structuring material, and method for the treatment of an underground formation

专利摘要:
STRUCTURING MATERIAL, AND, METHOD FOR THE TREATMENT OF AN UNDERGROUND FORMATION. Structuring materials and methods for the production of structuring materials are provided. In one embodiment, the structuring material comprises a substrate material, a polymeric material disposed over the substrate material, and a surface wettability modifier disposed over the polymeric material. Methods of production and use of structuring materials are also described.
公开号:BR112014007649B1
申请号:R112014007649-9
申请日:2012-09-26
公开日:2021-05-04
发明作者:John William Green；John Mario Terracina；Jerry Francis Borges；Scott Edward Spillars；Samantha Huixian Mah
申请人:Hexion Inc；
IPC主号:

专利说明:

RELATED ORDER DATA
[0001] This application claims the benefit of US Provisional Application No. 61/541,253, filed September 30, 2011, and this application claims the benefit of Provisional Application No. 61/549,083 filed October 19, 2011, whose total contents of both requests are incorporated in this one, by way of reference. FIELD OF THE INVENTION
[0002] The report refers to structuring materials and methods for producing and using them. In particular, the invention relates to structuring materials having wettability characteristics. FUNDAMENTALS OF THE INVENTION
[0003] The term "structuring" is indicative of a particulate material, which is injected into fractures in underground formations, which surround gas wells, water wells, and even other similar drill holes, in such a way that it is A support is then provided to hold (structure) these fractures open and in such a way as to allow gas or liquid to flow through the fracture into the borehole or from the formation. Coated and uncoated particles are often used as structuring so that fractures imposed by hydraulic fracturing in an underground formation are kept open, for example, in a stratum containing oil or gas, and a so that a conduit channel in the formation is then provided.
[0004] The fracture of the subterranean formation is conducted in such a way that the production of oil and/or gas is increased. Fracture is caused by injecting a fluid (either a hydrocarbon, water, foam or emulsion) into the formation at a rate that exceeds the formation's capacity for the flow to be accepted. The inability for fluid dissipation to form results in a buildup of pressure. When this build-up of pressure exceeds the strength of the formation's rock, a fracture is then initiated. Continued pumping of the fracture fluid will result in fracture growth in length, width and height directions. The rate required to initiate and extend the fracture is related to the injection rate and viscosity of the fracture fluid.
[0005] The fracture process also includes placing a particulate material, referred to as a "structuring material", "structuring agent" or "structuring" in the formation, so that the fracture is then maintained in a structured condition when injection pressure is released by resistive forces, which tend to close the fracture. As the fracture is formed, the structurants are then carried into the fracture by suspending them in a fracture fluid or additional fluid or foam, such that the fracture is then filled with a suspension. of structuring. When the injection of fluid is stopped, the structurants form a compaction, which serves to keep the fractures open. Structured fracture thus provides a highly conductive channel for hydrocarbon production and/or for the recovery of fracture process water from formation.
[0006] However, it has been observed that the fluids, which flow through the structured fracture, have flow rates lower than desirable or lower than expected. One theory is that the structurants, which form the structured fracture, are adversely affecting the flow rates through the structured fractures.
[0007] It was also observed that, during production from formations containing underground hydrocarbons, the wettability of the formation constitutes an important parameter, which affects the fluid flow through the reservoir. Wetability is the tendency of a fluid to preferentially adhere to a solid surface in the presence of another immiscible fluid. Although several strategies have been used to alter the wettability of the reservoir formation, current processes have not produced the desired wettability characteristics.
[0008] Thus, there is a need for a structuring material that is useful with regard to improving fluid rates through structured characteristics or by reducing the effect of structuring materials on fluid rates in a borehole. pit. SUMMARY OF THE INVENTION
[0009] The embodiments of the invention are directed to materials suitable for use as structuring materials. Structuring materials include at least one composite substrate, a polymeric coating material, or a surface wettability modifier, each of which can further improve the flowability of the organic materials, water, or both.
[00010] In yet one aspect of the invention, there is provided a structuring material, which includes a substrate material, a polymeric material disposed on the substrate material, and a surface wettability modifier disposed on the polymeric material. The structuring material may further exhibit a water contact angle of from about 59° to about 120° and a surface energy of from about 20 mJ/m2 to about 50 mJ/m2.
[00011] In yet another aspect of the invention, a structuring material is provided, which includes a substrate material and a polymeric material, disposed on the substrate material, wherein the polymeric material provides the structuring material with an angle of contact with the water from about 590 to about 120° and a surface energy from about 20 mJ/m2 to about 50 mJ/m2.
[00012] In yet another aspect of the invention, a structuring material is provided, which includes a composite substrate, which comprises a polymeric material comprising a contact angle with water of from about 59° to about 120°C and a surface energy of from about 20 mJ/m" to about 50 mJ/m and a filler material dispersed throughout the polymeric material.
[00013] In yet another aspect of the invention, a method for treating an underground formation is provided, which includes injecting a fracture fluid into the underground formation, wherein the fracture fluid comprises a structuring material selected from the group, consisting of a first structuring material, comprising a first substrate material, a first polymeric material disposed on the substrate material, and a surface wettability modifier disposed on the polymeric material, a second structuring material, comprising a second substrate material and a second polymeric material disposed over the substrate material, a third structuring material, comprising a composite substrate having a third polymeric material and a filler material dispersed throughout the third polymeric material, wherein the wettability modifier surface of the first, second or third polymeric material prov to the structuring material a contact angle with water of from about 59° to about 120° and a surface energy of from about 20 mJ/m2 to about 50 mJ/m2 . DETAILED DESCRIPTION OF THE PREFERRED MODALITIES
[00014] As used herein, the terms "first", "second" and the like do not denote any order of importance, but are preferably used to distinguish one element from another, and the terms "the ”, and “one” do not denote a quantity limitation, but rather denote the presence of at least one of the items referred to herein.
[00015] The wettability or surface wetting is defined here as the ability of a liquid to maintain contact with a solid surface, resulting from intermolecular interactions, when the two are placed together. Surface wetting can then be represented by a contact angle (θ), which is the angle at which the liquid-vapor interface meets the liquid-solid interface. Surface wettability can then be characterized by measuring the contact angle, the contact angles, which are situated in a range of between 0° and 70° indicating a surface wettable with water; while those between 70° and 110° describe intermediate or neutral wettability; and those, which range between 110° and 180° indicating an oil wetting system (a hydrophobic surface).
[00016] The surface energy quantifies the breakage of intermolecular bonds, which occur when a surface is created. Surface energy can thus be defined as the excess energy on the surface of a material compared to volume. For a liquid, the surface tension (force per unit length) and surface energy density are identical. For example, water at 25°C has a surface energy density of 0.0072 J/m2 and a surface tension of 0.072 N/m.
[00017] The embodiments of the invention are directed to materials suitable for use as structuring materials, also referred to as structuring. Structuring materials include at least one polymeric coating material or a surface wettability modifier disposed over a substrate material that provides the structuring material properties that improve the flowability of an organic material, water, or both. Alternatively, the substrate comprises a composite material, as described herein, with at least one polymeric material or a surface wettability material, such that the desired structuring material properties are provided. Organic materials can be hydrocarbon materials such as oil. Structuring materials are useful for structuring the opening of underground formation fractures and for improving fluid flow through underground formation fractures. Alternatively, the structuring materials can further include at least one polymeric coating material or a surface wettability modifier, which reduces or minimizes the flowability of an organic material (such as oil), water, or both .
[00018] It is believed that the surface wettability and surface energy of a structuring substrate material and resin coated structurants (polymeric material) can be changed in such a way that the production of hydrocarbons is improved in a way that to increase the recovery of the fracture processing water, or in a manner to reduce/prevent scale formation, as desired. It is further believed that surface wettability modifiers alter or "adjust" the surface of the structurant so that it has a desired surface wettability and energy without adversely affecting the bond strength of a so that the flowability of liquid hydrocarbons, gaseous hydrocarbons or water is improved as desired.
[00019] It is believed that if the structuring surface condition is changed to be made more wettable with water (a lower contact angle of about 90°), then it is expected that the surface modified structurant will show better wetting, than a so that the production of hydrocarbons is increased and in a way to reduce scale formation reactions, which adversely affect the conductivity (flow) of hydrocarbons.
[00020] If the surface condition of the builder is alternated in such a way that it is made more neutrally wettable or more wettable with oil, then it is expected that the surface-modified builder can then reduce the scale formation reactions that result in a reduced flow of hydrocarbon material through and around structuring materials and structuring material compacts. It is then believed that the neutrally wetted builder will reduce scale formation by preventing water from dissolving the structuring material. Additionally, better recovery of fracture processing water is then expected from formations treated with the structurant, in which the surface condition is altered, so that it is made more wettable with oil.
[00021] The formation of structuring scale, or scale formation, refers to the process, in which the minerals in the structuring substrate are then dissolved in an aqueous medium, react with the other dissolved minerals and salts, and are precipitated as particles of scale (mostly zeolite in the case of an uncoated ceramic substrate) which blocks porosity and reduces flow through the conductive path created by the compaction of the originally placed builder.
[00022] Presumably, if the surface of the structuring material is made less wettable with water, then there is a reduced tendency for water to be spread over and adhere to, or wet the solid structuring surface, in the presence of other immiscible fluids such as than liquid hydrocarbons. If the aqueous medium is blocked from contact with the surface of the structuring material in this way, then there is a significantly reduced probability that the water will either dissolve the minerals in the structuring substrate or act as a medium for the reaction of the dissolved minerals in a so that they can then react in a way that produces the unwanted fouling.
[00023] In yet an embodiment, the structuring material comprises a substrate material, a polymeric material disposed on the substrate material, and a surface wettability modifier, disposed on the polymeric material.
[00024] In yet such an embodiment of structuring material, the substrate material comprises from about 10% to about 98.99% by weight such that from about 89% to about 98.99% by weight , for example, from about 96% to about 98%, by weight, of structuring material; the polymeric material may further comprise from about 1% to about 6%, by weight, such that from about 1.5% to about 5%, by weight, for example, from about 1.8%, in weight, to about 4% by weight of structuring material; and the surface wettability modifier comprises from about 0.01% to about 5% by weight, such that from about 0.05% by weight to about 1% by weight, e.g. from 0.1% to about 1%, by weight, of the structuring material.
[00025] In yet another embodiment, the structuring material comprises a substrate material and a polymeric material disposed on the substrate material, and the polymeric material provides a surface modification of the external surface of the structuring material, in such a way that they are achieved the desired structuring material properties such as wettability and surface energy. In yet such an embodiment, the structuring material may still be free of a separate surface wettability modifier. Alternatively, a surface wettability modifier can be disposed on the polymeric material.
[00026] In yet another embodiment of a structuring material, comprising a substrate material and a polymeric material disposed thereon, the polymeric material having surface wettability modifier properties, such as described herein, the substrate material comprises about from 10% to about 99.99%, by weight, such that from about 95% to about 99.9%, by weight, for example, from about 99% to about 99.9%, by weight , of the structuring material. The polymeric material being a surface wettability modifier comprises from about 0.01% to about 5%, by weight, such that from about 0.5% to about 1%, by weight, for example, from about 0.1% to about 1% by weight of the structuring material.
[00027] In yet another embodiment, the substrate material may consist of one or more polymeric materials as described herein. The substrate material may also comprise a composite substrate material of a polymeric material and fillers disposed within the polymeric material. The fillers can be inorganic fillers, organic fillers, or even combinations thereof, as described herein. In yet another embodiment, the polymeric material may provide for surface modification of the outer surface of the structuring material such that desired structuring material properties such as wettability and surface energy are achieved. Optionally, a polymeric coating layer, a surface wettability modifier, or even combinations thereof, can be applied to the composite substrate material. The substrate material of one or more polymeric materials, as described herein, may be the same or different as an optional polymeric material, which forms a coating on the substrate material.
[00028] In yet another embodiment, the structuring material comprises a substrate material and a surface wettability modifier, disposed on the substrate material.
[00029] In yet another embodiment of a structuring material, comprising a substrate material and a surface wettability modifier disposed thereon, the substrate material comprises from about 10% to about 99.99% by weight, such that from about 95% to about 99.95%, by weight, for example, from about 99% to about 99.9%, by weight, of the structuring material.
[00030] Surface material of the structuring material, whether it is a polymeric material, a surface wettability modifier, or both, can be precured or a curable material. A curable structuring material has a coating, which includes a material that is usually at least partially, but not entirely, cured. In contrast, a “precured” structuring material has a coating of cured material. Materials used for curable coatings on structuring substrate materials can further result in a highly crosslinked coating on the surface of the substrates.
[00031] In yet one embodiment, the structuring materials, which are precured, include a substrate core and a coating of cured material prior to insertion into an underground formation. Structuring materials, which are curable, include a core of substrate and a coating of material at least partially cured downstream such that a consolidated structuring compact is formed.
[00032] The terms "cured" and "curable" may be further defined for this report by the bond strength of the surface material. In yet another embodiment described herein, curable is any surface material having a UCS Bond Strength of 10 psi (69 kPa) or greater, such as from 10 psi (69 kPa) to about 300 psi (2070 kPa), such as 10 psi (69 kPa) to about 1200 psi (8280 kPa).
[00033] For the purposes of this application, the terms "cured" and "cross-linked" are used interchangeably for the hardening that occurs in an organic material as described herein. However, the term "cured" also has a broader meaning in that it generally encompasses the hardening of any material, organic or inorganic, in such a way that a stable material is then formed. For example, cross-linking, ionic bonding and/or solvent removal, in such a way that a bonded material is formed in its final hardened form, may be considered curing. Thus, the mere removal of solvent from an organic binder, prior to cross-linking, . It may or may not constitute a cure, depending on whether the dry organic binder is in its final hardened form.
[00034] The structuring material may further be in the form of individual particles, which may have a particle size in a range of ASTM sieve sizes (USA Standard Test screen numbers) of about 6 to 200 mesh (apertures of screen from about 3360 µm or from about 0.132 inches (0.335 cm)) to about 74 µm or from about 0.0029 inches (0.007 cm). Typically, the structuring material or individual particles of the substrate gravel compaction have a particle size in a US Standard Test mesh number range of from 8 mesh to about 100 mesh (screen openings of about 2380 µm to about 0.0937 inches (2.37 cm) to about 150 µm or about 0.0059 inches (0.014 cm)), such as 20 to 80 mesh openings (screen openings of about 841 µm or about 0.0311 inches (0.078 cm to about 177 µm or 0.007 inches (0.017 cm)), for example, 40 to 70 mesh, (screen openings about 400 µm or about 0.0165 inches (0.0041 cm) to about 210 µm or 0.0083 inches (0.021 cm)) can be used in order to define the particle size.
[00035] In yet another embodiment according to the invention, the size of the structuring material is 20/40 mesh, 30/50 mesh, or 40/70 mesh. A size of 20/40 mesh is commonly used in the industry as a material having a size between 20 mesh and 40 mesh, as described herein. Smaller mesh builder materials, such as 40/70 mesh builder materials, can still be used in low viscosity fracturing fluids, and larger mesh materials, such as 20/40 mesh builder materials, can still be used. used in high viscosity fracturing fluids.
[00036] The structuring material may further comprise a substrate material of a particulate material. The substrate material can be any organic or inorganic particulate material normally used as the structuring material. Suitable particulate materials include inorganic materials (or substrates) such as exfoliated clays (e.g. expanded vermiculite), exfoliated graphite, blown glass or silica, hollow glass spheres, foamed glass spheres, cenospheres, foamed slag, sand, naturally occurring mineral fibers, such as zirconium and mullite, ceramics, sintered ceramics, such as sintered bauxite or sintered alumina, and other non-ceramic refractory materials, such as glass or ground beads, and combinations of same. Exemplary inorganic substrate materials can further be derived from silica sand, ground glass beads, sintered bauxite, sintered alumina, mineral fibers such as zirconium and mullite, or a combination comprising one of the inorganic substrate materials .
[00037] Organic particulate materials further include other organic polymer materials, naturally occurring organic substrates, and combinations thereof. Organic polymer materials can further include any of the polymeric materials described herein, which are carbon-based polymeric materials.
[00038] Naturally occurring organic substrates are crushed or ground nutshells, crushed or ground seed husks, crushed or ground fruit kernels, processed wood, crushed or ground animal bones, or a combination comprising at least one of the naturally occurring organic substrates. Examples of suitable crushed or ground shells are walnut shells, such as walnut, pecan, almond, ivory, Brazilian walnut, ground walnut (peanut), pine cone, cashew nut, sunflower seed, walnuts Filbert (hazelnuts), macadamia nuts, soybeans, pistachios, pumpkin seeds, or a combination comprising at least one of the preceding nuts. Examples of suitable ground or crushed nutshells (including fruit seeds) are fruit seeds such as plum, peach, cherry, apricot, olive, mango, pine fruit, guarana, apples, pomegranates, melon, ground or crushed seeds of other plants, such as corn (eg corn cobs or corn seeds), wheat, rice, jowar, or a combination comprising one of the foregoing processed wood materials, such as, for example, those derived from woods such as oak, North American walnut, walnut, poplar, mahogany, including such woods that have been processed through grinding, crushing or some other form of particle transformation. An exemplary naturally occurring substrate is a ground olive pit.
[00039] The substrate can be further a composite particle, such that at least one organic component and at least one inorganic component, two or more inorganic components, and two or more organic components. For example, the composite may further comprise an organic component of the organic polymeric material described herein having organic or inorganic filler materials introduced therein. In yet another example, the composite may further comprise an inorganic component of any inorganic polymeric material described herein, having organic and inorganic filler materials introduced therein.
[00040] Organic or inorganic fillers include various types of commercially available minerals, fibers, or even combinations thereof. Minerals include at least one member from the group, which consists of silica (quartz sand), alumina, mica, metasilicate, calcium silicate, clacine, kaolin, talc, zirconia, boron, glass and combinations thereof. The fibers further include at least one member selected from the group consisting of ground glass fibers, ground ceramic fibers, ground carbon fibers, synthetic fibers, and even combinations thereof.
[00041] The substrate material can also have any desired shape, such as spherical, ovoid, cubic, polygonal, or cylindrical, among others. It is further generally desirable for the substrate material to be spherical in shape. Substrate materials can also be porous or non-porous. Preferred substrate particles are hard and resist deformation. Alternatively, the substrate material may further be deformable such as a polymeric material. Deformation differs from crushing in that particles are usually deteriorated, creating fine particles that can impair fracture conductivity. In yet one embodiment, the inorganic substrate material is not melted at a temperature below 450°F (232°C) or 550°F (287°C).
[00042] The structuring material can further have one or more polymeric materials arranged on the substrate in one or more layers, which can be referred to as a coating or a coating layer. Each of the polymeric materials can be further arranged as a continuous or non-continuous coating layer. The continuous layer may further comprise the polymeric material and, optionally, additives, as further described herein. Each of the one or more layers can be the same or a different polymeric material than each of the other layers.
[00043] For example, the polymeric layer coating can be further deposited in a multi-stage process or in a multi-layer process of a first polymeric material of phenol-formaldehyde resol, a second polymeric material of a terpolymer of phenol-formaldehyde -furfuryl alcohol, a third polymeric layer of a novolac phenol-formaldehyde material, and then a fourth layer of phenol-formaldehyde resole resin. In yet another example, the polymeric layer coating can be further deposited in a multi-stage, multi-layer process of a first polymeric material of a liquid polymeric material of phenol-formaldehyde resol, a second polymeric material of a liquid polymeric material of phenol-formaldehyde resol, and a third polymeric material of a phenol-formaldehyde novolac material, were sequentially added to form the coating.
[00044] Suitable polymeric materials may further comprise thermosetting polymers. Additionally, suitable organic materials, which can further be used as the coating, are polymer precursors (eg, low molecular weight species such as monomers, dimers, trimers, or the like), oligomers polymers, copolymers, such as block copolymers, star block copolymers, terpolymers, random copolymers, staggered copolymers, graft copolymers, or the like; dendrimers, ionomers, or a combination comprising at least one of the foregoing.
[00045] Suitable polymeric materials can be further selected from the group of a phenol-formaldehyde resin, a silicone fluorine-free epoxy resin, a novolac phenol-formaldehyde resin modified with a silicone fluorine-free epoxy resin, a novolac phenol-formaldehyde resin, a phenol-formaldehyde resole resin, a phenol-furfuryl alcohol or (furfuryl aldehyde)-formaldehyde terpolymer, a polymerized furan (eg, furfuryl alcohol-formaldehyde), a polyurethane resin, a polymerized urea-aldehyde, a polymerized melamine-aldehyde, a polyester, a polyalkyd, a polymerized phenol-aldehyde, and combinations of mixtures thereof, copolymers thereof, and combinations thereof.
[00046] Epoxy resin blends and copolymers with one or more of resol resins, phenol terpolymers, furfuryl alcohol (or furfuryl aldehyde) and formaldehyde, furans, for example, alcohol-furfuryl-formaldehyde, and furans, for example, Furfuryl alcohol-formaldehyde are also suitable as the polymeric materials according to the present invention.
[00047] Fluorine-free and silicone-free epoxy resins, for example, can be further selected from glycidyl ethers produced from bisphenol A and epichlorohydrin. These resins are available in liquid form, having a typical viscosity of about 200 (200 mPa.s) to about 20,000 centipoises (20,000 mPa.s), and an epoxide equivalent weight of about 170 to about 500 and a weight weight average molecular weight from about 350 to 4000. Typical epoxy resins include ARALDITE 6005 sold by Hunstman Corporation or EPN 1139 novolac based epoxy resin, such as a liquid epoxy novolac resin manufactured by Ciba-Geigy Corporation or the resin Dow DER 331 epoxy, which is manufactured by Dow Chemical Company, Midland, Michigan. However, solid epoxy resins (solid in the pure state) can still be employed if they are soluble in the coating resin system and reactive. Preferred epoxies of the present invention include bisphenol A-based aromatic epoxies such as DGEBPA (diglycidyl ether of bis-phenol A, eg EPON 828, available from Momentive Specialty Chemicals, Inc), cycloaliphatic epoxies (eg Eponex 1510 , available from Momentive Specialty Chemcials, Inc.) and bisphenol F epoxy (eg, EPON 862, available from Momentive Specialty Chemicals, Inc.).
[00048] Vinyl esters are produced by reacting epoxy resins with ethylenically unsaturated carboxylic acids. Bisphenol A epoxy resins, epoxy novolac resins or brominated analogues can also be used as epoxy resins. Common acids used to esterify epoxy resins are acrylic acid and methacrylic acid, but crotonic acid, cinnamic acid and still other unsaturated acids can also be used. The resulting epoxy resins can be further cured in free radical reactions alone (homopolymerization) or can be further used with unsaturated monomers (copolymerization), such as styrene and still other monomers, such as those mentioned above for unsaturated polyester resins. The vinyl esters can then be cured using the methods described above for unsaturated polyesters. Examples of commercially available vinyl esters include DERAKANE supplied by Ashland, HYDROPEL resins supplied by AOC. Preferred vinyl esters are those made using acrylic acid and methacrylic acid.
[00049] Epoxy-modified novolac resins are described by U.S. Patent No. 4,923,714 to Gibb et al, incorporated herein by reference. The phenolic portion may further comprise a phenolic novolac polymer, a phenolic resole polymer, a combination of a phenolic novolac polymer and a phenolic resole polymer; a cured combination of phenolic/furan or a furan resin to form a precured resin (as described by U.S. Pat. No. 4,694,906 to Armbruster, incorporated herein by reference); or a furan/phenolic resin system curable in the presence of a strong acid such that a curable resin is formed (as described in U.S. Pat. No. 4,785,884 to Armbruster). The phenolics of the aforementioned novolac or resol polymers may further be phenol moieties or bisphenol moieties.
[00050] Yet an embodiment according to the present invention employs a polymeric material of a phenol-aldehyde resol polymer, which has an average molecular weight in a range from about 400 to about 2000. The resole resin phenol-aldehyde has a phenol:aldehyde molar ratio of from about 1:1 to about 1:3, and typically from about 1:1 to about 1:1.95. A preferred way of preparing the resol resin is to combine the phenol with an aldehyde source such as formaldehyde, acetaldehyde, propionaldehyde, furfural, benzaldehyde or paraformaldehyde under alkaline catalysis. During such a reaction, the aldehyde is present in a molar excess. It is further preferred that the resol resin has a molar ratio of phenol to formaldehyde of from about 1:1: to 1:1.6. The resol resins can further be resol resins free or with a low phenol, having less than 3% by weight, and even more preferably less than 2% by weight, of free phenol. However, higher free phenol ranges may also be employed, such as a free phenol specification range of 2.0% -4.0% resol OWR-262E or 8.0% or more free phenol resol Oil Well Resin 9200, available from Momentive Specialty Chemicals, Inc. The resoles may also be conventional resoles or modified resoles.
[00051] Modified resols are described by U.S Patent No. 5,218,038, incorporated herein by reference, in its entirety. Such modified resoils are prepared by reacting an aldehyde with a mixture of an unsubstituted phenol and at least one phenolic material selected from the group consisting of aryl phenol, alkyl phenol, alkoxy phenol and aryloxy phenol.
[00052] The term "novolac" refers to the resin products of substantially complete condensation of a phenol with an aldehyde, in such proportions that the condensation is not able to be effected in such a way that a non-melting product is formed. Novolacs are usually produced by condensing unsubstituted phenol with formaldehyde in approximately equimolecular proportions, and often with a slight excess of phenol. A novolac is meltable and, as it does not contain a sufficiently high proportion of formaldehyde, so that condensation is allowed to a thermosetting condition, it can then be heated to melt and solidified again without being subjected to a change. chemistry.
[00053] Novolac can still be produced through the condensation of phenol and formaldehyde. Alternatively, the phenolic species may further be an alkyl phenol, an aryl phenol, a diphenol or a bisphenol. Although the aldehyde is typically formaldehyde, acetaldehyde or other aldehydes can still be used. It is preferred that the novolac resin has a formaldehyde to phenol ratio of from about 0.60 to 0.90. The novolac resins can be novolac resins free or with a low phenol, having less than 1% by weight of free phenol, such as Durite SD-672D, available from Momentive Specialty Chemcials. However, higher free phenol ranges can still be employed, such as 1.0% -10.0% free phenol. The novolacs can be conventional novolacs or modified novolacs.
[00054] A phenol-formaldehyde-furfuryl alcohol terpolymer is prepared from the catalytic reaction of phenol, aldehyde (such as formaldehyde) and furfuryl alcohol, in which the catalyst is a water-soluble multivalent metal salt, and in which the reaction it is performed under essentially water conditions. Generally speaking, the molar ratio of phenol to furfuryl alcohol can further range from about 0.1:1 to about 10:1 respectively. The molar ratio of formaldehyde to phenol-furfuryl alcohol can further range from about 0.5:1 to 2:1, and respectively in moles of CH2O:phenol + furfuryl alcohol. The amount of catalyst can further range from about 0.2% to about 8% by weight of the total amount of phenol and furfuryl alcohol.
[00055] Furans, which can be used in the present invention, include resins produced from urea formaldehyde and furfuryl alcohol; urea formaldehyde, phenol formaldehyde and furfuryl alcohol; phenol formaldehyde and furfuryl alcohol; or formaldehyde and furfuryl alcohol. Furan resin, suitable for use as a binder or as a coating for the cores of the present invention is described by US Patent No. 4,694,905 to Armbruster, incorporated herein by reference, or other furan resins known in the art. technique. Alternatively, furfuraldehyde can be further used in place of furfuryl alcohol as described in the terpolymer herein.
[00056] Polyurethane resins are produced by mixing a polyisocyanate component, a polyhydroxy component and a catalyst. Typically, the polyhydroxy component consists of a polyhydroxy phenolic component, dissolved in the solvent. Generally speaking, solvents are mixtures of hydrocarbons and polar organic solvents, such as organic esters. Exemplary hydrocarbon solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethyl benzene, high boiling aromatic hydrocarbon mixtures, heavy naphtha, and the like. In addition, polyurethanes are further described by US Patent No. 5,733. 952 by Geoffrey, incorporated herein by reference.
[00057] Typical melamine phenolic resins for the coating substrate are described by US Patent Nos. 5,296. 584, 5,952,440 and 5,916,966 to Walisser, incorporated herein by reference. The term melamine resin is a generic term to encompass any melamine-formaldehyde resin with or without other ingredients, for example, urea groups. Typically, mixtures of resols and melamines are heated in such a way that a melamine formaldehyde reaction is carried out such that a dissolved melamine methylol reaction product is produced (See US Pat. No. 4,960 .826).
[00058] Unsaturated polyesters, commonly referred to as "alkyds", are formed by the condensation of polyols and carboxylic acids with olefinic unsaturation, being contributed by one of the monomers, in a usual way, the acid. Generally speaking, difunctional alcohols (glycols) and difunctional acids are used in the condensation reaction. Examples of commercially available unsaturated polyester resins suitable for application include AEROPOL from Ashland Chemical, DION, FINE-CLAD, and POLYLITE from Reichhold Chemicals, STYPOL from Cook Composites & Polymers, and AQUA SHIELD from Advance Coatings.
[00059] In yet one embodiment, thermosetting polymers can be further modified by functionalities or by polymer blocks, which are permanently attached, covalently or otherwise, to the backbone of the main polymer, or to a polymer, of a so that the desired structuring properties are provided, as described herein, with respect to contact angle, surface energy, bond strength, and combinations thereof. Examples of such polymer modifying agents may further include silanol groups (Si-OH group), siloxane groups, and combinations thereof. For example, a silanol group of a silanol-functional silicone can be reacted with a phenolic polymer, which can further provide a siloxane block-modified phenolic polymer material.
[00060] In yet one embodiment, thermosetting polymers can be further selected in such a way that the desired structuring properties are provided, as described herein with respect to contact angle with water and surface energy, and optionally, strength. binding as the surface wettability modifier. Such polymeric materials still provide the same changes in desired properties and functions and in the polymeric material's version of surface wettability modifiers described herein. Polymeric materials, which act as surface wettability modifiers, which can be used to form a coating of the structuring material, can further be selected from the group of polysilicones, an acrylate polymer, a silane-containing polymer, a fluorine-containing polymer, and from their combinations. In yet such an embodiment, the structuring material is further formed without the presence of a surface wettability modifier, as described herein.
[00061] Suitable polysilicon materials include, but are not limited to polyalkylene oxide copolymers. Examples of such copolymers include products sold under the trademarks L-7604 polymer, L-8500 polymer, Silbreak™ 321 polymer, L7605 polymer, Y-17233 polymer, and combinations thereof, which are commercially available from Momentive Performance Materials. Alternatively, the structuring materials described herein may be free of a siloxane-polyalkylene oxide copolymer.
Suitable acrylates include, but are not limited to, fluoroalkyl methacrylate copolymers, fluoroalkyl acrylate copolymers, polyester acrylates, epoxy-modified acrylates, urethane acrylate oligomers, and combinations thereof. Acrylates can also be provided in the form of an aqueous solution. Examples of suitable acrylates include compounds sold under the trademarks S-2005, a fluoroalkyl methacrylate copolymer, S-2042, an aqueous solution of fluoroalkyl methacrylate copolymer, S-2023 B, a fluoroalkyl acrylate copolymer, S -2059B, an aqueous solution of fluoroalkyl acrylate, and combinations thereof, which are commercially available from Daikin America, of Decatur, Alabama.
Suitable silane-containing materials may further include fluoroalkyl silanes. Examples of fluoroalkyl silanes include trifluoropropyl trimethoxy silane, nonafluorohexyl triethoxy silane, and combinations thereof.
[00064] The fluorine-containing polymer materials may further include the fluorinated derivatives of the polymer materials described herein and may further include the fluorine-containing copolymers as described herein. Examples of fluorine-containing polymer materials can further include fluorine-containing epoxy materials, fluoroacrylates, a copolymer of heptadecafluorodecyltrimethoxy silane polyalkylene dimethyl siloxane, and combinations thereof.
[00065] Suitable polymeric materials may also comprise thermoplastic polymers. Thermoplastic polymers can further be used in combination with thermosetting polymers as described herein. Thermoplastic polymers can also be selected from the group of polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polystyrene, among others, and from thermoplastic polymers, used for coating the polymeric material, which are exempt from the materials here described for surface wettability modifiers and for polymeric materials, which act as surface wettability modifiers, as described herein.
[00066] polymeric material disposed on the substrate material or the substrate material may be further described to, or treated with, or deposited with one or more surface wettability modifiers. In yet one aspect of the invention, the surface wettability modifiers described herein may be further disposed on, or added to, any described portions of the substrate material or both. In yet another aspect of the invention, surface wettability modifiers are added to a fracture fluid, in which structuring materials are disposed therein, and which can further alter the wettability characteristics of the structuring materials in the fracture fluid. The one or more surface wettability modifiers may be further deposited onto the polymeric material, the substrate material, or both, in one or more layers, and each layer may be a surface wettability modifying material equal to or different from one layer for the other.
[00067] Surface wettability modifiers and polymeric materials, which act as surface wettability modifiers are further used in such a way that a contact angle with water of about 59° to about 120° is provided, such that from more than 75° to about 110°, for example, from about 76° to about 95°, or from about 76° to about 87°. Alternatively, the angle of contact with the water may further be from about 590 to about 120°, such that from about 59° to about 110°, for example from about 59° to about 75°, or from about 76° to about 95°. It is believed that surface wettability modifiers can further provide an increase in water contact angle from about 1° to about 120°, such as from about 1° to about 65°, for example, from about 1° to about 35°, from the polymeric material, substrate material, or both. A method for determining wettability (water contact angle) is found in Application Note 402 “Wettability Studies for Porous Solids Including Powders and Fibrous Materials” by Christopher Rulison of Augustine Scientific of Newbury, Ohio, 2002.
[00068] Surface wettability modifiers include materials containing silicon, materials containing fluorine, acrylate materials, polyamides, and combinations thereof, among others.
[00069] In yet another alternative embodiment, the structuring material also includes a surface wettability material, disposed directly on the substrate material. In still a first aspect, the surface wettability material is disposed on a substrate material, in the absence of a polymeric material. In a still second aspect, the substrate wettability material is disposed on a substrate material, in the presence of a layer of polymeric material applied in a discontinuous manner. In yet a version of the second aspect, a discontinuous polymeric layer is firstly disposed with the discontinuous polymeric layer exposing a portion of the substrate material, onto which the surface wettability material can then be disposed. In yet a second version of the second aspect, the surface wettability layer is disposed over the substrate material, and then a discontinuous polymeric layer is disposed, by means of a discontinuous application, exposing a portion of the disposed surface wettability material.
[00070] Suitable silicon-containing materials include silanes, silicon-containing surfactants, silicones, silsesquioxanes, silicone-containing epoxy materials, and combinations thereof, among silicon-containing materials. Suitable silsesquioxanes include polyhedral oligomeric silsesquioxanes (POSS), polyhedral oligomeric silsesquioxanes, and combinations thereof.
[00071] Suitable polysilicone materials include, but are not limited to, polyalkylene oxide copolymers. Examples of such copolymers include products sold under the trademarks polymer L-7604, polymer L-8500, polymer Silbreak™ 321, polymer L-7605, polymer Y-17424, polymer Y-17233, and combinations thereof, which are commercially available from Momentive Performance Materials. Alternatively, the structuring materials described herein may further be free of a polyalkylene oxide siloxane copolymer.
[00072] Examples of silane materials include triethoxysilylpropoxy(hexaethyleneoxy)dodecanoate, triethoxysilylpropoxy(triethyleneoxy)octadecanoate, tridecafluoro-octyltriethoxysilane, heptadecafluorodecyltrimethoxysilane copolymer polyalkylenedimethylsiloxane, polyalkylene dimethylsiloxane thiopolymer polyalkylene dimethylsiloxane emulsion, polyalkyl dimethyl siloxane thiopolymer, polydimethyl siloxane thiopolymer. modified organo siloxane, modified alkyl siloxane, an alkyl aryl polydimethyl siloxane emulsion, modified organo silicone emulsion, trifluoropropyl trimethoxysilane, nonafluorohexyltriethoxysilane, and combinations thereof.
[00073] Suitable fluorine-containing materials include fluorinated or perfluorinated oligomers and polymers, fluorosurfactants, fluoroacrylates, fluorine-containing epoxy materials, and combinations thereof, among other fluorine-containing materials. Additionally, a perfluorinated or partially fluorinated group can be further added as a pendant group or as a backbone component of most polymers, fluoroacrylates, fluorine-containing epoxy materials, and combinations thereof.
[00074] Examples of fluorine-containing materials include 2-propenoic acid, 2-[methyl(nonafluorobutyl)sulfonyl]amino ethyl ester, tridecafluoro-octyltriethoxy silane, heptadecafluorodecyltrimethoxy silane-polyalkylenedimethyl siloxane, trifluoropropyltrimethoxy silane, none fluorohexyl copolymer fluoroalkyl acrylate, and combinations thereof. A commercial example of a fluorine-containing material is Novec FC-4430 fluorosurfactant, an available nonionic fluorochemical surfactant from 3M.
[00075] Additionally, suitable fluorine-containing materials further include fluorinated materials having one or more epoxy groups. Examples of fluorinated epoxy materials include the fluorinated version of the following epoxy materials: EPON HPT 1050 Resin, EPON Resin 1001F, EPON Resin 1002F, EPON Resin 1004F, EPON Resin 1007F, EPON Resin 1009F, EPON Resin 1031, EPON Resin 1123-A-80 EPON Resins 154, 160, 161, and 164, EPON Resins 2002, 2004, and 2005, EPON Resin 3002, EPON Resin 8021, EPON™ Resin 8161, EPON Resin 828, EPON Resin 830, EPON Resin 834, EPON Resin 862, EPON 863 resin, EPON 872 resin, EPON™ SU-8 resin, EPON™ SU-3 resin, Heloxy modifiers, and combinations thereof, as well as other epoxy resins, all available from Momentive Specialty Chemicals Inc., of Columbus Ohio. The fluorine-free versions of the above epoxy materials can be further used as polymeric materials as described herein.
[00076] Suitable acrylate materials include polyacrylates, polyacrylates, polyacrylamides, polyester acrylates, epoxy-modified acrylates, urethane acrylate oligomers, and combinations thereof. Examples of acrylate materials include 2-hydroxy ethyl methacrylate (HEMA), 2-hydroxy ethyl acrylate, n-butyl acrylate, methyl methacrylate, polymethyl methacrylate, and combinations thereof. Such acrylate materials were further observed to be of a hydrophilic nature. The acrylate materials can further be in the form of a copolymer, such as a copolymer of HEMA and the more hydrophobic methyl methacrylate.
[00077] Alternatively, in order to create a more hydrophobic surface, a material such as polypMMA (70° to 75° water contact angle) could be further mixed with a small amount of fluorinated, perfluorinated material or semi-fluorinated (0.01% to 5% by weight) in such a way that a more hydrophobic material is created (90°-160° water contact angle).
[00078] Alternatively, in order to decrease the wettability with water (increase the contact angle with water), a perfluorinated or semifluorinated acrylate could be copolymerized with a monomer such as methyl methacrylate. Examples of fluorinated acrylates include 1H,1H-perfluorooctyl acrylate, 1H,1H,2H,2H-perfluorooctyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, methacrylate 1H,1H,7H-dodecafluoroeptyl, 1H,1H,5H-octafluoropentyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, and combinations of memos, among other fluorinated acrylates and methacrylates.
[00079] Alternatively, siloxanes with acrylate and methacrylate functionality could be polymerized with or without monomers, such as methyl methacrylate, in such a way that the wettability with water is decreased. Examples of such compounds include methacryloxypropyl terminated polydimethyl siloxanes, (3-acryloxy-2-hydroxypropyl) terminated polydimethyl siloxane, acryloxy terminated dimethyl siloxane-ethylene oxide block copolymers, (methacryloxypropyl) methyl siloxane-dimethyl siloxane copolymers , (acryloxypropyl)methyl siloxane-dimethyl siloxane copolymers, monomethacryloxypropyl terminated polydimethyl siloxane, and monomethacryloxy-monotrimethylsiloxy terminated polyethylene oxide, T8 methacrylate cubes (POSS monomers), and combinations thereof.
[00080] Polyamides include Nylon 6, Polyamide 612, Polyamide 12, polyether block amides (PEBA), aromatic polyamides, and combinations thereof. Examples of polyamides include Vestamide L (available from Evonik of Mobile, Alabama), Rilsan PA11 (from Arkema of Pasadena, Texas), Amodel PA-6T Resins (from Amoco), Pebax polyether block amides (available from Elf Atochem) , and combinations thereof. Alternatively, the polyamide material also includes polyimides. An example of a polyimide material is Kapton HN, available from DuPont.
[00081] Other surface wettability modifiers can be selected from the group, consisting of glycols, ethylene oxides, propylene oxides, and combinations thereof, which can be used in combination with or as a substitute for the moisture modifiers. surface wettability described here.
[00082] Examples of surface wettability modifiers may further include compounds selected from the group consisting of polydimethyl siloxane, polyalkylene oxide-methyl siloxane copolymer, siloxane-polyalkylene oxide copolymers, a polyether polymer fluorosurfactant, methacrylate of 2-hydroxyethyl (EIEMA), 2-propenoic acid, [2-[methyl[(nonafluorobutyl)sulfonyl]amino]ethyl ether, triethoxysilylpropoxy(hexaethylenoxy) dodecanoate, triethoxysilylpropoxy(triethylenoxy)octadecanoate, tridecafluoro-octyl-octyltriethoxy or triethoxy silane, and combinations thereof.
[00083] It is believed that the surface wettability modifiers change the surface wettability, the surface energy, or both, of the structuring material from the original condition. Surface wettability modifiers can further modify the structuring material by imparting hydrophobic or hydrophilic characteristics to the structuring material surface. Through the proper selection of the surface wettability modifier, the surface of the structuring material can then be adjusted such that a water-wet, oil-wet, or intermediate-wet condition is achieved, as desired. Increasing (more) water wetting corresponds to lower water wetting angles, around 0°, and decreasing (less) water wetting corresponds to higher contact angles, around 90t°. In yet one embodiment, the wettability modifiers alter the surface wettability of the structuring material so that it is less wettable, and thus can then provide a higher contact angle.
[00084] With respect to the materials described herein, appropriately modified silanes, modified materials containing silicon, modified materials containing fluorine, and combinations thereof, should be expected to be capable of imparting hydrophobicity and as capable of taking the surface of a structuring agent moistened with water plus moistened in a neutral way or moistened with oil. Conventional resins (non-fluorinated/modified with fluorine and non-containing/modified with silicon) of any type, as described above, can still provide contact angles with water from 0° to 75°.
[00085] A mixture of polymeric material as described herein (not containing/not modified with fluorine/siloxane/silane) with the surface wettability modifiers described herein, such that containing/modified with siloxane or fluorinated/fluoro-modified will allow contact angles of more than 75°, with highly fluorinated perfluorinated materials being required to produce super-hydrophobic surfaces with water contact angles of more than 150°. In general terms, monomers and polymers with hydrophilic groups can still provide hydrophilic surfaces with low contact angles with water. For example, acrylates with hydroxyethyl functionalities (2-hydroxy ethyl methacrylate (HEMA), 2-hydroxy ethyl acrylate) can still provide a hydrophilic surface with a low contact angle with water.
[00086] Conversely, hydrophilic materials, such as glycols, ethylene oxides, propylene oxides and hydrophilic polyacrylics and polyacrylates, are further expected to take the surface of structuring agents moistened with oil or moistened in a manner neutral more wettable with water. However, silanes, other than silicon-containing materials and fluorine-containing materials, which provide wettability with water, can still be selected, such as polyacrylics, polyacrylates, polyamides, epoxies and polyacrylamides, which provide water repellency or intermediate the wettability with the oil.
[00087] The ability of a silane to generate a hydrophobic surface is believed to be its organic replacement, the extent of surface coverage, the residual unreacted groups (both silane and surface) and the distribution of the silane over the surface . Aliphatic hydrocarbon substituents or fluorinated hydrocarbon substituents are hydrophobic entities, which allow silanes to induce surface hydrophobicity. For example, similarly methyl substituted alkyl silanes and fluorinated alkyl silanes provide better hydrophobic surface treatments than linear alkyl silanes. Thus, it is believed that polymer materials described herein that are modified with aliphatic hydrocarbon substituents, partially or completely fluorinated hydrocarbon substituents, or siloxane substituents should induce surface hydrophobicity, due to the presence of the hydrophobic substituents of the modified resin.
[00088] It is believed that a successful hydrophobic coating can further eliminate or mitigate hydrogen bonding and protect polar surfaces from interaction with water by creating a non-polar interface. Hydroxyl groups are the most common sites for hydrogen bonding. The hydrogen atoms of the hydroxyl groups can be further removed by forming an oxane bond with an organosilane. Similarly, hydrophobic substituents of an appropriately modified resin, as described above, can prevent exposure of internal materials having polar surfaces (e.g., the internal phenolic polymeric material) against interaction with water, through creation of a non-polar interface (a non-polar external surface with a contact angle with water of about 70°-180°).
[00089] Hydrophobicity is often associated with oleophilicity (wetness with oil), the affinity of a substance for oils, as the non-polar organic substitution is often hydrocarbon in nature and shares structural similarities with many oils. The hydrophobic and oleophilic effect can then be differentiated and controlled. At critical surface energies of 20-30 mJ/m2, the surfaces are moistened by hydrocarbon oil and are water repellent. At critical surface energies below 20 mJ/m2, hydrocarbon oils no longer spread and surfaces are both hydrophobic and oleophobic. The more oleophobic silane surface treatments have long-chain alkyl silanes and methylated medium-chain alkyl silanes. With regard to the surface wetting modifiers described herein, the most oleophobic surface treatments are said to consist of materials modified with fluorinated long chain alkyl and/or polyalkyl siloxanes.
[00090] The polymeric materials and/or the surface wettability modifiers according to the invention can further include a wide variety of additive materials, in view of the adjustment properties.
[00091] In the practice of this invention, coupling agents can still be employed, in a way to promote the adhesion of the coating to the substrate. It is further desirable that a silane additive be included in such a way that a good bond between the polymeric materials and the substrate as a coupling agent is ensured. The use of organofunctional silanes as coupling agents in such a way that organic-inorganic interfacial adhesion is improved is especially preferred.
[00092] Such coupling agents include, for example, organosilanes, which are known coupling agents. The use of such materials can further increase the adhesion between the binder and the filler. Examples of useful coupling agents of this type further include amino silanes, epoxy silanes, mercapto silanes, hydroxy silanes and ureido silanes. The use of organofunctional silanes as the coupling agents to improve organic-inorganic interfacial adhesion is especially preferred. These organofunctional silanes are characterized by the formula XI: VII: R13—Si—(OR14)3 XI,
[00093] wherein R13 represents a reactive organic function and ORU represents a readily unstable alkoxy group, such as OCH3 or OC2H5. Particularly useful for coupling furan or phenolic resins to silica are amino functional silanes, of which Union Carbide Al 100 (gamma aminopropyltriethoxysilane is an example. The silane can further be premixed with the resin or added to the mixer in a manner). separate.
[00094] Polymeric materials and/or surface wettability modifiers may also optionally contain additives such as silicone lubricants, surfactants, impact modifiers, wetting agents, dyes, pigments, flow modifiers ( such as flow control agents and flow improvers) hardening agents, crosslinking agents, foaming agents, initiators, thermal stabilizers, light stabilizers, antioxidants, flame retardants, anti-drip agents, antiozonizers, stabilizers, additives anticorrosion, mold release agents, fillers, antistatic agents, waxes, and the like, or a combination comprising at least one of the foregoing. In yet one embodiment, a dye or pigment can be further added to polymeric materials and/or surface wettability modifiers.
[00095] Surfactants can be anionic, non-ionic, cationic, amphoteric or mixtures thereof. Certain surfactants can also act as flow control agents. Any surface active materials that may be added include materials other than the surface wettability modifiers described herein.
[00096] Other optional additives include liquid weight-forming agents, moisture resistant additives or thermo-reversible additives. Of course, the additives can also be added in a combined way or in a single way.
[00097] Elasticizers or plasticizers, such as bisphemol A or cashew nut oil, may still be present, so that the elasticity or plasticity of the resin (binder) is increased. Other known additives can still be present.
[00098] It is also optional to add a lubricant to the substrate and resin mixture, before the mixture is “broken up” into free-flowing curable coated particles. The lubricant is preferably one that is liquid at the mixing temperature and has a sufficiently high boiling point so that it is not lost during the mixing process. Suitable lubricants include vegetable oil, for example soybean oil or corn oil, a low vapor pressure lubricating oil, liquid silicone such as Dow Corning SILICONE 200, mineral oil, paraffin wax, petrolatum, or ACRAWAX CT synthetic lubricant (a bis-stearamide of a diamine, available from Henkel International of Germany or Lonza of Switzerland).
[00099] As mentioned above, the polymeric coating may optionally further contain an impact modifier. An impact modifier can further impart elastic properties to the polymeric coating. Suitable impact modifiers include natural and synthetic elastomeric polymers typically derived from monomers such as olefins (eg ethylene, propylene, 1-butene and 4-methyl-1-pentene), alkenyl monomers aromatics (eg styrene and a-methyl styrene), conjugated dienes (eg butadiene, isoprene and chloroprene), and vinyl carboxylic acids and their derivatives (eg vinyl acetate, acrylic acid, alkyl acrylic acids, acrylate of ethyl, methyl methacrylate and acrylonitrile). They further include graft and shell-core, radial block, block and random homopolymers and copolymers, or a combination comprising at least one of the foregoing.
[000100] A typical impact modifier is a polyalcohol, also known as a polyol. A particularly useful class of impact modifiers comprises Ab (diblock) and ABA (triblock) copolymers and shell-core graft copolymers of aromatic diene and alkenyl compounds, especially those comprising styrene and/or butadiene or isoprene blocks . Conjugated diene blocks can be partially or fully hydrogenated, whereby they can be represented as ethylene-propylene blocks and the like and exhibit properties similar to those of olefin block copolymers. Examples of triblock copolymers of this type are polystyrene-polybutadiene-polystyrene (SBS), polystyrene-polybutadiene-hydrogenated polystyrene (SEBS), polystyrene-polyisoprene-polystyrene (SIS), poly(a-methylstyrene)-polybutadiene-poly(a-methylstyrene) and poly(α-methylstyrene)-polyisoprene-polo(α-methylstyrene). Particularly preferred block copolymers are commercially available as CARIFLEX®, KRATON D®, and KRATONG® from Shell.
[000101] Also suitable as impact modifiers are shell-core type graft copolymers and ionomer resins, which can be fully or partially neutralized with metal ions. Generally, shell-core graft copolymers have a predominantly conjugated diene or rubbery crosslinked acrylate core and one or more shells polymerized thereon and derived from acrylic and/or monoalkenyl aromatic monomers alone or in combination with other vinyl monomers. Still further impact modifiers include the types described above containing units having polar groups or active functional groups, as well as miscellaneous polymers such as Thiokol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (e.g., polypropylene oxide ), epichlorohydrin rubber, ethylene-propylene rubber, thermoplastic polyester elastomers, thermoplastic ether-ester elastomers, and the like, as well as mixtures comprising any one or more of the foregoing. A suitable impact modifier among ionomer resins is SURLYN available from Du Pont.
[000102] The following parameters may be useful when characterizing the particles of the present invention.
[000103] The polymeric material and the substrate can be supplied to the mixing device in such a way that a weight ratio of polymeric material (on a water-free basis) to an uncoated substrate of about 1 is provided. to 5 parts polymeric material: 95 parts uncoated substrate or from about 2 to 4 parts polymeric material: 95 parts uncoated substrate. The amount of polymeric material can be determined by measuring Loss-on-Ignition (LOI). Preferably, sufficient polymeric material is applied to the substrate such that an LOI (based on the weight of the combined coating) of from at most about 5 percent by weight of a preferably from about 1 to about 5 percent by weight, and even more preferably from about 2 to about 4 percent by weight, due to the single layer of precured polymeric material.
[000104] The LOI is typically determined in a two-hour oven test, starting by preconditioning a series of crucibles with lids in an oven preheated to 1700°F (927°C) . Then, the crucible with the lid is placed in the oven at 1700°F (927°C), the oven is again allowed to heat up to 1700°F (927°C), and the crucible with the lid is then held at 1700 °F (927°C) for 15 minutes. The preconditioned crucibles and lids are placed in a desiccator containing the conventional desiccants and allowed to cool to room temperature. Then, the conditioned crucible with the lid is weighed and approximately 8 grams of sand coated with polymeric material is then placed in the crucible. Then, the covered crucible and sample are placed in the oven at 1700°F (927°C), the oven is again heated to 1700°F (927°C), and the samples are then held in the oven for 2 hours, until the oven temperature has then returned to 1700°F (927°C). Then, the crucible with the lid and the sample are transferred to the desiccator and allowed to cool to room temperature. The cooled crucible with the lid containing the sand sample was then weighed again using an analytical balance. Loss on ignition for each sample was then calculated as the difference between the original and final sample weight.
[000105] The surface wettability modifier can then be added such that it is formed from from about 0.01% to about 5.0% by weight such that from about 0 0.05% to about 1%, by weight, by way of example, from about 0.1% to about 1.0%, of the structuring material.
[000106] The substrate coated with the polymer material generally has an average particle size of about 200 to about 2000 micrometers (about 70 mesh to about 10 mesh). In yet one embodiment, the substrate coated with the polymer material has an average particle size of about 300 to about 1,000 micrometers (about 50 mesh to about 18 mesh). In yet another embodiment, the polymer material coated substrate has an average particle size of from about 350 to about 650 (about 45 mesh to about 28 mesh). The substrate coated with the polymer material may also have bimodal or higher distributions. The most common size designations are 20/40, 16/30, 30/50, and 40/70.
[000107] The structuring material formed may also have a contact angle with water of from about 59° to about 120°, such that from more than 75° to about 110°, for example, more than 75° to about 95°, or from about 76° to about 87°. The contact angle with water can further be determined by a force tensiometer, through the Washbum method, as is known in the art.
[000108] The structuring material formed may also have a surface energy of from about 50 mJ/m or less, such that from about 20 mJ/m to about 50 mJ/m, for example from about about from 30 mJ/m to about 40 mJ/uT. Surface energy can then be determined from a set of liquid/solid contact angles, developed by placing various liquids in contact with the solid. Prior knowledge of surface tension values for liquids is required. The most widely used two-component surface energy theory is Fowkes theory, which describes the surface energy of a solid as having a dispersive component and a polar component. One method for determining such surface energy is found in Application Note 401, “So You Want to Measure Surface Energy ” by Christopher Rulison of Augustine Scientific of Newbury, Ohio, 2002.
[000109] The structuring material may further have a superior material surface, as described herein, formed from the polymeric material, the surface wettability material, or both, with a bond strength of from 10 psi (69 kPa) to about 1000 psi (6900 kPa), such as from about 80 psi (52 kPa) to 300 psi (2070 kPa), for example, from about 100 psi (690 kPa) to about 200 psi (1380 kPa). Bond strength is then measured by unconfined compressive strength (UCS). In yet another embodiment described herein, curable is any surface material having a UCS Bond Strength of 10 psi (69 kPa) or greater, such as from 10 psi (69 kPa) to about 300 psi (2070 kPa), or more. Alternatively, the structuring material may still have a bond strength of less than 10 psi (69 kPa) for the precured modalities of the structuring material.
[000110] Determine the bond strength of a structuring material coated with a polymeric material under simulated downstream conditions, under atmospheric pressure, through a procedure that includes: preparing the liquid medium (2% KC1) and the material suspension structuring/fluid, molding or formation of resin coated structuring material (RCP) cores for consolidation and/or curing, consolidation and/or curing of the structuring material, measurement of the strength of the consolidated cores, and the calculation and reporting of results.
[000111] The molded samples, produced according to this procedure, are also suitable for the measurement of the Brazilian tensile strength and/or the unconfined compressive strength test (UCS) according to the Standard Test Method ASTM D 2938- 91 or ASTM D 2938-95 for Unconfined Compressive Strength and Intact Rock Core Samples. For compressive strength measurements, the test sample should be cut to a length of at least 2.25 inches (57.2 mm), in a length to diameter ratio of at least 2 to 1, and then broken accordingly. with ASTM Standard Test Method D 2938-91 for the Unconfined Compressive Strength of Intact Rock Core Samples. For Brazilian tensile strength measurements, the test sample should be cut to a length of at least 0.56 inches (14.2 mm), but not more than 0.85 inches (21.6 mm), a length to diameter ratio of at least 0.5-0.75 to 1 in accordance with ASTM standard Test Method D 3967-92 for Split Tensile Strength of Intact Rock Core Samples.
[000112] Precured coatings are coatings such that the coated particles do not have the ability to generate significant particle-to-particle bond strength, thus a bond strength of less than 510 psi (3519 kPa), (< 200° F) (93.3 °C) and under an atmospheric pressure closing stress. Typically, the wet compression test is performed on a 12 pound per gallon suspension in 2% KC1. However, a precured resin coating does not mean that the coating itself has zero cure. .
[000113] In yet another modality of the structuring material, the structuring material can have a contact angle with water of about 90° and a surface energy of about 35 mJ/m2, and also, optionally, a resistance minimum bonding capacity of about 50 psi (345 kPa).
[000114] The structuring material can be used to increase oil and/or gas production by providing a conductive channel in the formation. Fracture of the underground formation is then conducted in such a way as to increase oil and/or gas production. Fracture can be accomplished by injecting a fluid (whether a hydrocarbon, water, foam or emulsion) into a formation at a rate that exceeds the formation's ability to accept flow. The inability for the formation to dissipate fluid results in a build-up of pressure. When this pressure buildup exceeds the strength of the formation rock, then a fracture is initiated. Continued pumping of fracture fluid will result in fracture growth in length, width and height directions. The rate required to initiate and extend the fracture is related to the injection rate and the viscosity of the fracture fluid. This combination of injection rate and fluid viscosity is also a critical factor in the ability of the fracture fluid to then transport the structuring material to the most distant points of the fracture geometry being created.
[000115] During fracture formation, structuring materials can then be placed into the formation, in such a way that the fracture is then maintained in a structured condition when injection pressure is then released. As the fracture is formed, the structuring materials are transported into the fracture by suspending them in an additional fluid or foam, such that the fracture is then filled with a suspension of structuring materials in the fluid or foam. . When the injection of fluid ceases, the structuring materials then form a compaction, which serves to keep the fractures open. Additionally, it is believed that curable structuring materials (or partially curable structuring materials) could be expected to form a consolidated compaction.
[000116] The structured fracture thus provides a highly conductive channel in the formation, through the use of the structuring materials described here. The degree of stimulation provided by hydraulic fracture treatment is largely dependent on the parameters of the formation, fracture permeability, structured fracture length, structured fracture height, and structured fracture width.
[000117] In yet another embodiment of the present invention, structuring materials are used in a method of deforming a structurant compaction, including suspending the above-described free-flowing precured particles in a transport vehicle, in such a way that a suspension is then formed and then injection of the suspension into an underground formation.
[000118] It is believed that conventional sand structuring materials, including in the form of structuring compacts, arranged in fracture formations, results in an adhesion of water to the surface of the sand structuring materials, which are considered wettable with water. Hydrocarbon material, such as an oil, has a reduced flow through structuring materials because water is not entirely displaced. It is believed that structuring materials as described herein can be further formed in such a way that optimized wettability in water and in hydrocarbons such as oil is provided. In still some modalities, water is believed to have reduced or minimal binding to the surface of the structuring materials, allowing clear paths for the flow of hydrocarbon through and around the structuring materials; it is believed that the hydrocarbon material is not bonded to the surface of the structuring material, allowing for improved hydrocarbon flow through and around the structuring materials. This theory is believed to be supported by the information in the examples below.
[000119] In order to produce a structuring material from substrate materials coated with the polymeric coating as described herein, and optionally, the surface wettability modifier as described herein, and optionally further any additives, are mixed into conditions to which a coating composition is provided. The process for the structuring material to be formed can be a batch process, a semi-continuous process, or even a continuous process.
[000120] In yet one embodiment of the forming process, a substrate material, such as sand, is then heated to a temperature above 300°F (149°C), and may even be less than about 440 °F (226°C), and then introduced into a mixing device. Depending on the exact resin loadings, a more curable coating is obtained at lower starting sand temperatures (SSTs) and precured coatings are then achieved at higher SSTs. For example, the SST for a precured structuring material is about 440°F. Next, the polymeric material, such as a liquid phenolic resin, and further any additives, such as a coupling agent, are then added while under mixing. Next, additional polymeric material, such as the solid phenolic resin and the liquid phenolic resin, are then added while under mixing. Next, a surface wettability modifier is then added while stirring is continued. Finally, the batch is cooled by the addition of water and mixing is then continued so that free-flowing particles of coated structuring material are obtained.
[000121] In yet one embodiment, there may be two or more separate water additions and, optionally, in yet another embodiment, no water additions. In the modality with two or more water additions, the addition is said to stop or reduce any significant curing reaction, in such a way that the desired stage of the reaction can then be "held". The addition of water is said to allow the formation of a superior curable material from the polymeric material, the surface wettability modifier, or a combination thereof. In the case of a precured structuring material, no water or a limited rate of water can be added and any residual heat can continue to fuel the curing reaction so that a precured product is then produced.
[000122] Mixing can occur in a device, which uses shear force, extensional force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy, or even a combination, which comprises at least one of the forces and preceding energies. Mixing is then conducted in processing equipment, in which the aforementioned forces are exerted by a single screw, multiple screws, inter-engineered co-rotating screws or counter-rotating screws, non-engineered co-rotating screws or counter-rotating screws, reciprocating screws, screws with pins, rollers with pins, screen compacts, rollers, cams, helical rotors or even a combination comprising at least one of the foregoing. Exemplary mixing devices are the EIRICH™ mixer, WARING™ mixers, HENSCHEL™ mixers, BARBER GREEN™ batch mixers, ribbon mixers, or the like.
[000123] If the profiled rotating drum is employed as the mixer for the coating, this rotating drum apparatus typically has a rotation speed of 16-20 revolutions/minute. The polymeric material stream can be preheated, for example, to 122140°F (50-60°C) for an epoxy resin, and sprayed into a rotating drum apparatus (containing the formed particles) through a nozzle with air atomization. This rotating drum operates in a batch process with a process time period of about 5 to 20 minutes.
[000124] If an Eirich mixer is employed as the mixer for the coating, it typically operates at a vessel rotation speed of 20-40, typically 30-35 revolutions per minute ( rpm), with a process time period of 2-10 minutes, and preferably 2-5 minutes. However, if desired, Erich's standard foundry mixer can still operate at 20 to 80, eg 50 to 80 rpm. If desired, a coupling agent, such as the silane, is then added to the sand in the mixer and, about 10 to 20, for example about 15, seconds after the silane, then the liquid polymeric material is added. Alternatively, the silane could still be pre-mixed into the polymeric material.
[000125] The coated particles are then discharged from the mixer and passed through a screen and the desired particle sizes of the builder are then recovered. Particles are agitated during curing.
[000126] Surface wettability modifier can be added to the mixture in the mixer, or in any other subsequent stage, such as before or during a curing process. Optionally, other additives (not shown) can be further added to the blend in the blender. Alternatively, the surface wettability modifier can be further added to a liquid resin, such as a resol, or to a solid novolac resin, before the coating process is started.
[000127] Alternatively, no heat is added during these stages of mixing, coating and curing, with the proviso that, optionally, the substrate or coated substrate is heated to some nominal temperature, for example, in a range of 65°F (18°C) to 100°F (37°C) in order to standardize a formula and cycle period for a continuous process. This would then eliminate issues regarding cycle time period changes related to ambient conditions such as the outdoor temperature (in which the substrate is stored) in the winter time period.
[000128] The stream of coated particles is typically sent to a classification in order to collect a coated substrate having a desired particle size. A typical sieving apparatus is a vibrating sieve. The sieved particles of a predetermined mesh size range are then discharged as a sieved stream. A typical desired size range of coated particles is 20 mesh to 40 mesh. Oversized particles and undersized particles are then collected from the screen and considered as scrap.
[000129] In yet one embodiment of a production process, the substrate material is then coated in a continuous system. The substrate material is introduced into an elongated horizontal mixer (eg 20 ft (6.1 m) containing two horizontally mounted shafts having paddles in order to promote mixing of the ingredients and moving them horizontally along the mixer If the optional silane is employed, it is immediately added and then the polymer material mixture, which, for example, may still contain an epoxy material or a formaldehyde-phenolic material, is then added. This mixture moves to the bottom of the mixer The total time period in the mixer can still be in a range from 3-10 minutes, depending on the desired flow rate.
[000130] In yet another embodiment of a continuous coating system, in which the substrate material and the polymeric material are fed along the horizontally oriented mixer, in a longitudinal manner, which can be of variable length and diameter. The continuous coating system modality has two to four horizontal axes, which travel along the length of the mixer. Along the shaft, multiple sets of mixing paddles are positioned, mounted on the shaft. The paddles are oriented in such a way as to ensure both mixing and transport of the substrate from the beginning of the mixer to its exit point. At various points along the mixer, addition holes are positioned in such a way that chemical substances can then be added at the prescribed rates and time periods. For example, there may be addition holes for additives and wettability modifiers as described herein.
[000131] The structuring materials, as described in this invention, can be further injected into the underground formation as the only structuring material in a 100% structuring compaction (in hydraulic fracture) or as a part of the structuring materials replacement based on sand and/or ceramic, the coated and/or uncoated polymeric material, or even mixtures between them, for example, the coated particles constitute from 10 to 50% by weight of the structuring material injected into the well. For example, uncoated structuring materials can first be placed in a well and thereafter a curable structuring material (of the present invention) can be further placed in the fracture, which is closest to the fracture opening(s). This type of fracture treatment is carried out without interruption, so that the structurant is changed, and is known in the industry as a “tail treatment”.
[000132] The following examples, which are intended to be exemplary, but not limiting, illustrate the compositions and methods of manufacture of some of the various modalities of coated particles described herein. EXAMPLES
[000133] The following examples further serve to illustrate the present invention. Unless otherwise noted, all parts and percentages are by weight, and all mesh sizes are U.S. Standard mesh sizes.
[000134] In the Examples, the following compounds are used as described. FF-160 is trifluoropropylmethyl siloxane. SM-2162 is a polydimethyl siloxane emulsion. SM-2164 NPF is an alkyl aryl polydimethyl siloxane emulsion. SM-2169 is a polydimethyl siloxane emulsion. Y-12560 is an organomodified polydimethyl siloxane. Y-17233 is a siloxane polyalkylene oxide copolymer. Y-17260 is an alkyl modified siloxane. Y-17261 is an alkyl modified siloxane. Y-17424 is a polydimethyl siloxane modified with polyalkylene oxide. Y-17420 is an organomodified polydimethyl siloxane. Y-17557 is a polyether amino silicone copolymer. Y-17712 is an organomodified silicone emulsion. Y-17713 is an organomodified silicone emulsion. Magnasoft™ material is an amino modified polydimethyl siloxane. Magnasoft™ SilQ is a silicone fluid containing a polyether silicone quaternary amine. Silbreak™ 321 suds suppressor is a polyalkylene dimethyl siloxane copolymer. Silbreak™ 400 is an organomodified polymethyl siloxane. Silwet™ L-7510 is a siloxane polyalkylene oxide copolymer. Silwet™ L-7604 is a siloxane polyalkylene oxide copolymer. Silwet™ L-7605 is a polydimethyl siloxane modified with polyalkylene oxide. Silwet™ L-8500 is a siloxane polyalkylene oxide copolymer. All of the foregoing materials are commercially available from Momentive Performance Materials Inc, of Friendly, West Virginia or Waterford, New York.
[000135] FC-4430 is a 2-propenoic acid, a 2[methyl[(nonafluorobutyl)sulfonyl]amino]ethyl ester, a telomer with methyl oxirane polymer with oxirane di-2-propenoate and a methyl oxirane polymer with an oxirane non-propenoate material, which is commercially available from 3M of St. Paul, Minnesota. SIT 8176 is a tridecafluoro-1,1,2,2-tetrahydro-octyl trimethoxy silane from Gelest, Inc., of Morrisville, Pennsylvania.
[000136] S-2005 is a fluoroalkyl methacrylate copolymer emulsion, which is commercially available from Daikin America of Orangeberg, New York. S-2023B is a fluoroalkyl acrylate emulsion, which is commercially available from Daikin America of Orangeberg, New York. S-2042 is a fluoroalkyl acrylate copolymer emulsion, which is commercially available from Daikin America of Orangeberg, New York. S-2059B is a fluoroalkyl acrylate copolymer solution, which is commercially available from Daikin America of Orangeberg, New York.
[000137] Examples 40/70 were prepared as follows. A substrate material having 40/70 mesh sizes was added to a reactor and heated with a propane flame to a temperature of about 380°F (193°C) at atmospheric pressure. The substrate was added in about 1000 grams. Next, a portion of a liquid polymeric phenol-formaldehyde resol material was then added in about 10.3 grams. An additional amount of about 3.2 grams of a second liquid polymeric material of a phenol-formaldehyde-furfuryl alcohol terpolymer was then added to the mixture. Additional materials of about 0.4 grams of a silane additive, eg Al 100, about 0.55 grams of ammonium chloride, (10% NH4Cl), which is an acid catalyst for curing the liquid polymeric material , and about 6.2 grams of a phenol formaldehyde novolac material, such as SD-672D, were then added sequentially to the mixture. An additional polymeric phenol-formaldehyde resol material of about 8.0 grams was then added to the mixture. All trademarked materials are commercially available from Momentive Specialty Chemicals Inc., of Columbus, Ohio or Momentive Performance Materials Inc., of Albany, New York. SD-672D is commercially available from Momentive Specialty Chemicals Inc. of Louisville, Kentucky.
[000138] Next, the surface wettability modifier was added in an amount such as to provide about 1 gram of solid material. A total amount of about 11 grams of water was then added, via two separate additions of the mixture. In some examples, examples Y-17712 and Y-17713, less than 11 grams of water were added in this case because part of the 11 grams were added at the time of the surface wettability modifier, which in these two cases are dispersions. aqueous solutions, which had to be added in amounts greater than 1 gram in order to achieve the addition of 1 gram of solid material. The substrate was continuously agitated through the various additions. Stirring was then continued after the water additions, until the mass was broken up into free-flowing particles. The resulting mixture was then discharged and the structuring material was then analyzed. The results of the Examples are shown in Table 1.
[000139] Examples 20/40 were prepared as follows. A substrate having 20/40 mesh sizes was added to a reactor and then heated to a temperature of about 390°F-405°F (198°C -207°C) with a propane flame at atmospheric pressure. The subtraction was then added to about 1000 grams. After the substrate was heated to the appropriate temperature, a polymeric material of a liquid polymeric material of phenol-formaldehyde resol was then added in about 15.1 grams. Next, additional materials of about 0.4 grams of a silane additive, eg Al 100, was then added, about 6.2 grams of the liquid polymeric phenol-formaldehyde resol material, and about 18.55 grams of a phenol-formaldehyde novolac material, such as SD-672D, were then sequentially added to the mixture.
[000140] Surface wettability modifier was then added in such an amount as to provide about 1 gram of solid material. A total amount of about 24 grams of water was then added, via two separate additions, to the mixture. The substrate was then continuously agitated through the various additions. Stirring was then continued after the water additions, until the mass was then broken up into free-flowing particles. The resulting mixture was then discharged and the structuring material analyzed. The results of the Examples are shown in Table 1.
[000141] A white fractional sand, coated with a polymeric material without a surface wettability modifier, was then used as the control for the 40/70 mesh samples. White fractionated sand is commercially available from Unimin Corporation of Ottawa, Minnesota or Badger Mining Corporation of Berlin, Wisconsin. Brown fractionated sand is commercially available from Unimin Corporation of Voca, Texas.
[000142] polymeric material consists of a combination of the following materials, a liquid phenol-formaldehyde resol, used under the trademark Oil Well Resin (OWR) 9200, with the polymer material of a terpolymer of phenol, formaldehyde and alcohol furfuryl, used under the trademark Oil Well Resin (OWR) 685D, and a phenol-formaldehyde novolac polymeric material, used under the trademark SD-672D, and the material combination was then used as the polymeric material in all examples. The OWR 9200 and OWR 685D are commercially available from Momentive Specialty Chemicals Inc. of Louisville, Kentucky. SD-672D is commercially available from Momentive Specialty Chemicals Inc. of Louisville, Kentucky.
[000143] Structuring materials were tested or calculated as follows, 900 g of a structuring material was placed in a glass column. A two-pore volume of water was poured into the column. At least one pore volume of water was drained, until there was no free water above the structuring compaction. The two-pore volume of Isopar™ L fluid was then poured into the column. Isopar™ L fluid is a synthetic isoparaffinic hydrocarbon solvent, commercially available from ExxonMobil Chemical. Once at least one pore volume of Isopar™ L fluid had been collected, the flow test was then performed by measuring the flow rate in mL/minute. Duplicate tests were then performed and an average reporting flow rate was then determined, as described below. Pore volume is the volume of porosity in the structuring column. It was estimated that the pore volume was about 35% of the volume of the structuring material.
[000144] test is further detailed as follows. Weigh 900 g of the sample (Sand and Resin coated with structuring ONLY). Calculate the volume of sample used (mass of sample x duct fill sample). Record the mass and volume of the sample used. Place the glass wool (0.76 g) in the glass column prior to sample compaction. Weigh and record the mass of 2 empty beakers. One beaker is used to collect a pore volume of water and the other to collect a pore volume of Isopar™ L fluid. Weigh two pore volumes of water (35% of the volume of sand that is used). Make sure the retaining cap is open and then pour 2 pore volumes of water into the column. Open the retaining cap so that a pore volume of water is then drained out. If the free water level is running low before a pore volume of water has been collected, the addition of an additional 100 g of water can be used. Use a thin wire to compact the column so that the air pockets are then removed. Continue compaction until resistance is felt from compaction. Drain free water, which is located above the compaction. Record the mass of water collected. Weigh 2 pore volumes of Isopar™ L fluid. Place 2 pore volumes of Isopar™ L fluid into the column. Collect and record the remaining water, which is being displaced by the Isopar™ L fluid. At some point, both the water and the Isopar™ L fluid will move together through the column and collection of Isopar will then begin. in an empty pre-weighed beaker. Collect a pore volume of Isopar™ L fluid. If the level of free Isopar™ L fluid is running low before a pore volume of Isopar™ L fluid is collected, add an additional 70g of Isopar™ L fluid.
[000145] Use the separator funnel, in order to obtain the additional water, which is being displaced. Record the mass of water as needed to calculate the residual water left in compaction. Once a pore volume of Isopar™ L fluid has been collected, perform the flow test. Before the flow test has started, make sure the pressure load height is 8.5 cm. If not, add more Isopar™ L fluid and then record the mass of Isopar™ L fluid added. Use a beaker of known mass and collect Isopar™ L fluid for about t minutes. Calculate the total mass of Isopar™ L fluid collected and then convert it to volume. The flow rate is obtained by dividing the volume collected by t minutes. In order to then calculate the residual water in the compaction, add the total amount of water collected from the various stages. Subtract the total amount of water collected from the total amount of sweat water so that the amount of residual water in compaction is then obtained.
[000146] Table 1 presents the results of oil flow tests, comparing the uncoated white sand builder (control) to the resin coated builder, with various surface wettability modifiers. In all tests, the resin coated builder with surface wettability modifiers had a high oil flux compared to the control sample of the uncoated NorThem White sand builder. The sand and ceramics listed below are uncoated substrate materials as described herein. The control is a white sand coated with a novolac phenol-formaldehyde resin and a resol phenol-formaldehyde resin, without the addition of a surface wettability modifier. Table 1


[000147] Table 1 shows that the surface wettability modifiers have a much higher oil flux compared to the uncoated sand control sample. Structuring materials with surface wettability modifiers have higher water contact angles and lower energy compared to the uncoated sand control sample. Structuring material with surface wettability modifiers is neutrally wettable compared to control sand which is more wettable with water.
[000148] The 40/70 structuring materials, which have the surface wettability modifiers containing fluorine and containing silicone, present a significant increase in the contact angle with water, compared to the controls, sand and ceramic, while at the same time, they decrease surface energy compared to sand and ceramics. Thus, surface wettability modifiers make structuring materials less water-wettable (based on contact angle with water) and are more likely to be oil-wetted (based on surface energy). Surface wettability modifiers, which have the best ability to improve oil flow, are assumed to be hydrophobic and yet oleophilic, prior to any laboratory testing.
[000149] The surface wettability modifiers, which most modify the wettability, tend to modify the surface wettability, in such a way that the contact angle with water approaches 90 °. The structuring material becomes significantly less wettable with water than sand and ceramics. This increase in contact angle with water compared to control (sand or ceramic) is accompanied by a concomitant increase in liquid hydrocarbon flow (represented in our work by Isopar™ L fluid) through a compaction of the material/coated builder/ treated, suggesting better hydrocarbon recovery/productivity.
[000150] In addition, the surface energy relative to sand/ceramic decreases by applying surface wettability modifiers. There is a downward trend in surface energy, which is especially observable for substrate 40/70 (where there is greater surface area), and this trend is towards the range described here in surface energies of 20- 30 mJ/m", surfaces that are wetted by hydrocarbon oils and that are water repellent. At critical surface energies, below 20 mJ/m2, hydrocarbon oils no longer spread and the surfaces are both hydrophobic and oleophobic It is also believed that any phenolic coating (eg Prime Plus) tends to be better than the uncoated substrate in terms of increased contact angle with water and decreased surface energy.
[000151] The 20/40 structuring materials were observed to have the same general trend regarding the contact angle with water and the surface energies as the 40/70 structuring materials. It is also further noted that surface wettability modifiers increase the water content angle and reduce surface energy, which should make the 20/40 particles less wettable with water, but more likely to be wetted by the water. oil.
[000152] For those skilled in the art, it should be recognized that both 40/70 and 20/40 are in agreement that the oil flow can be further optimized by controlling the amount of surface wettability modifiers that make up the coating externally (1 g SWM per 1000 g substrate may not be enough or may be too much, but most likely not enough) and by controlling the amount of surface area covered by the SWM. Full coverage using a continuous coating is probably better than a discontinuous coating. The amount of surface wettability modifiers can be further varied, such that the water contact angle is assumed to be as close to 90°F (32°C) as possible, while simultaneously decreasing the surface energy decrease to the range of 20-50 mJ/m2' Theoretical Example 1:
[000153] In order to create a more water-wettable surface from a structuring material coated with resin, 1000 g of a 20/40 white sand, coated with 36.5 g of a liquid resol phenol-formaldehyde at 400°F (204°C) and post-baked for 5 minutes at 350°F (176°C) are treated with 10% of an embedded hydrophilic silane such as triethoxysilylpropoxy(hexaethyleneoxy)dodecanoate or triethoxysilylpropoxy(triethylenoxy)octadecanoate, such that a contact angle with water of —30° -70° is then achieved, indicating that the neutrally wettable (or intermediately wettable) surface has been changed to a water wettable surface, resulting in a structuring material, which would be expected to be better wettable in the mixer tube and would then facilitate the recovery of water from the fracturing process when used as the structuring agent during hydraulic fracturing operations. Theoretical Example 2:
[000154] In order to create a more oil-wettable surface from a structuring material coated with polymeric material, 100 g of a 20/40 white sand, coated with 36 g of phenol-formaldehyde novolac SD polymeric material -672D and 9 g of 40% aqueous hexa at 390°F (198°C) are then treated with 10% of a silane, such as tridecafluorooctyltriethoxysilane or heptadecafluorodecyltrimethoxysilane, such that a contact angle with the water of ~110° -120°, indicating that the neutrally wettable (or intermediately wettable) surface was then changed to a more oil-wettable surface, resulting in a structuring material, which could be expected to increase hydrocarbon production and which would reduce scale when used as the structuring agent during hydraulic fracturing operations.
[000155] Although the invention has been described herein with reference to exemplary embodiments, it should still be understood by those skilled in the art that various changes can be introduced and that equivalents can still be replaced by elements thereof, without departing from the scope of the invention. Furthermore, many modifications can be introduced, and in such a way as to adapt a particular situation or material to the teachings of the present invention, without departing from the essential scope of the same. Thus, it is further intended that the invention should not be limited to that particular embodiment described as being the best contemplated mode for this invention to be carried out.

权利要求:
Claims (16)
[0001]
1. Structuring material comprising: a substrate material; a polymeric material, wherein the polymeric material is a thermosetting material selected from the group of a phenol-formaldehyde resin, a fluorine-free silicon-free epoxy resin, a phenol-furfuryl alcohol-formaldehyde terpolymer, a furan polymerized, a polyurethane resin, a polymerized urea-aldehyde, a polymerized melamine-aldehyde, a polyester, a polyalkyd, a polymerized phenol-aldehyde, and combinations thereof disposed on the substrate material; and a surface wettability modifier disposed on the polymeric material, wherein the surface wettability modifier is selected from the group consisting of siloxane copolymer, acrylate copolymer, acrylate materials, and combinations thereof, characterized in that that the acrylate copolymer is selected from the group consisting of fluoroalkyl methacrylate copolymers, fluoroalkyl acrylate copolymers, acryloxy terminated dimethyl siloxane-ethylene oxide block copolymers, (methacryloxypropyl)methyl siloxane-dimethyl siloxane copolymers, (acryloxypropyl)methyl siloxane-dimethyl siloxane copolymers, and combinations thereof, wherein the acrylate material is selected from the group consisting of fluoroalkyl methacrylate copolymers, fluoroalkyl acrylate copolymers, polyester acrylates, epoxy-modified acrylates, oligomers of urethane acrylates, and combinations thereof.
[0002]
2. Structuring material according to claim 1, characterized in that the substrate material is a material selected from the group consisting of inorganic substrates, organic substrates, composite substrates and combinations thereof.
[0003]
3. Structuring material according to claim 1, characterized in that the polymeric material is arranged in one or more layers, and each layer is a continuous or non-continuous layer.
[0004]
4. Structuring material according to claim 1, characterized in that the siloxane copolymer and/or acrylate copolymer is one selected from the group of polyalkylene-methyl siloxane oxide copolymer, polyalkylene-oxide copolymer- siloxane, fluoroalkyl methacrylate copolymers, fluoroalkyl acrylate copolymers, heptadecafluorodecyltrimethoxysilane polyalkylenedimethylsiloxane copolymers, acryloxy-terminated dimethyl siloxane-ethylene oxide block copolymers, acryloxy(methacryloxy)propylsiloxypropyl methylsiloxane copolymers siloxane-dimethyl siloxane, and combinations thereof.
[0005]
5. Structuring material according to claim 1, characterized in that the structuring material has a particle size range of 10 mesh (2 mm) to 200 mesh (0.074 mm).
[0006]
6. Structuring material according to claim 1, characterized in that the structuring material has a contact angle with water of from 59° to 120° and a surface energy of from 20 mJ/m2 to 50 mJ/m2.
[0007]
7. Structuring material according to claim 1, characterized in that the phenol-formaldehyde resin is selected from the group consisting of a silicon-free, fluorine-free, epoxy-modified novolac phenol-formaldehyde resin, phenol-formaldehyde resol, a modified phenol-formaldehyde resol resin, and combinations thereof.
[0008]
8. Structuring material according to claim 1, characterized in that the surface wettability modifier is a material selected from the group consisting of polyalkylene-dimethyl siloxane oxide copolymer, polyalkylene-siloxane oxide copolymer, methacrylate of 2-hydroxy ethyl(HEMA), and combinations thereof.
[0009]
9. Structuring material according to claim 1, characterized in that the acrylate material is selected from the group consisting of fluoroalkyl methacrylate copolymers, fluoroalkyl acrylate copolymers, polyester acrylates, epoxy-modified acrylates, acrylate oligomers of urethane, and combinations thereof.
[0010]
10. A method for treating an underground formation comprising: injecting a fracture fluid into the underground formation, wherein the fracture fluid comprises a structuring material selected from the group consisting of: a first structuring material, comprising a first substrate material, a first layer of polymeric material disposed over the substrate material, and a surface wettability modifying layer disposed over the polymeric material; a second structuring material, comprising a second substrate material and a second layer of polymeric material disposed over the substrate material; and characterized in that it further consists of a third structuring material, comprising a composite substrate having a third layer of polymeric material and a filler material dispersed throughout the third layer of polymeric material, wherein the surface wettability modifier comprises a material selected from the group consisting of siloxane copolymer, acrylate copolymer, acrylate materials, and combinations thereof, and wherein each of the first, second or third polymeric material comprises a thermosetting material selected from the group consisting of a resin of phenol formaldehyde, a silicon-free, fluorine-free epoxy resin, a phenol-furfuryl alcohol-formaldehyde terpolymer, a polymerized furan, a polyurethane resin, a polymerized urea-aldehyde, a polymerized melamine-aldehyde, a polyester, a polyalkyd, a polymerized phenol-aldehyde, and combinations thereof.
[0011]
11. Method according to claim 10, characterized in that the siloxane copolymer and/or the acrylate copolymer is one selected from the group consisting of polyalkylene dimethyl siloxane oxide copolymer, polyalkylene oxide copolymer- siloxane, heptadecafluorodecyltrimethoxysilane polyalkylenedimethylsiloxane copolymer, acryloxy terminated dimethyl siloxane-ethylene oxide block copolymers, (methacryloxypropyl)methyl siloxane-dimethyl siloxane copolymers, (acryloxypropyl)methyl siloxane and combinations thereof.
[0012]
12. Method according to claim 10, characterized in that the substrate material is a material selected from the group consisting of inorganic substrates, organic substrates, composite substrates and combinations thereof.
[0013]
13. Method according to claim 10, characterized in that the phenol-formaldehyde resin is selected from the group consisting of a silicon-free and fluorine-free epoxy-modified novolac phenol-formaldehyde resin, phenol resins -formaldehyde resol, a modified phenol-formaldehyde resol resin, and combinations thereof.
[0014]
14. Method according to claim 10, characterized in that each of the first, second or third polymeric material is arranged in one or more layers, and wherein each layer is a continuous or non-continuous layer.
[0015]
15. Method according to claim 10, characterized in that the surface wettability modifier is a material selected from the group consisting of polyalkylene-dimethyl siloxane oxide copolymer, polyalkylene-siloxane oxide copolymer, methacrylate 2-hydroxy ethyl(HEMA), and combinations thereof.
[0016]
16. The method of claim 10, characterized in that the acrylate material is selected from the group consisting of fluoroalkyl methacrylate copolymers, fluoroalkyl acrylate copolymers, polyester acrylates, epoxy-modified acrylates, acrylate acrylates oligomers. urethane, and combinations thereof.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112014007649B1|2021-05-04|structuring material, and method for the treatment of an underground formation

---

RU2344040C2|2009-01-20|Material particles containing thermoplastic elastomer, methods of their obtainment and application

---

RU2441051C2|2012-01-27|Free flowing coating particles, production method and use thereof

---

US8796187B2|2014-08-05|Additives to suppress silica scale build-up

---

US9096790B2|2015-08-04|Low temperature coated particles comprising a curable liquid and a reactive powder for use as proppants or in gravel packs, methods for making and using the same

---

CA2718659C|2016-04-12|Low temperature coated particles for use as proppants or in gravel packs, methods for making and using the same

---

US8800658B2|2014-08-12|Control of particulate entrainment by fluids

---

CA2738978C|2013-06-25|Prevention of water intrusion into particulates

---

CN104769075B|2017-07-21|It is used as the silicone-modified phenolic resin of oil and natural gas well proppants

---

RU2703077C2|2019-10-15|Low-temperature curable propping filler

---

KR20150127229A|2015-11-16|A proppant

---

WO2013044861A1|2013-04-04|Preparation method for fracturing proppant, fracturing proppant and use thereof

---

WO2019222034A1|2019-11-21|Nanocomposite coated proppants and methods of making and use thereof

---

US10017688B1|2018-07-10|Resin coated proppants for water-reducing application

---

CN109401739A|2019-03-01|A kind of high-temperature-resistant shielding diverting agent, preparation method and application

---

US20210054263A1|2021-02-25|Nanoparticle coated proppants and methods of making and use thereof

---

US10954434B2|2021-03-23|Coated proppants and methods of making and use thereof

同族专利:

---

公开号 | 公开日

---

CA2849755A1|2013-04-04|

---

US20130081812A1|2013-04-04|

---

MX360976B|2018-11-23|

---

CN103917622A|2014-07-09|

---

EP2855618A1|2015-04-08|

---

BR112014007649A2|2017-04-18|

---

AU2012316133A1|2014-04-17|

---

US20180149009A1|2018-05-31|

---

MX2014003552A|2014-06-05|

---

US9879515B2|2018-01-30|

---

CA2849755C|2017-04-11|

---

US10301920B2|2019-05-28|

---

AR088063A1|2014-05-07|

---

WO2013049235A1|2013-04-04|

---

EP2855618B1|2021-01-13|

---

EP2855618A4|2016-01-20|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2966457A|1956-05-08|1960-12-27|Swift & Co|Gelled fracturing fluids|

---

US4195010A|1977-07-06|1980-03-25|Burns & Russell Company of Baltimore City|Ceramic coated quartz particles|

---

US4439489A|1982-02-16|1984-03-27|Acme Resin Corporation|Particles covered with a cured infusible thermoset film and process for their production|

---

US4840729A|1987-01-02|1989-06-20|Atlantic Richfield Company|Oil spill recovery apparatus|

---

ES2029297T3|1988-05-13|1992-08-01|Sarea A.G.|USE OF A COMPOSITION FOR THE TREATMENT OF SOIL SURFACES.|

---

US4993491A|1989-04-24|1991-02-19|Amoco Corporation|Fracture stimulation of coal degasification wells|

---

ID25832A|1998-07-22|2000-11-09|Borden Chem Inc|HOW TO PROPPAN COMPOSITION, HOW TO COMPOSITION TO THE FILTRATION MEDIA AND THE METHOD OF MAKING AND USE IT|

---

DE60120553T2|2000-04-28|2007-06-06|Ricoh Co., Ltd.|Toner, external additive, and imaging process|

---

US7153575B2|2002-06-03|2006-12-26|Borden Chemical, Inc.|Particulate material having multiple curable coatings and methods for making and using same|

---

US20040023818A1|2002-08-05|2004-02-05|Nguyen Philip D.|Method and product for enhancing the clean-up of hydrocarbon-producing well|

---

US7426961B2|2002-09-03|2008-09-23|Bj Services Company|Method of treating subterranean formations with porous particulate materials|

---

US7270879B2|2003-04-15|2007-09-18|Hexion Specialty Chemicals, Inc.|Particulate material containing thermoplastics and methods for making and using the same|

---

US7135231B1|2003-07-01|2006-11-14|Fairmont Minerals, Ltd.|Process for incremental coating of proppants for hydraulic fracturing and proppants produced therefrom|

---

US20050173116A1|2004-02-10|2005-08-11|Nguyen Philip D.|Resin compositions and methods of using resin compositions to control proppant flow-back|

---

US7244492B2|2004-03-04|2007-07-17|Fairmount Minerals, Ltd.|Soluble fibers for use in resin coated proppant|

---

JP2007532721A|2004-04-12|2007-11-15|カーボ、サラミクス、インク|Hydraulic fracturing proppant coating and / or treatment to improve wettability, proppant lubrication and / or reduce damage by fracturing fluid and reservoir fluid|

---

WO2006023172A2|2004-08-16|2006-03-02|Fairmount Minerals, Ltd.|Control of particulate flowback in subterranean formations using elastomeric resin coated proppants|

---

BRPI0515437A|2004-09-20|2008-07-22|Hexion Specialty Chemicals Inc|coated particle, anchor, gravel filler, and methods of producing a coated particle, treating an underground formation and forming a gravel filler|

---

US8227026B2|2004-09-20|2012-07-24|Momentive Specialty Chemicals Inc.|Particles for use as proppants or in gravel packs, methods for making and using the same|

---

EA200702129A1|2005-05-02|2008-04-28|Трайкэн Велл Сервис Лтд.|METHOD FOR OBTAINING TRANSPORTABLE WATER SUSPENSIONS BY INCREASING THE HYDROPHOBICITY OF SOLID PARTICLES|

---

US7363978B2|2005-05-20|2008-04-29|Halliburton Energy Services, Inc.|Methods of using reactive surfactants in subterranean operations|

---

US20070172654A1|2006-01-23|2007-07-26|Hexion Specialty Chemicals, Inc.|Core for proppant and process for its production|

---

US20080051300A1|2006-08-23|2008-02-28|Pope Gary A|Compositions and method for improving the productivity of hydrocarbon producing wells|

---

US9096790B2|2007-03-22|2015-08-04|Hexion Inc.|Low temperature coated particles comprising a curable liquid and a reactive powder for use as proppants or in gravel packs, methods for making and using the same|

---

CA2585065A1|2007-04-13|2008-10-13|Trican Well Service Ltd.|Aqueous particulate slurry compositions and methods of making same|

---

AU2008243667B2|2007-04-26|2013-11-07|Trican Well Service Ltd|Control of particulate entrainment by fluids|

---

EP2324196A4|2008-08-21|2012-10-31|Schlumberger Services Petrol|Hydraulic fracturing proppants|

---

CN101665682B|2008-09-01|2013-02-13|西部钻探克拉玛依钻井工艺研究院|Modified methyl glucoside treating agent for drill fluid|

---

CN101665686B|2008-09-04|2013-08-14|北京仁创科技集团有限公司|Method for preparing surface-modified proppant|

---

US7921911B2|2008-12-30|2011-04-12|Schlumberger Technology Corporation|Surface-modifying agents for wettability modification|

---

CN101531893B|2009-04-28|2013-06-05|北京奇想达科技有限公司|Functional resin tectorial membrane proppant and preparation method thereof|

---

US8466094B2|2009-05-13|2013-06-18|Clearwater International, Llc|Aggregating compositions, modified particulate metal-oxides, modified formation surfaces, and methods for making and using same|

---

WO2011050046A1|2009-10-20|2011-04-28|Soane Energy, Llc|Proppants for hydraulic fracturing technologies|

---

US20130161003A1|2009-12-31|2013-06-27|Schlumberger Technology Corporation|Proppant placement|

---

CA2691891A1|2010-02-04|2011-08-04|Trican Well Services Ltd.|Applications of smart fluids in well service operations|

---

CN102443387B|2010-09-30|2016-08-03|北京仁创砂业科技有限公司|A kind of hydrophobic proppant and preparation method thereof|

---

BR112015025644A2|2013-04-08|2017-07-18|Expansion Energy Llc|non-hydraulic fracturing and cold foam proppant distribution systems, methods and processes|

---

PL2722378T3|2012-10-18|2015-11-30|Linde Ag|Method for fracturing or fraccing a well|

---

WO2015148836A1|2014-03-28|2015-10-01|Arr-Maz Products, L.P.|Attrition resistant proppant composite and its composition matters|

---

WO2015175850A1|2014-05-15|2015-11-19|U.S. Silica Company|Resin-coated substrate compositions and methods of making the same|

---

US20160137904A1|2014-10-30|2016-05-19|Preferred Technology, Llc|Proppants and methods of use thereof|WO2014039968A1|2012-09-10|2014-03-13|Carbo Ceramics, Inc.|Proppant particles formed from slurry droplets and method of use|

---

US9175210B2|2011-03-11|2015-11-03|Carbo Ceramics Inc.|Proppant particles formed from slurry droplets and method of use|

---

US9670400B2|2011-03-11|2017-06-06|Carbo Ceramics Inc.|Proppant particles formed from slurry droplets and methods of use|

---

US8883693B2|2011-03-11|2014-11-11|Carbo Ceramics, Inc.|Proppant particles formed from slurry droplets and method of use|

---

US8865631B2|2011-03-11|2014-10-21|Carbo Ceramics, Inc.|Proppant particles formed from slurry droplets and method of use|

---

US9290690B2|2011-05-03|2016-03-22|Preferred Technology, Llc|Coated and cured proppants|

---

US9725645B2|2011-05-03|2017-08-08|Preferred Technology, Llc|Proppant with composite coating|

---

US8763700B2|2011-09-02|2014-07-01|Robert Ray McDaniel|Dual function proppants|

---

US9562187B2|2012-01-23|2017-02-07|Preferred Technology, Llc|Manufacture of polymer coated proppants|

---

US9708527B2|2012-05-03|2017-07-18|Halliburton Energy Services, Inc.|Particulates having hydrophobic and oleophobic surfaces and methods relating thereto|

---

JP5242841B1|2012-10-13|2013-07-24|日本アエロジル株式会社|Water- and oil-repellent coating films and articles containing the coating films|

---

US9701589B2|2012-10-23|2017-07-11|Hd Proppants Llc|Proppants for use in hydrofracking|

---

US9803131B2|2012-11-02|2017-10-31|Wacker Chemical Corporation|Oil and gas well proppants of silicone-resin-modified phenolic resins|

---

US20140262262A1|2013-03-13|2014-09-18|Landec Corporation|Compositions and Methods for the Controlled Release of Active Ingredients|

---

US9518214B2|2013-03-15|2016-12-13|Preferred Technology, Llc|Proppant with polyurea-type coating|

---

US10100247B2|2013-05-17|2018-10-16|Preferred Technology, Llc|Proppant with enhanced interparticle bonding|

---

US10640702B2|2013-08-01|2020-05-05|Covestro Llc|Coated particles and methods for their manufacture and use|

---

WO2015054406A1|2013-10-09|2015-04-16|The Regents Of The University Of Michigan|Apparatuses and methods for energy efficient separations including refining of fuel products|

---

US10472769B2|2013-10-10|2019-11-12|The Regents Of The University Of Michigan|Silane based surfaces with extreme wettabilities|

---

US20190031950A1|2013-10-30|2019-01-31|Baker Hughes, A Ge Company, Llc|Method of enhancing conductivity in a subterranean formation|

---

US20150114640A1|2013-10-30|2015-04-30|Baker Hughes Incorporated|Proppants with improved strength|

---

US10087365B2|2013-10-30|2018-10-02|Baker Hughes, A Ge Company, Llc|Proppants with improved strength|

---

CN105612306B|2013-11-25|2019-04-05|哈利伯顿能源服务公司|Super-hydrophobicity flow control apparatus|

---

PL3074480T3|2013-11-26|2020-03-31|Basf Se|A proppant|

---

US9790422B2|2014-04-30|2017-10-17|Preferred Technology, Llc|Proppant mixtures|

---

WO2015169344A1|2014-05-06|2015-11-12|Basf Se|Method for making modified proppants and their use for hydraulic fracturing|

---

US10017688B1|2014-07-25|2018-07-10|Hexion Inc.|Resin coated proppants for water-reducing application|

---

WO2016032478A1|2014-08-28|2016-03-03|Halliburton Energy Services, Inc.|Proppant suspension in hydraulic fracturing|

---

EP3194523B1|2014-09-16|2020-04-29|Durez Corporation|Low temperature curable proppant|

---

CA2952212C|2014-09-24|2019-02-19|Halliburton Energy Services, Inc.|Silane additives for improved sand strength and conductivity in fracturing applications|

---

US10196555B2|2014-10-30|2019-02-05|Chevron U.S.A. Inc.|Subterranean producing zone treatment|

---

US20160137904A1|2014-10-30|2016-05-19|Preferred Technology, Llc|Proppants and methods of use thereof|

---

WO2016183313A1|2015-05-13|2016-11-17|Preferred Technology, Llc|High performance proppants|

---

US9862881B2|2015-05-13|2018-01-09|Preferred Technology, Llc|Hydrophobic coating of particulates for enhanced well productivity|

---

US10294413B2|2015-11-24|2019-05-21|Carbo Ceramics Inc.|Lightweight proppant and methods for making and using same|

---

EP3173238A1|2015-11-30|2017-05-31|OCE-Technologies B.V.|Orifice surface, print head comprising an orifice surface and method for forming the orifice surface|

---

CN108779389A|2016-01-28|2018-11-09|瓦克化学股份公司|Modified reactive resin composition and its purposes for coating proppant|

---

CN106277956B|2016-07-25|2018-05-25|广西大学|A kind of preparation process of geo-polymer fracturing propping agents|

---

US11208591B2|2016-11-16|2021-12-28|Preferred Technology, Llc|Hydrophobic coating of particulates for enhanced well productivity|

---

US10696896B2|2016-11-28|2020-06-30|Prefferred Technology, Llc|Durable coatings and uses thereof|

---

US10851282B2|2016-12-12|2020-12-01|Lonza Solutions Ag|Foaming agent composition and method for removing hydrocarbon liquids from subterranean wells|

---

CN106832145B|2016-12-16|2019-10-11|中国石油天然气股份有限公司|A kind of gas suspension proppant for slippery water pressure break and preparation method thereof and application method|

---

CN107201221A|2017-05-26|2017-09-26|中国石油集团川庆钻探工程有限公司长庆井下技术作业公司|A kind of CO2The method that dry method pressure break functional material coats proppant|

---

CN110945102B|2017-07-20|2021-10-01|沙特阿拉伯石油公司|Mitigating condensate build-up through the use of surface modification|

---

US10385261B2|2017-08-22|2019-08-20|Covestro Llc|Coated particles, methods for their manufacture and for their use as proppants|

---

CN107725007B|2017-11-14|2020-09-18|中国石油大学|Method for wetting and modifying oil reservoir model|

---

WO2019104018A1|2017-11-21|2019-05-31|3M Innovative Properties Company|Particles, compositions including particles, and methods for making and using the same|

---

EP3728931A4|2017-12-18|2021-07-21|Whirlpool Corporation|Method and structure for improved insulation and filler materials|

---

EP3533854A1|2018-03-01|2019-09-04|Momentive Performance Materials Inc.|Method of inhibiting water penetration into oil- and gas- producing formations|

---

CN108611086B|2018-05-07|2020-09-04|中国石油天然气股份有限公司|Tectorial membrane proppant and preparation method thereof|

---

US10767101B2|2018-06-28|2020-09-08|Baker Hughes, A Ge Company, Llc|Methods of controlling fines migration in a well|

---

WO2020086309A1|2018-10-26|2020-04-30|Alchemy Sciences, Inc.|Chemical additives and surfactant combinations for favorable wettability alteration and improved hydrocarbon recovery factors|

---

CN109585750B|2018-10-26|2021-10-15|大连中比动力电池有限公司|Composite diaphragm and preparation method thereof|

---

US11180691B2|2019-01-22|2021-11-23|Baker Hughes Holdings Llc|Use of composites having coating of reaction product of silicates and polyacrylic acid|

---

US11155751B2|2019-01-22|2021-10-26|Baker Hughes Holdings Llc|Method of treating subterranean formations with composites having enhanced strength|

---

CA3143820A1|2019-01-23|2020-07-30|Saudi Arabian Oil Company|Mitigation of condensate and water banking using functionalized nanoparticles|

---

WO2020185373A1|2019-03-11|2020-09-17|Dow Global Technologies Llc|Coated proppants|

---

CN110330952A|2019-07-03|2019-10-15|济源市宏鑫实业有限公司|A kind of film forming sealing agent|

法律状态:
2018-02-06| B25D| Requested change of name of applicant approved|Owner name: HEXION INC. (US) |

---

2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-12-29| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

---

2021-03-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-05-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201161541253P| true| 2011-09-30|2011-09-30|

---

US61/541,253|2011-09-30|

---

US201161549083P| true| 2011-10-19|2011-10-19|

---

US61/549,083|2011-10-19|

---

PCT/US2012/057372|WO2013049235A1|2011-09-30|2012-09-26|Proppant materials and methods of tailoring proppant material surface wettability|

---