CN111087992A - Gel plugging agent composition and preparation method and application thereof - Google Patents
Gel plugging agent composition and preparation method and application thereof Download PDFInfo
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- CN111087992A CN111087992A CN201811237056.3A CN201811237056A CN111087992A CN 111087992 A CN111087992 A CN 111087992A CN 201811237056 A CN201811237056 A CN 201811237056A CN 111087992 A CN111087992 A CN 111087992A
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- 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
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP 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
Abstract
The invention relates to the technical field of oil exploitation, and provides a gel plugging agent composition, and a preparation method and application thereof. The gel blocking agent composition comprises: the water-soluble melamine formaldehyde resin paint comprises an acrylamide polymer, a water-soluble melamine formaldehyde resin, an oxygen scavenger, a urea compound and water, wherein the urea compound has a structure shown in a formula (1) and/or a formula (2), and R is1And R2Each independently selected from hydrogen or 2-propynyl; r3、R4Each independently selected from oxygen, sulfur or imino. The gel plugging agent composition provided by the invention is simple in preparation method, can effectively plug a steam channeling channel for a long time (30-90 days) at a higher temperature (150-.
Description
Technical Field
The invention relates to the technical field of oil exploitation, in particular to a gel plugging agent composition and a preparation method and application thereof.
Background
Steam stimulation is the main mode of heavy oil development, is considered to be a conventional, economical and effective method and is widely used by heavy oil fields. Along with the progress of the multiple times of huff and puff stages, the water invasion and steam channeling are serious, the water content of the oil well is greatly increased, different degrees of influence are brought to the thermal recovery of the heavy oil reservoir, and the thermal recovery effect is deteriorated. The high water content of an oil well in the thermal recovery process of a heavy oil reservoir becomes a main problem influencing the thermal recovery effect. At present, one of the most effective methods for solving the problem is to use a gel plugging agent to block a steam channeling channel and improve the utilization degree and recovery ratio of thick oil.
The existing gel plugging agent is compounded and injected into a stratum by taking a polyacrylamide aqueous solution as a thickening agent and phenolic resin as a crosslinking agent, and is crosslinked in situ at the deep part of the stratum to form gel for plugging water. However, the technology is only suitable for the environment below 120 ℃, and cannot stably block water for a long time in a high-temperature steam huff and puff environment, because the system is unstable at high temperature, the working fluid enters the stratum and is excessively crosslinked in the early stage to be dehydrated, and the working fluid is thermally degraded in the later stage. Therefore, for the water shutoff operation of the steam huff and puff of the heavy oil reservoir, the construction success rate is not high, the oil increasing effective period is short, and the oil increasing effect is limited. The gel plugging agent which is effective for a long time at a higher temperature and in a longer time range is a current technical difficulty and needs to be broken through urgently.
Disclosure of Invention
Aiming at the problem that the existing gel plugging agent can not be effectively applied to higher temperature and realize longer-time water plugging, the invention aims to provide a novel gel plugging agent composition, and a preparation method and application thereof. The gel plugging agent composition can effectively plug a steam channeling channel in a higher temperature environment and a longer time range, and realizes the high-efficiency development of a heavy oil reservoir.
According to a first aspect of the present invention, there is provided a gel plug composition comprising: acrylamide polymer, water-soluble melamine formaldehyde resin, deoxidant, urea compound and water, wherein the urea compound has a structure shown in a formula (1) and/or a formula (2),
wherein R is1And R2Each independently selected from hydrogen or 2-propynyl; r3And R4Each independently selected from oxygen, sulfur or imino;
the content of the urea compound is 0.1-2 wt% based on the total weight of the gel plugging agent composition.
According to a second aspect of the present invention, there is provided a method of preparing the gel plug composition, the method comprising:
(1) dissolving acrylamide polymer in water to obtain polymer water solution;
(2) and adding water-soluble melamine formaldehyde resin, urea compounds and an oxygen scavenger into the polymer aqueous solution, and stirring until the water-soluble melamine formaldehyde resin, the urea compounds and the oxygen scavenger are dissolved to obtain the gel plugging agent composition.
According to a third aspect of the invention, the invention provides the use of the gel plug composition in heavy oil steam stimulation thermal recovery.
The gel plugging agent composition provided by the invention is simple in preparation method, can effectively plug a steam channeling channel for a long time (30-90 days) at a higher temperature (150-. Compared with the existing gel plugging agent, the gel plugging agent has higher plugging rate and longer plugging time, and can be suitable for large pore path plugging operation in heavy oil steam huff and puff thermal recovery operation.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a gel plug composition comprising: acrylamide polymer, water-soluble melamine formaldehyde resin, deoxidant, urea compound and water.
In the present invention, the urea compound has a structure represented by formula (1) and/or formula (2),
wherein R is1And R2Each independently selected from hydrogen or 2-propynyl, R3And R4Each independently selected from oxygen, sulfur or imino.
Preferably, the urea compound is one or more of urea, 2-propynyl urea, biuret, thiobiuret and 2-imino-4-thiobiuret.
More preferably, the urea-based compound is urea. Urea has a smaller molecular weight and volume compared to its dimer (e.g. biuret) and its substituted compounds (e.g. 2-propynyl urea), has less steric hindrance and better mobility when reacted in the gel blocking agent system, and is able to compete better to some extent with polyacrylamide-based polymers during the condensation reaction with water-soluble melamine formaldehyde resins.
In the present invention, the urea compound is contained in an amount of 0.1 to 2% by weight, preferably 0.2 to 1% by weight, based on the total weight of the gel blocking agent composition.
In the present invention, the kind and amount of the acrylamide-based polymer may be selected with reference to the prior art, and the acrylamide-based polymer may be synthesized according to the prior art or commercially available. For the present invention, preferably, the acrylamide-based polymer is one or more of partially hydrolyzed polyacrylamide, partially hydrolyzed methylene polyacrylamide, acrylamide/acrylic acid/AMPS sodium salt copolymer, acrylamide/acrylic acid/acrylonitrile sodium salt copolymer, and acrylamide/sodium acrylate/cationic monomer copolymer. Wherein the partially hydrolyzed polyacrylamide and the acrylamide/acrylic acid/AMPS sodium salt copolymer are available from Shandong Baumo et al.
Preferably, the viscosity average molecular weight of the acrylamide polymer is 800 to 3500 ten thousand, more preferably 1000 to 3000 ten thousand; the degree of hydrolysis of the acrylamide-based polymer is 8 to 35%, and more preferably 10 to 25%, respectively.
In the present invention, the degree of hydrolysis is measured by the method for measuring the degree of hydrolysis of partially hydrolyzed polyacrylamide according to the national standard GB/T12005.6-1989.
Preferably, the acrylamide-based polymer is contained in an amount of 0.1 to 2% by weight, more preferably 0.2 to 1% by weight, based on the total weight of the gel blocking agent composition.
In the present invention, the water-soluble melamine-formaldehyde resin is preferably obtained by polymerizing melamine/formaldehyde monomers in a molar ratio of 0.08 to 0.5 at a high temperature of pH 8 to 9. Typically, the water-soluble melamine formaldehyde resin is a colorless transparent liquid.
Preferably, the water-soluble melamine formaldehyde resin is present in an amount of from 0.1 to 2% by weight, more preferably from 0.2 to 1.4% by weight, based on the total weight of the gel blocking composition.
In the invention, the oxygen scavenger can reduce the oxidative degradation of the polymer in the system, and the type and the dosage of the oxygen scavenger can be selected according to the prior art. In the present invention, preferably, the oxygen scavenger is one or more of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium hydrosulfite and erythorbic acid.
Preferably, the oxygen scavenger is present in an amount of 0.05 to 1 wt%, based on the total weight of the gel plug composition.
In the present invention, water is used as a solvent and a reaction medium in the gel blocking agent composition system, and the present invention has no particular limitation on the selection thereof. The degree of mineralization of water is usually less than 500 mg, and can be natural water, such as rivers, lakes, atmospheric water, seawater, groundwater and the like, and artificial water, such as tap water, distilled water, deionized water or heavy water. In the present invention, the water is contained in an amount of 93 to 99.65% by weight, preferably 95.6 to 99.35% by weight, based on the total weight of the gel blocking agent composition.
In the invention, the content of each component in the gel plugging agent composition is calculated by the feeding amount.
The gel plugging agent composition is particularly suitable for plugging a steam channeling pipeline in the process of steam stimulation and thermal heavy oil recovery. Specifically, hydroxyl in the water-soluble melamine formaldehyde resin and an amide group of the acrylamide polymer can undergo an in-situ dehydration condensation reaction at high temperature, so that the acrylamide polymer is crosslinked, the system gradually forms gel along with the reaction, and a steam channeling pipeline is blocked in the process of steam huff and puff thermal recovery of thick oil. In addition to the above reaction, the urea compound contained in the system can also undergo a dehydration condensation reaction with the water-soluble melamine formaldehyde resin, and the possible reaction mechanism is as follows (taking the urea compound represented by formula (1) as an example):
therefore, the urea compound competes with the condensation reaction of the acrylamide polymer and the water-soluble melamine formaldehyde resin, so that the crosslinking speed of the acrylamide polymer is reduced, and the crosslinking reaction of the acrylamide polymer can be continuously carried out for a long time. According to the determination, the gel plugging agent composition can be gelled in one day at the high temperature of 150 ℃ to form plugging.
In addition, the addition of the urea compound reduces the density of crosslinking active points in the system, inhibits the dehydration phenomenon caused by excessive crosslinking of the acrylamide polymer, can adjust the distance between the crosslinking active points, slows down the degree of coverage of the crosslinking active points, improves the crosslinking efficiency, increases the strength of gel formed by the crosslinking system, and enables the formed gel system to be stable at a higher temperature.
According to the invention, the gel plugging agent composition contains an s-triazine ring structure, and the introduction of the aromatic heterocyclic structure greatly enhances the conjugation effect in a crosslinking system, so that the C-N bond in the system is firmer, and the high temperature resistance of the formed gel is improved.
According to a second aspect of the present invention, there is provided a method of preparing a gel plug composition according to the first aspect of the present invention, the method comprising:
(1) dissolving acrylamide polymer in water to obtain polymer water solution;
(2) and adding water-soluble melamine formaldehyde resin, urea compounds and a deoxidant into the polymer aqueous solution, and stirring until the water-soluble melamine formaldehyde resin, the urea compounds and the deoxidant are completely dissolved to obtain the gel plugging agent composition.
According to a third aspect of the invention, the invention provides the use of the gel plug composition in heavy oil steam stimulation thermal recovery. As described above, the gel blocking agent composition of the present invention is particularly suitable for blocking a steam blow-by pipe in a process of steam stimulation thermal thickened oil recovery.
According to the invention, the application may comprise: injecting the gel plugging agent composition into the stratum so that the gel plugging agent composition is crosslinked in situ in the stratum to form gel.
Under the environment of steam stimulation thermal recovery of thick oil, the gel plugging agent formed by the gel plugging agent composition can be kept for 30-90 days at the temperature of 150-180 ℃.
The present invention will be described in detail below by way of examples.
Example 1
This example illustrates the gel plug composition and method of making the same according to the present invention.
At room temperature, 20 g of partially hydrolyzed polyacrylamide (viscosity average molecular weight 800 ten thousand, degree of hydrolysis 8%) is dissolved in 1L of water, and the mixture is stirred at 500 rpm until the partially hydrolyzed polyacrylamide is completely dissolved; then 20 g of water-soluble melamine formaldehyde resin (molar ratio of melamine/formaldehyde is 0.3), 10 g of urea and 10 g of sodium thiosulfate are added in sequence and stirred until the components are completely dissolved, thus obtaining the gel blocking agent composition.
The gel blocking agent composition was tested for blocking performance (blocking rate) at a temperature of 150 ℃ for 60 days of standing time, and the results are shown in Table 1.
The Darcy principle is applied to the test of the plugging performance, and the prior art can be specifically referred to. The method for testing the plugging performance comprises the following steps:
filling a simulation core (the diameter d of the core is 25mm, the length L of the core is 200mm), injecting water into the core at the flow rate of 2 ml/min (injection rate Q) after vacuumizing, and measuring the permeability (k) before core plugging0) (ii) a And then injecting 1.0-1.5PV of the gel plugging agent composition into the core model, plugging two ends of the core by using a plug, placing the core into a constant temperature box at 150 ℃ for standing for 60 days, injecting water again until the pressure is stable, recording the reading on a pressure gauge to obtain injection pressure difference, and calculating the permeability (k') after the core is plugged, thereby calculating the plugging rate.
For convenience of description and explanation, k will be given0And k' are collectively called as core permeability k, and the calculation formula is as follows:
wherein Q is the injection rate, mL · s-1(ii) a μ is the fluid viscosity, mPa · s; a is the cross section area of the sand-filled model in cm2,A=πd2(ii)/4; Δ P is the injection pressure difference, 10-1MPa;k,μm2。
example 2
This example illustrates the gel plug composition and method of making the same according to the present invention.
At room temperature, 4 g of partially hydrolyzed polyacrylamide (viscosity average molecular weight 2000 ten thousand, hydrolysis degree 22%) was dissolved in 1L of water, and stirred at 500 rpm until the partially hydrolyzed polyacrylamide was completely dissolved; 8 g of water-soluble melamine-formaldehyde resin (molar ratio of melamine/formaldehyde is 0.3), 3 g of urea and 4 g of sodium hydrosulfite are added in sequence and stirred until all the components are dissolved, so as to obtain the gel plugging agent composition of the embodiment.
The gel plugging agent composition was tested for plugging rates at 150 ℃/60 days, 150 ℃/75 days, 150 ℃/90 days, 165 ℃/60 days, 180 ℃/60 days, the same test method as in example 1, and the test results are shown in tables 1 and 2.
Example 3
This example illustrates the gel plug composition and method of making the same according to the present invention.
At room temperature, 1 g of acrylamide/acrylic acid/AMPS sodium salt copolymer (viscosity average molecular weight is 3500 ten thousand, hydrolysis degree is 35%) is dissolved in 1L of water, and the mixture is stirred at 500 revolutions per minute until the acrylamide/acrylic acid/AMPS sodium salt copolymer is completely dissolved; then, 1 g of water-soluble melamine formaldehyde resin (molar ratio of melamine/formaldehyde is 0.3), 1.5 g of urea and 0.5 g of sodium bisulfite were added in this order and stirred until all of them were dissolved, to obtain a gel blocking agent composition.
The gel blocking agent composition was tested for blocking rate at 150 ℃ for 60 days, the test method was the same as in example 1, and the test results are shown in table 1.
Example 4
This example illustrates the gel plug composition and method of making the same according to the present invention.
At room temperature, 4 g of partially hydrolyzed polyacrylamide (viscosity average molecular weight 2000 ten thousand, hydrolysis degree 22%) was dissolved in 1L of water, and stirred at 500 rpm until the partially hydrolyzed polyacrylamide was completely dissolved; 8 g of water-soluble melamine-formaldehyde resin (molar ratio of melamine/formaldehyde is 0.3), 5 g of biuret, and 4 g of sodium hydrosulfite were added in this order and stirred until all were dissolved to obtain the gel plugging agent composition of the present example.
The gel blocking agent composition was tested for blocking rate at 150 ℃ for 60 days, the test method was the same as in example 1, and the test results are shown in table 1.
Example 5
This example illustrates the gel plug composition and method of making the same according to the present invention.
At room temperature, 20 g of partially hydrolyzed polyacrylamide (viscosity average molecular weight 800 ten thousand, degree of hydrolysis 8%) is dissolved in 1L of water, and the mixture is stirred at 500 rpm until the partially hydrolyzed polyacrylamide is completely dissolved; then 20 g of water-soluble melamine formaldehyde resin (molar ratio of melamine/formaldehyde is 0.3), 20 g of urea and 10 g of sodium thiosulfate are added in sequence and stirred until the components are completely dissolved, so as to obtain the gel blocking agent composition.
The gel blocking agent composition was tested for blocking rate at 150 ℃ for 60 days, the test method was the same as in example 1, and the test results are shown in table 1.
Comparative example 1
At room temperature, 4 g of partially hydrolyzed polyacrylamide (viscosity average molecular weight 2000 ten thousand, hydrolysis degree 22%) was dissolved in 1L of water, and stirred at 500 rpm until the partially hydrolyzed polyacrylamide was completely dissolved; 8 g of a water-soluble melamine-formaldehyde resin (melamine/formaldehyde molar ratio of 0.3) and 4 g of sodium hydrosulfite were added in this order and stirred until completely dissolved to obtain a gel blocking agent composition of a comparative example.
The gel blocking agent composition was tested for blocking rate at 150 ℃ for 60 days, the test method was the same as in example 1, and the test results are shown in table 1.
And (3) a plugging rate test result:
TABLE 1
Note: table 1 shows the results of the test of the plugging rate (150 ℃ C./60 days) of examples and comparative examples.
TABLE 2
Note: table 2 shows the results of the plugging rate tests of example 2 under different test conditions.
As can be seen from Table 1, the gel blocking agent compositions of examples 1 to 5 had higher blocking rates than the gel blocking agent composition containing no urea compound under the condition of standing at 150 ℃ for 60 days, as compared with the gel blocking agent composition containing no urea compound of comparative example 1. As can be seen from Table 2, the gel plugging agent composition of the present invention can stably exist for at least 90 days at 150 ℃, and maintain a high plugging rate; can be stably stored for at least 60 days when the temperature is increased to 180 ℃. Therefore, the gel plugging agent composition is applied to heavy oil steam huff-puff thermal recovery, can effectively plug a steam channeling channel at a high temperature (150-.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A gel blocking composition, wherein said gel blocking composition comprises: acrylamide polymer, water-soluble melamine formaldehyde resin, deoxidant, urea compound and water, wherein the urea compound has a structure shown in a formula (1) and/or a formula (2),
wherein R is1And R2Each independently selected from hydrogen or 2-propynyl, R3And R4Each independently selected from oxygen, sulfur or imino;
the content of the urea compound is 0.1-2 wt% based on the total weight of the gel plugging agent composition.
2. The gel plug composition according to claim 1, wherein the urea-based compound is present in an amount of 0.2 to 1 wt.%, based on the total weight of the gel plug composition.
3. The gel plug composition according to claim 1 or 2, wherein the urea based compound is one or more of urea, 2-propynyl urea, biuret, thiobiuret and 2-imino-4-thiobiuret, preferably urea.
4. The gel plug composition according to claim 1 or 2, wherein the acrylamide-based polymer is contained in an amount of 0.1 to 2 wt%, the water-soluble melamine formaldehyde resin is contained in an amount of 0.1 to 2 wt%, and the oxygen scavenger is contained in an amount of 0.05 to 1 wt%, based on the total weight of the gel plug composition.
5. The gel plug composition according to claim 1 or 4, wherein the water soluble melamine formaldehyde resin is prepared from melamine, formaldehyde in a ratio of 0.08-0.5: 1, is polymerized.
6. The gel plug composition of claim 1 or 4, wherein the acrylamide-based polymer is one or more of partially hydrolyzed polyacrylamide, partially hydrolyzed methylene polyacrylamide, acrylamide/acrylic acid/AMPS sodium salt copolymer, acrylamide/acrylic acid/acrylonitrile sodium salt copolymer, and acrylamide/sodium acrylate/cationic monomer copolymer.
7. The gel plug composition according to claim 6, wherein the acrylamide-based polymer has a viscosity average molecular weight of 800 to 3500 ten thousand; the hydrolysis degree of the acrylamide polymer is 8-35%.
8. The gel plug composition of claim 1 or 4, wherein the oxygen scavenger is one or more of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium hydrosulfite, and erythorbic acid.
9. A method of preparing the gel plug composition of any one of claims 1 to 8, wherein the method comprises:
(1) dissolving the acrylamide polymer in water to obtain a polymer aqueous solution;
(2) and adding water-soluble melamine formaldehyde resin, urea compounds and an oxygen scavenger into the polymer aqueous solution, and stirring until the water-soluble melamine formaldehyde resin, the urea compounds and the oxygen scavenger are dissolved to obtain the gel plugging agent composition.
10. Use of the gel plug composition of any one of claims 1 to 8 in heavy oil steam stimulation thermal recovery.
11. The application of claim 10, wherein the application comprises: injecting the gel plugging agent composition into the stratum so that the gel plugging agent composition is crosslinked in situ in the stratum to form gel.
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