WO2022015932A1 - Water-based resin with elasticity for applications in cementing and subterranean structures - Google Patents
Water-based resin with elasticity for applications in cementing and subterranean structures Download PDFInfo
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- WO2022015932A1 WO2022015932A1 PCT/US2021/041752 US2021041752W WO2022015932A1 WO 2022015932 A1 WO2022015932 A1 WO 2022015932A1 US 2021041752 W US2021041752 W US 2021041752W WO 2022015932 A1 WO2022015932 A1 WO 2022015932A1
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- 0 CC(C)(C)C(C(C(C)(C)*)C(O1)=O)C1=O Chemical compound CC(C)(C)C(C(C(C)(C)*)C(O1)=O)C1=O 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/63—Macromolecular compounds
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/4857—Other macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/488—Other macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C04B41/4892—Polyamides
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
Definitions
- cement sheath isolates the well entirely from formation fluids. These formation fluids originate from different layers underground traversed while drilling, such as water tables, gas zones, and rock formations, like halite, carbonate, quartz, and metamorphic rocks. Cement works to isolate these zones from each other, i.e., zonal isolation. Once a well reaches the production zone, the cement must maintain optimal integrity for the entire life of the well. But many scenarios can cause the cement to fracture and fail. Cement is strong, but it is also brittle, leading to microfractures and micro-annuli to propagate in the cement sheath.
- compositions to seal off undesirable fluid paths such as gas flow channels, behind casings and fractured cement sheaths are typically based on non- aqueous epoxy monomers mixed with amines, furan resins, and polyester resins.
- composition including a poly-alkene maleic anhydride copolymer, a polyethylene glycol (PEG), and a crosslinker selected from an ethyleneamine, a benzenetricarboxylic acid, a benzimidazole, and combinations thereof.
- the poly-alkene maleic anhydride copolymer includes repeat units of formulae I and II (referred to herein as “repeat unit I” and “repeat unit II”): where R 1 , R 1’ , R 2 , and R 2’ are each independently selected from –H and –(C 1 -C 5 )alkyl.
- R 1 , R 1’ , R 2 , and R 2’ are each independently selected from –H and –CH 3 .
- one of R 1 and R 1’ is H and the other is –CH 3 .
- one of R 2 and R 2’ is H and the other is –CH 3 .
- one of R 1 and R 1’ is H and the other is –CH 3 ; and one of R 2 and R 2’ is H and the other is –CH 3 .
- R 1 and R 1’ are each H and R 2 and R 2’ are each independently selected from –H and –CH 3 .
- R 1 and R 1’ are each H and R 2 and R 2’ are each –CH 3 .
- repeat unit I is selected from: and combinations thereof.
- repeat unit I has the structure: .
- repeat unit I has the structure:
- repeat unit I has the structure: .
- repeat units I and II alternate in the maleic anhydride copolymer.
- the composition comprises a polyethylene glycol.
- the polyethylene glycol has a molecular weight of about 5000 kDa to about 50,000 kDa.
- the polyethylene glycol has a molecular weight of about 20,000 kDa.
- the composition comprises about 20 wt% to about 40 wt% of the poly-alkene maleic anhydride copolymer and PEG. In some embodiments, the composition comprises about 30 wt% of the poly-alkene maleic anhydride copolymer and PEG. In some embodiments, the composition comprises about 20 wt% of the poly-alkene maleic anhydride copolymer and about 10 wt% PEG. In some embodiments, the poly-alkene maleic anhydride copolymer is a poly-butene maleic anhydride copolymer.
- the poly-alkene maleic anhydride copolymer is a poly-isobutylene maleic anhydride copolymer.
- the crosslinker comprises an ethyleneamine selected from ethylenediamine (EDA), diethylenetriamine (DETA), aminoethylpiperazine (AEP), triethylenetetraamine (linear-TETA), tris(2- aminoethyl)amine (branched-TETA), N,N’-bis-(2-aminoethyl)piperazine (bis-AEP), N- [(2-aminoethyl)2-aminoethyl]piperazine), piperazinoethylethylenediamine (PEEDA), tetraethylenepentamine (TEPA), and mixtures thereof.
- EDA ethylenediamine
- DETA diethylenetriamine
- AEP aminoethylpiperazine
- linear-TETA linear-TETA
- tris(2- aminoethyl)amine branched-TETA
- the ethyleneamine is TEPA.
- the crosslinker comprises a benzenetricarboxylic acid selected from 1,2,3-benzenetricarboxylic acid (hemimellitic acid), 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,3,5-benzenetricarboxylic acid (trimesic acid), and mixtures thereof.
- the benzenetricarboxylic acid is trimesic acid.
- the crosslinker comprises a benzimidazole that is a substituted phenylbenzimidazole.
- the phenylbenzimidazole is substituted with one or more of –OH, –OR, –NH 2 , –NHR, – NR2, –NHCOR, –SH, –SR, –SeR, –Cl, –Br, –I, –F, –CN, and –CO 2 R, and combinations thereof, wherein R is alkyl.
- the benzimidazole is 5-amino-2-(4- aminophenyl)benzimidazole (APBZ).
- the crosslinker comprises TEPA, trimesic acid, and APBZ.
- the composition comprises a pH adjuster.
- the pH adjuster is sodium hydroxide (NaOH).
- the pH of the composition is between about 12 to about 15.
- the composition comprises an aqueous carrier.
- the composition has a viscosity of about 2,000 mPa ⁇ s to about 10,000 mPa ⁇ s at 22 oC.
- the composition has a density greater than about 1.10 g/cm 3 and an elasticity of greater than about 2000 N/m.
- compositions comprising: about 20 wt% to about 30 wt% of a poly-alkene maleic anhydride copolymer comprising repeat units I and II; about 5 wt% to about 15 wt% of a polyethylene glycol (PEG); and a crosslinker selected from an ethyleneamine, a benzenetricarboxylic acid, a benzimidazole, and combinations thereof, where the pH of the composition is between about 12 to about 15.
- repeat units I and II are: where repeat unit I is selected from: and combinations thereof.
- t , t p , t mesic acid, and APBZ are also provided in the present disclosure.
- the composition has a density of greater than about 1.10 g/cm 3 and an elasticity of greater than about 2000 N/m.
- the present disclosure also provides a method of treating a subterranean formation or cement construction, comprising providing to the subterranean formation or cement construction a composition comprising a poly-alkene maleic anhydride copolymer, a polyethylene glycol, and a crosslinker selected from an ethyleneamine, a benzenetricarboxylic acid, a benzimidazole, and combinations thereof.
- the poly-alkene maleic anhydride copolymer includes repeat units I and II: where R 1 , R 1’ , R 2 , and R 2’ are each independently selected from –H and –(C 1 -C 5 )alkyl.
- the composition further includes a polyethylene glycol (PEG).
- PEG polyethylene glycol
- the method includes crosslinking the composition to form a sealant. In some embodiments of the method, forming the sealant prevents or retards undesired loss or flow of wellbore fluid into the formation or construction; or the flow of formation fluids into the formation or construction.
- FIG. 1 is a graph showing the results of changing the pH of the composition System C as a function of molar concentration of sodium hydroxide (NaOH).
- FIG. 2 is a graph showing the correlation between the density and the elasticity of each of the compositions, using Hook’s law.
- FIG.3 illustrates the displacement tests used to measure elasticity using Hook’s law for Systems A, C, and E.
- the applied force was 1.071 kg onto a sample with a 2- inch diameter.
- System A had an overall spring constant of 1200 N/m; System C, 3400 N/m; and System E, 5000 N/m.
- FIGS.4A-4E show the shear modulus of Systems A-E at different temperatures at 1000 psi.
- the graphs show an elastic slope and the final G* value that is used for comparison.
- FIGS. 5A-5B show the shear modulus G* of Systems A, C, and E graphed at 1000 psi for comparison at temperatures: low (220-275 °F) and high (300-320 °F).
- FIG. 6 is a representation of test parameters and shear moduli measurements over time of viscoelastic sealant resins by the M5600 Grace Rheometer, under confined conditions at 1000 psi. The temperature was set at 250 °F (121 °C, brown line). In this sample, the actual temperature reached 226 °F (108 °C, red line).
- TGA green line
- DSC blue line
- Thermogravimetric (TGA) and differential scanning calorimetry (DSC) were performed of a non-elastic resin when thoroughly dehydrated into a hard- set, non-elastic resin. Dehydration occurs under unconfined conditions, at ambient pressure, while at temperature.
- TGA Thermogravimetric
- DSC differential scanning calorimetry
- the present disclosure provides a resin composition for sealing microfractures and annuli that develop in broken cement sheaths, in order to prevent unwanted flow and return wells to a desired safe and profitable state.
- the compositions described in this disclosure are designed for deepest possible penetration into microfractures and annuli to provide the best seal against unwanted fluid flow.
- compositions of the present disclosure contain a resin comprised of a poly-alkene maleic anhydride copolymer with repeat units I and II , a polyethylene glycol (PEG), and a crosslinker that includes an ethyleneamine, a benzenetricarboxylic acid, a benzimidazole, and combinations thereof.
- the poly-alkene maleic anhydride copolymer is a poly-butene maleic anhydride copolymer.
- the poly-alkene maleic anhydride copolymer is a poly-isobutylene maleic anhydride copolymer.
- compositions of the present disclosure have increased heat resistance, increased elasticity (elasticity and shear modulus), and increased density as compared to other resin compositions that do not contain the composition comprising the poly-alkene maleic anhydride copolymer, PEG, and crosslinker of the present disclosure.
- Embodiments of the compositions, as well as the methods of making and using the compositions for treating a subterranean formation or cement construction, are described in this document. Reference will now be made in detail to certain embodiments of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.
- Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
- a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (for example, 1%, 2%, 3%, and 4%) and the sub-ranges (for example, 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.
- section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section.
- the acts can be carried out in any order, except when a temporal or operational sequence is explicitly recited.
- specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.
- substituted refers to an organic group as defined herein or molecule in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms.
- functional group or “substituent” as used herein refers to a group that can be or is substituted onto a molecule or onto an organic group.
- alkyl refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms.
- straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups.
- branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups.
- alkyl encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl.
- Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.
- cycloalkyl groups include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
- the cycloalkyl group can have 3 to about 8-12 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 4, 5, 6, or 7.
- Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl.
- Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined herein.
- Representative substituted cycloalkyl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2,6-disubstituted cyclohexyl groups or mono-, di- or tri- substituted norbornyl or cycloheptyl groups, which can be substituted with, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.
- number-average molecular weight refers to the ordinary arithmetic mean of the molecular weight of individual molecules in a sample. It is defined as the total weight of all molecules in a sample divided by the total number of molecules in the sample.
- M n the number-average molecular weight
- the number-average molecular weight can be measured by a variety of well-known methods including gel permeation chromatography, spectroscopic end group analysis, and osmometry.
- molecular weights of polymers given herein are number- average molecular weights.
- weight-average molecular weight refers to Mw, which is equal to ⁇ M i 2 n i / ⁇ M i n i , where n i is the number of molecules of molecular weight M i .
- the weight-average molecular weight can be determined using light scattering, small angle neutron scattering, X-ray scattering, and sedimentation velocity.
- copolymer refers to a polymer that includes at least two different repeating units. A copolymer can include any suitable number of repeating units.
- a stimulation fluid refers to fluids or slurries used downhole during stimulation activities of the well that can increase the production of a well, including perforation activities.
- a stimulation fluid can include a fracturing fluid or an acidizing fluid.
- the term “clean-up fluid” refers to fluids or slurries used downhole during clean-up activities of the well, such as any treatment to remove material obstructing the flow of desired material from the subterranean formation or cement construction.
- a clean-up fluid can be an acidification treatment to remove material formed by one or more perforation treatments.
- a clean-up fluid can be used to remove a filter cake.
- fracturing fluid refers to fluids or slurries used downhole during fracturing operations.
- spotting fluid refers to fluids or slurries used downhole during spotting operations, and can be any fluid designed for localized treatment of a downhole region.
- a spotting fluid can include a lost circulation material for treatment of a specific section of the wellbore, such as to seal off fractures in the wellbore and prevent sag.
- a spotting fluid can include a water control material.
- a spotting fluid can be designed to free a stuck piece of drilling or extraction equipment, can reduce torque and drag with drilling lubricants, prevent differential sticking, promote wellbore stability, and can help to control mud weight.
- the term “completion fluid” refers to fluids or slurries used downhole during the completion phase of a well, including cementing compositions.
- the term “remedial treatment fluid” refers to fluids or slurries used downhole for remedial treatment of a well. Remedial treatments can include treatments designed to increase or maintain the production rate of a well, such as stimulation or clean-up treatments.
- the term “abandonment fluid” refers to fluids or slurries used downhole during or preceding the abandonment phase of a well.
- the term “acidizing fluid” refers to fluids or slurries used downhole during acidizing treatments.
- an acidizing fluid is used in a clean-up operation to remove material obstructing the flow of desired material, such as material formed during a perforation operation.
- an acidizing fluid can be used for damage removal.
- cementing fluid refers to fluids or slurries used during cementing operations of a well.
- a cementing fluid can include an aqueous mixture including at least one of cement and cement kiln dust.
- a cementing fluid can include a curable resinous material such as a polymer that is in an at least partially uncured state.
- water control material refers to a solid or liquid material that interacts with aqueous material downhole, such that hydrophobic material can more easily travel to the surface and such that hydrophilic material (including water) can less easily travel to the surface.
- a water control material can be used to treat a well to cause the proportion of water produced to decrease and to cause the proportion of hydrocarbons produced to increase, such as by selectively binding together material between water-producing subterranean formations and the wellbore while still allowing hydrocarbon-producing formations to maintain output.
- packer fluid refers to fluids or slurries that can be placed in the annular region of a well between tubing and outer casing above a packer.
- the packer fluid can provide hydrostatic pressure in order to lower differential pressure across the sealing element, lower differential pressure on the wellbore and casing to prevent collapse, and protect metals and elastomers from corrosion.
- fluid refers to liquids and gels, unless otherwise indicated.
- subterranean material or “subterranean formation” refers to any material under the surface of the earth, including under the surface of the bottom of the ocean.
- a subterranean formation or material can be any section of a wellbore and any section of a subterranean petroleum- or water-producing formation or region in fluid contact with the wellbore.
- Placing a material in a subterranean formation can include contacting the material with any section of a wellbore or with any subterranean region in fluid contact therewith.
- Subterranean materials can include any materials placed into the wellbore such as cement, drill shafts, liners, tubing, casing, or screens; placing a material in a subterranean formation can include contacting with such subterranean materials.
- a subterranean formation or material can be any below-ground region that can produce liquid or gaseous petroleum materials, water, or any section below-ground in fluid contact therewith.
- a subterranean formation or material can be at least one of an area desired to be fractured, a fracture or an area surrounding a fracture, and a flow pathway or an area surrounding a flow pathway, wherein a fracture or a flow pathway can be optionally fluidly connected to a subterranean petroleum- or water-producing region, directly or through one or more fractures or flow pathways.
- a “subterranean structure” includes oil and gas wells, as well as other cement constructions, such as buildings, bunkers, storage, underground architectures, semi- subterranean structures, tunnels, caves, mines, to avoid and mitigate leaks, loss of structural integrity, and fluid migrations.
- treatment of a subterranean formation or structure can include any activity directed to extraction of water or petroleum materials from a subterranean petroleum- or water-producing formation or region, for example, including drilling, stimulation, hydraulic fracturing, clean-up, acidizing, completion, cementing, remedial treatment, and abandonment.
- a “flow pathway” downhole can include any suitable subterranean flow pathway through which two subterranean locations are in fluid connection. The flow pathway can be sufficient for petroleum or water to flow from one subterranean location to the wellbore or vice-versa.
- a flow pathway can include at least one of a hydraulic fracture, and a fluid connection across a screen, across gravel pack, across proppant, including across resin-bonded proppant or proppant deposited in a fracture, and across sand.
- a flow pathway can include a natural subterranean passageway through which fluids can flow.
- a flow pathway can be a water source and can include water.
- a flow pathway can be a petroleum source and can include petroleum.
- a flow pathway can be sufficient to divert from a wellbore, fracture, or flow pathway connected thereto at least one of water, a downhole fluid, or a produced hydrocarbon.
- a “carrier fluid” refers to any suitable fluid for suspending, dissolving, mixing, or emulsifying with one or more materials to form a composition.
- the carrier fluid can be at least one of crude oil, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl formamide, diethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, butylglycidyl ether, propylene carbonate, D-limonene, a C 2 -C 40 fatty acid C 1 -C 10 alkyl ester (for example, a fatty acid methyl ester), 2-butoxy ethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethyl sulfoxide, dimethyl formamide, a petroleum distillation product of fraction (for example, diesel, keros), a petroleum distill
- the fluid can form about 0.001 wt% to about 99.999 wt% of a composition, or a mixture including the same, or about 0.001 wt% or less, 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more.
- Compositions for treating a subterranean formation or cement construction Provided in this disclosure are compositions that can be used as a sealant resin.
- compositions are useful for the recovery of oil and gas wells that have been shut-in due to, for example, fractured cement sheaths in order to minimize losses in production.
- the compositions provided in this disclosure include a poly-alkene maleic anhydride copolymer, a polyethyleneglycol (PEG), and a crosslinker selected from an ethyleneamine, a benzenetricarboxylic acid, a benzimidazole, and combinations thereof.
- the poly-alkene maleic anhydride copolymer includes repeat units I and II: R 1 , R 1’ , R 2 , and R 2’ are each independently selected from –H and –(C 1 -C 5 )alkyl.
- the composition can also include reaction products of the poly-alkene maleic anhydride copolymer and the one or more crosslinkers.
- the composition includes reaction products of a poly-butene maleic anhydride copolymer.
- the composition includes reaction products of a poly-isobutylene maleic anhydride copolymer.
- R 1 , R 1’ , R 2 , and R 2’ are each independently selected from –H and –CH 3 .
- one of R 1 and R 1’ is H and the other is –CH 3 .
- one of R 2 and R 2’ is H and the other is –CH 3 .
- R 1 and R 1’ is H and the other is –CH 3 ; and one of R 2 and R 2’ is H and the other is –CH 3 .
- R 1 and R 1’ are each H and R 2 and R 2’ are each independently selected from –H, and –CH 3 .
- R 1 and R 1’ are each H and R 2 and R 2’ are each –CH 3 .
- repeat unit I is selected from: and combinations thereof.
- repeat unit I has the structure: .
- repeat unit I has the structure: .
- repeat unit I has the structure: .
- suitable poly-alkene maleic anhydride copolymers containing repeat units I and II include ISOBAM® polymers from Kuraray Company (Tokyo, Japan), ethylene-maleic anhydride copolymers and propylene-maleic anhydride copolymers from Honeywell Corporation (USA), and ZEMAC® copolymers from Vertellus (Spain).
- the poly-alkene maleic anhydride copolymer is a poly-butene maleic anhydride copolymer.
- the poly-alkene maleic anhydride copolymer is a poly-isobutylene maleic anhydride copolymer.
- the poly-isobutylene maleic anhydride copolymer containing repeat units I and II is Isobam® 104.
- the poly-alkene maleic anhydride copolymer is mixed with polyethylene glycol (PEG).
- PEG polyethylene glycol
- the PEG is used in the compositions of the present disclosure as one or more of a polymer, a structure directing agent, and a crosslinker.
- the average molecular weight of the PEG is about 200 kDa to about 4,000,000 kDa, for example, about 500 kDa to about 2,000,000 kDa, about 1000 kDa to about 200,000 kDa, about 5000 kDa to about 50,000 kDa, or about 10,000 kDa to about 30,000 kDa.
- the average molecular weight of the PEG is about 200 kDa, about 300 kDa, about 400 kDa, about 500 kDa, about 540 kDa, about 600 kDa, about 1000 kDa, about 1450 kDa, about 1500 kDa, about 1540 kDa, about 2000 kDa, about 3350 kDa, about 4000 kDa, about 4600 kDa, about 5000 kDa, about 6000 kDa, about 8000 kDa, about 20,000 kDa, about 30,000 kDa, about 50,000 kDa, about 100,000 kDa, about 250,000 kDa, about 500,000 kDa, about 1,000,000 kDa, about 2,000,000 kDa, and about 4,000,000 kDa.
- the average molecular weight of the PEG is about 20,000 kDa.
- Examples of commercially available PEG that can be used in the compositions of the present disclosure include, but are not limited to, those sold by Wako Pure Chemical Industries, Ltd., Sanyo Chemical Industries, Ltd. (under the trade names of MACROGOL®), and by Dow Chemical Company (under the trade names of CARBOWAX ®).
- the poly-alkene maleic anhydride copolymer has a weight-average molecular weight of about 10,000 Da to about 500,000 Da.
- the poly-alkene maleic anhydride copolymer can have a weight-average molecular weight of about 10,000-100,000 Da, about 20,000-90,000 Da, about 30,000-70,000 Da, about 40,000-60,000 Da, or a weight-average molecular weight of about 45,000-55,000 Da, or a weight-average molecular weight of about 10,000 Da, 20,000 Da, 30,000 Da, 40,000 Da, 50,000 Da, 60,000 Da, 70,000 Da, 80,000 Da, 90,000 Da or about 100,000 Da.
- the poly-alkene maleic anhydride copolymer has a weight- average molecular weight of about 100,000-500,000 Da, about 200,000-400,000 Da, about 250,000-350,000 Da or a weight-average molecular weight of about 100,000 Da, 150,000 Da, 200,000 Da, 250,000 Da, 300,000 Da, 350,000 Da, 400,000 Da, 450,000 Da or about 500,000 Da. In some embodiments, the poly-alkene maleic anhydride copolymer has a weight-average molecular weight of about 50,000 Da. In some embodiments, the poly-alkene maleic anhydride copolymer has a weight-average molecular weight of about 300,000 Da.
- the poly-alkene maleic anhydride copolymer is a poly-butene maleic anhydride copolymer. In some embodiments, the poly-alkene maleic anhydride copolymer is a poly-isobutylene maleic anhydride copolymer. In some embodiments, the poly-alkene maleic anhydride copolymer has a number-average molecular weight of about 10,000 Da to about 500,000 Da.
- the poly-alkene maleic anhydride copolymer can have a number-average molecular weight of about 10,000-100,000 Da, about 20,000-90,000 Da, about 30,000- 70,000 Da, about 40,000-60,000 Da, or a number-average molecular weight of about 45,000-55,000 Da or a number-average molecular weight of about 10,000 Da, 20,000 Da, 30,000 Da, 40,000 Da, 50,000 Da, 60,000 Da, 70,000 Da, 80,000 Da, 90,000 Da or about 100,000 Da.
- the poly-alkene maleic anhydride copolymer has a number-average molecular weight of about 100,000-500,000 Da, about 200,000- 400,000 Da, about 250,000-350,000 Da or a number-average molecular weight of about 100,000 Da, 150,000 Da, 200,000 Da, 250,000 Da, 300,000 Da, 350,000 Da, 400,000 Da, 450,000 Da or about 500,000 Da. In some embodiments, the poly-alkene maleic anhydride copolymer has a number-average molecular weight of about 50,000 Da. In some embodiments, the poly-alkene maleic anhydride copolymer has a number-average molecular weight of about 300,000 Da.
- the poly-alkene maleic anhydride copolymer is a poly-butene maleic anhydride copolymer. In some embodiments, the poly-alkene maleic anhydride copolymer is a poly-isobutylene maleic anhydride copolymer.
- PEG primarily serves as a supportive scaffold, or a structure directing polymer, without degradation when tested up to 400 degrees Fahrenheit. The overall resin system is optimized and characterized by its strength, heat resistivity, and stability (with no syneresis at room temperature). PEG also can serve to crosslink any free carboxyl or amine group in the polymer matrix.
- the crosslinker is selected from an ethyleneamine, a benzenetricarboxylic acid, a benzimidazole, and combinations thereof. In some embodiments, the crosslinker contains an ethyleneamine.
- the ethyleneamine is selected from ethylenediamine (EDA), diethylenetriamine (DETA), aminoethylpiperazine (AEP), triethylenetetraamine (linear-TETA), tris(2-aminoethyl)amine (branched-TETA), N,N’-bis-(2- aminoethyl)piperazine (bis-AEP), N-[(2-aminoethyl)2-aminoethyl]piperazine), piperazinoethylethylenediamine (PEEDA), tetraethylenepentamine (TEPA), and mixtures thereof.
- the ethyleneamine is TEPA.
- the crosslinker contains a benzenetricarboxylic acid.
- the benzenetricarboxylic acid is selected from 1,2,3- benzenetricarboxylic acid (hemimellitic acid), 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,3,5-benzenetricarboxylic acid (trimesic acid), and mixtures thereof.
- the benzenetricarboxylic acid is trimesic acid.
- the crosslinker contains a benzimidazole. Benzimidazoles can be used to facilitate anionic polymerization and serve as a co-curing agent, along with a trifunctional monomer.
- the benzimidazole is a substituted benzimidazole.
- the benzimidazole is a phenylbenzimidazole having the following structure:
- the phenylbenzimidazole is a substituted phenylbenzimidazole, wherein one or more substituents are present at any of the open positions.
- the phenylbenzimidazole is substituted with one or more of –OH, –OR, –NH 2 , –NHR, –NR 2 , –NHCOR, –SH, –SR, –SeR, –Cl, –Br, –I, –F, –CN, and –CO 2 R, and combinations thereof, wherein R represents an alkyl group.
- the phenylbenzimidazole is substituted with one or more –NH 2 groups.
- the phenylbenzimidazole is substituted with two –NH 2 groups.
- the benzimidazole has at least two, such as two, three, or four nucleophilic groups, for example, -NH 2 groups, and allows for the nucleophilic attack on electrophiles to form many crosslinking bonds between the individual components of the compositions of the present disclosure.
- the electrophile is a benzenetricarboxylic acid.
- the benzenetricarboxylic acid is trimesic acid.
- the benzimidazole is 5-amino-2-(4- aminophenyl)benzimidazole (APBZ).
- Suitable benzimidazoles include, but are not limited to, 6-bromo-4- azabenzimidazole, 4-azabenzimidazole, 5-azabenzimidazole, 2-bromo-1H- benzimidazole, 6-bromo-1H-benzimidazole, 5-bromo-1,3-dihydrobenzoimidazol-2- one, 2-chlorobenzimidazole, 5-chlorobenzimidazole, 5,6-dichloro-1H-benzimidazole hydrochloride, 5-fluoro-1H-benzimidazole, 2-mercapto-5-benzimidazolesulfonic acid sodium salt dihydrate, 2-mercapto-5-nitrobenzimidazole, 5-nitro-2-benzimidazolinone, benzimidazole, 1H-benzoimidazol-4-ol, 2-hydroxybenzimidazole, 1H-benzimidazole- 2-sulfonic acid, 2-mercaptobenzimidazole, 1-aminobenzimi
- the benzimidazole is 5-amino-2-(4-aminophenyl)benzimidazole (APBZ).
- the crosslinker contains an ethyleneamine, a benzenetricarboxylic acid, and a benzimidazole.
- the crosslinker contains TEPA, trimesic acid, and APBZ.
- a polyaramide system (a polymer containing aromatic amides), such as formed by crosslinking the poly-alkene maleic anhydride copolymer, PEG, and crosslinker containing an ethyleneamine, a benzenetricarboxylic acid, a benzimidazole, and combinations thereof, allows for increased ductility and enhanced performance of a sealant resin that is thermally stable up to at least 400 oF. This is made possible by the high polymer density, crosslinking, and elasticity of the resin.
- the compositions of the present disclosure also remain water-thin to allow for high-volume application to seal the smallest of fractures in cement.
- the crosslinker for example, a crosslinker containing an amine (-NHR), reacts first with the maleic anhydride moiety of the copolymer, followed by reaction of any free maleic anhydride with the –OH of the PEG.
- PEG acts as a scaffold and then as a crosslinker, if permitted.
- the maleic anhydride converts to maleimide, and any free amine reacts with the PEG. This can further increase the overall crosslinking of the resin, which can increase the strength of the resin. This is especially true as the resin sets at higher temperatures and drives the production of maleimide.
- the compositions of the present disclosure contain about 15 wt% to about 50 wt% of the poly-alkene maleic anhydride copolymer, where the copolymer comprises repeat units I and II, and a PEG.
- the compositions can include about 15 wt% to about 45 wt%, about 15 wt% to about 40 wt%, about 15 wt% to about 35 wt%, about 15 wt% to about 30 wt%, about 15 wt% to about 25 wt%, about 15 wt% to about 20 wt%, about 20 wt% to about 50 wt%, about 20 wt% to about 45 wt%, about 20 wt% to about 40 wt%, about 20 wt% to about 35 wt%, about 20 wt% to about 30 wt%, about 20 wt% to about 25 wt%, about 25 wt% to about 50 wt%, about 25 wt%, about
- the composition contains about 20 wt% to about 40 wt% of the poly-alkene maleic anhydride copolymer and PEG. In some embodiments, the composition contains about 30 wt% of the poly-alkene maleic anhydride copolymer and PEG. In some embodiments, the poly-alkene maleic anhydride copolymer is a poly-butene maleic anhydride copolymer. In some embodiments, the poly-alkene maleic anhydride copolymer is a poly-isobutylene maleic anhydride copolymer.
- the compositions of the present disclosure contain about 15 wt% to about 50 wt% of the poly-alkene maleic anhydride copolymer, where the copolymer contains about 10 wt% to about 45 wt% of repeat units I and II and about 5 wt% to about 15 wt% of a PEG, for example, about 10 wt% to about 40 wt%, about 10 wt% to about 35 wt%, about 10 wt% to about 30 wt%, about 10 wt% to about 25 wt%, about 10 wt% to about 20 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 45 wt%, about 15 wt% to about 40 wt%, about 15 wt% to about 35 wt%, about 15 wt% to about 30 wt%, about 15 wt% to about 25 wt%, about 15 wt% to about 20
- the compositions contain about 20 wt% to about 30 wt% of a poly-alkene maleic anhydride copolymer and about 5 wt% to about 15 wt% of a PEG. In some embodiments, the compositions contain about 20 wt% of the poly-alkene maleic anhydride copolymer, with repeat units I and II, and about 10 wt% of a PEG. In some embodiments, the poly-alkene maleic anhydride copolymer is a poly-butene maleic anhydride copolymer. In some embodiments, the poly-alkene maleic anhydride copolymer is a poly-isobutylene maleic anhydride copolymer.
- the composition includes an aqueous carrier.
- the aqueous carrier can include water, brine, produced water, flowback water, brackish water, Arab- D-brine, sea water, or combinations thereof.
- the aqueous carrier is about 1% to about 99% by weight of the composition. In some embodiments, the aqueous carrier is about 5% to about 99% by weight of the composition.
- the aqueous carrier can be about 10%-98%, about 20%-98%, about 30%-98%, about 40%-98%, about 50%-98%, about 60%-98%, about 70%-98%, about 80%-98%, or about 85%-98% by weight of the composition or about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 85%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, or about 98% by weight of the composition.
- the aqueous carrier is about 60-68% by weight of the composition. In some embodiments, the aqueous carrier is about 63% by weight of the composition.
- compositions of the present disclosure can contain an aqueous carrier. This results in an environmentally-friendly system. Because water begins to boil at its boiling point (i.e., 212 oF), water-based systems typically have a temperature limit. The compositions of the present disclosure, however, can be used at temperatures above the boiling point of the solvent (water) due to the robustness of the compositions.
- the resin of the compositions of the present disclosure sets uniformly and with mechanical strength. In some embodiments, the compositions are used in applications at temperatures of about 200 oF to about 400 oF, such as about 200 oF, about 250 oF, about 300 oF, about 350 oF, or about 400 oF.
- the compositions of the present disclosure have a basic pH.
- the compositions can have a pH of about or greater than 12, for example, about 12 to about 15.
- the pH of the composition is about 12 to about 15, about 12 to about 14, about 12 to about 13, about 13 to about 15, about 13 to about 14, about 14 to about 15, or about 12, about 13, about 14, or about 15.
- the composition has a pH of about 12 to about 15.
- the composition has a pH of about 14.
- compositions of the present disclosure maintained a water-thin rheology, which is important in order to allow the compositions to reach the ends of the fractures and form a seal after setting.
- the compositions of the present disclosure have a viscosity of about 2000 mPa ⁇ s to about 10,000 mPa ⁇ s at 22 oC, for example, about 2000 mPa ⁇ s to about 9000 mPa ⁇ s, about 2000 mPa ⁇ s to about 8000 mPa ⁇ s, about 2000 mPa ⁇ s to about 7000 mPa ⁇ s, about 2000 mPa ⁇ s to about 6000 mPa ⁇ s, about 2000 mPa ⁇ s to about 5000 mPa ⁇ s, about 2000 mPa ⁇ s to about 4000 mPa ⁇ s, about 2000 mPa ⁇ s to about 3500 mPa ⁇ s, about 2000 mPa ⁇ s to about 3000 mPa ⁇ s, about 3000 mPa ⁇ s to about 10,000 mP
- the viscosity of the compositions is about 3000 to about 5000 mPa ⁇ s at 22 oC. In some embodiments, the viscosity of the compositions is about 5000 mPa ⁇ s at 22 oC. In some embodiments, the density of the cured composition is greater than about 1.10 g/cm 3 , such as between about 1.11 g/cm 3 and about 1.50 g/cm 3 .
- the density of the cured composition is about 1.11 g/cm 3 , 1.12 g/cm 3 , 1.13 g/cm 3 , 1.14 g/cm 3 , 1.15 g/cm 3 , 1.16 g/cm 3 , 1.17 g/cm 3 , 1.18 g/cm 3 , 1.19 g/cm 3 , 1.2 g/cm 3 , 1.25 g/cm 3 , 1.3 g/cm 3 , 1.35 g/cm 3 , 1.4 g/cm 3 , 1.45 g/cm 3 , or 1.5 g/cm 3 .
- the density of the cured composition is about 1.15 g/cm 3 .
- the composition of the present disclosure has an elasticity of greater than about 2000 N/m, such as between about 2000 N/m and about 10,000 N/m.
- the elasticity of the cured composition is about 2000 N/m, about 2500 N/m, about 2800 N/m, about 3000 N/m, about 3400 N/m, about 4000 N/m, about 4500 N/m, about 5000 N/m, about 5500 N/m, about 6000 N/m, about 6100 N/m, about 6500 N/m, about 7000 N/m, about 8000 N/m, about 9000 N/m, or about 10,000 N/m.
- the elasticity of the cured composition is about 3400 N/m.
- the composition of the present disclosure has a density greater than about 1.10 g/cm 3 and an elasticity greater than about 2000 N/m.
- the composition has a density between about 1.11 g/cm 3 and about 1.50 g/cm 3 and an elasticity between about 2000 N/m and about 10,000 N/m.
- the composition has a density of about 1.15 g/cm 3 and an elasticity of about 3400 N/m.
- compositions containing about 20 wt% to about 30 wt% of a poly-alkene maleic anhydride copolymer comprising: repeat units I and II: where repeat unit I is selected from: and combinations thereof; a polyethylene glycol (PEG); and a crosslinker selected from an ethyleneamine, a benzenetricarboxylic acid, a benzimidazole, and combinations thereof, where the pH of the composition is between about 12 to about 15.
- the poly-alkene maleic anhydride copolymer is a poly-butene maleic anhydride copolymer.
- the poly-alkene maleic anhydride copolymer is a poly-isobutylene maleic anhydride copolymer.
- the crosslinker contains TEPA, trimesic acid, and APBZ.
- the composition has a density of greater than about 1.10 g/cm 3 and an elasticity of greater than about 2000 N/m. Additional components
- the compositions including the poly-alkene maleic anhydride copolymer, PEG, and crosslinker can further include one or more suitable additional components.
- the compositions of the present disclosure contain a pH adjuster.
- pH adjusters examples include, but are not limited to, an organic amine, hydrochloric acid, ammonium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen carbonate, and aqueous ammonia.
- the pH adjuster is sodium hydroxide (NaOH).
- the compositions of the present disclosure contain a gel time control agent. The gel time control agent can accelerate or retard the crosslinking of the poly-alkene maleic anhydride copolymer and the crosslinker and thus can accelerate or retard the gelling of the composition.
- Suitable gel time control agents include, but are not limited to, salts that yield a basic solution when dissolved in water, salts that yield an acidic solution when dissolved in water, uncharged organic molecules that yield a basic solution when dissolved in water, uncharged organic molecules that yield an acidic solution when dissolved in water (for example, citric acid), and pH buffers.
- Salts and uncharged organic molecules that yield a basic solution when dissolved in water can retard the gel time (decelerate gelling) of the composition.
- Salts and uncharged organic molecules that yield an acidic solution when dissolved in water can shorten the gel time (accelerate gelling) of the composition.
- Buffers prepared from Bronsted acids and Bronsted bases, such as citric acid and sodium hydroxide, or Bronsted acids and Lewis bases, such as citric acid and monoethanolamine, and buffers produced from Lewis acids and Lewis bases, such as boric acid and monoethanolamine, can retard or accelerate the gel time of the composition.
- compositions can be formulated with a buffer to achieve a gel time suitable for specific downhole requirements.
- suitable Bronsted acids include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, and organic acids such as tartaric acid and benzene sulfonic acid, and methane sulfonic acid.
- Bronsted bases include sodium carbonate, sodium bicarbonate, potassium hydroxide, and ammonium hydroxide.
- Lewis bases include diethanolamine, triethanolamine, triisopropanolamine, and dimethylaminoethanol.
- the gel time control agent accelerates the crosslinking reaction and therefore accelerates formation of the gel from the maleic anhydride and the crosslinker.
- the acceleration occurs in the absence of set cement. In other aspects of these embodiments, the acceleration occurs in the presence of set cement.
- the gel time control agent retards the crosslinking reaction, and therefore retards formation of the gel from the maleic anhydride and the crosslinker. In some aspects of these embodiments, the retardation of the crosslinking reaction occurs in the absence of set cement. In other aspects of these embodiments, the retardation of the crosslinking reaction occurs in the presence of set cement.
- the compositions contain citric acid. In some embodiments, the compositions contain trisodium phosphate (TSP). In some embodiments, the compositions contain citric acid and TSP.
- the total amount of gel time control agent is about 0.01 wt% to about 0.5 wt%.
- the composition including the poly-alkene maleic anhydride copolymer, PEG, and crosslinker can be combined with any suitable downhole fluid before, during, or after the placement of the composition in a subterranean formation or cement construction or the contacting of the composition and a subterranean material or cement construction.
- the composition including the poly-alkene maleic anhydride copolymer, PEG, and crosslinker can be combined with a downhole fluid above the surface, and then the combined composition is placed in a subterranean formation or cement construction or contacted with a subterranean material.
- the composition including the poly-alkene maleic anhydride copolymer, PEG and crosslinker can be injected into a subterranean formation or cement construction to combine with a downhole fluid, and the combined composition is contacted with a subterranean material or is considered to be placed in the subterranean formation or cement construction.
- the composition is used in the subterranean formation or cement construction alone or in combination with other materials, as a drilling fluid, stimulation fluid, fracturing fluid, spotting fluid, clean-up fluid, completion fluid, remedial treatment fluid, abandonment fluid, pill, acidizing fluid, cementing fluid, packer fluid, or a combination thereof.
- a drilling fluid also known as a drilling mud or simply “mud,” is a specially designed fluid that is circulated through a wellbore as the wellbore is being drilled to facilitate the drilling operation.
- the drilling fluid can be water-based or oil-based.
- the drilling fluid can carry cuttings up from beneath and around the bit, transport them up the annulus, and allow their separation. Also, a drilling fluid can cool and lubricate the drill head as well as reduce friction between the drill string and the sides of the hole. The drilling fluid aids in support of the drill pipe and drill head, and provides a hydrostatic head to maintain the integrity of the wellbore walls and prevent well blowouts.
- Specific drilling fluid systems can be selected to optimize a drilling operation in accordance with the characteristics of a particular geological formation.
- the drilling fluid can be formulated to prevent unwanted influxes of formation fluids from permeable rocks and also to form a thin, low permeability filter cake that temporarily seals pores, other openings, and formations penetrated by the bit.
- a pill is a relatively small quantity (for example, less than about 500 bbl, or less than about 200 bbl) of drilling fluid used to accomplish a specific task that the regular drilling fluid cannot perform.
- a pill can be a high-viscosity pill to, for example, help lift cuttings out of a vertical wellbore.
- a pill can be a freshwater pill to, for example, dissolve a salt formation.
- a pipe- freeing pill to, for example, destroy filter cake and relieve differential sticking forces.
- a pill is a lost circulation material pill to, for example, plug a thief zone.
- a pill can include any component described herein as a component of a drilling fluid.
- crosslinked reaction products of the poly-alkene maleic anhydride copolymer, PEG, and the crosslinker can form a sealant, such as a sealant gel.
- the sealant is a stiff gel, a ringing gel, or a lipping gel.
- Method of treating a subterranean formation or cement construction including providing to a subterranean formation or cement construction a composition and crosslinking the composition to form a sealant.
- the composition includes a poly-alkene maleic anhydride copolymer, a PEG, and a crosslinker selected from an ethyleneamine, a benzenetricarboxylic acid, a benzimidazole, and combinations thereof.
- the poly-alkene maleic anhydride copolymer includes repeat units I and II, as described in the present disclosure, where R 1 , R 1’ , R 2 , and R 2’ are each independently selected from –H and –(C1-C5)alkyl.
- the poly-alkene maleic anhydride copolymer is a poly-butene maleic anhydride copolymer.
- the poly-alkene maleic anhydride copolymer is a poly-isobutylene maleic anhydride copolymer.
- the providing occurs above-surface. The providing can also occur in the subterranean formation or cement construction.
- forming the sealant occurs near at least one of a casing, a casing-casing annulus, a tubing-casing annulus, or a casing-formation annulus. In some embodiments, forming the sealant occurs in a void (for example, cracks, microannuli) in at least one of a cement, cement sheath, and pipe. In some embodiments, forming the sealant prevents or retards undesired loss or flow of wellbore fluid into the formation or of formation fluids into the wellbore. In some embodiments, the sealant prevents or retards undesired loss or leak off of fluid into the formation.
- the composition including the poly-alkene maleic anhydride copolymer, PEG, and crosslinker is provided in a weighted or unweighted “pill” for introduction into the wellbore.
- Such “pills” typically include the composition blended with a required amount of water, base oil, water base drilling fluid, or non- aqueous base drilling fluid and in some cases a weighting agent such as barite, calcium carbonate, or a salt.
- the amount of the composition used in the pill will depend on the size of the subterranean fracture, opening, or lost circulation zone to be treated.
- drilling is stopped while the pill containing the composition is introduced into the wellbore.
- the composition can enter lost circulation zones or porous or fractured portions of the formation where it will prevent or retard the entry of drilling and other wellbore fluids. Further, pressure can be used to squeeze the pill into the lost circulation zone and de- fluidize a slurry.
- a method of servicing a wellbore includes providing a composition including a poly-alkene maleic anhydride copolymer and PEG as described in the present disclosure and a crosslinker within a portion of at least one of a wellbore, a cement construction, and a subterranean formation.
- the composition is introduced into at least one of a wellbore, a cement construction, and a subterranean formation using a pump.
- the poly- alkene maleic anhydride copolymer, PEG, and the crosslinker can be pumped together from at least one source or simultaneously from at least two different sources.
- the poly-alkene maleic anhydride copolymer and PEG can be pumped first and the crosslinker can be pumped second.
- the crosslinker can be pumped first and the poly-alkene maleic anhydride copolymer and PEG can be pumped second.
- compositions of the present disclosure can be used in a variety of applications, including, but not limited to, as secondary barriers above primary cement jobs, for high pressure squeeze jobs, for tight casing leaks, for remediation, as gravel packers, for permanent plug and abandonment, and in disposal wells.
- the compositions are used as a self-leveling resin.
- the compositions are used for bonding cement.
- the compositions are used as a resin with a filler, for example, as a mixture with silica flour as a filler.
- the composition can be used with cement, such as Portland cement, and hydraulic systems.
- the solid content is a ratio of about 1:1 silica to resin, or about 1:2 silica to resin, or about 1:3 silica to resin, or about 1:4 silica to resin, or about 1:5 silica to resin, or about 2:3 silica to resin.
- Example 1 A series of compositions (Systems A-E) that contained a polymer content ranging from 15% (System A – comparative sample) to more than 30% (System C) were prepared using the components shown in Table 1.
- Table 2 illustrates the specific components and amounts used in each of the compositions. Table 1.
- the viscosity of the hydro region was measured at 22 oC and is shown in Table 3.
- the pH of each of the compositions was kept between 12-15 in order to increase reagent solubility and for compatibility with cement surface chemistry.
- the high pH allowed for solubilization of the copolymer into solution and increased the polymer load of the compositions. Even though water was the main solvent, resins that had low viscosity and high ductility were obtained (see Table 3).
- the resins remained water- thin when the viscosity was within the range of 2,000-10,000 mPa•s.
- the polymer content was 15% (System A) to about 30% (Systems B-E); these compositions exhibited increased crosslinking as compared to System A. Table 3.
- G > G’ (hydro region) viscosity
- the high pH helped to maintain the low viscosity of the resin.
- the resins behaved differently.
- a soft elastic and gummy-like resin was sought that could stretch and yield to the strains downhole, and not thermally degrade or soften with temperature.
- the pH of System C was varied by adjusting the molar concentration of NaOH, as shown in Figure 1 and Table 4.
- An elastic-like resin, instead of a hard-set resin, is needed to withstand the cyclic stress-strain events downhole. As the pH increased to 14, the resin surprisingly became more ductile and soft.
- the highest pH value (pH 14.42) resulted in a gel that was not stiff, but rather a product that looked like putty.
- the PEG/PEI was not a crosslinker, but rather passive, increasing the body (or density) of the overall resin system.
- the most rigid resin was System D which contained PEI and had a density of 1.20 g/cm 3 .
- System C had PEG and had a density of 1.15 g/cm 3 .
- Table 5 G’ > G” (cured gel) density and elasticity
- the addition of crosslinking monomers in System B caused an increase in ductility by 57.1%.
- System C With the addition of copolymers to the base formulation, System C (with PEG) increased by 64.7% when compared to System A from Phase I; and System E (with both copolymers) increased its ductility by 76% (System E).
- the increase in aromaticity also increased the heat-resistance, ductility, and density of the resin product (Systems B-E).
- the products are stable gel systems up to about 400 °F.
- the crosslinkers were monomers used to increase the number of polyaramide bonds in the system.
- Monomer concentrations of APBZ and TMA were tailored to increase the degree of polymerization. These monomers were aromatic and multi- functionalized to react with polymers and copolymers, and increased bonding by forming more polyaramide bonds.
- the change in density from 1.10 to 1.20 showed how polymerization increased elasticity as well (also seen in Table 5).
- Temperature resistance To measure temperature stability of the compositions, the shear modulus at various temperatures was measured.
- the shear modulus is the response of the material to an outside force and is a measure in its degree of deformation of the resin matrix to frictional forces in the opposite direction.
- the shear modulus of the Systems A-E shown in Table 2 are graphed in Figures 4A-4E for comparison. Different mechanical properties were tested in order to predict resin reliability and resin failure. At temperatures up to 250 oF, the samples cured continuously without any degradation. At higher temperatures (up to 400 oF), the graphs for the storage modulus became noisier. From this, the temperature limits for each of these systems was determined. The two systems designed with and without the aromatic crosslinkers behaved differently at low and high temperatures. System A (without aromatic crosslinkers) was compared to Systems C and E (with aromatic crosslinkers).
- Example 2 Several resins were prepared (Formulas S1-S3) and cured under ambient pressure and at temperatures >200 °F, resulting in resins with densities up to 1.4 g/cm 3 .
- Table 7 shows compositions S1-S3 and applications for each of the systems.
- Hard-set resin (S1) A resin system was allowed to cure under unconfined conditions (S1). The resin was dehydrated and water removed for a hard-set plastic resin without fractures or cracks. The resin was hard-set and film-forming, and produced little to no gas by- product for a smooth finished surface. Film-forming, the resin filled the bottom of the container without curling around the edges or shrinking away from the walls of the container.
- the resin When cured at ambient pressure and at 250 °F, the resin formed a solid smooth and hard-set material that was opaque in color. At ambient pressure, the polymer dehydrated and cured into a hard material after shrinking 90% into a material with 1.39 g/cm 3 density.
- Table 8 shows data from a TGA (green line) and DSC (blue line) of resin thermal response. Thermogravimetric (TG) and differential scanning calorimetry (DSC) were performed with a TA Instrument Q600 series, and measurements were made at a heating rate of 10 °C min -1 in nitrogen. The resin was shown to perform under high temperatures relevant to oil well conditions.
- thermogravimetric curve of this hard-set resin synthesized in-lab showed the first weigh loss at 196 °C which can be attributed to polyaramide and polymaleimide. The most significant weight loss was near 349 °C (660 °F) which indicates the onset decomposition temperature of the resin.
- Formulation S2 in water Resin with filler (S3) Weighing agents such as silica flour and barite, even Portland cements and other cementitious materials, can be used to increase the density of the resin in order to achieve rheological hierarchy. Subsequent to downhole repairs in order to recover the well, the resin displaces the formation fluid and is placed to seal the fractures. To maintain density hierarchy, the resin is designed with a higher density to displace all previous fluids in the hole. Maintaining effective laminar flow rules are critical to properly recover wells using this sealant resin. In one example, 21% (w/w) barite (BaSO4) was added to the liquid resin for an increase in density by 14.77%, as required for a specific application.
- silica flour and barite even Portland cements and other cementitious materials
- silica flour was mixed into the resin to increase structural rigidity and density. Samples contained: 85% resin and 15% silica flour; 60% resin and 40% silica (% w/w); 50% resin and 50% silica flour (1:1). The preferred solid content was a 1:2 ratio of silica to resin (more resin). Because the cement was water-based and highly alkaline, the resin was compatible with Portland cement and hydraulic systems. An exemplary formulation is shown on Table 10. Table 10. Water-based formulation to make a resin system with silica flour as a filler.
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
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| Application Number | Priority Date | Filing Date | Title |
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| SA523442161A SA523442161B1 (en) | 2020-07-15 | 2023-01-13 | Water based resin with flexibility for applications in cement and underground structures. |
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| US16/930,027 US11795367B2 (en) | 2020-07-15 | 2020-07-15 | Water-based resin with elasticity for applications in cementing and subterranean structures |
| US16/930,027 | 2020-07-15 |
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| US11708522B1 (en) | 2022-03-08 | 2023-07-25 | Saudi Arabian Oil Company | Water-based hydrogel polymer composition and methods of treating subterranean formations or cement constructions comprising contaminants |
| CN116925717B (en) * | 2022-04-04 | 2025-04-22 | 四川大学 | Selective epoxy resin water shutoff agent for natural gas field and preparation method thereof |
| CN115010486A (en) * | 2022-07-14 | 2022-09-06 | 中钢集团洛阳耐火材料研究院有限公司 | Near-net-shape preparation method of high-purity zirconia refractory ceramic |
| CN117659975B (en) * | 2022-08-30 | 2026-01-30 | 中国石油化工股份有限公司 | Gas well water shut-off composition, gas well gel water shut-off agent |
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| US20170073569A1 (en) * | 2015-09-14 | 2017-03-16 | Saudi Arabian Oil Company | Maleic Anhydride Polymers and Methods of Treating Subterranean Formations |
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| EP3350282B1 (en) | 2015-09-14 | 2020-11-04 | Saudi Arabian Oil Company | Pendant epoxide polymers and methods of treating subterranean formations |
| EP3535345A1 (en) | 2016-11-04 | 2019-09-11 | Saudi Arabian Oil Company | Compositions and methods for sealing off flow channels in contact with set cement |
| US9932512B1 (en) | 2017-08-22 | 2018-04-03 | Saudi Arabian Oil Company | Compositions with polyaziridine crosslinkers for treating subterranean formations |
-
2020
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| US20170073569A1 (en) * | 2015-09-14 | 2017-03-16 | Saudi Arabian Oil Company | Maleic Anhydride Polymers and Methods of Treating Subterranean Formations |
Non-Patent Citations (1)
| Title |
|---|
| SHANG QIUSHUN ET AL: "Gel-tape-casting of aluminum nitride ceramics", JOURNAL OF ADVANCED CERAMICS, vol. 6, no. 1, 1 March 2017 (2017-03-01), pages 67 - 72, XP055856401, ISSN: 2226-4108, Retrieved from the Internet <URL:https://link.springer.com/content/pdf/10.1007/s40145-016-0211-3.pdf> DOI: 10.1007/s40145-016-0211-3 * |
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| US20240093081A1 (en) | 2024-03-21 |
| US12378463B2 (en) | 2025-08-05 |
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| US20220017811A1 (en) | 2022-01-20 |
| SA523442161B1 (en) | 2024-10-02 |
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