CN116265563A - Binary composite resin sealing agent and preparation method and application thereof - Google Patents
Binary composite resin sealing agent and preparation method and application thereof Download PDFInfo
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- CN116265563A CN116265563A CN202111552820.8A CN202111552820A CN116265563A CN 116265563 A CN116265563 A CN 116265563A CN 202111552820 A CN202111552820 A CN 202111552820A CN 116265563 A CN116265563 A CN 116265563A
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- binary composite
- composite resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 89
- 239000011347 resin Substances 0.000 title claims abstract description 89
- 239000011218 binary composite Substances 0.000 title claims abstract description 80
- 238000007789 sealing Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 72
- 239000003822 epoxy resin Substances 0.000 claims abstract description 52
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 29
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000005011 phenolic resin Substances 0.000 claims abstract description 28
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 230000000903 blocking effect Effects 0.000 claims description 8
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 238000005553 drilling Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004886 process control Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 13
- 230000005465 channeling Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 description 10
- 239000004568 cement Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001907 coumarones Chemical class 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- FIMVMYXUGWSJKE-UHFFFAOYSA-N 1,4-xylene Chemical compound CC1=CC=C(C)C=C1.CC1=CC=C(C)C=C1 FIMVMYXUGWSJKE-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
- E21B33/138—Plastering the borehole wall; Injecting into the formation
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical & Material Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a binary composite resin sealing agent, which comprises bisphenol A type epoxy resin and thermosetting phenolic resin; and a reconciling agent, a solvent, a plasticizer, a solvent and a curing agent. Wherein the bisphenol a type epoxy resin comprises bisphenol a type epoxy resin E51 or bisphenol a type epoxy resin E44; the thermosetting phenolic resin comprises thermosetting phenolic resin YJDJ. The application also provides a preparation method of the binary composite resin sealing agent and application of the binary composite resin sealing agent in chemical sealing of a normal-low-temperature oil-water well. The binary composite resin sealing agent can realize controllable reaction at the temperature of between 20 and 50 ℃ and can be used for sealing channeling of an oil-water well sealing layer at the temperature of between normal temperature and low temperature and repairing and treating a casing pipe, thereby meeting the requirements of oilfield production.
Description
Technical Field
The application relates to the technical field of oil and gas fields, in particular to a binary composite resin sealing agent and a preparation method and application thereof.
Background
Along with the later period of high water content exploitation of the old oil field, along with the development mode adjustment of layered oil extraction, water injection, gas injection and the like, the problems of shaft integrity such as oil, water well channeling, leakage and the like caused by oil and water well water outlet, gas channeling, sleeve damage and sleeve change and the like are more and more prominent, and particularly, the gas drive well and the gas storage well have good well completion requirement, high bearing requirement and plagued the oil field production, and the treatment is needed urgently.
Aiming at water outlet, gas channeling, sleeve damage and sleeve deformation, common solutions include overhaul technology and chemical reinforcement and blocking technology by taking mechanical plastic blocking as a means. The overhaul technology comprises the following steps: (1) overhaul shaping by mechanical expansion; (2) The sleeve replacing operation is suitable for the oil-water well above the cementing cement return surface; (3) repairing and sealing the sleeve; and (4) clamping the packer section by the lower packer. For shallow wells with the well depth of less than 1000m, the major repair technologies such as mechanical plastic clamping and sealing are more common, but the problems of high operation technical difficulty, influence on subsequent production operation due to reducing the drift diameter and the like exist.
The chemical reinforcing plugging technology comprises cement, gel and resin, has certain limitation in use at normal temperature to low temperature, and the existing plugging strength can not meet the special high pressure-bearing requirement. Among them, cement is most used. If CN1896176A, CN111363527A discloses silicate or sulphoaluminate cement, an early strength agent is added to lead cement paste to be dehydrated and solidified in advance, and reinforcing and toughening materials such as superfine fibers, fillers and the like are matched, the plugging requirement of normal temperature to 60 ℃ can be met. But limited by the performance of cement materials, the cement material has lower tensile strength and shearing strength, low compressive strength at normal low temperature (8-30 MPa), poor adaptability to various seepage channels, high volume shrinkage (more than 10%), extremely low operation success rate and difficult practical use effect to meet the production requirement. The low-temperature reaction rate of the resin material is difficult to control, particularly the thermosetting resin has strict control on the dosage of the catalyst and the temperature, the formation strength is slower when the catalyst dosage and the temperature are less, the curing time is long, and the explosion polymerization is initiated more. At present, research or technical means for a normal-temperature to low-temperature resin plugging method are lacking.
Disclosure of Invention
In order to solve the technical problems, the application provides a binary composite resin sealing agent, which comprises the following components:
binary composite resin material: bisphenol a type epoxy resin and thermosetting phenolic resin;
and a reconciling agent, a solvent, a plasticizer, a solvent and a curing agent.
According to one embodiment of the present invention, the bisphenol a type epoxy resin includes bisphenol a type epoxy resin E51 or bisphenol a type epoxy resin E44.
According to one embodiment of the present invention, the bisphenol A type epoxy resin accounts for 60 to 90% by weight of the binary composite resin material
According to one embodiment of the invention, the thermosetting phenolic resin comprises thermosetting phenolic resin YJDJ.
According to one embodiment of the invention, the thermosetting phenolic resin comprises 40 to 10% by weight of the binary composite resin material.
According to one embodiment of the invention, the blending agent comprises one or more of ethanol, glycol or span-80; according to another embodiment of the present invention, the concentration of the ethanol or the ethylene glycol is 1.2 to 3% by weight and the concentration of the span-80 is 0.8 to 2% by weight based on 100% by weight of the binary composite resin material.
According to one embodiment of the invention, the plasticizer comprises dibutyl phthalate, and/or the concentration of dibutyl phthalate comprises 0.5 to 2% by weight based on 100% by weight of the binary composite resin material.
According to one embodiment of the present invention, the solvent includes ethyl acetate, and/or the ethyl acetate concentration is 1.5 to 3% by weight based on 100% by weight of the binary composite resin material.
According to one embodiment of the present invention, the curing agent includes ethylenediamine, and/or the concentration of ethylenediamine is 0.6 to 1% by weight based on 100% by weight of the binary composite resin material.
According to one embodiment of the invention, the accelerator comprises tris (2-hydroxyethyl) amine, and/or the concentration of the tris (2-hydroxyethyl) amine comprises 5 to 8% by weight based on 100% by weight of the binary composite resin material.
The invention also provides a preparation method of the binary composite resin sealing agent, which comprises the following steps:
weighing thermosetting phenolic resin according to the weight proportion, adding a blending agent into a stirring kettle, fully stirring until the mixture is uniform, adding bisphenol A epoxy resin, mixing, stirring until the mixture is uniform, adding a solvent and a plasticizer, and continuously mixing and stirring until the mixture is uniform to obtain binary composite resin for later use; and
preparing liquid from a liquid preparation tank on site: pouring the mixed binary composite resin into a liquid distribution tank, adding a curing agent and an accelerator, and stirring until the mixture is uniform, thus obtaining the binary composite resin sealing agent.
The third aspect of the invention provides an application of the binary composite resin sealing agent, wherein the binary composite resin sealing agent is used for chemically sealing a normally low-temperature oil-water well, and comprises the following steps:
1) Preparing equipment required by chemical plugging of a normally low temperature oil-water well, wherein the equipment comprises a liquid distribution pool, a clean water pool, a pump truck, a tank truck and one or more of pressure gauges;
2) The plugging step comprises the following steps:
(1) Barreling the binary composite resin material for standby;
(2) Downhole preparation: lifting a primary production pipe column in a well, dredging the well, flushing the well to an artificial bottom of the well, and putting in a gloss oil pipe or a blocking pipe column with a packer to test the upper part of a blocking layer;
(3) Setting a bridge plug, filling sand and injecting ash below a plugging section, completing a plugging tubular column to a designed depth, and installing a wellhead device;
(4) The clean water is squeezed in a test way, the apparent water absorption indexes under different discharge volumes and pressures are measured, and the process control parameters are determined;
(5) Preparing the binary composite resin sealing agent by using a site liquid preparation tank, and sequentially extruding and injecting a plugging agent and a displacement liquid according to a pumping sequence;
(6) Closing the well under pressure, condensing, and testing the pressure by drilling and plugging.
The binary composite resin sealing agent can be used for chemically sealing an oil-water well under the condition of normal low temperature, for example, the condition of normal temperature of 20-50 ℃.
Compared with the prior art, the binary composite resin sealing agent has at least the following advantages:
1) The inventor finds that by utilizing the principles of mixing two different resins (such as density adjustment or emulsification method), anionic ring-opening polymerization, mannich reaction, polycondensation and the like, the advantages of the two types of resins are combined, and the two-stage controllable low-temperature reaction of initial setting and polymerization curing is realized through two-stage catalytic polymerization reaction;
2) The binary composite resin sealing agent at normal temperature to low temperature has the characteristics of low volume shrinkage, high plugging strength, strong toughness and the like, can realize controllable reaction at normal temperature of 20-50 ℃, has controllable initial setting time of 2-8 h, solidification time of less than 72h, compressive strength of 58-88 MPa, volume shrinkage of 0.5-2.3%, and acid, alkali and salt dissolution rate of less than 1%, and can be used for sealing channeling of oil-water well sealing layers at normal temperature to low temperature, repairing and treating casings and meeting the requirements of oilfield production.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the specific embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
In one embodiment of the present invention, a binary composite resin sealer is provided having the following composition
Binary composite resin material: bisphenol a type epoxy resin and thermosetting phenolic resin;
and a reconciling agent, a solvent, a plasticizer, a solvent and a curing agent.
In the present application, epoxy resin refers to a resin compound containing at least two reactive epoxy groups. The epoxy resin includes various types of epoxy resins known in the art, including, but not limited to, bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, phenolic (phenolic) epoxy resin, trifunctional (trifunctional) epoxy resin, tetrafunctional (tetrafunctional) epoxy resin, multifunctional (multifunctional) phenolic epoxy resin, dicyclopentadiene-containing (DCPD-containing) epoxy resin, phosphorous-containing epoxy resin, p-xylene (p-xylene) epoxy resin, naphthalene-containing (naphthol) epoxy resin, benzofurans (benzofurans) type epoxy resin, and isocyanate-modified (isocyanate) epoxy resin, for example, but not limited thereto.
In one embodiment of the invention, the bisphenol A epoxy resin comprises epoxy resin obtained by ring opening and ring closing reaction of bisphenol A and epichlorohydrin under alkaline conditions (such as in sodium hydroxide aqueous solution). In one specific embodiment of the present application, the bisphenol a type epoxy resin comprises a diphenol propane epoxy resin, a glycerol epoxy resin, a butene epoxy resin; cyclopentadiene epoxy resin, and is not limited to this list.
In some embodiments of the present invention, the bisphenol a epoxy resin comprises a low relative molecular mass epoxy resin (C 11 H 2 O 3 ) n The n average value of the epoxy resin with low relative molecular mass is less than 2, and the softening point is less than 50 ℃; or the bisphenol A type epoxy resin comprises medium relative molecular weight epoxy resin, wherein the n value of the medium relative molecular weight epoxy resin is between 2 and 5, and the softening point is between 50 and 95 ℃; or the bisphenol a type epoxy resin includes a resin having n of more than 5 (softening point of 100 ℃ or more) and a high relative molecular mass resin.
According to one embodiment of the present invention, the bisphenol a type epoxy resin includes bisphenol a type epoxy resin E51 or bisphenol a type epoxy resin E44.
According to one embodiment of the present invention, the bisphenol a type epoxy resin accounts for 60 to 90% by weight of the binary composite resin material; according to other embodiments of the present invention, the bisphenol a type epoxy resin comprises 65 to 85% by weight of the binary composite resin material; according to other embodiments of the present invention, the bisphenol a type epoxy resin comprises 70 to 85% by weight of the binary composite resin material; according to other embodiments of the present invention, the bisphenol a type epoxy resin comprises 75 to 80% by weight of the binary composite resin material; according to other embodiments of the present invention, the bisphenol a type epoxy resin comprises 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90% by weight of the binary composite resin material.
According to one embodiment of the invention, the thermosetting phenolic resin comprises thermosetting phenolic resin YJDJ; according to one embodiment of the invention, the thermosetting phenolic resin comprises 40 to 10% by weight of the binary composite resin material. According to some embodiments of the invention, the thermosetting phenolic resin comprises 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40% by weight of the binary composite resin material.
According to one embodiment of the invention, the blending agent comprises one or more of ethanol, glycol or span-80; according to another embodiment of the present invention, the concentration of the ethanol or the ethylene glycol is 1.2 to 3% by weight and the concentration of the span-80 is 0.8 to 2% by weight based on 100% by weight of the binary composite resin material.
According to one embodiment of the invention, the plasticizer comprises dibutyl phthalate, and/or the concentration of dibutyl phthalate is comprised between 0.5 and 2% by weight, based on 100% by weight of the binary composite resin material.
According to one embodiment of the present invention, the solvent includes ethyl acetate, and/or the ethyl acetate concentration is 1.5 to 3% by weight based on 100% by weight of the binary composite resin material.
According to one embodiment of the present invention, the curing agent includes ethylenediamine, and/or the concentration of ethylenediamine is 0.6 to 1% by weight based on 100% by weight of the binary composite resin material.
According to one embodiment of the invention, the accelerator comprises tris (2-hydroxyethyl) amine and/or the concentration of the tris (2-hydroxyethyl) amine comprises 5 to 8% by weight based on 100% by weight of the binary composite resin material.
According to some embodiments of the present invention, there is also provided a method for preparing the above binary composite resin sealing agent, the method comprising the steps of:
weighing thermosetting phenolic resin according to the weight proportion, adding a blending agent into a stirring kettle, fully stirring until the mixture is uniform, adding bisphenol A epoxy resin, mixing, stirring until the mixture is uniform, adding a solvent and a plasticizer, and continuously mixing and stirring until the mixture is uniform to obtain binary composite resin for later use; and
preparing liquid from a liquid preparation tank on site: pouring the mixed binary composite resin into a liquid distribution tank, adding a curing agent and an accelerator, and stirring until the mixture is uniform, thus obtaining the binary composite resin sealing agent.
According to some embodiments of the invention, the time for adding the blending agent and fully stirring comprises 5-10 min; adding the bisphenol A epoxy resin, mixing and stirring for 15-20 min; adding the solvent and the plasticizer, and continuously mixing and stirring for 20-30 min;
according to some embodiments of the invention, the liquid preparation tank in the in-situ liquid preparation tank comprises 5-10 m 3 The stirring time after adding the curing agent and the accelerator into the liquid preparation tank is 10-20 min to be uniform.
According to some embodiments of the present invention, there is also provided the use of the binary composite resin sealing agent for chemical plugging of a low temperature oil-water well, comprising the steps of:
1) Preparing equipment required by chemical plugging of a normally low temperature oil-water well, wherein the equipment comprises a liquid distribution pool, a clean water pool, a pump truck, a tank truck and one or more of pressure gauges;
2) The plugging step comprises the following steps:
(1) Barreling the binary composite resin material for standby;
(2) Downhole preparation: lifting a primary production pipe column in a well, dredging the well, flushing the well to an artificial bottom of the well, and putting in a gloss oil pipe or a blocking pipe column with a packer to test the upper part of a blocking layer;
(3) Setting a bridge plug, filling sand and injecting ash below a plugging section, completing a plugging tubular column to a designed depth, and installing a wellhead device;
(4) The clean water is squeezed in a test way, the apparent water absorption indexes under different discharge volumes and pressures are measured, and the process control parameters are determined;
(5) Preparing the binary composite resin sealing agent by using a site liquid preparation tank, and sequentially extruding and injecting a plugging agent and a displacement liquid according to a pumping sequence;
(6) Closing the well under pressure, condensing, and testing the pressure by drilling and plugging.
The technical scheme of the invention is further described by the following specific examples:
example 1
The concentration percentages of the components are as follows:
90 parts of bisphenol A epoxy resin; thermosetting phenolic resin, 10 parts; ethanol, 1.2 parts; dibutyl phthalate, 1 part; ethyl acetate, 2 parts; 0.85 part of ethylenediamine; tris (2-hydroxyethyl) amine was used in an amount of 6 parts.
The preparation method of the binary composite resin sealing agent for the chemical plugging of the oil-water well at normal low temperature comprises the following steps:
the method adopts a mode of combining chemical plant mixing with on-site liquid preparation and liquid preparation, wherein the chemical plant mixing: weighing thermosetting phenolic resin according to a formula, metering the thermosetting phenolic resin in a stirring kettle, adding a blending agent, fully stirring for 8min to be uniform, then slowly adding a metered amount of bisphenol A epoxy resin, mixing, stirring for 18min to be uniform, adding a solvent and a plasticizer with preset amounts, continuously mixing, stirring for 30min to be uniform, and barreling for later use; preparing liquid from a liquid preparation tank on site: pouring the mixed composite resin into a container with a thickness of 5-10 m 3 Adding a curing agent and an accelerator in a preset amount into the liquid preparation tank, and stirring for 15min until the mixture is uniform. Obtaining the normal low temperature binary composite resin sealing agent.
Indoor tests show that the binary composite resin sealing agent for chemical plugging of the normally low-temperature oil-water well, which is prepared according to the formula proportion, has controllable initial setting time of 2-4 h, curing time of 48-60 h, compressive strength of 82MPa, volume shrinkage of 1.5%, and acid dissolution, alkali dissolution and salt dissolution rates of 0.2%, 0.1% and 0.2%.
Example 2
The concentration percentages of the components are as follows:
bisphenol A type epoxy resin with the dosage of 80 parts; thermosetting phenolic resin, 20 parts; ethanol, 1.8 parts; dibutyl phthalate, 1 part; ethyl acetate, 1.5 parts; 0.80 part of ethylenediamine; the preparation method of the binary composite resin sealing agent for the chemical plugging of the oil-water well at normal low temperature comprises the following steps of:
the method adopts a mode of combining chemical plant mixing with on-site liquid preparation and liquid preparation, wherein the chemical plant mixing: weighing thermosetting phenolic resin according to a formula, metering the thermosetting phenolic resin in a stirring kettle, adding a blending agent, fully stirring for 8min to be uniform, then slowly adding a metered amount of bisphenol A epoxy resin, mixing, stirring for 20min to be uniform, adding a solvent and a plasticizer with preset amounts, continuously mixing, stirring for 25min to be uniform, and barreling for later use; preparing liquid from a liquid preparation tank on site: pouring the mixed composite resin into a 5-10 m3 liquid distribution tank, adding a curing agent and an accelerator in preset amounts into the liquid distribution tank, and stirring for 20min until uniform. Obtaining the normal low temperature binary composite resin sealing agent.
Indoor experiments show that the binary composite resin sealing agent for chemical plugging of the normally low-temperature oil-water well, which is prepared according to the formula proportion, has controllable initial setting time of 2.5-4 h, curing time of 48-60 h, compressive strength of 76MPa, volume shrinkage of 1.8%, and acid dissolution, alkali dissolution and salt dissolution rates of 0.2%, 0.2% and 0.1%.
Example 3
The concentration percentages of the components are as follows:
bisphenol A type epoxy resin, 70 parts; thermosetting phenolic resin, 30 parts; span-80, 1.0 part; dibutyl phthalate, 1 part; ethyl acetate, 1 part; 0.75 part of ethylenediamine; tris (2-hydroxyethyl) amine was used in an amount of 8 parts.
The preparation method of the binary composite resin sealing agent for the chemical plugging of the oil-water well at normal low temperature comprises the following steps:
the method adopts a mode of combining chemical plant mixing with on-site liquid preparation and liquid preparation, wherein the chemical plant mixing: weighing thermosetting phenolic resin according to a formula, metering the thermosetting phenolic resin in a stirring kettle, adding a blending agent, fully stirring for 10min to be uniform, then slowly adding a metered amount of bisphenol A epoxy resin, mixing, stirring for 20min to be uniform, adding a solvent and a plasticizer with preset amounts, continuously mixing, stirring for 25min to be uniform, and barreling for later use; preparing liquid from a liquid preparation tank on site: pouring the mixed composite resin into a 5-10 m3 liquid distribution tank, adding a curing agent and an accelerator in preset amounts into the liquid distribution tank, and stirring for 20min until uniform. Obtaining the normal low temperature binary composite resin sealing agent.
Indoor experiments show that the binary composite resin sealing agent for chemical plugging of the normally low-temperature oil-water well, which is prepared according to the formula proportion, has controllable initial setting time of 2-4.5 h, curing time of 45-56 h, compressive strength of 64MPa, volume shrinkage of 2.0%, and acid dissolution, alkali dissolution and salt dissolution rates of 0.1%, 0.2% and 0.1%.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A binary composite resin sealing agent comprises the following components:
binary composite resin material: bisphenol a type epoxy resin and thermosetting phenolic resin;
and a reconciling agent, a solvent, a plasticizer, a solvent and a curing agent.
2. The binary composite resin sealing agent according to claim 1, wherein the bisphenol a type epoxy resin comprises bisphenol a type epoxy resin E51 or bisphenol a type epoxy resin E44; and/or the thermosetting phenolic resin comprises thermosetting phenolic resin YJDJ.
3. The binary composite resin sealing agent according to claim 1 or 2, wherein the bisphenol a type epoxy resin accounts for 60 to 90% by weight of the binary composite resin material; and/or the thermosetting phenolic resin accounts for 40-10% of the weight of the binary composite resin material.
4. The binary composite resin sealing agent according to claim 1, wherein the blending agent comprises one or more of ethanol, ethylene glycol or span-80; the concentration of the ethanol or the glycol is 1.2-3% by weight, and the concentration of the span-80 is 0.8-2% by weight, based on 100% by weight of the binary composite resin material.
5. The binary composite resin sealing agent according to claim 1, wherein the plasticizer comprises dibutyl phthalate, and/or the concentration of dibutyl phthalate is comprised between 0.5 and 2% by weight based on 100% by weight of the binary composite resin material.
6. The binary composite resin sealing agent according to claim 1, wherein the solvent comprises ethyl acetate, and/or the ethyl acetate concentration is 1.5 to 3% by weight based on 100% by weight of the binary composite resin material.
7. The binary composite resin sealing agent according to claim 1, wherein the curing agent comprises ethylenediamine, and/or the concentration of ethylenediamine is 0.6 to 1% by weight based on 100% by weight of the binary composite resin material.
8. A binary composite resin sealing agent according to claim 1, wherein the accelerator comprises tris (2-hydroxyethyl) amine and/or the concentration of tris (2-hydroxyethyl) amine comprises 5 to 8% by weight based on 100% by weight of the binary composite resin material.
9. A method for preparing the binary composite resin sealing agent according to any one of claims 1 to 8, comprising the steps of:
1) Weighing thermosetting phenolic resin according to the weight ratio, adding a blending agent into a stirring kettle, fully stirring until the mixture is uniform, adding bisphenol A epoxy resin, mixing, stirring until the mixture is uniform, adding a solvent and a plasticizer, and continuously mixing and stirring until the mixture is uniform to obtain binary composite resin for later use;
2) Preparing liquid from a liquid preparation tank on site: pouring the mixed binary composite resin into a liquid distribution tank, adding a curing agent and an accelerator, and stirring until the mixture is uniform, thus obtaining the binary composite resin sealing agent.
10. Use of the binary composite resin sealing agent according to any one of claims 1-8 for chemical plugging of low temperature oil-water wells, comprising the steps of:
1) Preparing equipment required by chemical plugging of a normally low temperature oil-water well, wherein the equipment comprises a liquid distribution pool, a clean water pool, a pump truck, a tank truck and one or more of pressure gauges;
2) The plugging step comprises the following steps:
(1) Barreling the binary composite resin material for standby;
(2) Downhole preparation: lifting a primary production pipe column in a well, dredging the well, flushing the well to an artificial bottom of the well, and putting in a gloss oil pipe or a blocking pipe column with a packer to test the upper part of a blocking layer;
(3) Setting a bridge plug, filling sand and injecting ash below a plugging section, completing a plugging tubular column to a designed depth, and installing a wellhead device;
(4) The clean water is squeezed in a test way, the apparent water absorption indexes under different discharge volumes and pressures are measured, and the process control parameters are determined;
(5) Preparing the binary composite resin sealing agent by using a site liquid preparation tank, and sequentially extruding and injecting a plugging agent and a displacement liquid according to a pumping sequence;
(6) Closing the well under pressure, condensing, drilling and plugging to test the pressure;
and/or the normal low temperature condition comprises normal temperature 20 ℃ to low temperature 50 ℃.
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