CA1274767A

CA1274767A - Method for treating subterranean formations

Info

Publication number: CA1274767A
Application number: CA000556639A
Authority: CA
Inventors: Wilhelm E. Walles; Donald L. Tomkinson; Trevor D. Williamson
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1987-01-16
Filing date: 1988-01-15
Publication date: 1990-10-02
Anticipated expiration: 2007-10-02
Also published as: US4741401A; GB8800526D0; GB2199872B; GB2199872A; NO177199B; NO880165L; NO177199C; IN170553B; MY102194A; AU582320B2; CN1018011B; CN88100379A; MX172677B; NO880165D0; BR8800186A; AU1023188A

Abstract

ABSTRACT
Control release capsules comprising a breaker contained within a enclosure member are employed to break fracturing fluids. The enclosure member is permeable to at least one liquid in the subterranean formation or a liquid that is injected with the capsules such that upon sufficient exposure to the liquid, rupture of the capsules is delayed for a predetermined time interval, thereafter releasing the breaker to the formation. The time of release of the breaker can be conducted in a controlled manner such that the entire amount of the breaker introduced into the formation.

Description

METHOD FOR TREATING SUBTERRANEAN FORMATIONS

The present invention relates to a method for breaking an aqueous fracturing fluid for fracturing a 3ubterranean formation u~ing a controlled release capsule to deliver a breaker to the fracturing fluid, and to an aqueous fracturing fluid containing such controlled release capsule.
In the drilling of a well and the subsequent recovery of fluids such as crude oil and natural gas from subterranean Pormations, various material~ are added to the well bore and/or subterranean formation to improve the ef~iciency of the well drilling operation, to increa3e production of the fluids from the formation and/or to terminate and seal a non-producing well.
The~e treating agent~ are generally added, in their active form, above ground and flowed into the well bore or through the well bore to the subterranean formation.
For examplea a subterranean formation is often subjected to a fracturing treatment with a treating agent, generally referred to in the art as a fracturing 35,069-F

~2--fluid (a liquid such as water, brine, and the like), to stimulate the recovery of fluids. In fracturing the Pormation, the fracturing fluid is introduced into the well at a rate and pressure sufficient to produce one or more fractures in the formation and/or enlarge or extend existing fractures. The fluid can contain a propping agent such as sand or sintered bauxite which is deposited in the fractures ~o maintain the fraotures open and/or an acid which reacts with the acid-soluble components oY the formation thereby creating and enlarging passageways for the flow of fluids from the formation.

Heretofore, in both hydraulic fracturing and fracture acidizing operations, a high viscosity, gelled aqueous fluid, a high viscosity water/hydrocarbon emulsion~ or a foam of a gas/water dispersion has typically been employed. These high viscosity fluids are capable of the necessary penetration to realize maximum benefits from the fracturing operation and in ~uspending the propping agents, if employed, without excessive settling. In addition, the high viscosity fluids are capable in opening the fractures to a greater width than is possible with the low viscosity fluid.

After the high visc03ity aqueous solution or emulsion has been pumped into a subterranean formation and the fractures formed, it is generally desirable to convert the gel or emulsion into a low viscosity fluid, thereby allowing the fluid to be rzmoved from the formation and the desired material such as oil or natural gas, to flow back through the fractures into the well bore. This reduction in the visc03ity of the fracturing ~luid is commonly referred to as "breaking"
the gel or emulsion. Conventionally, breaking of the gel or emulsion is carried out by adding a viscosity reducing agent (commonly called a "breaker") to the formation at the desired time. Unfortunately, the described techniques often result in insufficient breaking (i.eO, an insuf~icient reduction in the viscosity of the ~racturing fluid) or premature breaking of the fluid. Premature breaking of the fluid causes a reduction in the viscosity of the fracturing fluid prior to the desired termination of the fracturing operation, thereby reducing the overall effectiveness of the operation.

One proposed method for controlling and/or delaying the activity of the viscosity reducing ag0nt or "breaker" consists of introducing to the subterranean formation the breaker in a prill or pellet formed by combining the breaker with a hydratable gelling agent and gel degrading substance and ~orming the resulting mixture into the desired prill or pellet form. See, for example, U.S. Patent No. 4,202,795.
Upon exposure of the prills or pellets to an aqueous ~luid, the gelling agent i~ said to hydrate and form a protective gel around each of the pellets, thereby preventing the release of the breaker into the aqueous fluid until the protective gel is broken by the gel-degrading substance. In thi~ manner, it has heretoforebeen c].aimed that the breaker can be released to the aqueous fluid in a controlled manner. It has been found, however, that a relatively large amount of the hydratable gelling agent is required to prepare the pellets and that the amounts of the hydratable gelling agent must be carefully controlled. In addition, the 35,069-F -3-~2~7~7 time period over which the pellet3 are released may vary substantially.

In another method for delaying the release of a breaker, U~S. Patent No. 4,5069734 proposes introducing a viscosity reducing chemical contained within hollow or porous, crushable beads in the hydraulic fracturing fluid. The visc03ity reducing agent is said to be released upon the crushing of the beads which results from the closing of the fractures caused by the fracturing fluid passing or leaking off into the formation or by removing the fluid by backflowing.
Unfortunately, the stresses caused by the closing of the formation will affect the percentage of beads being crushed so that a large percentage of beads may remain unbroken, particularly if the formation closes at a ~low rate. In addition, a large percentage of the beads may be crushed in one area of the formation being treated, whereas in another area of the formation, a substantially lower amount of the beads may be crushed.
Therefore, inconsistent performance can be expected.

Although the foregoing methods appear to provide for delayed release of a breaker into the subterranean formation, it remains desirable to provide an alternative method and commercially more practicable method which gives equivalent or superior performance.

Accordingly, in one aspect, the present invention is a method for breaking an aqueous fracturing fluid comprising the steps of injecting into a subterranean formation controlled release capsules, wherein each capsule comprises an enclosure member enclosing a breaker for the aqueous fracturing fluid;

35,o69-F -4-j7 -5-~

the enclo ure member being sufPieiently permeable to at least one fluid exi~ting in the qubterranean environment or injected with the controlled release capsule such that the enclosure member is capable of releasing the breaker upon sufficient exposure to the fluido Using the method of the present invention, breaking of fracturing fluids is significantly improvedO Specifically, regardless of the release mechaniqm~ all or substantially all the controlled release capsules will release their contained breaker, at some time, into the formation. There~ore, although it is contemplated that the breaker may, and often will, be released by the stres~e~ generated on the capsules by closure of the formation, crushing due to formation clo~ure i~ not required for release. In addition, even if ~uch crush release is the primary release mechaniqm, the capsules which are not crushed will still release the breaker to the formation.
Therefore, a more con~istent performance using less materials is achieved by the method of the present invention.

In addition, the release of the breaker can be effected in a relatively controlled manner.
Specifically, the capsule can be designed quch that the relea~e of the active sub~tance (e~g. the breaker) can be delayed for a desired period of time. The delay can be for a~ little as e.g., a number of hours, or as much a~ dayq or weeks, followed by the relatively rapid release of the encapsulated breaker to the formation at the desired time. In addition, using the method of the present invention, it i~ possible to add the 35,069-F -5-encapsulated material to a well bore above ground and flow the ma~erial to the desired location in the subterranean formation without releasing the breaker to the fracturing fluid prior to the desired time or until it reache~ the desired location. Upon arrival at the desired location and/or a given amount of time, the encap~ulated breaker can be released~

In another aspect, the present invention is an aqueou~ ~racturing Pluid comprising a carrier liquid, a viscosifying polymer7 and controlled release capsules, each capsule comprising an enclosure member enclosing a breaker for the viscosifying polymer, wherein the enclosure member is permeable to the carrier liquid or a fluid existing in the subterranean environment such that upon exposure to the carrier liquid for a predetermined time period the enclosure member is capable o~ rupturing, thereby releasing the breaker to the fracturing fluid.

A~ used herein, the term "permeable" means that the controlled relea~e cap~ules 9 when dispersed in the fracturing ~luid, do not release an undesired amount of the breaker at ambient mixing temperatures and pressures, i.e., temperature and pressure of the mix water or other fluid, during the time required for mixing and delivery but which release an amount of breaker e~fective to reduce the visco~ity of the thickened fracturing fluid at the pressures and temperatures of the reservoir being treated. In general, the fracturing .fluid is an aqueous liquid and, to provide the desired performance, the controlled release capsules will release less than 10, more preferably less than 5 9 most preferably less than 1 9 35~069-F -6-`7 . . ., ~ ~3 --7~

weight percent of the encapsulated breaker within the fir~t 0.5 hour of exposure at a temperature of from 10C
to 30C and standard pressure, and will r0leaqe at least 50, more preferably at least 60, weight percent of the encapsulated breaker within 48 hours after initial exposure at a temperature o~ from 10C to 200C and standard pressure. In such manner, the controlled release capsules are capable of containing the breaker during normal ~torage and, preferably~ until delivery of the capsules to the formation and when the pressure in the interior of the capsules increases sufficiently due to penetration of the fluid into the capsules to cause rupture of the enclosure members. As the term i~
used herein, a ~ubstantially impermeable enclosure member is one which does not release the encapsulated breaker within the hereinbefore described time period.

The enclosure member i3 ~uitably any coating material which i3 permeable, either due to the permeability of the coating material per 3e, and/or ~rom flaws, ~issures, soluble additives, and the like, in the coating. The enclosure member is permeable to at least one liquid (generally, water or brine) found in the ~ubterranean formation being treated or in the fracturing fluid itself which i~ injected with the cap~ules into the formation and which is capable of releaqing the breaker at the temperatures existing in the formation due to an increase in the pressure inside of the capsule as compared to the environmental pressure. In general, the enclosure member is preferably prepared from a material which i~ permeable to a fluid existing in the subterranean environment or to the fluid which is injected with the capsules into the formation. In such manner, the penetration of the 35,069-F -7-~luid into the capsule through the wall of the enclosure member creates an increased pres~ure within the capsule.

The material most advantageously employed as the enclosure member will vary depending on a variety of ~actor~ Among the various factors are the physical and chemical properties of the material being employed as the enclo~ure member; the operating conditions (including the temperature) to which the capsule is to be exposed; the breaker employed and its compatibility with the enclosure member9 and the desired time and mechanism for release. For example, the amount of stress created by the closure of the formation as well as the desired time for release after injection o~ the capsules should the capsule~ be exposed to no external stres~, will need to be considered in selecting the most preferred enclo~ure member for an application.
The enclosure member is generally a water-in oluble, water-permeable material. The permeability, as well as, to a le~ser extent, the thickness and elasticity, of the enclo~ure member determines the rate at which the environmental water, i.e. rain, water, river water, and the like, can be imbibed into the cap~ule followed by rupture of the enclosure member and release of the encapsulated breaker material. The water permeabilities of materials which can be employed for the enclosure member can vary widely. For example, if applied as a relatively thick coating, a cellulosic material ~uch a~ cellulose acetate or cellulose acetate butyrate, both of which have a relatively high water permeability, can be employed as the enclosure member.
However, in general 9 in the practice o~ the present 35,069-F -8-_9~

invention, the water permeable enclosure member preferably has a water permeability such that the ~ater vapor transmission rate ("WVTR") of the material is less than about 3 grams of water per 100 cm2 of a coating (determined as a film) having a thickness of 25 micrometer (~m) per 24 hour period (g/100 cm2/24 hours) at 3~C. Althouyh materials h~ving a higher WVTR can be employed, thicker coatings are generally required which can make their use impractical. Preferably, the WVTR of 10 a 25 ~m thick coating is less than about 1.25, more preferably less than about 0.775, g/100 cm2/2~ hours at 38C. Although an enclosure member which has at least a measurable WVTR can be employed, given the proper set of circumstances, in general, the WVTR of the material employed as the enclosure member is advantageously greater than 0.015 g/100 cm2/24 hours at 3~C, for a coating thickness of 25 ~m. Preferably, the WVTR of a 25 ~m thickness of the material employed as the enclosure member is prepared from a material which, as a 25 ~m thick coating, has a WVTR of greater than about 0.03, more preferably greater than about 0.077 g/100 cm2/24 hours.
Representative materials having the desired water permeabilities include various polymers, including homopolymers and copolymers, of ethylenically unsaturated monomers such as ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, styrene, ethyl cellulose and cellulosic materials of similar properties, and vinyl acetate. In addition, hydrocarbon waxes; polymers of ethylene oxide, propylene oxide or combinations thereof; epoxides; and polycarbonates can also be employed as the enclosure member. Of such materials, polyethylene, polypropylene, 3~.0~9-F _g_ ' I ;, polyisobutylene, polyvinylacetate, copolymers of vinyl chlorlde and vinylidene chloride, copolymers of styrene and butadiene, copolymers of vinylidene chloride and an ester of an unsaturated carboxylic acid such as methylacrylate, copolymers of ethylene and an unsaturated carboxylic acid and/or salt thereof such as acrylic acid or its sodium qalt and copolymers of ethylene and vinyl acetate, are preferred.
The breaker employed in the present invention can be any solid or liquid material which does not adver3ely interact or chemically react with the material of the enclosure member to destroy its integrity prior to the desired release of the breaker to the fracturing fluid. Representative examples include enzymes such a~ cellulase, oxidizers, tran~ition metal ~alt~, in ionized form, 3uch as the ionized form of iron (e.g., FeCl3), silver (AgN03) or copper (CuS04); acids such as mineral acids (e.g., HCl) or certain organic acids ~uch a~ acetic acid or mixtures of two or more breakers. These compounds may be employed following absorption into porous clay or other porou~ material and then encapsulated.

In the method of the present invention, the pres~ure generated within the enclosure member, due olely to the liquid penetrating into the capsule, will de~troy the integrity of the enclosure member. In certain cases, the speed of rupture will be increased when a breaker material reacts or otherwise interacts with the fluid which has penetrated into the capsule to generate a gas, thereby increa~ing the pressure within the capqule and accelerating rupture of the enclosure memberO For example, when the breaker material and the 35,069-F -10-~ ~ r~4 ~ 7 fluid react to form a gas, the generated gas increases the internal pressure in the capsule a~ the reaction progresses, di~tending the enclosure member until it rupture~. For thi~ reason, in an aqueou~ environment5 the method of the present invention i3 often employed with an oxidizing agent which is useful as a viscosity reducing agent or breaker. Many of these oxidi~ing materials react with the water penetrating into the capsule to form a gaq. Of the oxidizing agents, the preferred oxidizing agents include ammonium, sodium or potassium persulfate; sodium peroxide; sodium chlorite;
sodium, lithium or calcium hypochlorite; chlorinated lime; potassium perphosphate; qodium perborate;
magnesium monoperoxyphthalate hexahydrate; and a number of organic chlorine derivatives such as N9N'-dichlorodimethylhydantoin and N-chlorocyanuric acid and/or salts thereof. Most preferably, the viscosity reducing agent is ammonium or sodium per~ulfate, lithium hypochlorite or sodium salt of dichloroisocyanuric acid.

The breaker is coated with the enclosure member to form a controlled released capsule o~ the desired ~hape and size with a coating of a desired thickness.
The shape, size and composition of the controlled release capsule which is mo~t advantageously employed herein will be dependent on a variety of Eactors inoluding the specific fracturing treatment, the proppants, if any, employed, the specific controlled release capsule, the amount of the particular breaker to be delivered to the fluid, the desired release mechanism, and the desired time of release. Although capsules, containing as much as 10 grams (g) of the breaker 9 are easily prepared using injection molding ~.~7~7~7 =~

techniques or by coating the active material with a lacquer comprising a material use~ul in ~orming an enclo~ure member~ in general, khe cap~ules are prepared such that they contain ~rom 5 nanograms to 1 g, more preferably ~orm 0O05 to 500 milligrams o~ the breaker.
In general 9 at such amounts, the controlled release capsules will exhibit an average particle size of from 0001 to 5 millimeters (mm) 9 preferably from 0O05 to 2 mmO Capsules having two or more distinct particle size can alYo be employed in any given operation.

The controlled release capsules can be prepared such that the enclosure member surrounds one or more particle~ of the active liquid or solid materialO For example, the capsules may be prepared a~ a mononuclear particle having a liquid or solid core of the breaker encapsulated by the enclo~ure member, as a mononuclear core having a multiple wall enclosure member or as a polynuclear core wherein each core is encapsulated by a permeable enclo~ure member but agglomerated or otherwise attached to ~orm a single particle. Of the various particle configurations, the controlled release capsule is mo~t advantageously prepared having a mononuclear core with the liquid or solid breaker encapsulated within a single layer o~ the permeable material. The capsules can be o~ essentially any ~hape, including 3pherical, oubic or irregular, with generally 3pherical bead~ such as are prepared in a fluidizing bed proce~s beinK pre~erred.

Prior to the coating operation, it i~ often advantageou~ to separate, where possible, a solid breaker by its particle size to remove any fines and/or clumps. In thi~ manner, the subsequently prepared 35,069-F -12 ~4 ~Ç~7 3 ~

capsules contain approximately equal amounts of the material ~uch that the time of release of the material from the capsule can be more clearly defined, i.e., the partîcles tend to release within a narrower time span.
Alternatively9 ~uch size classification can be conducted after the coating operation, but this is less preferred.

Any of a variety of technique well known in the art can be employed for producing the controlled release capsules and re~erence is made thereto Por the purpose of this invention. Of the various methods which can be employed 9 the controlled release capsule i~ most advantageously prepared using a fluidized bed process wherein the breaker particle is sprayed with a ~uitable permeable material which is suspended in a rapid flow of air or other ga30 Illustrative of such fluidized bed proces~eq are described in Knack H., "Microencapsulation Techniques, Application~ and Problems", J. Soc. Co~. Chem , 21, 85-98 (Feb 4 1970) and U.S. Patent Nos. 3,237,596 and 3,382,093. Although the fluidized bed method for preparing controlled release capsules is most advantageously employed in coating breaker~ which are ~olid at the temperature at which the coating operation is being conducted, it can al~o be employed in coating liquid~, particularly if the liquids are frozen before or during fluidization in the coating process or absorbed into porous particles such as a porous fired clay. Other coating processes such a~ phase separation, coacervation and acoustic levitation can also be employed in preparing the controlled release capsule, but are generally less preferred. Preferably, the coating operation is conducted at conditions ~o as to prevent individual ~_~.a74 ~i7 14~

particle~ from sticking to one another during the operation and to minimize particle~ which are only partially coated. After preparation of the controlled release capsule, the capsule may be further treated 9 e~g~, hea~ treatment9 to alter the properties of the coating~

In preparing the controlled release capsule, the permeable material is applied at a thickness ~ufficient to delay the release o~ the breaker for a desired period of time at the temperatures encountered in the operation. In addition, the controlled release capsules useful in the practice of the present invention are preferably sufficiently strong and ductile to prevent the cap~ule's breakup during processing including the passage of the controlled release capsule through surface pumps and blending equipment commonly utilized in the operation and when being introduced into the formakion. In general, the coating thickness of the water permeable enclosure member is from 0.5 to 100 ~m. More preferably7 the coating thickness if from 5 to 60 ~m.
The method of addition and the amount of the controlled release capsules employed are dependent on a variety of factors including the specific end use application and the desired time for the rupture of the enclosure member. As an example, in the reduction of the viscosity of a fracturing fluid, the controlled relea~e capsules containing the viscosity reducing agent can be added with (as well as, in certain ca~es, prior to or after) the addition of the fracturing fluid to the subterranean formation. In general, the method preferably co~prises adding the fracturing fluid and 35,069-F _14_ 7~i7 5~

thereafter adding the controlled release capsules containing the viscosity reducing agent.

In general~ the controlled release capsule~ are added above ground to the well bore as a di~persion in an aqueous carrier and conveyed to the desired location in the subterranean formation. As u~ed herein, the term "subterranean formation" include3 the formation as well as the well bore penetrating the formation. The term "aqueous carrier~' refers to water (including alkaline or acidic aqueou~ solutions), brines9 and mixtures of water and one or more water miscible liquid such a~ a lower alkanol, eOg., ethanol or propanol, a lower ketone, eOg., acetone or methyl ethyl ketone9 and the like. The aqueous carrier containing the controlled release agent, can be the fracturing Yluid which generally contains from 0.001 to 2, pre~erably from 0001 to 1, weight percent of the controlled release cap~ules based on the weight of the aqueous carrier employed.

The controlled rel0ase capsules are often advantageously added with a fracturing fluid.
Fracturing fluid~ and their component3 are well known in the art and reference is made thereto for the purpose of this invention. Essentially all fracturing fluids contain a carrier liquid which is conventionally an aqueou~ carrier and a visco~ifying polymer. In addition, the fracturing fluid will also generally contain one or more additives ~uch as surfactants, salts such a3 pota~sium chloride, anti-foaming agents, bacterîcides and cross-linking agents for the polymeric thickener.

35,069-F ~15-47~7 In the practice of the present invention, the breaker can be relea~ed from the capsule to the formation when the pressure differential between the environmental pressure and the interior of the capsule caused by fluid migration into the capsule is sufficient to rupture the enclosure member However, in the general practice of the present invention, it i~
contemplated that release of the breaker will not result from this mechanism only and that this release mechanism may not be the only, or even the primary mechanism, eausing the release of the breaker to the formation. For example, primary release of the breaker from the capsules may result Prom stresseq caused by the closure of the formation. Rupture of the enclosure member (and the subsequent release of breaker to the formation) from increased internal pressures i3 then exhibited only in those capsules not 30 broken.
The method of the present invention can also be employed to place a mixture o~ two or more different encapsulated breaker materials, or a mixture of one or more encapsulated breaker material~ with a second treating agent into the subterranean formation. For example, a controlled release cap~ule containing a ~ingle breaker material can be blended with a controlled release capsule containing a breaker of the same or different type (or, alternatively, a different treating agent) for introduction into the well bore and subssquently into the subterranean ~ormation.
Alternatively, two or more breaker materials or at least one breaker material and at least one treating agent can be combined into a single controlled release capsule. In another method, the controlled release capsules can be employed in conjunction with other 35,069-F -16-capsules in which the enclosure member is substantially impermeable to the fluids exi~ting in the ~ormation or injected with the capsules and containing the same or diP~erent treating agent as contained by the controlled release capsule. In thi~ method, the different cap~ules can be added as a mixture to the well bore and/or subterranean formation or sequentially.

In the method o~ the present invention~ the premature release of the breaker may be occasioned by an incomplete coating o~ the breaker by the enclosure member, the unintended or unpreventable rupture of the enclosure member during the mixing and delivery step, or the like. In many cases~ this premature release of the breaker can adversely affect the operation.
Therefore, it i~ often advantageous to add some material, e.g. sodium thiosulfate and other reducing agents to counteract the oxidizer; with the controlled release capsule which will neutralize the af~ect of the unintentionally released material on the operation.

The following examples are presented to illustrate the invention and should not be construed to limit its scope. All percentages and parts are by weight unless otherwise indicated.

35,069-F -17-~ i7 Example 1 About 40Q grams (g) of ammonium persulfate crystals (the breaker) having a diameter of about 1 millimeter (mm) are fluidized in a Uni-Glatt~ fluidiz0d bed apparatus using a Wurster column. The~e crystals are then sprayed with a polymer latex (enclosure member) consisting of about 15 percent eolids. The polymer is a copolymer derived from about 90 mole percent vinylidene chloride and about 10 mole percent methyl acrylate. A ~pray nozzle with level setting and air pressure o~ 3 bars (300 kPa) combined with an exhaust filter bumping scheme of 5 second duration with a 45 second interval is employed in the coating operation. The inlet temperature is 60C and the feed rate about 15 milliliters (ml) per minute. The spray time is about 10 minute~. The capsules (coated breaker crystal~) have a coating thicknes~ which vary from 20 to 50 micrometer (~m) and an average coating thickness of 30 ~m.

Ten grams of the capsules are placed in 1000 g water at room temperature, Due to the irregularities in the coating and the fact tha~ all breaker cry~tals are not completely coated with the enclosure member, about 20 weight percent of the persulfate breaker is released within about 5 hours of the initial contact of the capsules with water. Le~ than ten percent of the persulfate breaker originally contained by the enclosure member is released in the subsequent 45 hour~, which indicates that the enclo~ure member will effectively retain the persulfate breaker until the time at which release i3 desired.

35,069-F 18-~7~

When 10 g of the capsules are placed in lO0 of water maintained at a temperature of 65C, again about 20 weight percent of the persulfate breaker crystals are released within the first 5 hours. No appreciable amount of the cry~tals are then relsased until about 20 hours after initial contact. After this time, the capsules begin to burst and within 30 hours after initial contaot of the capsule~ with water, about 90 weight percent of the crystals are released into the water, indicating that release can be delayed until a desired time and then the active component can be substantially completely released within a short period of time.
When 10 g of the capsules are placed in water at 81C, the entire amount of persulfate crystals contained by the capsule~ is completely released within 5 hours after initial contact.

During the release of the breaker crystal~ from the capsule~, it is noted, by observing the capsule~
under a microscope (50 x magnification) that the coating is being lifted ~rom the encapsulated material by gas bubbles ~ormed by reaction of the oxidizing agent and water~

By varying the coating thickness, the release aharacteristic~ of the cap~ules can be varied to almost any extent. For example, when lithium hypochlorite cry~tals having a diameter of about 2 mm are coated by the ~oregoing technique at conditions such that the capsules have a coating thickness of about 50 ~m, the burst release time in water at room temperature is --~o--expected to be about 4.75 hourq from the time of the initial contact of the capsule~ with the water.

When magnesium monoperoxyperphthalate hexahydrate crystals having a diameter of about 1 mm are coated with the same polymer using similar techniques but at conditions to achieve a coating thicknes~ of only about 1605 ~m, the burst release time is found to be about only 9 minutes. This shorter release time is due to the substantially thinner coating on the crystals Similarly, sodium perborate crystals having a 1.5 mm diameter coated with the polymer latex to give a coating thickness of about 7.9 ~m is expected to have an average release time of about 35 minutesO

Example 2 About 1800 g of ammonium persulfate crystals pas~ing through a 20 mesh screen U.S. Standard (841 micron) and being stopped by a 40 mesh screen U.S.
Standard (420 micron) are fluidi~ed in a UniGlatt fluidi~ed bed apparatus operating in the Wurster mode.
These crystal~ are sprayed with a polymer latex consiqting of about 12.5 percent ~olids The polymer is a copolymer derived from about 92 mole percent vinylidene chloride, about 5 mole percent methyl acrylate and about 3 mole percent acrylonitrile. The polymer solution i~ atomized at a pressure of about 2 bars (200 kPa) and ~prayed at a rate of 10 milliliters (ml) per minute for a total time of 240 seconds. The inlet temperature was 43C. The capsules so produced have an average coating thickness of about 30 ~m.

~7~7~j7 Seventeen grams of the thus prepared capsules are placed in 80g of water at a temperature of 65C~
Less than two percent of the persul~ate crystals contained by the capsules are released during the ~irst

2 hours after initial contact of the capsules with water. The crystals are then released at a rate such that 13 weight percent i released at 4 hours after initial contact of the capsules with water, 40 percent is relea~ed at 6 hour3 and 47 percent is released after 8 hours from initial contact.

Example 3 Following the procedure of Example 2, 1500 g of ammonium persulfate cry~tals are coated in a UniGlatt fluidized bed apparatus operating in the ~urster mode using a polymer latex containing about 12 percent of the polymer latex of Example 1 and 0.3 percent of an antiblocking compound to produce free flowing capsules.
When placed in water maintained at a temperature of 65C, the capsules released the ammonium persulfate at about the same rate as the capsules described in Example 2.

Sufficient amounts o~ the capsules containing the ammonium persulfate are added, with agitation, to a 50 ml solution of about 1 percent hydroxypropylguar in

3 water maintained in a viscometer cup to give a 0.2 percent di~persion (Sample No. 1) of the capsules in the solution. The viscometer cup i~ then le~t static (iOe., the dispersion is not agitated) for a period of about 30 minutes after which the viscosity is measured.
The viscometer cup is then placed under pressure of 35,069-F -21-7~ ~67 2700 kPa with nitrogen gas and the dispersion is then sheared at a rate of 170 sec~l, heated up to a temperature of 65C at a rate of about 505C/minute for four hours, and the viscosity measured every 30 minutes over the four hour period. The dispersion is then left static for an additional 44 hours9 with the viscosity being measured every four hours. The percentages of the original viscosity of the solution retained as a function of time after initial contact of the solution with the capsules containing the ammonium persulfate is set forth in the following table.

2~

35,069-F -22-7 4 7 ~; !7 Time after Initial Contact 9 Viscosity hrs Retained, 30~ 92 3~5 90 800 66~5 l~oO 47 16~0 42 20~0 49 24 ~ 0 37 28 ~ 0 35 32~0 3205 36 ~ 0 30 40~0 25~5 44 ~ 0 24 It is evident from the data set forth in the foregoing Table, that the viscosity o~ the solution is substantially retained for a period of 4 hours~
30 Between the 4th and the 12th hour, the viscosity decreases rapidly. This indicates that mo~t o~ the capsules retain the ammonium persulfate for a period o~
time between 4 and 8 hours after initial contact with the aqueous solution, at which time tha ammonium 35 persulfate breaker is released to the solution and the viscosity broken. A~ter 12 hours, the vi~cosity -2~

remains relatively ~tableg with a small decrease in viscosity being noted. This indicates that only small amounts of ammonium persul~ate are being released from the capsules a~ter the initial 12 to 16 hours o~
contact. In this manner, the breaking of a solution can e~fectively be controlled.

Testing i3 repeated ln an identical manner except that the ammonium persulfate is added directly to the thickened solution. Within 0.5 hours at a temperature o~ 65C, the viscosity of the solution has dropped to less than 20 percent o~ it~ initial viqcosity. Thus, when added directly to the thickened ~olution, the breaking o~ the viscosity occurs too rapidly and is undesirable. When no breaker is added to the thickened solution, the solution viscosity is still over 80 percent o~ its original solution visco~ity after 44 hours time. This high viscosity after such a long period of time is also undesirable.

3o 35,069-F -24-

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:

1. A method for breaking an aqueous fracturing fluid comprising the steps of injecting into a subterranean formation controlled release capsules comprising an enclosure member enclosing a breaker for the aqueous fracturing fluid; the enclosure member being permeable to at least one liquid existing in the subterranean environment or a liquid that is injected with the controlled release capsules such that the enclosure member is capable of maintaining a substan-tial portion of the encapsulated breaker until a predetermined time period following exposure to the liquid.

2. The method of Claim 1, wherein the controlled release capsules are injected into the formation as a dispersion in an aqueous carrier, said carrier containing from 0.001 to 2 weight percent of the controlled release capsules, based on the weight of the carrier.

3. The method of Claim 1, wherein the controlled release capsules are injected in a mixture or sequentially with capsules having an enclosure 35,069-F -25-member which is substantially impermeable to the fluid or fluids existing in the formation or injected with the capsules having such an impermeable enclosure member or the controlled release capsules and which impermeable capsules contain the same or different breaker as contained by the controlled release capsules.

4. The method of Claim 1 t wherein the enclosure member is prepared from a membrane material having a film thickness of 25µm and a water vapor transmission rate of less than 3g/100 cm2/24 hours at a temperature of 38°C and greater than 0.015g/100 cm2/24 hours at 38°C.

5. The method of Claim 4, wherein the material has a water vapor transmission rate of less than 1.25 g/100 cm2/24 hours at 38°C and greater than 0.03 g/100 cm2/24 hours at 38°C.

6. The method of Claim 1, wherein the enclosure member material is selected from a homopolymer or copolymer of ethylene, propylene, isobutylene, vinyl chloride and vinylidene chloride, and mixtures thereof.

7. The method of Claim 6, wherein the enclosure member is selected from polyethylene, polypropylene, polyisobutylene, a copolymer of vinyl chloride and vinylidene chloride, a copolymer of vinylidene chloride and an ester of an unsaturated carboxylic acid, a copolymer of ethylene and an unsaturated carboxylic acid, and mixtures thereof.

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8. The method of Claim 1, wherein the enclosure member is selected from an epoxide, polycarbonate, a polymer of ethylene oxide or propylene oxide, ethyl cellulose,and mixtures thereof.

9. The method of Claim 1, wherein the breaker is a material which will react with the liquid which has penetrated into the capsule to form a gas.

10. The method of Claim 1, wherein the breaker is selected from an enzyme, an oxidizing agent, a transition metal salt in ionized form, an acid, and mixtures thereof.

11. The method of Claim 10, wherein the oxidizing agent is selected from ammonium, sodium or potassium persulfate; sodium peroxide; sodium chlorite;
sodium, lithium or calcium hypochlorite; chlorinated lime; potassium perphosphate; sodium perborate;
magnesium monoperoxyphthalate hexahydrate; N,N'--dichlorodimethylhydantoin,and mixtures thereof.

12. The method of Claim 1, wherein the enclosure member has a thickness of from 0.5 to 100 µm.

13. The method of Claim 1, wherein the controlled release capsules have an average particle size of from 0.1 to 2 mm and the enclosure member is applied as a coating having a thickness of from 5 to 60 µm.

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14. The method of Claim 1, wherein the controlled release capsule comprises a multiple wall enclosure member.

15. The method of Claim 1, wherein the controlled release capsule comprises a polynuclear core wherein each core is encapsulated by a permeable enclosure member but agglomerated or otherwise attached to form a single particle.

16. A fracturing fluid for fracturing a subterranean formation comprising an aqueous carrier liquid, an viscosifying polymer, and controlled release capsules, each capsule comprising an enclosure member containing a breaker for the viscosifying polymer, wherein the enclosure member is permeable to the carrier liquid or at least one liquid existing in the subterranean formation, said capsules being capable of maintaining a substantial portion of the breaker in an encapsulated condition for a predetermined time period following exposure to the liquid and before release of the breaker to the carrier liquid.

17. The fracturing fluid of Claim 16, including an additive selected from a surfactant, a salt, an anti-foaming agent, a bactericide and a cross-linking agent for the polymeric viscosifier.

18. The fracturing fluid of Claim 16, wherein the fracturing fluid contains from 0.001 to 2 weight percent of the controlled release capsules based on the weight of the carrier liquid.

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19. The fracturing fluid of Claim 16, wherein the enclosure member is prepared from a coating material having a thickness of 25 µm and a water vapor transmission rate of less than 3 g/100 cm2/24 hours at 38°C and greater than 0.015 g/100 cm2/24 hours at 38°C.

20. The method of Claim 4, wherein the material has a water vapor transmission rate of less than 1.25 g/100 cm2/24 hours at 38°C and greater than 0.03 g/100 cm2/24 hours at 38°C.

21. The fracturing fluid of Claim 16, wherein the breaker is selected from an enzyme, an oxidizing agent, a transition metal salt in ionized form, and mixtures thereof.

22. The method of Claim 1 wherein the oxidizing agent is selected from ammonium, sodium or potassium persulfate; sodium peroxide; sodium chlorite;
sodium, lithium or calcium hypochlorite; chlorinated lime; potassium perphosphate; sodium perborate;
magnesium monoperoxyphthalate hexahydrate; N,N'-dichlo--rodimethylhydantoin, and mixtures thereof.

23. The fracturing fluid of Claim 16, wherein the enclosure member for the breaker has a coating thickness of from 0.5 to 100 µm.

24. The fracturing fluid of Claim 23, wherein the controlled release capsules have an average particle size of from 0.1 to 2 millimeters, and the enclosure member is applied as a coating having a thickness of from 5 to 60 µm.

25. The fracturing fluid of Claim 16, wherein the controlled release capsule comprises a multiple wall enclosure member.

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