Prevention of water intrusion into particulates.

(54) Title: PREVENTION OF WATER INTRUSION IN PARTICLES.

(54) Title: PREVENTION OF WATER INTRUSION INTO PARTICULATES.

(57) Summary

Treatments and compounds useful in underground formations are discussed, with particular attention to those where particles can be subjected to water intrusion. Certain methods are suitable for providing diffusion barriers for particles. Of these, certain diffusion barriers can provide hydrophobic coatings to the particles, certain diffusion barriers can provide fillers that can act to prevent water intrusion into a characteristic particle surface, and certain diffusion barriers can be initiated with the source material diagenesis.

(57) Abstract

Treatments and compounds useful in subterranean formations are discussed, with particular attention to those where particulates may be subject to water intrusion. Certain methods pertain to providing diffusion barriers for particulates. Of these, certain diffusion barriers may provide hydrophobic coatings to the particulates, certain diffusion barriers may provide fillers that may act to prevent water intrusion into surface features of particulates, and certain diffusion barriers may be initiated with diagenesis source material.

IMPI '* ha> *

PATENT TITLE No. 347993

<td>Headlines):</td><td>HALLIBURTON ENERGY SERVICES, INC.</td>

<td>D micilio:</td><td>10200 Bellaire Boulevard, Houston, Texas, 77072, USA</td>

<td>D nomination:</td><td>PREVENTION OF WATER INTRUSION IN PARTICLES.</td>

<td>Classification:</td><td>CIP: C09K8 / 80; E21B43 / 267 CPC: C09K8 / 528; C09K8 / 57; C09K8 / 66; CO9K8 / 805; E21B43 / 267</td>

<td>inventor (s):</td><td>PHILIP DUKE NGUYEN; RICHARD D. RICKMAN; JIMMIE D. WEAVER; ENRIQUE REYES; DAVID EUGENE MCMECHAN; MATTHEW ERIC BLAUCH; LUO HONGYU</td>

Number:

MX / a / 2011/003786

REQUEST

International Presentation Coot:

,, ... 0 $, October &lt;fe 2009

Country:

US US

PRIORIDAI '' Fiéiiaí i October 10 &lt;October 10th.

Number:

61/104,610 61/104,620

Validity: Twenty years

Expiration Date: October 9, 2029.

Issue Date: May 22, 2017

The patent of referenoe, will be based on the arhqáos 1^or, Wrapéióti \ Z, '^ 1íapci ^ ll

In accordance with article 23 of the Industrial Property Law, the patent is valid as of the filing date: "The application will be subject to s * * pag * aeéírWifa for maetenel lll, and 59 of the Law? of Industrial Property, valid for twenty non-extendable Ways, counting the rights

Whoever signs this title does so based on the provisions of articles 6^or fractions lll and 7^or Ws 2 of Industrial Property (Official Gazette of the Federation (DOF) 06/27/1991, amended on 0208/1994, ^ / 10/1996, 12/26/1997. 05/17/1999, 01/26/2004 , 06/16/2005, 01/25/2006, 05/06/2009, 01/06/2010, 06/06/2010, 06/28/2010, 01/27/2012 and 04/09/2012); items 1 ° 3^or fraction V mciso a), 4^or and 12th sections I and III of the Regulations of the Mexican Institute ·· Teduítrial Impiety (DOF 1Í / 12/1999, refownadd he 0W7 / Z002, '15 / 07/2004, 28/07/2004 and 7/09/2007) ; items 1^or, 3^or, 4^or, 5^or fraction V subsection a) 16 sections I and lll y-SOségUát ^ MpUbrOánico of the Mexican Institute of Industrial Property (DOF 12/27/1999, amended on 10/10/2002, 07/29/2004, 08/04/2004 / 09/13/2007); 1st, 3^or and 5th subsections) of the Agreement that delegates powers to the Deputy General Directors, Coordinator, NDtaaionalés Directors. Titatefés de Ja »* '&lt;MCIIÍM-« ftégNmles. Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexiqanó Institute of Property tndustrtáL /DÓ.F. 45/12/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13 2007). '' '·'

This document is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 fraction lll, 2 fraction V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Payment and Electronic Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.

THE DIVISIONAL DIRECTOR OF PATENTS

NAHANNY CANAL REYES

H Original Chain:

: i NAHANNY MARISOL CANAL REYES | 00001000000403252793 | Administration Service

I Tax | 1695 || MX / 2017/40937 | MX / a / 2011/003786 | PCT patent title | 1220 | RRGO | Page (s)

2 | eNT8J1mjF / E / aFQNAhwM1kNkdaA =

<img file="MX347993B_D0001.tif" />

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(55) 53340700 www.gob.mx/impi

<img file="MX347993B_D0002.tif" />

WATER INTRUSION PREVENTION IN PAIR!

<img file="MX347993B_D0003.tif" />

FIELD OF THE INVENTION

The present discussion is related to treatments and compounds useful in underground formations, and, at least in some modalities, with treatments and compounds where particles can be subjected to water intrusion.

BACKGROUND OF THE INVENTION

In the production of fluids, such as hydrocarbons or water, from an underground formation, the underground formation must be sufficiently conductive to allow the flow of secretion suitable for a wellbore to penetrate the formation. Among others, hydraulic fracturing can be a useful treatment to increase the conductivity of an underground formation. Hydraulic fracturing operations in general may involve pumping a treatment fluid (for example, a fracturing fluid or a fill fluid) into a downhole borehole that penetrates an underground formation at a hydraulic pressure sufficient to create or enhance a or more trajectories, or fractures, in the underground formation.

<img file="MX347993B_D0004.tif" />

² IMPI

INSTITUTE

Improving a fracture in general involves extending ^ í * ^^! a natural or pre-existing fracture in the ήη. These fractures generally increase the permeability of that portion of the formation. The treatment fluid may comprise particles, including consolidation particles that are deposited in the resulting fractures. The particles are believed to help prevent fractures from fully closing on release of hydraulic pressure, forming conductive channels through which fluid can flow between the formation and the wellbore.

In general, particle surfaces in general are believed to comprise minerals, which can react with other substances (e.g., water, minerals, treatment fluids, and the like) that reside in the underground formation in induced chemical reactions, at least in part, by the conditions created by mechanical stresses on these minerals (for example, the fracturing of mineral surfaces or the compaction of particles). These reactions are referred to herein as stress-activated reactions or stress-activated reactivity. One type of these stress-activated reactions can be diagenesis reactions. In the sense in which it is used in the³ IMPI ^ present, the terms reactions of ° * eagsS?) Diagenesis reactivity, and diagpnp.gi g inninyAn p ^^ c ^ c · chemical and / or physical which, in the presence of water, move a portion of the mineral into a particle and / or convert a portion of the mineral into a particle in some other form. A mineral that has been moved or converted is referred to as a diagenesis product or a diagenic product. Any particle comprising a mineral can be susceptible to these diagenesis reactions, including natural silicate minerals (eg, quartz), synthetic silicates and vitreous materials, metal oxide minerals (both natural and synthetic), and the like.

Two of the main mechanisms that diagenesis reactions are believed to involve are pressure dissolution and precipitation processes. When two mineral surfaces impregnated with water come into contact with each other at a low point of formation, it can increase localized mineral solubility near that point, causing the minerals to dissolve. Minerals in solution can diffuse through the water film out of the region where mineral surfaces are in contact (for example, the pore spaces of a particle pack), where they can precipitate out of solution. The dissolution and precipitation of minerals in iNnurrRMi reactions can reduce the conductivity of a particle pack, inter alia, by clogging the pore spaces in the particle pack with a mineral precipitate and / or by collapsing the pore spaces by dissolving the solid mineral on the walls of those pore spaces. In other cases, minerals on the surface of a particle may exhibit a tendency to react with substances in the reservoir, formation, and / or treatment fluids that are in contact with the particles, such as water, gelling agents (e.g. example, polysaccharides, biopolymers, etc.), and other substances commonly found in these fluids. The molecules from these substances can be anchored to the mineral surface of the particle. These types of reactivity can further decrease the conductivity of an underground formation, inter alia, through the obstruction of conductive fractures in the formation by whatever molecules have anchored to the resident particles within those fractures. Both types of reactions generally require the presence of a fluid, such as water, to be present to any significant degree.

SUMMARY OF THE INVENTION

This exhibition is

<img file="MX347993B_D0005.tif" />

it relates to treatments and compounds useful in underground formations, and, at least in some modalities, with treatments and compounds where the particles can be subjected to water intrusion.

In one embodiment of the present invention a method is provided. The method comprises providing a plurality of particles, wherein at least a first portion of the particles comprises a diffusion barrier. The method further comprises introducing the plurality of particles into an underground formation. The method further comprises allowing an aqueous fluid to flow through the plurality of the particles. The method further comprises allowing a diffusion barrier to prevent aqueous fluid interactions between the aqueous fluid and the plurality of particles.

Another embodiment of the invention provides another method. The method comprises providing a plurality of particles. The method further comprises providing a diffusion barrier initiator. The method further comprises introducing the plurality of particles into an underground formation. The method further comprises introducing the initiator of the diffusion barrier into the formation

1 I saw go underground. The method further comprises

M LA MOHEDAI Vwr-ij ^ Gf INmimiAL ** 7— Aqueous fluid flow through the plurality of particles.

The method further comprises allowing the diffusion barrier initiator to form a diffusion barrier for at least a portion of the plurality of particles. The method further comprises allowing the diffusion barrier to prevent aqueous fluid interactions between the aqueous fluid and the plurality of particles.

Still another embodiment of the invention provides yet another method. The method comprises providing a plurality of particles. The method further comprises providing a coating material. The method further comprises allowing the coating material to form a diffusion barrier for at least a first portion of the plurality of particles.

The features and advantages of the present invention will be apparent to those skilled in the art. While many changes can be made by those skilled in the art, these changes are within the spirit of the invention.

DETAILED DESCRIPTION OF ΙΑ INVENTION

This discussion is related to useful compounds and treatments in underground formations, ^ΙΜΡΙ^^ and, at least in some modalities, with '^ To ^ Sia ^ encá ^

IMF * fSTlIAL compounds where particles can be subjected to water intrusion.

The term "coating" as used herein refers to at least a partial coating of some or all of the particles. The term "coating" does not imply complete or substantial coverage of the particles or mixture of particles. Instead, a particle can be coated if it has, for example, at least a partial coating.

The term derivative, herein is defined to include any compound that is prepared from one of the listed compounds, for example, by replacing an atom in the listed compound with another atom or group of atoms, by rearranging two or more atoms in the listed compound, by ionizing one of the listed compounds, or by creating a salt of one of the listed compounds. A derivative of a material can include, but is not limited to, a composition of a composite based on a plurality of base materials, a composite material, or an aggregate material of various compositions.

As used herein, the terms diagenesis reactions, diagenesis reactivity, and diagenesis include chemical and physical processes that, in the presence of water, convert a mineral into some other movement.

<img file="MX347993B_D0006.tif" />

shape. Examples of these minerals include, but are not limited to, oxides or hydroxides of zirconium, magnesium, aluminum, titanium, calcium, strontium, barium, radium, zinc, cadmium, boron, gallium, iron, or any other element suitable to form a diagnostic product. These minerals can be found in a particle, in a formation, and / or introduced into a formation as a source material for diagenesis. A mineral that has been moved or converted is referred to as a diagenesis product or a diagenic product.

As used herein, the term aqueous fluid interaction includes a variety of possible interactions between an aqueous fluid and Ib a particle. These interactions can include infiltration of the aqueous fluid into the particle, for example, through pores, voids, fissures, cracks, and / or channels in or near the surface of the particle. These interactions can also include diagenesis.

As used herein, the term "diffusion barrier" includes any classification of materials, including a coating, on or near a particle that prevents and / or prevents the interaction of the aqueous fluid with the particle. For example,

TMPT some diffusion barriers fill or

FROM THE PRDHWAD line »SaíaSy ΙΝΟ '^,.ΤΓ »ΙΑΙ ^&gt; wth holes, fissures, cracks, or channels in or near the surface of the particle to prevent and / or avoid infiltration by the aqueous fluid. As another example, some diffusion barriers prevent and / or prevent diagenesis.

As used herein, the term "diagenic protective materials" refers to one or more diagenic products that can be selectively stimulated to form a diffusion barrier.

As used herein, the term "filler material" or "filler material" means a particulate material that is capable of being filled into a pore, hole, fissure, crevice, or channel on or near the surface. of a particle or on the surfaces within the porous matrix of the individual particles.

As used herein, the term "relatively low molecular weight" refers to a molecular weight that could encompass short chain monomers and polymers having physical dimensions from a few Angstroms to several hundred manometers.

As used herein, a monolayer refers to a coating of a material. IMPI about one unit thick ^ srmrr ^ gtg ^ Nvp

INBnrmAL chemicals, this can mean a coating as fine as a molecule, and for particle compositions, it can mean a coating of a particle grain depth.

As used herein, the terms pores, voids, fissures, cracks, and channels refer to features on or near the surface of a particle. Any given particle may have one or more pores, voids, fissures, cracks, or channels, or it may be free of these characteristics. One or more of these features can generally be referred to as surface features. The use of the terms together is in no way intended to indicate that all three must be present simultaneously, or totally, for the teachings of this disclosure to apply.

As used herein, the terms particle, macroparticle, consolidation particle, and gravel are all used to refer to either a single particle or a plurality of particles that can be used to support a fracture at an underground formation, to form a consolidation package, or to be used in the formation of a

IMPIAS PACK OF GRAVEL. These particles can be found in underground formation, including in spaces in the rock itself, fractures within the rock, and / or borehole drilling that penetrates the underground formation.

As used herein, the term particle packet refers to a collection of particles within an enclosed volume, where the particles can be juxtaposed and / or in contact with each other, and in where pore spaces can be placed between the particles. Examples of packages may include consolidation packages, which may refer to a collection of consolidation particles within a fracture, and / or gravel packages, which may refer to a grouping of particles that are packed close enough to avoid passage. of certain materials throughout the package.

The term on the fly, as used herein, indicates that a flow stream comprising particles is introduced into another flow stream comprising a hydrophobic coating agent in such a way that the streams combine and merge. mixed to flow as a single stream, in some cases the streams can be combined to flow as a single stream as part of a progressive job site treatment. This mixing is also not mixed in real time.

If there is any conflict in the uses of a word or term in this specification and one or more of the patent or other documents that may be incorporated herein by reference, definitions that are consistent with this specification should be adopted for the purposes understanding of this invention.

There are many advantages of the present invention, only a few of them are mentioned here. An advantage of the present invention may be the reduction or prevention of the degradation of the mechanical strength of the particles due to the interaction of aqueous fluid with a particle, for example, through the infiltration of an aqueous fluid into the particle and / or diagenesis. In some embodiments, the methods set forth herein are desirable to provide a diffusion barrier on a particle such that surface characteristics (i.e., pores, voids, fissures, cracks, or channels in or near the surface of the particle) can be filled to be coated with a material that prevents and / or avoids the interaction of an aqueous fluid with the particle. By avoiding the interaction of an aqueous fluid, the degradation of the mechanical strength of the particles can be reduced or avoided. Each particle can^1J IΜ PI contain several of these features supl ^ l ^ a®lá ^ ^x industrial cells act as conduits for the intrusion of aqueous fluid into the particle itself. These surface characteristics can contribute to diagenesis reactions by providing a pathway for aqueous fluid intrusion into the interior of the particle resulting in degradation of the particle. By limiting the interactions of the particles with an aqueous fluid, the particles can retain a higher percentage of strength relative to initial placement at the bottom of the hole. Treatments of underground formations, including the rock itself, fractures within the rock, and / or a borehole drilling that penetrates the underground formation, with these particles can then result in increased permeability of the particle packet to over time than with untreated particles.

Another advantage of the present invention may be the ability to quickly and easily coat particles using a pre-treated filler material that acts as a carrier or initiates a diffusion barrier. This filler material can be pre-coated with a material such as a hydrophobic coating or a reagent that can allow a diffusion barrier to grow over the particle once the particles settle to the bottom of the bore.

<img file="MX347993B_D0007.tif" />

Alternatively, the filler material covering material that is coated in an outer liner that can dissolve or degrade. Once placed at the bottom of the perforation, the outer liner can dissolve or degrade, allowing a diffusion barrier to grow over the particle. These methods can avoid aqueous fluid infiltration and / or particle diagenesis. These methods can also allow the particles to be easily coated with a pre-treated filler material at or near the point of placement in the formation.

A further advantage of the present invention may be the ability to at least partially coat the particle with a very fine diffusion barrier that can prevent interactions of an aqueous fluid. For example, in an embodiment in which a diffusion barrier is precoated over a filler material, a monolayer of the filler material can be created when the particle is exposed to the filler material. In another embodiment, a very thin layer of the filler material can be coated onto the particle through the use of relatively low molecular weight materials with one or more of the coating techniques discussed herein.

Protection of particles from harmful interactions with aqueous fluids can be achieved

<img file="MX347993B_D0008.tif" />

¹⁵ IMPI INSTITUTO MEXICANO in several days. According to the modál ^ g ^^ present invention, these in general piipHon, i nrl η Ί rp! treating a particle with a diffusion barrier that acts to prevent interaction of the particles with aqueous fluids during and / or after placement in the formation. The diffusion barrier can comprise one of several types of materials, including hydrophobic materials, diagenic protective materials, and various polymeric compositions. Some embodiments of the present invention may utilize a filler material to fill pores, voids, fissures, cracks, or channels that may be present in a particle surface. Alternatively, a filler material can be used to generate and / or place the diffusion barrier. For example, a hydrophobic material can be used to coat a filler material, and the filler material can then generate a diffusion barrier (eg, comprising a diagenesis product) on the particles. The filler material can fill the pores, voids, fissures, cracks, or channels on the particle surfaces, resulting in a surface that can be more hydrophobic than the original particle surface. Each of these materials and methods will be described in more detail later.

IMPI

MEXICAN INSTITUTE

D £ LA rWBTIlttAl can you use * i?^{t ,, T}* ^ h

<img file="MX347993B_D0009.tif" />

The particles that are embodiments of the present invention, include · 'tualeyqulurd particles of consolidation or gravel that can be used in an underground application. suitable particles can include sand, sintered bauxite, alumina silica, glass beads, etc. Other suitable particles include, but are not limited to, sand, bauxite, garnets, fumed silica, ceramic materials, glass materials, polymeric materials, polytetrafluoroethylene materials, walnut shell pieces, seed shell pieces, fruit stone pieces, wood, composite particles, consolidation particles, degraded particles, coated particles, gravel, and combinations thereof. Suitable composite materials may comprise a binder and a particulate material wherein suitable particulate materials may include, silica, alumina, garnets, smoked carbon, carbon black, graphite, mica, titanium dioxide, meta-silicate, silicate calcium, kaolin, talc, zirconia, boron, fly ash, hollow glass microspheres, solid glass, and combinations thereof, in certain embodiments, the particles can comprise ordinary sand. In some embodiments, a derivative of one or more of the particulate materials can also be used. Derivatives may include materials such as ____ ______.___ __. _ · Τ__. ΙΝΓΠΠΤΧ MEXICAN as composites, composite materials, Dt ^ monBatenaSw 'aggregates of various compositions. In some embodiments of the present invention, some or all of the particles may consist of a source material of diagenesis. In this embodiment, the particles can comprise oxides or hydroxides of zirconium, magnesium, aluminum, titanium, calcium, strontium, barium, radium, zinc, cadmium, boron, gallium, iron, or any other element suitable to form a diagenic product. Suitable particles can take any shape including, but not limited to, the physical form of platelets, chips, flakes, ribbons, bars, strips, spheres, spheroids, ellipsoids, toroids, granules, or tablets. Although a variety of particle sizes can be useful in the present invention, in certain embodiments, the particle sizes can range from about 200 mesh to about 8 mesh.

The particle embodiments of the present invention may contain pores, voids, fissures, cracks, or channels on or near the surface. For example, high power SEM micrographs can show that particle surfaces, such as particles made from bauxite, can become loaded with pores, voids, fissures, cracks, and channels. Without being limited by theory, it is believed that these pores, voids, channels on or near the surface of

<img file="MX347993B_D0010.tif" />

PE LA FRCHÍDAO C · INDUSTRIAL particle can provide a direct path to allow harmful interaction between aqueous fluids and particles that can lead to degradation of the particles under formation pressure and temperature.

In some embodiments, the particles can be treated or coated with one or more suitable substances. In general, the particles can be treated or coated with any substance that is suitable for traditional particle treatments. In certain embodiments, the particles are coated to prevent water intrusion into the particles. For example, the particles can be coated and / or used as discussed in Geochemical Control of Fracturing Fluids by Reyes et al., US Patent Application Serial Number 12/574 054, Additives to Suppress Silica Scale Build-up de Reyes et al., United States Patent Application No. 09/737 117, and / or Ceramic Coated Particulates de Reyes et al., United States Patent Application No. 12/574 018, each filed on the same day, and the total exposures thereof are incorporated herein by reference in their entirety. In one embodiment, a portion of the particles can be coated to limit

IMPI

<img file="MX347993B_D0011.tif" />

MEXICAN INSTTTVTO

...,.,.,. . M LA MOHEBaO its diagenetic reactivity while others can uncoated pwfTOan to provide a site of pure L '^ - jllIiiii υ · 1 source material of diagenesis.

The particle compositions used in some of the embodiments of the present invention may comprise at least one particle and a diffusion barrier, which may comprise a hydrophobic, or water repellent material. Diffusion barriers can be started and / or formed from a variety of materials. For example, certain materials can initiate diffusion barriers in some embodiments of the present invention. Suitable materials can be any chemical agent capable of forming a hydrophobic coating on the surface of the particles. In certain embodiments, the particles that comprise a diffusion barrier may have a conserved strength greater than or equal to about 30%, as will be discussed in more detail below. In some embodiments, these diffusion barriers can enhance the recovery of a reservoir, formation, and / or treatment fluid; in certain embodiments, a surfactant can be included in the coating material to enhance the coating process. Suitable coating materials can include oligomeric materials, monomeric materials, oil-impregnated composites, and combinations thereof for monomolecular ratio or film, which can make mineral surfaces water repellent or hydrophobic.

In one embodiment, a diffusion barrier can comprise the reaction products of a compound having a reactive silyl group. The diffusion barrier can be formed by forming a layer of silicon oxide or a hybrid organosilicon oxide anchor from a humidified reaction product of silicon tetrachloride or trichloromethylsilane, followed by the vapor deposition of a chloroalkylsilane. In another embodiment, the diffusion barrier can comprise a trimethylsilyl functional group. For example, if a fumed silica filler particle is used, the surface hydroxyl groups can be replaced with trimethylsilyl functional groups to form a hydrophobic filler particle. The diffusion barrier can also comprise silicones or siloxanes. In one embodiment, the diffusion barrier can comprise an organosilicon compound, which can include, for example, an organosiloxane, an organosilane, a fluoro-organosiloxane, and a fluoro-organosilane. The diffusion barrier can also comprise a polysiloxane or an organomodified polysiloxane, which can include a di-betaine polysiloxane or a di-quaternary polysiloxane.

²¹ IMPI INSTITUTO MUIGANC In another embodiment, the barrier of comprising polymers of a gilanano compound or a fluoroalkyl group, and the polymers can include at least dimers and trimers of the silane compound. This diffusion barrier can be produced when preparing a solution, the solution will be produced by subjecting a silane compound containing a fluoroalkyl group to hydrolysis and condensation polymerization to produce at least dimers and trimers of the silane compound, coating the solution on the surface of the particle or filler material, and heating the material to cause the fluoroalkyl group in the solution to bind to the surface of the particle solids to form a hydrophobic film on the material. In another embodiment, the diffusion barrier may comprise a fluoro-organosiloxane compound or a fluoro-organosilane compound, which may include, for example, 2- (n-perfluoro-octyl) -ethyltriethoxysilane and perfluoro-octyldimethyl elorosilane.

In still another embodiment, a diffusion barrier can comprise a polyamide. In still another embodiment, the diffusion barrier may comprise a silyl-modified polyamide.

In one embodiment, a diffusion barrier can comprise polytetrafluoroethylene, vegetable oils, hydrocarbons, copolymerized polyvinylidene chloride

IMPI

INSTITUTO MEXICANO M LA PWPftDAn INDU5TWIAL

<img file="MX347993B_D0012.tif" />

any other substance capable of hindering or preventing the penetration, permeation, or wetting of a particle with aqueous fluid.

The filler material may comprise micron-sized, submicron-sized, nano-sized particulate materials, or a combination thereof. The filler material can be reinforced or unreinforced. Fillers may include, for example, fumed silica, fused silica, garnet dust, clay, mica, alumina, finely divided quartz dust, amorphous silicas, metasilicates, calcium silicates, calcine, kaolin, talc, zirconia, ash flywheels, boron, carbon black, smoked carbon, graphite, diamond, silicone carbide, aluminum hydrates, metal nitrides (such as boron nitride, and aluminum nitrides), metal oxides (such as aluminum oxide, zinc oxide, titanium dioxide or iron oxide), and any combination thereof, in another embodiment, the filler material may comprise metallic particles, such as aluminum, zirconium, titanium, or derivatives thereof. In one embodiment, the average diameter of the filler material particles can be less than about 20 microns. In one embodiment, the average particle diameter of the filler material

IMPI INSTITUTO MÜUCaMC can vary between about 0.05 mid ¥ 0fjí ^ § | g ^ s about 10 microns, or between aprcYirnaHamonto or microns up to about 10 microns. In another embodiment, the filler material particles can range in size from about 0.1 microns to about 0.5 microns, or from about 0.2 microns to about 0.5 microns.

In accordance with one embodiment of the present invention, the particle sizes of the filler material can be selected, among other purposes, to achieve a coating of a particle including the pore spaces on the surface of the particle. The choice of a particle size of the filler material can be based on a consideration of the surface characteristics of the particle, which can be based on the choice of the particle material, the crystalline structure, and / or other characteristics, in one embodiment , the particle size of the filler material can be such that the maximum particle size of the filler material can be at least equal to, and in some embodiments, less than, the expected diameter of a pore, hole, fissure, crack, or channel at or near the surface of the particle. Consideration of any additional coating thickness than the backing material²⁴ IMPI

INSTITUTO MEXICANO coating can be added to the material can be a consideration for splprrinnar nn mahariai fill that has certain sizes and particle shapes.

In some embodiments of the present invention, some or all of the fillers may consist of a material useful to stimulate a diagenesis reaction, such as a source material for diagenesis. For example, the filler material can comprise oxides or hydroxides of zirconium, magnesium, aluminum, titanium, calcium, strontium, barium, radium, zinc, cadmium, boron, gallium, iron, or any other suitable element to form a diagenic product.

In one embodiment, the filler material may comprise certain metallic compositions that may have the ability to fill the pores, voids, fissures, cracks, or channels of the particles, which, among other things, can limit the interaction between the particles and aqueous fluids. Metallic compositions can have physicochemical properties that can render dissolution in aqueous fluids negligible under certain conditions. Metallic compositions can be chemically resistant. For example, certain metal compositions may be capable of forming diagenic protective materials when placed in contact with reservoir, formation, and / or treatment fluids at the bottom of the cell.

IMPI ___ £ _____ _x„„ „_ ____Q,, _Ί _ _ _ _. ικηττυτο Mexican drilling. In one embodiment, the compositions may include, but are not limited to, metal alkoxides, organometallic compounds (such as metal esters) of aluminum, zirconium, titanium, antimony, silicon, tin, boron, chromium, iron, and rare earth elemental compounds. In another embodiment, the metal compounds may include metal cationic cross-linking agents selected from boron (such as boric acid, borax, metal borates including tetraborates, tetrafluoroborates, boron mineral), aluminum, zirconium, titanium, and antimony. In some embodiments of the present invention, some or all of the metal compositions may consist of a material useful for stimulating a diagenesis reaction. In this embodiment, the consolidation particles can comprise oxides or hydroxides of zirconium, magnesium, aluminum, titanium, calcium, strontium, barium, radium, zinc, cadmium, boron, gallium, iron, or any other element suitable to form a diagenic product. .

In an alternative embodiment, polymeric materials that include the metallic elements can also be used to coat the particles. For example, silicon polymers (such as, polymethylsilsesquioxane, polydimethylsiloxanes, and polysiloxazane) or any other metallic polymer capable of being provided in embodiments, those in polymeric form can be used

<img file="MX347993B_D0013.tif" />

Suitable monomeric compositions can be used to coat the particles and then polymerize using a suitable activator.

One skilled in the art, with the benefit of this discussion, will be able to determine which metal compound or polymer composition should be included for a particular application based on, for example, formation chemistry, particle composition, and potential growth of diagenic protective materials. Without limiting the invention to a particular theory or mechanism of action, it is currently believed that the introduction of the metallic or polymeric compositions can be used to stimulate a protective layer of diagenic product around the

Ib particle once the coated particle is placed within the formation. In one embodiment, the coating can be a source material for diagenesis and can be used to create a diagenic product in an underground formation. For example, a silicon-based compound can be used to stimulate the growth of silicates when brought into contact with an aqueous fluid under the conditions of formation. For a silicon compound properly placed within the pores, voids, fissures, cracks, or channels of a particle, the growth of the

IMPIíg ^ silicate can fill pores, voids, or channels, thereby limiting the interaction between the aqueous fluid and the interior of the particle. In one embodiment, the diagenic product can also grow between individual binding particles to act as a binder.

In one embodiment, the diffusion barrier can be applied to the particles using any coating technique known in the art. In one embodiment, one or more of a variety of techniques may be used, including chemically coating the particle by spraying, dipping, or soaking the particle in a liquid solution of the hydrophobic material; applying a sheet of film such as copolymerized polyvinylidene chloride to essentially pack the particle and Ib encapsulate it in a chemically suitable coating; fusing the material to the particle by placing hot particles into a meltable powder, such as a glass or enamel frit, that can be attached to the particle; galvanizing using electrostatic techniques known to those of ordinary skill in the art to transfer a diffusion barrier, including a chemically less reactive metallic layer, to the particle; plasma spray; sputum deposition; fluidization of the particle in a fluidized bed; and powder coating. the particles too

IMPI ^

ΙΗΓΠΤυΤΟ MUCAMO νζ- ^ jeC DE LA Ploma »D can be coated with a solid coating,^INDTJ.^,l^L Glass frit, high alumina clays, or bauxites, metals, or other hydrophobic powders. These diffusion barriers could be applied by spraying, dumping, or other means known in the art to apply powder coatings.

In another embodiment of the present invention, a method of initiating a fluid barrier may comprise coating a filler particle with a protective coating, such as a hydrophobic material, and then mixing the coated filler particle with a particle to form a barrier. diffusion. For example, a fumed silica nanoparticle can be treated in such a way that the surface hydroxyl groups are replaced with trimethylsilyl functional groups to form a protective coating on the filler material. In this example, the particles may exhibit hydrophobic properties when mixed with the coated filler material. For another example, the filler material may be a metallic compound capable of stimulating the formation of diagenic products when placed in the formation. In this example, the particles can be coated with filler material, and a diffusion barrier can be formed with placement in the formation. In one embodiment, the

IMPIp ^ filler can be a free flowing material in se ^ oSSe ^ waSoNS ^^^ mixed with a particle. The treated filler material can be mixed with the particles in an amount sufficient to impart a diffusion barrier to the particles. This may be an amount sufficient to partially coat the particles but not provide 100% coverage of each particle. In one embodiment, the treated filler material can be mixed with the particles in an amount ranging from about 0.025% to 50% by weight of the particles, or from about 0.25% to 50% by weight of the particles. In an alternative embodiment, the treated filler material can be mixed with the particles in an amount ranging from about 0.25% to 5% by weight of the particles.

In an embodiment in which the primer filler material is treated with a protective coating, the treated filler material can be mixed with the particles during making and processing of the particles, or can be mixed on the fly at or near the time of which will be placed in a formation, as will be discussed in more detail later. One skilled in the art, with the benefit of this discussion, may be able to determine when the particles should be coated with the treated filler material.

IMPIí otltA ^ rKmsñAD INDUSTRIAL

In some embodiments, also a diffusion barrier on the particle using a solvent to carry the coating material into the pores, voids, fissures, cracks, or channels of the particles. In these embodiments, a suitable solvent for a protective compound can be used to dissolve a quantity of the coating material. The particles can then be sprayed, dipped, or soaked in the resulting liquid solution of solvent and coating material. One skilled in the art should be aware of suitable solvents and solubilities for the various coating materials described herein. A drying step can then be used to remove the solvent and leave behind a diffusion barrier. This drying step can be carried out at a pressure sufficient to ensure that the drying temperature is below the decomposition temperature of the coating material. In some embodiments, the drying step can be carried out under vacuum pressure.

In still another embodiment, a carrier fluid, a solvent, a sol (eg, a colloidal suspension of solid particles in a liquid), a gel (eg, a soft, elastic, solid, or semisolid material consisting of at least two components, one of which is a liquid),

IMPI ^ a microemulsion, a suspension, or any ^ r &amp; L ^ Í &amp; £ r ^ r: ^

INDUSTRIAL 'S "¹These can be used to supply a filler material and a coating material to the particles, thereby forming a diffusion barrier. In these embodiments, a filler material or a treated filler material can be mixed with a fluid capable of supporting the filler material. In these embodiments, the fluid may comprise a coating material that coats the particles and the filler material during mixing. The resulting mixture can then be mixed with the particles for a sufficient time to allow the fillers and / or treated fillers to coat the particles, and / or enter the pores, voids, fissures, cracks, or channels of the particles. The particles can then be allowed to dry, undergo a rinse step to remove carrier fluid, solvent, sol, gel, microemulsion, and / or suspension, or will be placed directly into the formation, depending on the application.

In yet another embodiment, any of the above methods can be used to coat a polymeric or monomeric composition on the particles, either alone or in combination with a filler material, thereby forming a diffusion barrier. In these modalities, an activator may be required to bind the

IMPI composition with the surface of the partícur $ 5 £ ^ $ w * ^^ voids, fissures, cracks, or channels, or both. Any method of initiating polymerization known to those skilled in the art can be used to perform this function, and the selection of a suitable method may depend, among other things, on the type of polymeric or monomeric composition used. For example, exposure to an ultraviolet light source or chemical initiators prior to placement in the formation can be used to initiate a polymerization reaction capable of forming polymers within the particles.

To practice certain embodiments of the present invention, the process of coating the plurality of particles can be performed at any stage of the preparation and / or use of the particles. This coating can be carried out in treatments performed before transporting the particles to a job site, or in a treatment performed on the fly. An on-the-fly mixing method may involve continuously conveying the particles and the hydrophobic coating agent (eg, a treated filler material) into a mixing vessel, eg, using a sand auger. Once inside the mixing vessel, the particles can be brought into contact with the coating material and

ΙΜΡΙ ^ withdraw continuously from the container of me z CT ^^^^ gn ^ ga ^

INDUSTRIAL situation, the sand auger can be used both to aid in mixing the particles with the hydrophobic coating agent and to remove the hydrophobic coating agent from the mixing tank. Batch or partial batch mixing can also be used to coat a site in the well prior to introducing the particles into an underground formation, in accordance with the embodiments of the present invention.

Certain methods of the present invention can result in a very fine diffusion barrier, comprising a protective material, a diagenic product, a treated filler material, or any combination thereof in one particle. The use of relatively low molecular weight compounds in coating methods can result in diffusion barriers as fine as a monolayer. In another embodiment, the fillers can act to produce a diffusion barrier on a particle smaller than about 10 microns thick. In an alternative embodiment, the diffusion barrier can be less than about 1 micron thick, or alternatively less than about 0.5 microns thick. These thin coatings can

ΙΜΡΙ ^&gt;

INSTTTUTV MUIGANO

Μ LA ΠΟΤΙΒΑΓ 'effectively allow coating of the por'S ^ T ^' W'ueCTTsr 'fissures, cracks, or particle channels. This can help limit particle degradation due to aqueous fluid interactions while avoiding any harmful interactions between particles due to agglomeration of the particle package.

One embodiment of the present invention provides a method. The method comprises providing a plurality of particles, wherein at least a first portion of the particles comprises a diffusion barrier. The method further comprises introducing the plurality of particles into an underground formation. The method further comprises allowing an aqueous fluid to flow through the plurality of particles. The method further comprises allowing a diffusion barrier to prevent aqueous fluid interactions between the aqueous fluid and the plurality of particles. In some modalities, this method can be useful in the recovery of fluids from the underground formation. The fluids to be recovered may be a fluid previously introduced into the underground formation, an aqueous reservoir and / or a formation fluid, a hydrocarbon fluid, or a combination thereof.

Another embodiment of the invention provides another method. The method comprises providing a plurality of particles.

The method comprises

<img file="MX347993B_D0014.tif" />

initiator of the diffusion barrier. The method further comprises introducing the plurality of particles into an underground formation. The method further comprises introducing the initiator of the diffusion barrier into the underground formation. The method further comprises allowing an aqueous fluid to flow through the plurality of particles. The method further comprises allowing the diffusion barrier initiator to form a diffusion barrier for at least a portion of the plurality of particles. The method further comprises allowing the diffusion barrier to prevent aqueous fluid interactions between the aqueous fluid and the plurality of particles. In some embodiments, this method may be useful in recovering fluids from the underground formation. The fluids to be recovered may be a fluid previously introduced into the underground formation, an aqueous reservoir and / or a formation fluid, a hydrocarbon fluid, or a combination thereof.

Still another embodiment of the invention provides another method. The method comprises providing a plurality of particles. The method further comprises providing a coating material. The method further comprises allowing the coating material to form a barrier

Diffusion IMPIOS for at least one first AfmB ^ Sfiiáh ¿WííX

OF INDUmiAI PROmtAD plurality of particles. In some embodiments, this method may be useful for the preparation of particles for underground treatments and / or the use of the particles in underground treatments.

To quantify the mechanical strength of the particles and the permeability of the particle package, both before and after exposure to formation conditions and fluids, various test procedures can be used to determine various properties of the particles. The first test method studies the temperature-stimulated diagenesis of a particle package by exposing a particle package to a flowing solution of simulated formation fluid at an approximate formation temperature. The second procedure studies stress / temperature stimulated diagenic growth through exposure of a particle packet to a static flow environment under simulated formation pressures and temperatures. The mechanical strength of individual particles can be measured before and after test procedures to determine the percentage of strength loss of the particles due to exposure to the formation temperature or pressure.

Alternatively, the permeability of the particle pack

IMPI can be measured before and after the temperature stimulated test to determine a conserved permeability value for the particle package. As might be understood by one of ordinary skill in the art with the benefit of this discussion, the expected subsurface formation conditions (eg, temperature, pressure, formation fluid composition) for a selected subsurface formation will determine the formation conditions. suitable for testing procedures.

In the temperature-stimulated diagenesis test procedure, deionized water can first be heated to a test temperature between approximately 93.33 ° C (200 degrees Fahrenheit (° F)) and approximately 315.56 ° C (600 ° F) by turning it to through a heat exchange coil. The simulated forming fluid can be formed by passing deionized water through multiple packages of crushed forming material arranged in series. The number of formation packs required for the test can vary such that the simulated formation fluid leaving the last pack can be in equilibrium with the crushed formation material. Through experimentation, the typical number of training packages in general can be between about 1 and

<img file="MX347993B_D0015.tif" />

about 10.

The material of

IMPI form XSMi

INXfSTRlAL can sieve to remove fines and approximately 8/35 mesh fraction can be used in training packages.

In one embodiment, once a simulated formation fluid is obtained in equilibrium with the ground formation material, the simulated formation fluid can be directed to a column containing a packet of particles. The temperature in the particulate package can be maintained at an approximate formation temperature between approximately 93.33 ° C (200 ° F) and approximately 315.56 ° C (600 ° F), which roughly corresponds to the temperature of the deionized water that enters first To the system. A mock-forming secretion flow rate can be maintained at approximately 1 milliliter per minute during testing.

The flow test can be maintained for between about 10 to about 200 days, and in one modality, for at least about 20 days. After this time, the particle pack can be disassembled to test the mechanical properties of the individual particles, as will be discussed in more detail later. For example, a surface and compositional analysis can be performed after disassembling to³⁹ IMPIWí

INSTITUTO MUUCANV determine what types of materials are being foajgrw ^ simulated training conditions. At eske mome ^ -h ^ a permeability test can be performed. In this test, the permeability of the particle packets can be measured at room temperature prior to the particle pack disassembly. The measured permeability of the package can then be compared to an initial permeability measurement made of the package at room temperature before the package is placed in the testing apparatus. Comparison of the initial permeability measurement with the permeability measurement obtained after the package is subjected to the test conditions can allow a preserved permeability to be calculated.

The test method for stress / temperature stimulated diagenesis may involve testing the particle pack under conditions of static flow at approximate formation pressures and temperatures. In this method, a particle pack can be loaded into a test cell and filled with a saline solution. The test cell can be loaded between about 2.44 kg / m² (0.5 pounds per square foot (lb / ft²)) of particles up to approximately 14.64 kg / m² (3.0 lb / ft²) of particles. In one embodiment, a KC1 solution at about 2% can be used as the fluid medium. Forming wafers, whether manufactured to⁴⁰ IMPI INSTITUTO MEXICANO starting from the formation core material or rocky outcrop material, can be p ^ -r ann-ima and below the particle pack in the test column. The system can then be closed and placed under simulated formation pressure and heated to approximate formation temperatures. In one embodiment of this method, the temperature can be maintained between about 37.77 ° C (100 ° F) and about 287.78 ° C (550 ° F). In another mode, the temperature can be maintained between approximately 37.77 ° C (100 ° F) and up to approximately

176.67 ° C 350 ° F). The pressure can be kept between about 140.62 kg / cm² (2,000 psi) and approximately 703.1 kg / cm² (10,000 psi). In another embodiment, the pressure can be maintained between approximately 351.55 kg / cm² (5,000 psi) and approximately 562.48 kg / cm² (8,000 psi). In one embodiment, the test can be conducted for about 1 to about 50 weeks, and in another embodiment, the test can be conducted for at least about 4 weeks (about 28 days).

With the completion of the stress / temperature stimulated diagenesis test, the test cell can be disassembled and the particle pack can be removed for testing. As with the flow test method, tests can also be performed at this time

<img file="MX347993B_D0016.tif" />

IMPIgg ^,. ._Ί , _Ί INSTITUTO MEAIGA NO additional. For example, surface and compositional flanges can be made after stripping to determine what types of materials are forming under simulated forming conditions. Alternatively, the resulting interstitial fluid can be analyzed to determine the relative solubility of the particles under the conditions of formation.

Changes in the mechanical properties of the particles obtained from either the stress / temperature stimulated diagenesis or the temperature stimulated diagenesis test can be determined using an individual grain crush resistance analysis. The analysis can use a Weibull statistical analysis procedure based on a plurality of crushed particle samples. The crushing test can be based on a one-axial compressive point load of a particle. Under compressive load in the uni-axial direction, a spherical particle can be under tension in the directions perpendicular to the load with a tensile strength, σ, calculated by

2.8 F π d¹ where d is the diameter of each particle and F is the charge.

IMPI ^

THE rHOEIBDA · C »iNrxiyrniAi

A Weibull analysis can inc-tu-i ^ --- ur ....... wúmo.KQ. statistically significant number of grinding samples, which can range from about 10 to about 50 individual grinding samples, or from about 20 to about 40 individual grinding samples. In one embodiment, a sample size between about 25 and about 30 samples can be used in the analysis for individual particle grinding. All resistance data points can then be classified from low to high as σι &lt;σ2 &lt;σ3 &lt;... &lt;σ_Ν, where N represents the total number of samples. A probability of failure can be calculated from the equation:

where, as before, N is the total number of samples, for example about 30 samples, and # is the index number for the ranked resistance values ​​(for example, 1 through N). by graphing a linear graph can be obtained

<img file="MX347993B_D0017.tif" />

<img file="MX347993B_D0018.tif" />

Λ \ η k ln k

against

1 «(σ)

IMPI

INSTITUTO MEXICANO • F LA PROWtDAO INDUSTSIAt

A Weibull distribution can be found by linear fit and by generating an equation:

1 «(k σ \^σο) where m is the Weibull modulus and σ is the characteristic resistance. The resistance will tend to increase along with the reliability of the resistance calculation when the σ values ​​increase.₀ and m. The characteristic resistance changes in the particles can then be determined. By comparing the characteristic resistance of the particles before exposure to the simulated formation fluid with the characteristic resistance of the particles after exposure to the simulated formation fluid, a conserved resistance can be calculated from the equation:

^ Oconserved exposed asm expose and where σ₀ exposed is the characteristic resistance of the particles after exposure to the simulated formation fluid

And σ₀ without exposing characteristic of the particles before exposure. Pe ... Similarly, a conserved permeability can be calculated by dividing the permeability measured at the end of the temperature-stimulated diagenesis test with the permeability measured at the beginning.

In one embodiment, a single set of test conditions can be used for the comparison of different sets of particles that comprise diffusion barriers and / or fillers. It is defined that the conserved strength value will be measured by the stress / temperature stimulated diagenesis test.

In this method, a test column is loaded with a packet of particles and filled with a saline solution comprising a KC1 solution of approximately 2%. The test cell is loaded with approximately 21.36 kg / m² (2 lb / ft² ) of particles. Formation wafers are placed above and below the particles in the test cell. The system is then closed and placed under a pressure that will be approximately equal to the pressure expected in the formation in which the particles are expected to settle. The temperature can be maintained at a temperature that is approximately equal to the formation temperature where the particles are expected to be placed. For example, him⁴⁵ IMPI

ΙΗΓΠΤυΤΟ system can be placed under simulated pressure ** of approximately 632.79 kg / cm² f qp / iO ·. ·). and ..nn? ...

temperature of approximately 121.11 ° C (250 ° F). These conditions are then maintained for approximately 28 days.

With the completion of the stress / temperature stimulated diagenesis test, the test cell is disassembled and the particle matrix is ​​removed for testing. Changes in the mechanical properties of the particles are obtained using particles tested using the stress / temperature stimulated diagenesis test. The analysis uses a statistical analysis procedure

Weibull based on a plurality of samples for particle crushing, as discussed above. An individual analysis includes a statistically significant number of samples, which can be between about 20 and about 40 samples, for example, from about 30 individual particle crushed samples. However, in some cases, the sample size can vary such that the actual number of samples is smaller or larger to obtain a statistically significant number of samples. The characteristic resistance changes in the particles can then be determined. When comparing the characteristic resistance of the «IMPI ^

MUiCAN INSTITUTE *

D € LA FVO? IEDM V2 ** ®P * particles before exposure to the simulated fluid d ^ 'Tb'fmaSton with the characteristic resistance of the particles after exposure to the simulated formation fluid, from the equation is calculated a value of conserved strength ^ Qconserved ^ Oexposed ^ Osno exposed, where σ_{0 and}xp_uesta is the characteristic resistance of the particles after exposure to the simulated formation fluid, and σο unexposed is the characteristic resistance of the particles before exposure.

Similarly, it is defined that the conserved permeability value of the particle pack will be measured by the temperature-stimulated diagenesis test. In the temperature-stimulated diagenesis test procedure, an initial permeability measurement is made of a particle package while the particle package is at room temperature. Deionized water is then heated to a test temperature of approximately 260 ° C (500 ° F) by passing it through a heat exchange coil. Lower test temperatures can also be used depending on the specific particulate material and coating used. For example,

IMPIO '. . . . .... someone with normal experience in the art may know that a test temperature is required for the thermal decomposition of the particles, the diffusion barrier, or the filler material. The simulated forming fluid is formed by passing deionized water through multiple packages of crushed forming material arranged in series. The number of formation packs required for testing can be varied such that the simulated formation fluid allows the last pack to be in equilibrium with the crushed formation material at the flow rate used during the test of approximately 1 milliliter per minute . The typical number of training packages in general is between about 2 and about 5. The crushed forming material is screened and an 8/35 mesh fraction is used in the forming packages. Formation material is obtained by crushing a core removed from a specific well during drilling or from drill chips obtained while the well is being drilled for drilling through a zone of interest.

The simulated formation fluid is then directed to a column containing a particle packet. The temperature in the particle package is maintained at a temperature of approximately 260 ° C (500 ° F). You can use a coating particle material temperature used.

minor test

IMPIAS specific Mexican institute and. the ,, thicket · - of

For example, one of ordinary skill in the art may determine that a lower test temperature is required to avoid thermal decomposition of the particles, the diffusion barrier, or the filler material. A mock-forming secretion flow rate is maintained at approximately 1 milliliter per minute during the test. The flow test is maintained for approximately 30 days. After this time, the permeability of the particle pack is measured before disassembly and after the particle pack has been allowed to cool to room temperature, allowing a conserved permeability to be calculated from the equation:

Permeability _comda 'Permeability ^,'

Permeability ^_{exf&gt; uner and} where, Permeability_exposed is the permeability of the particles after exposure to the simulated formation fluid, and Permeability_Si_n expose is the permeability of the particles before exposure.

The particles prepared and tested according to the methods of the present invention using the

IMPI mode characteristic conditions conserved resistance value greater than ^ about the. twenty%. Alternatively, the particles may exhibit a conserved strength value greater than about 60%. In still another embodiment, the particles may exhibit a conserved strength value greater than about 80%. In still another embodiment, the particles may exhibit a conserved strength value greater than about 90%. In one embodiment, the particles used to form a package can be characterized by a conserved permeability value of at least about 40%. In another embodiment, the particles can be characterized by a preserved permeability of at least about 60%. In still another embodiment, the particles can be characterized by a retained permeability of at least about 80%. In some embodiments, the preserved permeability can be at least about 99%.

Therefore, the present invention will be adapted to obtain the aforementioned ends and advantages as well as those that are inherent herein. The particular modalities set out above are only illustrative, since the present invention can be modified and practiced in different but equivalent ways, which "IMPIOS

ΙΝΓΓΓΤυΤΟ ΜΕ * (CAH ·. A?

, Dt LA ΧΜΪΠΠΜΙ is evident for those experts in the .technic ^^! ^ Teñq &amp; n described in the claims below. Therefore, it will be apparent that the particular illustrative embodiments set forth above may be altered or modified and all such variations are considered to be within the scope and spirit of the present invention. While the compositions and methods are described in terms of comprising, containing, or including various components or steps, the compositions and methods can also consist essentially of or consist of the various components and steps. All of the numbers and variations listed above may vary by some amount. Wherever a numerical variance with a lower bound and an upper bound is exposed, any number and any included variance that fall within the variance are exposed. In particular, each variation of values ​​(of the form, from about a to about b. or, equivalently, from about a to b or, equivalently, from about b) set forth herein are to be understood to establish each number and variation encompassed within the broader variation of ⁵¹ IMPI

MEXICAN INSTITUTE. _m .. . _Ί , -A _ _ η OBLA r * pHJDV · values. Also, the terms in reiVMW4. &lt;: AíS3E3sr have their clear meaning, norm unless¹ what¹· Explicitly and clearly defined otherwise by the owner. Furthermore, the indefinite articles one or one, as used in the claims, are defined herein to mean one or more than one of the elements presented. If there is any conflict in the uses of a word or term in this specification and one or more patent or other documents that may be incorporated herein by reference, definitions that are consistent with this specification shall be adopted.

IMPI ^

NOVELTY OF THE INVENTION industrial ^ 5 * ^

Having described the present invention, it is considered as a novelty and, therefore, the content of the following is claimed as property