WO2006079208A1 - Agent de soutenement leger et son procede de fabrication - Google Patents

Agent de soutenement leger et son procede de fabrication Download PDF

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Publication number
WO2006079208A1
WO2006079208A1 PCT/CA2006/000104 CA2006000104W WO2006079208A1 WO 2006079208 A1 WO2006079208 A1 WO 2006079208A1 CA 2006000104 W CA2006000104 W CA 2006000104W WO 2006079208 A1 WO2006079208 A1 WO 2006079208A1
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Prior art keywords
ceramic precursor
pore former
proppants
microspheres
group
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PCT/CA2006/000104
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English (en)
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Thomas Wilhelm Urbanek
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Global Synfrac Inc.
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Publication of WO2006079208A1 publication Critical patent/WO2006079208A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C04B35/443—Magnesium aluminate spinel
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/448—Sulphates or sulphites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/94—Products characterised by their shape
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • Lightweight particles commonly referred to as proppants, are provided for use in oil and gas wells.
  • the particles are useful to prop open subterranean formation fractures.
  • Hydraulic fracturing is a process of injecting fluids into an oil or gas bearing formation at sufficiently high rates and pressures such that the formation fails in tension and fractures to accept the fluid.
  • a propping agent proppant
  • Hydraulic fracturing increases the flow of oil or gas from a reservoir to the well bore in at [east three ways: (1) the overall reservoir area connected to the well bore is increased, (2) the proppant in the fracture has significantly higher permeability than . the formation itself, and (3) highly conductive (propped) channels create a large pressure gradient in the reservoir past the tip of the fracture.
  • Proppants are preferably spherical particulates that resist high temperatures, pressures, and the corrosive environment present in the formation. If proppants fail to withstand the closure stresses of the formation, they disintegrate, producing fines or fragments, which reduce the permeability of the propped fracture.
  • proppants were based on silica sand, glass beads, sand, walnut shells, or aluminum microspheres. For its sensible balance of cost and compressive strength, silica sand (frac-sand) is still the most widely used proppant in the fracturing business. Its use, however, is limited to depth with closure stresses of 41 MPa. Beyond this depth resin-coated and ceramic proppants are used. Resin-coated and ceramic proppants are limited to closure stresses of 55 and 83 MPa, respectively.
  • United States Patent No. 4,493,875 to Beck et a discloses the manufacture of lightweight composite particles, the core of which is a conventional proppant particle, such as silica sand.
  • the core has a thin coating containing hollow glass microspheres.
  • Proppant particles manufactured in accordance with the invention have apparent densities ranging from of 1.3 to 2.5 g/cm-Sup.3. Proppants manufactured according to this invention are not much stronger than the core particle itself and are, due to the cost of the resin and hollow glass spheres, quite expensive to manufacture.
  • United States Patent No. 5,030,603 to Rumpf and Lemieux teaches the manufacture of lightweight ceramic proppants with apparent specific gravities ranging from 2.65 to 3.0 g/cm.su ⁇ .3 from calcined Kaolin clay having particle sizes of less than 8 micron- The clay is mixed with an organic binder, then pelletized and sintered at 1 4, 00. degrees. C. Disadvantages of this invention are that the proppants have a relative high apparent specific gravity and are limited to closure stresses of 55 MPa.
  • United States Patent No. 5,120,455 to Lunghofer discloses the manufacture of lightweight ceramic proppants with apparent specific gravities of approximately 2-65 g/cm-su ⁇ .3 by sintering a mixture largely containing alumina and silica at 1 ,200 to i,650.degrees. C.
  • the proppants show significant conductivity at closure stresses of 83 MPa.
  • the main disadvantage of this invention is that the proppants still have a relative high apparent specific gravity.
  • United States Patent No, 6,753,299 to Lunghofer et al claims the use of using quartz, shale containing quartz, bauxite, talc, and wollastonite as raw materials.
  • the proppant contains as much as 65% quartz, and has yielded sufficient strength to be used in wells to a pressure of 69 MPa.
  • the apparent specific gravity of the proppant is approximately 2.62 g/cm.su ⁇ .3.
  • the invention provides some improvements on US patent 5,120,455, cited above, by reducing the specific gravity of the proppants and by introducing cost savings due to an increased use of silica.
  • the present invention seeks to address the perceived limitations in the art by providing a novel lightweight proppant and method of manufacturing the same.
  • composition and method useful in the manufacture of lightweight and high-strength proppants are provided.
  • the proppants are composed of porous ceramics. Pores in proppants according to this invention are ⁇ f sufficient physical stability at high temperatures to permit accurate and independent control of porosity and the sintering process. Thus, durable porous ceramics can be manufactured with repeatable accuracy, which are useful in the manufacture of lightweight and high-strength proppants.
  • Porosity is achieved by homogenously blending ceramic precursors with pore formers and sintering of the continuous phase of the ceramic precursors, preferably to near theoretical density.
  • Ceramic precursors may comprise ceramic oxides, preferably selected from the group consisting of alumina, aluminum hydroxide, boehmite, pseudo boehmite, kaolin clay, kaolinite, silica, clay, talc, magnesia, cordierite, and mullite.
  • Pore formers comprise a predetermined particle size, particle size distribution, morphology, specific gravity, and reactivity at elevated temperatures. Pore formers may inherently have a low thermal reactivity and are hereafter referred to as 'inert pore formers', or have a high thermal reactivity and are hereafter referred to as fugitive pore formers'.
  • the term 'thermal reactivity' refers to chemical reactions, which may occur at elevated temperatures.
  • the thermal reactivity of pore formers may be reduced by heating the disclosed compositions in the presence of non- oxydizing atmospheres, hereafter referred to as 'inert atmospheres', or enhanced by heating in oxidizing atmospheres, if pore formers are substantially inert at elevated temperatures, they are chosen to have a lower specific gravity than the sintered ceramic.
  • Pore formers are preferably comprised of finely divided natural or man-made materials, including walnut shells, alginates, saccharides, polymers, or carbon modifications, such as carbon black.
  • Proppants are formed by methods comprising the steps of: (a) homogen ⁇ usly blending ceramic precursors and pore formers, and other components which may improve the technical or economic performance of proppants during the stages of manufacture, storage, and field use;
  • microspheres (b) pelletizing the homogenous blend to form microspheres.
  • erm 'microspheres' refers to preferably spherical bodies of less than 5 mm in diameter;
  • components may be ground or ball m illed together in dry form.
  • Components may also be blended or dispersed with a liquid to improve homogeneity and the process of forming and sintering the microspheres.
  • Homogenous blends utilized in this invention have properties that allow them to be shaped and sintered to form proppant particles. These properties may be controlled by varying the solids content, temperature, pH, particle size, particle size distribution, and particle morphology, and through the use of inorganic and organic additives, commonly known to be rheology modifiers, such as fillers, fibres, binders, fugitive binders, surfactants, plasticizers, and thickeners.
  • inorganic and organic additives commonly known to be rheology modifiers, such as fillers, fibres, binders, fugitive binders, surfactants, plasticizers, and thickeners.
  • the method of forming the blends into 'green' proppants may be caused by techniques selected from the group consisting of agglomeration, spray granulation, wet granulation, spheronizing, extruding and pelletizing, vibration- induced dripping, spray nozzle formed droplets, and selective agglomeration.
  • 'green proppants' refers to microspheres of this invention, which have been shaped from the disclosed compositions but are not sintered.
  • Green proppants are then heated in stages to sintering temperatures. During the initial stages of heating evaporation and pyrolysis of pore formers and other additives occurs.
  • the present invention permits sintering of the continuous phase of ceramic precursors to less than or near theoretical density. Any economical heating process may be selected to heat the blended materials.
  • the method may comprise the further step of coating the microspheres after forming the proppants, the coating of the proppants then preferably comprising use of a coating selected from the group consisting of organic coating, epoxy, furan, phenolic resins and combinations thereof.
  • the invention provides a composition and method useful to economically manufacture proppants with repeatable accuracy.
  • the proppants have an apparent specific gravity of 1.0 to 2.9 g/cm.su ⁇ .3 and a compressive strength of 5 to 140 MPa.
  • the following is a detailed description of preferred embodiments of the present invention wherein is described a composition and method useful in the manufacture of particulate ceramics, commonly referred to as proppants.
  • the prappants comprise porous ceramics.
  • Porous ceramics have previously been used in many applications, such as refractories, filters, abrasives, fuel cells, bone implants, catalyst substrates, catalysts, drying agents, diffusion layers, heat exchange components, thermal insulators, sound barriers, and wicks.
  • the utility of ceramics in these applications depends on material properties such as bend and compressive strength, thermal shock resistance, thermal expansion, modulus of elasticity, fracture toughness, thermal conductivity, hardness, density, catalytic actiyity, and chemical inertness.
  • Pore volumes can be controlled to a certain degree through initial ceramic particle properties and sintering profiles. Extended sintering periods and high temperatures, however, generally decrease the amount of pores present (see Peng, Fukasawa, Ando, Zhang and Ohji, 'Microstructure and Mechanical Properties of Porous Alumina Ceramics Fabricated by the Decomposition of Aluminum Hydroxide', Journal of the American Ceramic Society. Vol. 84 (11), 2638, 2001). Sintering, therefore, must be restricted at times to achieve certain pore volumes while other mechanical properties are neglected.
  • lightweight ceramics would be produced according to a method which controls pore size, pore size distribution, and total pore volume independent of the sintering process. The method may also permit sintering of ceramic precursors to near theoretical density and thereby improvements of mechanical properties, including compressive strength.
  • microporous ceramic compositions are prepared by first forming an intimate mixture of oligomeric or polymeric ceramic precursors with additive particles to provide a composite intermediate, followed by pyrolysis of the composite intermediate under an inert atmosphere in sequential stages.
  • porosity of ceramics is controlled by the volume percentage, particle size, and particle shape of a fugitive material, which is added to the original refractory material slurry.
  • the method is used to fabricate setter tiles and contact sheets.
  • the fugitive phase is used independently to introduce porosity or in conjunction with partial densification. Since porosity is not solely dependent upon partial sintering, higher porosity levels can be achieved with less impact on subsequent mechanical properties of the sintered refractory material.
  • This prior art uses carbon black as a pore former to improve mechanical properties other than compressive strength and to control pore volumes of ceramics containing contiguous pores after sintering. The use of inert atmospheres to control porosity is not mentioned.
  • the porous ceramics are useful in the manufacture of lightweight and high-strength proppants. Control of porosity and sintering processes is achieved by improving the stability of intentionally introduced pores at high temperatures.
  • the invention permits sintering of the pore- encompassing ceramic precursors to less than or near theoretical density.
  • Pore formers of this invention may be fugitive or inert. Fugitive pore formers are substantially reactive and undergo chemical reactions at elevated temperatures. Such reactivity may encompass thermal and redox processes.
  • the composition of final reaction products therefore depends on the chemical composition of pore formers initially present, intermediates formed during heating, and the reactivity of both with optional oxidizing atmospheres at elevated temperatures.
  • pore formers initially present, intermediates formed during heating, and the reactivity of both with optional oxidizing atmospheres at elevated temperatures.
  • thermal and oxidative processes are jointly referred to hereafter as 'pyroiyses'.
  • Inert pore formers inherently have low thermal reactivity and do not experience substantial pyroiyses with heating.
  • pores are occupied by materials that have a lower specific gravity than the continuous phase of sintered ceramics.
  • pyroiyses of pore formers may be reduced by heating in non-oxidizing atmospheres or enhanced by heating in oxidizing atmospheres.
  • Inert atmospheres may be produced by replacing air with gases such as nitrogen, argon, or ammonia.
  • Oxidizing atmospheres may comprise oxygen by itself or in presence of other gases, such as the composition of air.
  • pore formers also have a predetermined concentration, particle size, particle size distribution, morphology, including porous, foamed, or hollow particles, and specific gravity. These parameters jointly permit accurate and independent command of pore sizes, pore size distribution, total pore volumes, and pore connectivity from sintering. Since pores of this invention can be managed throughout the manufacturing cycle, sintering of ceramic precursors can be independently controlled by choosing methods and conditions. Thus, sintering of the continuous phase of ceramic precursors to near theoretical density can be achieved, resulting in porous ceramics of improved mechanical properties, such as compressive strength.
  • the at least one pore former may comprise finely divided natural or man- made, organic or inorganic materials, including walnut shells, alginate, saccharides, polymers, or carbon modifications, such as carbon black.
  • carbon black is the preferred pore former, other materials that have well-controlled particle size distributions and are easily blended or dispersed, preferably as fine powders, may be utilized in the present invention.
  • the particle size of pore formers is preferably less than 5 microns, and most preferably less than 1 micron.
  • Pore formers of appropriate particle size, particle size distribution, and particle morphology may be produced by any suitable and economical process, such as grinding, ball milling, precipitating, dispersing, flame pyrolysis, gas condensation, spray conversion, crystallization, polymerization, chemical synthesis, or sol-gel techniques.
  • Pore formers are homogenously blended with at least one ceramic precursor, which may comprise a finely divided ceramic oxide, preferably selected from the group consisting of alumina, aluminum hydroxide, boehmite, pseudo boehmite, Kaolin clay, Kaolinite, silica, clay, talc, magnesia, cordierite, and muUite.
  • a ceramic precursor which may comprise a finely divided ceramic oxide, preferably selected from the group consisting of alumina, aluminum hydroxide, boehmite, pseudo boehmite, Kaolin clay, Kaolinite, silica, clay, talc, magnesia, cordierite, and muUite.
  • the particle size of ceramic precursors is preferably less than 10 microns, and most preferably less than 5 microns. Ceramic precursors of appropriate particle size, particle size distribution, and particle morphology may be produced by any suitable and economical process, such as grinding, ball milling, precipitating, dispersing, flame pyr ⁇ iysis, gas condensation, spray conversion, crystallization, chemical synthesis, or so
  • any process providing for homogenous mixtures may be selected to blend the components of this invention.
  • components may be blended by grinding, ball milling, or pulverizing together in dry form.
  • Components may also, be plended or dispersed with at least one liquid to improve homogeneity and the process of forming and sintering the microspheres.
  • the liquid preferably has a boiling point less than i50.degrees. C. More preferably, the liquid is water. Concentrations of liquid may range from 2 to 75 Wt. percent-
  • Homogenous blends utilized in this invention have properties that allow them to be shaped and sintered to form proppant particles. These properties may be controlled by varying the solid content, temperature, pH, particle size, particle size distribution, and particle morphology, and through the use of inorganic and organic additives, commonly Known to be rheology modifiers, such as fillers, fibres, binders, fugitive binders, surfactants, plasticizers, and thickeners. Fillers may be added to achieve desired economic targets, specific mechanical and chemical properties during mixing of the chemical components, forming and sintering of green proppants, and the field performance of the final product.
  • inorganic and organic additives commonly Known to be rheology modifiers, such as fillers, fibres, binders, fugitive binders, surfactants, plasticizers, and thickeners. Fillers may be added to achieve desired economic targets, specific mechanical and chemical properties during mixing of the chemical components, forming and sintering of green proppants, and the field
  • Compatible fillers include waste materials, such as fly ash, sludges, slags, volcanic aggregates, expanded perlite, pumice, obsidian, diatomaceous earth mica, borosilicates, clays, oxides, fluorides, sea shells, silica, inorganic pore formers, mineral fibres, or chopped fjbreglass.
  • Inorganic pore formers may be added to increase porosity and. are preferably selected from the group consisting of carbonates, acetates, nitrates, silica and alumina hollow spheres.
  • the addition of binders may improve the process of dispersing, shaping, or sintering of the composition. Binders may include natural or man-made materials such as acrylic polymers, alginates, saccharides, silicates, and monomer-catalyst combinations used in processes commonly Known as 'reactive bonding'.
  • Homogenousiy blended materials are heated in several stages to sintering temperatures. At temperatures below 500.degree. C, liquids are volatilized. At higher temperatures, pyrolysis of polymers occurs and low-molecular- weight organics are volatilized. Pyrolysis Is also performed at temperatures below 500.degree. C. The remaining organic compounds are typically burned off above temperatures of about 800.degree. C. Sintering and densificati ⁇ n may also occur above these temperatures. Any economical heating process may be selected to heat the blended materials. While partial densificatjon produces even higher levels of porosity, full densification of ceramic precursors is preferred- The resulting porous ceramics are lightweight, have high compressive strength, and can be produced with repeatable accuracy.
  • the disclosed lightweight proppants may be coated with organic coatings, such as epoxy, furan, and phenolic resins ⁇ United States Patent : No- 5,639,806 ⁇ , and combinations of these coatings to improve their performance characteristics and utility.
  • coatings may be used to sea! open pores connecting to the surface of sintered proppants. Applications may be carried out in accordance with known methods for coating proppants or ceramics.
  • porous ceramics such as compressive strength and specific gravity
  • the selection of raw materials and manufacturing conditions would be clearly evident to those skilled in the art. It is therefore another object of this invention to provide durable porous ceramics, which can be manufactured with repeatable accuracy, and are useful in the manufacture of proppants for oil and gas wells.
  • the proppants are strong in compression, have a low apparent specific gravity, and can be made more economically than presently available materials,
  • a composition and method to accurately and independently control sintering of ceramics precursors and porosity of the sintered ceramic is disclosed.
  • the resulting porous ceramics are lightweight and high in compressive strength.
  • the ceramics are suitable for the manufacture of proppants and have an apparent specific gravity of 1.0 to 2.9 g/cm,sup.3 and a compressive strength of 14 to 104 MPa.
  • the method of the present invention may comprise the step of homogenousiy blending or dispersing the at least one finely divided ceramic precursor and pore former, and other additives using conventional blending or dispersing techniques.
  • the properties of the disclosed blends permit use of sphere- forming techniques such as agglomeration, spray granulation, wet granulation, spheronizing, extruding and pelletizing, vibration-induced dripping (United States Patent No. 5,500,162), spray nozzle formed droplets (United States Patent No. 4,392,987), selective agglomeration (United States Patent No. 4,902,666), the use of which is incorporated herein by reference.
  • Trie techniques allow manufacture of green proppants from the disclosed compositions. Green proppants are heated in stages to sintering temperatures. The continuous phase of ceramic precursors may be sintered to less than or near theoretical density using conventional heating techniques.
  • Proppants manufactured according to the present invention have an apparent specific gravity of 1.0 to 2.9 g/cm.su ⁇ .3 and a compressive strength of 5 to 140 MPa.
  • the disclosed lightweight proppants may be coated with organic coatings, such as epoxy, furan, and phenolic resins, and combinations of these coatings to improve their performance characteristics and utility.
  • the coating may be carried out in accordance with known metho d s of coating proppants or ceramics.
  • porous ceramics When compared on volume bases to presently manufactured lightweight proppants, high pore volumes and lower heat capacities of the porous ceramics both permit reduction in manufacturing costs.
  • the properties of the disclosed blends permit production of highly spherical and near monodisperse particles.
  • Proppants manufactured according to the present invention can meet a wide range of economic and mechanical requirements. As porosity of the ceramics is increased, proppants show less compressive strength, but also material and energy costs to manufacture the same volume of proppants are significantly reduced. Highly porous proppants, therefore, can be manufactured according to this invention to compete with frac-sand, and denser proppants can be tailored to be competitive with current ceramic proppants. This range is not readily adapted by other techniques.
  • a lightweight, high-strength proppant comprising the formation of porous ceramics by sintering ceramic precursors in the presence of pore formers.
  • a method of manufacturing such a proppant is also disclosed, comprising the steps of preferably blending ceramic precursors, pore formers, and additives homogenously. These blends have properties, which permit the shaping of spheres using conventional pelletizing techniques. Staged heating of the microspheres to sintering temperatures produces porous ceramics with repeatable accuracy.
  • the pelletized porous ceramics are useful as lightweight and high-strength proppa ⁇ ts.
  • the following example illustrates the use of porous ceramics in the manufacture of lightweight proppants.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)

Abstract

L'invention concerne un procédé destiné à la formation d'agents de soutènement très résistants et légers, consistant : à former un mélange homogène à partir d'au moins un précurseur céramique et d'au moins un composant porogène ; à former des granulés à partir du mélange pour former des microsphères ; à chauffer les microsphères formées jusqu'à des températures inférieures à des températures de frittage, pour évaporer les composants volatils et produire la pyrolyse des composants fugitifs ; à chauffer davantage les microsphères jusqu'à des températures suffisantes pour obtenir le frittage de la phase continue du précurseur céramique et former des particules frittées ; puis à former les particules frittées pour obtenir des agents de soutènement globalement sphéroïdaux. Ces agents de soutènement globalement sphéroïdaux, qui, de préférence, ont été frittés jusqu'à une densité proche d'une densité théorique, peuvent être revêtus. Le chauffage des microsphères peut comprendre une série d'étapes de chauffage.
PCT/CA2006/000104 2005-01-26 2006-01-26 Agent de soutenement leger et son procede de fabrication WO2006079208A1 (fr)

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WO2009038491A1 (fr) * 2007-09-18 2009-03-26 Schlumberger Canada Limited Agent de soutènement, son procédé de fabrication et procédé de fracturation hydraulique utilisant cet agent de soutènement
WO2010021559A1 (fr) * 2008-08-22 2010-02-25 Medmat Innovation - Materiais Médicos, Lda. Pastilles à base d'hydroxyapatite et de bioverre, procédé de production et applications de celles-ci
CN102071006A (zh) * 2010-11-22 2011-05-25 大庆油田有限责任公司 一种利用油页岩渣制备的石油支撑剂及其制备方法
RU2474549C1 (ru) * 2011-10-24 2013-02-10 Юлия Алексеевна Щепочкина Керамическая масса для изготовления облицовочной плитки
CN106495731A (zh) * 2016-11-30 2017-03-15 青岛易生态环保科技有限公司 以江河湖海污泥和贝壳类粉为原料生产的陶粒及其制备方法
CN107805081A (zh) * 2017-10-31 2018-03-16 湖南镭目科技有限公司 一种多孔陶瓷及其制备方法
CN107829731A (zh) * 2017-11-06 2018-03-23 陈国军 一种黏土蚀变的火山岩孔隙度校正方法
US10017687B2 (en) 2014-05-14 2018-07-10 California Institute Of Technology Ultra-light ultra-strong proppants
CN109913197A (zh) * 2019-03-21 2019-06-21 中国石油天然气股份有限公司 一种驱油支撑剂及其制备方法
CN110368918A (zh) * 2019-08-15 2019-10-25 西南化工研究设计院有限公司 一种拟薄水铝石粉体的喷雾造粒方法
CN112661492A (zh) * 2019-10-16 2021-04-16 国家能源投资集团有限责任公司 用于生产粉煤灰陶瓷膜的组合物以及粉煤灰陶瓷膜及其制备方法和应用
CN112790445A (zh) * 2021-01-08 2021-05-14 惠州市新泓威科技有限公司 除重金属多孔陶瓷的制备方法、除重金属的多孔陶瓷及雾化芯
CN113513295A (zh) * 2020-04-10 2021-10-19 中国石油化工股份有限公司 一种提高段内多簇裂缝均匀延伸和支撑的方法
CN115364677A (zh) * 2021-05-21 2022-11-22 三达膜科技（厦门）有限公司 一种热稳定性改性球形氧化铝陶瓷微滤膜的制备方法
CN116023152A (zh) * 2022-12-30 2023-04-28 中南大学 一种高温烧结助剂及其应用

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US10087365B2 (en) 2013-10-30 2018-10-02 Baker Hughes, A Ge Company, Llc Proppants with improved strength
US11155751B2 (en) 2019-01-22 2021-10-26 Baker Hughes Holdings Llc Method of treating subterranean formations with composites having enhanced strength
US11180691B2 (en) 2019-01-22 2021-11-23 Baker Hughes Holdings Llc Use of composites having coating of reaction product of silicates and polyacrylic acid
CN115028430B (zh) * 2022-07-11 2023-03-24 郑州市新郑梅久实业有限公司 一种低密度陶粒支撑剂的制备方法

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Cited By (23)

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US8496057B2 (en) 2007-09-18 2013-07-30 Schlumberger Technology Corporation Proppant, a method for production thereof and formation hydraulic fracturing method using the produced proppant
WO2009038491A1 (fr) * 2007-09-18 2009-03-26 Schlumberger Canada Limited Agent de soutènement, son procédé de fabrication et procédé de fracturation hydraulique utilisant cet agent de soutènement
WO2010021559A1 (fr) * 2008-08-22 2010-02-25 Medmat Innovation - Materiais Médicos, Lda. Pastilles à base d'hydroxyapatite et de bioverre, procédé de production et applications de celles-ci
CN102071006A (zh) * 2010-11-22 2011-05-25 大庆油田有限责任公司 一种利用油页岩渣制备的石油支撑剂及其制备方法
RU2474549C1 (ru) * 2011-10-24 2013-02-10 Юлия Алексеевна Щепочкина Керамическая масса для изготовления облицовочной плитки
US10017687B2 (en) 2014-05-14 2018-07-10 California Institute Of Technology Ultra-light ultra-strong proppants
CN106495731A (zh) * 2016-11-30 2017-03-15 青岛易生态环保科技有限公司 以江河湖海污泥和贝壳类粉为原料生产的陶粒及其制备方法
CN107805081A (zh) * 2017-10-31 2018-03-16 湖南镭目科技有限公司 一种多孔陶瓷及其制备方法
CN107829731A (zh) * 2017-11-06 2018-03-23 陈国军 一种黏土蚀变的火山岩孔隙度校正方法
CN107829731B (zh) * 2017-11-06 2020-10-09 陈国军 一种黏土蚀变的火山岩孔隙度校正方法
CN109913197B (zh) * 2019-03-21 2021-03-09 中国石油天然气股份有限公司 一种驱油支撑剂及其制备方法
CN109913197A (zh) * 2019-03-21 2019-06-21 中国石油天然气股份有限公司 一种驱油支撑剂及其制备方法
CN110368918A (zh) * 2019-08-15 2019-10-25 西南化工研究设计院有限公司 一种拟薄水铝石粉体的喷雾造粒方法
CN112661492A (zh) * 2019-10-16 2021-04-16 国家能源投资集团有限责任公司 用于生产粉煤灰陶瓷膜的组合物以及粉煤灰陶瓷膜及其制备方法和应用
CN113513295A (zh) * 2020-04-10 2021-10-19 中国石油化工股份有限公司 一种提高段内多簇裂缝均匀延伸和支撑的方法
CN113513295B (zh) * 2020-04-10 2023-06-13 中国石油化工股份有限公司 一种提高段内多簇裂缝均匀延伸和支撑的方法
CN112790445A (zh) * 2021-01-08 2021-05-14 惠州市新泓威科技有限公司 除重金属多孔陶瓷的制备方法、除重金属的多孔陶瓷及雾化芯
WO2022148126A1 (fr) * 2021-01-08 2022-07-14 惠州市新泓威科技有限公司 Procédé de fabrication de céramique poreuse ayant fait l'objet d'une élimination de métaux lourds, céramique poreuse ayant fait l'objet d'une élimination de métaux lourds, et noyau d'atomisation
CN112790445B (zh) * 2021-01-08 2024-03-15 海宁新纳陶科技有限公司 除重金属多孔陶瓷的制备方法、除重金属的多孔陶瓷及雾化芯
CN115364677A (zh) * 2021-05-21 2022-11-22 三达膜科技（厦门）有限公司 一种热稳定性改性球形氧化铝陶瓷微滤膜的制备方法
CN115364677B (zh) * 2021-05-21 2024-03-19 三达膜科技（厦门）有限公司 一种热稳定性改性球形氧化铝陶瓷微滤膜的制备方法
CN116023152A (zh) * 2022-12-30 2023-04-28 中南大学 一种高温烧结助剂及其应用
CN116023152B (zh) * 2022-12-30 2024-01-26 中南大学 一种高温烧结助剂及其应用

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