CN117736710B - Plugging agent capable of crosslinking into gel and absorbing water and expanding in water, preparation and application thereof - Google Patents
Plugging agent capable of crosslinking into gel and absorbing water and expanding in water, preparation and application thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000004132 cross linking Methods 0.000 title description 9
- 239000002245 particle Substances 0.000 claims abstract description 93
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 42
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 42
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 23
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 18
- 235000019198 oils Nutrition 0.000 claims description 18
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 18
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 18
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 17
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- 239000002283 diesel fuel Substances 0.000 claims description 7
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
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Abstract
The invention belongs to the field of oilfield chemistry and plugging compositions, and particularly relates to a plugging agent which is crosslinked into glue when meeting water and swells when absorbing water, and preparation and application thereof. The plugging agent which is crosslinked into glue when meeting water and swells when absorbing water consists of polymer particles, urea and an oil phase dispersion medium; the polymer particles comprise anionic polymer particles and cationic polymer particles; the polymer particles are prepared from the following components in percentage by mass: urea: oil phase dispersion medium=1:0.1-0.3:1-2. The plugging agent disclosed by the invention can be crosslinked into glue when meeting water, so that the difficult problem of retention in a fracture hole can be effectively solved, and the difficult problem of difficult complete filling of the fracture hole can be effectively solved when the plugging agent swells when absorbing water.
Description
Technical Field
The invention belongs to the field of oilfield chemistry and plugging compositions, and particularly relates to a plugging agent which is crosslinked into glue when meeting water and swells when absorbing water, and preparation and application thereof.
Background
Along with the expansion of exploration and development to deep ultra-deep, unconventional, low-grade and other resource fields, the drilling engineering faces increasingly severe geological conditions, and the problem of malignant lost circulation is prominent, so that the method has become one of the important technical problems for restricting the quality improvement and efficiency improvement of the drilling engineering.
In addition, along with the long-term water injection development of the oil and gas field, a large amount of large-pore-canal water layers appear after long-term water injection scouring, so that the oil layer is extremely easy to flood, and the large-pore-canal water layers need to be effectively plugged.
The gel is gradually applied to solve malignant leakage and blocking a water layer (CN 115160998A) due to good viscoelasticity and deformation self-adaptation capability, but is difficult to effectively stay in a large karst cave and a large crack before a gel system is crosslinked, is easy to dilute and carry under the impact of stratum water flow, and is difficult to fully fill a fracture tunnel channel after the gel system is crosslinked into gel. For the problem of difficult retention, the flow state is generally regulated by a flow-type regulator, and the gel is expanded to fill the gap by adding expanded graphite (CN 112980407B) or a gas-generating expanding agent (CN 116023914B), but the problem of difficult regulation exists.
Disclosure of Invention
In view of the above problems, the invention provides a plugging agent which is crosslinked into glue when meeting water and swells after absorbing water, and preparation and application thereof, wherein the plugging agent can effectively solve the difficult problem of retention in a fracture hole when meeting water and the difficult problem of completely filling the fracture hole when swelling after absorbing water.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A plugging agent which is crosslinked into gel when meeting water and swells when absorbing water comprises polymer particles, urea and an oil phase dispersion medium; the polymer particles comprise anionic polymer particles and cationic polymer particles; the polymer particles are prepared from the following components in percentage by mass: urea: oil phase dispersion medium=1:0.1-0.3:1-2.
Anionic polymer particles in mass ratio: cationic polymer particles = 1:2-2:1.
The oil phase dispersion medium is diesel oil or biodiesel or corn oil or soybean oil or castor oil or rapeseed oil.
The preparation method of the plugging agent which is crosslinked into glue when meeting water and swells when absorbing water comprises the following steps:
and (3) mixing and stirring the polymer particles and urea uniformly, crushing the mixture to 150-300 meshes, and stirring and mixing the mixture with an oil phase dispersion medium uniformly to obtain the plugging agent which is crosslinked into glue when meeting water and swells when absorbing water.
More specifically, the method comprises the steps of,
Process for the preparation of anionic polymer particles: preparing anionic polymer particles by a solution polymerization method; the anionic polymer synthesis reaction system takes Acrylamide (AM), 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate (SSS) and Acrylic Acid (AA) as synthesis monomers, and the mixing ratio is 1:0.15-0.3:0.05-0.1:0.05-0.1; n, N '-Methylene Bisacrylamide (MBA) is taken as a cross-linking agent, and the addition amount of the N, N' -Methylene Bisacrylamide (MBA) is 3-4% of the total mass of the monomers; ammonium persulfate is taken as an initiator, and the addition amount is 1-3% of the total mass of the monomer; water is 2-3 times of the mass of the monomer; the reaction temperature is 50-80 ℃, the reaction time is 4-6 hours, and the gel block is dried and crushed after the reaction is finished, so that the anionic polymer particles are obtained.
The preparation method of the cationic polymer particles comprises the following steps: preparing cationic polymer particles by a solution polymerization method; the cationic polymer synthesis reaction system takes Acrylamide (AM), methacryloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) as synthesis monomers, and the mixing ratio is 1:0.2-0.4:0.05-0.1; n, N '-Methylene Bisacrylamide (MBA) is taken as a cross-linking agent, and the addition amount of the N, N' -Methylene Bisacrylamide (MBA) is 3-4% of the total mass of the monomers; ammonium persulfate is taken as an initiator, and the addition amount is 1-3% of the total mass of the monomer; water is 2-3 times of the mass of the monomer; the reaction temperature is 50-80 ℃, the reaction time is 4-6 hours, and the gel blocks are dried and crushed after the reaction is finished, so that the cationic polymer particles are obtained.
The dosage and proportion of various monomers in the invention are determined by a large number of experiments, so that not only the defects of low crosslinking density and insufficient gel forming strength, but also the defects of high crosslinking density, severe aggregation after gel forming, poor expansion effect and weak blocking capability are avoided. In the prior art, although the plugging agent is prepared by adopting the same monomer as the part of the plugging agent, the plugging agent is a pre-crosslinked gel plugging agent, the pre-crosslinking mechanism is delayed expansion, the water absorption expansion rate is slow (the expansion multiple of 0.5h is 3-7 times), and the property of the plugging agent in the process of rapidly crosslinking into gel and expanding when meeting water is completely opposite to that of the plugging agent.
Regarding the oil phase dispersion medium, the inventors found that if the oil used contained waxy and asphaltene, the system could not be gelled, and thus diesel oil was primarily selected, while considering how the oil field would be made without the diesel oil, and considering transportation safety, vegetable oils were decided to be used, but there are many kinds of vegetable oils, and the palm oil having a freezing point higher than 20 ℃ was also destroyed to gel, thereby excluding the lowest priced palm oil, and finally biodiesel or corn oil or soybean oil or castor oil or rapeseed oil was selected.
The plugging agent can be used for plugging a malignant leakage layer of a well drilling shaft or plugging a large-pore water layer.
The plugging agent which is crosslinked into glue when meeting water and swells when absorbing water has the following characteristics: (1) The surfaces of the anionic polymer particles and the cationic polymer particles respectively have a large number of short molecular chains carrying negative charges and positive charges; (2) After contacting with water, the dispersion medium is quickly replaced with water, and the anionic polymer particles and the cationic polymer particles are mutually attracted and crosslinked into gel by positive and negative charge molecular chains in the water, so that the crosslinking speed is high, and the gel forming strength is high; while the anionic polymer particles and the cationic polymer particles swell upon absorption of water; (3) The addition of urea can prevent aggregation among particles with the same electrical property through hydrogen bonds, reduce the number of hydrogen bonds among molecular chains, obviously reduce the phenomenon of agglomeration, and promote crosslinking to be possibly attracted into gel through positive and negative charges. The oil phase dispersion medium can lead the dispersion of the anionic polymer particles and the cationic polymer particles to be more uniform, and the combined action of the urea and the oil phase dispersion medium effectively solves the problem that the anionic polymer particles and the cationic polymer particles form a fish-eye structure after being contacted with water, and the urea and the oil phase dispersion medium provide guarantee for uniform crosslinking and gel formation; (4) In order to prevent the plugging agent from contacting with the water in the pumping pipe column in the pumping process, a certain volume of isolating liquid (such as diesel oil) needs to be pumped before and after the plugging agent section to serve as a slug isolated from the water, the plugging agent can be prevented from contacting with the water by means of isolating liquid isolation due to the limitation of the space in the pipe column, the plugging agent enters into a stratum after being pumped, the space in the stratum is large, and the plugging agent is easy to contact with the stratum water.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular forms also are intended to include the plural forms unless the context clearly indicates otherwise, and furthermore, it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, and/or combinations thereof.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
The plugging agent which is crosslinked into glue when meeting water and swells when absorbing water is prepared by the following components and the method:
Anionic polymer particles: acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate (SSS) and Acrylic Acid (AA) are used as synthetic monomers, the mass ratio is 1:0.15:0.05:0.05, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 3% of the total mass of the monomers; the addition amount of ammonium persulfate is 1% of the total mass of the monomers; water 3 times the mass of the monomer; the reaction temperature is 50 ℃, and the materials are dried and crushed after 4 hours of reaction.
Cationic polymer particles: acrylamide (AM), methacryloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) are used as synthetic monomers, the mass ratio is 1:0.2:0.05, N' -methylene bisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the double-dispersion reverse-phase suspension polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 4% of the total mass of the monomers; the addition amount of ammonium persulfate is 3% of the total mass of the monomers; water is 2 times of the mass of the monomer; the reaction temperature is 80 ℃, and the materials are dried and crushed after the reaction for 6 hours.
The mass ratio of the anionic polymer particles to the cationic polymer particles is 1:2, the addition amount of urea is 10% of the total mass of the anionic polymer particles and the cationic polymer particles, and the mixture is uniformly mixed and crushed to 150 meshes; the oil phase dispersion medium is diesel oil, the addition amount is 100% of the total mass of the anionic polymer particles and the cationic polymer particles, and the product A is marked.
Example 2
The plugging agent which is crosslinked into glue when meeting water and swells when absorbing water is prepared by the following components and the method:
Anionic polymer particles: acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate (SSS) and Acrylic Acid (AA) are used as synthetic monomers, the mass ratio is 1:0.3:0.1:0.1, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 4% of the total mass of the monomers; the addition amount of ammonium persulfate is 1.5% of the total mass of the monomers; water is 2 times of the mass of the monomer; the reaction temperature is 55 ℃, and the materials are dried and crushed after 5 hours of reaction.
Cationic polymer particles: acrylamide (AM), methacryloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) are used as synthetic monomers, the mass ratio is 1:0.4:0.1, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 3% of the total mass of the monomers; the addition amount of ammonium persulfate is 2% of the total mass of the monomers; water 3 times the mass of the monomer; the reaction temperature is 70 ℃, and the materials are dried and crushed after 5 hours of reaction.
The mass ratio of the anionic polymer particles to the cationic polymer particles is 2:1, the addition amount of urea is 20% of the total mass of the anionic polymer particles and the cationic polymer particles, and the mixture is uniformly mixed and crushed to 200 meshes; the oil phase dispersion medium is corn oil, the addition amount is 150% of the total mass of the anionic polymer particles and the cationic polymer particles, and the product B is marked.
Example 3
The plugging agent which is crosslinked into glue when meeting water and swells when absorbing water is prepared by the following components and the method:
Anionic polymer particles: acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate (SSS) and Acrylic Acid (AA) are used as synthetic monomers, the mass ratio is 1:0.2:0.07:0.06, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 3.5% of the total mass of the monomers; the addition amount of ammonium persulfate is 2% of the total mass of the monomers; water 3 times the mass of the monomer; the reaction temperature is 60 ℃, and the materials are dried and crushed after 4 hours of reaction.
Cationic polymer particles: acrylamide (AM), methacryloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) are used as synthetic monomers, the mixing ratio is 1:0.3:0.06, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 3.5% of the total mass of the monomers; the addition amount of ammonium persulfate is 1% of the total mass of the monomers; water is 2 times of the mass of the monomer; the reaction temperature is 60 ℃, and the materials are dried and crushed after 4 hours of reaction.
The mass ratio of the anionic polymer particles to the cationic polymer particles is 1:1, the addition amount of urea is 30% of the total mass of the anionic polymer particles and the cationic polymer particles, and the mixture is crushed to 250 meshes after uniform mixing; the castor oil addition was 200% of the total mass of anionic and cationic polymer particles, noted as product C.
Example 4
The plugging agent which is crosslinked into glue when meeting water and swells when absorbing water is prepared by the following components and the method:
Anionic polymer particles: acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate (SSS) and Acrylic Acid (AA) are used as synthetic monomers, the mixing ratio is 1:0.25:0.08:0.08, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 3% of the total mass of the monomers; the addition amount of ammonium persulfate is 2.5% of the total mass of the monomers; water is 2 times of the mass of the monomer; the reaction temperature is 65 ℃, and the materials are dried and crushed after 6 hours of reaction.
Cationic polymer particles: acrylamide (AM), methacryloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) are used as synthetic monomers, the mixing ratio is 1:0.3:0.08, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 3% of the total mass of the monomers; the addition amount of ammonium persulfate is 2% of the total mass of the monomers; water 3 times the mass of the monomer; the reaction temperature is 50 ℃, and the materials are dried and crushed after 4 hours of reaction.
The mass ratio of the anionic polymer particles to the cationic polymer particles is 1:1, the addition amount of urea is 20% of the total mass of the anionic polymer particles and the cationic polymer particles, and the mixture is uniformly mixed and crushed to 200 meshes; rapeseed oil was added in an amount of 150% of the total mass of the anionic polymer particles and the cationic polymer particles, designated as product D.
Example 5
The plugging agent which is crosslinked into glue when meeting water and swells when absorbing water is prepared by the following components and the method:
anionic polymer particles: acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate (SSS) and Acrylic Acid (AA) are used as synthetic monomers, the mixing ratio is 1:0.3:0.06:0.08, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 3.5% of the total mass of the monomers; the addition amount of ammonium persulfate is 3% of the total mass of the monomers; water 3 times the mass of the monomer; the reaction temperature is 70 ℃, and the materials are dried and crushed after 5 hours of reaction.
Cationic polymer particles: acrylamide (AM), methacryloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) are used as synthetic monomers, the mixing ratio is 1:0.3:0.08, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 4% of the total mass of the monomers; the addition amount of ammonium persulfate is 3% of the total mass of the monomers; water is 2 times of the mass of the monomer; the reaction temperature is 55 ℃, and the materials are dried and crushed after 5 hours of reaction.
The mass ratio of the anionic polymer particles to the cationic polymer particles is 2:1, the addition amount of urea is 10% of the total mass of the anionic polymer particles and the cationic polymer particles, and the mixture is uniformly mixed and crushed to 200 meshes; the soybean oil was added in an amount of 150% of the total mass of the anionic polymer particles and the cationic polymer particles, designated as product E.
Comparative example 1
The plugging agent which is crosslinked into glue when meeting water and swells when absorbing water is prepared by the following components and the method:
Anionic polymer particles: acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate (SSS) and Acrylic Acid (AA) are used as synthetic monomers, the mass ratio is 1:0.15:0.05:0.05, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 3% of the total mass of the monomers; the addition amount of ammonium persulfate is 1% of the total mass of the monomers; water 3 times the mass of the monomer; the reaction temperature is 50 ℃, and the materials are dried and crushed after 4 hours of reaction.
Cationic polymer particles: acrylamide (AM), methacryloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) are used as synthetic monomers, the mass ratio is 1:0.2:0.05, N' -methylene bisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the double-dispersion reverse-phase suspension polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 4% of the total mass of the monomers; the addition amount of ammonium persulfate is 3% of the total mass of the monomers; water is 2 times of the mass of the monomer; the reaction temperature is 80 ℃, and the materials are dried and crushed after the reaction for 6 hours.
The mass ratio of the anionic polymer particles to the cationic polymer particles is 1:2, the adding amount of urea is 0, and the mixture is crushed to 150 meshes after uniform mixing; the oil phase dispersion medium is diesel oil, the addition amount is 100% of the total mass of the anionic polymer particles and the cationic polymer particles, and the product is marked as a product F.
Comparative example 2
Anionic polymer particles: acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate (SSS) and Acrylic Acid (AA) are used as synthetic monomers, the mass ratio is 1:0.15:0.05:0.05, N' -methylenebisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the aqueous solution polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 3% of the total mass of the monomers; the addition amount of ammonium persulfate is 1% of the total mass of the monomers; water 3 times the mass of the monomer; the reaction temperature is 50 ℃, and the materials are dried and crushed after 4 hours of reaction.
Cationic polymer particles: acrylamide (AM), methacryloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) are used as synthetic monomers, the mass ratio is 1:0.2:0.05, N' -methylene bisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and the double-dispersion reverse-phase suspension polymerization method is adopted to prepare the catalyst; wherein: n, N' -Methylenebisacrylamide (MBA) is added in an amount of 4% of the total mass of the monomers; the addition amount of ammonium persulfate is 3% of the total mass of the monomers; water is 2 times of the mass of the monomer; the reaction temperature is 80 ℃, and the materials are dried and crushed after the reaction for 6 hours.
The mass ratio of the anionic polymer particles to the cationic polymer particles is 1:2, the addition amount of urea is 10% of the total mass of the anionic polymer particles and the cationic polymer particles, and the mixture is uniformly mixed and crushed to 150 meshes; the addition amount of the oil phase dispersion medium was 0 and was designated as product G.
Experimental example 1
And (3) testing the gel forming time and the volume expansion times: adding 50ml of plugging agent into a beaker with the volume of 2000ml, then pouring 1000ml of water, recording the gel formation time, namely the gel formation time, and recording the volume V of the gel, wherein the expansion multiple ρ is calculated according to the following formula:
ρ=（V-50）/50
And (3) carrying out bearing capacity test: and testing leakage conditions when different pressures are applied by adopting a high-temperature high-pressure static plugging instrument, and evaluating the pressure-bearing plugging capability of the plugging agent on the cracks. The steel fracture module is used for simulating a fracture leakage stratum, the fracture module is a single wedge-shaped fracture, the entrance fracture width is 3mm respectively, the exit fracture width is 1mm respectively, the fracture length is 200mm, and the fracture height is 50mm. 2000ml of water is added into the kettle body of the high-temperature high-pressure static plugging instrument at first, then 100ml of plugging agent is injected, after 10min waiting, the test temperature is room temperature, the initial pressure of 1MPa is set, the pressure of the plugging instrument is slowly increased until the corresponding pressure is the maximum plugging bearing strength when the leakage occurs.
The results are shown in table 1 below:
。
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. The plugging agent which is crosslinked into glue when meeting water and swells when absorbing water is characterized by comprising polymer particles, urea and an oil phase dispersion medium; the polymer particles comprise anionic polymer particles and cationic polymer particles; the polymer particles are prepared from the following components in percentage by mass: urea: oil phase dispersion medium=1:0.1-0.3:1-2;
the anionic polymer particles are prepared by adopting acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, sodium p-styrenesulfonate and acrylic acid as synthetic monomers, N, N' -methylenebisacrylamide as a cross-linking agent and ammonium persulfate as an initiator through aqueous solution polymerization;
The cationic polymer particles are prepared by adopting acrylamide, methacryloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride as synthetic monomers, N, N' -methylene bisacrylamide as a cross-linking agent and ammonium persulfate as an initiator through aqueous solution polymerization;
Anionic polymer particles in mass ratio: cationic polymer particles = 1:2-2:1.
2. The water-crosslinkable and water-swellable plugging agent according to claim 1, wherein the oil-phase dispersion medium is diesel oil or biodiesel or corn oil or soybean oil or castor oil or rapeseed oil.
3. The method for preparing the plugging agent which is crosslinked into gel when meeting water and swells when absorbing water according to any one of claims 1-2, which is characterized in that polymer particles and urea are mixed and stirred uniformly, crushed to 150-300 meshes, and stirred and mixed uniformly with an oil phase dispersion medium, thus obtaining the plugging agent which is crosslinked into gel when meeting water and swells when absorbing water.
4. The method for preparing the plugging agent which is crosslinked into gel and swells in water when meeting water according to claim 3, wherein the anionic polymer particles are prepared by adopting an aqueous solution polymerization method: acrylamide: 2-acrylamido-2-methylpropanesulfonic acid: sodium p-styrenesulfonate: acrylic acid=1:0.15-0.3:0.05-0.1:0.05-0.1; the addition of the cross-linking agent is 3-4% of the total mass of the monomers, the addition of the initiator is 1-3% of the total mass of the monomers, the reaction temperature is 50-80 ℃, the water is 2-3 times of the total mass of the monomers, and the reaction time is 4-6 hours.
5. The method for preparing the plugging agent which is crosslinked into gel and swells in water when meeting water according to claim 3, wherein the cationic polymer particles are prepared by adopting an aqueous solution polymerization method: acrylamide: methacryloyloxyethyl trimethylammonium chloride: dimethyl diallyl ammonium chloride=1:0.2-0.4:0.05-0.1; the addition of the cross-linking agent is 3-4% of the total mass of the monomer, the addition of the initiator is 1-3% of the total mass of the monomer, the addition of water is 2-3 times of the total mass of the monomer, the reaction temperature is 50-80 ℃, and the reaction time is 4-6 hours.
6. Use of a water-crosslinkable and water-swellable plugging agent according to any one of claims 1-2 for plugging a malignant thief zone of a well bore or for plugging a large pore water layer.
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