Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
2~6~2
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2 The present invention relates to a procass for the
3 enhanced recovery of oil from a ~ubterranean oll-bsaring
4 formation using a surfa~tant-~tabilized foam.
~ 9~ 9E~$~INVEN~LQN
6 In the recovery of oil from a subterranean oil-bearing
7 formatio~ only between about ten to fifty percent o~ the oil in
8 place is recoverable using combined primary and secondary
9 production mode~. As a result, tertiary or enhanced oil recovery
processes have been developed. Such proces~es include thermal
11 procesqes exemplary of which are steam flooding and in-~itu
12 combustion, chemical flooding techniques and gassou3 di~placement
13 drives. The gase~ used may include steam, carbon dioxlde or
14 hydrocarbons.
However, saveral problems occur when a g3s pha~e is
16 used as the displaaing medium. First, fingering o~ the ga~ pha~e
17 into the oil will degrade the unifo~m displacement front with
18 co~comitant reduction in oil recovery. This is a result of the
19 adverse mobility ratio between the displacing gas and the oil.
2~ Seoondly, the density differance between the gas and oil phase
21 will cause gravity override wherein the gas will tend to move
22 upwardly, sweeping onl~ th'e upper portion of the oil-bearing
23 zone. Finally, reservoir heterogeneities and zones o~ relatively
24 well swept (i.e. low oil) rock can cause the displacement fluid
to channel through the oil-bearing zones. All of these phenomena
26 act to reduce the amount of vil recovered.
27 The use of surfactant-stabilized foams comprises a
28 relatively new technology for circumventing these problems.
2 ~ 8 2
1 The foam, having a viscosity greater than the
2 displacing medlum, will preferentially accumulate in the well-
3 swept and/or hlgher permeability zones of the formation. The
4 di~placing m~dium is thus forced to move into the unswept or
underswept areas of the formation. It is from these latter areas
6 that the additional oil is recovered. However, when a foam i~
7 used to fill a low oil content area of the reservoir, the oll
8 contained therein i8, for all practical purpose~, lost. This is
9 because the foam functions to divert the displacement fluid from
~uch areas.
11 The selection of suitable foam-forming surfactants
12 which produce foams having the neoessary stability to collapse
13 and viscosity i~ crucial. Such properties as solublllty, surface
14 tension and bulk foam stability must be taken into consideration.
Typical tests for the evaluation of surfactants would include
16 solubility tests in the salinity and temperature environment of
17 the particular reservoir, bulk foam te~t~ to ensure the stability
18 of the foam to collapse, and permeabllity or pressure drop
19 measurements made in packed sand beds or cores containing
in~ected foam. U.S. Patents 4,589,276 to Djabbarah and 4,601,336
21 to Dilgra~ et. al. cover some of these tests.
22 Rscent ~tudies have indicated that many foams are
23 destroyed upon being brought into contact with an oil pha3e. It
24 is desirable that the foam not collapse upon contact with the
residual oil in the swept portions of the reservoir, nor block
2& unswept portions thereof.
27 The clas~ical description of foam-oil 1nteraction~ has
28 been outlined by S. Ross, J. Phys. Colloid Chem. 54(3) 429-436
29 (1950). Ross sets forth that foam stability ln the presence of -~
o~l can bs described from thermodynamics in ter~ of the `~
` 2~6~2
1 Spreading and Entering Coefficients S and E respectively. ~he~e
2 coefficients are defined as followB:
3 S = Y F ~ Y OF Y O
4 wherein
YOF i8 the foamlng solution surface ten~ion;
6 ~OF i the ~oaming solution-oil interfacial ten3ion;
7. and
8 ~O is the surface tension of the oil.
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9 E = Y F t YOF YO :~
wherein ~`
11 r F~ rOF and yO are as de~ined ~La. ~-
12 Based on these coefficients, one can predict that three
13 typos of oil-foam interactions could take place. First, (Type
14 Aj an oll will neither spread over nor enter the surface of ~oam
lamellae when E and S are le8~ than zero. Seoondly, (Type H) oil
16 wlll enter but not spread over the surface of foam lamellaa when
17 E is greater than zero but S is le~s than zero. Thirdly, ~Type
18 C) oil w~l~ ente~ the ~urfaae of foam la~ellae and then spr2ad
l9 over the lamellae surfaces i~ both E and S are greater than zero.
This latter behaviour, typically, will destabilize the foam.
21 However, experimental results have not borne out these
22 predictions. Furthermore, tha theory was developsd
23 assuming that the oil droplets are readily imbibed into the
24 foam lamellaa. Again however, experimental results show that ~-~
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1 some foams, particularly those of type A ~B do not read~ly
2 lmbibe oil.
3There exl8t8, therefore, a need to distinguish betwe~n
4 foams which are stable to oil but ~lo not signi~icantly imbibe
oil, as in type A su~a, foams which are ~table to oil and do
6 imblbe oil as in the second type above and flnally, foam~ that
7 are unstable to oil a~ in the third predicted type.
8~ 5~LIY~Y351~
9In accordancs with the present invention, it has been
discovered that foams having the propertie~ of being stable in
11 the presence of an oil phase or additionally being func~ional to
12 imbibe and tran~port the oil phase can be realized.
13Furthermora, it has been found that each foam-forming
14 ~urfa¢tant provlding these propertie3 ¢an be determined by one
15o~ two methods. :
16The first method reliea on the discovery that there
17exi~ts a correlation between foam ~tablllty and oil lmbibing ~.
18proparties and a coefficient referred to herein as the ~amella ~ .
19Number (L). More ~pecif~cally, the lamella numbor L is defined :~
as~
21YOF rO ~
2~ L = ; -~:
2 3 ' ' YOF rp
24 wherein
25~OF is the foaming solution surface tenslon;
26rO i3 the radius of an emulsified drop;
27YOF is the foaming solution-oil interfacial tension;
28and
29rp is the radius of a foam lamella Plateauborderwhere
30it initially contacts the oil. ~he Plateau border ~-
11. refers to the part of a foam lamella that has cur~ed
2 ~ 8 2
1 surfaces. Plateau borders occur where a ~oam lamella
2 meet~ either another foam lamella, or a ~urface of
3 another material such as oil or solid.
4 It is to be noted that, becau6e oil imbibition i8 of
interest, rO can be equated to one-half the thicknes~ of a foam
6 lamella.
7 Thu3, when L i8 greater than one, emulsification and
8 imbibition of oil into a foam will occur. If L is substantially
9 equal to, or greater than about seven, the imb~bition of large
amounts of small droplets will result in foam de~truction. Thu~,
11 a surfactant generating a foam which is stable to collapse in the
12 presence of an oil phase would be one having a lamella number
13 le~s than seven. Additionally a foam having the stabllity and
14 which will imbiba and transport an oil phase would be one having
a lamella numbar ranging between one and seven.
16 The second method involves uslng dlrect observatlon of
17 foam behavlour uslng micro-vlsualizatlon apparatus and comparing
18 the observed behaviour with known models 80 as to catagorize said
19 surfactants fun~tional to generate a foam which is stabl~ to ~;:
2~ collapse in the presence of an oil pha~e or which additionally
21 are aapabl~of both imbibing and transporting the oil pha3e.
22 In one broad aspect, the invention provides a method
23 for testing;whethsr a surfactant-containing foam is stable ;~
24 against collapse in the presence of an oil pha~e in a
subterranean format:ion, comprising~
26 determini.ng the lamella number, L, of the foam, by:
27 (a) detsrmining the surface tension of the fo~m, YF;
28 (b) cont:acting the foam with an oil phase;
- 6 - ~
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2 ~ 8 2
1 (c) determining the radills of a foa~ lamella plateau
2 berder where it initially contacts the oil phases
3 rp;
4 (d) determlning the radl~ of an emulsiflad drop of
oil in the foam, rO;
6 (e) determining the inte.rfacial tenslon between the
7 foam and the oil pha~e, ~OF; and
a ( f) calculating L from the mathematical model
9 ~F r
L =
1 1 ~ OF rp
12 and
13 determining whether the L of the foam i8 le~s than
14 seven, said range being indicative of foams which are ~table
lS against collapse in the presence of an oil phase.
16 In another broad aspect, the invention provldes
17 an apparatus for use in selecting a aurfactant-contalning foam
18 which i~ stable again~t collapse in the presence of an oil phase
19 in a subterranean formation, comprising:
a tran~parant cell; ~:
21 a ftrst channel providing for the flow of foam lamella
22 through the cell; and ~.
23 a second channel providing for the flow of oil into the
24 cell, ~aid s~cond channel intersecting and terminating at!said
first channel.
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1 DESCRIPTION OF THE DRAWINGS
2 Figure 1 is a schematic showing the micro-visualization
,: 1
3 apparatus used in one aspect of the practice of the present
4 invention.
; 5 Figure 2 is an illustrative representation of a Type A
6 foam which upon contact wit:h an oil phase shows little
7 interaction therewith.
. , .
8 Figure 3 is an illustrative representation of a Type B
g foam which upon contact with an oil phase has the capability of
imbibing and transporting said oil.
11 Figure 4 is an illustrative representation of a Type C
12 foam which upon contact with an oil phase is destroyed by
13 rupturing of its lamella.
14 Figure 5 is a schematic showing the core flood test
apparatus.
16 Figure 6 is a plot of coreflood MRF (defined below)
17 versus micromodel breakage frequency to illustrate the
18 correlation between coreflood MRF (Residual Oil) and micromodèl
19 foam stabilities.
Figure 7 is a plot of coreflood MRF ratio (Residual oil
21 to MRF oil-free) versus micromodel breakage frequency to
22 illustrate the correlation between normalized coreflood, MRF, MRF
23 (Residual Oil/MRF (Oil-free) and micromodel foam stabilities.
24 Figure 8 is a graph of the oil recovered from
corefloods hy the foam versus the micromodel lamella number to
26 illustrate the correlation therebetween.
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1 DESCRIPTION OF THE PREFERRED EMBODIMENT
2 Having reference to the accompanying drawings there is
3 provided in a first aspect a process for enhancing the recovery
4 of oil in a subterranean formation which involves injecting a
foam having oil imbibing and transporting properties.
6 The foam exhibiting such properties is selected by
7 either of the two methods described herebelow.
8 Determination of the Lamella Number
g There e~ists a correlation between foam stability and
oil imbibing properties and a coefficient referred to herein as
11 the Lamella Number (L). More specifically, the lamella number L
12 is defined as:
O
13 L YF rO
14 ~OF rp
wherein
16 YF is the foaming solution surface tension;
17 rO is the radius o~ an emulsified drop;
18 rOF is the foaming solution-oil interfacial tension; and
19 rp is the radius of a foam lamella plateau border where
it initially contacts the oil.
21 It is to be noted, that because oil imbibition is of
22 interest, rO can be equated to one-half the thickness of a foam
23 lamella.
24 The surface tension can be determined usin~ the
standard du Nouy ring technique as is described in standard ~-
26 textbooks of colloid chemistry. `~
27 The interfacial tensions between the oil and the foam
28 forming solution may be measured using the spinning drop
29 tensiometer as described by J. L. Cayias, R.S. Schechter, and W.
~0~ 2
,~
1 H. Wade in Adsorption at Interfaces, ACS Symp. Ser., No. 8, 234-
2 247 (1975).
3 The radius of an emulsified drop (rO) was determined
using the micro-visualization apparatus described below.
5imilarly, the radius of a foam lamella Plateau border where it
6 initially contacts the oil (rp) was determined using the same
7 apparatus. However, the ratio of the radius rO/rp was measured
8 for a number of surfactant stabilized foams of 95~ quality and
9 found to have a constant value of about 0.15. By ~5% quality is
meant 95 volume percent gas and 5 volume percent aqueous
11 solution. Thus a useful approximation is to use a value of about
12 0.15. In this case the micro-visualization apparatus is not
13 needed and only the surface and interfacial ~ensions have to be
14 measured, which can be done using readily available apparatus.
It is to be noted that the lamella number is the ratio
16 of two forces namely a) the capillary suction force exerted by
17 the foam lamellae causing oil to be drawn up into the lamellae
18 where it is pinched off into droplets and b) the resisting force
19 provided by the interfacial tension of the oil which counteracts
the capillary suction force.
21 Micro-visualization Determination
22 Having particular reference to Figure 1, the micro-
23 visualization apparatus of the present invention utilizes a pair
24 of glass plates 2. A flow pattern 3 is etched into one of the
two glass plates 2a. A key feature of the flow pattern is that
26 advancing foam lamellae and oil could be brought into contact in
27 a con~rollable fashion. The etched pattern represented a model
28 of a small part of the micro-structure in a porous medium. The
: 1 typical pore areas ranged from 380-3000 X 55-65 ~ m. The plates
2 2 were placed together in a holder (not shown) adapted for
observation in a conventional microscope (again, not shown). A
. , .
4 first inlet part 3 was provided for the introduction of foam
therein. A second inlet port 4 communicating with a series of
6 divided inlet ports 5 was provided for introduction of the oil
between the plates 2 and its subsequent contact with the foam.
The novel features of the flow network are (1) that
9 separate injection and control of the flow of foam lamellae and
of the oil are possible, and (2) that channels are provided such
11 that flowing foam lamellae can be observed under two very
12 important conditions as follows. First, the flow behaviour of
13 foam lamellae can be observed in pores and throats in the absence
14 of oil (upper pathways in Figure 1). Secondly, the behaviour of
the foam lamellae can be observed during their initial and
16 subsequent encounters with oil in khe region of the cell where
17 the oil channels intersect the foam channels.
18 The microvisualization apparatus permits assessment of
19 two properties: (1) the ability to imbibe and transport oil,
which can be observed directly, and (2) the stability to breakage
21 in the presence of the oil, which can be measured in the
22 apparatus. The combination of these is assessed versus known
23 models.
24 EXPERIMENTAL
-
The experimental results given in Table I herebelow
26 show the interaction of various foams with David crude oil. The
27 crude oil used was a well head sample produced from the
28 Lloydminster sand, in the David field having a density of 0.9259
:
r)J)6~2
1 g/mL and viscosity of 207 mPa.s, both at 23.0C.
2 TABLE I
O O
3 Surfactant Brine ~F Yo ~OF E S L fb Foam
4 (0.5% mass) Solution mN/N mN/m mN/m mN/m mN/m Type
5 Concentration mass% s-l
6 Fluorad FC-751 0.0 19.3 29.3 6.6 -3.4 -16.6 0.4 0.00 A
7 Fluorad FC 751 2.1 1~.0 29.37.0 -3.3 -17.3 0.4 0.00 A
8 Dow XS84321.05 0.0 35.0 29.34.5 10.2 1.2 1.1 0.02 B
g Dow XS84321.05 2.1 32.2 29.31.2 4.1 1.7 3.9 0.02 B
10 Stepanflo 60 0.0 29.2 29.3 2.5 2.4 -2.6 1.7 0.02 B
11 Varion CAS 0.0 36.0 29.3 0.8 7.5 6.0 7.1 0.03 C
12 Atlas CD-413 o.o 35.0 29.3 0.4 6.1 5.3 13.8 0.03 C
13 Atlas CD-413 2.1 30.7 29.3 0.2 1.6 1.2 23.4 0.05 C ;;
14 Example II ~-
The crude oil was a well head sample produced from the
16 Judy Creek field, Beaverhill Lake pool having a density of 0.8296
17 g/mL and viscosity of 4.6 mPa.s, both at 23.0+ 0~5C. Values
18 obtained for the physical properties and fb are given in!Table II ~`
19 herebelow.
Examples I and II show that for a range of oils ancl
21 foams there is a correlation between the micro-visual method
22 (combination f fb and Foam Type columns) and the first method (L
23 column). Thus either method yields the same needed information.
1 TABLE II
2 Surfactant Brine Foam Oil E S L fb Foam
~ 0.5% mass Conc. Surface Surface Initial Type
4 Tension Tension IFT
mass~ mN/m mN/m mN/m mN/m mN/m s~
.
6 Fluorad FC 751 0.0 19.3 24.3 4.7 -0.3 -9.7 0.60 0.002 A
7 2.1 19.0 24.3 5.2 -0.1 -10.50.53 0.000 A
8 Mixture + 2.1 30.6 24.3 0.667.0 5.6 6.7 0.020 B
Na Dodecyl
~0 Sulfate 0.0 38.3 24.3 5.119.1 8.9 l.1 0.013 B
11 Dow XS84321.05 0.0 35.0 24.32.3 13.0 8.4 2.2 0.018 B
12 2.1 32.2 24.3 0.628.5 7.3 7.6 0.041 C
13 Varion CAS o,o 36.0 24.3 0.5712.3ll.1 9.2 0.042 C
14 2.1 35.7 24.3 0.5011.910.9 10.4 0.039 C
15 Atlas CD-413 0.0 35.0 24.3 0.5111.210.2 10.0 0.039 C
16 2.1 30.7 24.3 0.416.~ 6.0 10.9 0.037 C
. _ .
17 + Mixture of 0.49% VarLon CAS plus 0.01% Fluorad FC-751 surfactants.
Example III
18
19 Using the same light crude oil as in Example II, the
invention was tested in low pressure ambient temperature
21 corefloods.
22 Method. The porous medium used was Berea sandstone cut
23 into 2.5 x 2.5 x 20 cm blocks that had been wrapped in fiberglass
24 tape and cast in epoxy resin. These blocks had pore volumes of
about 30 mL and absolute air permeabilities of about 630 to 1040
26 md. Although the Berea cores were selected to have similar
27 properties there is some unavoidable variation. Th~ cores were
28 flooded using the coreflooding apparatus illustrated in Figure 5.
12
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1 Foam was pregenerated by passing gas and surfactant solution
2 throu~h a 7 micrometre in-line filter. Oil and aqueous phase
3 productions were measured by separating them in a glass buret and
4 drawing off the aqueous phase to a separate container. The kests
were conducted at constant imposed rates of gas and liquid
6 injection. For each ~xperiment a fresh epoxy-coated sandstone
7 core was prepared and saturated with brine by imbibition.
8 Subsequently, the core was flooded as follows: -
9 l. Brine was injected to saturate the core and measure the
absolute permeability to brine.
11 2. Oil was injected into the core, displacing brine, until
12 the residual water saturation was attained. The first
13 few pore volumes were injected from the top down with
14 the core in a vertical orientation and at a very low
rate (2 mL/hr), subsequently 6-8 pore volumes (PV) were
16 injected with the core horizontal, at a high rate (72
17 mL/hr).
18 3. The core was mounted in the apparatus and brineflooded
l9 at a rate of 2-18 mL/hr (linear superficial velocity =
0.3-3 m/day), until the (unchanging) residual oil
21 saturation was obtained, usually after 6-8 PV of brine.
22 4. Gas and brine were injected simultaneously at pre-
23 determined rates in order to measure the pressure drop
24 base lines.
5. Surfactant solution was injected for surfactant pre-
26 equilibration (to satisfy the adsorption requirement of
27 the core and to determine any oil recovery due to
28 surfactant alone); 6-7 PV were injected in 24-48 hours
29 at a :rate of 2-18 mL/hr.
- 13
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1 6. Foam was pregenerated in the in-line filter and
2 injected into the core at an initial pressure smaller
3 than the expected pseudosteady-state injection
4 pressure.
To assure the repeatability of the tests, foam flooding
6 was carried out in a series where rate and foam quality were
7 changed in such a way that the pressure drop was always
8 increasing. Each surfactant was tested using total volumetric
g rates of about l9 mL/hr (3 m/day) and foam qualities of about
g6%. Sufficient time was allowed to attain the pseudosteady-
11 state, an average duration was 2 weeks of continuous operation.
12 From the data in Example III, ~oams predicted to yield
13 types A, B and C behaviour were selected for coreflood testing.
14 The efficiency of the selected foams with re~ard to their
capacity to improve volumetric sweep efficiency in porous media
16 was evaluated based on mobility reduction factor (MRF): a ratio
17 of the pseudo-steady state pressure drops across a core with foam
18 and with only gas and brine flowing at rates equivalent to those
19 in the foam. Figure 6 shows the MRF's measured for foam in the
presence of residual oil versus micromodel breakage frequencies
21 in the presence of oil. Since each foam did not behave
22 identically in the oil-free cores, that is the oil-free core
23 MRF's were not all the same, the ratio of residual oil NRF to
24 oil-free core MRF for each foam is plotted in Figure 7. These
results establish the correlation between micromodel and
26 coreflood foam stabilities to oil.
14
~0~ 2
1 Example IV
2 The final example illustrates the use of the invention
3 in a secondary flood application using the surfactant found to
4 yield type B behaviour in Example II and used in a tertiary foam
flood in Example III. In a sepa:rate experiment a Berea core was
6 brine and oil saturated as in Example III, but instead of
7 flooding with a sequence of brine (waterflooding), then
8 gas/brine, surfactant solution and foam, in this case it was
9 flooded directly with foam. Thus the foam was injected as a
secondary recovery process. The results are shown in Table III
11 herebelow.
12 TABLE III
13 Foam Initial Residual Oil Saturations Total Oil
14Injection Oil After After Recovery
Mode Saturation Brine Foam
16 (~ PV) (~ PV) (% PV) (% OOIP)
17Brine only 63 28 n.a. 56
18Tertiary Foam 63 28 23 63
19Secondary Foam 63 n.a. 20 68
.~
n.a. : not applicable.
21 % PV : percent of pore volume
22 % OOIP : percent of original oil in place
23 Examples III and IV show that having selected the
24 stable oil-imbibing and transporting type of foam using the
methods of the present invention more efficient enhanced and
26 secondary oil recovery processes are achieved. This is shown for ~ -
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1 enhanced recovery by the optimal incremental oil recovery (i.e.,
2 above and beyond that from brine flooding and surfactant solution
3 flooding) of the Type B foam compared with the poorer recoveries
4 for the Types ~ and C foams. The Type B foam matches both of our
selection method criteria (micro-visual criteria of behaviour and
6 fb:~ and the correlation: L=6.7 is between 1 and 10). Example IV
7 shows that the Type B foam is not only optimal for enhanced oil
8 recovery but in a secondary oil process the total oil recovery is
g even better. The extra oil recoveries are due to the oil-
imbibing and transporting property of the Type B foams selected
11 from by the present methods.
16