# Patent

## Title
Proppants for hydraulic fracturing technologies

## Abstract

The invention is directed to systems and methods for forming and using proppant particles having desirable attributes.

## Background
RELATED APPLICATION
This application is a division of application Ser. No. 12/908,411, filed Oct. 20, 2010, which claims the benefit of U.S. Provisional Application No. 61/253,359, filed Oct. 20, 2009. The entire teachings of the above applications are incorporated herein by reference.


FIELD OF APPLICATION
This application relates generally to systems and methods for fracturing technologies.
BACKGROUND
In the process of acquiring oil and/or gas from a well, it is often necessary to stimulate the flow of hydrocarbons via hydraulic fracturing. The term fracturing refers to the method of pumping a fluid into a well until the pressure increases to a level which is sufficient to fracture the subterranean geological formations containing the entrapped materials. This results in cracks and breaks that disrupt the underlying layer to allow the hydrocarbon product to be carried to the well bore at a significantly higher rate. Unless the pressure is maintained, the newly formed openings close. In order to open a path and maintain it, a propping agent or proppant is injected along with the hydraulic fluid to create the support needed to preserve the opening. As the fissure is formed, the proppants are delivered in a slurry where, upon release of the hydraulic pressure, the proppants form a pack or a prop that serves to hold open the fractures.
The behavior of the proppants in the fracturing fluids has to meet certain performance requirements. First, in order to place the proppants inside the fracture, proppant particles are suspended in a fluid that is then pumped to its subterranean destination. To prevent the particles from settling, a high viscosity fluid is often required to suspend them. The viscosity of the fluid is typically managed by addition of synthetic or natural based polymers. If the particles were more buoyant, a less viscous suspension fluid could be used, which would still convey the particles to the target area but which would be easier to pump into the formation. Second, it is desirable that the proppants remain where they are placed throughout the lifetime of the well after they have been injected into a fracture line. If changes within the reservoir during well production force the proppants out of position, production equipment can be damaged, and the conductivity of the reservoir formation can be decreased as its pores are plugged by the displaced proppants. Third, the proppants in the system should be resistant to closure stress once they are placed in the fracture. Closure stresses can range from 1700 psi in certain shale gas wells, up to and exceeding 15,000 psi for deep, high temperature wells. Care must be taken that the proppants do not fail under this stress, lest they be crushed into fine particles that can migrate to undesirable locations within the well, thereby affecting production. Desirably, a proppant should resist diagenesis during fracture treatment. The high pressures and temperatures combined with the chemicals used in fracturing (frac) fluids can adversely affect the proppant particles, resulting in their diagenesis, which can eventually produce fine particulate matter that can scale out and decrease the productivity of the well over time.
Current proppant systems endeavor to address these concerns, so that the proppants can be carried by the fracturing fluids, can remain in place once they arrive at their target destination, and can resist the closure stresses in the formation. One approach to preparing suitable proppants includes coating the proppant materials with resins. A resin-coated proppant can be either fully-cured or partially-cured. The fully-cured resin can provide crush resistance to the proppant substrate by helping to distribute stresses among the grain particles. A fully-cured resin can furthermore help reduce fine migration by encapsulating the proppant particle. If initially partially-cured, the resin may become fully cured once it is placed inside the fracture. This approach can yield the same benefits as the use of a resin that is fully-cured initially. Resins, though, can decrease the conductivity and permeability of the fracture, even as the proppants are holding it open. Also, resins can fail, so that their advantages are lost. Finally, resin-based systems tend to be expensive.
Another approach to preparing suitable proppants involves mixing additives with the proppant itself, such as fibers, elastomeric particles, and the like. The additives, though, can affect the rheological properties of the transport slurry, making it more difficult to deliver the proppants to the desired locations within the fracture. In addition, the use of additives can interfere with uniform placement of the proppant mixture into the fracture site. While there are known methods in the art for addressing the limitations of proppant systems, certain problems remain. There is thus a need in the art for improved proppant systems that allow precise placement, preserve fracture conductivity after placement, and protect well production efficiency and equipment life. It is further desirable that such improved systems be cost-effective.
SUMMARY
The invention is directed to composite proppant particles, and systems and method for the use thereof.
In certain aspects, the invention is directed to a composite proppant particle, comprising:
a proppant particulate substrate,
an inner polymeric layer deposited on the particulate substrate, and
a hydrophilic outer coating layer deposited upon the first layer or on an optional intermediate layer,
wherein the inner layer comprises a first polymeric material and the outer layer comprises a second polymeric material.
In another aspect, the invention is directed to an aggregate proppant particle comprising:
a first proppant particulate substrate, and
a second proppant particulate substrate affixed thereto,
wherein the first proppant particulate substrate comprises a dense material and the second proppant particulate substrate comprises a lower density material.
In one embodiment of the composite proppant particle of the invention, the proppant particulate substrate is an aggregate proppant particle.
The invention also encompasses a proppant system, wherein the system comprises
the composite proppant particle and/or aggregate proppant particle of the invention and a fluid delivery vehicle.
In another embodiment, the invention is directed to a treatment fluid comprising a fracturing fluid and a multiplicity of composite proppant particles, wherein the composite proppant particles are suspended in the fracturing fluid and wherein the composite proppant particle comprise:
a proppant particulate substrate,
an inner polymeric layer deposited on the particulate substrate, and
a hydrophilic, outer coating layer deposited upon the first layer or on an optional intermediate layer,
wherein the inner layer comprises a first polymeric material and the outer layer comprises a second polymeric material.
The invention also encompasses a method of fracturing a subterranean geological formation comprising introducing into said formation a treatment fluid wherein the fluid comprises suspended composite proppant particles, wherein each composite proppant particle comprises:
a proppant particulate substrate,
an inner polymeric layer deposited on the particulate substrate, and
a hydrophilic, outer coating layer deposited upon the first layer or on an optional intermediate layer,
wherein the inner layer comprises a first polymeric material and the outer layer comprises a second polymeric material.


DETAILED DESCRIPTION
Disclosed herein are compositions and systems comprising proppant particles and methods for forming and using proppant particles having desirable attributes such as a lower friction coefficient in the wet state, good bonding adhesion with each other after placement in a fracture site, resistance to uncontrolled fines formation, and hydrophilic surface properties to prevent fouling. In embodiments, the disclosed systems for forming proppant particles can be applied to the types of proppant substrates most widely used, e.g., sand and ceramics. In other embodiments, the proppant particles can be formed from a variety of substrates, as would be available to those having ordinary skill in the art. In certain embodiments, the proppant particles can be fabricated so that they resist crush or deformation, so that they resist displacement, and so that they can be suspended in less viscous fluid carriers for transporting into the formation.
In embodiments, the surface of a proppant particulate substrate can be coated with a selected polymer, either as a single layer or as a series of multiple coating layers. The coating (either single layer or multilayer) can show switchable behavior under certain circumstances. As used herein, the term “switchable behavior” or “switching behavior” refers to a change in properties with a change in circumstances, for example, a change from one set of properties during the transport phase and another set of properties inside the fracture. Switching behavior can be seen, for example, when a particle demonstrates hydrophilic properties in the fracturing fluid and adhesive properties when in place within the fractures. Such behavior can be triggered by circumstances like the high closing pressures inside the fracture site so that the outer layer of the coating rearranges itself to exhibit more advantageous properties.
In more detail, the coated particle can switch from hydrophilic to hydrophobic when subjected to the high pressures inside the fractures. During the transport phase, when the hydrophilic covering of the particle is exposed to the water-based fracturing fluid, it will tend to be fully distended. As a result, the coating will provide the particle with lubrication, facilitating its movement through the proppant slurry. When the particle has been conveyed to its destination within the fractures in the formation, the high pressures there will overcome the steric repulsions of the external hydrophilic polymer chains, forcing the outer layer to rearrange itself so that the inner layer is exposed. In embodiments, the switchable inner layer can be hydrophobic or adhesive, or both. As the inner layer becomes exposed, its properties manifest themselves. If the inner layer has adhesive properties, for example, it can fix the particles to each other to prevent their flowback. This inner layer can also be configured to capture fines in case the proppant particle fails. Moreover, the residual intact hydrophilic groups present in the outer coating can allow easy flow of oil through the proppant pack.
In embodiments, a coated proppant particle can be produced that bears the following layers of coating. First, a pressure-activated fixative polymer can be used to coat the proppant substrate. This coating layer can be elastomeric, thereby providing strength to the proppant pack by helping to agglomerate the proppant particles and distribute stress. In addition, this coating layer can encapsulate the substrate particles and retain any fines produced in the event of substrate failure. Second, a block copolymer can be adsorbed or otherwise disposed onto the first layer of coating. The copolymer can have a section with high affinity for the first polymeric layer, allowing strong interaction (hydrophobic interaction), and can have another section that is hydrophilic, allowing for easy transport of the proppant in the transport fluid.
In certain embodiments, a stronger interaction between the first and second coating layers may be useful. To accomplish this, a swelling-deswelling technique can be implemented. For example, the block copolymer can be adsorbed onto the surface of the elastomeric-coated particle. Then, the first coating layer can be swelled with small amount of an organic solvent that allow the hydrophobic block of the copolymer to penetrate deeper into the first coating layer and to become entangled in the elastomeric coating. By removing the organic solvent, the layered polymeric composite will deswell, resulting in a stronger interaction of copolymer with the elastomeric particle. A method for swelling-deswelling technique is set forth in “Swelling-Based Method for Preparing Stable, Functionalized Polymer Colloids,” A. Kim et al., J. Am. Chem. Soc (2005) 127: 1592-1593, the entire contents of which are incorporated by reference herein.
While the systems described herein refer to a two-layer coating system, it is understood that there may be multiple coating layers forming the composite proppant particles disclosed herein, with the each of the multiple coating layers possessing some or all of the attributes of the two coating layers described in the exemplary embodiments.
1. Particulate Substrate Materials
Composite proppant particles in accordance with these systems and methods can be formed using a wide variety of proppant substrate particles. Proppant particulate substrates for use in the present invention include graded sand, resin coated sand, bauxite, ceramic materials, glass materials, walnut hulls, polymeric materials, resinous materials, rubber materials, and the like. In embodiments, the substrates can include naturally occurring materials, for example nutshells that have been chipped, ground, pulverized or crushed to a suitable size (e.g., walnut, pecan, coconut, almond, ivory nut, brazil nut, and the like), or for example seed shells or fruit pits that have been chipped, ground, pulverized or crushed to a suitable size (e.g., plum, olive, peach, cherry, apricot, etc.), or for example chipped, ground, pulverized or crushed materials from other plants, such as corn cobs. In embodiments, the substrates can be derived from wood or processed wood, including but not limited to woods such as oak, hickory, walnut, mahogany, poplar, and the like. In embodiments, aggregates can be formed, using an inorganic material joined or bonded to an organic material. Desirably, the proppant particulate substrates will be comprised of particles (whether individual substances or aggregates of two or more substances) having a size in the order of mesh size 4 to 100 (US Standard Sieve numbers). As used herein, the term “particulate” includes all known shapes of materials without limitation, such as spherical materials, elongate materials, polygonal materials, fibrous materials, irregular materials, and any mixture thereof.
In embodiments, the particulate substrate can be formed as a composite from a binder and a filler material. Suitable filler materials can include inorganic materials such as solid glass, glass microspheres, fly ash, silica, alumina, fumed carbon, carbon black, graphite, mica, boron, zirconia, talc, kaolin, titanium dioxide, calcium silicate, and the like. In certain embodiments, the proppant particulate substrate can be reinforced to increase its resistance to the high pressure of the formation which could otherwise crush or deform them. Reinforcing materials can be selected from those materials that are able to add structural strength to the proppant particulate substrate, for example high strength particles such as ceramic, metal, glass, sand, and the like, or any other materials capable of being combined with a particulate substrate to provide it with additional strength.
In certain embodiments, the proppant particulate substrate can be fabricated as an aggregate of two or more different materials providing different properties. For example, a core particulate substrate of a dense material, preferably having high compression strength, can be combined with a material having a lower density than the high-compression-strength material. In one embodiment, the material having high compression strength is a dense material. A “dense material”, as this term is used herein, is a material having a density greater than about 1.5 g/cm3, preferably in the range of 1.5 to 3 g/cm3. A “lower density material” is a material having a density less than the density of the dense material. In an embodiment, the lower density material has a density which is from about 0.1 to about 2.5 g/cm3 less than that of the dense material. In an embodiment, the lower density material has a density less than about 1.5 g/cm3. The combination of these two materials as an aggregate can provide a core particle having an appropriate amount of strength, while having a lower density than the dense material. Preferably, the lower density material is buoyant in the medium in which the proppant is to be suspended. In one embodiment, the medium is a fracturing fluid. The fracturing fluid can be water or an aqueous solution having a density from about 1 g/cm3 to about 1.4 g/cm3. As a lower density particle, it can be suspended adequately in a less viscous fracturing fluid, allowing the fracturing fluid to be pumped more easily, and allowing more dispersion of the proppants within the formation as they are propelled by the less viscous fluid into more distal regions. High density materials used as proppant particulate substrates, such as sand, ceramics, bauxite, and the like, can be combined with lower density materials such as hollow glass particles, other hollow core particles, certain polymeric materials, and naturally-occurring materials (nut shells, seed shells, fruit pits, woods, or other naturally occurring materials that have been chipped, ground, pulverized or crushed), yielding a less dense aggregate that still possesses adequate compression strength.
As used herein, the term “buoyant” refers to particles or materials having either neutral or positive buoyancy with respect to the suspending medium, such that the particles have a lower density than the suspending medium and they do not settle in the direction of gravity.
Aggregates suitable for use as proppant particulate substrates can be formed using techniques to attach the two components to each other. As one preparation method, a proppant particulate substrate can be mixed with a lower density material having a particle size similar to the size of the proppant particulate substrates. The two types of particles can then be mixed together and bound by an adhesive, such as a wax, a phenol-formaldehyde novolac resin, etc., so that a population of doublet aggregate particles are formed, one subpopulation having a proppant particulate substrate attached to another similar particle, one subpopulation having a proppant particulate substrate attached to lower density particle, and one subpopulation having a low density particle attached to another lower density particle. The three subpopulations could be separated by their difference in density: the first subpopulation would sink in water, the second subpopulation would remain suspended in the liquid, and the third subpopulation would float.
In other embodiments, a proppant particulate substrate can be engineered so that it is less dense by covering the surface of the particulate substrate with a lower density coating comprising, for example, a foamy material. The thickness of the foamy material can be designed to yield a composite that is effectively neutrally buoyant. To produce such a coated proppant particulate, a particle having a desirable compression strength can be coated with one reactant for a foaming reaction, followed by exposure to the other reactant. With the triggering of foam formation, a foam-coated proppant particulate will be produced.
As an example, a water-blown polyurethane foam can be used to provide a coating around the particles that would lower the overall particle density. To make such a coated particle, the particle can be initially coated with Reactant A, for example a mixture of one or more polyols with a suitable catalyst (e.g., an amine). This particle can then be exposed to Reactant B containing a diisocyanate. The final foam will form on the particle, for example when it is treated with steam while being shaken; the agitation will prevent the particles from agglomerating as the foam forms on their surfaces.
The foamy material can be applied to an uncoated proppant particle or a proppant particle having a single coating layer, such as an inner coating layer and optional intermediate layers as described herein. In an embodiment, the foamy material is applied to a composite proppant particle of the invention. In another embodiment, the proppant particle is a composite particle of the invention and the foamy layer is hydrophilic and is the outer layer of the composite particle.
2. Inner Polymeric Layer
In designing the polymers for the inner polymeric layer, a variety of pressure-sensitive adhesive polymers can be used, having different functionalities and molecular weights. As used herein, the inner polymer layer is the first coating layer that is applied to the proppant particulate substrate. Polymeric design for this inner polymeric layer can be directed by such variables as chemical resistance, ultimate adhesion, service temperature, and the like, so that a coating material can be selected that is targeted to the projected proppant usage temperature. The coating can be optimized to produce strong adhesion among proppant particles at different temperatures. For example, in formulating the inner polymeric layer, it will be recognized that the temperature in the formation is relatively high (from 30° to 100° C.), so that an adhesive would need to be designed to withstand such high temperatures while still retaining its stickiness. A formulation may be required comprising polymers with relatively high glass transition temperatures, for example, in order to withstand these high temperatures.
In embodiments, coating thickness can be varied, which can have specific effects on the strength of adhesion of the proppant particles as well. Appropriate coating methods can include solution coating or in-situ coating where the polymer is synthesized in the presence of the proppant substrate particle.
In embodiments, the inner polymeric layer can be made from a phenolic resin, an epoxy resin, a furan resin, a phenolic formaldehyde resin, a melamine formaldehyde resin, a urethane resin, a phenolic, furan resin mixture, a urea-aldehyde resin, a urethane resin, a furan/furfuryl alcohol resin, a phenolic/latex resin, a polyester resin, an acrylate resin, or a combination of two or more thereof. In another embodiment of the invention, the inner polymeric layer with adhesive material can be a thermoplastic resin. Examples of suitable thermoplastic resins include: styrene block copolymers such as: SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), SEBS (styrene-ethylene/butylene-styrene), SEP (styrene-ethylene/propylene); ABS copolymers (i.e., acrylonitrile-butadiene-styrene); EVA (ethylene vinyl acetate) copolymers; acrylic polymers; vinyl ethers; and silicone rubbers. A commercial thermoplastic, for example the ENABLE family of products available from ExxonMobil Chemical Co, can be used; these materials are a family of n-butyl acrylate copolymers (e.g., ENABLE EN 33900 and 60 ENABLE 33330).
In embodiments, these materials can be mixed with other resins (tackifiers) that will increase their stickiness. Examples of tackifiers are: rosins and their derivatives, terpenes and their derivatives, shellac resin, small molecular weight aliphatic, cycloaliphatic and aromatic resins (less than 10 carbons), terpene-phenol resin, saturated hydrocarbon resin. As an example of composition, the tackifier agent can comprises 30-70% by weight of the combined weight of tackifier agent and thermoplastic resin.
In embodiments, the inner polymeric layer can be applied to the particulate substrate by methods familiar to artisans of ordinary skill. For example, the application of the inner layer can be performed by solution coating or by 100% solid coating (no solvent needed). In embodiments, the inner layer can be applied in an amount of 0.25 to 10 weight percent of the proppant substrate, for example, in an amount of 0.5 to 5 percent.
3. Outer Coating Layer
It is desirable to impart hydrophilic features to the coated particle. In the aqueous environment of the hydraulic fracturing fluid, a hydrophilic coating can create a thin, water-like layer on the surface of the particle, making it slippery and reducing the friction between particles. This can facilitate the transport of the particles in the fluid.
A second coating layer can be applied as an outside layer to provide the desirable hydrophilic features to the overall particle. In other embodiments, one or more intermediate layers can be applied to the particle, then the outermost hydrophilic layer can be provided. In the description that follows, the second coating layer forms the outer coating of the particle. It is understood, though, that the outer hydrophilic coating may be applied to any number of inner, intermediate layers, while still maintaining the advantageous properties of the particles in accordance with the present disclosure.
In embodiments, the outer layer can be partially or wholly formed from a polymer. For example, a suitable block copolymer can be designed having hydrophobic and hydrophilic sections or regions. Variables involved in copolymer design include the molecular weight of polymer, ratio of hydrophobic to hydrophilic section, and the functionalities of the copolymer. The outer layer, for example a second coating layer, can be adsorbed onto the first layer or onto an intermediate layer using conventional methods of polymer adsorption, as would be known in the art, and/or swelling-deswelling using organic solvents.
In embodiments where a polymer layer is used as the outer coating layer, the polymer coating can be made from hydrophilic polymers like ethylene oxide/propylene oxide (EO/PO) copolymers, polyvinyl acetate, polyethylene-co-vinyl acetate, polyvinyl alcohol, polysaccharides, and the like. In embodiments, the outer layer can be fabricated from block copolymers having hydrophilic and hydrophobic segments. Such materials can be diblock, triblock or multiblock copolymers. For example, an ethylene oxide/propylene oxide block copolymer can be used, for example the Pluronic family of copolymers (BASF). As another example, Guerbet alcohol ethoxylates, lauryl alcohol-tridecyl alcohol-stearyl alcohol-nonylphenol- or octylphenol-ethoxylates, for example the Lutensol family of products (BASF). In embodiments, the selected materials will have a high hydrophilic-lipophilic balance, so that the product is substantially more hydrophilic than hydrophobic. Examples of such materials include certain stearyl alcohol and nonylphenol-ethoxylates.
In embodiments, the outer layer can be applied to the first layer or to an intermediate layer using a swelling-based method. According to such a method, the first layer or an intermediate layer can be exposed to a solvent that can swell this layer without dissolving it. The polymer for the second layer, having both hydrophilic and hydrophobic segments, can be dissolved in the same solvent. When the solution bearing the second layer polymer is put into contact with the particles bearing the swollen first layer, the hydrophobic segments of the polymer will tend to interact with the hydrophobic first layer, resulting in entanglement of the two hydrophobic entities. When the solvent is removed, the first layer will deswell, locking the hydrophobic attachments of the second-layer polymer in place. The hydrophilic segments of the second-layer polymer will be directed outwardly, away from the inner layer.
In other embodiments, the outer layer can be formed by chemical reaction or modification of the inner polymer layer or an intermediate layer. For example, the outer surface of the inner polymer layer or an intermediate layer can be oxidized, etched, epoxidized, ethoxylated, hydrolyzed, or otherwise coated to protect the inner polymer layer from the fluid environment in the fracture.
EXAMPLES
Example 1
Preparation of Inner Polymeric Layer Material
A material suitable for the inner polymeric layer of a coated proppant particle can include a pressure sensitive adhesive. Such an adhesive can be prepared as follows:
15 gm of a 10 wt % tetrahydrofuran solution of Polystyrene-block-polyisoprene-block-polystyrene (22 wt % styrene and a viscosity of 750-1250 cps at a 25% solution in toluene at 25° C.) (Aldrich) was mixed with 15 g of a 10 wt % tetrahydrofuran solution of Colophony rosin gum (acid value of 150-170) (Aldrich).
Example 2
Coating Sand Particles with Inner Polymeric Layer Material
Quartz sand particles (50-70 mesh particle size) (Aldrich) were coated with 0.5 wt % of the material prepared in Example 1 by solution coating using the following procedure:
30 gm of the solution from Example 1 was added to approximately 270 gm of tetrahydrofuran in a 1 liter round bottom flask, and mixed thoroughly. Once the solution was homogeneous, 300 g of the quartz sand was added. The solvent was then evaporated under vacuum in a rotary evaporator to yield sand particles with adhesive properties. The coated sand particles were further characterized in Examples 4 and 5 below.
Example 3
Applying an Outer Polymeric Layer to the Coated Sand Particles
To 100 ml of ethyl alcohol (Aldrich) was added 0.5 g of PLURONIC® F127 Prill (BASF 100 Campus Drive, Florham Park, N.J. 07932). The mixture was stirred under mild heat until the entire solid dissolved. To the resulting solution was added 100 g of the product from Example 2. The mixture was stirred for 30 minutes and the solvent evaporated under vacuum in a rotary evaporator to yield sand particles with adhesive and hydrophilic properties. The coated sand particles were further characterized in Examples 4 and 5 below.
Example 4
Characterization of Frictional Forces Between Coated Sand Particles
Coated sand particles prepared in accordance with Examples 2 and 3 were analyzed by the high solids rheology test. Control samples (Aldrich) without any treatment (as-received sand) were tested along with the samples prepared in accordance with Example 2 and Example 3. All samples were analyzed in the dry and water wet state (a minimum amount of water was added to the dry sample to wet all the particles). A Brookfield model DV-III Viscometer with a #4 spindle was employed. The test was performed by rotating the spindle at 20 rpm for 1 minute: then the applied torque was turned off and the maximum torque at this point was recorded. The results of these tests are set forth in Table 1.










TABLE 1







Sample
% Torque - Maximum









As-received sand - Dry
  28.1



As-received sand - Wet
  42.8



Example 2 - Dry
>100(*)



Example 2 - Wet
>100(*)



Example 3 - Dry
>100(*)



Example 3 - Wet
50







(*)110% Torque is the maximum reading for the instrument






The maximum torque, as measured by these tests, gives an indication of the frictional forces between particles. The higher values of Maximum % Torque for particles in Example 2 and 3 compared to the as-received sand, indicate that the coating applied to the sand act as an adhesive, consolidating the particles together and increasing the maximum torque needed to rotate the spindle. The comparison of the Maximum % Torque of the wet samples in Example 2 with the samples prepared in Example 3 shows a smaller value for Example 3 sample, indicating that the second layer (which is hydrophilic) has affected the surface of the particles so as to provide better lubrication when water-wet.
Example 5
Characterization of Cohesiveness of Coated Sand Particles
A 5 gm sample of the particles prepared in each of Examples 2 and 3, and 5 gms of the control samples (Aldrich) as received was placed on a stainless steel circular plate (2.24 inches diameter). Another plate of same shape and size was placed on top of the sample. Then the 2 plates containing the sample were placed in a Carver Laboratory Press (Model C) and the desired pressure applied (1269, 2539 or 3808 psi) for 1 minute. Next, the top plate was carefully removed and the amount of sample adhered to it weighted. The bottom part of the mold was then elevated at an angle of approximately 45° and tapped several times. The amount of sample adhering to the plate was then removed and weighed. The results are set forth in Table 2.











TABLE 2









Example 2
Example 3
As-received sand














Weight/
Weight/
Weight/
Weight/
Weight/
Weight/


Pres-
g
g
g
g
g
g


sure/
Top
Bottom
Top
Bottom
Top
Bottom


psi
plate
plate
plate
plate
plate
plate
















1269
0
0.561
0
0.522
0
0


2539
0
2.335
0
0.581
0
0


3808
0.411
3.711
0
1.009
0
0









The results in Table 2 indicate that the as-received sand does not stick to the plates at all. For samples from Example 2 and 3 there is a fraction of the sample that remained on the plates, demonstrating the cohesiveness of the particles. At the higher applied pressure, a larger amount of the samples remained on the plates. More of the samples from Example 2 remained attached to the plates at both pressure levels, indicating higher cohesiveness than for Example 3.
Example 6
Preparation of Polyurethane-Foam-Encapsulated Sand Particles
Polyurethane-foam-encapsulated sand particles can be prepared as follows:
A prepolymer of poly(propylene oxide) glycol and 2,4-toluenediisocyanate can be prepared by placing 200 g of dried polypropylene glycol (molecular weight 2,000, hydroxyl number 56.1) in a reactor equipped with a stirrer, condenser with drying tube, thermometer and gas inlet with nitrogen flush. Next, 0.8 g of water can be added. After stirring the mixture for a few minutes, 29.4 g of toluene diisocyanate can be added. The mixing can be continued and the temperature increased to 110° C. for 1 hour. The resulting material is a prepolymer ready to be coated and foamed onto the sand particles.
25 gm of 50-70 mesh sand can then be placed in a plastic container. To this can be added 1 g of the prepolymer prepared in the previous step and 1 drop of triethylamine. The mixture can be mixed in a speed mixer at 3,000 rpm for 1 minute to yield homogeneously coated sand particles. Next the coated particles were placed in an oven at 100° C. for 30 minutes while steam is flown though it in order to finalize the foaming process. The foam as described in this Example would be designed to have a density of approximately 40 kg/m3. The coating encapsulating the sand particles would comprise about 50% by volume of the total volume of the coated particle. The thickness of the coating has been designed to give a neutral buoyant particle according to Stokes' law.
Example 7
Preparation of Sand Particle Attached to Buoyant Particles
This experiment shows a method of attaching low density particles to sand to yield composite particles with improved buoyant properties. In a plastic container was placed 2.68 gm of sand (50-70 mesh size from Aldrich), 0.63 g of 3MTM Glass Bubbles K20 (hollow glass microspheres with density 0.2 g/cm3), and 0.3 g of a paraffin wax (53-57° C.) from Aldrich. The mixture was mixed in a speed mixer at 3,000 rpm for 5 minutes. The resulting product was a homogeneous free flowing solid. The sample was characterized by comparing the settling rate of the glass-bubbles-treated sand with the as-received sand in water (control). To characterize the samples, 2 burettes were filled with water; and approximately 0.5 g of the treated and as-received sand was added to each burette. The settling rate for each sample was monitored by following the time needed for the particles to reach the bottom of the burette. The results indicated that for the treated sand the settling rate was approximately half of the as-received sand, showing the improved buoyant properties of the treated sand.
EQUIVALENTS
While specific embodiments of the subject invention have been disclosed herein, the above specification is illustrative and not restrictive. While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims. Many variations of the invention will become apparent to those of skilled art upon review of this specification. Unless otherwise indicated, all numbers expressing reaction conditions, quantities of ingredients, and so forth, as used in this specification and the claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties sought to be obtained by the present invention.

## Claims

1. A method of fracturing a subterranean geological formation comprising introducing into said formation a treatment fluid wherein the fluid comprises an aqueous hydraulic fracturing fluid and suspended proppant particles having hydrophilic properties while suspended during transport, wherein the suspended proppant particles comprise:
a proppant particulate substrate,
an inner polymeric layer made from a first polymeric material deposited on the particulate substrate, and
a distended hydrophilic outer coating layer made from a second polymeric material deposited upon the first layer, wherein the distended hydrophilic outer coating layer comprises a hydrophilic polymer selected from the group consisting of EO/PO copolymers, polyvinyl acetate, polyethylene-co-vinyl acetate, polyvinyl alcohol, polysaccharides and combinations thereof, wherein the second polymeric material is selected so that
(a) when this outer coating layer is exposed to the aqueous fracturing fluid, it distends and imparts hydrophilic properties to the suspended proppant particles, and
(b) the outer coating layer protects the inner polymeric layer from the fluid in the fracture.

2. The method of claim 1, wherein the inner polymeric layer comprises a pressure sensitive polymeric adhesive.

3. The method of claim 1, wherein the first polymeric material comprises a hydrophobic polymer.

4. The method of claim 1, wherein the outer coating layer is affixed to the inner polymeric layer.

5. The method of claim 4, wherein the outer coating layer is affixed to the inner polymeric layer by swelling-deswelling.

6. The method of claim 1, wherein the proppant particulate substrate comprises sand.

7. The method of claim 1, wherein the proppant particulate substrate comprises ceramic.

8. The method of claim 1, wherein the proppant particulate substrate has a specific gravity from about 1.0 to about 2.7 g/cc.

9. The method of claim 1, wherein the proppant particulate substrate comprises a material having lower density than sand.

10. The method of claim 1, wherein the inner polymeric layer is deposited on the proppant particulate substrate by solution coating.

11. The method of claim 1, wherein the inner polymeric layer is deposited on the proppant substrate particle by in-situ coating.

12. The method of claim 1, wherein the inner polymeric layer comprises a polymer selected from the group consisting of phenolic resins, epoxy resins, furan resins, phenolic formaldehyde resins, melamine formaldehyde resins, urethane resins, phenolic/ furan resin mixtures, urea-aldehyde resins, furan/furfuryl alcohol resins, phenolic/latex resins, polyester resins, acrylate resins, and combinations thereof.

13. The method of claim 1, wherein the outer coating layer comprises a block copolymer having hydrophilic and hydrophobic sections.

14. The method of claim 1, wherein the outer coating layer is produced by chemical modification of the inner layer or an intermediate layer.

15. The method of claim 1, further comprising a low density layer external to the outer coating layer.

16. The method of claim 15, wherein the low density layer comprises a foam.

17. The method of claim 1, wherein when the suspended proppant particles reach their destination within the subterranean geological formation, the distended hydrophilic outer coating layer rearranges itself to expose the inner polymeric layer, thereby enabling multiple composite proppant particles to fix themselves to one another.

18. The method of claim 1, wherein the outer polymer coating remains substantially intact until the suspended proppant particles have been conveyed to their destinations in the subterranean formation.

19. The method of claim 1 wherein the hydrophilic outer layer creates a water-like layer on the surface of the particle, making it slippery and one of reducing friction between particles or reducing drag against water.