The fact that sulfonate relaxation rates
total relaxing species. In the sandstone core were not enhanced by the ceramic or sandstone
the short relaxation time equaled 24 msec and the surfaces does not necessarily mean that adsorp-
long relaxation time 120 msec. The fast species tion did not occur. However, the number of
amounted to 27% of the total relaxing component. adsorbed sulfonate molecules must be small rela-
The major conclusion to be drawn from the data tive to the total number under these conditions.
shown in Figures 4 and 5 is that the water in an
oil-external micellar solution with a small Figures 8 and 9 show relaxation curves ob-
amount of water, i.e., on the order of 20% by tained with mic~llar solutions containing NAA in-
weight, was influenced by the pore surfaces. stead of IPA. This cosurfactant is predominantly
525
SPE 5838 K. D. Dreher and R. D. Sydansk
oil soluble as opposed to the predominatly water no oil is displaced in the first 25% of a pore·
soluble IPA. Data shown in Figure 8 were obtain- volume injection. Following this, oil and water
ed with a water-external micellar solution of are displaced in amounts proportional to their
composition VII. The bulk micellar system had a relative saturations. At 1 PV micellar solution
fast relaxation time of 220 msec (49% of the injection both core water and residual oil should
protons) and a long relaxation time of 1100 msec. have been completely displaced.
In the ceramic core these times were 120 msec
(35% of the protons) and 540 msec, respectively. Figure ll shows a typical core preparation
In the sandstone core the short time was 54 msec sequence. A T1 relaxation was obtained at 100%
(29% of the protons) and the long time, 270 msec. water saturation, at 25% of a pore volume decane
Again as with the water-external micellar system injection, at 50% decane injection, at 1 PV dec-
containing IPA, the NAA is influenced by pore ane injection, and at 5 PV decane injection.
surfaces -- more so by the sandstone than by the These curves were analyzed. by fitting the T1
ceramic. decays with the two component model. The relax-
ation time for decane was the only parameter
Figure 9 shows data obtained for a micellar fixed at a constant time in the data analysis.
sys tern of composition VII I . This oil-external The times and fractions genera ted do not corre-
micellar solution had a fast relaxation component spond to the amount of decane present in the core
of 150 msec (49% of the protons) and a long time until 5 PV of decane injection have been reached.
of 750 msec. In the ceramic core these values This suggests that as the decane displaces the
were 120 msec (47% of the protons) and 480 msec, water, water is emulsified into the decane.
respectively. In the sandstone core the fast
component was 67 msec (46% of the protons) and Figure 12 shows data obtained during the
the long component, 240 msec. As with a water- waterflood. For comparison, the relaxation curve
external system containing NAA, NJV\ in the oil- obtained at 5 PV of decane injection is shown.
external system is influenced by pore surfaces. This is followed by 25%, 50%, 100% and 500% of a
pore volume of water injection. Following 50% of
Thus, both predominantly oil soluble and a pore volume of water injection, all relaxation
predominantly water soluble cosurfactants in curves were identical both with regard to frac-
both oil-external and water-external micro- tions and times for the oil-in-place. This sug-
emulsions have enhanced relaxation rates in the gests that residual oil saturation was obtained
presence of pore surfaces. This implies drastic during the first 50% PV of water injection. The
structural changes in the micellar system are short relaxation time obtained at 5 PV of water
brought about by the presence of the porous media injection corresponds closely to an average for
or that the lifetime of a single micellar unit the short and long times one would expect for
is much less than the fast component of the water in this core at this saturation.
relaxation rate.
As 9n example of a miscible displacement,
OIL-BANK FORMATION BY MICELLAR FLUIDS decane and D20 were displaced from a sandstone
core by IPA. Data were fit with a two component
The next series of figures will show the model, and the saturation of decane relative to
displacement of tertiary oil by some of these other relaxing species was determined.· Since IPA
micellar solutions. In all displacements, the and decane respond, their relaxation times in the
oil used was decane. To evaluate the relaxation core were imposed on the data analysis. The
curves obtained at various points of fluid in- fraction of decane (fclo) is shown in Figure 13.
jection, relaxation times were fixed at constant As can be seen, the displacement follows the
values depending on what fluid saturations should model values up to half of a pore volume IPA
be present in the core at various pore volumes of injection. Following this there is little or no
injection. Saturations so generated were compar- decane displacement .. This suggests that the dec-
ed to a miscible piston-like displacement. Fig- ane was bypassed by the IPA probably due to a
ure 10 shows the model with hypothetical satura- lack of mobility control. Note that the decane
tions to which these displacements were compared. fraction does not follow the oil saturation de-
Core material was initially saturated with dis- picted in Figure 10. This is because D20 used as
tilled water. This was displaced by decane to pore water does not respond to the NMR.
residual water saturation. Following this, water
was injected to displace oil. Approximately 5 PV The next series of figures shows displace-
of water were injected. At the end of oil pro- ments of decane and water from porcelain and
duction a T1 decay was obtained with the NMR for sandstone cores with the micellar solutions de-
the proton containing materials. Then 25% of a scribed in Figures 2 through 5 and Table I. Fig-
pore volume of micellar solution was injected and ure 14 shows data for the displacement of decane
another decay obtained. In the experiments re- from ceramic cores with micellar solution campo-
ported here, decays were taken at 25%, 50%, and sitions I, II, III, and IV in Table I. The fc1o
l PV of slug injection. Figure 10 shows what the represents the fraction of decane responding.
oil and water saturations should ~e for a misci- Again it should be pointed out that these frac-
ble piston-like displacement. It is assumed that tions do not indicate saturations based on pore
526
OBSERVATION OF OIL-BANK FORMATION DURING MICELLAR FLOODING SPE 5838
volume but represent the fraction of proton con- fraction of in-place core water did attain a
taining species with the relaxation time for dec- relatively long relaxation time.
ane in the core. Displacements with compositions
I and II (water-external micellar solutions) rep- EFFECT OF SALT, COSURFACTANT, AND SULFONATE
resent repeat experiments except that H20 was re- CONCENTRATION
placed by D20 in the micellar solution. The same
is true for compositions III and IV. The next series of displacements was direct-
ed at examining the effect of reservoir water
Deviation of the NMR data from the expected CaCl2 concentration and micellar solution co-
result during displacement with micellar solu- surfactant concentration on oil-bank formation.
tions I and II is in a direction that suggests Results obtained with different amounts of CaCl2
more decane is in the core than the initial sat- in D20 used to initially saturate sandstone core
uration. Since this cannot occur, oth~r-mate­ material are shown in Figure 17. This micellar
rial, surfactant or H20, was altered during the solution had composition IX. With 0 ppm CaCl2 ir
displacement so that these materials had a relax- the core D20, fc 10 values were close to the ex-
ation rate comparable to decane. The fact that pected indicating good oil-bank formation. At
displacements I and II were similar indicates 250 ppm CaCl2 deviation of observed and expected
that a fraction of core water may have been plac- resu 1ts was· s i gni fi cant suggesting a detrimenta 1
ed in an environment where it no longer was ex- effect of this concentration. At 750 ppm CaCl2,
posed to pore surfaces. there was improvement, and at 4000 ppm CaCl 2 ex-
pected and observed values agreed at all points.
In the case of displacements III and IV Although this concentration of CaCl2 in the mi-
(oil-external micellar solutions) shown in Fig- cellar solution aqueous phase had a detrimental
ure 14, deviation was below the expected values effect on system stability, it did not inhibit
indicating the absence of oil-bank formation. oil-bank formation when present in the reservoir
Decane was either solubilized into the micellar aqueous phase. This result again suggests an
solution and the time shortened or it was dis- influence of core material on micellar solution
placed during the first 25% PV of micellar solu- phase stability and behavior. Finally, this
tion injection. Comparing displacement by micel- particular result may not be observed with a
lar solutions I and II with III and IV shows that different sulfonate.
the water-external system was much more efficient
than the oil-external system. Figures 18 and 19 show the effect of co-
surfactant concentration and type on oil-bank
Figure 15 shows the results of similar dis- formation with a micellar solution of composition
placements for sandstone core material. Again, X. As can be seen observed values for fc 10 were
fc1o exceeded expected values during the dis- less than expected with no cosurfactant in the
placement by micellar solutions I and II (water- micellar solution. Addition of 0.75 ml PAA/100 g
external). During displacement with micellar mi-cellar solution (composition X) or 0.6 ml PHA/
solutions III and IV (oil-external) expected and 100 g micellar solution (composition XI) improved
observed values agreed closely but ultimate re- agreement between observed and expected results.
covery was poor. This is shown by the high value The exact role of cosurfactant in tertiary oil
for fc1 0 at 1 PV micellar solution injection. displacement cannot be deduced from these re-.
This result indicates that decane was bypassed by sults. Improved compatibility of cannate fluids
the micellar solution. Thus, in both the ceramic with micellar solution may be involved (4).
and sandstone cores displacement by the water-
external system was more efficient. Data obtain- Figure 20 shows fc1o obtained for a series
ed during these displacements showed that micel- of displacements with a micellar solution that
lar solution integrity was maintained better in initially had composition XII. This system was
the sandstone core than the ceramic core, sug- diluted with tap water to give sulfonate concen-
gesting significant influence of the core mate- trations of 9.95, 4.98, 1.99, and 1.00 wt %. As
ria 1. can be seen sulfonate concentrations 19.9, 9.95,
and 4.98 wt % performed in an almost identical
To further evaluate the possibility of the manner. Significantly, oil-bank formation was
alteration of in-place water, a sandstone core similar for these three floods at 25% PV micellar
was initially saturated with D20 instead of H20. solution injection. This is shown by agreement
Displacement of decane was with micellar solution between observed and expected values at this
II. These results are shown in Figure 16. As point. The other sulfonate concentrations gave
can be seen, fc1o falls below the expected values results that deviated from the expected values
for this displacement indicating that the hydro- (in a direction suggestive of micellar solution
carbon is being displaced throughout the flood. components mixing with decane, i.e., solubiliza-
This is shown further when fc1a is plotted as a tion) and essentially no decane was displaced as
percentage of the pore volume. This is contrary shown by the value of fc1a at 1 PV injection.
to the displacements in sandstone cores in which These results suggest that a minimum sulfonate
water was used and the hydrocarbon values exceed- concentration is required to produce an oil-bank
ed the expected values thus confirming that a ahead of the micellar solution.
'--------------------------'----
527
SPE 5838 K. D. Dreher and R. D. Sydansk
CONCLUSIONS
Certain observations were made from the NMR Therefore, because of the influence of the core
data presented here. However, these conclusions material on phase behavior, miscibility need
must be limited to the specific compositions and not be involved in the displacement of tertiary
displacement systems used. Other types of mi- decane by concentrated surfactant systems.
cellar solution components, such as different
petroleum sulfonates, may not give the same re- Further:
sults. Also, the effect of core material on
oil/water relative permeabilities (and thus, 6) high divalent ion concentrations in
oil-bank formation) may be a significant factor. reservoir brines need not be detrimental
to oil-bank formation,
For the micellar solution compositions
reported here:
7} cosurfactants appear to aid in oil-bank
l) the relaxation rate of water in an oil- formation, and
external micellar solution is enhanced
in both ceramic and sandstone cores 8) there appears to be a minimum sulfonate
indicating contact with pore surfaces, concentration for efficient oil-bank
formation.
2) both water soluble and oil soluble co-
surfactants show enhanced relaxation REFERENCES
rates in oil-external and water-external
11
microemulsions due to the presence of 1. Seevers, D. 0., A Nuc 1ear Magnetic Method
pore surfaces, and for Determining the Permeability of Sand-
stones,11 Trans. SPWLA 138:682 (1966).
3) sulfonate relaxation rates in micellar
solutions are not influenced to the same 2. Timur, A., 11 Pulsed Nuclear Magnetic Resonance
extent as other components by pore Studies of Porosity, Movable Fluid, and
surfaces. Permeabi 1i ty of Sands tones, 11 Trans. AIME
246:775 (1969).
Thus, the lifetime of a microemulsion droplet in 11
core material is short relative to the relaxa- 3. Loren, J. Dq and J. D. Robinson, Relations
tion rate or the core material causes a micellar Between Pore Size, Fluid and Matrix Proper-
system structure different from a simple oil- ties and NML Measurements. 11 SPE 2529 --
external or water-external microemulsion. At presented at the 44th Annual Meeting of SPE
100% micellar solution saturation, sulfonate ad- (1969).
sorption is small relative to the total number 11
of sulfonate molecules present. 4. Jones, S. C., and K. D. Dreher, Cosurfac-
tants in Micellar Systems used for Tertiary
During displacement: Oil Recovery. 11 SPE 5566 -- presented at the
50th Annual Meeting of SPE (1975).
4) the high water content micellar solution
(410 eq wt sulfonate) was more efficient NOTE
at banking decane than the oil-external
micellar solution in both ceramic and Compositions VIII through XII shown in
sandstone cores, and Table l do not total 100 wt %. The difference
represents the amount of salt present in each
5) the high water content system caused a system.
portion of the in-place water (not
micellar solution water) to be confined
or structured so as to reduce the water-
core surface interaction.
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _____;L-..-.--
~
_
_
TABLE 1 - MICELLAR FLUID COMPOSITIONS

C001posi ti on I II III IV v VI VII VIII IX X XI XII


Sulfonate 8.5 wt % {410 eq wt) 8.0 (410) 7.1 (470) 6.9 (470) 6.3 (470) 8.0 (410) 8.0 {320) 5.2 (425) 16.3 (440) 14.9 (440) 14.9 (440) 19.9 (440)
Ch 1orocarbon 28.6 wt % 27.0 71.0 69.7 63.3 26.9 26.8 77.4
H20 59.6 wt % 19.1 - 73.5 74.3 74.3 67.7
020 - wt% 61.8 - 20.6 27.6 61.5 61.8 14.5
IPA 3. 3 wt % 3. 2 2.8 2.8
D-IP A - wt% - 2.9 3.6
NAA - wt % 3.4 1.6
Na Hexane Sulfonate - wt %
Hydrocarbon - wt % - - 6.5 5.9 5.9 7.9
( NH~) 2so~ - wt % - - - - - 3.1 4.3 4.3 3.8
PAA - ml/100 g slug - - - 1.25 o. 75
PHA - ml/100 g slug - - 0.6
TO lOcc RURET

1/16" NYLON TUBING

0.89CM DIAMETER CORE


PAINTED 3 TIMES WITH
EPOXY PAINT
PRESSURE
TRANSDUCER

FIG, 1 - ScHEMATIC OF CORE FLOODING APPARATUS USED FOR


DISPLACING DECANE FROM CORE MATERIAL SUITABLE FOR
ANALYSIS WITH THE NMR.

--Bulk
- - Ceramic Core
-··-Sandstone Core

Time (m sec)
FIG, 2 -SPIN-LATTICE RELAXATION CURVES FOR MICELLAR
SOLUTION IN BULK, CERAMIC CORE, AND SANDSTONE CORE,
CoMPOSITION 1.
--Bulk
--Ceramic Core
- · · - Sandstone Core

Time (m sec)
FIG, 3 - SPIN-LATTICE RELAXATION CURVES FOR MICELLAR
SOLUTION IN BULK) CERAMIC CORE) AND SANDSTONE CORE,
CoMPOSITION 2.

I.J
::::E
........

::::E
's
::::E

--Bulk
--Ceramic
- .. -Sandstone Core

Time ( m- sec)
FIG, 4 - SPIN-LATTICE RELAXATION CURVES FOR MICELLAR SOLUTION
IN BULK) CERAMIC CORE) AND SANDSTONE CORE, COMPOSITION 3,
--Bulk
--Ceramic
-··-Sandstone

Time (msec)
FIG, 5 - SPIN-LATTICE RELAXATION CURVES FOR MICELLAR SOLUTION
IN BULK) CERAMIC CORE) AND SANDSTONE CORE, COMPOSITION 4,

:E 0.1
·s
:E

--Bulk
f --Ceramic Core
-··-Sandstone Core

Time (m sec}
FIG, 6 - SPIN-LATTICE RELAXATION CURVES FOR MICELLAR SOLUTION
IN BULK) CERAMIC CORE) AND SANDSTONE CORE, COMPOSITION 5,·
~ 0.1
B
:E

--Bulk
--Ceramic Core
-··-Sandstone Core

Time (msec)
FIG, 7 - SPIN-LATTICE RELAXATION CURVES FOR MICELLAR SOLUTION
IN BULK, CERAMIC CORE, AND SANDSTONE CORE, CoMPOSITION 6,

··~
.,
"·"\. ""
\.. "
.
\ .. ',
\ '
:E 0.1
18
"
::E

--Bulk
--Ceramic Core
-··-Sandstone Core

Time (m sec)

FIG, 8 - SPIN-LATTICE RELAXATION CURVES FOR MICELLAR SOLUTION


IN BULK, CERAMIC CORE, AND SANDSTONE CORE, COMPOSITION 7,
,\""'
. ,
.
........
I So • 0.40
Sw = 0.60
I
JL ~L
PV Slug Injected
·.
,
'··'··"
.........

..
.................
......... , ', 0.25
-
JL ~L
9
:E
........
i" 0.1
'
9
:E
I

Ss = 1.0
So = 0.53

Sw = 0.47
JL_ ~b_
0.5

--Bulk

JL
--Ceramic Core

~~
-··-Sandstone Core

0.75

Time (m sec)

I ~L ~~
FIG, 9 - SPIN-LATTICE RELAXATION CURVES FOR MICELLAR SOLUTION
IN BULK, CERAMIC CORE, AND SANDSTONE CORE. COMPOSITION 8,
I s,•LO

FIG. 10 - DISPLACEMENT MODEL TO WHICH FRACTIONS OBTAINED FROM


NMR DATA WERE COMPARED. SS = MICELLAR SOLUTION SATURATION,
SW = WATER SATURATION, AND S0 = OIL SATURATION,
e --100%H20
:E
....... - - 0.25 PV Decane Injected
i"I 0.1 - · - 0.5 PV Decane Injected
e - · · - l.O PV Decane Injected
:E
-···- 5.0 PV Decane Injected

100% H20 fs =0.32 Ts =30, TL =290


0.25 PV C10 fs =0.58 Ts =86 Tc 10 =1700
0.50 PV C10 fs =0.42 Ts =55 Tc 10 =1700
1.00 PV c10 fs =0.37 Ts =38 Tc 10 =1700
5.00 PV C10 fs =0.29 Ts =33 Tc 10 =1700

Time (m sec)
FIG, 11 - FRACTIONS OBTAINED FROM NMR DATA AFTER SATURATING
WITH WATER AND FLOODING TO Sw 1 WITH DECANE,

--5.0 PV Decane Injected


---0.25PV H20 Injected
.} ---5.0 PV H20 Injected
.......
i" 0.1
'e
:E

5.0 PV Decane fs=0.29 T5 = 3_3, Tc 10 =1700


0.25 PV H20 fs = 0.55 T5 =106, Tc 10 =1700
0.5 PV H20 fs =0.57 Ts =110, Tc 10 =1700
1.0 PV H20 fs =0.56 Ts =104, Tc 10 =1700
5.0 PV H20 fs =0.61 Ts =110, Tc 10 =1700

100 200 300 400 500 600


Time (m sec)
FIGA 12 - FRACTIONS OBTAINED FROM NMR DATA DURING WATERFLOOD
TO ~?R'
I rr
1.0
1.00
~
~
u
0.75
c:
.Q
uc 0
._§
"-
LL
Q)
c:
c
u
Q)
0

0.25 0.50 0.75 1.00

PV Micellar Solution lniected


0.5
PV IPA Injected
FIG. 13 - MISCIBLE DISPLACEMENT OF DECANE
FROM A SANDSTONE CORE WITH IPA. 0-0 MODEL.
•-• Nr·1R DATA.
:nr TI[

1.00 1.00

~
u
'+-

00 0.25 0.50 0.75 1.00 0.25 0.50 0.75 1.00

PV Micellar Solution lniected


FIG. 14 - DECANE FRACTION OBTAINED FROM NMR DATA DURING DISPLACE-
MENT FROM CERAMIC CORE BY: A) MICELLAR SOLUTION IJ B) MICELLAR
SOLUTION llJ c) MICELLAR SOLUTION lllJ AND D) MICELLAR SOLUTION
IV. 0-0 MODEL DISPLACEMENT. ·-· NMR DATA.
I Ir

.. 00

0 0

.........u .........u

I I I
li 1I
'6
0.25 0.50 0.75

1.00
PV Micellar Solution Injected
I ~
0.75
>

05t
a..
~

~
y
0
~ 0.50
u
1[[ TI[ () .., .:;; 0.25

l.OOr 1.001 '"'o 0.25 0.50 0.75 1.00 00 0.25 0.50 0.75 1.00

~ PV Micellar Solution Injected


.........u
FIG, 16 - DECANE FRACTION OBTAINED FROM NMR DATA DURING DIS-
PLACEMENT FROM SANDSTONE CORE BY MICELLAR SOLUTION II. CoRE
WAS INITIALLY SATURATED WITH D20 INSTEAD OF H20. 0-0~0DEL
DISPLACEMENT. ·-· NMR DATA.
0.25 0.50 0.75 1.00 0. 25 0.50 0.75 1.00

PV Micellar Solution lniected


FIG .. 15- DECANE FRACTION OBTAINED FROM NMR DATA DURING DIS-
PLACEMENT FROM SANDSTONE CORE BY: A) MICELLAR SOLUTION IJ
B) MICELLAR SOLUTION II c) MICELLAR SOLUTION IIIJ AND D)
MICELLAR SOLUTION IV, 6-0 MODEL DISPLACEMENT, ~-~ NMR DATA,
' '

Oppm 250ppm

PV Micellar Solution Injected

750 ppm 4,000ppm

PV Micellar Solution Injected


FIG, 17 - DECANE FRACTION OBTAINED FROM NMR DATA DURING
DISPLACEMENT FROM SANDSTONE CORE BY MICELLAR SOLUTION,
COMPOSITION 9, CONCENTRATION OF CAC12 JN CORE D?O:
A) 0 PPM, B) 250 PPM, c) 750 PPM, AND D) 4000 PPM,
0-0 MODEL DISPLACEMENT, 1-1 NMR DATA,

0 ml PAA .75ml PAA 1.58 ml PAA

1.00

0.25

0.25 0.50 0.75 1.00

PV Micellar Solution Injected


FIG, 18 - DECANE FRACTION OBTAINED FROM NMR DATA DURING
DISPLACEMENT FROM SANDSTONE CORE BY MICELLAR SOLUTIO~,
CoMPOSITION 10. A) 0 ML PAA/100 G MICEL~AR soLUTION,
B) 0.75 ML PAA/100 G, AND c) L.58 ML PAA/100 G,
0-0 MODEL DISPLACEMENT, 1-1 NMR DATA,
0 ml PHA 0.6 ml PHA 1.30 ml PHA

1.00

0
o 0.25 0.50 0.75

PV Micellar Solution Injected


FIG, 19 - DECANE FRACTION OBTAINED FROM NMR DATA DURING
DISPLACEMENT FROM SANDSTONF, CORE BY MICELLAR SOLUTION.
CoMPOSITION 11. A) 0 ML PHA/100 G MICELLAR SOLUTION,
B) 0.6 ML/100 G, AND 1.30 ML/100 G, 0-0 MODEL DISPLACE-
MENT, ·-· NMR DATA.

19.9 9.95

PV Micellar Solution Injected

4.98 1.99 1.00


1.00

0.75

0.25 0.50 0.75 1.00

PV Micellar Solution Injected


FIG, 20 - DECANE FRACTION OBTAINED FROM NMR DATA DURING
DISPLACEMENT FROM SANDSTONE CORE BY MICELLAR SOLUTION,
CoMPOSITION 12 DILUTED WITH TAP WATER TO OBTAIN SULFO-
NATE CONCENTRATIONS SHOWN, 0-0 MODEL DISPLACEMENT.
·-· NMR DATA.

You might also like