Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
  • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
• • E—FIXED CONSTRUCTIONS
  • E21—EARTH OR ROCK DRILLING; MINING
  • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
  • E21B43/25—Methods for stimulating production
  • E21B43/26—Methods for stimulating production by forming crevices or fractures
  • E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
  • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
  • C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
• • 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
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/62605—Treating the starting powders individually or as mixtures
  • C04B35/62695—Granulation or pelletising
• • 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
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/628—Coating the powders or the macroscopic reinforcing agents
  • C04B35/62802—Powder coating materials
  • C04B35/62805—Oxide ceramics
  • C04B35/62807—Silica or silicates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
  • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
  • C09K8/805—Coated proppants
• • C—CHEMISTRY; METALLURGY
  • 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
  • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
  • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
• • 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
  • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3427—Silicates other than clay, e.g. water glass
  • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
• • 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
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/52—Constituents or additives characterised by their shapes
  • C04B2235/528—Spheres
• • 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
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
  • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S507/00—Earth boring, well treating, and oil field chemistry
  • Y10S507/904—Process of making fluids or additives therefor
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S507/00—Earth boring, well treating, and oil field chemistry
  • Y10S507/906—Solid inorganic additive in defined physical form

Definitions

• the present invention relates to proppants and methods to make the proppants and uses of the proppants.
• the proppant or a portion thereof has a glass- ceramic material present.
• the presence of a glass-ceramic material can provide one or more benefits, such as increased stiffness (or modulus of rigidity, "MOR"), a desirable coefficient of thermal expansion, and/or other benefits.
• MOR modulus of rigidity
• Proppants are materials pumped into oil or gas wells at extreme pressure in a carrier solution (typically brine) during the hydrofracturing process. Once the pumping-induced pressure is removed, proppants "prop" open fractures in the rock formation and thus preclude the fracture from closing. As a result, the amount of formation surface area exposed to the well bore is increased, enhancing recovery rates.
• a carrier solution typically brine
• Ceramic proppants are widely used as propping agents to maintain permeability in oil and gas formations.
• High strength ceramic proppants have been used in the hydrofracture of subterranean earth in order to improve production of natural gas and/or oil.
• the proppant beads need to withstand 10 kpsi or higher pressure to be effective to prop the fracture generated by the hydrofracture process.
• proppants formed from high strength materials such as sintered bauxite and alumina have sufficient compressive and flexural strength for use in deep wells.
• These conventional high strength materials are expensive, however, because of a limited supply of raw materials, a high requirement for purity, and the complex nature of the manufacturing process.
• a feature of the present invention is to provide a proppant having an improved coefficient of thermal expansion. Another feature of the present invention is to provide a proppant that can provide increased stiffness (modulus of rigidity).
• An additional feature of the present invention is to provide a proppant having better resistance to fracturing.
• a further feature of the present invention is to provide a proppant that can have less discreet interfaces between various layers that can form the proppant.
• the present invention relates to a proppant having a template sphere.
• the proppant optionally has a shell that can be sintered around the entire outer surface of the template sphere.
• the optional shell can comprise glass- ceramic.
• the optional shell which can comprise one or more layers, can contain one or more metal oxides, a ceramic material or oxide thereof, and/or other suitable materials.
• the outer surface of the template sphere can include or have a glass-ceramic material.
• a glass-ceramic containing layer can be present on the outer surface of the template sphere.
• the present invention further relates to a method to prop open subterranean formation fractions using one or more proppants of the present invention, which can be contained in proppant formulations.
• the present invention further relates to methods of making the various proppants of the present invention.
• one method includes crystallizing at least an outer surface of a template material to form glass-ceramic, and coating the template material with a formulation comprising a ceramic material or oxide thereof and/or one or more metal oxides and/or other material to form a shell around the template and then hardening the shell, such as by sintering or calcining.
• Other methods are further described.
• Figure 1 is a graph showing the density of the cenosphere powder-derived glass- ceramics of the present invention as a function of Ti0 2 content. All the samples were sintered at 1200°C for 4h.
• Figure 2 is a graph showing the diametral splitting tensile strength of the cenosphere- derived glass-ceramics of the present invention as a function of Ti0 2 content. All the samples were sintered at 1200°C for 4h.
• Figure 3 is a graph showing the specific diametral splitting tensile strength of the cenosphere-derived glass-ceramics of the present invention as a function of Ti0 2 content.
• the present invention relates to a proppant, methods of making the proppant, and uses for the proppant, including using the proppant for assisting in hydrocarbon recovery.
• the present invention relates to a proppant having present a glass-ceramic or a glass- ceramic material as part of the proppant.
• the proppant comprises one or more components
• one or more of the components can contain the glass-ceramic.
• the proppant can be a template sphere or core, and at least the outer surface of the template sphere or core can be or can comprise or consist essentially of or consist of one or more glass-ceramics.
• the proppant can be a template sphere having one or more layers located on the sphere. At least one of these layers can comprise, consist essentially of, or consist of one or more glass-ceramics.
• a proppant can be a template sphere (which can optionally contain a glass-ceramic) that has a glass-ceramic containing layer in contact (direct contact or in contact with a layer located on said template sphere) with at least the outer surface of the template sphere.
• the proppant can be a template sphere having an outer surface wherein the outer surface of the template sphere comprises a glass-ceramic(s) and further has at least one layer in contact (direct contact or in contact with a layer located on said template sphere) with the outer surface of the template sphere, wherein the layer(s) comprises a glass-ceramic(s).
• the glass- ceramic containing layer can at least partially diffuse into the outer surface of the template sphere.
• the template sphere (which also can be referred to as a core or substrate) can be a solid sphere or a hollow sphere, or a sphere having one or more voids or a sphere having porosity. It should be understood that a solid sphere, as used herein, does not contain a void space in the center, although a porous material would be suitable. A fully dense material is not a requirement of a solid sphere. It should be understood that a hollow sphere, as used herein, has at least one void space inside with a defined size and shape.
• the template sphere can have a void volume % of at least 30%.
• the template sphere can be formed from a glass or substantially glassy material.
• the cenosphere can be a commercially produced ceramic or glass hollow sphere that is made as a side product in various industrial processes.
• the term "sphere” is used, it is to be understood that the "sphere” can have irregular shapes (e.g., non- spheroidal) and, therefore, can be a consistently round spherical object or it can be less than perfect with respect to sphericity and/or roundness or can have other shapes.
• the template sphere can have a Krumbein sphericity of at least about 0.3, such as at least 0.4, at least 0.5, at least 0.6, at least 0.7, such as from 0.3 to 0.9 or higher.
• the template sphere alternatively, or in addition, can have a roundness of at least about 0.1, such as at least about 0.3, at least 0.4, at least 0.5, at least 0.7, such as from 0.1 to 0.9 or higher.
• the overall proppant which can be the template sphere, alone or with one or more layers on the template, can have the same Krumbein sphericity and/or roundness values mentioned for the template.
• the proppant can have a Krumbein sphericity of at least about 0.5 (such as at least 0.6, at least 0.7, at least 0.8, at least 0.9, such as from 0.5 to 0.9 or higher) and/or the proppant can have a roundness of at least about 0.4 (such as at least 0.5, at least 0.7, at least 0.8, such as from 0.4 to 0.9 or higher).
• the proppant can have one or more layers located on the template sphere. At least one of these layers can form a shell around the entire outer surface of the template sphere.
• the shell can be a continuous shell or a non-continuous shell.
• the shell can have a thickness of from about 5 micrometers to 150 micrometers or thicker.
• the shell can be sintered.
• the shell can include ceramic.
• the shell can include glass-ceramic.
• the glass- ceramic or glass-ceramics can be present in one or more components (or parts) of the proppant.
• the glass-ceramic can be present on at least the outer surface of the template sphere.
• the glass-ceramic can be present on the entire circumference of the outer surface of the template sphere or a portion thereof.
• the outer surface can comprise the exposed, outer most surface.
• the presence of the glass-ceramic can include portions beneath this exposed surface, such as 0.1% to 100% of the inner volume or area of the template sphere, e.g., from 1% to 90%, from 5% to 80%, 10% to 70%, 15% to 60%, 20% to 50%, and the like.
• the glass-ceramic can be distributed uniformly or non-uniformly in the outer surface and/or inner volume of the template sphere.
• the glass-ceramic of the template sphere can be in solid form.
• the glass-ceramic of the template sphere can be in porous or hollow form.
• the glass-ceramic can be present uniformly throughout the shell or distributed non- uniformly in one or more portions of the shell.
• the glass-ceramic of the shell can be in solid form.
• the glass-ceramic of the shell can be in porous or hollow form.
• the glass-ceramic of the shell can be the same or different from the glass-ceramic of the template sphere.
• the glass-ceramic of the shell can have the same or different degree of crystallinity as the glass-ceramic of the template sphere, and/or the same or different composition as the glass-ceramic of the template sphere.
• the glass-ceramic can comprise from about 0.5% by weight to about 100% by weight of the overall proppant, based on the total weight percent of the proppant.
• the glass-ceramic can be present in an amount from about 5 wt% to about 90 wt% or higher, from about 10 wt% to about 75 wt%, from about 15 wt% to about 50 wt%, from about 20 wt% to about 30 wt% or higher, all based on the total weight of the proppant.
• Glass-ceramic refers to any glass-ceramic that is formed when glass or a substantially glassy material is annealed at elevated temperature to produce a substantially crystalline material with limited crystallinity or controlled crystallite size.
• limited crystallinity should be understood as crystallinity of from about 5% to about 100%, by volume (e.g., 10% to 90%; 20% to 80%; 30% to 70%; 40% to 60% by volume).
• the crystallite size can be from about 0.01 micrometers to 20 micrometers, such as 0.1 to 5 micrometers. Preferably the crystallite size is less than 1 micrometer.
• the glass-ceramic can be composed of aluminum oxide, silicon oxide, boron oxide, potassium oxide, zirconium oxide, magnesium oxide, calcium oxide, lithium oxide, phosphorous oxide, and/or titanium oxide or any combination thereof.
• the glass-ceramic can comprise from about 35% to about 55% by weight Si0 2 ; from about 18% to about 28% by weight A1 2 0 3 ; from about 1% to about 15% by weight (e.g., 1 to 5 wt%) CaO; from about 7% to about 14% by weight MgO; from about 0.5% to about 15% by weight Ti0 2 (e.g., 0.5 to 5 wt%); from about 0.4% to about 3% by weight B 2 0 3 , and/or greater than 0% by weight and up to about 1% by weight P 2 0 5 , all based on the total weight of the glass- ceramic.
• the glass-ceramic can comprise from about 3% to about 5% by weight Li 2 0; from about 0% to about 15% by weight A1 2 0 3 ; from about 10% to about 45% by weight Si0 2 ; from about 20% to about 50% by weight MgO; from about 0.5% to about 5% by weight Ti0 2 ; from about 15% to about 30% by weight B 2 0 3 , and/or from about 6% to about 20% by weight ZnO, all based on the total weight of the glass-ceramic.
• the template sphere can comprise a mixture of aluminum oxide, silicon oxide, titanium oxide, iron oxide, magnesium oxide, calcium oxide, potassium oxide and/or sodium oxide, and/or any combination thereof.
• the glass-ceramic can be fully or nearly fully crystalline or can contain a glass component (e.g., phase(s)) and a crystalline component (e.g., phase(s)) comprising crystallites.
• the glass-ceramic can have a degree of crystallinity of from about 5% to about 100%, or from about 15% to about 80%.
• the glass-ceramic can have from about 50% to 80%) crystallinity, from about 60% to 78% crystallinity or from about 70% to 75%» crystallinity by volume.
• the crystallites can have a random and/or directed orientation.
• the crystal orientation of the crystals in the glass-ceramic can be primarily random or can be primarily directed in a particular orientation(s) (e.g., non-random).
• the crystal orientation of the glass-ceramic can be primarily random such that at least 50% or higher of the orientations are random orientations based on the overall orientation of the crystals present.
• the random orientation can be at least 60%, at least 70%, at least 80%, at least 90%, such as from about 51% to 99%, from 60% to 90%, from 70% to 95% or higher with respect to the percent of the crystals that are random based on the crystals measured.
• X-ray diffraction can be used to determine the randomness of the crystallites.
• the glass-ceramic can have both crystal and glass components, the glass-ceramic can have certain properties that are the same as glass and/or crystalline ceramics.
• the glass-ceramic can provide an ideal gradient interface between the template sphere and the ceramic shell, if present.
• the glass-ceramic can be impervious to thermal shock.
• the proportion of the glass and crystalline component of the glass-ceramic can be adjusted to match (e.g., within 10%, within 5%, within 1%, within 0.5%, within 0.1%) the coefficient of thermal expansion (CTE) of the shell or other material to which it will be bonded or attached or otherwise in contact with, in order to prevent premature fracture(s) resulting from cyclic stresses due to temperature changes, or thermal fatigue.
• CTE coefficient of thermal expansion
• the glass-ceramic has from 70% to 78% crystallinity, the two coefficients balance such that the glass-ceramic as a whole has a thermal expansion coefficient mismatch that is very close to zero.
• the present invention can provide a proppant with improved stiffness and/or lower density.
• the proppant of the present invention can be either a monolithic structure or a composite having a gradient interface between composite components, or a gradient in composite properties.
• the proppant of the present invention has little or none of the stress associated with proppants having a distinct linear interface between dissimilar materials.
• the stress, or internal locked stress, of the proppant can be measured by any suitable technique known in the art.
• the stress of the proppant can be determined by X-ray diffraction peak profile analysis, for example.
• the proppant of the present invention is therefore, less prone to fracture than conventional proppants.
• the proppant can be a multi-phase system or a single-phase system. In a multi-phase system, such as a two phase system, the proppant can comprise a template sphere or core and a second phase(s) that can be different or dissimilar from the template sphere or core.
• the second phase of the two-phase system can coat or encapsulate or act as a shell to the supporting or template first phase, and/or infiltrate (e.g., partially to optional varying degrees or gradients or completely) the supporting or template first phase, and/or react with the supporting or template first phase.
• the template sphere can include, at least partially, glass or a glass-containing ceramic material.
• the second phase can be a ceramic or glass-ceramic shell. The present inventors have found that a sharp interface between the shell and the template sphere of the proppant should be avoided in order to achieve a proppant with improved properties.
• a sharp interface between a glassy template sphere and a ceramic shell can be avoided by crystallizing at least the outer surface of the template sphere, to form glass-ceramic, by providing a glass-ceramic layer between this interface, and/or by providing a shell that is at least partially glass-ceramic.
• the glass-ceramic can serve as a functionally gradient material.
• the glass-ceramic can permit a gradual transition of ratios between glass content and ceramic content, and thereby, a gradient in composite properties.
• glass-ceramics can have improved properties compared to glass.
• the proppant can achieve increased stiffness, improved fracture toughness, low thermal expansion coefficient, high hardness, high Young's Modulus, thermal stability, and/or high strength.
• Sizes e.g., particle diameters
• the particle diameter can be in the range of from 50 micrometers to 2,000 micrometers or 100 micrometers to 2000 micrometers.
• the sizes of the template spheres e.g., particle diameters
• the template sphere can, for example, have a diameter that is from about 20 micrometers to about 1000 micrometers, such 100 micrometers to 1000 micrometers.
• the glass-ceramic in the proppant can be a mechanically strong material and can sustain temperatures of up to about 800° C to 1500° C.
• the glass-ceramic can withstand temperature changes of 100° C in a span of one minute or less (e.g., 60 seconds to 1 second, 10 seconds to 50 seconds).
• the glass-ceramic can have a density of from about 1.0 to about 3.5 g/cm 3 , such as 1.5, 2.0, 2.52, or 2.5 g/cm 3 .
• the glass-ceramic can have a Young's Modulus of from about 50 to about 80 GPa, such as 68, 66.9, or 70 GPa.
• the glass-ceramic can have a shear modulus (at 25° C) of from about 20 to about 50 GPa, such as 25 GPa or 25.5 GPa.
• the glass- ceramic can have a modulus of rupture (at 25° C) of from about 50 to about 150 MPa, such as 60 MPa, 70 MPa, 80 MPa, or 100 MPa.
• the glass-ceramic can have a compressive strength of from about 300 MPa to about 500 MPa, such as 360 MPa.
• the glass-ceramic can have a fracture toughness of from about 1 to about 10MPa.m 1 2 , such as 1.52, 1.53, or 1.54 MPa.m 1 2 .
• the glass- ceramic can have a thermal conductivity of 1.45 to about 1.53 W/(m-K) or higher, such as 1.47 W/(m-K).
• the proppant can have properties similar to those described for the glass-ceramic.
• the proppant can have at least one of the following properties: a density of from about 1.5 to about 3.0 g/cm 3 ; a Young's Modulus of from about 50 to about 80 GPa; a MOR (at 25° C) of from about 50 to about 150 MPa, such as 90 to 110 MPa, or 93 to 97 MPa; a shear modulus (at 25° C) of from about 20 to about 50 GPa; a compressive strength of from about 300 MPa to about 500 MPa; and/or a fracture toughness of about 1 to about 10 MPa.m 1/2 , such as 1.54 to about 1.55 MPa.m 172 .
• the proppant can have a specific gravity of from about 1.0 to about 4.0.
• the proppant can have a specific gravity of about 3 or less (e.g., 0.5 to 3, 0.8 to 2.5, 0.9 to 2.3, 1 to 2, 1.1 to 1.8, 1.2 to 1.7, from 0.8 to 2, and the like).
• the proppant can have a coefficient of thermal expansion (CTE at from 25° C to 300° C) of from 0.1 x 10 "6 /K to 13 10 '6 K (e.g., 0.1 x 10 "6 /K to 12 ⁇ 10 "6 /K, 0.3 ⁇ 10 "6 /K to 5 ⁇ 10 "6 /K, 0.5 ⁇ 10 "6 /K to 1.0 10 " 6 /K, 0.75 x 10 "6 /K to 1.5 x 10 "6 /K).
• the proppant can have a thermal conductivity of from about 0.01 W/(m-K) to 3.0 W/(m-K) (e.g. 1.45 W/(m-K) to about 1.47 W/(m-K)).
• the proppants of the present invention can have a crush strength of 1,000 psi to 20,000 psi or higher (e.g., from 1,500 psi to 10,000 psi, from 3,000 psi to 10,000 psi, from 5,000 psi to 10,000 psi, from 9,000 psi to 12,000 psi). Other crush strengths below or above these ranges are possible.
• the template sphere can have a coefficient of thermal expansion (CTE at from 25° C to 300° C) of from about 0.1 ⁇ 10 '6 /K to about 13 ⁇ 10 _6 / ⁇ , such as from 0.1 ⁇ 10- 6 /K to 2 ⁇ 10 _ 6 /K or 1.2 x 10 "6 /K to 1.7 * 10 "6 /K .
• the template sphere can have a specific gravity of from 0.01 to about 3.
• the template sphere can have a MOR of from about 1 to about 100 MPa, such as 10 to 90 MPa.
• the amount of glass-ceramic present in the template sphere can be about 0.1% to 100% by weight of the template sphere.
• the amount of glass-ceramic present in the template sphere can be from about 1% to about 90%, from about 10% to 80%», from about 20% to 70%, from about 30% to 60%, from about 40% to 50%, from about 5% to 75%, from about 50% to 70%, from about 65% to 85%, from about 15% to 65%, or from about 90% to 99% by weight of the template sphere, wherein all percents are percent by weight based on the weight of the template sphere.
• the remaining portion of the template sphere can be made from glass or a mixture of glass and crystalline ceramic materials, and/or other materials, e.g., metal, metal oxides, and the like.
• the template sphere may also include crystal initiators.
• Crystal initiators can include, but are not limited to, alkali metals (or oxides thereof), such as, lithium, sodium, potassium, rubidium, cesium, and francium, as well as transition metals or oxides of transition metals, such as, scandium titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, rutherfordium, dubnium, seaborgium, bohrium, hassium, meitnerium, ununnilium, unununium, ununbium, or any combinations thereof.
• the amount of crystal initiators present in the template sphere can be from about 0.1%-25% by weight, such as 0.1%-
• Glass can be any inorganic, non-metallic solid non-crystalline material, such as prepared by the action of heat and subsequent cooling.
• the glass can be any conventional glass such as, for example, soda-lime glass, lead glass, or borosilicate glass.
• Crystalline ceramic materials, as used herein, can be any inorganic, non-metallic solid crystalline material prepared by the action of heat and subsequent cooling.
• the crystalline ceramic materials can include, but are not limited to, alumina, zirconia, stabilized zirconia, mullite, zirconia toughened alumina, spinel, aluminosilicates (e.g., mullite, cordierite), perovskite, perchlorate, silicon carbide, silicon nitride, titanium carbide, titanium nitride, aluminum oxide, silicon oxide, zirconium oxide, stabilized zirconium oxide, aluminum carbide, aluminum nitride, zirconium carbide, zirconium nitride, iron carbide, aluminum oxynitride, silicon aluminum oxynitride, aluminum titanate, tungsten carbide, tungsten nitride, steatite, and the like, or any combination thereof.
• the template sphere can have at least an outer surface that is glass-ceramic. For example, at least 1% to 100% (e.g., 10% to 90%, 20% to 70%, 0.5% to 5%, 1% to 5%, 2% to 10%, 1% to 20%, 5% to 30%, 5% to 40%, 10% to 50%) of the radius starting from the outer surface of the template sphere going to the center of the sphere, can be glass-ceramic.
• the template sphere can include aluminum oxide, silicon oxide, iron oxide, magnesium oxide, calcium oxide, potassium oxide, etc., or mixtures thereof.
• the glass-ceramic of the template sphere can have a thickness of any amount, such as from 1 micron to about 150 micrometers or from about 5 micrometers to about 120 micrometers.
• the glass-ceramic can be formed to have a substantially uniform thickness around the template sphere.
• the thickness of the glass-ceramic can be substantially uniform in thickness by not varying in thickness by more than 20% or more preferably by not varying more than 10% in overall thickness.
• the glass-ceramic can be non-continuous or continuous. Continuous, for purposes of the present invention means that the entire outer surface of the template sphere is glass-ceramic. Preferably, at least the entire outer surface of the template sphere is glass-ceramic.
• the outer surface can have a thickness of from about 0.1 to about 1000 ⁇ .
• the degree of crystallinity in the glass-ceramic can vary from one portion of the template sphere to another portion of the template sphere.
• the glass-ceramic forming the outer surface of the template sphere, or the portion of the template sphere nearest to the shell can have a greater crystallinity than glass-ceramic which is formed deeper (depth in the sphere) within the template sphere and further from the shell.
• the crystallinity of the glass-ceramic beginning at the outer surface of the template sphere can be from about 10% to 100%, for example, and then progressively decrease as the glass-ceramic approaches the non-crystalline glass portion of the template sphere, ending at a crystallinity of from about 1% to 100%.
• the template sphere can be entirely glass-ceramic.
• the template sphere can be a cenosphere formed from both glass and ceramic, and have an outer surface that is glass ceramic.
• the second phase as a layer or layers can coat the supporting or template first phase, and/or infiltrates the supporting or template first phase, and/or reacts with the supporting or template first phase.
• the second phase or shell can be partially ceramic, partially glass-ceramic, entirely ceramic, or entirely glass-ceramic.
• the shell can be crystalline or amorphous.
• the shell can include an oxide, such as aluminum oxide called alumina.
• the shell can include a silicon oxide, sodium oxide, potassium oxide, calcium oxide, zirconium oxide, aluminum oxide, lithium oxide, iron oxide, magnesium oxide, calcium oxide, cerium oxide, yttrium oxide, scandium oxide, titanium dioxide, cordierite, spinel, spodumene, steatite, a silicate, a substituted aluminosilicate clay or any combination thereof.
• the shell can include a metal oxide, a metal carbide, a metal nitride, a metal boride, a metal silicide or any combination thereof, derived from any metal sources and any combination thereof.
• the shell can include a mixed metal oxide of aluminum called an aluminate, a silicate, or an aluminosilicate, such as mullite or cordierite.
• the shell can include an amorphous silica.
• the aluminate or ceramic may contain magnesium, calcium, yttrium, titanium, lanthanum, barium, and/or silicon.
• the ceramic may be formed from a nanoparticle precursor such as an alumoxane.
• Alumoxanes can be chemically functionalized aluminum oxide nanoparticles with surface groups including those derived from carboxylic acids such as acetate, methoxyacetate, methoxyethoxyacetate, methoxyethoxyethoxyacetate, lysine, and stearate, and the like.
• the shell may further include crystal initiators, such as Ti0 2 or Li 2 0.
• the amount of crystal initiators present in the shell can be from about 0.1% to 25%, such as 1% to 15%, 3% to 13 wt%, 0.1% to 7%, 0.1% to 5%, or 0.1% to 3% by weight, based on the weight of the shell.
• the shell can comprise one or more layers (e.g., two, three, four, five, or more layers). Each of the shell layers can vary in composition from an adjacent shell layer. For example, the amount of one or more components in each shell layer (if one or more are the same) can gradually increase or decrease from layer to layer. Additionally or alternatively, one or more components of one shell layer can be different from another shell layer.
• the shell can have a coefficient of thermal expansion (CTE at from 25° C to 300° C) of from 0.1 ⁇ 10 "6 /K to 13 ⁇ 10 "6 /K, such as from 0.1 10 "6 /K to 12x 10 "6 /K or 1.2 ⁇ 10 "6 /K to 5 x 10 "6 /K.
• CTE coefficient of thermal expansion
• the proppants of the present invention can comprise a single particle or multiple particles and can be a solid, partially hollow, partially hollow and randomly distributed or completely ho,llow in the interior of the particle.
• the particle can be spherical, nearly spherical, polygonal, oblong in shape (or any combination thereof) or have other shapes suitable for purposes of being a proppant.
• the proppant can also be in the shape of, for example, rods, pillars, spikes, gears, donuts, cylinders, or peanuts.
• the desired proppant shape can be achieved in any suitable manner.
• the desired proppant shape can be achieved using, for example, extrusion, granulation, fluid bed coating, a fluid bed granulator, a fluid spray dryer, or a pelletizer, such as an Eirich mixer.
• the particles can have any aspect ratio (L/D), such as from 2: 1 to 1 :2 (e.g., 1.2: 1 to 1 : 1.12, such as 1 : 1 or about 1 : 1).
• L/D aspect ratio
• the overall proppant can have any particle size.
• the proppant can have a particle diameter size of from about 90 micron to about 2 mm, or a diameter of from about 90 micrometers to about 20,000 micrometers, or a diameter of from about 100 micrometers to about 2,000 micrometers, or a diameter of from about 200 micrometers to about 1000 micrometers.
• Other particle sizes can be used.
• the particle sizes as measured by their diameter can be above the numerical ranges provided herein or below the numerical ranges provided herein.
• the proppant in a single-phase system, can comprise a sphere, but does not include a second phase as a shell that is different or dissimilar from the template sphere or core.
• the sphere in the single-phase system can have the same composition and dimensions, as the template sphere of the multi-phase system, described above.
• the sphere of the single-phase system can have at least an outer surface that is glass-ceramic.
• the sphere of the single-phase system can be entirely glass-ceramic.
• the sphere of the single-phase system can, for example, have a composition of from about 44% to 48% Si0 2 , 14% to 18% A1 2 0 3 , 5% to 10% B 2 0 3 , 8% to 12% K 2 0, and 13% to 18% MgO, all weight percents that are based on the total weight of the sphere.
• the sphere of the single-phase system can have 46 wt% Si0 2 , 16 wt% A1 2 0 3 , 7 wt% B 2 0 3 , 10 wt% K 2 0, and 17 wt% MgO, based on the weight of the sphere.
• the proppants of the present invention can be used to prop open subterranean formation fractions.
• the proppant can be suspended in a liquid phase or other medium to facilitate transporting the proppant down the well to a subterranean formation and placed such as to allow the flow of hydrocarbons out of the formation.
• the medium chosen for pumping the proppant can be any desired medium capable of transporting the proppant to its desired location including, but not limited to, a gas and/or liquid, energized fluid, foam, like aqueous solutions, such as water, brine solutions, and/or synthetic solutions.
• Any of the proppants of the present invention can have a crush strength sufficient for serving as a proppant to prop open subterranean formation fractures.
• the crush strength can be 1,000 psi or greater, 3,000 psi or greater, greater than 4,000 psi, greater than 9,000 psi, or greater than 12,000 psi.
• Suitable crush strength ranges can be from about 3,000 psi to about 20,000 psi, or from about 5,000 psi to about 20,000 psi, and the like.
• a crush strength below 3,000 psi can be useful, such as 500 psi to 3,000 psi, or 1,500 psi to 2,000 psi.
• the proppant can be suspended in a suitable gas, foam, energized fluid, or liquid phase.
• the carrier material, such as a liquid phase is generally one that permits transport to a location for use, such as a well site or subterranean formation.
• the subterranean formation can be one where proppants are used to improve or contribute to the flow of hydrocarbons, natural gas, or other raw materials out of the subterranean formation.
• the present invention also relates to a well site or subterranean formation containing one or more proppants of the present invention.
• the preparation of the glass-ceramic can involve heat treating a glass article at a temperature where crystal nuclei are allowed to form in the glass and treating the glass article at a temperature where the crystallites of the desired phases are allowed to grow to a desired extent.
• the crystalline grains of the glass-ceramic can be annealed from a glass or substantially glass sphere or template sphere. Annealing induces nucleation of one or more crystalline phases. Nucleation may be accelerated by seeding the glass with crystal initiators, such as titanium dioxide and/or lithium oxide.
• Annealing is completed when the intended level of crystallinity is reached, typically from 1% to 100%, from 15% to 80%, from 50% to 80%, from 60% to 78% and from 70% to 75%, in weight percents by weight of the article (e.g., template sphere or layer).
• the template sphere can be formed from a glass or substantially glassy material.
• the template sphere can be a glass or glass-like hollow sphere.
• the glass sphere can be either partially or entirely converted to glass-ceramic upon heating of the glass sphere or upon sintering of the shell.
• Temperature can be regulated by introducing a temperature gradient and degree of cooling or first heating, then cooling and followed by a heating to promote glass-ceramic formation or conversion. It is also possible to achieve an oriented crystal alignment, however, which may further enhance stiffness.
• crystalline grains nucleate, begin to grow, and ultimately comprise a majority of the material.
• High melting point compounds or crystal initiators can facilitate nucleation and/or act as a catalyst.
• the nucleation temperature is a temperature at which crystals begin to form and grow within the glass.
• the selected nucleation temperature should be below a temperature at which the glass would thermally deform. Below its melting temperature, a crystal typically has significantly lower thermal deformation than a corresponding glass.
• the crystal initiators can be in the form of a solid powder.
• the particle size of the powder can be modified by milling.
• the crystal initiators can, alternatively, be in liquid form.
• the crystal initiators can be derived from precursors that convert to oxide from either liquid, solid or gaseous forms.
• the precursors can include, TiCl 4 , LiCl, Ti(OC 2 H 5 ) 4 , or Li(OH).
• the oxides convert partially or entirely, to glass-ceramic.
• the shell can be formed from a silica, an alumina, and/or other ceramics, such as cordierite and mullite.
• the silica can be, for example, an amorphous silica. Crystal initiators may be used to facilitate converting the amorphous silica or alumina to oxides.
• the shell can be applied to the template sphere before or after the template sphere has achieved the desired crystallinity.
• the shell can be formed on the template sphere once the template sphere is comprised at least partially of glass-ceramic.
• the shell coating can be applied to the surface of a glass template sphere prior to crystallization of the template sphere.
• the template sphere can be coated with the shell coating and sintered. Upon heat treatment of the composite shell and template sphere, any glass material in the shell as well as glass in the template sphere can be partially, or entirely converted to a glass-ceramic.
• the shell can be formed from ceramics, such as cordierite and/or mullite, and/or with crystal initiators, such as Ti0 2 or Li 2 0.
• the crystal initiators can be added to a coating slurry as a solid powder, or as liquid, solid, or gaseous precursors which convert to oxides. If a solid powder is used, the size of the powder particles can be controlled by milling.
• the precursors can be, for example, TiCl 4 , LiCl 2 , Ti (OC 2 H 5 ) 4 , and/or Li(OH).
• the template sphere can be coated with the ceramic shell coating and sintered.
• the sintered ceramic grain size can be less than 1 micron, such as 0.1 to 0.8 micrometers, or 0.2 to 0.5 micrometers.
• the shell can be formed from amorphous silica and/or alumina.
• the amorphous silica and/or alumina are glass-ceramic precursors which, with the addition of crystal initiators, can be converted to oxides.
• the oxides, once obtained, can convert, entirely, or at least partially to glass-ceramic.
• the shell can be formed from glass-ceramic precursors and other ceramics, such as cordierite or mullite.
• the composite of the glass-ceramic precursors and ceramic materials in the shell can be heat treated with the template sphere. Upon heating, the glass materials in the template sphere and shell can be converted entirely, or at least partially to glass-ceramic.
• the shell can be prepared from one or more different coating slurries to form one or more shell layers on the template sphere.
• At least one coating slurry can include ceramic materials, such as cordierite or mullite. Crystal initiators can be added into the coating slurry.
• a spray coater may be programmed to alternately spray from at least two different coating slurries onto the template. After coating the template sphere with at least two different coating slurries, the proppant can be heated to achieve a layered shell structure. During heating, the top shell layer is exposed to more heat than the underlying shell layers and the template sphere. As such, small-glass ceramic particles which can form in the top shell layer can fuse together and result in a dense top layer.
• the substrate or template preferably prior to the optional second phase or optional coating or optional shell being present, can be treated in one or more ways to remove or diminish flaws on the surface of the substrate or template.
• These flaws may be convex or concave in nature or both. This can be especially beneficial when the template or substrate is an inorganic material.
• the removal or diminishing of these flaws, especially strength-limiting flaws, can permit the second phase or coating or shell to provide more enhanced strengthening of the substrate or template and the overall proppant.
• the flaws can include, but are not limited to, peaks, protuberances, ridges, craters, and other flaws which can include surface undulations, which are significantly different from the overall surface texture or surface smoothness of the substrate or template.
• a flaw in a material system can be considered as anything which negatively impacts the apparent strength of a material system.
• Flaws can be physical and/or chemical in nature. Physical flaws may include such things as protuberances, bumps, scratches, grooves, pores, pits, dislocations, and/or defects in the crystal structure of the material. Chemical flaws may include phases that prevent solid state bonding, e.g. grain boundary phases, modification of the crystal structure through atomic substitution, and the like.
• the sharp protuberances or peaks or ridges can be removed or diminished, and a surface can be created that is "smoother and more spherical" which can permit the second phase or coating or shell to be more effective in providing strength to the overall proppant.
• a surface can be created that is "smoother and more spherical" which can permit the second phase or coating or shell to be more effective in providing strength to the overall proppant.
• an aspect ratio (AR) test can be used and/or the radius of curvature (RC) can be compared.
• the AR can be 5 or less, such as from 0.1 to 5, or from 0.2 to 5, or from 0.5 to 5, or from 0.1 to 4, or from 0.1 to 3, or from 0.1 to 2, or from 0.8 to 1, or from 0.1 to 1.8, or from 0.1 to 1.5, or from 0.5 to 1.3, or from 0.7 to 1.2 and other ranges.
• the AR is about 1.
• the RC can typically range from 0.5 ⁇ to 100 ⁇ , with the upper limit of the radius of curvature being the radius of the template.
• various devices and methods can be used which provide sufficient temperature to allow crystallization to occur.
• These devices and/or methods include, but are not limited to, static bed furnaces, dynamic bed furnaces (e.g., rotating tube furnaces), fluidized bed furnaces, direct injection into high temperature flames (for instance, oxidizing flames), use of a gas flame contained within a combustion tube mounted vertically and/or injection into a high temperature plasma flame.
• the template sphere can be heated to any temperature sufficient to crystallize all or a portion of the template sphere, for instance, to temperatures of from about 300° C to 1,300° C or 500° C to 1,500° C.
• the heat treatment can occur for any time sufficient to crystallize all or a portion of the template sphere.
• the heat treatment can occur for a period of, for example, 10 minutes to 50 hours or more, such as 2 hours to 10 hours.
• pressures can be used to control the template structure or the physical properties of the template. For instance, pressures may be used from less than 0.1 atm to 10 atm or greater, such as from 1 atm to 5 atm.
• the localized pressure is reduced to values below that of ambient pressure, this can lead to the expansion of the template and consequently a reduction in the density of the template.
• the localized pressure is increased above ambient pressure, this can result in the contraction of the template to smaller overall diameters and hence an increase in the density of the template.
• this technique provides the ability to "dial in” or control certain densities of the proppant material.
• the reduction or increase in pressure can improve the morphology of the template, especially when the template is held or is very near the glass transition temperature of the template material.
• the change in localized pressure can be achieved through the use of various pressure control devices and techniques, such as a sealed ceramic tube surrounded by heating elements and containing the template material, wherein the ceramic tube is connected to either a pressure source or sink.
• Pressurizing fluid can be used to achieve the desired localized pressure, such as air, nitrogen, inert gases, such as argon, or any gas.
• crystal initiators Prior to heat treatment, it is an option to include crystal initiators, as described elsewhere herein, in order to facilitate crystallization of the glass.
• Heat treatment may also be carried out in alternate atmospheres, other than that of air to induce the formation of new phases, for example thermal treatment in a nitriding atmosphere to form the nitrides, or thermal treatment in a carburizing atmosphere to form the carbides.
• atmospheres include inert gases, carbon monoxide, nitrogen, nitrogen oxide, nitrogen dioxide, dinitrogen pentoxide, anhydrous ammonia, and the like.
• the properties of the template or substrate may be modified by way of pressure and/or temperature effects.
• a variation in pressure with the application of thermal energy may be used to alter the specific gravity of the template material.
• the template and/or the shell can be surface modified, such as with the addition of silicon oxide, sodium oxide, potassium oxide, calcium oxide, zirconium oxide, aluminum oxide, lithium oxide, iron oxide, cordierite, spinel, spodumene, steatite, a silicate, an alumino silicate material, an aluminum containing material, a silicon containing material, an aluminum-silicon containing material, a substituted alumino silicate clay or any combination thereof.
• the shell can be surface modified, for instance, by the addition of one or more inorganic materials or phases, or the attachment (e.g., chemical attachment or bonding) of one or more chemical groups, such as hydrophilic groups or hydrophobic groups.
• the chemical groups can be surfactants, polymers, ionic groups, ionizable groups, acid groups, salts, surface active agents, and the like.
• the surface modification can improve the surface morphology of the proppant, especially after the proppant is a sintered proppant.
• the inorganic material or phases used for surface modification can include glassy materials, such as silicon oxide, alone or with the addition of oxides of sodium, potassium, calcium, zirconium, aluminum, lithium, iron, or any combination thereof.
• the amount of the silicon oxide can be from about 70 wt% to about 99 wt%, such as from about 85 wt% to about 95 wt%, and the addition of the one or more other oxides, such as sodium oxide and the like, can be from about 1 wt% to about 15 wt%, such as from about 2 wt% to about 10 wt%.
• the surface modification of the shell can include the application of one or more organic materials (e.g., aliphatic compounds, ionic compounds, surfactants, aromatic compounds, polymeric compounds) or the application of an organic phase(s).
• the organic material or chemical groups can be bonded to the shell surface or adsorbed, or absorbed or otherwise attached.
• the organic material or organic phase can modify the proppant's propensity to interact with aqueous solutions, thus making the proppant either hydrophobic, hydrophilic, or hydro-neutral.
• the surface modification of the shell can include the use of substances that are effectively activated by temperature elevation of the proppant to yield a modification of the proppant transport fluid (e.g., breaking the gel used to transport the proppant through the subterranean regions).
• the surface treating which can occur after sintering of the proppant, can have the ability to improve one or more chemical and/or mechanical properties, such as enhanced transportability.
• the template or substrate and/or shell can be modified, such as surface modified, through a variety of techniques.
• the surface of the template or substrate can be modified through one or more heat treatments prior to the formation of the shell on the template.
• Another form of surface treatment can be to modify chemically the surface of the template, such as by glazing, application of a bond coat, or chemical etching.
• the chemical modification can improve the performance and/or stabilize the template surface. Removal of residual impurities, cleaning of the surface, reduction of residual stain distributions prior to coating, increasing the microscopic roughness of the surface to improve coating bond strength or removing and/or improving the morphology of protuberances.
• the modification can be achieved by the preferential removal of one or more constituent phases on the template. For example, a wash with caustic soda may dissolve silica from the template.
• the present invention includes the following aspects/embodiments/features in any order and/or in any combination:
• a proppant comprising a template sphere, said template sphere having a Krumbein sphericity of at least about 0.3 and a roundness of at least about 0.1, said proppant having a Krumbein sphericity of at least about 0.5 and a roundness of at least about 0.4, and a continuous sintered shell around the entire outer surface of said template sphere, wherein at least the outer surface of said template sphere comprises a glass-ceramic or a glass-ceramic containing layer in contact with said outer surface of said template sphere.
• glass-ceramic comprises crystallites having an orientation that is random.
• glass-ceramic comprises crystallites having an orientation that is non-random.
• said template sphere has a coefficient of thermal expansion (CTE at from 25° C to 300° C) of from 0.1 x 10 "6 /K to 13 ⁇ 10 "6 /K ; and/or
• said shell has a coefficient of thermal expansion (CTE at from 25° C to 300° C) of from 0.1 ⁇ 10 "6 /K to 13 ⁇ 10 "6 /K .
• CTE coefficient of thermal expansion
• said proppant has a specific gravity of about 3 or less; and/or a coefficient of thermal expansion (CTE at from 25° C to 300° C) of from about 0.1 ⁇ 10 "6 /K to about 13 ⁇ 10 "6 /K ; and/or a thermal conductivity of from about 0.01 W/m-K to about 3.0 W/m-K.
• the glass-ceramic has at least one of the following properties: a density of from about 1.5 to about 3.5 g/cm 3 ; a Young's Modulus of from about 50 to about 80 GPa; and/or a MOR of from about 50 to about 150 MPa.
• template sphere has a MOR of from about 1 to about 100 MPa.
• a fracture toughness of from about 1 to about 10 MPa.m 1/2 ; or e) a thermal conductivity of from about 0.01 to about 3 W7(m-K).
• template sphere comprises a mixture of aluminum oxide, silicon oxide, titanium oxide, iron oxide, magnesium oxide, calcium oxide, potassium oxide and sodium oxide.
• glass-ceramic of said template sphere comprises aluminum oxide, silicon oxide, boron oxide, potassium oxide, zirconium oxide, magnesium oxide, calcium oxide, titanium oxide or any combination thereof.
• glass-ceramic of said template sphere comprises from about 10% to about 55% by weight Si0 2 ; from about 0% to about 28% by weight A1 2 0 3 ; from about 1% to about 5% by weight CaO; from about 7% to about 50% by weight MgO; from about 0.5% to about 25% by weight Ti0 2 ; from about 0.4% to about 30% by weight B 2 0 3 , and greater than 0% and up to about 5% by weight P 2 0 5 , based on the weight of the glass-ceramic.
• glass-ceramic of said template sphere comprises from about 3% to about 10% by weight Li 2 0; from about 0% to about 28% by weight A1 2 0 3 ; from about 10% to about 55% by weight Si0 2 ; from about 7% to about 50% by weight MgO; from about 0.5% to about 25% by weight Ti0 2 ; from about 0.4% to about 30% by weight B 2 0 3 , and from about 6% to about 20% by weight ZnO, based on the weight of the glass-ceramic.
• proppant of any preceding or following embodiment/feature/aspect wherein the proppant is rod-, pillar-, spike-, gear-, donut-, cylinder-, polygon- or peanut-shaped.
• a proppant comprising a sphere, said sphere having a Krumbein sphericity of at least about 0.3 and a roundness of at least about 0.1, said proppant having a Krumbein sphericity of at least about 0.5 and a roundness of at least about 0.4, wherein at least the outer surface of said sphere comprises a glass-ceramic or a glass-ceramic containing layer in contact with said outer surface of said sphere.
• glass-ceramic comprises crystallites having an orientation that is non-random.
• said template sphere has a coefficient of thermal expansion (CTE at from 25° C to 300° C) of from about 0.1 ⁇ 10 "6 /K to about 13 x 10 " 6 /K .
• proppant of any preceding or following embodiment/feature/aspect wherein the proppant has at least one of the following properties: a density of from about 1.5 to about 3.0 g/cm 3 ; and/or a Young's Modulus of from about 50 to about 80 GPa; and/or a MOR of from about 50 to about 150 MPa
• proppant of any preceding or following embodiment/feature/aspect wherein said proppant has at least one of the following properties; shear modulus (at 25° C) of from about 20 to about 50 GPa; a modulus of rupture (at 25° C) of from about 50 to about 150 MPa; a compressive strength of from about 300 MPa to about 500 MPa; a fracture toughness of from about 1 to about 10 MPa. m 1/2 ; a thermal conductivity of from about 0.01 to about 3 W/(m-K).
• proppant of any preceding or following embodiment/feature/aspect wherein said proppant comprises from about 10% to about 55% by weight Si0 2 ; from about 0% to about 28% by weight A1 2 0 3 ; from about 1% to about 5% by weight CaO; from about 7% to about 50% by weight MgO; from about 0.5% to about 25% by weight Ti0 2 ; from about 0.4% to about 30% by weight B 2 0 3 , and greater than 0% and up to about 5% by weight P 2 0 5 , based on the weight of the glass-ceramic.
• a method of forming the proppant comprising providing a template sphere comprising glass; optionally hardening the template sphere; crystallizing at least an outer surface of said template sphere by heat treatment to form an outer surface comprising glass-ceramic; and, optionally, providing a shell around the entire outer surface of said template sphere; and sintering said shell to form a continuous sintered shell.
• a proppant comprising a template sphere, said template sphere having a Krumbein sphericity of at least about 0.3 and a roundness of at least about 0.1, said proppant having a Krumbein sphericity of at least about 0.5 and a roundness of at least about 0.4, and a continuous sintered shell around the entire outer surface of said template sphere, wherein at least the continuous sintered shell comprises a glass-ceramic.
• the present invention can include any combination of these various features or embodiments above and/or below as set forth in sentences and/or paragraphs. Any combination of disclosed features herein is considered part of the present invention and no limitation is intended with respect to combinable features.
• a proppant according to the present invention can be prepared by coating conventional glass cenospheres with alkali metals.
• the alkali metals can be dip-coated, spin coated, and spray-coated onto the glass cenospheres.
• the cenospheres can be doped with transitional metal oxides. Once the cenospheres are coated or doped, as described, they are subjected to heat treatment for crystallization.
• the cenospheres are heated to temperatures of 500° C to 1,000° C for a period of time sufficient to crystallize at least an outer surface of the cenospheres.
• the amount of time in which the cenospheres are heated can vary depending on the degree of crystallization desired.
• the cenospheres can be heated, for example, for a period of about 30 minutes to 12 hours, or from 2 hours to 10 hours. If full crystallization of the cenospheres is desired, the cenospheres should be heated for a fraction of an hour to several hours, for example, 0.1 to 10 hours or more.
• the cenospheres can be coated with a ceramic shell, such as cordierite.
• the cordierite can be granulated or pelletized through a granulator to achieve particles of about 200 micrometers in diameter or larger.
• the formed cordierite particles are then dried and used to coat the cenospheres which have at least a glass- ceramic outer layer.
• the cenospheres are then sintered.
• the sintering can be conducted in a conventional manner, known in the art.
• the coated cenospheres can be fired at temperatures of about 1,200° C to about 1,450° C, preferably 1,250° C to 1,420° C to form a sintered cordierite proppant.
• additional proppants were prepared using the first cenosphere powder in Table 1 with cordierite.
• the mixture (before taking into account the amount of the Ti0 2 present) was composed of 25 wt% cenosphere powder and 75 wt% cordierite and this mixture was formed into spheres, with the indicated additions of Ti0 2 , and sintered at 1260°C for 6 h.
• the density and strength data of the samples are set forth in Table 3.
• the splitting strength of the composite increased gradually with the content of the Ti0 2 and reached the maximum at 7 wt% Ti0 2 .
• the amount of Ti0 2 is based on the total weight of the pellet or sphere.
• the strength at this Ti0 2 level was more than doubled (108% net strength increase over the control) higher than the sample without any Ti0 2 .
• the strength increase is mainly attributed to the glass-ceramic formation in the cenosphere powder.
• the strength of these 1260°C sintered composite samples increased and then reached a maximum point and then dropped down, although the density kept increasing. This is so because when the Ti0 2 reached a certain level, further increasing of Ti0 2 would simply decrease the relative content of cenosphere powder. Again, this indicates the contribution of glass-ceramics from the cenosphere in the composite.
• the microstructures of the composites of 25%:75% cenosphere- cordierite matrix without and with 7 wt% Ti0 2 are shown in Figure 4. It is seen that the sample with 7 wt% Ti0 2 is denser than without Ti0 2.

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