CN117586759A - Dilution-resistant gel composition, dilution-resistant gel plugging agent, and preparation methods and application thereof - Google Patents
Dilution-resistant gel composition, dilution-resistant gel plugging agent, and preparation methods and application thereof Download PDFInfo
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- 239000012895 dilution Substances 0.000 title claims abstract description 147
- 238000010790 dilution Methods 0.000 title claims abstract description 147
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 51
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 51
- 239000000661 sodium alginate Substances 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000005011 phenolic resin Substances 0.000 claims abstract description 43
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 43
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 35
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 51
- 229920001577 copolymer Polymers 0.000 claims description 23
- 239000003292 glue Substances 0.000 claims description 23
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 18
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 12
- 230000033558 biomineral tissue development Effects 0.000 claims description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 4
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000008398 formation water Substances 0.000 abstract description 56
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 17
- 230000001681 protective effect Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 168
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000003085 diluting agent Substances 0.000 description 16
- 239000002981 blocking agent Substances 0.000 description 13
- 235000015110 jellies Nutrition 0.000 description 10
- 239000008274 jelly Substances 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- MSXHSNHNTORCAW-WTFUTCKNSA-M sodium;(2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical group [Na+].O[C@@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@@H]1O MSXHSNHNTORCAW-WTFUTCKNSA-M 0.000 description 1
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of oilfield chemical profile control and water shutoff, and discloses a dilution-resistant gel composition, a dilution-resistant gel plugging agent, a preparation method and application thereof. The dilution-resistant gel composition comprises polyacrylamide, a phenolic resin cross-linking agent and a dilution-resistant auxiliary agent which are stored independently, wherein the dilution-resistant auxiliary agent is sodium alginate, and the sodium alginate is a polymer obtained by polymerizing a G section shown in a formula (1) and/or an M section shown in a formula (2): the saidThe polymerization degree of the sodium alginate is 80-750; the dilution-resistant auxiliary agent in the dilution-resistant gel composition can form a compact viscoelastic protective film with calcium ions in formation water to isolate water bodies and prevent dilution of formation water to gel forming liquid, so that the dilution-resistant gel plugging agent has good gel forming performance, high strength after gel forming and strong long-term thermal stability;
Description
Technical Field
The invention relates to the technical field of oilfield chemical profile control and water shutoff, in particular to a dilution-resistant gel composition, a dilution-resistant gel plugging agent, a preparation method and application thereof.
Background
The high-temperature high-salt fracture-cavity type oil and gas reservoir exploitation technology is becoming more and more perfect. In the existing high-temperature high-salt fracture-cavity type oil and gas reservoir development technology, water injection/gas exploitation is mature, and the natural energy development, water injection development and gas injection development technology of the high-temperature high-salt fracture-cavity type oil and gas reservoir is the main technology. But bottom water coning and water channeling caused by reservoir heterogeneity become important factors affecting the development of high-temperature high-salt fracture-cavity type oil and gas reservoirs. Unlike conventional pore-type reservoirs, many wells in fracture-cavity reservoirs are shut in by sudden flooding (about 50% of the rate) after water injection. The heterogeneous regulation and control of the reservoir becomes an effective mode for the development of the assisted high-temperature high-salt fracture-cavity type oil and gas reservoir, and the core is the research and development of a regulator. The gel regulator has stable gel forming effect, controllable gel performance and simple preparation, and is widely applied. However, the high-temperature high-salt fracture-cavity type oil-gas reservoir can dilute injected gel solution by a large amount of stratum water, so that the conventional gel has poor gel effect and even can not be gelled due to the reduction of the concentration of chemical agents.
CN114427378A discloses a method for designing a selective water plugging slug of a disconnected solution oil reservoir, and discloses a dilution-resistant gel composition, wherein the dilution-resistant gel composition comprises a polymer SDCA-8, a polymer SDCA-70 and a cross-linking agent, and the pre-slug thixotropic gel composition resists high temperature 130 ℃ and salt 20 multiplied by 10 4 mg/L, dynamic thickening time>8h, static quick thickening, density of 1.07-1.1 mg/L, viscosity of 30-50 mPa.s, compressive strength>1MPa. After the composition is injected into a stratum, the composition can rely on the thixotropic characteristic of the composition, and the composition stands for thickening to reduce the leakage of a subsequent plugging agent, but the composition cannot completely isolate stratum water, and the composition can have a certain influence on the dilution resistance effect due to the slow flow of the composition and the dynamic interference of the stratum water.
CN109280542a discloses a high temperature resistant gel blocking agent, a preparation method and application thereof, the raw material components of the high temperature resistant gel blocking agent comprise: 2-5% of sulfonated modified polysaccharide, 0.01-0.025% of peroxide initiator, 20-25% of acrylamide micromolecule monomer, 1.2-1.5% of aldehyde cross-linking agent A, 1.3-1.7% of amine cross-linking agent B, 0.04-0.1% of ammonium salt curing agent, 0.03-0.3% of alkaline pH regulator and the balance of water, and has the advantages of strong thermal stability, good viscoelasticity and high gel strength, and can be used at 100-150 ℃. However, the gel was not evaluated for salt tolerance and did not have dilution tolerance.
CN113897189a discloses a gel composition suitable for profile control of high-temperature high-salt fracture-cavity oil reservoir and application, the composition consists of nonionic polyacrylamide, urotropine, hydroquinone and the balance of water, and can be gelled at about 130 ℃, the mineralization tolerance is 22 ten thousand mg/L, the calcium ion concentration is 11273mg/L, and the magnesium ion concentration is 1519mg/L. However, the invention does not investigate its ability to withstand dilution by formation water.
Therefore, development of gel resistant to dilution of formation water is needed to meet the control of heterogeneity of high-temperature high-salt fracture-cavity reservoirs.
Disclosure of Invention
Aiming at solving the problems that the prior art cannot form gel or has poor gel strength after the formation water is diluted by the fracture-cavity type oil-gas reservoir gel regulator with high temperature and high salt (more than or equal to 110 ℃), mineralization degree more than or equal to 20 ten thousand mg/L and calcium-magnesium ion more than or equal to 5000 mg/L), the invention provides a dilution-resistant gel composition, a dilution-resistant gel plugging agent, a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a dilution-resistant gel composition, wherein the dilution-resistant gel composition comprises polyacrylamide, a phenolic resin cross-linking agent and a dilution-resistant auxiliary agent which are stored independently, wherein the dilution-resistant auxiliary agent is sodium alginate, and the sodium alginate is a polymer obtained by polymerizing a G segment shown in a formula (1) and/or an M segment shown in a formula (2):
wherein the polymerization degree of the sodium alginate is 80-750.
The second aspect of the invention provides a preparation method for preparing a dilution-resistant gel plugging agent by adopting the composition, wherein the preparation method comprises the following steps:
(1) Under the stirring condition, contacting liquid preparation water with polyacrylamide for first mixing to obtain a polymer solution;
(2) Contacting the polymer solution with a phenolic resin cross-linking agent for second mixing to obtain a glue solution;
(3) And (3) contacting the gel forming liquid with a dilution-resistant auxiliary agent for third mixing, and then performing gel forming treatment to obtain the dilution-resistant gel plugging agent.
The third aspect of the invention provides a dilution-resistant gel plugging agent prepared by the preparation method.
The fourth aspect of the invention provides application of the dilution-resistant gel plugging agent in high-temperature high-salt fracture-cavity type hydrocarbon reservoirs.
Through the technical scheme, the invention has the following beneficial effects:
(1) The dilution-resistant gel plugging agent disclosed by the invention has good gel forming performance, high strength after gel forming and strong long-term thermal stability.
(2) The diluent-resistant gel composition has good compatibility among all components, simple preparation of a gel solution, no influence on gel formation due to the existence of diluent-resistant auxiliary agents, and can be used for preparing a liquid from clear water and a liquid from high-mineralization oilfield reinjection water, thereby relieving the problem of shortage of fresh water resources in complex and severe construction processes such as deserts, gobi, oceans and the like.
(3) The diluent-resistant gel composition has wide raw material sources of all components, and is suitable for industrial production and large-scale on-site preparation operation.
Drawings
FIG. 1 is a schematic diagram of a dilution-resistant gel-forming fluid prepared in example 1 of the present invention isolated from formation water;
FIG. 2 is a schematic diagram of the dilution-resistant gel plugging agent prepared in example 1 of the invention for high-temperature isolation of formation water into gel;
FIG. 3 is a schematic diagram showing the gel of the anti-dilution gel blocking agent prepared in example 1 of the present invention;
FIG. 4 is an SEM photograph of the micro-network structure of the diluted gel blocking agent prepared in example 3 of the present invention after gelling;
FIG. 5 is a schematic diagram showing the conventional jelly prepared in comparative example 1 in a macroscopic view after being diluted with formation water;
fig. 6 is an SEM photograph of the micro network structure of the general jelly prepared in comparative example 2;
fig. 7 is a graph showing the comparison of the elastic modulus and the viscoelastic modulus of the dilution-resistant jelly (example 4) diluted with formation water, the undiluted ordinary jelly (comparative example 1), and the ordinary jelly diluted with formation water.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a dilution-resistant gel composition, where the dilution-resistant gel composition includes polyacrylamide, a phenolic resin cross-linking agent and a dilution-resistant auxiliary agent that are each independently stored, where the dilution-resistant auxiliary agent is sodium alginate, and the sodium alginate is a polymer obtained by polymerizing a G segment shown in formula (1) and/or an M segment shown in formula (2):
wherein the polymerization degree of the sodium alginate is 80-750.
According to the invention, the polymerization degree of the sodium alginate is 100-750.
According to the invention, M is sodium beta-D-mannuronate (beta-D-mannuronic), and G is sodium alpha-L-guluronate (alpha-L-guluronic).
According to the invention, in the sodium alginate, the connection mode between G and M can be one or more of GG shown in a formula (a), MM shown in a formula (b) and GM shown in a formula (c).
According to the invention, the molar ratio of M to G content is between 0.6 and 2.22; preferably, the molar ratio of M to G content is 1.88-2.1.
The inventors of the present invention found that: the dilution-resistant auxiliary agent can form a compact viscoelastic protective film with calcium ions in formation water, can isolate water bodies, prevents formation water from diluting a glue solution, and further can avoid incapability of forming glue or poor glue forming performance of the glue solution.
Specifically, for example, by adopting one of connection modes of G and M, the dilution-resistant auxiliary agent can be subjected to crosslinking reaction with calcium ions in formation water, and the dilution-resistant auxiliary agent is specifically shown as follows:
the gel-forming liquid is contacted with the formation water, the dilution-resistant auxiliary agent and calcium ions on the contact surface rapidly undergo a crosslinking reaction, and a water-resisting layer is rapidly formed on the contact surface to prevent the formation water from being diluted into the gel-forming liquid.
Furthermore, the phenolic resin cross-linking agent adopted by the invention can form a main network structure, the dilution-resistant auxiliary agent participates in forming a secondary network structure, the network density of the gel can be encrypted, and the gel forming strength is stronger.
According to the invention, the polyacrylamide is an AM/AMPS copolymer, wherein AM (water-soluble Acrylamide (AM), AMPS (sodium 2-acrylamido-2-methylpropanesulfonate) and the content of AM is 60-70 wt% and the content of AMPS is 30-40 wt%, based on the total weight of the AM/AMPS copolymer.
According to the invention, the AM/AMPS copolymer has a relative molecular weight of 500 to 1000 tens of thousands.
According to the invention, the AM/AMPS copolymer has a degree of hydrolysis of 3 to 10%.
According to the present invention, the phenolic resin crosslinking agent is selected from one or more of phenol type phenolic resin, hydroquinone type phenolic resin, catechol type phenolic resin and resorcinol type phenolic resin.
According to the invention, the polyacrylamide content is 0.5-1 wt%, based on the total weight of the dilution-resistant gel composition; the phenolic resin cross-linking agent accounts for 0.3 to 1.5 weight percent, the dilution-resistant auxiliary agent accounts for 0.2 to 0.8 weight percent, and the balance is liquid water; preferably, the polyacrylamide is present in an amount of 0.5 to 1 wt%, based on the total weight of the dilution-resistant gel composition; the phenolic resin cross-linking agent accounts for 0.3 to 1.2 weight percent, the dilution-resistant auxiliary agent accounts for 0.2 to 0.8 weight percent, and the balance is liquid water; more preferably, the polyacrylamide is present in an amount of 0.6 to 0.8 wt%, based on the total weight of the dilution-resistant gel composition; the phenolic resin cross-linking agent accounts for 0.6-0.8 wt%, the diluting-resistant auxiliary accounts for 0.4-0.6 wt% and the balance is liquid water.
The second aspect of the invention provides a preparation method for preparing a dilution-resistant gel plugging agent by adopting the composition, wherein the preparation method comprises the following steps:
(1) Under the stirring condition, contacting liquid preparation water with polyacrylamide for first mixing to obtain a polymer solution;
(2) Contacting the polymer solution with a phenolic resin cross-linking agent for second mixing to obtain a glue solution;
(3) And (3) contacting the gel forming liquid with a dilution-resistant auxiliary agent for third mixing, and then performing gel forming treatment to obtain the dilution-resistant gel plugging agent.
According to the invention, the liquid preparation water can be clear water and/or high-mineralization oilfield reinjection water after decalcification, so that the problem of fresh water resource shortage in complex and severe construction processes such as deserts, gobi, oceans and the like is relieved; preferably, the water may be a liquid formulation having a mineralization degree of 200,000 mg/L.
According to the present invention, the stirring conditions include: stirring was carried out at a stirring rate of 400-600 revolutions per minute.
According to the invention, the conditions of the first mixing include: the temperature is 20+ -5deg.C, and the time is 60-90min, preferably 60-70min.
According to the invention, the conditions of the second mixing include: the temperature is 20+ -5deg.C, and the time is 10-20min, preferably 10-15min.
According to the invention, the conditions of the third mixing include: the temperature is 20+ -5deg.C, and the time is 10-30min, preferably 10-20min.
According to the present invention, in step (3), the conditions of the gelling treatment include: in a pressure-resistant bottle, forming glue for 2-48h at the temperature of 110-150 ℃; preferably, the glue is formed for 2 to 12 hours at the temperature of 130 to 150 ℃.
The third aspect of the invention provides a dilution-resistant gel plugging agent prepared by the preparation method.
The fourth aspect of the invention provides application of the dilution-resistant gel plugging agent in high-temperature high-salt fracture-cavity type hydrocarbon reservoirs.
According to the invention, the conditions of the high-temperature high-salt fracture-cavity type oil and gas reservoir comprise: the temperature is 110-150 ℃, the mineralization degree is 20-30 ten thousand mg/L, and the content of calcium and magnesium ions is 5000-15000 mg/L.
According to a particularly preferred embodiment of the invention, a method for preparing a dilution-resistant gel plugging agent comprises the following steps:
at room temperature (20+/-5 ℃), adding AM/AMPS copolymer accounting for 0.6-0.8% of the total components into liquid water, and stirring for 60-90 minutes under the condition of stirring speed of 500-600 r/min to obtain polymer solution; adding 0.6-0.8% of phenolic resin cross-linking agent while stirring, stirring for 10-20min until the phenolic resin cross-linking agent is dissolved, and forming a glue solution with high temperature resistance; and finally, adding 0.4-0.6% of dilution-resistant auxiliary agent by weight while stirring, stirring for 20-30 minutes to obtain formation water dilution-resistant gel solution, and then forming the gel at 130-150 ℃ to obtain the high-temperature high-salt fracture-cavity type oil-gas reservoir formation water dilution-resistant gel plugging agent.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
the gel strength parameter is measured by a GSC strength code method;
the strength retention parameter is measured by a rheometer elasticity test method;
the core plugging rate parameter is measured by a high-temperature high-salt core displacement experiment method;
SEM was purchased from Hitachi manufacturer under the model number Hitachi S-4800;
rheometers were purchased from Haake manufacturer under model Haake Rheostree RS;
the AM/AMPS copolymer raw material is a commercial product of North Biotech Co.Ltd;
the raw materials of the phenol type, hydroquinone type, catechol type and resorcinol type phenolic resin cross-linking agents are commercial products of Lifeng chemical new materials Co., ltd;
diluent sodium alginate was purchased from Qingdao Mingya seaweed Co.
Example 1
The dilution-resistant gel composition comprises: the AM/AMPS copolymer with the relative molecular weight of 1000 ten thousand and the hydrolysis degree of 10 percent has the mass fraction of 0.8 percent; hydroquinone type phenolic resin cross-linking agent with mass fraction of 0.6%; the mass fraction of the dilution-resistant auxiliary sodium alginate is 0.6%; the balance of liquid water, the mass fraction of which is 98.0%, and the sum of the mass fractions of the components is 100%.
In the sodium alginate as diluent aid, the connection mode between G and M may be one or more of GG shown in the formula (a), MM shown in the formula (b) and GM shown in the formula (b), the molar ratio M/G of M to G is 1.88, and the polymerization degree (n) of the sodium alginate is 600-750.
Adding 0.8gAM/AMPS copolymer into clear water at a stirring rate of 600 revolutions per minute at room temperature (20+/-5 ℃), and stirring for 60 minutes to obtain a polymer solution; adding 0.6g of hydroquinone-type phenolic resin cross-linking agent while stirring, and stirring for 10 minutes to obtain a glue solution; then 0.6g of dilution-resistant auxiliary sodium alginate is slowly added while stirring, stirring is carried out for 30 minutes until the dilution-resistant auxiliary sodium alginate is fully dissolved, a gel solution which is resistant to dilution of formation water is obtained, and then the gel solution is mixed with simulated formation water with the mineralization degree of 200,000mg/L (wherein sodium ion 73282mg/L, calcium ion 6000mg/L and magnesium ion 1000 mg/L) according to the volume ratio of 1:1 is placed in a pressure-resistant bottle, a viscoelasticity protective film is formed once a gel solution containing a dilution-resistant auxiliary agent is contacted with calcium ions, and the gel is formed in a baking oven at 130 ℃ for 8 hours, so that the gel plugging agent A1 which is resistant to formation water dilution of a high-temperature high-salt fracture-cavity type oil-gas reservoir is obtained, the gel plugging agent A is always and obviously layered and not mutually dissolved with simulated formation water before and after the gel formation of the system, the stable period can reach 90 days after the gel formation, the strength retention rate is 95%, and the core plugging rate is 97%.
Fig. 1 is a macroscopic schematic diagram of the dilution-resistant gel plugging agent prepared in example 1 of the present invention before and after gel formation, and it can be seen from fig. 1: the glue forming liquid is obviously separated from the stratum water, a layer of waterproof film is formed in the middle of the glue forming liquid, so that the dilution of the stratum water to the glue forming liquid is prevented, namely, the stratum water cannot be diluted under the action of a dilution-resistant auxiliary agent; fig. 2 is a macroscopic schematic diagram of the dilution-resistant gel plugging agent prepared in example 1 of the present invention after high temperature aging, and as can be seen from fig. 2: after high-temperature aging, the waterproof film protects the gel forming liquid to be stable and gel, namely, the aging effect at high temperature cannot damage the effect of the dilution-resistant auxiliary agent on isolating water; fig. 3 is a macroscopic schematic diagram of the gel formation of the dilution-resistant gel blocking agent prepared in example 1 of the present invention, and it can be seen from fig. 3: gel inside the diluent-resistant auxiliary agent protective film; the dilution-resistant auxiliary agent can obviously separate formation water from gel forming liquid, so that the gel can effectively form the gel without dilution of the formation water.
Example 2
The dilution-resistant gel composition comprises: the AM/AMPS copolymer with the relative molecular weight of 1500 ten thousand and the hydrolysis degree of 12 percent has the mass fraction of 0.6 percent; hydroquinone type phenolic resin cross-linking agent with mass fraction of 0.8%; the mass fraction of the dilution-resistant auxiliary sodium alginate is 0.5%; the balance of liquid water, the mass fraction of which is 98.1 percent, and the sum of the mass fractions of the components is 100 percent.
In the sodium alginate as diluent aid, the connection mode between G and M may be one or more of GG shown in the formula (a), MM shown in the formula (b) and GM shown in the formula (b), the molar ratio M/G of M to G is 1.88, and the polymerization degree (n) of the sodium alginate is 600-750.
Adding 0.6gAM/AMPS copolymer into clear water at a stirring rate of 600 revolutions per minute at room temperature (20+/-5 ℃), and stirring for 60 minutes to obtain a polymer solution; adding 0.8g of hydroquinone-type phenolic resin cross-linking agent while stirring, and stirring for 10 minutes to obtain a glue solution; then 0.5g of dilution-resistant auxiliary sodium alginate is slowly added while stirring, stirring is carried out for 30 minutes until the dilution-resistant auxiliary sodium alginate is fully dissolved, a gel solution which is resistant to dilution of formation water is obtained, and then the gel solution is mixed with simulated formation water with the mineralization degree of 200,000mg/L (wherein sodium ion 73282mg/L, calcium ion 6000mg/L and magnesium ion 1000 mg/L) according to the volume ratio of 1:4, placing the gel solution containing the dilution-resistant auxiliary agent into a pressure-resistant bottle, forming a viscoelastic protective film once the gel solution is contacted with calcium ions, and forming gel in a baking oven at 130 ℃ for 6 hours to obtain the gel plugging agent A2 for resisting formation water dilution of the high-temperature high-salt fracture-cavity type oil-gas reservoir, wherein the gel plugging agent A2 is obviously layered and not mutually dissolved with simulated formation water all the time before and after the gel formation of the system, the stable period can reach 90 days after the gel formation, the strength retention rate is 93%, and the core plugging rate is 92%.
Example 3
The dilution-resistant gel composition comprises: the AM/AMPS copolymer with the relative molecular weight of 800 ten thousand and the hydrolysis degree of 8 percent has the mass fraction of 0.8 percent; catechol type phenolic resin cross-linking agent, the mass fraction is 0.8%; the mass fraction of the dilution-resistant auxiliary sodium alginate is 0.5%; the balance of liquid water, the mass fraction of which is 97.9%, and the sum of the mass fractions of the components is 100%.
In the sodium alginate as diluent aid, the connection mode between G and M may be one or more of GG shown in the formula (a), MM shown in the formula (b) and GM shown in the formula (b), the molar ratio M/G of M to G is 2.10, and the polymerization degree (n) of the sodium alginate is 400-600.
Adding 0.8gAM/AMPS copolymer into clear water at a stirring rate of 600 revolutions per minute at room temperature (20+/-5 ℃), and stirring for 60 minutes to obtain a polymer solution; adding 0.8g of catechol type phenolic resin cross-linking agent while stirring, and stirring for 10 minutes to obtain a glue solution; then 0.5g of dilution-resistant auxiliary sodium alginate is slowly added while stirring, stirring is carried out for 30 minutes until the dilution-resistant auxiliary sodium alginate is fully dissolved, a gel solution which is resistant to dilution of formation water is obtained, and then the gel solution is mixed with simulated formation water with the mineralization degree of 200,000mg/L (wherein sodium ion 73282mg/L, calcium ion 6000mg/L and magnesium ion 1000 mg/L) according to the volume ratio of 2:3, placing the gel solution containing the dilution-resistant auxiliary agent into a pressure-resistant bottle, forming a viscoelastic protective film once the gel solution is contacted with calcium ions, and forming gel in a baking oven at 150 ℃ for 4 hours to obtain the gel plugging agent A3 for resisting formation water dilution of the high-temperature high-salt fracture-cavity type oil-gas reservoir, wherein the gel plugging agent A3 is obviously layered and not mutually dissolved with simulated formation water all the time before and after the gel formation of the system, the stable period can reach 90 days after the gel formation, the strength retention rate is 91%, and the core plugging rate is 91%.
Fig. 4 is an SEM photograph of the micro network structure of the diluted gel blocking agent prepared in example 3 according to the present invention after gelling, as can be seen from fig. 4: the microcosmic appearance of the gel containing the dilution-resistant additive has a fine three-dimensional network structure; the dilution-resistant auxiliary agent can obviously encrypt the density of the three-dimensional network structure, which is more beneficial to the stability of the gel.
Example 4
The dilution-resistant gel composition comprises: the AM/AMPS copolymer with the relative molecular weight of 800 ten thousand and the hydrolysis degree of 8 percent has the mass fraction of 0.8 percent; hydroquinone phenolic resin and catechol type phenolic resin cross-linking agent, the mass fraction is 0.4% respectively; the mass fraction of the dilution-resistant auxiliary sodium alginate is 0.4%; the balance of liquid water, the mass fraction of which is 98.0%, and the sum of the mass fractions of the components is 100%.
In the sodium alginate as diluent aid, the connection mode between G and M may be one or more of GG shown in the formula (a), MM shown in the formula (b) and GM shown in the formula (b), the molar ratio M/G of M to G is 2.10, and the polymerization degree (n) of the sodium alginate is 400-600.
Adding 0.8gAM/AMPS copolymer into clear water at a stirring rate of 600 revolutions per minute at room temperature (20+/-5 ℃), and stirring for 60 minutes to obtain a polymer solution; adding 0.4g of hydroquinone type phenolic resin and 0.4g of catechol type phenolic resin crosslinking agent while stirring, and stirring for 10 minutes to obtain a glue solution; then 0.4g of dilution-resistant auxiliary sodium alginate is slowly added while stirring, stirring is carried out for 30 minutes until the dilution-resistant auxiliary sodium alginate is fully dissolved, a gel solution which is resistant to dilution of formation water is obtained, and then the gel solution is mixed with simulated formation water with the mineralization degree of 200,000mg/L (wherein sodium ion 73282mg/L, calcium ion 6000mg/L and magnesium ion 1000 mg/L) according to the volume ratio of 3:7, placing the gel solution containing the dilution-resistant auxiliary agent into a pressure-resistant bottle, forming a viscoelastic protective film once the gel solution is contacted with calcium ions, and forming gel in a baking oven at 150 ℃ for 3 hours to obtain the gel plugging agent A4 for resisting formation water dilution of the high-temperature high-salt fracture-cavity type oil-gas reservoir, wherein the gel plugging agent A4 is obviously layered and not mutually dissolved with simulated formation water all the time before and after the gel formation of the system, the stable period can reach 90 days after the gel formation, the strength retention rate is 92%, and the core plugging rate is 93%.
Example 5
The dilution-resistant gel composition comprises: the AM/AMPS copolymer with the relative molecular weight of 600 ten thousand and the hydrolysis degree of 5 percent has the mass fraction of 1.2 percent; resorcinol type phenolic resin cross-linking agent, the mass fraction is 0.6%; the mass fraction of the dilution-resistant auxiliary sodium alginate is 0.4%; the balance of liquid water, the mass fraction of which is 97.9%, and the sum of the mass fractions of the components is 100%.
In the sodium alginate as diluent aid, the connection mode between G and M may be one or more of GG shown in the formula (a), MM shown in the formula (b) and GM shown in the formula (b), the molar ratio M/G of M to G is 1.95, and the polymerization degree (n) of the sodium alginate is 100-400.
Adding 1.2gAM/AMPS copolymer into clear water at a stirring rate of 600 revolutions per minute at room temperature (20+/-5 ℃), and stirring for 60 minutes to obtain a polymer solution; adding 0.6g resorcinol type phenolic resin cross-linking agent while stirring, and stirring for 10 minutes to obtain a glue solution; then 0.4g of dilution-resistant auxiliary sodium alginate is slowly added while stirring, stirring is carried out for 30 minutes until the dilution-resistant auxiliary sodium alginate is fully dissolved, a gel solution which is resistant to dilution of formation water is obtained, and then the gel solution is mixed with simulated formation water with the mineralization degree of 200,000mg/L (wherein sodium ion 73282mg/L, calcium ion 6000mg/L and magnesium ion 1000 mg/L) according to the volume ratio of 1: and 4, placing the gel solution containing the dilution-resistant auxiliary agent into a pressure-resistant bottle, forming a viscoelastic protective film once the gel solution is contacted with calcium ions, and forming gel in a baking oven at 120 ℃ for 2 hours to obtain the gel plugging agent A5 for resisting formation water dilution of the high-temperature high-salt fracture-cavity type oil-gas reservoir, wherein the gel plugging agent A5 is obviously layered and not mutually dissolved with simulated formation water all the time before and after the gel formation of the system, the stable period can reach 90 days after the gel formation, the strength retention rate is 89%, and the core plugging rate is 90%.
Example 6
The dilution-resistant gel composition comprises: the AM/AMPS copolymer with the relative molecular weight of 600 ten thousand and the hydrolysis degree of 5 percent has the mass fraction of 1.2 percent; the mass fraction of the phenol type phenolic resin cross-linking agent is 1.5%; the mass fraction of the dilution-resistant auxiliary sodium alginate is 0.8%; the balance of liquid water, the mass fraction of which is 96.5%, and the sum of the mass fractions of the components is 100%.
In the sodium alginate as diluent aid, the connection mode between G and M may be one or more of GG shown in the formula (a), MM shown in the formula (b) and GM shown in the formula (b), the molar ratio M/G of M to G is 1.95, and the polymerization degree (n) of the sodium alginate is 100-400.
Adding 1.2gAM/AMPS copolymer into clear water at a stirring rate of 600 revolutions per minute at room temperature (20+/-5 ℃), and stirring for 60 minutes to obtain a polymer solution; adding 1.5g of phenol type phenolic resin cross-linking agent while stirring, and stirring for 10 minutes to obtain a glue solution; then 0.8g of dilution-resistant auxiliary sodium alginate is slowly added while stirring, stirring is carried out for 30 minutes until the dilution-resistant auxiliary sodium alginate is fully dissolved, so that a gel solution which is resistant to dilution of formation water is obtained, a viscoelastic protective film is formed after the gel solution containing the dilution-resistant auxiliary is contacted with calcium ions, and then the gel solution is mixed with simulated formation water with the mineralization degree of 200,000mg/L (wherein sodium ions are 73282mg/L, calcium ions are 6000mg/L and magnesium ions are 1000 mg/L) according to the volume ratio of 1:1 is placed in a pressure-resistant bottle, and is glued in an oven at 110 ℃ for 10 hours, so that the gel plugging agent A6 which is resistant to formation water dilution of a high-temperature high-salt fracture-cavity type oil-gas reservoir is obtained, the gel plugging agent A is obviously layered and not mutually dissolved with simulated formation water all the time before and after the glue formation of the system, the stable period can reach 90 days after the glue formation, the strength retention rate is 96%, and the core plugging rate is 94%.
Comparative example 1
A dilution-resistant gel blocking agent was prepared in the same manner as in example 4 except that: and no dilution-resistant auxiliary agent is added, so that the gel plugging agent B1 is obtained, the gel formation is carried out for 13 hours, the stability period is only 6 days, the strength retention rate is 7%, and the core plugging rate is 29%.
Fig. 5 is a schematic macroscopic view of the ordinary jelly prepared in comparative example 1 diluted with formation water, as can be seen from fig. 5: the first plot in fig. 5 shows that the gel-forming fluid is significantly incapable of formation water separation, and the gel-forming fluid is completely diluted by the formation water; the second sheet in fig. 5, after high temperature aging, fails to gel due to dilution; the third in fig. 5, dilution does not allow gelling; it is shown that the gel-forming liquid is completely diluted by the formation water, so that the gel cannot be formed.
In addition, fig. 7 is a graph showing the comparison of the elastic modulus and the viscoelastic modulus of the dilution-resistant jelly (example 4), the undiluted ordinary jelly (comparative example 1) and the ordinary jelly diluted with formation water, wherein G' -elastic modulus, G "-viscous modulus; as can be seen from fig. 7: the addition of the dilution-resistant auxiliary sodium alginate can not only effectively isolate the water body and prevent the water body from diluting the gel-forming liquid, but also increase the strength of the gel; in addition, the gel containing the dilution-resistant auxiliary agent has higher viscoelasticity modulus.
Comparative example 2
A dilution-resistant gel blocking agent was prepared in the same manner as in example 5 except that: and no dilution-resistant auxiliary agent is added, so that the gel plugging agent B2 is obtained, the gel is formed for 10 hours, the stability period is only 4 days, the strength retention rate is 11%, and the core plugging rate is 34%.
Fig. 6 is an SEM photograph of the micro network structure of the general jelly prepared in comparative example 2, as can be seen from fig. 6: the three-dimensional network structure of the gel without the diluent resistance auxiliary agent is sparse and not stable enough; the gel without diluent resistance auxiliary agent has loose three-dimensional network structure, which is unfavorable for locking water molecules and has insufficient stability.
Comparative example 3
A dilution-resistant gel blocking agent was prepared in the same manner as in example 6 except that: and no dilution-resistant auxiliary agent is added, so that the gel plugging agent B3 is obtained, the gel formation is carried out for 11 hours, the stability period is only 14 days, the strength retention rate is 8%, and the core plugging rate is 31%.
Comparative example 4
A dilution-resistant gel blocking agent was prepared in the same manner as in example 5 except that: the diluent-resistant auxiliary sodium alginate is replaced by the auxiliary sodium silicate to obtain the gel plugging agent B4, and the gel plugging agent B4 can effectively isolate simulated formation water, but the obtained gel-forming liquid cannot form gel.
Comparative example 5
A dilution-resistant gel blocking agent was prepared in the same manner as in example 6 except that: the diluent-resistant auxiliary sodium alginate is replaced by the auxiliary sodium carbonate to obtain the gel plugging agent B5, and the gel plugging agent B5 can effectively isolate simulated formation water, so that the obtained gel-forming liquid can not be formed into gel.
Comparative example 6
A dilution-resistant gel blocking agent was prepared in the same manner as in example 4 except that: the content of each component in the diluent-resistant gel composition is different, in particular:
the dilution-resistant gel composition comprises: the AM/AMPS copolymer with the relative molecular weight of 800 ten thousand and the hydrolysis degree of 8 percent has the mass fraction of 0.5 percent; hydroquinone phenolic resin and catechol type phenolic resin cross-linking agent, the mass fraction is 0.3% respectively; the mass fraction of the dilution-resistant auxiliary sodium alginate is 0.2%; the balance of liquid water, the mass fraction of which is 99.0%, and the sum of the mass fractions of the components is 100%.
As a result, a stable waterproof film cannot be formed, the waterproof layer is extremely easy to damage, and the gel forming liquid is still diluted by stratum water, so that the gel forming strength is very low.
In addition, the properties of the dilution-resistant gel blocking agents prepared in examples 1 to 6 and comparative examples 1 to 6 are shown in Table 1.
TABLE 1
In conclusion, the dilution-resistant gel plugging agent prepared by the invention can be quickly crosslinked with calcium and magnesium ions in formation water to form a compact viscoelastic protective film, so that the gel plugging agent is prevented from being diluted by the formation water and not being formed into gel or being poor in gel forming effect. Meanwhile, the gel forming time of the dilution-resistant gel plugging agent is controllable, and after the gel is formed, the strength is high, so that the water outlet of the seam hole can be controlled.
In comparative examples 1 to 3, since no dilution-resistant auxiliary agent was added, the gel-forming liquid was diluted by the formation water under disturbance of the flow of the formation water, and calcium and magnesium ions in the formation water reacted with each other due to the mutual dissolution and crosslinking sites, which was not conducive to the stabilization of the gel-forming, so that the gel-forming effect was poor.
In comparative examples 4 to 5, the gel-forming liquid reacts with calcium and magnesium ions to form a dense water-resistant layer due to the addition of a dilution-resistant auxiliary agent like sodium alginate, so that the water body can be effectively isolated, but the gel-forming liquid cannot form gel under the environment due to the influence of silicate/carbonate on the pH of the water body, so that the effect is poor.
In comparative example 6, the gel-forming effect was poor because the gel-forming liquid was diluted with the formation water due to the insufficient strength of the formed water-resistant layer due to insufficient content of the dilution-resistant auxiliary agent of sodium alginate.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. The dilution-resistant gel composition is characterized by comprising polyacrylamide, a phenolic resin cross-linking agent and a dilution-resistant auxiliary agent which are stored independently, wherein the dilution-resistant auxiliary agent is sodium alginate, and the sodium alginate is a polymer obtained by polymerizing a G section shown in a formula (1) and/or an M section shown in a formula (2):
wherein the polymerization degree of the sodium alginate is 80-750.
2. The composition of claim 1, wherein the molar ratio of M to G content is 0.6-2.22;
preferably, the molar ratio of M to G content is 1.88-2.1.
3. Composition according to claim 1 or 2, wherein the polyacrylamide is present in an amount of 0.5-1% by weight, based on the total weight of the dilution-resistant gel composition; the phenolic resin cross-linking agent accounts for 0.3 to 1.5 weight percent, the dilution-resistant auxiliary agent accounts for 0.2 to 0.8 weight percent, and the balance is liquid water;
preferably, the polyacrylamide is present in an amount of 0.5 to 1 wt%, based on the total weight of the dilution-resistant gel composition; the phenolic resin cross-linking agent accounts for 0.3 to 1.2 weight percent, the dilution-resistant auxiliary agent accounts for 0.2 to 0.8 weight percent, and the balance is liquid water;
more preferably, the polyacrylamide is present in an amount of 0.6 to 0.8 wt%, based on the total weight of the dilution-resistant gel composition; the phenolic resin cross-linking agent accounts for 0.6-0.8 wt%, the diluting-resistant auxiliary accounts for 0.4-0.6 wt% and the balance is liquid water.
4. A composition according to claim 1 or 3, wherein the polyacrylamide is an AM/AMPS copolymer;
and/or, based on the total weight of the AM/AMPS copolymer, the content of AM is 60-70 wt%, and the content of AMPS is 30-40 wt%;
and/or the AM/AMPS copolymer has a relative molecular weight of 500 to 1000 tens of thousands;
and/or the AM/AMPS copolymer has a degree of hydrolysis of 3 to 10%.
5. A composition according to claim 1 or 3, wherein the phenolic resin cross-linking agent is selected from one or more of a phenol type phenolic resin, a hydroquinone type phenolic resin, a catechol type phenolic resin and a resorcinol type phenolic resin.
6. A method of preparing a dilution-resistant gel plugging agent using the composition of any one of claims 1-5, comprising:
(1) Under the stirring condition, contacting liquid preparation water with polyacrylamide for first mixing to obtain a polymer solution;
(2) Contacting the polymer solution with a phenolic resin cross-linking agent for second mixing to obtain a glue solution;
(3) And (3) contacting the gel forming liquid with a dilution-resistant auxiliary agent for third mixing, and then performing gel forming treatment to obtain the dilution-resistant gel plugging agent.
7. The method of claim 6, wherein the liquid water is clear water and/or hypersalinity oilfield reinjection water.
8. The production method according to claim 7, wherein the stirring condition comprises: stirring at a stirring rate of 400-600 rpm;
and/or, the conditions of the first mixing include: the temperature is 20+/-5 ℃ and the time is 60-90min;
and/or, the conditions of the second mixing include: the temperature is 20+/-5 ℃ and the time is 10-20min;
and/or, the conditions of the third mixing include: the temperature is 20+ -5deg.C, and the time is 10-30min.
9. The production method according to claim 7, wherein in the step (3), the conditions of the gelling treatment include: in a pressure-resistant bottle, forming glue for 2-48h at the temperature of 110-150 ℃; preferably, the glue is formed for 2 to 12 hours at the temperature of 130 to 150 ℃.
10. A dilution-resistant gel plugging agent prepared by the preparation method of any one of claims 6 to 9.
11. An application of the dilution-resistant gel plugging agent of claim 10 in high-temperature high-salt fracture-cavity type hydrocarbon reservoirs.
12. The use of claim 11, wherein the conditions of the high temperature high salt fracture-cave reservoir comprise: the temperature is 110-150 ℃, the mineralization degree is 20-30 ten thousand mg/L, and the content of calcium and magnesium ions is 5000-15000 mg/L.
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