"Composition And Method For Recovering Hydrocarbon Fluids From A Subterranean Reservoir"
Abstract:
This invention is directed to a composition comprising crosslinked expandable polymeric microparticles comprising structured polymers having labile crosslinks or having a labile core and non-labile crosslinks. The starting configuration of the structured polymers constrains the microparticle to an unexpanded volume average particle size diameter of from about 0.05 to about 5,000 microns. Labile crosslinks or the labile core of the structured polymers are subject to degradation which results expansion of the microparticle. The invention is further directed to the use of the composition for modifying the permeability of subterranean formations and increasing the mobilization and/or recovery rate of hydrocarbon fluids present in the formations.
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Notices, Deadlines & Correspondence
1601 W. DIEHL ROAD, NAPERVILLE, IL 60563-1198, UNITED STATES OF AMERICA
Inventors
1. KURIAN PIOUS
2590 ROURKE DR., AURORA, IL 60503, UNITED STATES OF AMERICA
2. CHANG KIN-TAI
1126 MISTY LAKE DRIVE, SUGAR LAND, TX 77478, UNITED STATES OF AMERICA
Specification
TITLE OF THE INVENTION
COMPOSITION AND METHOD FOR RECOVERING HYDROCARBON FLUIDS FROM A
SUBTERRANEAN RESERVOIR
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0001] Not Applicable.
INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC
[0002] Not Applicable.
FIELD OF THE INVENTION
[0003] This invention relates to compositions and methods for the recovery of hydrocarbon
fluids from a subten^nean reservoir and more particularly to an expandable polymeric
microparticle composition that modifies the permeability of subterranean formations, thereby
increasing the mobilization and/or recovery rate of hydrocarbon fluids present in the formations.
BACKGROUND
[0004] In the first stage of hydrocarbon recovery an energy source present in a reservoir is
allowed to move to a producing wells(s) where the hydrocarbon can flow or be pumped to a
surface handling facility. Typically a relatively small proportion of reservoir hydrocarbon can be
recovered by this means. To increase production fluids are injected down adjacent wells to
force an additional amount of hydrocarbon to the surface. This is commonly known as
secondary recovery. The fluids nonnally used are water (such as aquifer water, river water, sea
water, or produced water), or gas (such as produced gas, carbon dioxide, flue gas and various
others). Additionally, if the fluid encourages movement of nonnally immobile residual oil or other
hydrocarlsons, such a process is termed tertiary recovery.
[0005] A prevalent problem with secondary and tertiary recovery projects relates to the
heterogeneity of &)e reservoir rock strata. The mobility of the injected fluid typically is different
from the hydrocarbon. For instance, when the fluid is more mobile various mobility control
processes are required to make the sweep of the reservoir more uniform and the consequent
hydrocarijon recovery more efficient. Unfortunately such processes have limited value wrtien
high permeability zones, commonly called thief zones or streaks, exist within the reservoir rock.
The injected fluid follows a low resistance route from the injection well to the production well. In
such cases the injected fluid does not effectively sweep the hydrocarbon from adjacent, lower
permeability zones. Further, when the produced fluid is re-used this can lead to fluid cycling
through the thief zone with little resulting benefit and at great cost in terms of fuel and
maintenance of the pumping system.
1
[0006] Numerous physical and chemical methods have been used to divert injected fluids out
of the thief zones and into or near production and injection wells. When the treatment is applied
to a producing well it is usually termed a water (or gas etc.) shut-off treatment. When it is
applied to an injection well it Is termed a profile control or conformance control treatment.
[0007] In cases where the thief zone(s) are isolated fi'om the lower permeability adjacent
zones, mechanical seals or "plugs" can be set in the well to block the entrance of the injected
fluid. If the fluid enters or leaves the formation from the bottom of the well, cement can also be
used to fill the well bore to above the zone of ingress.
[0008] When the completion of the well allows the injected fluid to enter both the thief and the
adjacent zones, a cement squeeze is often a suitable means of isolating the watered out zone.
Certain cases, however, are not amenable to such methods because communication exists
between layers of the reservoir rock outside the reach of cement. Typical examples of this are
when fractures or rubble zones or washed out caverns exist behind the casing. In such
Instances chemical gels, capable of moving through pores in reservoir rock have been applied to
seal the swept out zones.
[0009] When such methods fail the only remaining alternatives are to produce the well with
poor recovery rate, sidetrack the well away from the prematurely swept zone, or abandon tiie
well. Occasionally the producing well is converted to a fluid injector to increase the field
injection rate above the net hydrocarbon extraction rate and increase the pressure in the
reservoir. This can lead to improved overall recovery, but It is worth noting that the injected fluid
will mostly enter the thief zone at the new injector and is likely to cause similar problems in
nearby wells. Further, all of these methods are expensive.
[0010] Near wellbore conformance control methods always fail when the thief zone is in
widespread contact with the adjacent, hydrocarbon containing, lower permeability zones. The
reason for this is that the injected fluids can bypass the treatment and re-enter the thief zone
having only contacted little or none of the remaining hydrocarbon. It Is commonly known
amongst those skilled in the art, that such near wellbore treatments do not succeed in
significantly improving recovery in reservoirs having crossflow of the injected fluids between
zones.
[0011] A few processes have been developed with the aim of reducing the penneability in a
substantial proportion of the thief zone and, or at a significant distance from the injection and
production wells. One example of this is the Deep Diverting Gel process patented by Morgan et
al (1). This has been used in the field and suffered from sensitivity to unavoidable variations In
quality of the reagents, which resulted in poor propagation. The gelant mixture is a twocomponent
formulation and it is believed that this contributed to poor propagation of the
treatment into the fomiatlon.
[0012] The use of swellable cross linked superabsorbent polymer microparticles for modifying
the permeability of subterranean formations is disclosed in U.S. Pat. Nos. 5,465,792 and
2
5,735,349. However, swelling of the superabsorbent microparticles described therein is induced
by changes of the carrier fluid from hydrocarbon to aqueous or from water of high salinity to
water of low salinity.
[0013] Crosslinked, expandable polymeric microparticles and their use for modifying the
permeability of subten^nean fonnations and increasing the mobilization and/or recovery rate of
hydrocarbon fluids present in the fomriation are disclosed in U.S. Patent Nos. 6,454,003 B1,
6,709,402 B2, 6,984,705 B2 and 7,300,973 82 and in published U.S. Patent Application No.
2007/0204989 A1.
SUMMARY
[0014] We have discovered novel expandable polymeric microparticles comprising structured
polymers with reversible (labile) crosslinlcs, or with labile core units and non-labile crosslinkers.
The initial microparticle conformation and unexpended size are constrained by the physical
limits imposed by the structured polymers. The structured polymers maintain the unexpanded
size of the microparticle until the opccurence of a desired activating event degrades the labile
crosslinks or labile core-units and allows for overall expansion of the microparticle. The
unexpanded microparticle properties, such as average particle size distribution and density,
allow for efflcient propagation through the pore structure of hydrocarbon reservoir matrix rock,
such as sandstone. On exposing the microparticles to an activating event such as a change in
temperature and/or at a predetermined pH, the reversible (labile) internal crosslinks, or the labile
core units in the structured polymers begin to degrade, allowing the microparticle to expand by
absorbing the injection fluid (normally water).
[0015] The ability of the microparticle to expand from its original size (at the point of injection)
depends on the presence of conditions that induce the breaking of the labile crosslinkers or
labile core units in the structured polymers forming the microparticle. The particles of this
invention can propagate through the porous structure of the reservoir without using a designated
fluid or fluid with salinity higher than the reservoir fluid.
[0016] The released, expanded primary polymeric mk:roparticle is engineered to have a
particle size distribution and physical characteristics, for example, particle rheology, that allow it
to impede the flow of injected fluid in the pore structure. In doing so it is capable of diverting
chase fluid into less thoroughly swept zones of the reservoir.
[0017] The rheology and expanded partk:le size of the particle can be designed to suit the
reservoir target. For example, characteristics of a microparticle for use in a particular reservoir
are influenced by selecting a particular backbone monomer or comonomer ratio in the structured
polymer. Another way to influence the characteristics of the microparticle is the relative
contribution of reversible (labile) and irreversible crosslinking introduced during manufacture of
the structured polymers of the microparticle.
3
[0018] Accordingly, this invention can be directed to a composition comprising expandable
polymeric microparticles comprising structured polymers having labile cross-linkers or a labile
core, the microparticles having an unexpanded volume average particle size diameter of from
about 0.05 to about 5,000 microns. The invention is further directed to a method of modifying
the water permeability of a subteranean fonmation by injecting into the subtenanean fonnation a
composition comprising expandable polymeric microparticles comprising structured polymers
having labile cross-linl-2-methyl
propanesulfonic acid sodium salt is more preferred.
[0027] "Anionic polymeric microparticle" means a crosslinked polymeric microparticle
containing a net negative charge. Representative anionic polymeric microparticles include
copolymers of acrylamide and 2-acrylamido-2-methyl propane sulfonic acid, copolymers of
acryiamide and sodium acrylate, terpolymers of acrylamide, 2-acrylamido-2-methyl propane
sulfonic acid and sodium acrylate and homopolymers of 2-acrylamido-2-methyl propane sulfonic
acid. Preferred anionic polymeric microparticles are prepared from about 95 to about 10 mole
percent of nonionic monomers and from about 5 to about 90 mole percent anionic monomers.
More preferred anionic polymeric microparticles are prepared from about 95 to about 10 mole
percent acrylamide and from about 5 to about 90 mole percent 2-acrylamido-2-methyl propane
sulfonic acid.
[0028] Betaine-containing polymeric mbroparticte" means a crosslinked polymeric
microparticle prepared by polymerizing a betaine monomer and one or more nonionic
monomers.
[0029] "Betaine monomer" means a monomer containing cationically and anionically charged
functionality in equal proportions, such that the monomer is net neutral overall. Representative
betaine monomers include N,N-dimethyl-N-acryloyloxyethyl-N-(3-sulfopropyl)-ammonium
betaine, N,N-dimethyl-N-methacryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine, N,Ndimethyl-
N-acrylamidopropyl-N-(2-cart)oxymethyl)-ammonium betaine, N,N-dimethyl-NacrylamKlopropyl-
N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-N-acryloxyethyl-N-{3-
suIfopropyl)-ammonium betaine, N,N-dimethyl-N-acryIamidopropyl-N-(2-carboxymethyl)-
ammonium betaine, N-3-suifopropylvinylpyridine ammonium betaine, 2-(methylthio)ethyl
methacryloyi-S-(suffopropyl)-sulfonium betaine, 1-(3-sulfopropyl)-2-vinylpyridinium betaine, N-(4-
sulfobutyl)-N-methyldiallylamine ammonium betaine (MDABS), N,N-diaIlyl-N-methyl-N-(2-
sulfoethyl) ammonium betaine, and the like. A preferred betaine monomer is N,N-dimethyl-Nmethacryloyloxyethyl-
N-(3-sulfopropyl)-ammonium betaine.
[0030] "Cationic Monomer" means a monomer unit as defined herein which possesses a net
positive charge. Representative cationic monomers include the quaternary or acid salts of
dialkylaminoalkyi acrylates and methacrylates such as dimethylaminoethyiacrylate nnethyl
chloride quaternary salt (DMAEAMCQ), dimethylaminoethylmethacrylate methyl chloride
quaternary salt (DMAEM MCQ), dimethylaminoethyiacrylate hydrochloric acid salt,
dimethylaminoethyiacrylate sulfuric acid salt, dimethylaminoethyl acrylate benzyl chloride
quatemary salt (DMAEA BCQ) and dimethylaminoethyiacrylate methyl sulfate quaternary salt;
the quatemary or acid salts of dialkylaminoalkylacrylamides and methacrylamides such as
dimethylaminopropyl acrylamide hydrochloric acid salt, dimethylaminopropyl acrylamide sulfuric
5
acid salt, dimethylaminopropyl methacrylamide hydrochloric acid salt and dimethylaminopropyl
methacrylamide sulfuric acid salt, methacr^amidopropyl trimethyl ammonium chloride and
acrylamidopropyl trimethyl ammonium chloride; and N,N-diallyldiall(yl ammonium halides such
as diallyldimethyl ammonium chloride (DADMAC). Prefenred cationic monomers include
dimethylaminoethylacrylate metiiyl chloride quatemary salt, dimethylaminoeth^methacrylate
methyl chloride quaternary salt and diallyldimethyl ammonium chloride. Diallyldimethyl
ammonium chloride is more preferred.
[0031] "Cross linking monomer" means an ethylenically unsaturated monomer containing at
least two sites of ethylenic unsaturation which is added to constrain the microparticle
conformation of the polymeric microparticles of this invention. The level of cross linking used in
these polymer microparticles is high, compared to conventional super-absorbent polymers, to
maintain a rigid non-expandable microparticle configuration. Cross linking monomers according
to this invention include both labile cross linking monomers and non-labile cross linking
monomers.
[0032] "Structured polymers" means any non linear polymers such as star polymers,
dendrimers, hyperbranched, short-chain and tong-chain branched polymers or a combination
thereof. Polymer architectures can be controlled using controlled radical polymerizations or
living cationic and anionic polymerizations.
[0033] "Emulsion", "microemulsion" and "inverse emulsion" mean a water-in-oil polymer
emulsion comprising a polymeric microparticle according to this invention in the aqueous phase,
a hydrocarbon oil for the oil phase and one or more water-in-oil emulsifying agents. Emulsion
polymers are hydrocarbon continuous with the water-soluble polymers dispersed within the
hydrocarbon matrix. The emulsion polymer are optionally "inverted" or converted into watercontinuous
form using shear, dilution, and, generally an inverting surfactant. See U.S. Pat. No.
3,734,873, incorporated herein by reference.
[0034] "Fluid mobilit/' means a ratio that defines how readily a fluid moves through a porous
medium. This ratio is known as the mobility and is expressed as the ratio of the permeability of
the porous medium to the viscosity for a given fluid.
[0035] 1. EQUATION 1 for a single fluid x flowing in a porous medium.
[0036] When more than one fluid is flowing the end point relative pemieabilities must be
substituted for the absolute permeability used in equation 1.
[0037] 2. EQUATION 2 for a fluid X flowing in a porous medium in the presence of one or
more other fluids.
Ax = —
Vx
6
[0038] When two or more fluids are flowing the fluid mobilities may be used to define a
IVIobility ratio:
[0039] 3. EQUATION 3
[0040] The mobility ratio is used in the study of fluid displacement, for example in water
flooding of an oil reservoir where x is water and y is oil, because the efficiency of the
displacement process can be related to it. As a general principle at a mobility ratio of 1 the fluid
front moves almost in a "Plug flow" manner and the sweep of the reservoir is good. When the
mobility of the water is ten times greater than the oil viscous instabilities, known as fingering,
develop and the sweep of the reservoir is poor. When the mobility of the oil is ten times greater
than the water the sweep of the reservoir is almost total.
[0041] "Ion-pair polymeric microparticle" means a crosslinked polymeric microparticle
prepared by polymerizing an ampholytic ion pair monomer and one more anionic or nonionic
monomers.
[0042] "Labile cross linking monomer" means a cross linking monomer which can be degraded
by certain conditions of heat, pH or a combination thereof, after it has been incorporated into the
polymer stmcture, to reduce the degree of crosslinking in the polymeric microparticle. The
aforementioned conditions are such that they can cleave bonds in the "cross linking monomer"
without substantially degrading the rest of the polymer backbone. Representative labile cross
linking monomers include diacrylamkles and methacrylamides of diamines such as the
diacrylamide of piperazine, acrylate or methacrylate esters of di, tri, tetra hydroxy compounds
including ethyleneglycol diacrylate, polyethyleneglycol diacrylate, ^'metiiylopropane
trimethacrylate, ethoxylated trimethylol triacrylate, ethoxylated pentaerythritol tetracrylate, and
the like; divinyl or diallyl compounds separated by an azo such as the diallylamide of 2,2'-
Azobis(isbutyric acid) and the vinyl or allyl esters of di or tri functional acids. Prefen-ed labile
cross linking monomers include water soluble diacrylates such as PEG 200 diacrylate and PEG
400 diacrylate and polyfunctional vinyl derivatives of a polyalcohol such as ethoxylated (9-20)
trimethylol triacrylate. The labile cross linker may be present in an amount of from about 100 to
about 200,000 ppm. In alternative aspects, the labile cross linker is present in the amount of
about 1,000 to about 200,000 ppm, about 9,000 to about 200,000 ppm, about 9,000 to about
100,000 ppm, about 20,000 to about 60,000 or about 1,000 to about 20,000 ppm, about 500 to
about 50,000 ppm based on total moles of monomer.
[0043] "Monomer" means a polymerizable allylic, vinylic or acrylic compound. The monomer
may be anionic, cationic, nonionic or zwitterionic. Vinyl monomers are preferred, acrylic
monomers are more preferred.
7
[0044] "Nonionic monomer" means a monomer as defined herein wiiich is electrically neutral.
Representative nonionic monomers Include N-lsopropylacrylamide, N.N-dimethylacryiamide,
N,N-dtethylacrylamide, dimethylaminopropyl acrylamlde, dimethylamlnopropyl methacrylamide,
acryloyi morphollne, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate,
hydroxypropyl methacrylate, dimethylaminoethylacrylate (DMAEA), dimethylaminoethyl
methacrylate (DMAEM), maleic anhydride, N-vinyl pyrrolidone, vinyl acetate and N-vinyl
formamide. Preferred nonionic monomers include acrylamlde, N-methylacrylamide, N,Ndlmethylacrylamide
and methacrylamide. Acrylamlde Is more preferred.
[0045] "Non-labile cross linking monomer" means a cross linking monomer which is not
degraded under the conditions of temperature and/or pH which would cause incorporated labile
cross linking monomer to disintegrate. Non-labile cross linking monomer is added, in addition to
the labile cross linking monomer, to control the expanded conformation of the polymeric
micropartlcle. Representative non-labile cross linking monomers Include methylene
bisacrylamide, diallylamine, triallylamine, divinyl sulfone, diethyleneglycol diallyl ether, and the
like. A preferred non-labile cross linking monomer is methylene bisacrylamide.
[0046] The structured polymer for making the microparlicles can be any non linear polymer
such as star polymers, dendrimers, hyperbranched, short-chain and long-chain branched
polymers or a combination thereof. Polymer architectures can be controlled using controlled
radical polymerizations or living cationic and anionic polymerizations. As disclosed herein, such
structured polymers are used to make crosslinked, expandable polymeric microparticles as
otherwise described in U.S. Patent Nos. 6,454,003 B1, 6,709,402 B2, 6,984,705 B2 and
7,300.973 B2 and In published U.S. Patent Application No. 2007/0204989 A1. An advantage of
using structured polymers in creating the crosslinked expandable mcroparticles of the present
invention is that either the labile crosslinks or non-labile crosslinks can be eliminated while
maintaining the expandability of the micropartlcle. For example, a star polymer with all labile
crossllnkers wrill function very similarly to the crosslinked microparticles described in U.S. Patent
Nos. 6.454,003 81, 6,709,402 B2.6,984,705 B2 and 7,300,973 B2, and in published U.S.
Patent Application No. 2007/0204989 A1 without requiring non-labile crosslinks. Upon
decomposition of all the labile crosslinks, the final polymer expands and the star core will act as
a permanent crosslinker. Altematively, a labile core-unit having all non-labile crosslinkers also
yieWs polymeric microparticles with properties to those previously described for crosslinked
expandable microparticles having both labile and non-labile crosslinkers.
[0047] Star polymers are produced either by polymerization from multifunctional cores or by
post modification reactions. Polymerization from a multifunctional core Is desirable for very high
molecular weight polymers. Star polymer synthesis by post modification reactions is well
known, and described for example In B. Charleus and J. Nicolas, Polymer 48:5813 (2007); and
in S. Abraham et al., J Poly Sci A: Poly Chem 45:5559 (2007). WO2008016371 describes flie
preparation of degradable star polymers using Atom Transfer Radical Polymerization (ATRP).
8
Labile or degradable crosslinks that can be used include those that are photodegradable,
ozonolyzabte, biodegradable, hydrolyzable. Nondegradable crosslinks may also be used. An
example of a suitable degradable (thennolyzable) star polymer for the micnsparticfes described
herein is described in C.S. Patrickios et al., J Poly Sci A: Poly Chem 45: 5811 (2007). Recent
introduction of the tetrafunctional peroxide initiator JWEB5D, available from Arkema Inc. of
Philadelphia, PA, now permits synthesis of star polymers by traditional radical polymerization as
well. JWEB50 is a tetrafunctional initiator that yields a four-ami star polymer after
polymerization. (M.J. Scorah et al., Macromol React Eng 1:209 (2007).
[0048] Dendritic polymers are another structured polymer suitable for making the expandable
microparticles. Dendrimers and hyperbranched polymers belong to the dendritic family of
polymers and can be configured to provide low bulk viscosity products. A relatively simple
approach is to start with ABz monomers, or ABC2 monomers from a chain-growth polymerization
process involving the copolymerization of an AB monomer with a C monomer. The "2" subscript
denotes dual functionality of the monomers. In an ABCjthe C monomer has dual functionality.
The AB group is a polymerizable vinyl group that is able to react with an active moiety such as
an anion, a cation, a radical or a conventional initiating or propagating moiety of the type well
known in vinyl polymerization. The C monomer contains a polymerizable group that can be
initiated by A*, B* or by another suitable initiator including alkyl aluminum halides, Lewis acids,
bases, heat, light and radiation. Once the reaction of C with an A* or B* unit or other initiator
has occurred, C becomes a new activated C* gnDup capable of further reaction with any Acontaining
moiety present in the system, and also with any C monomer remaining in the system.
The reactive moiety of the C monomer may be exactly the same as the AB monomer, or it may
be another type of vinyl group having a reactivity or polymerizability similar to that of A with
respect to B* or to A*. US Pat. No. 5,663,260 for example describes the method of synthesis of
such hyperbranched polymers by an ABC2 system. U.S. Pat. No. 5,587,441 describes the
synthesis of AB2 polymers where the B monomer is the polymerizable initiator molecule. For the
expandable microparticles, such polymers are configured as labile molecules \mth dual
functionality so that the molecule degrades or decomposes with changes in the environment
such as a change in temperature, pH, ionic strength, pressure or stress to obtain expandable
microparticles with properties like those described in U.S. Pat. Nos. 6,454,003 and 6,984,705.
[0049] In one aspect, the polymers fonning the constrained expandable microparticle are
crosslinked expandable structured polymers. The structured polymers can be made with labile
and non-labile crosslinkers such as, but not limited to, those described in U.S. Pat. No.
6,454,003. For example, in one aspect the non-labile cross linker is present in the expandable
microparticles in an amount of from 0 to about 300 ppm, in another aspect from about 2 to about
300 ppm, in another aspect from about 0 to about 200 ppm, in another aspect from about 0 to
about 100 ppm, in another aspect from about 01 to about 300 ppm, in another aspect from
about 2 to about 300 ppm and in another aspect from about 5 to about 300 ppm based on total
9
moles of monomer. However, an advantage of the structured polymers is the ability to eliminate
the labile crosslinkers or the non-labile crosslinkers. In the absence of a non-labile cross linker,
the polymer microparticle, upon complete scission of labile cross linker, is converted into a
mixture of linear polymer strands. Similarly, in the absence of labile crosslinkers, but with a
structured polymer having a labile core, the polymer microparticle upon complete scission of the
labile core is converted into a mixture of linear polymer strands. In either case, the particle
dispersion is thereby changed into a polymer solution. This polymer solution, due to its
viscosity, changes the mobility of the fluid in a porous medium. In the presence of a small
amount of non-labile cross linker, the conversion from particles to linear molecules is
incomplete. The particles become a loosely linked netvi/ork but retain certain 'structure'. Such
'stnjctured' particles can block the pore throats of porous media and create a blockage of flow.
[0050] Thus, in one aspect, the structured polymers forming the expandable polymeric
microparticles are any crosslinked structured polymers with all labile crosslinks, and which are
capable of fonning unexpanded polymeric particles of a size of about 5,000 microns or less. In
another aspect, the structured polymers forming the expandable polymeric microparticles are
any crosslinked structured polymers with all non-labile crosslinks and a labile core that are
capable of fomiing unexpanded polymeric particles of a size of about 5,000 microns or less.
[0051] When used with to reference to crosslinks or the polymer core, the tenri "labile" means
degradable, for example, photodegradable ozonolyzable, biodegradable, hydrolyzable or
thermolyzable. In another aspect of the present invention, structured polymers fonn a
micropartk:le that may be used advantageously in recovery of hydrocarbon from the
subterranean fonnation.
[0052] In an exemplary embodiment, structured polymers are made using labile crosslinks that
degrade upon exposure to an activating event or condition such as a change in temperature,
pH, salinity or the like. In one aspect, the crosslinkers degrade at the higher temperatures
encountered in the subterranean formation. Once the crosslinkers degrade, the microparticle
configuration degrades and allows the microparticle to expand or swell. Examples of suitable
labile crosslinkers for structured polymers include, but are not limited to, diester and other types
of labile crosslinkers such as polyethyleneglycol diacrylate (e.g. PEG-200 diacrylate) as
described in detail in U.S. 6,454,003. In addition, cationic ester monomers can be used as ionic
crosslinkers for the structured polymers, because they form ionic bonds with any anionic
polymers forming the underling unejqsanded polymeric microparticle. In the higher
temperatures encountered in the formation, the cationic ester mer units will hydrolyze,
eventually converting the initially cationic labile polymers to an anionic polymer that is no longer
capable of forming an ionic interaction with the anionic polymers forming the underlying
unexpanded polymeric microparticle. Examples of suitable cationic ester monomers include
N,N-dimethylaminoethyl acyrylate and N,N-dimethylaminoethyI methacrylate.
[0053] Structured polymers may be formed using labile crosslinks Uiat can be selected for
10
susceptibility to degradation upon exposure to any one of a number activating events.
Temperature and pH changes are exemplary activating events, but other activating events for
sufficient degradation of labile cross-linlts in the labile polymers are contemplated, including a
change in pressure, saiinrty, shear, or dilution. The activating event may be for example
exposure to an activating agent such as exposure to an oxidant, a reductant, an acid, a base, a
biological agent, an organic or inorganic cross-linking agent, or a salt, or to a combination
thereof. Upon exposure to the activating event and consequent degradation of the structrured
polymers the expandable polymeric microparticles are free to expand to several times the
original size of the microparticle while yet constrained by the initial configuration of the
structured polymer
[0054] Preferred Embodiments
[0055] In one aspect, the polymeric microparticles are composed of expandable structured
polymers that are prepared using an inverse emulsion or microemulsion process to assure
certain particle size range. In an embodiment, the unexpanded volume average particle size
diameter of the stmctured polymers is from about 0.05 to about 5,000 microns. In an
embodiment, the unexpanded volume average particle size diameter of the structured polymers
is about 0.1 to about 3 microns. In another embodiment, the unexpanded volume average
particle size diameter of the structured polymers is about 0.1 to about 1 microns. In another
embodiment, the unexpanded volume average particle size diameter of the structured polymers
is about 0.05 to about 50 microns.
[0056] Representative preparations of crosslinked expandable polymeric microparticles using
a microemulsion process are described in U.S. Pat. Nos. 4,956,400, 4,968,435, 5,171,808,
5,465,792 and 5,737,349.
[0057] In an inverse emulsion or microemulsion process, an aqueous solution of monomers
and cross linkers is added to a hydrocarbon liquid containing an appropriate surfactant or
surfactant mixture to forni an inverse monomer microemulsion consisting of small aqueous
droplets dispersed in the continuous hydrocarbon liquid phase and subjecting the mon(»ner
microemulsion to free radical polymerization.
[0058] In addition to the monomers and cross linkers, the aqueous solution may also contain
other conventional additives including chelating agents to remove polymerization inhibitors, pH
adjusters, initiators and other conventional additives.
[0059] The hydrocarbon liquid phase comprises a hydrocarbon liquid or mixture of
hydrocarbon liquids. Safeirated hydrocarbons or mixtures thereof are preferred. Typically, the
hydrocarbon liquid phase comprises benzene, toluene, fuel oil, kerosene, odorless mineral
spirits and mixtures of any of the foregoing.
[0080] Surfactants useful in the mk:roemulsion polymerization process described herein
include sorbitan esters of fatty acids, ethoxylated sorbitan esters of fatty acids, and the like or
11
mixtures thereof. Preferred emulsifying agents include ethoxyfated sorbitol oleate and sorbitan
sesquioleate. Additional details on these agents may be found in McCutcheon's Detergents and
Emulsifiers, North American Edition, 1980.
[0061] Polymerization of the emulsion may be carried out in any manner known to those
skilled in the art. Initiation may be effected with a variety of thermal and redox free-radical
initiators including azo compounds, such as azobisisobutyronitrile; peroxides, such as t-butyl
peroxide; organic compounds, such as potassium persulfate and redox couples, such as sodium
bisuifite/sodium bromate. Preparation of an aqueous product from the emulsion may be
effected by inversion by adding it to water, which may contain an inverting surfactant.
[0062] Alternatively, the structured polymers cross linked with labile cross links are prepared
by internally cross linking polymer particles which contain polymers with pendant carboxylic acid
and hydroxy! groups. The cross linking is achieved tiirough the ester fomiation between the
carboxylic acid and hydroxy! groups. The esterification can be accomplished by azeotropic
distillation (U.S. Pat. No. 4,599,379) or thin film evaporation technique (U.S. Pat. No. 5,589,525)
for water removal. For example, a polymer microparticle prepared from inverse emulsion
polymerization process using acrylic acid, 2-hydroxyethyiacrylate, acrylamide and 2-acrylamido-
2-methylpropanesulfonate sodium as monomer is converted into cross linked polymer particles
by the dehydratbn processes described above.
[0063] The polymeric microparticles are optionally prepared in dry form by adding the
emulsion to a solvent which precipitates the polymer such as isopropanol, isopropanol/acetone
or methanol/acetone or other solvents or solvent mixtures that are miscible with both
hydrocarbon and water and filtering off and drying the resulting solid.
[0064] An aqueous suspension of the polymeric microparticles is prepared by redispersing the
dry polymer in water.
[0065] In another embodiment, this invention is directed to a method of modifying the
permeability to water of a subterranean formation by injecting into the subterranean fomiation a
composition comprising expandable microparticles which comprise structured polymers. The
microparticles have an unexpanded volume average particle size diameter of from about 0.05 to
about 5,000 microns and have a smaller diameter ttian the pores of the subterranean fonnation.
The labile crosslinks or labile core of the structured polymers degrade under a change in
environmental conditions in the subterranean fomiation so that the expandable polymeric
microparticles are free to expand. The composition then flows through a zone or zones of
relatively high permeability in the subterranean formation under increasing temperature
conditions, until the composition reaches a location where the temperature or pH is sulficiently
high to promote degradation of the labile crosslinks or labile core in the labile polymers,
triggering expansion of the microparticles.
[0066] In one embodiment, about 100 ppm to about 10,000 ppm of the composition, more
preferably 500 ppm to about 1500 ppm of the composition, and even more preferably about 500
12
ppm to about 1000 ppm, based on polymer actives, is added to the subterranean formation.
The subterranean fomiation is for example a sandstone or cartionate hydrocarbon reservoir. In
one embodiment, the composition is added to injection water as part of a secondary or tertiary
process for the recovery of hydrocarbon from the subten-anean fomiation. The injection water is
added to the subterranean formation, for example a producing well, at a temperature lower than
the temperature of the subterranean fomiation. The higher temperature within the fomiation
causes the labile crosslin)