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CA2595686C - Soluble diverting agents - Google Patents

️Tue Sep 18 2012

CA2595686C - Soluble diverting agents - Google Patents

Soluble diverting agents Download PDF

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Publication number

CA2595686C

CA2595686C CA2595686A CA2595686A CA2595686C CA 2595686 C CA2595686 C CA 2595686C CA 2595686 A CA2595686 A CA 2595686A CA 2595686 A CA2595686 A CA 2595686A CA 2595686 C CA2595686 C CA 2595686C Authority

Canada

Prior art keywords

diverting

collagen

poly

fluid

water

Prior art date

2005-01-21

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Active

Application number

CA2595686A

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French (fr)

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CA2595686A1 (en

Inventor

A. Richard Sinclair

Syed Akbar

Patrick R. Okell

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Covia Solutions Inc

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Fairmount Minerals Ltd

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2005-01-21

Filing date

2006-01-20

Publication date

2012-09-18

2006-01-20 Application filed by Fairmount Minerals Ltd filed Critical Fairmount Minerals Ltd

2006-08-24 Publication of CA2595686A1 publication Critical patent/CA2595686A1/en

2012-09-18 Application granted granted Critical

2012-09-18 Publication of CA2595686C publication Critical patent/CA2595686C/en

Status Active legal-status Critical Current

2026-01-20 Anticipated expiration legal-status Critical

Classifications

- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
- C09K8/487—Fluid loss control additives; Additives for reducing or preventing circulation loss
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/14—Obtaining from a multiple-zone well
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/261—Separate steps of (1) cementing, plugging or consolidating and (2) fracturing or attacking the formation

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Life Sciences & Earth Sciences (AREA)
Engineering & Computer Science (AREA)
General Life Sciences & Earth Sciences (AREA)
Geology (AREA)
Mining & Mineral Resources (AREA)
Chemical & Material Sciences (AREA)
Physics & Mathematics (AREA)
Environmental & Geological Engineering (AREA)
Fluid Mechanics (AREA)
Geochemistry & Mineralogy (AREA)
Materials Engineering (AREA)
Organic Chemistry (AREA)
Inorganic Chemistry (AREA)
Compositions Of Macromolecular Compounds (AREA)
Paints Or Removers (AREA)
Medicinal Preparation (AREA)
Biological Depolymerization Polymers (AREA)
Materials For Medical Uses (AREA)
Peptides Or Proteins (AREA)
Physical Or Chemical Processes And Apparatus (AREA)
Processes Of Treating Macromolecular Substances (AREA)

Abstract

Methods and compositions for stimulating single and multiple intervals in subterranean wells by diverting well treatment fluids into a particular direction or into multiple intervals using water soluble coated diverting agents are described. The water soluble coating of the diverting material is preferably a collagen, poly(alkylene) oxide, poly(lactic acid), polyvinylacetate, polyvinylalcohol, polyvinylacetate/polyvinylalcohol polymer or a mixture thereof applied as a coating on any number of proppants. The method allows for the diverting of the flow of fluids in a downhole formation during a well treatment, such as during a fracturing process. Following completion of a treatment such as a hydraulic stimulation, the soluble diverting agent can be dissolved and removed by the water component of the well production.

Description

SOLUBLE DIVERTING AGENTS
[0001]

FIELD OF THE INVENTION

[0002] The present invention provides methods and compositions for treating subterranean wells and, more specifically, provides methods and compositions for stimulating multiple intervals in subterranean wells. In particular, this invention provides methods and compositions for diverting well trealment fluids into multiple intervals by introducing propping materials coated with a water soluble polymer e.g. collagen, polyvinyl acetate/polyvinyl alcohol, polyalkyl oxides, poly(lactic acid), periodic chart elements of group I or II (alkali metal or alkaline earth metal) silicate polymer, or combinations thereof with materials that are slowly water soluble for use in redirecting the flow of stimulation fluids from a tubing string into the subterranean environment.
DESCRIPTION OF RELATED ART

[0003] Well treatments, such as acid and fracture treatments of subterranean formations are routinely used to improve or stimulate the recovery of hydrocarbons. In many cases, a subterranean formation may include two or more intervals having varying permeability and/or injectivity. Some intervals may possess relatively low injectivity, or ability to accept injected fluids, due to relatively low permeability, high in-situ stress, and/or formation damage. Such intervals may be completed through preparations in a cased wellbore and/or may be completed open hole. In some cases, such formation intervals may be present in a highly deviated or horizontal section of a wellbore, for example, a lateral open hole section. In any case, when treating multiple intervals having variable injectivity it is often the case that most, if not all, of the introduced well treatment fluid will be displaced into one, or only a few, of the intervals having the highest injectivity. Even if there is only one interval to be treated, the tendency for the growth of the fracture can be either up or down. This depends on the in situ formation stress and the permeability variation in the formation layer. Below the created fracture can be a water zone.
If the created fracture breaks into this zone, the well can be ruined due to excess water and a cut off of the petroleum components of the productive interval. Above the created fracture zone a gas cap may exist which would cause harm to the production of the well because of gas bypassing the liquid petroleum components of the well.

[0004] In an effort to more evenly distribute displaced well treatment fluids into each of the multiple intervals being treated, methods and materials for diverting treatment fluids into intervals of lower permeability and/or injectivity have been developed.
However, conventional diversion techniques may be costly and/or may achieve only limited success. In this regard, mechanical diversion techniques are typically complicated and costly.
Furthermore, mechanical diversion methods are typically limited to cased hole environments and depend upon adequate cement and tool isolation for achieving diversion.

[0005] The efficient and simultaneous treatment of multiple sets of perforations over an extended vertical section has thus been a problem in well stimulation for numerous years.
Numerous treatment diversion methods, such as oil-soluble calcium soap, sulfuric acid, and Dowell's "Fixafrac" (a mixture of lime, kerosene, a graded calcium chloride soap, and a gelling agent, and Dowell's FLAX-2TM as described by Harrison in his comprehensive review Journal of Petroleum Technology, pp. 593-598 (1972), have been used to treat multiple zones with a wide variety of effectiveness. A great variety of chemical based diverting agents have been used in attempts to plug formation openings and divert treating fluids to other zones of the formation.
For example, wax beads have been used as diverting agents. However, the wax beads have limited melting points, from about 138 F to about 192 F, making them useless if the formation temperature exceeds their melting point.

[0006] Naphthalene (moth balls) and sodium chloride particles have also been described to be useful as effective diverting agents. Naphthalene particles are readily soluble in oil, but melt at about 180 F, thereby limiting their use to applications in lower-temperature formations. Sodium chloride, having a melting point of about 1,470 F, while useful at high temperatures, requires that the well be cleaned with water or dilute acid after the formation has been treated in order to fully remove the sodium chloride particles. Furthermore, sodium chloride cannot be used with hydrofluoric acid to treat subterranean wells due to the formation of insoluble precipitates which can problematically block the wellbore.

[0007] Alternatively, diversion agents such as polymers, suspended solid materials and/or foam have been employed when simultaneously treating multiple intervals of variable injectivity. Such diversion agents are typically pumped into a subterranean formation prior to a well treatment fluid in order to seal off intervals of higher permeability and divert the well treatment fluid to intervals of lower permeability. However, the diverting action of such diversion agents is often difficult to predict and monitor, and may not be successful in diverting treatment fluid into all desired intervals. These problems may be further aggravated in open hole completions, especially in highly deviated completions having large areas of a formation open to the wellbore.
The presence of natural fractures may also make diversion more difficult.

[0008] Several attempts to address the issues of areas of differing permeability within a wellbore have been addressed over the years. U.S. Patent No. 2,803,306 to Hower offers a process for increasing the permeability of an underground formation having several zones of varying permeability. The steps described include introducing into a well bore a treatment fluid containing hydrochloric acid which has oil-soluble particles dispersed therein, the material being selected from gilsonite, naphthalene, para-dichlorobenzene, anthracene, and [i-naphthol. Upon treatment, the particles provide a partial blockage of the more permeable zones of the subterranean formation, allowing the treatment fluid to enter the less-permeable zones.

[0009] U.S. Patent No. 3,797,575 assigned to Halliburton discloses diverting-forming additives comprised of relatively water insoluble solid material dissolved in a solvent such as methanol or isopropanol. When the additive is combined with an aqueous treatment fluid, the solid material, dissolved in the additive, is precipitated in the aqueous treating fluid into a finally divided form, which then act as a diverting agent. U.S. Patent No. 3,724,549, also assigned to Halliburton, describes a diverting agent material for diverting aqueous treatment fluids into progressively less permeable subterranean formations. The material is composed of a carrier liquid and graded particles of cyclic or linear hydrocarbon resins having between about 20 and about 1,400 carbon atoms, and a melting point of about 200 F. This material is described as being largely water and acid insoluble, but soluble in oil, such that the resin can be removed by the produced oil after the completion of the oil treatment operation.

[0010] The use of radiation-induced polymers as either temporary or permanent diverting agents has been described by Knight, et al. in U.S. Patent No. 3,872,923. According to the specification, temporary or permanent reductions in permeability can be obtained by injecting an aqueous solution containing a water-soluble polymer obtained by radiation-induced polymerization of acrylamide and/or methacrylamide and acrylic acid, methacrylic acid, and/or alkali metal salts of such acids. The resultant polymeric diverting agent has properties, such as temperature and pH stability, so as to effect a reduction of permeability of the porous medium.
Permeability within the formation can be restored by subsequent treatment with a chemical to break down the polymer, such as hydrazine hypochlorite solution or strong mineral acids.

[0011] U.S. Patent Nos. 3,954,629 and 4,005,753 to Scheffel, et al., offer polymeric diverting agents, and methods of treating subterranean formations with such polymeric diverting agents, respectively. The polymeric composition is described to comprise solid particles of a homogenous mixture of polyethylene, ethylene-vinyl acetate copolymer, a polyamide, and a softening agent such as long chain aliphatic diamides. These polymeric diverting agents are reported to be suitable for use in subterranean formations where formation temperatures are 350 F or greater.

[0012] Methods of temporarily plugging a subterranean formation using a diverting material comprising an aqueous carrier liquid and a diverting agent comprising a solid azo component and a methylenic component are described by Dill, et al. in U.S. Patent No.
4,527,628. The diverting agent is preferably Hansa Yellow G (Fanchon Yellow YH-5707 pigment) or Fast Yellow 4RLF
dye, both of which have an azo component and a methylenic component and are further characterized as having a melting point of at least 332.6 F, a degree of solubility in water at a temperature of water from about 200 to about 425 F, and a degree of solubility in kerosene at a temperature of from about 200 F to about 425 F.

[0013] In U.S. Patent No. 6,367,548, Purvis, et al. describes methods and compositions for stimulating multiple intervals in subterranean wells by diverting well treatment fluids into multiple intervals. According to the specification, this is accomplished by alternately displacing diverting agent from the annulus of the weilbore into a subterranean formation and displacing treatment fluid from a tubing string into the subterranean formation.

[0014] Other methods for diverting a fracture treatment include the limited-entry technique described by LaGrone, et al.,SPE 530, pp. 695-702 (1963), and the Technique of Multi-Fracture Fracturing Using a Diverting Agent (TMFUD) suggested by Dingxiang, et al., SPE
30816, pp.
80-86 (1988), the latter of which has shown an average oil production improvement of 15.0 t/d for each well, and a cumulative production improvement of 340.3 x 104 tons. A
viscoelastic surfactant-based diverting agent for use in acid stimulations has also been described (Alleman, D., et al., SPE 80222 (2003)), which is a VES gel (polyQuat) characterized by a distinctive vesicle structure stable at high pH and a thermal stability of about 250 F.
This gel-type diversion agent is typically pumped into a subterranean formation prior to a well stimulation fluid in order to seal off intervals of high permeability and divert the well treatment fluid to intervals of low permeability.

[0015] In light of all these advances and new techniques, the diverting action of diverting agents is often difficult to predict and monitor, and may not be successful in diverting treatment fluid into all the desired intervals, thereby failing to allow maximum benefit from the fracture procedure. These problems can be further aggravated in open hole completions, especially in highly-deviated completions having large areas of a formation open to the wellbore. The presence of natural fractures within the subterranean formation can also serve to make diversion more challenging. Thus, there exists a need for new compositions and methods for diverting well treatment fluids into multiple intervals of varying permeability within a subterranean formation.

SUMMARY OF THE INVENTION

[0016] The present invention provides a method of using particles having a soluble outer coating as diverting agents in subterranean formations. The soluble outer coating will dissolve after a desired period of time at downhole temperatures and pressures in the presence of standard downhole fracturing fluids and breaker compositions. Examples of the soluble outer coating include collagen, poly(alkylene) oxides, poly(lactic acid), polyvinylacetate, polyvinyl alcohol, polyvinylacetate/polyvinylalcohol, polylactone, polyacrylate, latex, polyester, group I or II
silicate polymer or mixtures thereof.

[0017] The present invention provides water soluble polymer coated proppants as diverting agents and methods of using such diverting agents for treating a subterranean formation. The diverting agent together with a carrier liquid is introduced into a subterranean formation. The liquid carrier flows into fractures and/or intervals within the subterranean formation. The fractures or intervals present varying degrees of permeability. In accordance with the methods of the present invention, the liquid carrier with diverting agent will flow to the most permeable interval first. The temperature of the formation will cause the water soluble polymer coating of the diverting agent to soften and swell, thereby plugging the fracture.

[0018] In one embodiment, a diverting agent suitable for diverting well treatment fluids into a single or a multiple interval is described, wherein the diverting agent is comprised of a particulate substrate and a water-soluble outer layer. Such water soluble outer layer polymer is exemplified, without limitation, by collagen, poly(alkylene) oxides, poly(lactic acid) polyvinylacetate, polyvinylalcohols, polyvinylacetate/polyvinylalcohol, polymeric lactones, water-soluble acrylics, latex, polyester, group I or II silicate polymer, and admixtures thereof.

[0019] In a further embodiment, a diverting agent suitable for diverting well treatment fluids into a single or a multiple interval is described, wherein the diverting agent is comprised of a particulate substrate an intermediate water insoluble layer and a water soluble polymer outer layer. The water soluble outer layer polymer is exemplified, without limitation, by collagen, poly(alkylene) oxides, poly(lactic acid), polyvinylacetate, polyvinylalcohols, polyvinylacetate/polyvinylalcohol, polymeric lactones, water-soluble acrylics, latex, polyester, group I or II silicate polymer and admixtures thereof. The water insoluble intermediate layer is exemplified by phenol-aldehyde novolac polymers and phenol-aldehyde resole polymers.

[0020] In yet another embodiment, a diverting agent suitable for diverting well treatment fluids into a single or a multiple interval within a wellbore is described, wherein the diverting agent is substantially a water-soluble polymer particle such as a collagen bead or granular particles of poly(alkylene) oxide, poly(lactic acid), polyvinylacetate, polyvinylalcohol, polyvinylacetate/polyvinylalcohol, polymeric lactones, water-soluble acrylics, latex, polyester, group I or II silicate polymer, or mixtures thereof

[0021] In a further embodiment, a method of stimulating individual intervals of a subterranean formation is disclosed, the method including the steps of introducing a diverting agent having a water-soluble component on its outer layer into an inner pipe of a wellbore in combination with a low viscosity fluid or a fracturing fluid; displacing the diverting agent and fracturing fluid into the subterranean formation, allowing the diverting agent to progressively plug portions of the formation being treated; and repeating the process as necessary, adding the diverting agent to the carrier fluid in slugs during the fracturing operation.

DESCRIPTION OF THE FIGURES

[0022] The following figures form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these figures in combination with the detailed description of specific embodiments presented herein.

[0023] FIG. 1 shows an elevational cross-sectional view of a downhole portion of a subterranean formation having a vertical casing and a single treatment interval, wherein variously coated diverting agents are being injected into the hydrocarbon-bearing formation in accordance with an aspect of the present disclosure.

[0024] FIG. 2 illustrates the elevational cross-sectional view of the subterranean formation of FIG. 1, wherein proppants are being injected into a hydrocarbon-bearing formation having diverting agents of the present invention injected.

[0025] FIG. 3 shows a well with a vertical casing and multiple treatment intervals 58, 60 and 62 and variously coated diverting agents being injected, in accordance with an aspect of the present disclosure.

DEFINITIONS

[0026] The following definitions are provided in order to aid those skilled in the art in understanding the detailed description of the present invention.

[0027] The term "carrier liquid" as used herein refers to oil or water based liquids that are capable of moving particles (e.g., proppants) that are in suspension. Low viscosity carrier fluid have less carrying capacity and the particles can be affected by gravity so that they either rise if they are less dense than the liquid or sink if they are more dense than the liquid. High viscosity liquids can carry particles with less settling or rising since the viscosity overcomes gravity effects.

[0028] The term "crosslinker" or "cross-linking agent", as used herein, refers to those compounds used to covalently modify proteins, such as collagen, and includes both homobifunctional crosslinkers that contain two identical reactive groups, and heterobifunctional crosslinkers which contain two different reactive groups.

[0029] The term "diverting agent", as used herein, means and refers generally to an agent that functions to prevent, either temporarily or permanently, the flow of a liquid into a particular location, usually located in a subterranean formation, wherein the agent serves to seal the location and thereby cause the liquid to "divert" to a different location.

[0030] The term "proppant", as used herein, refers to those sized particles that are used in well work-overs and treatments, such as hydraulic fracturing operations, to hold fractures open following the treatment. Such sized particles are often mixed with fracturing fluid(s) to hold fractures open after a hydraulic fracturing treatment or similar downhole well treatment. In addition to naturally occurring sand grains and nut hulls, the term "proppant"
includes man-made or specially engineered proppants, such as resin-coated sand or high-strength ceramic materials like sintered bauxite. Resin coated proppants are typified by those that are coated with phenol-aldehyde novolac polymers or phenol-aldehyde resole polymers. Typically, but not necessarily, proppant materials are carefully sorted for size and sphericity to provide an efficient conduit for production of fluid from the reservoir to the wellbore.

[0031] In embodiments described and disclosed herein, the use of the term "introducing"
includes pumping, injecting, pouring, releasing, displacing, spotting, circulating, or otherwise placing a fluid or material within a well, wellbore, or subterranean formation using any suitable manner known in the art. Similarly, as used herein, the terms "combining", "contacting", and "applying" include any known suitable methods for admixing, exposing, or otherwise causing two or more materials, compounds, or components to come together in a manner sufficient to cause at least partial reaction or other interaction to occur between the materials, compounds, or components.

[0032] The term "water soluble" as used herein refers to resins, polymers, or coatings which are stable (do not dissolve) under ambient, surface conditions, but which become soluble after a given time (usually over several hours or several days) when placed in a subterranean environment.

[0033] The term "treatment", as used herein, refers to any of numerous operations on or within the downhole well, wellbore, or reservoir, including but not limited to a workover type of treatment, a stimulation type of treatment, such as a hydraulic fracturing treatment or an acid treatment, isolation treatments, control of reservoir fluid treatments, or other remedial types of treatments performed to improve the overall well operation and productivity.

[0034] The term "stimulation", as used herein, refers to productivity improvement or restoration operations on a well as a result of a hydraulic fracturing, acid fracturing, matrix acidizing, sand treatment, or other type of treatment intended to increase and/or maximize the well's production rate or its longevity, often by creating highly conductive reservoir flow paths.

DETAILED DESCRIPTION OF THE INVENTION

[0035] In embodiments of the disclosed diverting agent, single and multiple intervals of a subterranean formation can be treated or stimulated in stages by successively introducing the diverting agent comprising a particulate substrate and a slowly water-soluble outer coating comprising collagen or a combination of collagen and a slowly water-soluble, non-collagenous material.

[0036] The invention provides particle compositions comprising soluble material coatings comprising collagen, as well as processes for preparing such compositions.
These compositions are useful in subterranean formations for diverting well treatment fluids in a single interval to increase the fracture length or in multiple intervals of a subterranean formation having varying permeability and/or injectivity during a hydraulic fracturing operation. In using the diverting agents of the present invention in fracturing processes, the proppant (or particulate substrate) coated with a slowly water-soluble coating such as a collagen alone or in combination with a non-collagenic water-soluble, plastic coating material acts to divert the fracture, as the coatings on the proppants act as the defining boundaries of the initial fracture.
Following the fracturing treatment, the coating can be removed due to the slow-dissolution characteristics of the coating, leaving standard propping agents with high permeability to flow into the fracture and act as proppants.

[0037] While compositions and methods are described in terms of "comprising"
various components or steps, the compositions and methods can also "consist essentially of' or "consist of the various components and steps.

A. Substrate

[0038] Particulate material, also referred to herein as substrate material, suitable for use with the present invention includes a variety of particulate materials known to be suitable or potentially suitable propping agents which can be employed in downhole operations. In accordance with the present invention, the particulate material (or substrate material) which can be used include any propping agent suitable for hydraulic fracturing known in the art. Examples of such particulate materials include, but are not limited to, natural materials, silica proppants, ceramic proppants, metallic proppants, synthetic organic proppants, mixtures thereof, and the like.

[0039] Natural products suitable for use as proppants include, but are not limited to, nut shells such as walnut, brazil nut, and macadamia nut, as well as fruit pits such as peach pits, apricot pits, olive pits, and any resin impregnated or resin coated version of these.
Typical resin coatings or impregnations include bisphenols, bisphenol homopolymers, blends of bisphenol homopolymers with phenol-aldehyde polymer, bisphenol-aldehyde resins and/or polymers, phenol-aldehyde polymers and homopolymers, modified and unmodified resoles, phenolic materials including arylphenols, alkyiphenols, alkoxyphenols, and aryloxyphenols, resorcinol resins, epoxy resins, novolak polymer resins, novolak bisphenol-aldehyde polymers, and waxes, as well as the precured or curable versions of such resin coatings.

[0040] Silica proppants suitable for use with the present invention include, but are not limited to, glass spheres and glass microspheres, glass beads, silica quartz sand, and sands of all types such as white or brown. Typical silica sands suitable for use include Northern White Sands (Fairmount Minerals, Chardon, OH), Ottawa, Jordan, Brady, Hickory, Arizona, St. Peter, Wonowoc, and Chalfort, as well as any resin coated version of these sands. In the case of silica fibers being used, the fibers can be straight, curved, crimped, or spiral shaped, and can be of any grade, such as E-grade, S-grade, and AR-grade. Examples of suitable resin-coated silica proppants for use with the present invention include deformable proppants such as FLEXSAND
LSTM and FLEXSAND MSTM (available from BJ Services, Inc., Houston, TX) and Tempered HS , Tempered LC , Tempered DC , and Tempered TF tempered proppants, all available from Santrol, Fresno, TX.

[0041] Ceramic proppants suitable for use with the methods of the present invention include, but are not limited to, ceramic beads; spent fluid-cracking catalysts (FCC) such as those described in U.S. Patent No. 6,372,378; ultra lightweight porous ceramics; economy lightweight ceramics such as "ECONOPROPTM" (Carbo Ceramics, Inc., Irving, TX); lightweight ceramics such as "CARBOLITETM"; intermediate strength ceramics such as "CARBOPROPTM" (available from Carbo Ceramics, Inc., Irving, TX); high strength ceramics such as "CARBOHSPTM" and "Sintered Bauxite" (Carbo Ceramics, Inc., Irving, TX), and "HYPERPROP G2TM"
DYNAPROP G2TM, or OPTIPROP G2TM encapsulated, curable ceramic proppants (available from Santrol, Fresno, TX) as well as any resin coated or resin impregnated versions of these, such as described above.

[00421 Metallic proppants suitable for use with the embodiments of the present invention include, but are not limited to, aluminum shot, aluminum pellets, aluminum needles, aluminum wire, iron shot, steel shot, and the like, as well as any resin coated versions of these metallic proppants.

[0043] Synthetic proppants are also suitable for use with the present invention. Examples of suitable synthetic proppants include, but are not limited to, plastic particles or beads, nylon beads, nylon pellets, SDVB (styrene divinyl benzene) beads, carbon fibers such as PANEXTM
carbon fibers from Zoltek Corporation (Van Nuys, CA), and resin agglomerate particles similar to "FLEXSAND MSTM" (BJ Services Company, Houston, TX), as well as resin coated versions thereof.

[0044] Additionally, soluble materials suitable for use as proppants are also envisioned to be useful with the methods of the present invention. For example, soluble proppants which are placed in the channels of the created perforations include, but are not limited to, marble or limestone chips or any other suitable carbonate particulates. Additionally, wax, plastic, or resin particles, either coated or uncoated, which are either soluble through contact with a treatment chemical or can melt and flowback from the fracture are suitable for use as proppants with the present invention.

[0045] Suitable with the present invention, propping agents are typically used in concentrations from about 1 to about 18 pounds per gallon (about 120 g/L to about 2,160 g/L) of fracturing fluid composition, but higher or lower concentrations may also be used as required.

[0046] Similarly, the particulate substrate suitable for use with the present invention has a particle size in the range of USA Standard Testing screen numbers from about 4 to about 200 (i.e., screen openings of about 0.18 inch to about 0.003 inch). More particularly, particulate substrate sizes suitable for use with the present invention include size ranges from about 4 mesh (4750 microns) to about 200 mesh (75 microns). Also suitable for use with the present invention are particulate materials or proppants having size designations of 6/12, 8/16, 12/18, 12/20, 16/20, 16/30, 20/40, 30/50, 40/70 and 70/140, although any desired size distribution can be used, such as 10/40, 14/20, 14/30, 14/40, 18/40, and the like, as well as any combination thereof (e.g., a mixture of 10/40 and 14/40). The preferred mesh size, in accordance with the present invention, is 20/40 mesh.

B. Soluble Coating [0047] The soluble coatings used in accordance with the present invention can be any number of known soluble agents that are slowly soluble in downhole, subterranean formations over a period of time. Soluble polymer materials used in accordance with the present invention should be soluble (that is, capable of dissolving in) in brines, water, oil, organic solvents, acid or acidic media, and/or in fluids having a pH in the range from about 1 to about 14, as well as mixtures thereof under the conditions found in downhole, subterranean formation.

[0048] Preferably, the soluble coating is a structural protein such as collagen or atelocollagen, a vegetable protein such as found in wheat, maize, oat or almonds, or a collgen originating from a marine environment. The latter type of collagen can be extracted from fish, algae, plankton, micro-plankton, and the like. More preferably, the soluble coating is collagen, including Type I
collagen, Type II collagen, Type III collagen, Type IV, or Type V collagen, as well as combinations thereof. Most preferably, in accordance with the present invention, the soluble coating is a Type I collagen or an atelocollagen.

[0049] Type I collagens or atelocollagens suitable for use as soluble coatings in accordance with the present invention are those collagens containing at least one hydroxyproline residue. Such Type I collagens or atelocollagens include collagens found in tendons, skin, bone, scar tissue, and the like, such as tropocollagens, as well as products derived from the controlled, enzymatic or chemical reduction of collagen proteins. Such collagens preferably have a molecular weight from about 10,000 Daltons to about 500,000 Daltons, and more preferably from about 100,000 Daltons to about 300,000 Daltons. Suitable molecular weights of about 100,000 daltons, 125,000 daltons, 150,000 daltons, 175,000 daltons, 200,000 daltons, 225,000 daltons, 250,000 daltons, 275,000 daltons, 300,000 daltons, as well as molecular weights between any two of these values, e.g., collagens having a molecular weight from about 225,000 to about 275,000 daltons. For example, a preferred Type I collagen suitable for use with the present invention is tropocollagen with a molecular weight of about 250,000 as supplied by Milligans and Higgins, Inc. (Johnstown, NY).

[0050] Collagens suitable for use within the present invention have Bloom strengths from about 100 psi to about 900 psi, and more preferably from about 300 psi to about 700 psi. Most preferably, collagens suitable for use with the present invention have Bloom strengths from about 400 psi to about 600 psi. Suitable Bloom strengths, in accordance with the present invention, are about 400 psi, about 410 psi, about 420 psi, about 430 psi, about 440 psi, about 450 psi, about 460 psi, about 470 psi, about 480 psi, about 490 psi, about 500 psi, about 510 psi, about 520 psi, about 530 psi, about 540 psi, about 550 psi, about 560 psi, about 570 psi, about 580 psi, about 590 psi, and about 600 psi, as well as Bloom strengths between any two of these values, e.g., from about 400 psi to about 520 psi, such as 512 psi.

[0051] Bloom strength, as used herein, refers to the measured value of the strength and/or rigidity of a gelatinous substance, such as collagen, formed by a standard solution of definite concentration that has been retained at a constant temperature for a specified period of time, in accordance with standardized bloom testing procedures, such as BS757:1975, GMIA Testing Standard B5757, International Standard IS09665 for testing adhesive animal glues, or similar standards as described in "Official Methods of Analysis of AOAC INTERNATIONAL
(OMA) ", 17th Edition, Volume II; AOAC International Publications (2003). Bloom strength values are typically given in "pounds per square inch" (psi) or grams, reflecting the force required to depress a chosen area of the surface of the sample a distance of 4 mm. In a typical procedure, a gel product, such as collagen or gelatin, is formed to a specified consistency (e.g., 6 and 2/3 %
solution) and kept at a constant temperature in a constant temperature bath at 10 C for 18 hours.
A device called a Texture Analyzer (e.g., the TA.XT2i Texture Analyzer, Scarsdale, NY) then measures the weight in grams (or the pressure, in psi) required to depress a standard AOAC
[Associateion of Official Analytical Chemists] gelometer plunger having a sharp, lower edge 4 mm into the gel; alternatively, a BS plunger which has a bottom edge rounded to a radius of 0.4 mm can be used as the plunger. For example, if this procedure requires 200 grams to depress the plunger, then the gelatin has a Bloom strength of 200.

[0052] Type I collagens suitable for use within the present invention have a sieve distribution /size designation of 6/12, 8/16, 12/18, 12/20, 16/20, 16/30, 20/40, 30/50, 40/70 and 70/140, as well as sieve distributions between any two of these designations, although any desired size distribution can be used, such as 8/40, 10/40, 14/20, 14/30, 14/40, 18/40, and the like, as well as any combination thereof (e.g., a mixture of 10/40 and 14/40). The preferred mesh size, in accordance with the present invention, is 8/40 mesh.

[0053] Collagens, as used herein as soluble coatings, can be either cross-linked, uncross-linked, or a combination of both, and the type and degree of cross-linking will depend upon the specific application of the collagen-based soluble coating. There are four fundamental strategies for fixing collagenous materials and materials constructed of processed collagen fibers or purified collagen. These include exogenous chemical cross-linking using agents that covalently couple neighboring collagen fibrils using targeted reactive moieties in the collagen fibrillar system and the cross-linking molecules themselves; physiochemical cross-linking techniques such as photo-oxidation, microwave irradiation, dehydration and dehydrothermal treatment, that covalently join collagen fibrils via the naturally occurring reactive amino acid side chains;
chemical catalysis of intramolecular cross-links between amino acid side chains on the collagen fibrils; and polymerizing compounds mixed with collagenous assemblies and forming polymeric non-covalent or covalent interactions that do not chemically react with collagen fibrils [Koob, T.J., "Collagen Fixation", in Encyclopedia of Biomaterials and Biomedical Engineering, Wnek, G.E., Bowlin, G.L., Eds., 2004]. In accordance with the present invention, the collagen used as a soluble coating is preferably cross-linked using chemical cross-linking techniques. These include, but are not limited to, aldehyde-based cross-linking techniques, polyepoxy compound-based cross-linking techniques, the use of isocyanates, carbodiimide cross-linking, and acyl azide based crosslinking. More preferably, the collagen is cross-linked using aldehyde-based cross-linking techniques, such as by using glutaraldehyde or formaldehyde.

[0054] Aldehyde-based cross-linking techniques includes those techniques using a reagent containing two reactive aldehyde groups to form covalent cross-links between neighboring collagen proteins, especially the e-amino groups of lysine residues in collagen [Khor, E., Bioraterials, Vol. 18: pp. 95-105 (1997)]. Aldehydes suitable for use with the present invention include but are not limited to glutaraldehyde, formaldehyde, propionaldehyde, and butyraldehyde.

[0055] Polyepoxy based cross-linking techniques and agents include the use of compounds, such as short, branched polymers, terminating in reactive epoxy functionalities.
Polyepoxy compounds suitable for use as cross-linking agents in the present invention include but are not limited to glycerol ethers, glycol, and glycerol polyglycidyl ethers.

[0056] Isocyanates are also suitable for use as cross-linking agents in the present invention.
Generally, the isocyanates (R-NCO) react with primary amines to form a urea bond (R-H-CO-NH-R); difunctional isocyanates therefore have the ability to cross-link collagen via its lysine side chains. Isocyanates suitable for use as cross-linking agents in the present invention are preferably diisocyanates, including biphenyl diisocyanate, dimethoxy-4,4'-biphenyl diisocyanante, dimethyl-4,4'-biphenyl diisocyanate, 1,3-bis(isocyanatomethyl)benzene, phenyl diisocyanate, toluene diisocyanate, tolylene diisocyanate, diisocyanato hexane, diisocyanato octane, diisocyanato butane, isophorone diisocyanante, xylene diisocyanate, hexamethylene diisocyanante, octamethylene diisocyanante, phenylene diisocyanate, and poly(hexamethylene diisocyanate). Preferably, the isocyanate used as a cross-linking agent of the collagen molecules of the present invention is hexamethylene diisocyanate.

[0057] Carbodiimide cross-linking agents and techniques can also be used within the scope of the present invention. These agents react with the carboxyl groups of aspartic and glutamic acid side chains within the collagen to form isoacylurea derivatives/iso-peptide bonds [Khor, E., ibid.]. Carbodiimides suitable for use as cross-linking agents with the collagen of the present invention include but are not limited to N,N'-dicyclohexylcarbodiimide (DCC);
N,N'-diisopropylcarbodiimide (DIC); N,N'-di-tert-butylcarbodiimide; 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC; EDAC); water-soluble EDC (WSC); 1-tert-butyl-3-ethylcarbodiimide; 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide;
bis(trimethylsilyl)-carbodiimide; 1,3-bis(2,2-diinethyl-1,3-dioxolan-4-ylmethyl)carbodiimide (BDDC, as described in U.S. Patent No. 5,602,264); N-cyclohexyl-N'-(2-morpholinoethyl) carbodiimide; N,N'-diethylcarbodiimide (DEC); 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide methyl-p-toluenesulfonate [e.g., Sheehan, J.C., et al., J. Org. Chem., Vol. 21: pp. 439-441 (1956)];
oligomeric alkyl cyclohexylcarbodiimides, such as those described by Zhang, et al. [J. Org.
Chem., Vol. 69: pp. 8340-8344 (2004)]; polymer bound DCC; and polymer bound EDC, such as cross-linked N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide on JANDAJELTM.
Additionally, N-hydroxysuccinimide (NHS), 1-hydroxy-7-azabenzotriazole (HOAt), or similar reagents can be utilized in conjunction with the carbodiimide to minimize internal rearrangement of the activated isoacylurea derivative and provide more efficient cross-linking.

[0058] As with carbodiimide treatment, acyl azide crosslinking agents produce covalent bonds between the carboxylic acid side chains of aspartic acid and glutamic acids and the E-amino groups of the lysines of collagen [Petit, H., et al., J. Biomed. Mater. Res., Vol. 24: pp. 179-187 (1990)]. Following esterification of the carboxyl groups in which a methyl group is added to the acid, the biomaterial is treated with hydrazine to form the corresponding hydrazide; sodium nitride is then added to react with the hydrazide and form the acyl azide. Any number of hydrazines known in the art can be used in this method, including maleimidopropionic acid hydrazide (MPH).

[0059] Other chemical cross-linking agents suitable for use in the present invention to provide cross-linked collagen molecules which act as soluble coatings on proppant particles include but are not limited to homobifunctional cross-linkers such as BMME, BSOCOES, DSP
(a thio-cleavable cross-linker), DSS, EGS, water-soluble EGS, and SATA, as well as heterobifunctional cross-linking agents including GMB, NMS, PMPI, SMCC, SPDP, and MPH
(maleimidopropionic acid hydrazide), MCH, EMCH (maleimidopaprionic acid hydrazide), KMUH (N-(k-Maleimidoundecanoic acid)hydrazide), and MPBH (4-(4-N-MaleimidoPhenyl)butyric acid hydrazide), all available from Interchim (Cedex, France).

[0060] Other techniques suitable for crosslinking the collagen fibers for use as soluble proppant coatings include but are not limited to dehydration, UV irradiation at 254 nm, glucose-mediated cross-linking (glycation) in conjunction with UV irradiation, and biological cross-linking. The latter technique includes using natural products such as genipin and its related iridoid compounds which are isolated from the fruits of the gardenia plant (Gardenia j asminoides), which are dialdehydes in aqueous solution and thereby can react with the c-amino groups on lysine side chains of neighboring collagen molecules to provide a cross-link. Other biological cross-linking systems suitable for use with the present invention include catechol-quinone tanning systems, such as 3,4-dihydroxytyrainine, and nordihydroguaiaretic acid (NDGA), isolated from the creosote bush, which acts as a cross-linking agent via the two catechols on NDGA [Koob, T.J., Comp. Biochem. Physiol., Part A, Vol. 133: pp. 1171-1192 (2002)].

[0061] The slowly water-soluble coatings on the particulate substrates, in accordance with the present disclosure, can also be non-collagenic materials such as synthetic polymers that are slowly water soluble. Such non-collagenic materials include but are not limited to: polyethylene oxides, polypropylene oxides, polycaprolactones; grafts of polyethylene/polypropylene and polycaprolenes; grafts of polyethylene/polypropylene oxides and polycaprolactones; water soluble or water reducible acrylics; water reducible phenoxy resin; latex;
polyesters; soluble block copolymers; grafts of polyvinyl alcohol (PVA) and polyvinyl acetates;
polyactides and derivatives of polylactic acid; polyglycolic acid (PGA); polyglycoliclactic acid (PGLA). Also useful for a water soluble coating are periodic chart elements of group I or II (alkali metal or alkaline earth metal) silicate polymers, e.g. SOLOSILTM (Foseco International, Ltd., Great Britain), a sodium silicate polymer.

C. Method of Using [0062] In embodiments of the disclosed method, single or multiple intervals of a subterranean formation may be treated or stimulated in stages by successively introducing diverting agent of the present invention into the formation followed by introduction of well treatment fluid into the formation. As used herein, "wellbore" includes cased and/or open hole sections of a well, it being understood that a wellbore may be vertical, horizontal, or a combination thereof. The term "pipe string" refers to any conduit suitable for placement and transportation of fluids into a wellbore including, but not limited to, tubing, work string, drill pipe, coil tubing, etc.
Furthermore, it will be understood with benefit of this disclosure that the disclosed diversion agents and diversion treatment techniques are suitable for use with any type of well treatment fluid including, but not limited to, acid treatments, condensate treatments, hydraulic fracture treatments, and the like. Furthermore, it will be understood that the benefits of the disclosed methods and compositions may be realized with well treatments performed below, at, or above a fracturing pressure of a formation.

[0063] First: WELLBORE USE: In this aspect of the invention, the use of fully soluble particles in the wellbore (such as collagen or other water soluble polymer plastics or mixtures of these) to divert fluid flow from one zone to another and then dissolve is disclosed. The use of collagen (in both the uncrosslinked and crosslinked form) and soluble plastics are useful in diverting the flow of fluids in the well. These diverting materials should be in the range of 1 to 100 mesh size, preferably 4 to 50 mesh size and can be used in combination with other additives or plastic materials to enhance performance by diverting the flow of fluids from one zone to another.
[0064] These materials have been used as diverting ball sealers but recent tests have shown that the material could be used as a diverting agent to block fluid from flowing into one zone and into another of either higher pore pressure or lower permeability.
[0065] The present invention provides a method treating a cased wellbore to divert flow of fluids from one zone to another. The method involves pumping into a wellbore a diverting fluid that is made up of an aqueous carrier liquid having dispersed therein a particulate form of a water soluble polymer and wherein the particulate polymer has a density greater than or less than the density of the carrier liquid. As the diverting fluid is pumped into the wellbore the particulate polymer settles into zones of the wellbore and thereby diverts flow of a treating fluid from one zone to another. Generally the treating fluid is diverted or blocked from flowing into a zone of higher pore pressure or lower permeability.

[0066] In the methods of this invention relating to wellbore use, the water-soluble particulate polymer is collagen, poly(alkylene) oxide, poly(lactic acid), polyvinylacetate, polyvinylalcohol, polyvinylacetate/polyvinylalcohol, polylactone, polyacrylate, latex, polyester, periodic chart elements of group I or II (alkali metal or alkaline-earth metal) silicate polymer or mixtures thereof. Typically the particulate polymer is present in the carrier liquid in an amount from about 0.001 pounds per gallon to about 10 pounds per gallon of the carrier liquid.
Advantageously, the particulate polymer is comprised of varying densities greater or less than the density of the carrier fluid. Typically, the carrier liquid is water, brine, aqueous acid solutions, or gelled acid solutions.

[0067] Second: GENERATED FRACTURE USE: In this aspect of the invention, the use of coated particles of various propping agents (coated with either fully soluble or a mix of soluble and insoluble collagen or polymeric plastic materials) can be pumped into the fractured formations to prevent fractures from diverting out of the producing zone. For example, a dense sintered bauxite particle with a soluble or partially soluble coating would fall to the bottom of the fracture and divert the fracture from the lower strata or a water zone. Also, a low- density walnut shell with a soluble or partially soluble coating would tend to rise inside the fracture to divert the fracture from upward growth into a gas or water zone. The coating can be either fully or partially soluble since the proppant will remain in place in the fracture and provide conductivity in the fracture after the frac job is completed. Some of the coating on the proppant should be soluble but a mixture of both soluble and insoluble plastics or collagen is desirable to prevent movement of the propping agent in the fracture.

[0068] The use of diverting agents in fractures is that a proppant or propping agent would be coated with a soluble or partially soluble coating - using a collagen and/or polymeric plastic coating material or any mixture of these. The fracture would be diverted by using these soluble coatings on proppants as the defining boundaries of the initial fracture.
After the fracturing treatment, the coating would disappear and the previously coated particles would return to normal propping agents, which have high permeability. Coatings on various density proppants could cause the fracture boundaries to be set early in the fracture process since a low viscosity fluid would allow a high density coated proppant to settle or fall inside the fracture to make a lower boundary on the fracture and divert it out from the wellbore to make a longer fracture and increase the productivity of the well. Likewise, a low density coated proppant would tend to rise to the top part of the growing fracture to form a top boundary and divert the growing fracture away from upper zones that may harm the production of the well. With the fracture contained at top and bottom the fracture could grow outward and a longer contained fracture would improve the well potential productivity.

[0069] Figure 1 illustrates a well with a vertical cased wellbore section and a single interval formation that is to be treated in accordance with one embodiment of the present disclosure. The well 10 of FIG. 1 has a casing 12 extending from the wellhead 11 for at least a portion of its length and is cemented around the outside with cement sheath 14 to hold the casing 12 in place and isolate the penetrated formation or intervals. The cement sheath 14 extends upward from the bottom of the wellbore in the annulus between the outside of the casing 12 and the inside wall of the wellbore at least to a point above the producing strata/hydrocarbon bearing formation 18.
The reasons for the inclusion of this sheath are many, but essentially the cement sheath 14 helps to ensure the integrity of the well-bore (i.e., so it does not collapse), or to isolate specific, different geologic zones (i.e., an oil-bearing zone from an (undesirable) water-producing zone).
The wellbore is also optionally equipped with a casing or liner shoe 16 so as to help guide the casing string 12 past ledges or obstacles during its placement in the wellbore. For the hydrocarbons in the producing strata 18 to be produced, it is necessary to establish fluid communication between the producing strata 18 and the interior of casing 12.
This is accomplished by perforations 15 made through casing 12 and the cement sheath 14 by means known to those of ordinary skill in the art. Such means include, but are not limited to, perforation guns, shaped charge devices, and phase charge devices, such as those described in U.S. Patent Nos. 6,755,249, 5,095,099, and 5,816,343; Horizontal Oriented Perforating Systems (HOPS), such as those manufactured by Owen Oil Tubes, Inc. (Ft. Worth, TX);
mechanical perforating devices such as laterally movable punches (U.S. Patent No.
2,482,913), needle punch perforators, and toothed wheel perforators such as those described in U.S.
Patent No. 4,220,201;
and shearable plugs such as described in U.S. Patent No. 4,498,543. The perforations 15 form a flow path for fluid from the formation into the casing 12, and vice-versa.

[0070] The hydrocarbons flowing out of the producing strata 18 through the perforations 15 and into the interior of the casing 12 can be transported to the surface through a production tubing 20.
A production packer, 22, can optionally be installed near the lower end of the production tubing 20 and above the highest perforation 15 in order to achieve a pressure seal between the production tubing 20 and the casing 12. Optionally, and equally acceptable in accordance with the present invention, production tubings 20 need not be used, in which case the entire volume of casing 12 is used to conduct the hydrocarbons to the surface of the earth.

[0071] When diversion is needed during a well treatment operation, heavy weight proppant diverting agents 26a and/or light weight proppant diverting agents 26b, both of which are substantially coated with a soluble coating in accordance with the present invention (i.e., have a collagen-containing coating), are used to substantially seal the upper and lower sections of the producing strata 18. This substantial sealing, or border formation, occurs when the temporary diverting agents 26a and/or 26b are introduced into the casing 12 at a predetermined time during the treatment. When the diverting agents 26a and/or 26b are introduced into the fluid upstream of the perforated parts of the casing 12, they are carried down the production tubing 20 or casing 12 by the treating fluid 24 flow. Once the treating fluid 24 arrives at the perforated interval in the casing, it flows outwardly through the perforations 15 and into the strata 18 being treated.
The flow of the treating fluid 24 through the perforations 15 carries the temporary diverting agents 26a and/or 26b through the perforations and out into the strata 18. At this point, the heavy weight proppant diverting agents 26a, having a density greater than that of the treating fluid 24, settle to the bottom of the created fracture (as indicated by the arrows), forming a temporary "lower border" between the fracture and, for example a sand, shale or clay layer 19 or other area to which it is desirable to seal off from the producing strata. Similarly, light weight proppant diverting agents 26a, having a density less than that of treating fluid 24, rise to the top of the created fracture (as indicated by the arrows), thereby forming another temporary "upper border"
between the fracture and an undesirable layer, such as a shale or clay band of strata.

[0072] Figure 2 illustrates the next step of this aspect of the present invention. Once the temporary diverting agents 26a and 26b are seated at the top and/or bottom of the created fracture, respectively, the fluid flow rate and viscosity of the treating fluid 24, containing regular proppant particles 28, is increased. In this manner, the fracture can grow outward, away from the wellbore (in the direction of the arrow) and in doing so increase the overall length of the fracture, thereby aiding in increasing the stimulation and/or longevity of the well. At the completion of the well treatment, the soluble coating on the temporary diverting agents 26a and 26b will dissolve, allowing the remaining proppant particles to be removed with the treating fluid 24 through perforations 15, or to remain and act as additional proppants in propping open the fractured strata.

[0073] FIG. 3 illustrates a further embodiment of the present invention. A
well 50 having a vertical cased wellbore with a casing 54 extended from the wellhead 52 for at least a portion of the length of the wellbore, and a cement sheath 56 extending upwards from the bottom of the wellbore in the annulus between the outside of the casing 54 and the inside wall of the wellbore, at least to a point above the existing strata, similar to that shown in FIG.
1. Exposed within the open hole section of the wellbore is a subterranean formation having multiple treatment intervals 58, 60 and 62. Although three separated intervals are illustrated in FIG. 3, it will be understood with benefit of this disclosure that anywhere from two treatment intervals up to any number of treatment intervals can be treated using the presently disclosed methods and compositions.
Furthermore, it will be understood that such treatment intervals can be contiguously disposed rather than separated by relatively impermeable areas such as shale breaks.
Although FIG. 3 illustrates a fully cased wellbore, it will also be understood that disclosed treatment methods may be utilized with virtually any type of wellbore completion scenario. For example, the disclosed methods may advantageously be employed to treat well configurations including, but not limited to, vertical wellbores, fully cased wellbores, horizontal wellbores, wellbores having multiple laterals, and wellbores sharing one or more of these characteristics.

[0074] In FIG. 3, treatment intervals 58, 60 and 62 represent identified intervals of a subterranean formation that have been identified for treatment. In this regard, any number of intervals or only a portion thereof present in the subterranean formation may be so identified.
Alternatively, such intervals may also represent perforated intervals in a cased wellbore. As shown in FIG. 3, perforations 66 extend through casing 54 and cement sheath 56 by means known to those of skill in the art, and in doing so form a flow path for fluid from the formation into the casing 54, and vice-versa.

[0075] The hydrocarbons flowing out of the producing strata in treatment intervals 58, 60 and 62 through the perforations 66 and into the interior of the casing can be transported to the surface through a production tubing, 64. Further, and as illustrated in FIG. 3, a production packer 68 can be optionally installed substantially near the lower end of the production tubing 64 and above the highest perforation 66 in order to achieve a pressure seal between the production tubing 64 and the casing 54. Production tubing 64 need not always be used, and in those instances the entire interior volume of casing 54 is used to conduct the hydrocarbons to the surface to wellhead 52.

[0076] When diversion is needed during a well treatment, diverting agents 72 are used to substantially seal some of the perforations 66. Substantial sealing occurs when flow through a perforation 66 is significantly reduced, as often indicated by an increase in wellbore pressure as a diverting agent 72 blocks off one or more perforations 66. In accordance with this aspect of the present invention, diverting agents 72 are preferred to be substantially spherical in shape, although other geometries can be used. Using diverting agents 72 of the present invention to plug some of the perforations 66 is accomplished by introducing the diverting agents 72 into the casing 12 at a pre-determined time during the treatment. When the diverting agents 72 are introduced into the fluid upstream of the perforated parts (66) of the casing 12, they are carried down the production tubing 64 or casing 12 by a flowing fracturing fluid 70.
Once the fracturing fluid 70 arrives at the perforated interval in the casing, it flows outwardly through perforations 66 and into the treatment intervals 58, 60, and 62 being treated. The flow of the fracturing fluid 70 through the perforations 66 carries the diverting agents 72 toward the perforations 66, causing them to seat on the perforations 66. Once seated on the perforations 66, diverting agents 72 are held onto the perforations 66 by the fluid pressure differential which exists between the inside of the casing 54 and the treatment intervals 58, 60 and 62 on the outside of casing 54. The diverting agents 72 are preferentially sized to substantially seal the perforations 66 when seated upon them. The seated diverting agents 72 thereby serve to effectively close those perforations 66 until such time as the pressure differential is reversed and the diverting agents released, or the diverting agents 72 dissolve over a period of time due to changes in their environment (e.g., the introduction of water).

[0077] The diverting agents 72 will tend to first seal the perforations 66 through which the fracturing fluid 70 is flowing most rapidly. The preferential closing of the high flow rate perforations 66 tends to equalize treatment of the treatment intervals 58, 60 and 62 over the entire, perforated interval. For maximum effectiveness in seating on perforations 66, the diverting agents 72 should have a density less than the density of the treating fluid 70 in the wellbore at the temperature and pressure conditions encountered in the perforated area downhole. Generally, and in accordance with this aspect of the present invention, the diverting agent 72 will have at least a substantial outer surface comprised of collagen or a mixture of collagens. The number of diverting agents 72 needed during a workover or well treatment depends upon the objectives and characteristics of the individual well and the stimulation treatment to be used, and can be determined by one skilled in the art.

[0078] In the practice of disclosed methods, the diverting agent or medium suitable for achieving diversion of fluids into the identified treatment intervals that is employed is the diverting agent of the present invention comprising a particulate substrate and a slowly water-soluble collagen outer layer. In one embodiment, a neutrally buoyant variation of this collagen-containing diverting system can be employed, so as to reduce the chance of segregation of the diverting agent and particulate diverting agent carrier fluid. A "neutrally buoyant"
diverting system is a system in which a particulate diverting agent is suspended in a carrier fluid having sufficiently close density or specific gravities to result in a mixture in which solid components of the diverting agent do not substantially settle or rise in the system under static conditions. Such segregation can result in, for example, accumulation of diverting agent at one or more locations in the wellbore and sticking of the pipe string within wellbore sections.
Furthermore, segregation can result in loss of diversion action due to movement of the diverting agent away from the intervals to be treated. Neutrally buoyant diverting systems may be of particular advantage in highly deviated or horizontal wells, where gravity segregation of a non-neutrally buoyant diverting system may prevent efficient blockage or reduction in permeability of the entire circumference of formation face exposed in the wellbore due, for example, to migration of diverting agent upwards or downwards in the highly deviated or horizontal section of the wellbore.

[0079] Diverting agents which may be employed include the diverting agents of the present invention, having a slowly water-soluble outer coating, alone or in combination with any diverting agent (e.g., oil soluble, acid soluble, etc.) suitable for diverting subsequent treatment fluids into intervals having lower injectivity. One suitable diverting agent in accordance with the present invention is a diverting agent that is substantially collagen.
Examples of suitable diverting agents which can be combined with the diverting agent of the present invention include, but are not limited to, benzoic acid flakes, wax (such as "Divert VI"
available from BJ
Services), cement grade gilsonite or unitaite, polymers (including, but not limited to, natural polymers such as guar, or synthetic polymers such as polyacrylate), rock salt, and the like. Other types of suitable diverting agents that can be employed include, but are not limited to, acid soluble diverting agents such as those described in U.S. Pat. No. 3,353,874, and phtalimide particles such as those as described in U.S. Pat. No. 4,444,264.

[0080] In one embodiment of the present invention, any type of carrier fluid having a density suitable for forming a neutrally buoyant diverter system may be employed, including natural or synthetic brines (such as KCl water, etc.) and carrier fluids including gelling agents (such as normal or synthetic polymers) or other weighting materials known in the art.
Cement grade gilsonite (also known as "Uintate") is a natural variety of asphalt that is crushed and sorted into multiple-size particles. This diverting agent composition may be blended at the well site with specific chemically-modified fresh water (water containing for example, about 0.05% to about I% of a wetting surfactant) to disperse the gilsonite and optionally, a weighting agent (including but not limited to salts such as KC1, NH4Cl, NaCl, CaC12, etc.) for density adjustment and/or formation-clay control, and a gelling agent (a polymer such as guar gum, hydroxy propylguar, carboxy methylhydroxy proprylguar, carboxy methyl hydroxyethyl cellulose, xanthan gum, carboxy methyl cellulose, etc.) for viscosity adjustment and/or drag reduction.

[0081] The diverting agent of the present invention is preferably present in the carrier fluid in concentrations of from about 0.001 pounds per gallon to about 10 pounds per gallon of carrier liquid but concentrations outside this range can also be used. The most preferred concentrations of diverting agents are from about 0.01 to about 6 pounds per gallon of carrier fluid. Diverting agent concentrations of less than about 0.001 pound per gallon will not as readily plug formations when used in carrier fluids volumes which are normally available at an oil well site.
A progressively large volume of carrier fluid would be required to create adequate formation plugs at concentrations of less than 0.001 pounds per gallon.

[0082] Concentrations of diverting agent greater than about 10 pounds per gallon would not increase the diverting of the treating fluid to an appreciable extent and therefore are not particularly desirable in carrying out the present invention.

[0083] The carrier liquid is typically composed of water, brine, aqueous acid solutions, or gelled acid solutions. The acid solutions can be gelled with a celluloses, gums, polysaccharides, polyacrylamides, alkoxylated fatty amines and mixtures thereof.

[0084] The diverting agent may be added to the carrier fluid as the treatment is started, continuously as the treating fluid is pumped into the well bore or may be added in intervals in the carrier fluid between stages of the treatment. For instance, in acidizing procedures the diverting agent may be added to the acidizing fluid continuously. Thus, the diverting agent will progressively plug portions of the formation being treated, thereby frustrating the tendency of the acid to flow only into the most permeable portions of the formation and, instead, creating an evenly acidized formation. When the treating fluid is pumped in stages, the first stage is followed by a volume of the diverting material composed of a carrier fluid, usually gelled or emulsified water or acid, containing the bridging agent. The diverting agent seals off the portion of the formation penetrated by the first stage of treating fluid. The second stage of treating fluid is then pumped into another portion of the formation. Alternating volumes of treating fluid and diverting material may be continued to provide a uniformly acidized formation.
Although the same technique of continuously introducing the diverting agent in the carrier fluid may be used for fracturing treatments, it is usual for the diverting agent to be added to the carrier fluid in slugs during fracturing operations.

[0085]A fracturing liquid is known to preferentially flow into the portion of the subterranean formation which most readily accepts the liquid. After this portion of the formation is fractured, the bridging agent may be added to the fracturing liquid so that it will plug the already fractured portion of the formation. Because the fracturing fluid is preferentially flowing into the fracture zone, it will carry the bridging agent with it. The fractured zone is thereby plugged and the fracturing fluid is diverted to the most permeable portion of the formation that is still accepting fluids.

[0086] This method of fracturing and diverting can, in one aspect of the present invention, be repeated to obtain multiple fractures.

[0087] The diverting agent is removed from the formation by means of sublimation of the diverting agent or by solubilization of the diverting agent by the produced fluids. Increasing formation temperatures result in a greater rate of dissolution or sublimation of the diverting agent. For instance, it has been found that at about 250 F, approximately 80 percent by weight of the slightly water-soluble collagen sublimates in 24 hours, while at 300 F, about 95 percent by weight sublimates in 24 hours, and at a temperature of about 400 OF, about 99% of the slightly water-soluble collagen sublimates/dissolves in about 24 hours. This shows that the rate of sublimation/dissolution of the diverting agent increases with increasing formation temperature.

[0088]The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventors to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the scope of the invention.

EXAMPLES
Example 1: Prophetic Example [0089] The following prophetic example describes a method of how the soluble coating on the propping agent or agents of the present invention can be used to divert fracture growth and extend the fractures into the productive zone of an oil or gas well. The primary purpose of the soluble coated proppant is to define an upper and lower boundary in the hydraulically generated vertical fracture so that the main direction of growth continues to extend outward in length away from the wellbore. This additional length of the conductive fracture aids in draining additional areas of the productive formation, allowing oil, gas, and/or water recovery production to be improved and greater flow rates to be established as a result of longer fracture length.

[0090] The following steps can be followed, using the soluble coated proppant materials of the present invention.

1. A fracture injection rate is established with a low viscosity fracturing fluid.

2. A soluble coated proppant, such as walnut hulls coated with a cross-linked collagen, bauxite coated with cross-linked collagen, or a combination of both, is added at the blender tub in order to form a slurry in the fracturing fluid.

3. The fracturing fluid containing the soluble coated proppant is pumped downhole.
The first part of the slurry enters the initial crack, taking the most fluid.
In doing so, it slowly plugs the borders of the created fracture due to the use of a soluble diverting agent, such as collagen, that slowly softens and swells in the fluid.

4. Once the flow rate is slowed or substantially reduced in the first crack, pressure builds up until another flow path, crack, or zone begins to take the soluble coated proppant-containing slurry.

5. In the instance that both the top and the bottom of the fracture need to be contained by the soluble coated proppant, two different proppant densities are preferably used. For example, a high density bauxite particle is coated with a soluble, collagen coating that slowly softens and swells as it falls in the fracture to the bottom of the vertically-created fracture. To slow the growth upwards in the vertical fracture, a second proppant of low density, such as a soluble-coated walnut hull, is added to the injection fluid. As the injection fluid enters the formation, the low-density, soluble-material coated proppant rises in the vertical fracture and slows down fluid loss and growth in an upward direction.

6. As the fracture is still being injected with fluid above the fracture rate and pressure, the fracture continues to grow away from the wellbore and control of the fracture growth is maintained by controlling the flow rate of the fracturing fluid.
Injection is continued until the regular proppant fills the fracture, pressure reaches a pre-set limit, or until the total planned volume is injected.

7. Standard, non-soluble coated proppants, such as Ottawa Sand (20/40), ceramic, or any number of resin-coated proppants, are injected into the formation, once the top and bottom growth is diminished. Pumping is continued until the full amount of designated proppant (or proppants) are placed in the created fractures.

8. The well is shut in, and the pumping equipment is removed.

9. The well is returned to production, and the soluble collagen-coating on the walnut hulls or bauxite is removed as the water in the formation dissolves the soluble coating on the proppant over time.

Example 2: Procedure for determining the rate and degree of polymer dissolution [0091] Sand substrate was coated with various water-soluble polymers:

Chemical Name Trade Name Supplier Poly(ethylene) oxide WSR 80 Dow Chemicals Poly(propylene) oxide WSRN 750 Dow Chemicals Poly(proplylene) oxide UCAR309 Dow Chemicals Poly(lactic acid) PLA6551-D E&M specialties Poly(lactic acid) PLA5600 E&M specialties Poly(vinylacetate/alcohol) PVA/Hydrolene Idroplax Inc.
Collagen 1 Glue 512 Milligans and Higgins Collagen 2 GM Bond Hormel foods [0092] Thereafter, the following test procedure was used to determine rate and degree of solubility:

Determine the total mass of the polymer on the sand by regular LOI procedure.
Add 500 grams of coated sand in 1 liter of water. Take a 400mm filter paper and weight it on an analytical balance up to 4 decimal places. Prepare vacuum filtration apparatus by using 400mm filter paper, perforated ceramic funnel, 2 liters Erlenmeyer flask with side opening connected to the vacuum pump by a rubber tube. Filter the coated sand and water slurry through 400mm filter paper after each one-minute interval.
Remember to add coated sand back in the "filtered" water. Remove the filter paper from the perforated funnel after filtration is complete, and allow it to dry by keeping it in desiccators. Weigh the filter paper. This is the combined weight of dissolved polymer and filter paper, and thus it should be greater than the weight of the filter paper before it was used in filtration process. Calculate the % of dissolved polymer by using the following formula:

X = ((C-B)/A))x 100 Where, X = the percentage of dissolved polymer A = mass (gms) of the polymer on the sand grains B = mass (gms) of the filter prior to filtration process C = mass (gms) of the filter after filtration process Particles that swell and then dissolve Particles that dissolve without swelling COLLAGEN I. WSRN750 [0093] The results of this test procedure were that a polyethylene oxide(WSR
80 from Dow Chemical) reach full dissolution at 80 F in about 300 minutes, at 150 F it required about 180 minutes, and at 200 F it required about 90 minutes.
[0094] The same test was run using another polymer. These results showed that the polypropylene oxide polymer(WSRN 750 from Dow Chemicals) reached full dissolution at 80 F
in about 390 minutes, at 150 F it required about 320 minutes, and at 200 F it required about 245 minutes to fully dissolve.
[0095] Polymers that swell show 100% solubility within 30 minutes, but microscopic analysis shows retention on the filter paper due to swelling instead of dissolution.
Formation of gelatinous mass and noticeable increase in the volume of the sand/water slurry indicate polymer swelling instead of polymer dissolution.
[0096] All of the compositions, methods, and/or processes disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions, methods, and/or processes and in the steps or in the sequence of steps of the methods described herein without departing from the concept and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope and concept of the invention.

Claims (29)

Claims:

1. A diverting fluid for diverting oil well treating liquids to progressively less permeable portions of a subterranean formation, the diverting fluid comprising an aqueous carrier liquid having dispersed therein a particulate diverting material comprising a mixture of a first diverting agent and a second diverting agent having a density different from the density of the first diverting agent, wherein the first and second diverting agents each comprise a particulate substrate and a water-soluble polymer coating forming a substantial outer coating on the particulate substrate.

2. The diverting fluid of claim 1, wherein the first diverting agent has a density greater than the density of the aqueous carrier liquid and the second diverting agent has a density less than the density of the aqueous carrier liquid.

3. The diverting fluid of claim 1, wherein the particulate substrates of the first and second diverting agents are each independently selected from the group consisting of natural materials, silica proppants, ceramic proppants, metallic proppants, synthetic organic proppants, and mixtures thereof.

4. The diverting fluid of claim 1, wherein the particulate substrate of at least one of the diverting agents is a resin coated proppant.

5. The diverting fluid of claim 1, wherein the water-soluble polymers of the first and second diverting agents are each independently selected from the group consisting of collagen, poly(alkylene) oxide, poly(lactic acid), polyvinylacetate, polyvinylalcohol, polylactone, polyacrylate, polyester, silicate polymers of alkali metals, silicate polymers of alkaline earth metals, and mixtures thereof.

6. The diverting fluid of claim 1, wherein the particulate substrates of the first and second diverting agents each have a particle size of from about 3 mesh to about 200 mesh.

7. The diverting fluid of claim 1, wherein the water-soluble polymers of the first and second diverting agents are each independently selected from the group consisting of Type I collagen, Type II collagen, Type III collagen, Type IV collagen, Type V
collagen, and mixtures thereof.

8. The diverting fluid of claim 7, wherein the water-soluble collagen in at least the first or second diverting agent is crosslinked with a cross-linking agent selected from the group consisting of aldehydes, carbodiimides, isocyanates, and acyl azides.

9. The diverting fluid of claim 1, wherein at least one of the first and second diverting agents further comprises a non-water-soluble polymer.

10. The diverting fluid of claim 9, wherein the non-water-soluble polymer is phenol-aldehyde novolac polymers and phenol-aldehyde resole polymers.

11. The diverting fluid of claim 1, wherein the water-soluble polymer in at least one of the first and second diverting agents is poly(alkylene) oxide, poly(lactic acid), polyvinylacetate, polyvinylalcohol, polyvinylacetate/polyvinylalcohol graft polymers or admixtures thereof.

12. The diverting fluid of claim 11, wherein the poly(alkylene) oxide is poly(ethylene) oxide, poly(propylene) oxide, poly(ethylene oxide)-poly(propylene oxide) block copolymers, or mixtures thereof.

13. The diverting fluid of claim 1, wherein the diverting material is present in the carrier liquid in an amount from about 0.001 pounds per gallon to about 10 pounds per gallon of the carrier liquid.

14. The diverting fluid of claim 1, wherein the carrier liquid is water, brine, aqueous acid solutions, or gelled acid solutions.

15. A method for treating a subterranean formation during fracturing treatment so as to increase the stimulation of the subterranean formation, the method comprising pumping into the subterranean formation a diverting fluid of claim 1, allowing the carrier liquid to permeate into the formation so as to carry the diverting material into the subterranean formation, and allowing the diverting material to plug porous portions of the formations thereby diverting flow of treating fluid to less permeable portions of the formation.

16. The method of claim 15, wherein the treating of the subterranean formation is a fracturing treatment, and wherein the stimulation increased is the length of the fractures.

17. The method of claim 15, wherein the first diverting agent has a density greater than the density of the aqueous carrier liquid and the second diverting agent has a density less than the density of the aqueous carrier liquid.

18. The method of claim 15, wherein the particulate substrates of the first and second diverting agents are each independently selected from the group consisting of natural materials, silica proppants, ceramic proppants, metallic proppants, synthetic organic proppants, and mixtures thereof.

19. The method of claim 15, wherein the particulate substrate of at least one of the diverting agents is a resin coated proppant.

20. The method of claim 15, wherein the water-soluble polymers of the first and second diverting agents are each independently selected from the group consisting of collagen, poly(alkylene) oxide, poly(lactic acid), polyvinylacetate, polyvinylalcohol, polylactone, polyacrylate, polyester, silicate polymers of alkali metals, silicate polymers of alkaline earth metals, and mixtures thereof.

21. The method of claim 15, wherein the particulate substrates of the first and second diverting agents each have a particle size of from about 3 mesh to about 200 mesh.

22. The method of claim 15, wherein the water-soluble polymers of the first and second diverting agents are each independently selected from the group consisting of Type I collagen, Type II collagen, Type III collagen, Type IV collagen, Type V
collagen, and mixtures thereof.

23. The method of claim 22, wherein the water-soluble collagen in at least the first or second diverting agent is crosslinked with a cross-linking agent selected from the group consisting of aldehydes, carbodiimides, isocyanates, and acyl azides.

24. The method of claim 15, wherein at least one of the first and second diverting agents further comprises a non-water-soluble polymer.

25. The method of claim 24, wherein the non-water-soluble polymer is phenol-aldehyde novolac polymers and phenol-aldehyde resole polymers.

26. The method of claim 15, wherein the water-soluble polymer in at least one of the first and second diverting agents is poly(alkylene) oxide, poly(lactic acid), polyvinylacetate, polyvinylalcohol, polyvinylacetate/polyvinylalcohol graft polymers or admixtures thereof.

27. The method of claim 26, wherein the poly(alkylene) oxide is poly(ethylene) oxide, poly(propylene) oxide, poly(ethylene oxide)-poly(propylene oxide) block copolymers, or mixtures thereof.

28. The method of claim 15, wherein the diverting material is present in the carrier liquid in an amount from about 0.001 pounds per gallon to about 10 pounds per gallon of the carrier liquid.

29. The method of claim 15, wherein the carrier liquid is water, brine, aqueous acid solutions, or gelled acid solutions.

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Cited By (1)

* Cited by examiner, † Cited by third party

Publication number	Priority date	Publication date	Assignee	Title
CN109826590A (en) *	2019-02-27	2019-05-31	杨凌单色生物科技有限公司	A kind of old well water blockoff fracturing process of hypotonic oil gas field High water cut

Families Citing this family (174)

* Cited by examiner, † Cited by third party

Publication number	Priority date	Publication date	Assignee	Title
US10316616B2 (en)	2004-05-28	2019-06-11	Schlumberger Technology Corporation	Dissolvable bridge plug
US8211247B2 (en) *	2006-02-09	2012-07-03	Schlumberger Technology Corporation	Degradable compositions, apparatus comprising same, and method of use
CA2577998A1 (en)	2004-09-14	2006-03-23	Carbo Ceramics Inc.	Sintered spherical pellets
AU2006218614A1 (en)	2005-03-01	2006-09-08	Carbo Ceramics Inc.	Methods for producing sintered particles from a slurry of an alumina-containing raw material
US20070023187A1 (en) *	2005-07-29	2007-02-01	Carbo Ceramics Inc.	Sintered spherical pellets useful for gas and oil well proppants
US8567494B2 (en) *	2005-08-31	2013-10-29	Schlumberger Technology Corporation	Well operating elements comprising a soluble component and methods of use
US20070087941A1 (en) *	2005-10-19	2007-04-19	Bj Services Company	Storable fracturing suspensions containing ultra lightweight proppants in xanthan based carriers and methods of using the same
US8231947B2 (en) *	2005-11-16	2012-07-31	Schlumberger Technology Corporation	Oilfield elements having controlled solubility and methods of use
US8220554B2 (en) *	2006-02-09	2012-07-17	Schlumberger Technology Corporation	Degradable whipstock apparatus and method of use
US8770261B2 (en)	2006-02-09	2014-07-08	Schlumberger Technology Corporation	Methods of manufacturing degradable alloys and products made from degradable alloys
US7934556B2 (en) *	2006-06-28	2011-05-03	Schlumberger Technology Corporation	Method and system for treating a subterranean formation using diversion
US8211248B2 (en) *	2009-02-16	2012-07-03	Schlumberger Technology Corporation	Aged-hardenable aluminum alloy with environmental degradability, methods of use and making
US7828998B2 (en)	2006-07-11	2010-11-09	Carbo Ceramics, Inc.	Material having a controlled microstructure, core-shell macrostructure, and method for its fabrication
US7708069B2 (en) *	2006-07-25	2010-05-04	Superior Energy Services, L.L.C.	Method to enhance proppant conductivity from hydraulically fractured wells
CA2661799A1 (en)	2006-08-30	2008-03-06	Carbo Ceramics Inc.	Low bulk density proppant and methods for producing the same
US7490667B2 (en) *	2006-10-02	2009-02-17	Fairmount Minerals, Inc.	Proppants with soluble composite coatings
US7565929B2 (en) *	2006-10-24	2009-07-28	Schlumberger Technology Corporation	Degradable material assisted diversion
US8205673B2 (en) *	2006-12-18	2012-06-26	Schlumberger Technology Corporation	Differential filters for removing water during oil production
US7637320B2 (en) *	2006-12-18	2009-12-29	Schlumberger Technology Corporation	Differential filters for stopping water during oil production
EA201000114A1 (en)	2007-07-06	2010-06-30	Карбо Керамикс Инк.	PROPPANT AND METHOD OF HYDRAULIC PLASTING OF THE PLATE (OPTIONS)
US8490698B2 (en)	2007-07-25	2013-07-23	Schlumberger Technology Corporation	High solids content methods and slurries
US10011763B2 (en)	2007-07-25	2018-07-03	Schlumberger Technology Corporation	Methods to deliver fluids on a well site with variable solids concentration from solid slurries
US9080440B2 (en)	2007-07-25	2015-07-14	Schlumberger Technology Corporation	Proppant pillar placement in a fracture with high solid content fluid
US8496056B2 (en)	2007-07-25	2013-07-30	Schlumberger Technology Corporation	System and method for low damage fracturing
US8490699B2 (en)	2007-07-25	2013-07-23	Schlumberger Technology Corporation	High solids content slurry methods
US8119574B2 (en)	2007-07-25	2012-02-21	Schlumberger Technology Corporation	High solids content slurries and methods
US7784541B2 (en) *	2007-07-25	2010-08-31	Schlumberger Technology Corporation	System and method for low damage fracturing
US8936082B2 (en)	2007-07-25	2015-01-20	Schlumberger Technology Corporation	High solids content slurry systems and methods
US9040468B2 (en)	2007-07-25	2015-05-26	Schlumberger Technology Corporation	Hydrolyzable particle compositions, treatment fluids and methods
US7580796B2 (en) *	2007-07-31	2009-08-25	Halliburton Energy Services, Inc.	Methods and systems for evaluating and treating previously-fractured subterranean formations
US8714250B2 (en) *	2007-10-18	2014-05-06	Schlumberger Technology Corporation	Multilayered ball sealer and method of use thereof
US9856415B1 (en)	2007-12-11	2018-01-02	Superior Silica Sands, LLC	Hydraulic fracture composition and method
US20170137703A1 (en)	2007-12-11	2017-05-18	Superior Silica Sands, LLC	Hydraulic fracture composition and method
US10920494B2 (en)	2007-12-11	2021-02-16	Aquasmart Enterprises, Llc	Hydraulic fracture composition and method
US9057014B2 (en)	2007-12-11	2015-06-16	Aquasmart Enterprises, Llc	Hydraulic fracture composition and method
US8006760B2 (en) *	2008-04-10	2011-08-30	Halliburton Energy Services, Inc.	Clean fluid systems for partial monolayer fracturing
US9212535B2 (en) *	2008-04-15	2015-12-15	Schlumberger Technology Corporation	Diversion by combining dissolvable and degradable particles and fibers
US8936085B2 (en)	2008-04-15	2015-01-20	Schlumberger Technology Corporation	Sealing by ball sealers
EP2110508A1 (en) *	2008-04-16	2009-10-21	Schlumberger Holdings Limited	microwave-based downhole activation method for wellbore consolidation applications
US20100051274A1 (en) *	2008-08-28	2010-03-04	Tommy Johnson	Methods, apparatus and products for drilling wells
CN101724384B (en) *	2008-10-29	2012-07-18	中国石油天然气股份有限公司	Preparation method of high-strength elastic slow-expansion water-absorbing particle diverting agent
US9714378B2 (en)	2008-10-29	2017-07-25	Basf Se	Proppant
US9719011B2 (en)	2008-10-29	2017-08-01	Basf Se	Proppant
US8561696B2 (en)	2008-11-18	2013-10-22	Schlumberger Technology Corporation	Method of placing ball sealers for fluid diversion
CN101839124B (en) *	2009-03-18	2013-03-27	中国石油天然气股份有限公司	Method for controlling extension of fracturing fracture of oil and gas field reservoir
US8062997B2 (en) *	2009-04-24	2011-11-22	Halliburton Energy Services Inc.	Method for enhancing stability of oil based drilling fluids at high temperatures
US7833947B1 (en)	2009-06-25	2010-11-16	Schlumberger Technology Corporation	Method for treatment of a well using high solid content fluid delivery
US8109335B2 (en) *	2009-07-13	2012-02-07	Halliburton Energy Services, Inc.	Degradable diverting agents and associated methods
US20110048697A1 (en) *	2009-08-25	2011-03-03	Sam Lewis	Sonically activating settable compositions
US7923415B2 (en) *	2009-08-31	2011-04-12	Schlumberger Technology Corporation	Methods to reduce settling rate of solids in a treatment fluid
US20110198089A1 (en) *	2009-08-31	2011-08-18	Panga Mohan K R	Methods to reduce settling rate of solids in a treatment fluid
US8016034B2 (en) *	2009-09-01	2011-09-13	Halliburton Energy Services, Inc.	Methods of fluid placement and diversion in subterranean formations
WO2011050046A1 (en) *	2009-10-20	2011-04-28	Soane Energy, Llc	Proppants for hydraulic fracturing technologies
US8646530B2 (en) *	2009-12-21	2014-02-11	Schlumberger Technology Corporation	Chemical diversion technique
US8833452B2 (en)	2009-12-21	2014-09-16	Schlumberger Technology Corporation	Chemical diversion technique
CA2691891A1 (en) *	2010-02-04	2011-08-04	Trican Well Services Ltd.	Applications of smart fluids in well service operations
US8662172B2 (en)	2010-04-12	2014-03-04	Schlumberger Technology Corporation	Methods to gravel pack a well using expanding materials
AU2011252819A1 (en) *	2010-05-14	2012-12-06	Chemical Delivery Systems, Inc.	Materials and methods for temporarily obstructing portions of drilled wells
US8936095B2 (en)	2010-05-28	2015-01-20	Schlumberger Technology Corporation	Methods of magnetic particle delivery for oil and gas wells
US8505628B2 (en)	2010-06-30	2013-08-13	Schlumberger Technology Corporation	High solids content slurries, systems and methods
US8511381B2 (en)	2010-06-30	2013-08-20	Schlumberger Technology Corporation	High solids content slurry methods and systems
US20120043085A1 (en) *	2010-08-19	2012-02-23	Schlumberger Technology Corporation	Wellbore service fluid and methods of use
CN102399549B (en) *	2010-09-15	2013-07-03	中国石油天然气集团公司	Rock breaking agent for stabilizing well walls and preparation method thereof
US8607870B2 (en)	2010-11-19	2013-12-17	Schlumberger Technology Corporation	Methods to create high conductivity fractures that connect hydraulic fracture networks in a well
US8950476B2 (en) *	2011-03-04	2015-02-10	Accessesp Uk Limited	Coiled tubing deployed ESP
US10808497B2 (en)	2011-05-11	2020-10-20	Schlumberger Technology Corporation	Methods of zonal isolation and treatment diversion
US8905133B2 (en)	2011-05-11	2014-12-09	Schlumberger Technology Corporation	Methods of zonal isolation and treatment diversion
US20120285695A1 (en) *	2011-05-11	2012-11-15	Schlumberger Technology Corporation	Destructible containers for downhole material and chemical delivery
US9133387B2 (en)	2011-06-06	2015-09-15	Schlumberger Technology Corporation	Methods to improve stability of high solid content fluid
US9297244B2 (en)	2011-08-31	2016-03-29	Self-Suspending Proppant Llc	Self-suspending proppants for hydraulic fracturing comprising a coating of hydrogel-forming polymer
US20140000891A1 (en)	2012-06-21	2014-01-02	Self-Suspending Proppant Llc	Self-suspending proppants for hydraulic fracturing
US9868896B2 (en)	2011-08-31	2018-01-16	Self-Suspending Proppant Llc	Self-suspending proppants for hydraulic fracturing
WO2013033391A1 (en)	2011-08-31	2013-03-07	Soane Energy, Llc	Self-suspending proppants for hydraulic fracturing
CN102561989A (en) *	2012-02-21	2012-07-11	重庆市能源投资集团科技有限责任公司	Coal mine underground hydraulic fracturing hole sealing method
US9863228B2 (en)	2012-03-08	2018-01-09	Schlumberger Technology Corporation	System and method for delivering treatment fluid
US9803457B2 (en)	2012-03-08	2017-10-31	Schlumberger Technology Corporation	System and method for delivering treatment fluid
US20130292112A1 (en) *	2012-05-02	2013-11-07	Los Alamos National Security, Llc	Composition and method for locating productive rock fractures for fluid flow
GB201216004D0 (en) *	2012-09-07	2012-10-24	Oilflow Solutions Holdings Ltd	Subterranean formations
US9528354B2 (en)	2012-11-14	2016-12-27	Schlumberger Technology Corporation	Downhole tool positioning system and method
US9598927B2 (en) *	2012-11-15	2017-03-21	Halliburton Energy Services, Inc.	Expandable coating for solid particles and associated methods of use in subterranean treatments
CN103849374B (en) *	2012-11-30	2017-01-25	亿利资源集团有限公司	Fracturing propping agent and preparation method thereof
CN104937070A (en) *	2012-12-14	2015-09-23	巴斯夫欧洲公司	Proppant
US20140262231A1 (en) *	2013-03-13	2014-09-18	Halliburton Energy Services, Inc.	Methods for treatment of a subterranean formation
US9822625B2 (en)	2013-03-13	2017-11-21	Halliburton Energy Services, Inc.	Methods for treatment of a subterranean formation
MX2015014605A (en) *	2013-04-19	2016-05-31	Lubrizol Oilfield Solutions Inc	Hydraulic diversion systems to enhance matrix treatments and methods for using same.
RU2691183C2 (en) *	2013-06-10	2019-06-11	Сумитомо Сейка Кемикалз Ко., Лтд.	Fluid viscosity regulating fluid for use in hydraulic fracturing of formation
US9388335B2 (en)	2013-07-25	2016-07-12	Schlumberger Technology Corporation	Pickering emulsion treatment fluid
US9546534B2 (en) *	2013-08-15	2017-01-17	Schlumberger Technology Corporation	Technique and apparatus to form a downhole fluid barrier
WO2015026355A1 (en) *	2013-08-22	2015-02-26	Halliburton Energy Services, Inc.	Compositions including a particulate bridging agent and fibers and methods of treating a subterranean formation with the same
US20150060069A1 (en) *	2013-08-27	2015-03-05	Schlumberger Technology Corporation	Swellable ball sealers
AU2014202934B2 (en) *	2013-09-09	2016-03-17	Korea Institute Of Geoscience And Mineral Resources (Kigam)	Apparatus and method for solution mining using cycling process
WO2015038146A1 (en) *	2013-09-13	2015-03-19	Halliburton Energy Services, Inc.	Compositions for treating subterranean formations
CA2919534C (en) *	2013-09-16	2018-09-25	Halliburton Energy Services, Inc.	Conductivity enhancement of complex fracture networks in subterranean formations
CN103484095B (en) *	2013-10-11	2015-07-22	陕西延长石油(集团)有限责任公司研究院	Fracturing inclusion self-dissolving diversion agent and preparation method thereof
US10316243B2 (en) *	2013-11-15	2019-06-11	Dow Global Technologies Llc	Proppants with improved dust control
CN104695923A (en) *	2013-12-05	2015-06-10	中国石油天然气股份有限公司	Method for realizing staged multi-cluster fracturing of horizontal well by adopting soluble balls
CN103756659B (en) *	2013-12-28	2016-08-03	北京国海能源技术研究院	Flexible particle diverter and preparation method thereof
US10865465B2 (en)	2017-07-27	2020-12-15	Terves, Llc	Degradable metal matrix composite
CN106029255B (en)	2014-02-21	2018-10-26	特维斯股份有限公司	The preparation of rate of dissolution controlled material
US10758974B2 (en)	2014-02-21	2020-09-01	Terves, Llc	Self-actuating device for centralizing an object
US10689740B2 (en)	2014-04-18	2020-06-23	Terves, LLCq	Galvanically-active in situ formed particles for controlled rate dissolving tools
US10150713B2 (en)	2014-02-21	2018-12-11	Terves, Inc.	Fluid activated disintegrating metal system
US20170268088A1 (en)	2014-02-21	2017-09-21	Terves Inc.	High Conductivity Magnesium Alloy
US11167343B2 (en)	2014-02-21	2021-11-09	Terves, Llc	Galvanically-active in situ formed particles for controlled rate dissolving tools
US9932521B2 (en)	2014-03-05	2018-04-03	Self-Suspending Proppant, Llc	Calcium ion tolerant self-suspending proppants
WO2015134022A1 (en) *	2014-03-06	2015-09-11	Halliburton Energy Services, Inc.	Far-field diversion with pulsed proppant in subterranean fracturing operations
US10400535B1 (en)	2014-03-24	2019-09-03	Nine Downhole Technologies, Llc	Retrievable downhole tool
US9915114B2 (en) *	2015-03-24	2018-03-13	Donald R. Greenlee	Retrievable downhole tool
RU2652592C1 (en) *	2014-03-28	2018-04-27	Бейджинг Рёчсанд Сайенс Энд Текнолоджи Груп Ко., Лтд	Self-advancing proppant, its preparation and usage
CA2942184C (en)	2014-04-18	2020-04-21	Terves Inc.	Galvanically-active in situ formed particles for controlled rate dissolving tools
US9790422B2 (en) *	2014-04-30	2017-10-17	Preferred Technology, Llc	Proppant mixtures
US10287865B2 (en)	2014-05-19	2019-05-14	Baker Hughes, A Ge Company, Llc	Use of an acid soluble or degradable solid particulate and an acid liberating or acid generating composite in the stimulation of a subterranean formation
US10001613B2 (en)	2014-07-22	2018-06-19	Schlumberger Technology Corporation	Methods and cables for use in fracturing zones in a well
US10738577B2 (en)	2014-07-22	2020-08-11	Schlumberger Technology Corporation	Methods and cables for use in fracturing zones in a well
AU2015301423B2 (en) *	2014-08-15	2019-01-17	Baker Hughes, A Ge Company, Llc	Diverting systems for use in well treatment operations
CN105350948B (en) *	2014-08-22	2019-01-01	中国石油化工股份有限公司	Shale gas horizontal well fracturing method and shale gas horizontal well completion method
US9470078B2 (en) *	2014-09-29	2016-10-18	Baker Hughes Incorporated	Fluid diversion through selective fracture extension
MX2017004433A (en) *	2014-10-06	2017-10-23	Schlumberger Technology Bv	Methods of zonal isolation and treatment diversion with shaped particles.
WO2016076747A1 (en) *	2014-11-14	2016-05-19	Schlumberger Canada Limited	Chemical assisted selective diversion during multistage well treatments
WO2016077359A1 (en) *	2014-11-14	2016-05-19	Schlumberger Canada Limited	Well treatment
US9810051B2 (en) *	2014-11-20	2017-11-07	Thru Tubing Solutions, Inc.	Well completion
US20160145483A1 (en) *	2014-11-26	2016-05-26	Schlumberger Technology Corporation	Well treatment
CN104531116B (en) *	2014-12-31	2017-03-08	中国石油天然气股份有限公司	Oil reservoir deep liquid flow diverting agent and preparation method and application thereof
CN104624623B (en) *	2015-01-30	2017-09-12	浙江博世华环保科技有限公司	A kind of contaminated site original position extracting restorative procedure
CN104624633B (en) *	2015-01-30	2017-09-12	浙江博世华环保科技有限公司	A kind of contaminated site injection restorative procedure in situ
US9976390B2 (en) *	2015-03-30	2018-05-22	Baker Hughes, A Ge Company, Llc	Drilling fluids with leakoff control and drill cuttings removal sweeps
CN104974739B (en) *	2015-07-10	2018-06-15	四川大学	A kind of cellulose blending modified polyvinylalcohol fracturing fluid and preparation method thereof
CN105041288A (en) *	2015-07-13	2015-11-11	中国石油大学(北京)	Carbonate oil-gas reservoir fracture steering acid fracturing method
US20170166798A1 (en) *	2015-08-25	2017-06-15	FracSolution Technologies, LLC	Diversion sand and methods
US20170081585A1 (en) *	2015-09-18	2017-03-23	Baker Hughes Incorporated	Method of Diversion and Zonal Isolation in a Subterranean Formation Using a Biodegradable Polymer
CA2997706C (en) *	2015-10-15	2020-10-06	Halliburton Energy Services, Inc.	Micro-proppant fracturing fluid and slurry concentrate compositions
US10246632B2 (en) *	2015-10-30	2019-04-02	Carbo Ceramics Inc.	Proppant having amphiphobic coatings and methods for making and using same
WO2017086905A1 (en) *	2015-11-16	2017-05-26	Halliburton Energy Services, Inc.	Subterranean stimulation operations utilizing degradable pre-coated particulates
US20170159404A1 (en)	2015-11-25	2017-06-08	Frederic D. Sewell	Hydraulic Fracturing with Strong, Lightweight, Low Profile Diverters
US10815750B2 (en)	2015-11-25	2020-10-27	Frederic D. Sewell	Hydraulic fracturing with strong, lightweight, low profile diverters
WO2017111640A1 (en)	2015-12-21	2017-06-29	Schlumberger Technology Corporation	Pre-processed fiber flocks and methods of use thereof
US20170198179A1 (en) *	2016-01-12	2017-07-13	River Canyon Investments, Llc	Ball sealers for use in subterranean wells, methods of making and using same
BR112018011362B1 (en)	2016-01-28	2022-09-13	Halliburton Energy Services, Inc	METHOD TO TREAT UNDERGROUND FORMATION AND TREATMENT FLUID
US20190010383A1 (en) *	2016-03-18	2019-01-10	Halliburton Energy Services, Inc.	Self-degradable diverters for propped fracture acidizing
US10161235B2 (en)	2016-06-03	2018-12-25	Enhanced Production, Inc.	Hydraulic fracturing in highly heterogeneous formations by resisting formation and/or sealing micro-fractures
RU2656054C1 (en) *	2016-06-14	2018-05-30	Открытое акционерное общество "Сургутнефтегаз"	Method of hydraulic fracturing of a reservoir
CN106350043B (en) *	2016-07-22	2019-04-12	北京斯迪莱铂油气技术有限公司	Complex Temporary Blocking agent and Complex Temporary Blocking method for temporarily blocking up in turnaround fracture
DK201970186A1 (en) *	2016-09-20	2019-04-03	Fairmount Santrol Inc.	Degradable ball sealers with improved solubility characteristics
CN106957642A (en) *	2016-11-28	2017-07-18	青岛科技大学	Polymer waste recycles technique in a kind of preparation from suspended prop
WO2018101960A1 (en)	2016-12-02	2018-06-07	Halliburton Energy Services, Inc.	Dissolvable whipstock for multilateral wellbore
WO2018111749A1 (en) *	2016-12-13	2018-06-21	Thru Tubing Solutions, Inc.	Methods of completing a well and apparatus therefor
AU2017386384A1 (en) *	2016-12-29	2019-07-04	Shell Internationale Research Maatschappij B.V.	Fracturing a formation with mortar slurry
CN106677756B (en) *	2017-03-07	2018-02-02	库尔勒金川矿业有限公司	A kind of coal petrography softening active fracturing device and coal petrography pressing crack construction technique
US11061154B2 (en) *	2017-06-12	2021-07-13	Battelle Memorial Institute	Acoustic proppant for fracture diagnostic
CA3053330C (en)	2017-06-15	2022-04-26	Halliburton Energy Services, Inc.	Plasticized polyvinyl alcohol diverter materials
JP7326741B2 (en) *	2017-08-10	2023-08-16	三菱ケミカル株式会社	Diverting agent and method for plugging cracks in a well using the same
US10385261B2 (en)	2017-08-22	2019-08-20	Covestro Llc	Coated particles, methods for their manufacture and for their use as proppants
CN107722958A (en) *	2017-08-24	2018-02-23	中国石油天然气股份有限公司	Water-soluble diverter dissolved at 60-90 ℃ and preparation method thereof
CN107699224B (en) *	2017-10-10	2020-03-27	西南石油大学	Guiding agent for controlling extension height of upper end of hydraulic fracturing crack
WO2019088999A1 (en) *	2017-10-31	2019-05-09	Halliburton Energy Services, Inc.	Diversion using solid particulates
US10808162B2 (en)	2017-11-17	2020-10-20	Fairmount Santrol Inc.	Crush resistant buoyant ball sealers
CA3082801A1 (en)	2017-11-28	2019-06-06	Ecolab Usa Inc.	Diverter composition comprising deformable and non-deformable particles
US20200048532A1 (en) *	2018-08-10	2020-02-13	Bj Services, Llc	Frac Fluids for Far Field Diversion
US20200063015A1 (en)	2018-08-22	2020-02-27	Carbo Ceramics Inc.	Composite diversion particle agglomeration
US11098236B2 (en)	2018-08-28	2021-08-24	Kuraray Co., Ltd.	Particulate polyvinyl alcohol compositions having reduced dust content
US11118105B2 (en)	2018-08-28	2021-09-14	Kuraray Co., Ltd.	Polyvinyl alcohol based diverting agents
WO2020060755A1 (en)	2018-09-21	2020-03-26	Conocophillips Company	Leak-off control in acid stimulation using dissolvable material
WO2020106655A1 (en)	2018-11-21	2020-05-28	Self-Suspending Proppant Llc	Salt-tolerant self-suspending proppants made without extrusion
CA3112252C (en) *	2018-11-30	2023-12-19	Halliburton Energy Services, Inc.	Wellbore treatment fluids comprising composite diverting particulates
US11118107B2 (en)	2019-09-26	2021-09-14	Oil Field Packaging Llc	Method of using micro-particle amorphous silicate in well stimulation
CN110593841A (en) *	2019-10-16	2019-12-20	荆州市现代石油科技发展有限公司	Online filling device and temporary plugging method of water-soluble temporary plugging agent for steering fracturing
CN111271037A (en) *	2020-03-11	2020-06-12	西南石油大学	Intelligent steering and fracturing process for coal bed gas
US11293252B2 (en) *	2020-04-16	2022-04-05	Halliburton Energy Services, Inc.	Fluid barriers for dissolvable plugs
CN111849441B (en) *	2020-06-29	2022-06-03	山东华茂石油技术开发有限公司	Low-temperature oil layer blast hole plugging agent, preparation method and use method thereof
CN111892917B (en) *	2020-10-09	2020-12-11	山东科兴化工有限责任公司	Preparation method of calcium chloride-based water-soluble temporary plugging material for oil field
US11370962B1 (en)	2021-02-08	2022-06-28	Saudi Arabian Oil Company	Methods for designing coated proppant in low viscosity carrier fluid
CN114033331A (en) *	2021-03-24	2022-02-11	中国石油天然气集团有限公司	Rope knot type temporary plugging agent and temporary plugging method
US12018206B2 (en)	2021-12-07	2024-06-25	Lyondellbasell Advanced Polymers Inc.	Drill-in fluid compositions and methods
CN115849798A (en) *	2023-03-01	2023-03-28	成都理工大学	High-strength temporary plugging cement for geothermal well based on surface modified ceramic and preparation method thereof

Family Cites Families (31)

* Cited by examiner, † Cited by third party

Publication number	Priority date	Publication date	Assignee	Title
US2803306A (en) *	1955-04-13	1957-08-20	Halliburton Oil Well Cementing	Process for increasing permeability of underground formation
US3724549A (en) *	1971-02-01	1973-04-03	Halliburton Co	Oil soluble diverting material and method of use for well treatment
US3797575A (en) *	1972-06-19	1974-03-19	Halliburton Co	Additives for temporarily plugging portions of subterranean formations and methods of using the same
US3872923A (en) *	1972-11-06	1975-03-25	Ici America Inc	Use of radiation-induced polymers as temporary or permanent diverting agent
US3954629A (en) *	1974-06-03	1976-05-04	Union Oil Company Of California	Polymeric diverting agent
US4005753A (en) *	1974-06-03	1977-02-01	Union Oil Company Of California	Method of treating a subterranean formation with a polymeric diverting agent
US4045398A (en) *	1975-11-24	1977-08-30	Monsanto Company	Resole resin binder composition
US4269949A (en) *	1979-06-27	1981-05-26	Borden, Inc.	Phenol formaldehyde resin for hardboard applications
US4240948A (en) *	1979-11-30	1980-12-23	Monsanto Company	Accelerated resole binder
US4509598A (en) *	1983-03-25	1985-04-09	The Dow Chemical Company	Fracturing fluids containing bouyant inorganic diverting agent and method of use in hydraulic fracturing of subterranean formations
US4527628A (en) *	1983-08-15	1985-07-09	Halliburton Company	Method of temporarily plugging portions of a subterranean formation using a diverting agent
US4829100A (en) *	1987-10-23	1989-05-09	Halliburton Company	Continuously forming and transporting consolidatable resin coated particulate materials in aqueous gels
US4904516A (en) *	1988-01-12	1990-02-27	Certain Teed Corp	Phenol-formaldehyde resin solution containing water soluble alkaline earth metal salt
US5128390A (en) *	1991-01-22	1992-07-07	Halliburton Company	Methods of forming consolidatable resin coated particulate materials in aqueous gels
CZ285982B6 (en) *	1991-05-09	1999-12-15	Isover Saint-Gobain	Process for preparing phenol binding agent, the phenol binding agent intended for glass fibers and its use
GB2265398B (en) *	1992-03-27	1995-10-25	Hepworth Minerals & Chemicals	Method of sustaining fractures radiating from a well bore and compositions for use in the method
US5425994A (en) *	1992-08-04	1995-06-20	Technisand, Inc.	Resin coated particulates comprissing a formaldehyde source-metal compound (FS-MC) complex
US5420174A (en) *	1992-11-02	1995-05-30	Halliburton Company	Method of producing coated proppants compatible with oxidizing gel breakers
US6528157B1 (en) *	1995-11-01	2003-03-04	Borden Chemical, Inc.	Proppants with fiber reinforced resin coatings
US6169058B1 (en) *	1997-06-05	2001-01-02	Bj Services Company	Compositions and methods for hydraulic fracturing
US6114410A (en) *	1998-07-17	2000-09-05	Technisand, Inc.	Proppant containing bondable particles and removable particles
US6367548B1 (en) *	1999-03-05	2002-04-09	Bj Services Company	Diversion treatment method
US6380138B1 (en) *	1999-04-06	2002-04-30	Fairmount Minerals Ltd.	Injection molded degradable casing perforation ball sealers fluid loss additive and method of use
US6279656B1 (en) *	1999-11-03	2001-08-28	Santrol, Inc.	Downhole chemical delivery system for oil and gas wells
US6605570B2 (en) *	2001-03-01	2003-08-12	Schlumberger Technology Corporation	Compositions and methods to control fluid loss in surfactant-based wellbore service fluids
US7080688B2 (en) *	2003-08-14	2006-07-25	Halliburton Energy Services, Inc.	Compositions and methods for degrading filter cake
US6699958B1 (en) *	2003-02-13	2004-03-02	Borden Chemical, Inc.	Colorless phenol-formaldehyde resins that cure colorless
US7044220B2 (en) *	2003-06-27	2006-05-16	Halliburton Energy Services, Inc.	Compositions and methods for improving proppant pack permeability and fracture conductivity in a subterranean well
US7036587B2 (en) *	2003-06-27	2006-05-02	Halliburton Energy Services, Inc.	Methods of diverting treating fluids in subterranean zones and degradable diverting materials
US7178596B2 (en) *	2003-06-27	2007-02-20	Halliburton Energy Services, Inc.	Methods for improving proppant pack permeability and fracture conductivity in a subterranean well
US7066258B2 (en) *	2003-07-08	2006-06-27	Halliburton Energy Services, Inc.	Reduced-density proppants and methods of using reduced-density proppants to enhance their transport in well bores and fractures

2006
- 2006-01-20 MX MX2007008850A patent/MX2007008850A/en active IP Right Grant
- 2006-01-20 CA CA2595686A patent/CA2595686C/en active Active
- 2006-01-20 RU RU2007131659/03A patent/RU2433157C2/en not_active IP Right Cessation
- 2006-01-20 WO PCT/US2006/001916 patent/WO2006088603A1/en active Application Filing
- 2006-01-20 CN CN2006800093692A patent/CN101146888B/en not_active Expired - Fee Related
- 2006-01-20 US US11/336,344 patent/US20060175059A1/en not_active Abandoned
- 2006-01-20 GB GB0714796A patent/GB2437869B/en not_active Expired - Fee Related
2007
- 2007-08-20 NO NO20074239A patent/NO20074239L/en not_active Application Discontinuation

Cited By (2)

* Cited by examiner, † Cited by third party

Publication number	Priority date	Publication date	Assignee	Title
CN109826590A (en) *	2019-02-27	2019-05-31	杨凌单色生物科技有限公司	A kind of old well water blockoff fracturing process of hypotonic oil gas field High water cut
CN109826590B (en) *	2019-02-27	2021-05-14	杨凌单色生物科技有限公司	Water plugging and fracturing method for high-water-content old well in low-permeability oil and gas field

Also Published As

Publication number	Publication date
MX2007008850A (en)	2008-01-16
WO2006088603A1 (en)	2006-08-24
RU2433157C2 (en)	2011-11-10
US20060175059A1 (en)	2006-08-10
NO20074239L (en)	2007-10-15
GB0714796D0 (en)	2007-09-12
CN101146888B (en)	2012-08-08
GB2437869A (en)	2007-11-07
CN101146888A (en)	2008-03-19
RU2007131659A (en)	2009-02-27
GB2437869B (en)	2010-06-16
CA2595686A1 (en)	2006-08-24

Publication	Publication Date	Title
CA2595686C (en)	2012-09-18	Soluble diverting agents
US7296625B2 (en)	2007-11-20	Methods of forming packs in a plurality of perforations in a casing of a wellbore
US7216705B2 (en)	2007-05-15	Methods of placing treatment chemicals
US7823642B2 (en)	2010-11-02	Control of fines migration in well treatments
US7325608B2 (en)	2008-02-05	Methods of hydraulic fracturing and of propping fractures in subterranean formations
US7281581B2 (en)	2007-10-16	Methods of hydraulic fracturing and of propping fractures in subterranean formations
US7273099B2 (en)	2007-09-25	Methods of stimulating a subterranean formation comprising multiple production intervals
US20130048282A1 (en)	2013-02-28	Fracturing Process to Enhance Propping Agent Distribution to Maximize Connectivity Between the Formation and the Wellbore
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US8967263B2 (en)	2015-03-03	Methods of treating a subterranean formation with stress-activated resins
CN109689836A (en)	2019-04-26	Use the method for far field diversion system enhancing crack complexity
WO2017100222A1 (en)	2017-06-15	Method and composition for controlling fracture geometry
US10000692B2 (en)	2018-06-19	Fracturing or gravel-packing fluid with CMHEC in brine
US9365763B2 (en)	2016-06-14	Low-viscosity treatment fluids for transporting proppant
WO2018026375A1 (en)	2018-02-08	Amaranth grain particulates for diversion applications
US20240247183A1 (en)	2024-07-25	In-situ composite polymeric structures for far-field diversion during hydraulic fracturing
US10294411B2 (en)	2019-05-21	Fracturing or gravel-packing fluid with CMHEC in brine
US9234124B2 (en)	2016-01-12	Dimer acid grafted polymer for stabilizing particulate in a well
US11091977B2 (en)	2021-08-17	Methods for diversion and controlling fluid-loss using formate brine compositions

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2011-01-17	EEER	Examination request

CA2595686C - Soluble diverting agents - Google Patents