US20210139767A1 - Durable coatings and uses thereof - Google Patents
Durable coatings and uses thereof Download PDFInfo
- Publication number
- US20210139767A1 US20210139767A1 US16/906,020 US202016906020A US2021139767A1 US 20210139767 A1 US20210139767 A1 US 20210139767A1 US 202016906020 A US202016906020 A US 202016906020A US 2021139767 A1 US2021139767 A1 US 2021139767A1
- Authority
- US
- United States
- Prior art keywords
- polyurethane
- polyurethane dispersion
- coated particulate
- dispersion
- particulate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 0 *.*.*.CC.CC.CC.C[1*]C.C[1*]C.C[1*]C.C[3*]C Chemical compound *.*.*.CC.CC.CC.C[1*]C.C[1*]C.C[1*]C.C[3*]C 0.000 description 2
- ZIUNFUKPNZXQCM-UHFFFAOYSA-N CC.CC.OC1=CC=CC(O)=C1.OC1=CC=CC=C1 Chemical compound CC.CC.OC1=CC=CC(O)=C1.OC1=CC=CC=C1 ZIUNFUKPNZXQCM-UHFFFAOYSA-N 0.000 description 1
- RPHYLOMQFAGWCD-UHFFFAOYSA-N CC.OC1=CC=CC=C1 Chemical compound CC.OC1=CC=CC=C1 RPHYLOMQFAGWCD-UHFFFAOYSA-N 0.000 description 1
Images
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
- C09K8/805—Coated proppants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
Definitions
- Well fracturing is an often used technique to increase the efficiency and productivity of oil and gas wells. Overly simplified, the process involves the introduction of a fracturing fluid into the well and the use of fluid pressure to fracture and crack the well strata. The cracks allow the oil and gas to flow more freely from the strata and thereby increase production rates in an efficient manner.
- proppant to keep the strata cracks open as oil, gas, water and other fluids found in well flow through those cracks.
- the proppant is carried into the well with the fracturing fluid which itself may contain a variety of viscosity enhancers, gelation agents, surfactants, etc.
- Proppants can be made of virtually any generally solid particle that has a sufficiently high crush strength to prop open cracks in a rock strata at great depth and temperatures of about 125° C. and higher. Sand and ceramic proppants have proved to be especially suitable for commercial use.
- a proppant that is flushed from the well is said to have a high “flow back.” Flow back is undesirable.
- the flushed proppants are abrasive and can damage or clog valves and pipelines in downstream processing facilities.
- Synthetic resin coatings can be used to impart a degree of adhesion to the proppant so that flow back is substantially reduced or eliminated.
- resins can include phenol resin, epoxy resin, polyurethane-phenol resin, furane resin, etc. See published US Patent Application Nos. 2002/0048676, 2003/0131998, 2003/0224165, 2005/0019574, 2007/0161515 and 2008/0230223 as well as U.S. Pat. Nos. 4,920,192; 5,048,608; 5,199,491; 6,406,789; 6,632,527; 7,624,802; and published international application WO 2010/049467, the disclosures of which are herein incorporated by reference.
- Proppants based on polyurethane chemistries have a number of potential advantages over coating systems.
- polyurethane coated proppants also have disadvantages in that they can be not as durable as some other coatings.
- the present embodiments solves these issues and others as will be apparent from the present disclosure.
- coated particulates are provided.
- the coatings comprise an inner coating adjacent to the particulate comprising a polyurethane and an outer coating comprising an polyurethane dispersion; a coating comprising a polyurethane admixed with a polyurethane dispersion; or a polyurethane dispersion layer and is free of an inner polyurethane layer.
- methods of preparing a multi-layer coated particulate comprise a) coating the particulate with a first layer, wherein the first layer is a polyurethane to produce a polyurethane coated particulate; and coating the polyurethane coated particulate with a second layer to produce the multi-layer coated particulate, wherein the second layer comprises a polyurethane dispersion.
- methods of extracting oil and/or gas from a subterranean stratum comprising injecting into the subterranean stratum the coated particulates described herein; and extracting the oil and/or gas from the subterranean stratum.
- FIG. 1 illustrates a non-limiting embodiments of the improved performance and durability of coatings described herein.
- FIG. 2 illustrates a non-limiting embodiments of the improved performance and durability of coatings described herein.
- FIG. 3 illustrates a non-limiting embodiments of the improved performance and durability of coatings described herein.
- coated particulates are provided.
- the coating comprises an inner coating adjacent to the particulate comprising a polyurethane and an outer coating comprising an polyurethane dispersion; a coating comprising a polyurethane admixed with a polyurethane dispersion; or a polyurethane dispersion layer and is free of an inner polyurethane layer.
- the coating resists dissolution under the rigorous combination of high heat, agitation, abrasion and water found downhole in a well.
- the coating exhibits a sufficient resistance to a 10 day autoclave test or 10 day conductivity test so that the coating resists loss by dissolution in hot water (“LOT loss”) of less than 25 wt %, less than 15 wt %, or a loss of less than 5 wt %.
- LOT loss dissolution in hot water
- the multi-layer coating can in some embodiments resist dissolution in the fractured stratum while also exhibiting sufficient resistance to flow back and sufficiently high crush strength to maintain conductivity of the fractures.
- a testing method for the above is described in ISO 13503-5:2006(E) “Procedures for measuring the long term conductivity of proppants”, the disclosure of which is herein incorporated by reference.
- ISO 13503-5:2006 provides standard testing procedures for evaluating proppants used in hydraulic fracturing and gravel packing operations.
- ISO 13503-5:2006 provides a consistent methodology for testing performed on hydraulic fracturing and/or gravel packing proppants.
- the “proppants” mentioned henceforth in this part of ISO 13503-5:2006 refer to sand, ceramic media, resin-coated proppants, gravel packing media, and other materials used for hydraulic fracturing and gravel-packing operations.
- ISO 13503-5:2006 is a non-limiting example of a consistent method by which downhole conditions can be simulated and compared in a laboratory setting
- the isocyanate component comprises an isocyanate with at least 1, 2, 3, or 4 reactive isocyanate groups.
- Other isocyanate-containing compounds may be used, if desired.
- suitable isocyanate with at least 2 isocyanate groups an aliphatic or an aromatic isocyanate with at least 2 isocyanate groups (e.g. a diisocyanate, triisocyanate or tetraisocyanate), or an oligomer or a polymer thereof can also be used.
- These isocyanates with at least 2 isocyanate groups can also be carbocyclic or heterocyclic and/or contain one or more heterocyclic groups.
- the isocyanate is a mixture of a diisocyanate or a triisocyanate.
- the isocyanate comprises 4,4′-methylenediphenyl diisocyanate. In some embodiments, the isocyanate comprises 4,4′-methylenediphenyl diisocyanate is present in a concentration amount of about 18 to about 25%. In some embodiments, the isocyanate comprises a diphenylmethane diisocyanate and as described herein.
- the isocyanate with at least 2 isocyanate groups is a compound of the formula (III) or a compound of the formula (IV):
- A is each, independently, an aryl, heteroaryl, cycloalkyl or heterocycloalkyl.
- A is each, independently, an aryl or cycloalkyl. More preferably A is each, independently, an aryl which is preferably phenyl, naphthyl or anthracenyl, and most preferably phenyl. Still more preferably A is a phenyl.
- heteroaryl is preferably a heteroaryl with 5 or 6 ring atoms, of which 1, 2 or 3 ring atoms are each, independently, an oxygen, sulfur or nitrogen atom and the other ring atoms are carbon atoms. More preferably the heteroaryl is selected among pyridinyl, thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, isoxazolyl or furazanyl.
- cycloalkyl is preferably a C 3-10 -cycloalkyl, more preferably a C 5-7 -cycloalkyl.
- heterocycloalkyl is preferably a heterocycloalkyl with 3 to 10 ring atoms (more preferably with 5 to 7 ring atoms), of which one or more (e.g. 1, 2 or 3) ring atoms are each, independently, an oxygen, sulfur or nitrogen atom and the other ring atoms are carbon atoms.
- heterocycloalkyl is selected from among tetrahydrofuranyl, piperidinyl, piperazinyl, aziridinyl, acetidinyl, pyrrolidinyl, imidazolidinyl, morpholinyl, pyrazolidinyl, tetrahydrothienyl, octahydroquinolinyl, octahydroisoquinolinyl, oxazolidinyl or isoxazolidinyl.
- the heterocycloalkyl is selected from among tetrahydrofuranyl, piperidinyl, piperazinyl, pyrrolidinyl, imidazolidinyl, morpholinyl, pyrazolidinyl, tetrahydrothienyl, oxazolidinyl or isoxazolidinyl.
- each R 1 is, independently, a covalent bond or C 1-4 -alkylene (e.g. methylene, ethylene, propylene or butylene).
- each R 2 is a covalent bond.
- each R 2 is each, independently, a halogen (e.g. F, Cl, Br or I), a C 1-4 -alkyl (e.g. methyl, ethyl, propyl or butyl) or C 1-4 -alkyoxy (e.g. methoxy, ethoxy, propoxy or butoxy).
- a halogen e.g. F, Cl, Br or I
- a C 1-4 -alkyl e.g. methyl, ethyl, propyl or butyl
- C 1-4 -alkyoxy e.g. methoxy, ethoxy, propoxy or butoxy
- each R 2 is, independently, a C 1-4 -alkyl. More preferably each R 2 is methyl.
- R 3 is a covalent bond, a C 1-4 -alkylene (e.g. methylene, ethylene, propylene or butylene) or a group —(CH 2 ) R31 —O—(CH 2 ) R32 —, wherein R31 and R32 are each, independently, 0, 1, 2 or 3.
- R 3 is a —CH 2 — group or an —O— group.
- p is equal to 2, 3 or 4, preferably 2 or 3, more preferably 2.
- each q is, independently, an integer from 0 to 3, preferably 0, 1 or 2.
- the corresponding group A has no substitutent R 2 , but has hydrogen atoms instead of R 2 .
- each r and s are, independently, 0, 1, 2, 3 or 4, wherein the sum of r and s is equal to 2, 3 or 4.
- each r and s are, independently, 0, 1 or 2, wherein the sum of r and s is equal to 2. More preferably, r is equal to 1 and s is equal to 1.
- Examples of the isocyanate with at least 2 isocyanate groups are: toluol-2,4-diisocyanate; toluol-2,6-diisocyanate; 1,5-naphthalindiisocyanate; cumol-2,4-diisocyanate; 4-methoxy-1,3-phenyldiisocyanate; 4-chloro-1,3-phenyldiisocyanate; diphenylmethane-4,4-diisocyanate; diphenylmethane-2,4-diisocyanate; diphenylmethane-2,2-diisocyanate; 4-bromo-1,3-phenyldiisocyanate; 4-ethoxy-1,3-phenyl-diisocyanate; 2,4′-diisocyanate diphenylether; 5,6-dimethyl-1,3-phenyl-diisocyanate; 2,4-dimethyl-1,3-phenyldiiso
- the isocyanates with at least 2 isocyanate groups are toluol diisocyanate, diphenylmethane diisocyanate, an oligomer based on toluol diisocyanate or an oligomer based on diphenylmethane diisocyanate.
- the polyurethane is formed by reacting the isocyanate component with a polyol component.
- the polyol component may or may not have reactive amine functionality.
- the polyol is a mixture of a polyol and a polyether polyol.
- the polyol is a mixture of about 20 to about 30% polyol by weight and the polyether polyol is about 70 to about 80% by weight, wherein the total of the polyol and the polyether polyol is 100%.
- the polyurethane coating is a phenolic polyurethane made with a phenolic polyol according to a patent application that was filed with the German Patent Office under no. DE 10 2010 051 817.4 on Nov. 19, 2010 and entitled “Proppant Coating Technology”, the disclosure of which is herein incorporated by reference and summarized below in the context of coatings described herein.
- the polyol component comprises a phenol resin that comprises a condensation product of a phenol and an aldehyde, such as formaldehyde.
- the phenol resin is preferably a resole or novolak phenol resin and more preferably a benzyl ether resin.
- the resole-type phenol resin can be obtained, for example, by condensation of phenol or of one or more compounds of the following formula (I), with aldehydes, preferably formaldehyde, under basic conditions.
- Novolak-type phenol resin comprises the condensation product of phenol or of one or more compounds of the formula (I) defined above, with aldehydes, preferably formaldehyde, under acidic conditions.
- the polyol also comprises a polyether polyol.
- the polyol comprises a benzyl ether resin of the general formula (II):
- the polyol component is a phenol resin with monomer units based on cardol and/or cardanol.
- Cardol and cardanol are produced from cashew nut oil which is obtained from the seeds of the cashew nut tree.
- Cashew nut oil consists of about 90% anacardic acid and about 10% cardol.
- By heat treatment in an acid environment a mixture of cardol and cardanol is obtained by decarboxylation of the anacardic acid.
- Cardol and cardanol have the structures shown below:
- Cardol specifically refers to compound CAS-No. 57486-25-6 and cardanol specifically to compound CAS-No. 37330-39-5.
- Cardol and cardanol can each be used alone or at any particular mixing ratio in the phenol resin.
- Decarboxylated cashew nut oil can also be used.
- Cardol and/or cardanol can be condensed into the above described phenol resins, for example, into the resole- or novolak-type phenol resins.
- cardol and/or cardanol can be condensed e.g. with phenol or with one or more of the above defined compounds of the formula (I), and also with aldehydes, such as formaldehyde.
- the amount of cardol and/or cardanol which is condensed in the phenol resin is not particularly restricted and preferably is from about 1 wt % to about 99 wt %, more preferably about 5 wt % to about 60 wt %, and still more preferably about 10 wt % to about 30 wt %, relative to 100 wt % of the amount of phenolic starting products used in the phenol resin.
- the polyol component is a phenol resin obtained by condensation of cardol and/or cardanol with aldehydes, preferably formaldehyde.
- a phenol resin which contains monomer units based on cardol and/or cardanol as described above, or which can be obtained by condensation of cardol and/or cardanol with aldehydes, has a particularly low viscosity and can thus preferably be employed with a low addition or without addition of reactive thinners.
- this kind of long-chain, substituted phenol resin is comparatively hydrophobic, which results in a favorable shelf life of the coated proppants obtained process described herein.
- a phenol resin of this kind is also advantageous because cardol and cardanol are renewable raw materials.
- the polyol component can still contain other compounds containing hydroxyl groups.
- the other compounds containing hydroxyl groups can be selected from the compounds containing hydroxyl groups that are known to be useful for making polyurethanes, e.g., polyether polyols, hydroxy-functional polyethers, hydroxy-functional polyesters, alcohols or glycols.
- compound containing hydroxyl groups is, for instance, a polyether polyol.
- compounds containing hydroxyl groups depend on the desired properties of the proppant coating and can suitably be selected by the person skilled in the art. In some embodiments, compounds containing hydroxyl groups are in the range of between about 10 wt % and about 80 wt %, preferably from about 20 wt % to about 70 wt %, relative to 100 wt % of the polyol component or as described herein.
- the polyurethane layer is based upon a condensation reaction product that has been made with an excess of isocyanate component with respect to the polyol component.
- 100 parts by weight of the polyol component is used with about 105 wt % and about 300 wt %, preferably about 110 wt % to about 230 wt %, more preferably about 120 wt % to about 220 wt %, and still more preferably about 130 wt % to about 200 wt %, of the isocyanate base value.
- the weight can be the absolute weight or the functional weight of the isocyanate and polyol components.
- the isocyanate base value defines the amount of the isocyanate component which is equivalent to 100 parts by weight of the polyol component.
- the NCO-content (%) of the isocyanate component is defined herein according to DIN ISO 53185.
- To determine the OH-content (%) of the polyol component first the so-called OH-number is determined in mg KOH/g according to DIN ISO 53240 and this value is divided by 33, in order to determine the OH-content.
- an excess of NCO-groups or absolute weight in the isocyanate component of between about 5 and about 200%, about 10 to about 130%, about 20% to about 120%, about 30% to about 100%, relative to the OH-groups in the polyol component or the weight of the polyol component is used (corresponding to the above mentioned amount of isocyanate component of about 105% to about 300%, about 110% to about 230%, about 120% to about 220%, about 130% to about 200% of the isocyanate weight or base value).
- the isocyanate that is used to form the polyurethane has an equivalent weight of about 140. In some embodiments, the hydroxyl equivalent of the polyol that is used to form the polyurethane layer is about 85.
- one or more additives can be mixed with the proppant, the polyol component and the isocyanate component. These additives are not particularly restricted and can be selected from the additives known in the specific field of coated proppants. Provided that one of these additives has hydroxyl groups, it should be considered as a different hydroxyl-group-containing compound, as described above in connection with the polyol component. If one of the additives has isocyanate groups, it should be considered as a different isocyanate-group-containing compound. Additives with hydroxyl groups and isocyanate groups can be simultaneously considered as different hydroxyl-group-containing compounds and as different isocyanate-group-containing compounds.
- the coating comprises a reactive amine component, such as, but not limited to, an amine-terminated compound.
- This component can enhance crosslink density within the coating and, depending on component selection, can provide additional characteristics of benefit to the cured coating.
- the amine components for include, but are not limited to, amine-terminated compounds such as diamines, triamines, amine-terminated glycols such as the amine-terminated polyalkylene glycols.
- Non-limiting examples of diamines include primary, secondary and higher polyamines and amine-terminated compounds. Suitable compounds include, but are not limited to, ethylene diamine; propylenediamine; butanediamine; hexamethylenediamine; 1,2-diaminopropane; 1,4-diaminobutane; 1,3-diaminopentane; 1,6-diaminohexane; 2,5-diamino-2,5-dimethlhexane; 2,2,4- and/or 2,4,4-trimethyl-1,6-diaminohexane; 1,11-diaminoundecane; 1,12-diaminododecane; 1,3- and/or 1,4-cyclohexane diamine; 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane; 2,4- and/or 2,6-hexahydrotoluylene diamine; 2,4′ and
- aspartic esters which is a secondary amine derived from a primary polyamine and a dialkyl maleic or fumaric acid ester.
- useful maleic acid esters include dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, mixtures thereof and homologs thereof.
- Suitable triamines and higher multifunctional polyamines include, but are not limited to, diethylene triamine, triethylenetetramine, and higher homologs of this series.
- JEFFAMINE diamines include the D, ED, and EDR series products.
- the D signifies a diamine
- ED signifies a diamine with a predominately polyethylene glycol (PEG) backbone
- EDR designates a highly reactive, PEG based diamine. See also U.S. Pat. Nos. 6,093,496; 6,306,964; 5,721,315; 7,012,043; and Publication U.S. Patent Application No. 2007/0208156 the disclosure of which are hereby incorporated by reference.
- Amine-based latent curing agents can also be added to the coating formulation in the isocyanate component, the polyol component, the amine-reactive polyol component or added simultaneously as any of these components or pre-coated on the proppant.
- Suitable amine-based latent curing agents include, but are not limited to, triethylenediamine; bis(2-dimethylaminoethyl)ether; tetramethylethylenediamine; pentamethyldiethylenetriamine; and other tertiary amine products of alkyleneamines. Additionally, other catalysts that promote the reaction of isocyanates with hydroxyls and amines that are known by the industry can be used.
- the coated particulate can be coated with a polyurethane dispersion.
- the dispersion can be coated onto the particulate itself in a separate layer that is coated on top of an inner polyurethane layer or it can be coated onto the particulate with the polyurethane layer at the same time.
- the polyurethane dispersion is coated onto a particulate without an inner polyurethane layer.
- the polyurethane dispersion is an aqueous polyurethane dispersion.
- the polyurethane dispersion is siloxane-polyurethane dispersion. Without being bound to any particular theory, the presence of the siloxane groups allows the dispersion to crosslink to one another by a dehydration step or as the dispersion dries and water is evaporated.
- the polyurethane dispersion is a polycarbonate-polyurethane dispersion. In some embodiments, the polycarbonate-polyurethane dispersion is free of organic solvents and emulsifiers. In some embodiments, the polyurethane dispersion is a polyether-polyurethane dispersion. In some embodiments, the polyurethane dispersion is a polyester/acrylic polyurethane dispersion. In some embodiments, the polyurethane dispersion is an aliphatic polycarbonate polyurethane dispersion.
- the polyurethane dispersion is an aqueous, anionic, solvent-free, low viscous dispersion of an aliphatic polyester-polyurethane substantially free of free isocyanate groups. In some embodiments, the polyurethane dispersion is an aqueous, anionic, solvent-free, low viscous dispersion of an aliphatic polyester-polyurethane without free isocyanate groups. In some embodiments, the polyurethane dispersion is an aqueous, colloidal, anionic, low viscous dispersion of an aliphatic polyester-polyurethane without free isocyanate groups.
- the polyurethane dispersion is an aqueous, anionic, solvent-free dispersion of an aliphatic polyesterpolyurethane.
- the polyurethane dispersion is a self-crosslinking polycarbonate/polyester polyurethane dispersion.
- the polyurethane dispersion is a polyisocyanate crosslinked polycarbonate/polyester polyurethane dispersion.
- the polyurethane dispersion is a polyester, self-crosslinking polyurethane dispersion.
- the polyurethane dispersion is a solvent-free self-crosslinking acrylated polyurethane dispersion.
- the polyurethane dispersion is a waterborne, aliphatic polyurethane dispersion, free of solvents and emulsifiers. In some embodiments, the polyurethane dispersion is a polyester polyurethane dispersion.
- the polyurethane dispersion is free of organic solvents. In some embodiments, the polyurethane dispersion is free of emulsifiers.
- the polyurethane dispersion has a König hardness of about 50 to about 170. In some embodiments, polyurethane dispersion has a König hardness of about 50 to about 100. In some embodiments, the polyurethane dispersion has a König hardness of about 70 to about 80. In some embodiments, the polyurethane dispersion has a König hardness of about 100 to about 170. In some embodiments, the polyurethane dispersion has a König hardness of about 120 to about 140. In some embodiments, the polyurethane dispersion has a König hardness of about 150 to about 170. In some embodiments, the polyurethane dispersion has a König hardness of about 160. In some embodiments, the polyurethane dispersion has a König hardness of about 130. In some embodiments, the polyurethane dispersion has a König hardness of about 70.
- the polyurethane dispersion is Alberdingk Boley U 6100 (is an aqueous, colloidal, anionic, low viscous dispersion of an aliphatic polyester-polyurethane without free isocyanate groups); Alberdingk Boley U 8001 (an aqueous, anionic, solvent-free, low viscous dispersion of an aliphatic polyester-polyurethane without free isocyanate groups); Alberdingk Boley U 6150 (a solvent-free aliphatic polycarbonate polyurethane dispersion), Alberdingk Boley U 9150 (solvent free, self-crosslinking polycarbonate/polyester polyurethane dispersion), Alberdingk Boley U 9370 (a polyester polyurethane dispersion), Alberdingk Boley U 9900 (aqueous, anionic, solvent-free dispersion of an aliphatic polyesterpolyurethane), TakelacTM WS-4000 (polycarbonate-pol
- the polyurethane dispersion is crosslinked. It can be, for example, crosslinked by a dehydration step, a drying step, or be crosslinked with a chemical crosslinker.
- the chemical crosslinker is an aziridine crosslinker.
- the aziridine crosslinker is trimethylolpropane tris(2-methyl-1-aziridine propionate).
- the particulate coating compositions may also include various additives.
- the coatings may also include pigments, tints, dyes, and fillers in an amount to provide visible coloration in the coatings.
- Other materials conventionally included in coating compositions may also be added to the compositions. These additional materials include, but are not limited to, reaction enhancers or catalysts, crosslinking agents, optical brighteners, propylene carbonates, coloring agents, fluorescent agents, whitening agents, UV absorbers, hindered amine light stabilizers, defoaming agents, processing aids, mica, talc, nano-fillers and other conventional additives. All of these materials are well known in the art and are added for their usual purpose in typical amounts.
- the additives are preferably present in an amount of about 15 weight percent or less. In one embodiment, the additive is present in an amount of about 5 percent or less by weight of the coating composition.
- Silanes are a particularly preferred type of adhesion agent that improves the affinity of the coating resin for the surface of the proppant.
- Silanes can be mixed in as additives in step (a), but can also be converted chemically with reactive constituents of the polyol component or of the isocyanate component.
- Functional silanes such as amino-silanes, epoxy-, aryl- or vinyl silanes are commercially available and, as described above, can be used as additives or can be converted with the reactive constituents of the polyol component or of the isocyanate component. In particular, amino-silanes and epoxy-silanes can be easily converted with the isocyanate component.
- the proppants can be virtually any small solid with an adequate crush strength and lack of chemical reactivity. Suitable examples include sand, ceramic particles (for instance, aluminum oxide, silicon dioxide, titanium dioxide, zinc oxide, zirconium dioxide, cerium dioxide, manganese dioxide, iron oxide, calcium oxide or bauxite), or also other granular materials.
- the proppants to be coated preferably have an average particle size within the range from about 50 ⁇ m and about 3000 ⁇ m, and more preferably within the range from about 100 ⁇ m to about 2000 ⁇ m.
- methods of preparing a multi-layer coated particulate comprise coating the particulate with a first layer.
- the first layer is a polyurethane layer.
- the polyurethane layer is formed from the reaction of an isocyanate component and a polyol component.
- the isocyanate component is as described herein.
- the polyol component is as described herein.
- polyurethane coated particulate is coated with an outer layer that is a polyurethane dispersion.
- the polyurethane dispersion can be, for example, as described herein.
- the layers are coated onto the particulate by mixing the components and the particulate in a mixer.
- the first layer is produced by mixing the particulate with a polyol component and an isocyanate component under conditions sufficient to form the polyurethane coating coated onto the particulate.
- the particulates are preheated sufficient to evaporate any water present in the coating components or dispersions.
- the methods comprises drying the multi-layer coated particulate.
- the methods comprise crosslinking the second layer (e.g., polyuerthane dispersion layer) to produce a cross-linked second layer.
- the crosslinking comprises drying the second layer coated particulate to crosslink the polyurethane dispersion.
- the crosslinking comprises contacting the second layer with a crosslinker, such as the chemicals described herein.
- the cross-linking occurs by itself without the addition of an additional cross-linking chemical or component. This can be referred to as self-crosslinking.
- the methods for the production of coated particulates can be implemented without the use of solvents.
- the mixture one or more, or all of the steps are solvent-free (including but not limited to organic solvents), or is essentially solvent-free.
- the mixture is essentially solvent-free, if it contains less than 20 wt %, less than 10 wt %, less than 5 wt %, less than 3 wt %, or less than 1 wt % of solvent, relative to the total mass of components of the mixture.
- other than the water present in the polyurethane dispersion no additional water is added to the mixer to coat the particulates.
- the method is implemented without the use of organic solvents. In some embodiments, one of the steps is performed without the use of organic solvents.
- the inner polyurethane layer is formed free of organic solvents, or is essentially free of organic solvents. The mixture is essentially free of organic solvents, if it contains less than 20 wt %, less than 10 wt %, less than 5 wt %, and less than 3 wt %, or less than 1 wt % of solvent, relative to the total mass of components of the mixture.
- the particulate is heated to an elevated temperature and then contacted (e.g., mixed) with the coating components.
- the particulate is heated to a temperature from about 50° C. to about 150° C.
- the increased temperature can, for example, accelerate crosslinking reactions in the applied coating.
- the mixer used for the coating process is not particularly restricted and can be selected from among the mixers known in the specific field.
- a pug mill mixer or an agitation mixer can be used.
- a drum mixer, a plate-type mixer, a tubular mixer, a trough mixer or a conical mixer can be used.
- the components and formulations are mixed in a rotating drum.
- a continuous mixer, a worm gear can, for example, be used.
- Mixing can be carried out on a continuous or discontinuous basis. It is also possible to arrange several mixers in series, or to coat the proppants in several runs in one mixer.
- the temperature of the coating process is not particularly restricted outside of practical concerns for safety and component integrity.
- the coating steps are performed at a temperature of between about 10° C. and about 150° C., or about 10° C. to about 125° C., or about 50° C. to about 150° C.
- the coating material may be applied in more than one layer.
- each of the layers described herein are repeated as necessary (e.g. 1-5 times, 2-4 times or 2-3 times) to obtain the desired coating thickness.
- the thickness of the coating of the proppant can be adjusted and used as either a relatively narrow range of proppant size or blended with proppants of other sizes, such as those with more or less numbers of coating layers of polyurethane or polyurethane dispersions as described herein. This can also be used to form a particulate blend have more than one range of size distribution.
- the amount of the polyurethane coating that is applied or coated onto the particulate is about 0.5 wt % to about 10 wt %, about 0.65 wt % to about 1.5 wt %, about 0.75 wt % to about 1.3 wt %, 0.8 wt % to about 1.25 wt %, about 0.8 wt %, about 0.9 wt %, about 1.0 wt %, about 1.1 wt %, about 1.2 wt %, about 1.25 wt %, relative to the mass of the particulate as 100 wt %.
- the amount of the polyurethane dispersion coating that is applied or coated onto the particulate is about 0.1 wt % to about 0.5 wt %, about 0.1 wt %, about 0.15 wt %, about 0.2 wt %, about 0.3 wt %, about 0.4 wt %, about 0.5 wt %, or about 0.25 wt % to about 0.3 wt % relative to the mass of the particulate as 100 wt %.
- the coated particulates can additionally be treated with surface-active agents or auxiliaries, such as talcum powder or stearate, to improve pourability.
- auxiliaries such as talcum powder or stearate
- the coated particulates can be baked or heated for a period of time sufficient to substantially react at least substantially all of the available isocyanate, hydroxyl that might remain in the coated particulate.
- a post-coating cure may occur even if additional contact time with a catalyst is used after a first coating layer or between layers.
- the post-coating cure step is performed like a baking step at a temperature within the range from about 100° ⁇ 200° C. for a time of about 1-48 hours, or the temperature is about 125°-175° C. for 19-36 hours.
- the coated particulate is cured for a time and under conditions sufficient to produce a coated proppant that exhibits a loss of coating of less than 25 wt %, preferably less than 15 wt %, and even more preferably less than 5 wt % when tested according to ISO 13503-5:2006(E).
- the embodiments provided herein includes the use of the coated particulates in conjunction with a fracturing liquid for the production of petroleum or natural gas.
- the fracturing liquid is not particularly restricted and can be selected from among the frac liquids known in the specific field. Suitable fracturing liquids are described, for example, in WC Lyons, G J Plisga, Standard Handbook Of Petroleum And Natural Gas Engineering , Gulf Professional Publishing (2005).
- the fracturing liquid can be, for example, water gelled with polymers, an oil-in-water emulsion gelled with polymers, or a water-in-oil emulsion gelled with polymers.
- the fracturing liquid comprises the following constituents in the indicated proportions: 10001 water, 20 kg potassium chloride, 0.120 kg sodium acetate, 3.6 kg guar gum (water-soluble polymer), sodium hydroxide (as needed) to adjust a pH-value from 9 to 11, 0.120 kg sodium thiosulfate, and 0.180 kg ammonium persulfate.
- methods are provided for the production of petroleum or natural gas which comprises the injection of the coated particulate into the fractured stratum with the fracturing liquid, i.e., the injection of a fracturing liquid which contains the coated particulate, into a petroleum- or natural gas-bearing rock layer, and/or its introduction into a fracture in the rock layer bearing petroleum or natural gas.
- the method is not particularly restricted and can be implemented in the manner known in the specific field.
- the particulates can be coated at temperatures of about 10° C. and about 150° C. and, for example in some embodiments, in a solvent-free manner.
- the flow back effect can be controlled and adjusted in a reproducible manner.
- the coating requires a comparatively little equipment and if necessary can also be carried out on a short-term basis in the vicinity of the bore.
- Conductivity testing was performed at simulated downhole conditions using the method and procedures found in ISO 13503-5:2006. In such tests, a closure stress is applied across a test unit for 50 hours to allow the proppant sample bed to reach a semi-steady state condition. As the fluid is forced through the proppant bed, the pack width, differential pressure, temperature and flow rates are measured at each stress. Proppant pack permeability and conductivity are then calculated.
- test fluid is potassium chloride substitute solution filtered to 3 ⁇ m absolute.
- the initial conductivity, permeability and width is measured and compared to the final conductivity, permeability and width after each stress period. Stress is applied and maintained using an Isco 260D. Stress is applied at 100 psi/minute.
- Width of the proppant pack is determined by assembling the conductivity cell with the Ohio sandstone wafers and shims without the sample proppants. The distance between the width bars that are attached to each end of the conductivity cells are measured at each of the four corners and recorded. The cells are then assembled with the proppant samples. The measurements are made again at the beginning and ending of each stress period. Width is determined by subtracting the average of the zero from the average of each of the stress width values. Conductivity is calculated using Darcy's equation.
- k is the proppant pack permeability, expressed in Darcy's
- kW f is the proppant pack conductivity, expressed in millidarcy-feet
- ⁇ is the viscosity of the test liquid at test temperature, expressed in centipoises
- Q is the flow rate, expressed in cubic centimeters per minute
- ⁇ P is the differential pressure, expressed in psi
- W f is proppant pack width, expressed in inches.
- samples of the proppant pack are taken, dried in an oven and weighed. They are then subjected to a temperature of 960 C for 2.5 hours. At the end of this period the samples are cooled and weighed again. The difference between the sample weight after drying but before being subjected to the furnace compared to the sample weight after the time in the furnace, equates to the coating weight. Comparing this number to the same test performed on a sample of the coated material before being subjected to the conductivity test, will equate to the coating weight lost due to the long term exposure to the conditions of the conductivity tests.
- the autoclave test utilizes what amounts to a pressure cooker to subject the coated sands to a hot wet environment that is above the boiling temperature of water. Approximately 20 g of sample is placed in a jar along with 150 ml of distilled water. The lids are placed on sample jars but not tightened. The samples are placed in the autoclave and the chamber is sealed. Heat is applied until the autoclave temperature reaches 250-265° F. (121° ⁇ 129° C.). The samples are maintained under these conditions for the ten day period. At the end of the test period the autoclave is cooled down, opened and the sample jars removed. Each sample is washed with distilled water and then placed in an oven to dry.
- the dried samples are then put through a standard test for determination of LOI. This result is compared a the results of an LOI test that was run on the original sample. The difference in LOI before and after the autoclave test, quantifies the amount of LOI dissolved by the exposure to a hot water environment.
- Sand was coated with a polyurethane inner layer and a polyurethane dispersion outer layer.
- the polyurethane was formed by the reaction of a diisocyanate and a polyol comprising a polyol and a polyether polyol.
- the coatings were layered onto the particulate sequentially (polyurethane first and then the polyurethane dispersion) with the percentages as shown in the figures below.
- the first percentage is the wt % of the polyurethane coating and the second percentage is the dispersion coating as indicated.
- UCS was measured at the different temperatures as indicated.
- the coatings performed significantly better than particulates coated without the dispersion outer layer as discussed below and illustrated in FIG. 1 , FIG. 2 , and FIG. 3 .
- the sands coated with the polyurethane and polyurethane dispersions had improved performance and the coating was found to be durable.
- compositions, methods, and devices are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions, methods, and devices can also “consist essentially of” or “consist of” the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.
Abstract
Description
- This application claims priority to U.S. Provisional Application No. 62/426,888, filed Nov. 28, 2016, which is incorporated by reference in its entirety.
- Well fracturing is an often used technique to increase the efficiency and productivity of oil and gas wells. Overly simplified, the process involves the introduction of a fracturing fluid into the well and the use of fluid pressure to fracture and crack the well strata. The cracks allow the oil and gas to flow more freely from the strata and thereby increase production rates in an efficient manner.
- There are many detailed techniques involved in well fracturing, but one of the most important is the use of a solid “proppant” to keep the strata cracks open as oil, gas, water and other fluids found in well flow through those cracks. The proppant is carried into the well with the fracturing fluid which itself may contain a variety of viscosity enhancers, gelation agents, surfactants, etc.
- Proppants can be made of virtually any generally solid particle that has a sufficiently high crush strength to prop open cracks in a rock strata at great depth and temperatures of about 125° C. and higher. Sand and ceramic proppants have proved to be especially suitable for commercial use.
- A proppant that is flushed from the well is said to have a high “flow back.” Flow back is undesirable. In addition to closure of the cracks, the flushed proppants are abrasive and can damage or clog valves and pipelines in downstream processing facilities.
- Synthetic resin coatings can be used to impart a degree of adhesion to the proppant so that flow back is substantially reduced or eliminated. Such resins can include phenol resin, epoxy resin, polyurethane-phenol resin, furane resin, etc. See published US Patent Application Nos. 2002/0048676, 2003/0131998, 2003/0224165, 2005/0019574, 2007/0161515 and 2008/0230223 as well as U.S. Pat. Nos. 4,920,192; 5,048,608; 5,199,491; 6,406,789; 6,632,527; 7,624,802; and published international application WO 2010/049467, the disclosures of which are herein incorporated by reference.
- Proppants based on polyurethane chemistries have a number of potential advantages over coating systems. However, polyurethane coated proppants also have disadvantages in that they can be not as durable as some other coatings. The present embodiments solves these issues and others as will be apparent from the present disclosure.
- In some embodiments, coated particulates are provided. In some embodiments, the coatings comprise an inner coating adjacent to the particulate comprising a polyurethane and an outer coating comprising an polyurethane dispersion; a coating comprising a polyurethane admixed with a polyurethane dispersion; or a polyurethane dispersion layer and is free of an inner polyurethane layer.
- In some embodiments, methods of preparing a multi-layer coated particulate are provided. In some embodiments, the methods comprise a) coating the particulate with a first layer, wherein the first layer is a polyurethane to produce a polyurethane coated particulate; and coating the polyurethane coated particulate with a second layer to produce the multi-layer coated particulate, wherein the second layer comprises a polyurethane dispersion.
- In some embodiments, methods of extracting oil and/or gas from a subterranean stratum are provided, the method comprising injecting into the subterranean stratum the coated particulates described herein; and extracting the oil and/or gas from the subterranean stratum.
-
FIG. 1 illustrates a non-limiting embodiments of the improved performance and durability of coatings described herein. -
FIG. 2 illustrates a non-limiting embodiments of the improved performance and durability of coatings described herein. -
FIG. 3 illustrates a non-limiting embodiments of the improved performance and durability of coatings described herein. - In some embodiments, coated particulates are provided. In some embodiments, the coating comprises an inner coating adjacent to the particulate comprising a polyurethane and an outer coating comprising an polyurethane dispersion; a coating comprising a polyurethane admixed with a polyurethane dispersion; or a polyurethane dispersion layer and is free of an inner polyurethane layer.
- In some embodiments, the coating resists dissolution under the rigorous combination of high heat, agitation, abrasion and water found downhole in a well. In some embodiments, the coating exhibits a sufficient resistance to a 10 day autoclave test or 10 day conductivity test so that the coating resists loss by dissolution in hot water (“LOT loss”) of less than 25 wt %, less than 15 wt %, or a loss of less than 5 wt %. The multi-layer coating can in some embodiments resist dissolution in the fractured stratum while also exhibiting sufficient resistance to flow back and sufficiently high crush strength to maintain conductivity of the fractures.
- In some embodiments, a testing method for the above is described in ISO 13503-5:2006(E) “Procedures for measuring the long term conductivity of proppants”, the disclosure of which is herein incorporated by reference. ISO 13503-5:2006 provides standard testing procedures for evaluating proppants used in hydraulic fracturing and gravel packing operations. ISO 13503-5:2006 provides a consistent methodology for testing performed on hydraulic fracturing and/or gravel packing proppants. The “proppants” mentioned henceforth in this part of ISO 13503-5:2006 refer to sand, ceramic media, resin-coated proppants, gravel packing media, and other materials used for hydraulic fracturing and gravel-packing operations. ISO 13503-5:2006 is a non-limiting example of a consistent method by which downhole conditions can be simulated and compared in a laboratory setting
- In some embodiments, the isocyanate component comprises an isocyanate with at least 1, 2, 3, or 4 reactive isocyanate groups. Other isocyanate-containing compounds may be used, if desired. Examples of suitable isocyanate with at least 2 isocyanate groups an aliphatic or an aromatic isocyanate with at least 2 isocyanate groups (e.g. a diisocyanate, triisocyanate or tetraisocyanate), or an oligomer or a polymer thereof can also be used. These isocyanates with at least 2 isocyanate groups can also be carbocyclic or heterocyclic and/or contain one or more heterocyclic groups. In some embodiments, the isocyanate is a mixture of a diisocyanate or a triisocyanate.
- In some embodiments, the isocyanate comprises 4,4′-methylenediphenyl diisocyanate. In some embodiments, the isocyanate comprises 4,4′-methylenediphenyl diisocyanate is present in a concentration amount of about 18 to about 25%. In some embodiments, the isocyanate comprises a diphenylmethane diisocyanate and as described herein.
- In some embodiments, the isocyanate with at least 2 isocyanate groups is a compound of the formula (III) or a compound of the formula (IV):
- In the formulas (III) and (IV), A is each, independently, an aryl, heteroaryl, cycloalkyl or heterocycloalkyl. Preferably, A is each, independently, an aryl or cycloalkyl. More preferably A is each, independently, an aryl which is preferably phenyl, naphthyl or anthracenyl, and most preferably phenyl. Still more preferably A is a phenyl.
- The above mentioned heteroaryl is preferably a heteroaryl with 5 or 6 ring atoms, of which 1, 2 or 3 ring atoms are each, independently, an oxygen, sulfur or nitrogen atom and the other ring atoms are carbon atoms. More preferably the heteroaryl is selected among pyridinyl, thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, isoxazolyl or furazanyl.
- The above mentioned cycloalkyl is preferably a C3-10-cycloalkyl, more preferably a C5-7-cycloalkyl.
- The above mentioned heterocycloalkyl is preferably a heterocycloalkyl with 3 to 10 ring atoms (more preferably with 5 to 7 ring atoms), of which one or more (e.g. 1, 2 or 3) ring atoms are each, independently, an oxygen, sulfur or nitrogen atom and the other ring atoms are carbon atoms. More preferably the heterocycloalkyl is selected from among tetrahydrofuranyl, piperidinyl, piperazinyl, aziridinyl, acetidinyl, pyrrolidinyl, imidazolidinyl, morpholinyl, pyrazolidinyl, tetrahydrothienyl, octahydroquinolinyl, octahydroisoquinolinyl, oxazolidinyl or isoxazolidinyl. Still more preferably, the heterocycloalkyl is selected from among tetrahydrofuranyl, piperidinyl, piperazinyl, pyrrolidinyl, imidazolidinyl, morpholinyl, pyrazolidinyl, tetrahydrothienyl, oxazolidinyl or isoxazolidinyl.
- In the formulas (III) and (IV), each R1 is, independently, a covalent bond or C1-4-alkylene (e.g. methylene, ethylene, propylene or butylene). Preferably each R2 is a covalent bond.
- In the formulas (III) and (IV), each R2 is each, independently, a halogen (e.g. F, Cl, Br or I), a C1-4-alkyl (e.g. methyl, ethyl, propyl or butyl) or C1-4-alkyoxy (e.g. methoxy, ethoxy, propoxy or butoxy). Preferably, each R2 is, independently, a C1-4-alkyl. More preferably each R2 is methyl.
- In the formula (IV), R3 is a covalent bond, a C1-4-alkylene (e.g. methylene, ethylene, propylene or butylene) or a group —(CH2)R31—O—(CH2)R32—, wherein R31 and R32 are each, independently, 0, 1, 2 or 3. Preferably, R3 is a —CH2— group or an —O— group.
- In the formula (III), p is equal to 2, 3 or 4, preferably 2 or 3, more preferably 2.
- In the formulas (III) and (IV), each q is, independently, an integer from 0 to 3, preferably 0, 1 or 2. When q is equal to 0, the corresponding group A has no substitutent R2, but has hydrogen atoms instead of R2.
- In the formula (IV), each r and s are, independently, 0, 1, 2, 3 or 4, wherein the sum of r and s is equal to 2, 3 or 4. Preferably, each r and s are, independently, 0, 1 or 2, wherein the sum of r and s is equal to 2. More preferably, r is equal to 1 and s is equal to 1.
- Examples of the isocyanate with at least 2 isocyanate groups are: toluol-2,4-diisocyanate; toluol-2,6-diisocyanate; 1,5-naphthalindiisocyanate; cumol-2,4-diisocyanate; 4-methoxy-1,3-phenyldiisocyanate; 4-chloro-1,3-phenyldiisocyanate; diphenylmethane-4,4-diisocyanate; diphenylmethane-2,4-diisocyanate; diphenylmethane-2,2-diisocyanate; 4-bromo-1,3-phenyldiisocyanate; 4-ethoxy-1,3-phenyl-diisocyanate; 2,4′-diisocyanate diphenylether; 5,6-dimethyl-1,3-phenyl-diisocyanate; 2,4-dimethyl-1,3-phenyldiisocyanate; 4,4-diisocyanato-diphenylether; 4,6-dimethyl-1,3-phenyldiisocyanate; 9,10-anthracene-diisocyanate; 2,4,6-toluol triisocyanate; 2,4,4′-triisocyanatodiphenylether; 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,10-decamethylene-diisocyanate; 1,3-cyclohexylene diisocyanate; 4,4′-methylene-bis-(cyclohexylisocyanate); xylol diisocyanate; 1-isocyanato-3-methyl-isocyanate-3,5,5-trimethylcyclohexane (isophorone diisocyanate); 1-3-bis(isocyanato-1-methylethyl) benzol (m-TMXDI); 1,4-bis(isocyanato-1-methylethyl) benzol (p-TMXDI); oligomers or polymers of the above mentioned isocyanate compounds; or mixtures of two or more of the above mentioned isocyanate compounds or oligomers or polymers thereof.
- In some embodiments, the isocyanates with at least 2 isocyanate groups are toluol diisocyanate, diphenylmethane diisocyanate, an oligomer based on toluol diisocyanate or an oligomer based on diphenylmethane diisocyanate.
- In some embodiments, the polyurethane is formed by reacting the isocyanate component with a polyol component. The polyol component may or may not have reactive amine functionality. In some embodiments, the polyol is a mixture of a polyol and a polyether polyol. In some embodiments, the polyol is a mixture of about 20 to about 30% polyol by weight and the polyether polyol is about 70 to about 80% by weight, wherein the total of the polyol and the polyether polyol is 100%. In some embodiments, the polyurethane coating is a phenolic polyurethane made with a phenolic polyol according to a patent application that was filed with the German Patent Office under no. DE 10 2010 051 817.4 on Nov. 19, 2010 and entitled “Proppant Coating Technology”, the disclosure of which is herein incorporated by reference and summarized below in the context of coatings described herein.
- In some embodiments, the polyol component comprises a phenol resin that comprises a condensation product of a phenol and an aldehyde, such as formaldehyde. The phenol resin is preferably a resole or novolak phenol resin and more preferably a benzyl ether resin.
- The resole-type phenol resin can be obtained, for example, by condensation of phenol or of one or more compounds of the following formula (I), with aldehydes, preferably formaldehyde, under basic conditions.
- In the formula (I):
-
- “R” is in each case, independently, a hydrogen atom, a halogen atom, C1-16-alkyl (preferably C1-12-alkyl, more preferably C1-6-alkyl, and still more preferably methyl, ethyl, propyl or butyl) or —OH;
- “p” is an integer from 0 to 4, preferably 0, 1, 2 or 3, and more preferably 1 or 2. Those in the art will understand that when p is 0, the compound of formula (I) is phenol.
- Novolak-type phenol resin comprises the condensation product of phenol or of one or more compounds of the formula (I) defined above, with aldehydes, preferably formaldehyde, under acidic conditions.
- In some embodiments, the polyol also comprises a polyether polyol.
- In some embodiments, the polyol comprises a benzyl ether resin of the general formula (II):
- In the formula (II):
-
- A, B and D each are, independently, a hydrogen atom, a halogen atom, a C1-16-hydrocarbon residue, —(C1-16-alkylene)-OH, —OH, an —O—(C1-16-hydrocarbon residue), phenyl, —(C1-6-alkylene)-phenyl, or —(C1-6-alkylene)-phenylene-OH;
- the halogen atom is F, Cl, Br or I;
- the C1-16-hydrocarbon-residue is C1-16-alkyl, C2-16-alkenyl or C2-16-alkinyl, or C1-12-alkyl, C2-12-alkenyl or C2-12-alkinyl, or C1-6-alkyl, C2-6-alkenyl or C2-6-alkinyl, or C1-4-alkyl, C2-4-alkenyl or C2-4-alkinyl, or C1-12-alkyl, C1-6-alkyl, or methyl, ethyl, propyl or butyl, or methyl;
- The residue —(C1-16-alkylene)-OH is —(C1-12-alkylene)-OH, —(C1-6-alkylene)-OH, —(C1-4-alkylene)-OH, or a methylol group (—CH2—OH);
- The —O—(C1-16-hydrocarbon)-residue is C1-16-alkoxy, C1-12-alkoxy, C1-6-alkoxy, C1-4-alkoxy, —O—CH3, —O—CH2CH3, —O—(CH2)2CH3 or —O—(CH2)3CH3;
- The residue —(C1-6-alkylene)-phenyl can be —(C1-4-alkylene)-phenyl, or —CH2-phenyl;
- The residue —(C1-6-alkylene)-phenylene-OH can be —(C1-4-alkylene)-phenylene-OH, or —CH2-phenylene-OH;
- R is a hydrogen atom of a C1-6-hydrocarbon residue (e.g. linear or branched C1-6-alkyl). In some embodiments, R is a hydrogen atom. This is the case, for example, when formaldehyde is used as aldehyde component in a condensation reaction with phenols in order to produce the benzyl ether resin of the formula (II);
- m1 and m2 are each, independently, 0 or 1.
- n is an integer from 0 to 100, preferably an integer from 1 to 50, more preferably from 2 to 10, and still more preferably from 2 to 5; and
- wherein the sum of n, m1 and m2 is at least 2.
- In some embodiments, the polyol component is a phenol resin with monomer units based on cardol and/or cardanol. Cardol and cardanol are produced from cashew nut oil which is obtained from the seeds of the cashew nut tree. Cashew nut oil consists of about 90% anacardic acid and about 10% cardol. By heat treatment in an acid environment, a mixture of cardol and cardanol is obtained by decarboxylation of the anacardic acid. Cardol and cardanol have the structures shown below:
- As shown in the illustration above, the hydrocarbon residue (—C15H31-n) in cardol and/or in cardanol can have one (n=2), two (n=4) or three (n=6) double bonds. Cardol specifically refers to compound CAS-No. 57486-25-6 and cardanol specifically to compound CAS-No. 37330-39-5.
- Cardol and cardanol can each be used alone or at any particular mixing ratio in the phenol resin. Decarboxylated cashew nut oil can also be used.
- Cardol and/or cardanol can be condensed into the above described phenol resins, for example, into the resole- or novolak-type phenol resins. For this purpose, cardol and/or cardanol can be condensed e.g. with phenol or with one or more of the above defined compounds of the formula (I), and also with aldehydes, such as formaldehyde.
- The amount of cardol and/or cardanol which is condensed in the phenol resin is not particularly restricted and preferably is from about 1 wt % to about 99 wt %, more preferably about 5 wt % to about 60 wt %, and still more preferably about 10 wt % to about 30 wt %, relative to 100 wt % of the amount of phenolic starting products used in the phenol resin.
- In another embodiment, the polyol component is a phenol resin obtained by condensation of cardol and/or cardanol with aldehydes, preferably formaldehyde.
- A phenol resin which contains monomer units based on cardol and/or cardanol as described above, or which can be obtained by condensation of cardol and/or cardanol with aldehydes, has a particularly low viscosity and can thus preferably be employed with a low addition or without addition of reactive thinners. Moreover, this kind of long-chain, substituted phenol resin is comparatively hydrophobic, which results in a favorable shelf life of the coated proppants obtained process described herein. In addition, a phenol resin of this kind is also advantageous because cardol and cardanol are renewable raw materials.
- Apart from the phenol resin, the polyol component can still contain other compounds containing hydroxyl groups. The other compounds containing hydroxyl groups can be selected from the compounds containing hydroxyl groups that are known to be useful for making polyurethanes, e.g., polyether polyols, hydroxy-functional polyethers, hydroxy-functional polyesters, alcohols or glycols. In some embodiments, compound containing hydroxyl groups is, for instance, a polyether polyol.
- The amount of the other compounds containing hydroxyl groups depends on the desired properties of the proppant coating and can suitably be selected by the person skilled in the art. In some embodiments, compounds containing hydroxyl groups are in the range of between about 10 wt % and about 80 wt %, preferably from about 20 wt % to about 70 wt %, relative to 100 wt % of the polyol component or as described herein.
- In some embodiments, the polyurethane layer is based upon a condensation reaction product that has been made with an excess of isocyanate component with respect to the polyol component. For example, in some
embodiments 100 parts by weight of the polyol component is used with about 105 wt % and about 300 wt %, preferably about 110 wt % to about 230 wt %, more preferably about 120 wt % to about 220 wt %, and still more preferably about 130 wt % to about 200 wt %, of the isocyanate base value. Depending upon the factors being considered the weight can be the absolute weight or the functional weight of the isocyanate and polyol components. - Thus, in some embodiments, the isocyanate base value defines the amount of the isocyanate component which is equivalent to 100 parts by weight of the polyol component. The NCO-content (%) of the isocyanate component is defined herein according to DIN ISO 53185. To determine the OH-content (%) of the polyol component, first the so-called OH-number is determined in mg KOH/g according to DIN ISO 53240 and this value is divided by 33, in order to determine the OH-content.
- In some embodiments, an excess of NCO-groups or absolute weight in the isocyanate component of between about 5 and about 200%, about 10 to about 130%, about 20% to about 120%, about 30% to about 100%, relative to the OH-groups in the polyol component or the weight of the polyol component is used (corresponding to the above mentioned amount of isocyanate component of about 105% to about 300%, about 110% to about 230%, about 120% to about 220%, about 130% to about 200% of the isocyanate weight or base value).
- In some embodiments, the isocyanate that is used to form the polyurethane has an equivalent weight of about 140. In some embodiments, the hydroxyl equivalent of the polyol that is used to form the polyurethane layer is about 85.
- In some embodiments, one or more additives can be mixed with the proppant, the polyol component and the isocyanate component. These additives are not particularly restricted and can be selected from the additives known in the specific field of coated proppants. Provided that one of these additives has hydroxyl groups, it should be considered as a different hydroxyl-group-containing compound, as described above in connection with the polyol component. If one of the additives has isocyanate groups, it should be considered as a different isocyanate-group-containing compound. Additives with hydroxyl groups and isocyanate groups can be simultaneously considered as different hydroxyl-group-containing compounds and as different isocyanate-group-containing compounds.
- In some embodiments, the coating comprises a reactive amine component, such as, but not limited to, an amine-terminated compound. This component can enhance crosslink density within the coating and, depending on component selection, can provide additional characteristics of benefit to the cured coating. In some embodiments, the amine components for include, but are not limited to, amine-terminated compounds such as diamines, triamines, amine-terminated glycols such as the amine-terminated polyalkylene glycols.
- Non-limiting examples of diamines include primary, secondary and higher polyamines and amine-terminated compounds. Suitable compounds include, but are not limited to, ethylene diamine; propylenediamine; butanediamine; hexamethylenediamine; 1,2-diaminopropane; 1,4-diaminobutane; 1,3-diaminopentane; 1,6-diaminohexane; 2,5-diamino-2,5-dimethlhexane; 2,2,4- and/or 2,4,4-trimethyl-1,6-diaminohexane; 1,11-diaminoundecane; 1,12-diaminododecane; 1,3- and/or 1,4-cyclohexane diamine; 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane; 2,4- and/or 2,6-hexahydrotoluylene diamine; 2,4′ and/or 4,4′-diaminodicyclohexyl methane and 3,3′-dialkyl-4,4′-diamino-dicyclohexyl methanes such as 3,3′-dimethyl-4,4-diamino-dicyclohexyl methane and 3,3′-diethyl-4,4′-diaminodicyclohexyl methane; aromatic polyamines such as 2,4- and/or 2,6-diaminotoluene and 2,6-diaminotoluene and 2,4′ and/or 4,4′-diaminodiphenyl methane; and polyoxyalkylene polyamines (also referred to herein as amine terminated polyethers).
- Mixtures of polyamines may also be employed in preparing aspartic esters, which is a secondary amine derived from a primary polyamine and a dialkyl maleic or fumaric acid ester. Representative examples of useful maleic acid esters include dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, mixtures thereof and homologs thereof.
- Suitable triamines and higher multifunctional polyamines include, but are not limited to, diethylene triamine, triethylenetetramine, and higher homologs of this series.
- JEFFAMINE diamines include the D, ED, and EDR series products. The D signifies a diamine, ED signifies a diamine with a predominately polyethylene glycol (PEG) backbone, and EDR designates a highly reactive, PEG based diamine. See also U.S. Pat. Nos. 6,093,496; 6,306,964; 5,721,315; 7,012,043; and Publication U.S. Patent Application No. 2007/0208156 the disclosure of which are hereby incorporated by reference.
- Amine-based latent curing agents can also be added to the coating formulation in the isocyanate component, the polyol component, the amine-reactive polyol component or added simultaneously as any of these components or pre-coated on the proppant. Suitable amine-based latent curing agents include, but are not limited to, triethylenediamine; bis(2-dimethylaminoethyl)ether; tetramethylethylenediamine; pentamethyldiethylenetriamine; and other tertiary amine products of alkyleneamines. Additionally, other catalysts that promote the reaction of isocyanates with hydroxyls and amines that are known by the industry can be used.
- As described herein, the coated particulate can be coated with a polyurethane dispersion. The dispersion can be coated onto the particulate itself in a separate layer that is coated on top of an inner polyurethane layer or it can be coated onto the particulate with the polyurethane layer at the same time. In some embodiments, the polyurethane dispersion is coated onto a particulate without an inner polyurethane layer.
- In some embodiments, the polyurethane dispersion is an aqueous polyurethane dispersion. In some embodiments, the polyurethane dispersion is siloxane-polyurethane dispersion. Without being bound to any particular theory, the presence of the siloxane groups allows the dispersion to crosslink to one another by a dehydration step or as the dispersion dries and water is evaporated.
- In some embodiments, the polyurethane dispersion is a polycarbonate-polyurethane dispersion. In some embodiments, the polycarbonate-polyurethane dispersion is free of organic solvents and emulsifiers. In some embodiments, the polyurethane dispersion is a polyether-polyurethane dispersion. In some embodiments, the polyurethane dispersion is a polyester/acrylic polyurethane dispersion. In some embodiments, the polyurethane dispersion is an aliphatic polycarbonate polyurethane dispersion. In some embodiments, the polyurethane dispersion is an aqueous, anionic, solvent-free, low viscous dispersion of an aliphatic polyester-polyurethane substantially free of free isocyanate groups. In some embodiments, the polyurethane dispersion is an aqueous, anionic, solvent-free, low viscous dispersion of an aliphatic polyester-polyurethane without free isocyanate groups. In some embodiments, the polyurethane dispersion is an aqueous, colloidal, anionic, low viscous dispersion of an aliphatic polyester-polyurethane without free isocyanate groups. In some embodiments, the polyurethane dispersion is an aqueous, anionic, solvent-free dispersion of an aliphatic polyesterpolyurethane. In some embodiments, the polyurethane dispersion is a self-crosslinking polycarbonate/polyester polyurethane dispersion. In some embodiments, the polyurethane dispersion is a polyisocyanate crosslinked polycarbonate/polyester polyurethane dispersion. In some embodiments, the polyurethane dispersion is a polyester, self-crosslinking polyurethane dispersion. In some embodiments, the polyurethane dispersion is a solvent-free self-crosslinking acrylated polyurethane dispersion. In some embodiments, the polyurethane dispersion is a waterborne, aliphatic polyurethane dispersion, free of solvents and emulsifiers. In some embodiments, the polyurethane dispersion is a polyester polyurethane dispersion.
- In some embodiments, the polyurethane dispersion is free of organic solvents. In some embodiments, the polyurethane dispersion is free of emulsifiers.
- In some embodiments, the polyurethane dispersion has a König hardness of about 50 to about 170. In some embodiments, polyurethane dispersion has a König hardness of about 50 to about 100. In some embodiments, the polyurethane dispersion has a König hardness of about 70 to about 80. In some embodiments, the polyurethane dispersion has a König hardness of about 100 to about 170. In some embodiments, the polyurethane dispersion has a König hardness of about 120 to about 140. In some embodiments, the polyurethane dispersion has a König hardness of about 150 to about 170. In some embodiments, the polyurethane dispersion has a König hardness of about 160. In some embodiments, the polyurethane dispersion has a König hardness of about 130. In some embodiments, the polyurethane dispersion has a König hardness of about 70.
- In some embodiments, the polyurethane dispersion is Alberdingk Boley U 6100 (is an aqueous, colloidal, anionic, low viscous dispersion of an aliphatic polyester-polyurethane without free isocyanate groups); Alberdingk Boley U 8001 (an aqueous, anionic, solvent-free, low viscous dispersion of an aliphatic polyester-polyurethane without free isocyanate groups); Alberdingk Boley U 6150 (a solvent-free aliphatic polycarbonate polyurethane dispersion), Alberdingk Boley U 9150 (solvent free, self-crosslinking polycarbonate/polyester polyurethane dispersion), Alberdingk Boley U 9370 (a polyester polyurethane dispersion), Alberdingk Boley U 9900 (aqueous, anionic, solvent-free dispersion of an aliphatic polyesterpolyurethane), Takelac™ WS-4000 (polycarbonate-polyurethane dispersion), Takelac™ WS-5100 (polycarbonate-polyurethane dispersion), Takelac™ WS-5661 (polycarbonate-polyurethane dispersion), Takelac™ WS-6021 (polyether-polyurethane dispersion), Allnex 1265/36WA (aqueous, solvent-free self-crosslinking polyurethane dispersion), Allnex 6462/36WA (a solvent-free self-crosslinking acrylated polyurethane dispersion), Allnex 6490/35WA, or 7000/40WA, or any combination thereof.
- In some embodiments, the polyurethane dispersion is crosslinked. It can be, for example, crosslinked by a dehydration step, a drying step, or be crosslinked with a chemical crosslinker. In some embodiments, the chemical crosslinker is an aziridine crosslinker. In some embodiments, the aziridine crosslinker is trimethylolpropane tris(2-methyl-1-aziridine propionate).
- The particulate coating compositions may also include various additives. For example, the coatings may also include pigments, tints, dyes, and fillers in an amount to provide visible coloration in the coatings. Other materials conventionally included in coating compositions may also be added to the compositions. These additional materials include, but are not limited to, reaction enhancers or catalysts, crosslinking agents, optical brighteners, propylene carbonates, coloring agents, fluorescent agents, whitening agents, UV absorbers, hindered amine light stabilizers, defoaming agents, processing aids, mica, talc, nano-fillers and other conventional additives. All of these materials are well known in the art and are added for their usual purpose in typical amounts. For example, the additives are preferably present in an amount of about 15 weight percent or less. In one embodiment, the additive is present in an amount of about 5 percent or less by weight of the coating composition.
- Other additives can include, for example, solvents, softeners, surface-active agents, molecular sieves for removing the reaction water, thinners and/or adhesion agents can be used. Silanes are a particularly preferred type of adhesion agent that improves the affinity of the coating resin for the surface of the proppant. Silanes can be mixed in as additives in step (a), but can also be converted chemically with reactive constituents of the polyol component or of the isocyanate component. Functional silanes such as amino-silanes, epoxy-, aryl- or vinyl silanes are commercially available and, as described above, can be used as additives or can be converted with the reactive constituents of the polyol component or of the isocyanate component. In particular, amino-silanes and epoxy-silanes can be easily converted with the isocyanate component.
- The proppants can be virtually any small solid with an adequate crush strength and lack of chemical reactivity. Suitable examples include sand, ceramic particles (for instance, aluminum oxide, silicon dioxide, titanium dioxide, zinc oxide, zirconium dioxide, cerium dioxide, manganese dioxide, iron oxide, calcium oxide or bauxite), or also other granular materials. The proppants to be coated preferably have an average particle size within the range from about 50 μm and about 3000 μm, and more preferably within the range from about 100 μm to about 2000 μm.
- In some embodiments, methods of preparing a multi-layer coated particulate are provided. In some embodiments, the method comprises coating the particulate with a first layer. In some embodiments, the first layer is a polyurethane layer. In some embodiments, the polyurethane layer is formed from the reaction of an isocyanate component and a polyol component. In some embodiments, the isocyanate component is as described herein. In some embodiments, the polyol component is as described herein.
- In some embodiments, polyurethane coated particulate is coated with an outer layer that is a polyurethane dispersion. The polyurethane dispersion can be, for example, as described herein. In some embodiments, the layers are coated onto the particulate by mixing the components and the particulate in a mixer. For example, in some embodiments, the first layer is produced by mixing the particulate with a polyol component and an isocyanate component under conditions sufficient to form the polyurethane coating coated onto the particulate.
- In some embodiments, the particulates are preheated sufficient to evaporate any water present in the coating components or dispersions. In some embodiments, the methods comprises drying the multi-layer coated particulate. In some embodiments, the methods comprise crosslinking the second layer (e.g., polyuerthane dispersion layer) to produce a cross-linked second layer. In some embodiments, the crosslinking comprises drying the second layer coated particulate to crosslink the polyurethane dispersion. In some embodiments, the crosslinking comprises contacting the second layer with a crosslinker, such as the chemicals described herein. In some embodiments, the cross-linking occurs by itself without the addition of an additional cross-linking chemical or component. This can be referred to as self-crosslinking.
- In some embodiments, the methods for the production of coated particulates can be implemented without the use of solvents. Accordingly, the mixture one or more, or all of the steps are solvent-free (including but not limited to organic solvents), or is essentially solvent-free. The mixture is essentially solvent-free, if it contains less than 20 wt %, less than 10 wt %, less than 5 wt %, less than 3 wt %, or less than 1 wt % of solvent, relative to the total mass of components of the mixture. In some embodiments, other than the water present in the polyurethane dispersion no additional water is added to the mixer to coat the particulates.
- In some embodiments, the method is implemented without the use of organic solvents. In some embodiments, one of the steps is performed without the use of organic solvents. In some embodiments, the inner polyurethane layer is formed free of organic solvents, or is essentially free of organic solvents. The mixture is essentially free of organic solvents, if it contains less than 20 wt %, less than 10 wt %, less than 5 wt %, and less than 3 wt %, or less than 1 wt % of solvent, relative to the total mass of components of the mixture.
- In some embodiments, the particulate is heated to an elevated temperature and then contacted (e.g., mixed) with the coating components. In some embodiments, the particulate is heated to a temperature from about 50° C. to about 150° C. The increased temperature can, for example, accelerate crosslinking reactions in the applied coating.
- The mixer used for the coating process is not particularly restricted and can be selected from among the mixers known in the specific field. For example, a pug mill mixer or an agitation mixer can be used. For example, a drum mixer, a plate-type mixer, a tubular mixer, a trough mixer or a conical mixer can be used. In some embodiments, the components and formulations are mixed in a rotating drum. In some embodiments a continuous mixer, a worm gear can, for example, be used.
- Mixing can be carried out on a continuous or discontinuous basis. It is also possible to arrange several mixers in series, or to coat the proppants in several runs in one mixer.
- The temperature of the coating process is not particularly restricted outside of practical concerns for safety and component integrity. In some embodiments, the coating steps are performed at a temperature of between about 10° C. and about 150° C., or about 10° C. to about 125° C., or about 50° C. to about 150° C.
- The coating material may be applied in more than one layer. In some embodiments, each of the layers described herein are repeated as necessary (e.g. 1-5 times, 2-4 times or 2-3 times) to obtain the desired coating thickness. Thus, the thickness of the coating of the proppant can be adjusted and used as either a relatively narrow range of proppant size or blended with proppants of other sizes, such as those with more or less numbers of coating layers of polyurethane or polyurethane dispersions as described herein. This can also be used to form a particulate blend have more than one range of size distribution.
- In some embodiments, the amount of the polyurethane coating that is applied or coated onto the particulate is about 0.5 wt % to about 10 wt %, about 0.65 wt % to about 1.5 wt %, about 0.75 wt % to about 1.3 wt %, 0.8 wt % to about 1.25 wt %, about 0.8 wt %, about 0.9 wt %, about 1.0 wt %, about 1.1 wt %, about 1.2 wt %, about 1.25 wt %, relative to the mass of the particulate as 100 wt %.
- In some embodiments, the amount of the polyurethane dispersion coating that is applied or coated onto the particulate is about 0.1 wt % to about 0.5 wt %, about 0.1 wt %, about 0.15 wt %, about 0.2 wt %, about 0.3 wt %, about 0.4 wt %, about 0.5 wt %, or about 0.25 wt % to about 0.3 wt % relative to the mass of the particulate as 100 wt %.
- The coated particulates can additionally be treated with surface-active agents or auxiliaries, such as talcum powder or stearate, to improve pourability.
- In some embodiments, the coated particulates can be baked or heated for a period of time sufficient to substantially react at least substantially all of the available isocyanate, hydroxyl that might remain in the coated particulate. Such a post-coating cure may occur even if additional contact time with a catalyst is used after a first coating layer or between layers. Typically, the post-coating cure step is performed like a baking step at a temperature within the range from about 100°−200° C. for a time of about 1-48 hours, or the temperature is about 125°-175° C. for 19-36 hours.
- In some embodiments, the coated particulate is cured for a time and under conditions sufficient to produce a coated proppant that exhibits a loss of coating of less than 25 wt %, preferably less than 15 wt %, and even more preferably less than 5 wt % when tested according to ISO 13503-5:2006(E).
- Furthermore, the embodiments provided herein includes the use of the coated particulates in conjunction with a fracturing liquid for the production of petroleum or natural gas. The fracturing liquid is not particularly restricted and can be selected from among the frac liquids known in the specific field. Suitable fracturing liquids are described, for example, in WC Lyons, G J Plisga, Standard Handbook Of Petroleum And Natural Gas Engineering, Gulf Professional Publishing (2005). The fracturing liquid can be, for example, water gelled with polymers, an oil-in-water emulsion gelled with polymers, or a water-in-oil emulsion gelled with polymers. In one preferred embodiment, the fracturing liquid comprises the following constituents in the indicated proportions: 10001 water, 20 kg potassium chloride, 0.120 kg sodium acetate, 3.6 kg guar gum (water-soluble polymer), sodium hydroxide (as needed) to adjust a pH-value from 9 to 11, 0.120 kg sodium thiosulfate, and 0.180 kg ammonium persulfate.
- In addition, methods are provided for the production of petroleum or natural gas which comprises the injection of the coated particulate into the fractured stratum with the fracturing liquid, i.e., the injection of a fracturing liquid which contains the coated particulate, into a petroleum- or natural gas-bearing rock layer, and/or its introduction into a fracture in the rock layer bearing petroleum or natural gas. The method is not particularly restricted and can be implemented in the manner known in the specific field.
- In some embodiments, the particulates can be coated at temperatures of about 10° C. and about 150° C. and, for example in some embodiments, in a solvent-free manner. The flow back effect can be controlled and adjusted in a reproducible manner. The coating requires a comparatively little equipment and if necessary can also be carried out on a short-term basis in the vicinity of the bore.
- Conductivity testing was performed at simulated downhole conditions using the method and procedures found in ISO 13503-5:2006. In such tests, a closure stress is applied across a test unit for 50 hours to allow the proppant sample bed to reach a semi-steady state condition. As the fluid is forced through the proppant bed, the pack width, differential pressure, temperature and flow rates are measured at each stress. Proppant pack permeability and conductivity are then calculated.
- Multiple flow rates are used to verify the performance of the transducers, and to determine Darcy flow regime at each stress; an average of the data at these flow rates is reported. The test fluid is potassium chloride substitute solution filtered to 3 μm absolute. The initial conductivity, permeability and width is measured and compared to the final conductivity, permeability and width after each stress period. Stress is applied and maintained using an Isco 260D. Stress is applied at 100 psi/minute.
- Width of the proppant pack is determined by assembling the conductivity cell with the Ohio sandstone wafers and shims without the sample proppants. The distance between the width bars that are attached to each end of the conductivity cells are measured at each of the four corners and recorded. The cells are then assembled with the proppant samples. The measurements are made again at the beginning and ending of each stress period. Width is determined by subtracting the average of the zero from the average of each of the stress width values. Conductivity is calculated using Darcy's equation.
-
kW f=26.78μQ/(ΔP) Conductivity; -
k=321.4μQ/[(ΔP)W f] Permeability; - wherein:
k is the proppant pack permeability, expressed in Darcy's;
kWf is the proppant pack conductivity, expressed in millidarcy-feet
μ is the viscosity of the test liquid at test temperature, expressed in centipoises;
Q is the flow rate, expressed in cubic centimeters per minute;
ΔP is the differential pressure, expressed in psi;
Wf is proppant pack width, expressed in inches. - Sieve analysis is performed using the procedure found in ISO 13503-2 “Measurements of proppants used in hydraulic fracturing and gravel pack operations” Standard US mesh screens are used to separate the sample by size. Not more than 0.1% should be greater than the first specified sieve and not more than 1% should be retained in the pan. There should be at least 90% retained in the specified screens.
- To determine the magnitude of “LOI” loss during the conductivity test, samples of the proppant pack are taken, dried in an oven and weighed. They are then subjected to a temperature of 960 C for 2.5 hours. At the end of this period the samples are cooled and weighed again. The difference between the sample weight after drying but before being subjected to the furnace compared to the sample weight after the time in the furnace, equates to the coating weight. Comparing this number to the same test performed on a sample of the coated material before being subjected to the conductivity test, will equate to the coating weight lost due to the long term exposure to the conditions of the conductivity tests.
- The procedure used in an autoclave test would be as follows:
- The autoclave test utilizes what amounts to a pressure cooker to subject the coated sands to a hot wet environment that is above the boiling temperature of water. Approximately 20 g of sample is placed in a jar along with 150 ml of distilled water. The lids are placed on sample jars but not tightened. The samples are placed in the autoclave and the chamber is sealed. Heat is applied until the autoclave temperature reaches 250-265° F. (121°−129° C.). The samples are maintained under these conditions for the ten day period. At the end of the test period the autoclave is cooled down, opened and the sample jars removed. Each sample is washed with distilled water and then placed in an oven to dry. The dried samples are then put through a standard test for determination of LOI. This result is compared a the results of an LOI test that was run on the original sample. The difference in LOI before and after the autoclave test, quantifies the amount of LOI dissolved by the exposure to a hot water environment.
- Sand was coated with a polyurethane inner layer and a polyurethane dispersion outer layer. The polyurethane was formed by the reaction of a diisocyanate and a polyol comprising a polyol and a polyether polyol. The coatings were layered onto the particulate sequentially (polyurethane first and then the polyurethane dispersion) with the percentages as shown in the figures below. The first percentage is the wt % of the polyurethane coating and the second percentage is the dispersion coating as indicated. UCS was measured at the different temperatures as indicated. The coatings performed significantly better than particulates coated without the dispersion outer layer as discussed below and illustrated in
FIG. 1 ,FIG. 2 , andFIG. 3 . - Without being bound to any particular theory, these examples demonstrate that bond strength increases with increasing total LOI and that polyurethane loading level affects more for the bond strength at higher temperature (170 F).
- The sands coated with the polyurethane and polyurethane dispersions had improved performance and the coating was found to be durable.
- It must also be noted that as used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural reference unless the context clearly dictates otherwise.
- As used in this document, terms “comprise,” “have,” and “include” and their conjugates, as used herein, mean “including but not limited to.” While various compositions, methods, and devices are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions, methods, and devices can also “consist essentially of” or “consist of” the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.
- Various references and patents are disclosed herein, each of which are hereby incorporated by reference for the purpose that they are cited.
- This description is not limited to the particular processes, compositions, or methodologies described, as these may vary. The terminology used in the description is for the purpose of describing the particular versions or embodiments only, and it is not intended to limit the scope of the embodiments described herein. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. In some cases, terms with commonly understood meanings are defined herein for clarity and/or for ready reference, and the inclusion of such definitions herein should not necessarily be construed to represent a substantial difference over what is generally understood in the art. However, in case of conflict, the patent specification, including definitions, will prevail.
- From the foregoing, it will be appreciated that various embodiments of the present disclosure have been described herein for purposes of illustration, and that various modifications can be made without departing from the scope and spirit of the present disclosure. Accordingly, the various embodiments disclosed herein are not intended to be limiting.
Claims (27)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/906,020 US20210139767A1 (en) | 2016-11-28 | 2020-06-19 | Durable coatings and uses thereof |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662426888P | 2016-11-28 | 2016-11-28 | |
US15/823,699 US10696896B2 (en) | 2016-11-28 | 2017-11-28 | Durable coatings and uses thereof |
US16/906,020 US20210139767A1 (en) | 2016-11-28 | 2020-06-19 | Durable coatings and uses thereof |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/823,699 Continuation US10696896B2 (en) | 2016-11-28 | 2017-11-28 | Durable coatings and uses thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
US20210139767A1 true US20210139767A1 (en) | 2021-05-13 |
Family
ID=62192954
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/823,699 Active US10696896B2 (en) | 2016-11-28 | 2017-11-28 | Durable coatings and uses thereof |
US16/906,020 Abandoned US20210139767A1 (en) | 2016-11-28 | 2020-06-19 | Durable coatings and uses thereof |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/823,699 Active US10696896B2 (en) | 2016-11-28 | 2017-11-28 | Durable coatings and uses thereof |
Country Status (1)
Country | Link |
---|---|
US (2) | US10696896B2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10100247B2 (en) | 2013-05-17 | 2018-10-16 | Preferred Technology, Llc | Proppant with enhanced interparticle bonding |
CN108949140A (en) * | 2018-09-30 | 2018-12-07 | 重庆长江造型材料(集团)股份有限公司 | One kind is from suspension type support agent |
CN109880346B (en) * | 2019-03-05 | 2021-02-19 | 中原工学院 | Preparation method of organic-inorganic composite conductive gel |
Family Cites Families (287)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2163972A (en) | 1936-03-02 | 1939-06-27 | Fairbanks Morse & Co | Control system for dynamoelectric machines |
US2366007A (en) | 1942-08-11 | 1944-12-26 | Gen Electric | Production of synthetic polymeric compositions comprising sulphonated polymerizates of poly-vinyl aryl compounds and treatment of liquid media therewith |
US2653089A (en) | 1949-11-07 | 1953-09-22 | Phillips Petroleum Co | Recovery of heavy metals |
US2823753A (en) | 1955-12-27 | 1958-02-18 | Dow Chemical Co | Method of treating wells |
US3026938A (en) | 1958-09-02 | 1962-03-27 | Gulf Research Development Co | Propping agent for a fracturing process |
US3020250A (en) | 1959-08-04 | 1962-02-06 | Union Carbide Corp | Aqueous epoxy resin emulsions and coatings therefrom |
US3492147A (en) | 1964-10-22 | 1970-01-27 | Halliburton Co | Method of coating particulate solids with an infusible resin |
US3392148A (en) | 1964-12-21 | 1968-07-09 | Atlas Chem Ind | Aldehyde terminated urethanes |
DE1931053A1 (en) | 1969-06-19 | 1971-01-07 | Bayer Ag | Process for the production of synthetic resin concrete |
US3763072A (en) | 1970-11-23 | 1973-10-02 | Pacific Architects & Eng Inc | Soil adhesion composition of acrylic latex and sodium silicate |
US3805531A (en) | 1970-12-21 | 1974-04-23 | Minnesota Mining & Mfg | Consolidation of mineral aggregate |
US3837892A (en) | 1972-01-28 | 1974-09-24 | Owens Corning Fiberglass Corp | Glass fiber reinforced elastomers |
US3976135A (en) | 1972-10-02 | 1976-08-24 | Halliburton Company | Method of forming a highly permeable solid mass in a subterranean formation |
US3817939A (en) | 1973-02-21 | 1974-06-18 | Minnesota Mining & Mfg | Organic carbonate salts as isocyanate trimerization catalysts |
US3900611A (en) | 1973-03-09 | 1975-08-19 | Hemlab Ag | Particulate matter suppression using a solution of a surfactant and a polymer |
US3931428A (en) | 1974-01-04 | 1976-01-06 | Michael Ebert | Substrate coated with super-hydrophobic layers |
US3991225A (en) | 1974-02-01 | 1976-11-09 | Tennessee Valley Authority | Method for applying coatings to solid particles |
US3929191A (en) | 1974-08-15 | 1975-12-30 | Exxon Production Research Co | Method for treating subterranean formations |
US3971751A (en) | 1975-06-09 | 1976-07-27 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Vulcanizable silylether terminated polymer |
US4252655A (en) | 1978-04-17 | 1981-02-24 | Halliburton Company | Scavenging hydrogen sulfide in an oil well |
DE2623346C2 (en) | 1976-05-25 | 1978-07-13 | Bayer Ag, 5090 Leverkusen | Method for consolidating geological formations and two-chamber cartridge |
US4074536A (en) | 1976-08-02 | 1978-02-21 | Halliburton Company | Oil well consolidation treating |
US4074760A (en) | 1976-11-01 | 1978-02-21 | The Dow Chemical Company | Method for forming a consolidated gravel pack |
US4102703A (en) | 1976-11-08 | 1978-07-25 | Tulco, Inc. | Water-repellent coating compositions and method for their preparation |
CH625966A5 (en) | 1977-07-15 | 1981-10-30 | Kilcher Chemie Ag | |
US4199484A (en) | 1977-10-06 | 1980-04-22 | Halliburton Company | Gelled water epoxy sand consolidation system |
US4273910A (en) | 1979-12-05 | 1981-06-16 | Woellner-Werke | Cold hardening binding agent for particulate solids, such as molding sand, containing a nitrogen basic polyol |
US4417992A (en) | 1981-07-30 | 1983-11-29 | Nalco Chemical Company | Dust control |
US4518039A (en) | 1981-08-20 | 1985-05-21 | Graham John W | Method for treating subterranean formations |
US4732920A (en) | 1981-08-20 | 1988-03-22 | Graham John W | High strength particulates |
US4443347A (en) | 1981-12-03 | 1984-04-17 | Baker Oil Tools, Inc. | Proppant charge and method |
US4465815A (en) | 1981-12-28 | 1984-08-14 | Ford Motor Company | Polyhydroxy oligomers for high solids coatings II |
US4554188A (en) | 1981-12-28 | 1985-11-19 | Ford Motor Company | Chain-extendable crosslinkable urethane modified polyhydroxy oligomers and coating composition comprising same |
US4439489A (en) | 1982-02-16 | 1984-03-27 | Acme Resin Corporation | Particles covered with a cured infusible thermoset film and process for their production |
EP0096489A1 (en) | 1982-06-03 | 1983-12-21 | Imperial Chemical Industries Plc | Inorganic foams |
US4553596A (en) | 1982-10-27 | 1985-11-19 | Santrol Products, Inc. | Well completion technique |
US4592931A (en) | 1983-07-28 | 1986-06-03 | Exxon Research & Engineering Co. | Method for soil stabilization and fugitive dust control |
US4493875A (en) | 1983-12-09 | 1985-01-15 | Minnesota Mining And Manufacturing Company | Proppant for well fractures and method of making same |
US4580633A (en) | 1983-12-21 | 1986-04-08 | Union Oil Company Of California | Increasing the flow of fluids through a permeable formation |
US4680230A (en) | 1984-01-18 | 1987-07-14 | Minnesota Mining And Manufacturing Company | Particulate ceramic useful as a proppant |
US4585064A (en) | 1984-07-02 | 1986-04-29 | Graham John W | High strength particulates |
US4623589A (en) | 1985-02-13 | 1986-11-18 | Usm Corporation | Particulate polymeric materials and methods for using particulate polymeric materials |
US4594268A (en) | 1985-03-29 | 1986-06-10 | Calgon Corporation | Method for the control of dust using methacrylate containing emulsions and compositions |
US4632876A (en) | 1985-06-12 | 1986-12-30 | Minnesota Mining And Manufacturing Company | Ceramic spheroids having low density and high crush resistance |
DE3532387A1 (en) | 1985-09-11 | 1987-04-23 | Bergwerksverband Gmbh | METHOD FOR STRENGTHENING GEOLOGICAL FORMATIONS |
US4746543A (en) | 1985-12-10 | 1988-05-24 | Zinkan Enterprises, Inc. | Composition and method for dust control |
US4801635A (en) | 1985-12-10 | 1989-01-31 | Zinkan Enterprises, Inc. | Composition and method for dust control |
US5138055A (en) | 1986-05-16 | 1992-08-11 | American Cyanamid Company | Urethane-functional s-triazine crosslinking agents |
US4785884A (en) | 1986-05-23 | 1988-11-22 | Acme Resin Corporation | Consolidation of partially cured resin coated particulate material |
US4822425A (en) | 1987-03-19 | 1989-04-18 | Burch Richard M | Aggregate stabilization |
EP0308889B1 (en) | 1987-09-24 | 1992-01-22 | Murakashi Lime Industry Co., Ltd | A dust-control agent |
US4920192A (en) | 1989-01-31 | 1990-04-24 | Atlantic Richfield Company | Polyurethane quasi prepolymer for proppant consolidation |
US5048608A (en) | 1989-01-31 | 1991-09-17 | Atlantic Richfield Company | Consolidation of hydraulic fractures employing a polyurethane resin |
US5188175A (en) | 1989-08-14 | 1993-02-23 | Carbo Ceramics Inc. | Method of fracturing a subterranean formation with a lightweight propping agent |
US5092404A (en) | 1989-11-01 | 1992-03-03 | Marathon Oil Company | Polyvinyl sulfonate scale inhibitor |
US5264572A (en) | 1990-03-12 | 1993-11-23 | Asahi Denka Kogyo K.K. | Catalyst for isocyanate trimerization |
AU6949091A (en) | 1990-06-18 | 1991-12-19 | Betz International, Inc. | Methods for suppressing fugitive dust emissions |
US5073195A (en) | 1990-06-25 | 1991-12-17 | Dow Corning Corporation | Aqueous silane water repellent compositions |
GB9018832D0 (en) | 1990-08-29 | 1990-10-10 | British Petroleum Co Plc | Oil-based drilling muds |
CA2034851A1 (en) | 1991-01-24 | 1992-07-25 | Chak-Kai Yip | Amine functional silane modified epoxy resin composition and weatherstrip coatings made therefrom |
US5242248A (en) | 1991-02-22 | 1993-09-07 | Sts Products, Inc. | Method for treating soil in a performance arena |
US5181957A (en) | 1991-07-19 | 1993-01-26 | Nalco Chemical Company | Dust control and ore handling aid for bauxite ore |
US5199491A (en) | 1991-09-04 | 1993-04-06 | Atlantic Richfield Company | Method of using nitrile derivative for sand control |
US5256729A (en) | 1991-09-04 | 1993-10-26 | Atlantic Richfield Company | Nitrile derivative for sand control |
US5218038A (en) | 1991-11-14 | 1993-06-08 | Borden, Inc. | Phenolic resin coated proppants with reduced hydraulic fluid interaction |
TW206250B (en) | 1991-11-27 | 1993-05-21 | Union Carbide Chem Plastic | |
DE4203217A1 (en) | 1992-02-05 | 1993-08-12 | Bayer Ag | PROCESS FOR PREPARING COATINGS |
US5728302A (en) | 1992-04-09 | 1998-03-17 | Groundwater Services, Inc. | Methods for the removal of contaminants from subterranean fluids |
US5330836A (en) | 1992-09-03 | 1994-07-19 | Temple University-Of The Common Commonwealth System Of Higher Education | Functionalized silica particle and use thereof for cross-linking silicones |
US5420174A (en) | 1992-11-02 | 1995-05-30 | Halliburton Company | Method of producing coated proppants compatible with oxidizing gel breakers |
US5824462A (en) | 1993-05-17 | 1998-10-20 | Mitsubishi Paper Mills Limited | Resin-coated paper |
US5422183A (en) | 1993-06-01 | 1995-06-06 | Santrol, Inc. | Composite and reinforced coatings on proppants and particles |
US5849818A (en) | 1993-06-03 | 1998-12-15 | Walles; Wilhelm E. | Skin sulfonated particles in matrices |
DE69403398T2 (en) | 1993-07-13 | 1997-09-25 | Huntsman Spec Chem Corp | Modification of polypropylene by polyether amines |
US6031048A (en) | 1993-07-13 | 2000-02-29 | Huntsman Petrochemical Corporation | Polyether amine modification of polypropylene |
US5911876A (en) | 1994-06-20 | 1999-06-15 | Rose; Jane Anne | Insitu zeolite filter bed system for the removal of metal contaminants |
US5837656A (en) | 1994-07-21 | 1998-11-17 | Santrol, Inc. | Well treatment fluid compatible self-consolidating particles |
GB9503949D0 (en) | 1995-02-28 | 1995-04-19 | Atomic Energy Authority Uk | Oil well treatment |
US5582249A (en) | 1995-08-02 | 1996-12-10 | Halliburton Company | Control of particulate flowback in subterranean wells |
US6187892B1 (en) | 1995-06-07 | 2001-02-13 | Bayer Corporation | Method of making a coated substrate with polyurethane/urea contact adhesive formulations and the coated substrate by this method |
US5856271A (en) | 1995-06-07 | 1999-01-05 | Battelle Memorial Institute | Method of making controlled released devices |
DE19523115A1 (en) | 1995-06-26 | 1997-01-02 | Hoechst Ag | Dispersion powder with increased autoignition temperature |
US5733952A (en) | 1995-10-18 | 1998-03-31 | Borden Chemical, Inc. | Foundry binder of phenolic resole resin, polyisocyanate and epoxy resin |
US6528157B1 (en) | 1995-11-01 | 2003-03-04 | Borden Chemical, Inc. | Proppants with fiber reinforced resin coatings |
US20050028979A1 (en) | 1996-11-27 | 2005-02-10 | Brannon Harold Dean | Methods and compositions of a storable relatively lightweight proppant slurry for hydraulic fracturing and gravel packing applications |
US6772838B2 (en) | 1996-11-27 | 2004-08-10 | Bj Services Company | Lightweight particulate materials and uses therefor |
US6495624B1 (en) | 1997-02-03 | 2002-12-17 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
EP0918062B1 (en) | 1997-04-21 | 2004-02-18 | Asahi Glass Company Ltd. | Room temperature setting compositions |
US5924488A (en) | 1997-06-11 | 1999-07-20 | Halliburton Energy Services, Inc. | Methods of preventing well fracture proppant flow-back |
US6003600A (en) | 1997-10-16 | 1999-12-21 | Halliburton Energy Services, Inc. | Methods of completing wells in unconsolidated subterranean zones |
US5955609A (en) | 1997-12-31 | 1999-09-21 | Bayer Corporation | Trimer catalyst system for aliphatic and aromatic isocyanates |
EP0933498B1 (en) | 1998-02-03 | 2003-05-28 | Halliburton Energy Services, Inc. | Method of rapidly consolidating particulate materials in wells |
US6093496A (en) | 1998-05-12 | 2000-07-25 | Huntsman Petrochemical Corporation | Polyolefin containing polyetheramine modified functionalized polyolefin |
GB9904169D0 (en) | 1998-05-14 | 1999-04-14 | British Nuclear Fuels Plc | Waste minimisation |
US6093469A (en) | 1998-08-25 | 2000-07-25 | Callas; Michael T. | Mat and method of making mat |
CA2301141A1 (en) | 1998-06-15 | 1999-12-23 | The Lubrizol Corporation | Methods of using an aqueous composition containing a water-soluble or water-dispersible synthetic polymer and resultant compositions formed thereof |
US6114410A (en) | 1998-07-17 | 2000-09-05 | Technisand, Inc. | Proppant containing bondable particles and removable particles |
CN1274376B (en) | 1998-07-22 | 2011-08-10 | 翰森特种化学品公司 | Composite proppant, composite filtration media and methods for making and using same |
US6582819B2 (en) | 1998-07-22 | 2003-06-24 | Borden Chemical, Inc. | Low density composite proppant, filtration media, gravel packing media, and sports field media, and methods for making and using same |
US6406789B1 (en) | 1998-07-22 | 2002-06-18 | Borden Chemical, Inc. | Composite proppant, composite filtration media and methods for making and using same |
US6262216B1 (en) | 1998-10-13 | 2001-07-17 | Affymetrix, Inc. | Functionalized silicon compounds and methods for their synthesis and use |
US6316105B1 (en) | 1999-07-27 | 2001-11-13 | Alcatel | Radiation curable coating composition with hydrophobic properties for optical fibers and optical fibers coated thereby |
US6387501B1 (en) | 1999-08-02 | 2002-05-14 | Borden Chemical, Inc. | Phenolic coated refractory aggregates |
GB9925835D0 (en) | 1999-11-01 | 1999-12-29 | Enhanced Recovery Sys Ltd | Composition and process for oil extraction |
US6875728B2 (en) | 1999-12-29 | 2005-04-05 | Bj Services Company Canada | Method for fracturing subterranean formations |
US6413647B1 (en) | 2000-02-28 | 2002-07-02 | Jsr Corporation | Composition for film formation, method of film formation, and silica-based film |
ATE321105T1 (en) | 2000-04-13 | 2006-04-15 | Jsr Corp | COATING AGENT, METHOD OF PRODUCTION, HARDENED PRODUCT AND COATING FILM |
US6904972B2 (en) | 2000-05-03 | 2005-06-14 | Kewei Zhang | Fracturing with viscoelastic surfactant based fluid |
EP1199335B1 (en) | 2000-10-21 | 2010-12-22 | Evonik Degussa GmbH | Functionalized silicic acids |
US6439309B1 (en) | 2000-12-13 | 2002-08-27 | Bj Services Company | Compositions and methods for controlling particulate movement in wellbores and subterranean formations |
DE10063519A1 (en) | 2000-12-20 | 2002-07-04 | Nano X Gmbh | Low-solvent sol-gel systems |
US7012043B2 (en) | 2001-11-08 | 2006-03-14 | Huntsman Petrochemical Corporation | Drilling fluids |
US6767978B2 (en) | 2002-01-03 | 2004-07-27 | Atofina Chemicals, Inc. | Copolymers containing fluoro and silyl groups and their use in marine antifoulant composition |
US7216711B2 (en) | 2002-01-08 | 2007-05-15 | Halliburton Eenrgy Services, Inc. | Methods of coating resin and blending resin-coated proppant |
US7343973B2 (en) | 2002-01-08 | 2008-03-18 | Halliburton Energy Services, Inc. | Methods of stabilizing surfaces of subterranean formations |
US6668926B2 (en) | 2002-01-08 | 2003-12-30 | Halliburton Energy Services, Inc. | Methods of consolidating proppant in subterranean fractures |
US6691780B2 (en) | 2002-04-18 | 2004-02-17 | Halliburton Energy Services, Inc. | Tracking of particulate flowback in subterranean wells |
US6725930B2 (en) | 2002-04-19 | 2004-04-27 | Schlumberger Technology Corporation | Conductive proppant and method of hydraulic fracturing using the same |
US7153575B2 (en) | 2002-06-03 | 2006-12-26 | Borden Chemical, Inc. | Particulate material having multiple curable coatings and methods for making and using same |
US6732800B2 (en) | 2002-06-12 | 2004-05-11 | Schlumberger Technology Corporation | Method of completing a well in an unconsolidated formation |
US7183235B2 (en) | 2002-06-21 | 2007-02-27 | Ada Technologies, Inc. | High capacity regenerable sorbent for removing arsenic and other toxic ions from drinking water |
EP1380265A1 (en) | 2002-07-11 | 2004-01-14 | Olympus Optical Corporation Limited | Calculus treatment apparatus |
US20040023818A1 (en) | 2002-08-05 | 2004-02-05 | Nguyen Philip D. | Method and product for enhancing the clean-up of hydrocarbon-producing well |
US6906009B2 (en) | 2002-08-14 | 2005-06-14 | 3M Innovative Properties Company | Drilling fluid containing microspheres and use thereof |
US6705400B1 (en) | 2002-08-28 | 2004-03-16 | Halliburton Energy Services, Inc. | Methods and compositions for forming subterranean fractures containing resilient proppant packs |
US6913080B2 (en) | 2002-09-16 | 2005-07-05 | Halliburton Energy Services, Inc. | Re-use recovered treating fluid |
US6790245B2 (en) | 2002-10-07 | 2004-09-14 | Benetech, Inc. | Control of dust |
US7074257B2 (en) | 2002-10-15 | 2006-07-11 | Synlite Chemical Company, Llc | Method for removing heavy metals and radionuclides |
US20040102529A1 (en) | 2002-11-22 | 2004-05-27 | Campbell John Robert | Functionalized colloidal silica, dispersions and methods made thereby |
US6866099B2 (en) | 2003-02-12 | 2005-03-15 | Halliburton Energy Services, Inc. | Methods of completing wells in unconsolidated subterranean zones |
US7157021B2 (en) | 2003-02-19 | 2007-01-02 | Archer-Daniels-Midland Company | Methods and compositions for dust and erosion control |
US20040211561A1 (en) | 2003-03-06 | 2004-10-28 | Nguyen Philip D. | Methods and compositions for consolidating proppant in fractures |
JP2007524777A (en) | 2003-03-07 | 2007-08-30 | ポリタン システムズ,インコーポレイテッド | Method to consolidate sand or gravel into a solid mass |
BRPI0409410A (en) | 2003-04-15 | 2006-04-25 | Hexion Specialty Chemicals Inc | particulate material containing thermoplastic elastomer and methods for its manufacture and use |
US7772163B1 (en) | 2003-06-20 | 2010-08-10 | Bj Services Company Llc | Well treating composite containing organic lightweight material and weight modifying agent |
US7135231B1 (en) | 2003-07-01 | 2006-11-14 | Fairmont Minerals, Ltd. | Process for incremental coating of proppants for hydraulic fracturing and proppants produced therefrom |
US7344783B2 (en) | 2003-07-09 | 2008-03-18 | Shell Oil Company | Durable hydrophobic surface coatings using silicone resins |
US7050170B2 (en) | 2003-07-22 | 2006-05-23 | Picarro, Inc. | Apparatus and method for maintaining uniform and stable temperature for cavity enhanced optical spectroscopy |
US8541051B2 (en) | 2003-08-14 | 2013-09-24 | Halliburton Energy Services, Inc. | On-the fly coating of acid-releasing degradable material onto a particulate |
US20050059794A1 (en) | 2003-09-12 | 2005-03-17 | Glass Terry W. | Water-soluble polyhydroxyaminoether and process for preparing the same |
EP1559744A1 (en) | 2004-01-30 | 2005-08-03 | Rhodia Chimie | Use of a pretreated precipitated silica as a reinforcing filler for silicone elastomer and curable compositions thus obtained |
US20050173116A1 (en) | 2004-02-10 | 2005-08-11 | Nguyen Philip D. | Resin compositions and methods of using resin compositions to control proppant flow-back |
US7244492B2 (en) | 2004-03-04 | 2007-07-17 | Fairmount Minerals, Ltd. | Soluble fibers for use in resin coated proppant |
US7063151B2 (en) | 2004-03-05 | 2006-06-20 | Halliburton Energy Services, Inc. | Methods of preparing and using coated particulates |
US20080226704A1 (en) | 2004-03-23 | 2008-09-18 | Makoto Kigoshi | Method of Producing Coated Fine Particles |
WO2005103446A1 (en) | 2004-04-05 | 2005-11-03 | Carbo Ceramics, Inc. | Tagged propping agents and related methods |
KR100614976B1 (en) | 2004-04-12 | 2006-08-25 | 한국과학기술원 | Inorganic/Organic Hybrid Oligomer, Nano Hybrid Polymer for Optical Devices and Displays, and Manufacturing Method thereof |
MXPA06011762A (en) | 2004-04-12 | 2007-04-13 | Carbo Ceramics Inc | Coating and/or treating hydraulic fracturing proppants to improve wettability, proppant lubrication, and/or to reduce damage by fracturing fluids and reservoir fluids. |
US7723272B2 (en) | 2007-02-26 | 2010-05-25 | Baker Hughes Incorporated | Methods and compositions for fracturing subterranean formations |
US8567502B2 (en) | 2004-05-13 | 2013-10-29 | Baker Hughes Incorporated | Filtration of dangerous or undesirable contaminants |
US7541318B2 (en) | 2004-05-26 | 2009-06-02 | Halliburton Energy Services, Inc. | On-the-fly preparation of proppant and its use in subterranean operations |
CN100584917C (en) | 2004-06-03 | 2010-01-27 | 3M创新有限公司 | Compositions for dust suppression and methods |
US7213651B2 (en) | 2004-06-10 | 2007-05-08 | Bj Services Company | Methods and compositions for introducing conductive channels into a hydraulic fracturing treatment |
EP1615260A3 (en) | 2004-07-09 | 2009-09-16 | JSR Corporation | Organic silicon-oxide-based film, composition and method for forming the same, and semiconductor device |
WO2006023172A2 (en) | 2004-08-16 | 2006-03-02 | Fairmount Minerals, Ltd. | Control of particulate flowback in subterranean formations using elastomeric resin coated proppants |
US7281580B2 (en) | 2004-09-09 | 2007-10-16 | Halliburton Energy Services, Inc. | High porosity fractures and methods of creating high porosity fractures |
EP1791691A4 (en) | 2004-09-20 | 2010-06-23 | Hexion Specialty Chemicals Res | Particles for use as proppants or in gravel packs, methods for making and using the same |
US8227026B2 (en) | 2004-09-20 | 2012-07-24 | Momentive Specialty Chemicals Inc. | Particles for use as proppants or in gravel packs, methods for making and using the same |
US20060073980A1 (en) | 2004-09-30 | 2006-04-06 | Bj Services Company | Well treating composition containing relatively lightweight proppant and acid |
US7726399B2 (en) | 2004-09-30 | 2010-06-01 | Bj Services Company | Method of enhancing hydraulic fracturing using ultra lightweight proppants |
JP4103008B2 (en) | 2004-10-18 | 2008-06-18 | 東海ゴム工業株式会社 | Fluid filled vibration isolator |
US7281581B2 (en) | 2004-12-01 | 2007-10-16 | Halliburton Energy Services, Inc. | Methods of hydraulic fracturing and of propping fractures in subterranean formations |
MX2007007914A (en) | 2004-12-30 | 2007-08-14 | Sun Drilling Products Corp | Thermoset nanocomposite particles, processing for their production, and their use in oil and natural gas drilling applications. |
US8258083B2 (en) | 2004-12-30 | 2012-09-04 | Sun Drilling Products Corporation | Method for the fracture stimulation of a subterranean formation having a wellbore by using impact-modified thermoset polymer nanocomposite particles as proppants |
US8461087B2 (en) | 2004-12-30 | 2013-06-11 | Sun Drilling Products Corporation | Method for the fracture stimulation of a subterranean formation having a wellbore by using impact-modified thermoset polymer nanocomposite particles as proppants |
US7322411B2 (en) | 2005-01-12 | 2008-01-29 | Bj Services Company | Method of stimulating oil and gas wells using deformable proppants |
US7334635B2 (en) | 2005-01-14 | 2008-02-26 | Halliburton Energy Services, Inc. | Methods for fracturing subterranean wells |
WO2006083914A2 (en) | 2005-02-02 | 2006-08-10 | Total Separation Solutions, Llc | In situ filter construction |
US7491444B2 (en) | 2005-02-04 | 2009-02-17 | Oxane Materials, Inc. | Composition and method for making a proppant |
CA2599977C (en) | 2005-03-07 | 2011-01-25 | Baker Hughes Incorporated | Use of coated proppant to minimize abrasive erosion in high rate fracturing operations |
US8158691B2 (en) | 2005-04-04 | 2012-04-17 | Polymer Latex Gmbh & Co. Kg | Aqueous reinforced rubber dispersions and their use for making latex foams |
US7537702B2 (en) | 2005-04-12 | 2009-05-26 | Honeywell International Inc. | Water purification system and modes of operation |
US7528096B2 (en) | 2005-05-12 | 2009-05-05 | Bj Services Company | Structured composite compositions for treatment of subterranean wells |
US20060260808A1 (en) | 2005-05-20 | 2006-11-23 | Weaver Jim D | Methods of treating particulates and use in subterranean formations |
WO2006135892A2 (en) | 2005-06-13 | 2006-12-21 | Sun Drilling Products Corporation | Thermoset particles with enhanced crosslinking, processing for their production, and their use in oil and natural gas drilling applications |
US20060292345A1 (en) | 2005-06-14 | 2006-12-28 | Dave Bakul C | Micropatterned superhydrophobic silica based sol-gel surfaces |
US7258170B2 (en) | 2005-06-16 | 2007-08-21 | Halliburton Energy Services, Inc. | Methods for remediating subterranean formations |
US7318474B2 (en) | 2005-07-11 | 2008-01-15 | Halliburton Energy Services, Inc. | Methods and compositions for controlling formation fines and reducing proppant flow-back |
CA2747034A1 (en) | 2005-08-09 | 2007-02-15 | Momentive Specialty Chemicals Inc. | Methods and compositions for determination of fracture geometry in subterranean formations |
US20110272146A1 (en) | 2005-08-09 | 2011-11-10 | Green John W | Methods and compositions for determination of fracture geometry in subterranean formations |
US20070073590A1 (en) | 2005-08-22 | 2007-03-29 | Cosentino Louis C | Remote monitor for physiological parameters and durable medical supplies |
US20070066742A1 (en) | 2005-09-22 | 2007-03-22 | Vijay Mhetar | Reinforced styrenic resin composition, method, and article |
US20070079965A1 (en) | 2005-10-06 | 2007-04-12 | Halliburton Energy Services, Inc. | Methods for enhancing aqueous fluid recovery form subterranean formations |
US7767308B2 (en) | 2005-10-14 | 2010-08-03 | Chem Link, Inc. | Moisture-curable adhesive composition |
CA2573834A1 (en) | 2006-01-13 | 2007-07-13 | Diversifield Industries Ltd. | Polyurethane proppant particle and use thereof |
US7598209B2 (en) | 2006-01-26 | 2009-10-06 | Bj Services Company | Porous composites containing hydrocarbon-soluble well treatment agents and methods for using the same |
US20080221263A1 (en) | 2006-08-31 | 2008-09-11 | Subbareddy Kanagasabapathy | Coating compositions for producing transparent super-hydrophobic surfaces |
US8258206B2 (en) | 2006-01-30 | 2012-09-04 | Ashland Licensing And Intellectual Property, Llc | Hydrophobic coating compositions for drag reduction |
US7819192B2 (en) | 2006-02-10 | 2010-10-26 | Halliburton Energy Services, Inc. | Consolidating agent emulsions and associated methods |
US7510670B2 (en) | 2006-02-21 | 2009-03-31 | Momentive Performance Materials Inc. | Free flowing filler composition based on organofunctional silane |
US20070208156A1 (en) | 2006-03-01 | 2007-09-06 | Huntsman Petrochemical Corporation | Polyurea polymers with improved flexibility using secondary polyetheramines |
US8585753B2 (en) | 2006-03-04 | 2013-11-19 | John James Scanlon | Fibrillated biodegradable prosthesis |
US7494711B2 (en) | 2006-03-08 | 2009-02-24 | Bj Services Company | Coated plastic beads and methods of using same to treat a wellbore or subterranean formation |
US7407010B2 (en) | 2006-03-16 | 2008-08-05 | Halliburton Energy Services, Inc. | Methods of coating particulates |
US8133587B2 (en) | 2006-07-12 | 2012-03-13 | Georgia-Pacific Chemicals Llc | Proppant materials comprising a coating of thermoplastic material, and methods of making and using |
US7896080B1 (en) | 2006-09-08 | 2011-03-01 | Larry Watters | Method of improving hydrocarbon production from a gravel packed oil and gas well |
KR100818462B1 (en) | 2006-09-09 | 2008-04-01 | 재단법인서울대학교산학협력재단 | The Functionalized Silica Nanoparticle having PEG Linkage and Production Method Thereof |
DE102006058771B4 (en) | 2006-12-12 | 2018-03-01 | Schott Ag | Container with improved emptiness and method for its production |
RU2328341C1 (en) | 2007-01-09 | 2008-07-10 | Бадулин Николай Александрович | Sorbent for cleaning water off heavy metal ions |
WO2008104881A1 (en) | 2007-02-27 | 2008-09-04 | Az Electronic Materials Usa Corp. | Silicon-based antifrelective coating compositions |
US9096790B2 (en) | 2007-03-22 | 2015-08-04 | Hexion Inc. | Low temperature coated particles comprising a curable liquid and a reactive powder for use as proppants or in gravel packs, methods for making and using the same |
US7624802B2 (en) | 2007-03-22 | 2009-12-01 | Hexion Specialty Chemicals, Inc. | Low temperature coated particles for use as proppants or in gravel packs, methods for making and using the same |
RU2373253C2 (en) | 2007-03-26 | 2009-11-20 | Шлюмбергер Текнолоджи Б.В. | Granules of material used to reduce proppant carry-away from hydraulic rupture crack |
US8236738B2 (en) | 2007-04-26 | 2012-08-07 | Trican Well Service Ltd | Control of particulate entrainment by fluids |
US9458349B2 (en) | 2007-05-11 | 2016-10-04 | Georgia-Pacific Chemicals Llc | Phenol-formaldehyde novolac resin having low concentration of free phenol |
US7754659B2 (en) | 2007-05-15 | 2010-07-13 | Georgia-Pacific Chemicals Llc | Reducing flow-back in well treating materials |
US20090029097A1 (en) | 2007-06-11 | 2009-01-29 | Riddle Dennis L | Flooring products and methods |
US8728989B2 (en) | 2007-06-19 | 2014-05-20 | Clearwater International | Oil based concentrated slurries and methods for making and using same |
WO2009009370A1 (en) | 2007-07-06 | 2009-01-15 | Carbo Ceramics Inc. | Proppants for gel clean-up |
MX2010000999A (en) | 2007-07-27 | 2010-03-01 | Schlumberger Technology Bv | System, method and apparatus for acid fracturing with scale inhibitor protection. |
US8276664B2 (en) | 2007-08-13 | 2012-10-02 | Baker Hughes Incorporated | Well treatment operations using spherical cellulosic particulates |
DE102007060334A1 (en) | 2007-08-17 | 2009-02-19 | Evonik Degussa Gmbh | Silane-based and aqueous coating system, its preparation and use |
US9018144B2 (en) | 2007-10-01 | 2015-04-28 | Baker Hughes Incorporated | Polymer composition, swellable composition comprising the polymer composition, and articles including the swellable composition |
US8230923B2 (en) | 2007-10-31 | 2012-07-31 | Baker Hughes Incorporated | Controlling coal fines in coal bed operations |
US8397812B2 (en) | 2007-10-31 | 2013-03-19 | Baker Hughes Incorporated | Nano-sized particle-coated proppants for formation fines fixation in proppant packs |
GB0725015D0 (en) | 2007-12-21 | 2008-01-30 | Madison Filter 981 Ltd | Filter element frames |
US20090176667A1 (en) | 2008-01-03 | 2009-07-09 | Halliburton Energy Services, Inc. | Expandable particulates and methods of their use in subterranean formations |
CA2712270C (en) | 2008-01-18 | 2013-09-24 | M-I L.L.C. | Degradable non-aqueous gel systems |
US8006754B2 (en) | 2008-04-05 | 2011-08-30 | Sun Drilling Products Corporation | Proppants containing dispersed piezoelectric or magnetostrictive fillers or mixtures thereof, to enable proppant tracking and monitoring in a downhole environment |
EP2271726A1 (en) | 2008-04-17 | 2011-01-12 | Dow Global Technologies Inc. | Powder coated proppant and method of making the same |
US9029586B2 (en) | 2008-05-23 | 2015-05-12 | Barry C. Arkles | Silanes with embedded hydrophilicity, dispersible particles derived therefrom and related methods |
US8006755B2 (en) | 2008-08-15 | 2011-08-30 | Sun Drilling Products Corporation | Proppants coated by piezoelectric or magnetostrictive materials, or by mixtures or combinations thereof, to enable their tracking in a downhole environment |
EA023407B1 (en) | 2008-10-29 | 2016-06-30 | Басф Се | Proppant for hydraulic fracturing of a subterranean formation |
US8360149B2 (en) | 2008-12-16 | 2013-01-29 | Schlumberger Technology Corporation | Surface modification for cross-linking or breaking interactions with injected fluid |
US8709545B2 (en) | 2009-01-30 | 2014-04-29 | The Boeing Company | Hybrid coatings and associated methods of application |
TW201036810A (en) | 2009-02-18 | 2010-10-16 | Nippon Steel Corp | Surface-treated precoated metal sheet, process for producing same, and surface-treating solution |
US8261833B2 (en) | 2009-02-25 | 2012-09-11 | Halliburton Energy Services, Inc. | Methods and compositions for consolidating particulate matter in a subterranean formation |
US8240383B2 (en) | 2009-05-08 | 2012-08-14 | Momentive Specialty Chemicals Inc. | Methods for making and using UV/EB cured precured particles for use as proppants |
US8431220B2 (en) | 2009-06-05 | 2013-04-30 | Xerox Corporation | Hydrophobic coatings and their processes |
US8579028B2 (en) | 2009-06-09 | 2013-11-12 | Halliburton Energy Services, Inc. | Tackifying agent pre-coated particulates |
WO2011026232A1 (en) | 2009-09-03 | 2011-03-10 | Trican Well Service Ltd . | Well service compositions and methods |
US8513342B2 (en) | 2009-10-16 | 2013-08-20 | University of Pittsburgh—of the Commonwealth System of Higher Education | Durable superhydrophobic coatings |
WO2011050046A1 (en) | 2009-10-20 | 2011-04-28 | Soane Energy, Llc | Proppants for hydraulic fracturing technologies |
US8468968B2 (en) | 2009-10-22 | 2013-06-25 | Quest Inspar LLC | Method and apparatus for lining pipes with isocyanate and hydroxyl-amine resin based on castrol or soy oil |
US8796188B2 (en) | 2009-11-17 | 2014-08-05 | Baker Hughes Incorporated | Light-weight proppant from heat-treated pumice |
CA2694425C (en) | 2009-12-30 | 2013-12-31 | Amir A. Mirzaei | Viscosifying polymers and methods of use |
CN102753648B (en) | 2009-12-30 | 2017-11-14 | 普拉德研究及开发股份有限公司 | Hydraulic fracturing proppants containing inorfil |
WO2011093799A1 (en) | 2010-01-28 | 2011-08-04 | Agency For Science, Technology And Research | A nano-composite |
RU2437913C1 (en) | 2010-06-03 | 2011-12-27 | Общество С Ограниченной Ответственностью "Форэс" | Procedure for preparation of light-weight magnesium-silicate propping agent and propping agent |
EP2596077A1 (en) | 2010-07-21 | 2013-05-29 | Basf Se | A proppant |
DE102010031585A1 (en) | 2010-07-21 | 2012-01-26 | Evonik Degussa Gmbh | Silica powder with special surface properties and toner composition containing this powder |
WO2012068228A1 (en) | 2010-11-16 | 2012-05-24 | Owens Jeffrey R | Additives for highly repellent polymeric surfaces |
DE102010051817A1 (en) | 2010-11-18 | 2012-05-24 | Ashland-Südchemie-Kernfest GmbH | Process for the preparation of coated proppants |
EP2469020A1 (en) | 2010-12-23 | 2012-06-27 | Claude Vercaemer | Process of hydraulic fracturing to create a layered proppant pack structure alongside the faces of the fracture to prevent formation fines to damage fracture conductivity |
CA2764306A1 (en) | 2011-01-14 | 2012-07-14 | Gasfrac Energy Services Inc. | Methods of treating a subterranean formation containing hydrocarbons |
US9353646B2 (en) | 2011-01-19 | 2016-05-31 | President And Fellows Of Harvard College | Slippery surfaces with high pressure stability, optical transparency, and self-healing characteristics |
US9725645B2 (en) | 2011-05-03 | 2017-08-08 | Preferred Technology, Llc | Proppant with composite coating |
US9040467B2 (en) | 2011-05-03 | 2015-05-26 | Preferred Technology, Llc | Coated and cured proppants |
US8763700B2 (en) | 2011-09-02 | 2014-07-01 | Robert Ray McDaniel | Dual function proppants |
US8993489B2 (en) | 2011-05-03 | 2015-03-31 | Preferred Technology, Llc | Coated and cured proppants |
US9290690B2 (en) | 2011-05-03 | 2016-03-22 | Preferred Technology, Llc | Coated and cured proppants |
US8664151B2 (en) * | 2011-06-01 | 2014-03-04 | The Procter & Gamble Company | Articles comprising reinforced polyurethane coating agent |
US9267019B2 (en) | 2011-06-15 | 2016-02-23 | Lion Copolymer Holdings, Llc | Functionalized silica for silica wet masterbatches and styrene butadiene rubber compositions |
US9757603B2 (en) | 2011-08-11 | 2017-09-12 | Cbi Polymers, Inc. | Polymer composition |
US8952265B2 (en) | 2011-08-22 | 2015-02-10 | Samsung Electro-Mechanics Co., Ltd. | Electromagnetic interference noise reduction package board |
AU2013249743B2 (en) | 2012-04-19 | 2016-12-22 | Self-Suspending Proppant Llc | Self-suspending proppants for hydraulic fracturing |
US9297244B2 (en) | 2011-08-31 | 2016-03-29 | Self-Suspending Proppant Llc | Self-suspending proppants for hydraulic fracturing comprising a coating of hydrogel-forming polymer |
CA2845840C (en) | 2011-08-31 | 2020-02-25 | Self-Suspending Proppant Llc | Self-suspending proppants for hydraulic fracturing |
BR112013021905A2 (en) | 2011-09-26 | 2016-11-01 | Multi Chem Group Llc | hydrate anti-caking inhibitor composition, and method for applying an anti-caking hydrate inhibiting composition to a hydrocarbon stream |
EP2855618B1 (en) | 2011-09-30 | 2021-01-13 | Hexion Research Belgium SA | Proppant materials and methods of tailoring proppant material surface wettability |
DE102011121254A1 (en) | 2011-12-15 | 2013-06-20 | Ashland-Südchemie-Kernfest GmbH | Process for the preparation of coated proppants |
US9169351B2 (en) | 2011-12-22 | 2015-10-27 | Johns Manville | Methods for making reinforced thermoplastic composites |
US9650518B2 (en) | 2012-01-06 | 2017-05-16 | Massachusetts Institute Of Technology | Liquid repellent surfaces |
US9150713B2 (en) | 2012-01-18 | 2015-10-06 | Rantec Corporation | Tackifier and modified starch formulation, system and method |
US9562187B2 (en) | 2012-01-23 | 2017-02-07 | Preferred Technology, Llc | Manufacture of polymer coated proppants |
US8741987B2 (en) | 2012-02-02 | 2014-06-03 | Lion Copolymer Holdings, Llc | Polymer silica-reinforced masterbatch with nanomaterial |
US20130312974A1 (en) | 2012-04-19 | 2013-11-28 | Guy Lamont McClung, IV | Controlling hydrogen sulfide production in oilfield operations |
US9630224B2 (en) | 2012-07-13 | 2017-04-25 | President And Fellows Of Harvard College | Slippery liquid-infused porous surfaces having improved stability |
US8936083B2 (en) | 2012-08-28 | 2015-01-20 | Halliburton Energy Services, Inc. | Methods of forming pillars and channels in propped fractures |
US20140060831A1 (en) | 2012-09-05 | 2014-03-06 | Schlumberger Technology Corporation | Well treatment methods and systems |
US20140116698A1 (en) | 2012-10-26 | 2014-05-01 | Halliburton Energy Services, Inc. | Wellbore Servicing Fluids Comprising Foamed Materials and Methods of Making and Using Same |
US20140144631A1 (en) | 2012-11-28 | 2014-05-29 | Halliburton Energy Services, Inc | Methods of Forming Functionalized Proppant Particulates for Use in Subterranean Formation Operations |
WO2014144464A2 (en) | 2013-03-15 | 2014-09-18 | Carbo Ceramics Inc. | Composition and method for hydraulic fracturing and evaluation and diagnostics of hydraulic fractures using infused porous ceramic proppant |
US10167366B2 (en) | 2013-03-15 | 2019-01-01 | Melior Innovations, Inc. | Polysilocarb materials, methods and uses |
US9518214B2 (en) | 2013-03-15 | 2016-12-13 | Preferred Technology, Llc | Proppant with polyurea-type coating |
US9487692B2 (en) | 2013-03-19 | 2016-11-08 | Halliburton Energy Services, Inc. | Methods for consolidation treatments in subterranean formations using silicon compounds derived from furfuryl alcohols |
CA2908866A1 (en) | 2013-04-10 | 2014-10-16 | Ecolab Usa Inc. | Choline-based crosslinker compositions for fracturing fluids |
US10100247B2 (en) | 2013-05-17 | 2018-10-16 | Preferred Technology, Llc | Proppant with enhanced interparticle bonding |
US10640702B2 (en) | 2013-08-01 | 2020-05-05 | Covestro Llc | Coated particles and methods for their manufacture and use |
EP3055456A4 (en) | 2013-10-10 | 2017-05-24 | The Regents of The University of Michigan | Silane based surfaces with extreme wettabilities |
US20150119301A1 (en) | 2013-10-31 | 2015-04-30 | Preferred Technology, Llc | Flash Coating Treatments For Proppant Solids |
BR112016011806A2 (en) | 2013-11-26 | 2017-08-08 | Basf Se | STRUCTURING FOR HYDRAULICALLY FRACTURING AN UNDERGROUND FORMATION, AND METHOD FOR FORMING A STRUCTURING |
US20150322335A1 (en) | 2014-05-11 | 2015-11-12 | Clarence Resins & Chemicals, Inc. | Silicone-phenolic compositions, coatings and proppants made thereof, methods of making and using said compositions, coatings and proppants, methods of fracturing |
WO2016070044A1 (en) | 2014-10-30 | 2016-05-06 | Preferred Technology, Llc | Proppants and methods of use thereof |
US20160177129A1 (en) | 2014-12-23 | 2016-06-23 | Thomas McCarthy | Compositions and methods for preparing liquid-repellent articles |
WO2016144361A1 (en) | 2015-03-12 | 2016-09-15 | Halliburton Energy Services, Inc. | Low-energy proppants for downhole operations |
CA2987433A1 (en) | 2015-04-27 | 2016-11-03 | The Regents Of The University Of Michigan | Durable icephobic surfaces |
-
2017
- 2017-11-28 US US15/823,699 patent/US10696896B2/en active Active
-
2020
- 2020-06-19 US US16/906,020 patent/US20210139767A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US20180148636A1 (en) | 2018-05-31 |
US10696896B2 (en) | 2020-06-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20220169916A1 (en) | Coated and cured proppants | |
US20190249078A1 (en) | Coated And Cured Proppants | |
US10544358B2 (en) | Coated and cured proppants | |
US20210139767A1 (en) | Durable coatings and uses thereof | |
US11760924B2 (en) | Proppant with enhanced interparticle bonding | |
US10208242B2 (en) | Proppant with polyurea-type coating | |
WO2014052459A1 (en) | Coated and cured proppants | |
RU2591571C2 (en) | Method of producing proppants with coating | |
US20130186624A1 (en) | Manufacture of polymer coated proppants | |
US10611954B2 (en) | Polyamide resins for coating of sand or ceramic proppants used in hydraulic fracturing | |
US10844280B2 (en) | Polyurethane based proppant coatings | |
KR20150127230A (en) | A proppant | |
BR112019019542B1 (en) | PROPANT AND PREPARATION PROCESS OF A PROPANT |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PREFERRED TECHNOLOGY, LLC, PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MONASTIRIOTIS, SPYRIDON;LI, YU-CHIN;SIGNING DATES FROM 20171218 TO 20180104;REEL/FRAME:052986/0892 |
|
AS | Assignment |
Owner name: ALTER DOMUS (US) LLC, AS ADMINISTRATIVE AGENT, ILLINOIS Free format text: SECURITY INTEREST;ASSIGNOR:PREFERRED TECHNOLOGY, LLC;REEL/FRAME:054752/0323 Effective date: 20201222 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |