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CN105504158A - Intelligent gel particles capable of being crosslinked again under stratum condition and preparation method and application of intelligent gel particles - Google Patents

Intelligent gel particles capable of being crosslinked again under stratum condition and preparation method and application of intelligent gel particles Download PDF

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CN105504158A
CN105504158A CN201610099775.8A CN201610099775A CN105504158A CN 105504158 A CN105504158 A CN 105504158A CN 201610099775 A CN201610099775 A CN 201610099775A CN 105504158 A CN105504158 A CN 105504158A
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gel particles
water
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CN105504158B (en
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白宝君
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    • 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
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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    • C08K5/00—Use of organic ingredients
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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Abstract

The invention relates to intelligent gel particles capable of being crosslinked again under a stratum condition and a preparation method and application of the intelligent gel particles. The intelligent gel particles are prepared by acrylamide, anionic monomer, cationic monomer, N, N-vinyl pyrrolidone, pH regulator, initiator, cross-linking agent I, cross-linking agent II, stabilizer, nano particle material and water. The intelligent gel particles are applicable to oil field profile control and water plugging, filtration loss control and/or plugging during a drilling process and drilling and completion plugging, and the gel particles can be crosslinked again under the stratum condition after entering a stratum to form high-strength gel so as to achieve effective plugging.

Description

Intelligent gel particles capable of being re-crosslinked under stratum condition and preparation method and application thereof
Technical Field
The invention relates to intelligent gel particles capable of being crosslinked again among particles under stratum conditions, a preparation method and application thereof, and belongs to the technical field of oilfield chemistry.
Background
The heterogeneity of the reservoir is the most important reason for the low oil recovery and the water production from the well, and the large amount of washing of the injected water aggravates the heterogeneity of the reservoir. As many oilfield waterfloods are developed into periods of high water cut, very high water cut, water production has been a serious problem. The large amount of water discharged from the oil well causes serious corrosion, increases the load of equipment, pollutes the environment and the like, and even is forced to shut down the well. Treating the formation with a gel can reduce the permeability of the high permeability layer and has been considered an economically effective method of reducing reservoir heterogeneity. Generally, an underground crosslinking system is adopted to achieve the purpose, namely, a polymer, a crosslinking agent, other chemical agents and the like are prepared into a gelling agent, and after the gelling agent is injected underground, the gelling agent preferentially enters a high-permeability zone of a stratum to form gel with certain strength at the temperature of the stratum, so that the stratum is effectively blocked. Some uncertainty in the gel formation process, however, seriously affects the effectiveness of the gel treatment: the polymer is easy to be sheared and degraded when passing through a pump, a well hole, a stratum porous medium and the like, so that the gelation time and the gel property are influenced; the gelling agent is a mixture, when the gelling agent passes through a stratum porous medium, the interaction of various components and the pore surfaces of rocks is different, and the advancing speed in the stratum is different, so that the chromatographic separation phenomenon is generated, and the composition of the gelling agent in a near-wellbore area and the deep part of the stratum is different, so that the performance of the gelling agent is influenced; due to the presence of a large amount of groundwater, the gelling agent is diluted underground, the concentration of the gelling agent changes, and in addition, if the salinity of the groundwater is high, particularly if the content of calcium and magnesium ions is high, the performance of the gel is seriously affected, and even the gel cannot be formed by crosslinking.
To overcome the disadvantages of underground crosslinked gels, many oil fields began to be profile-driven with pre-crosslinked gel particles since the end of the 90 s. Pre-crosslinked particles means that a gel is formed under surface conditions and then formed into gel particles, and the particles are injected into the ground. The system is thus no longer gelled underground, thereby avoiding much of the uncertainty of conventional underground cross-linked systems in forming gels underground. The particle size of the gel particles is generally in the micrometer to millimeter level, the gel particles with different particle sizes can be selected according to the porosity and permeability of the stratum, and the particle technology is successfully used for reducing the effluent of old oil fields and improving the recovery ratio of crude oil. For example, CN1251856A discloses a gel particle comprising unsaturated alkenyl amide, unsaturated alkenyl carboxylic acid, cross-linking agent, persulfate and water, wherein the components are dissolved by stirring, subjected to polymerization cross-linking reaction to prepare gel, dried, crushed and sieved to obtain gel particles with adjustable particle size; the gel particles are used for profile control and profile flooding of a water injection well. The performance of the pre-crosslinked gel particles can be controlled in the reaction process, the particle size can be controlled according to production conditions, large channels can be blocked in a near-wellbore region, the deep part of an oil layer has the effect of diverting the liquid flow, the swept volume of injected water is enlarged, and the recovery ratio is improved. CN103184040A provides a formation pre-crosslinked gel plugging agent, which comprises the following components: 2-5% of main polymerization agent acrylamide and 0.2-1.0% of cross-linking agent urea-formaldehyde resin, wherein formaldehyde accounts for 2-4% and urea accounts for 0.2-1.0%; 0.01 to 0.2 percent of retarder; 0.01 to 0.1 percent of reinforcing agent; 0.001 to 0.1 percent of initiator; the balance of water; the retarder is aluminum trichloride; the reinforcing agent is N-N methylene bisacrylamide; the initiator is sodium persulfate; the base fluid of the plugging agent has the characteristics of similar viscosity to water, easiness in pumping, high curing strength and the like, can meet the water plugging requirement of an oil reservoir, particularly the water plugging requirement of a low-permeability oil field, and is low in cost and high in plugging strength. CN104119472A discloses an active pre-crosslinked gel particle and a preparation method thereof, comprising acrylamide, an anionic monomer, 3-alkyl-4-styrene fatty alcohol polyoxyethylene ether sodium sulfonate, N-methylene bisacrylamide, tetramethylethylenediamine and deionized water. The active pre-crosslinked gel particles are prepared by the steps of initiating polymerization crosslinking of acrylamide and anionic monomers by an initiator, and finally cutting, granulating, drying, crushing and other physical means. The active pre-crosslinked gel particles have interfacial activity and emulsibility due to the addition of 3-alkyl-4-styrene fatty alcohol polyoxyethylene ether sodium sulfonate, and can be used as a profile control agent, with a plugging rate as high as 72.56%.
Although the existing pre-crosslinked gel particle profile control and flooding technology has good effects on reducing the effluent of old oil fields and improving the crude oil recovery rate, some technical defects and application limitations are shown along with the popularization and application of gel particles, for example, millimeter-sized particles can reduce high-permeability strips, cracks, water flooding and CO2The permeability of large pores and slots generated by flooding, but the high-permeability slots cannot be effectively blocked due to the limitation of the particle size and the blocking characteristics of the particles; if the expansion ratio of the particles is too large, the mechanical strength of the particles is reduced, the particles are easy to break, and the precipitation effect of the particles is influenced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the intelligent gel particles capable of being re-crosslinked, wherein after the gel particles enter a stratum, the gel particles can be re-crosslinked under the stratum condition to form rubber-like integral gel, so that more effective plugging effect is realized.
The invention also provides a preparation method and application of the intelligent gel particles capable of being re-crosslinked.
The technical scheme of the invention is as follows:
the re-crosslinkable intelligent gel particle is prepared from the following components in percentage by mass:
the pH value regulator is proper, the pH value of the solution is regulated to 5.0-8.5,
the anionic monomer is one of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid or divinyl sulfonic acid;
the cationic monomer is one of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, octadecyl dimethyl allyl ammonium chloride, dimethylaminoethyl methacrylate or diethyl diallyl ammonium chloride;
the cross-linking agent I is one of or the combination of N, N-methylene bisacrylamide, diallylamine, trialkylamine, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, chromium acetate and aluminum citrate;
the cross-linking agent II is a compound of the following cross-linking agents: one or the combination of N, N-methylene bisacrylamide, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, formaldehyde, glutaraldehyde, phenolic resin, urea resin, polyethyleneimine, chromium acetate, chromium malonate, aluminum citrate, aluminum chloride, zirconium oxychloride, zirconium acetate, zirconium tetrachloride, N-butyl titanate or isopropyl titanate; alternatively, the crosslinking agent II is one of the above crosslinking agent compounds which is coated, and is referred to as a coated crosslinking agent.
The initiator is one or a combination of azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutyronitrile dimethyl ester, ammonium persulfate, potassium persulfate, sodium sulfite, potassium sulfite, benzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, dicumyl hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide and methyl ethyl ketone peroxide.
The stabilizer is ethylene diamine tetraacetic acid disodium salt (EDTA), sodium citrate, sodium lactate or resorcinol.
The nano-particle material is nano bentonite, nano silicon oxide, nano titanium oxide, nano aluminum oxide, nano calcium carbonate, a carbon nano tube or graphene. Preferably, the nanoparticle material has a particle size of 2nm to 500 nm.
The pH value regulator is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethanolamine, ethylenediamine or triethylamine. The addition amount is to adjust the pH value of the solution to 5.0-8.5.
The crosslinking agent coated in the crosslinking agent II can be coated according to the prior art, and only the crosslinking agent with a coating layer is formed. The preparation method of the coated cross-linking agent provided by the invention comprises the following steps:
dissolving the cross-linking agent compound in water to saturation, adding 15-20% of acrylamide by mass and 0.03-0.0.5% of initiator by mass based on the mass of the cross-linking agent compound solution, wherein the initiator is K2S2O8With NaHSO3Mixing according to the mass ratio of 2:1, heating to 48-52 ℃, performing polymerization reaction for 3-4 hours to form rubber blocks, drying, crushing and sieving to obtain the coated cross-linking agent.
The polymerization reaction described above occurs at the surface of the crosslinker compound, and the resulting polymer covers the surface of the core "crosslinker compound".
According to the present invention, preferably, the balance of water is deionized water.
According to the present invention, preferably, the intelligent crosslinked gel particles capable of being re-crosslinked are prepared from the following components by mass percent:
the pH value regulator is proper, and the pH value of the solution is regulated to 5.0-8.5;
according to the present invention, further preferred is a re-crosslinkable intelligent crosslinked gel particle, which comprises one of the following components by mass:
a. 30% of acrylamide, 10% of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 5% of methacryloyloxyethyl trimethyl ammonium chloride, 3% of N, N-vinyl pyrrolidone, 0.15% of azodiisobutyronitrile, a proper amount of sodium hydroxide, 0.1% of N, N-methylene bisacrylamide, 0.1% of N-butyl titanate, 0.1% of EDTA, 3.5% of nano bentonite and the balance of water.
b. 20% of acrylamide, 15% of Acrylic Acid (AA), 8% of dimethylaminoethyl methacrylate, 3% of N, N-vinyl pyrrolidone, 0.3% of benzoyl peroxide, 0.1% of polyethylene glycol diacrylate, a proper amount of sodium hydroxide, 0.2% of coated zirconium oxychloride, 0.3% of sodium citrate, 5% of nano silicon dioxide and the balance of water.
c. 30% of acrylamide, 15% of divinyl sulfonic acid, 8% of methacryloyloxyethyl trimethyl ammonium chloride, 3% of N, N-vinyl pyrrolidone, 0.2% of azodiisobutyronitrile, 0.1% of aluminum citrate, a proper amount of sodium hydroxide, 0.1% of isopropyl titanate, 0.3% of sodium citrate, 4% of nano titanium oxide and the balance of water.
d. 20% of acrylamide, 15% of Acrylic Acid (AA), 6% of dimethyl diallyl ammonium chloride, 5% of N, N-vinyl pyrrolidone, 0.3% of benzoyl peroxide, 0.1% of diethylene glycol diacrylate, a proper amount of triethanolamine, 0.1% of isopropyl titanate, 0.1% of coated aluminum chloride, 0.3% of sodium lactate, 3.5% of nano calcium oxide and the balance of water.
The re-crosslinkable intelligent gel particles are nano-scale, micron-scale or millimeter-scale particles prepared from monomers, crosslinking agents and additives, and the particle size is determined according to application requirements. The preferred particle size of the present invention is from 50nm to 5 mm.
According to the invention, the preparation method of the intelligent gel particles capable of being re-crosslinked comprises the following steps:
introducing nitrogen into water for at least 30min, adding a nano-particle material according to a formula, ultrasonically dispersing for 30-50min by using an ultrasonic cleaner (300W) at normal temperature, adding acrylamide, an anionic monomer, a cationic monomer and N, N-vinyl pyrrolidone, stirring and dissolving completely, adjusting the pH value of the solution (the pH value is 5.0-8.5, preferably 7.0-8.5) by using a pH value regulator, then sequentially adding a stabilizer, an initiator, a cross-linking agent I and a cross-linking agent II, stirring to form a uniform solution, standing and polymerizing for 3-12h at the temperature of 5-80 ℃ to obtain colloid, drying at the temperature of 40-80 ℃, and crushing to obtain the nano-particle material.
According to the invention, the application of the intelligent gel particles capable of being crosslinked is used for profile control and water shutoff, profile control and flooding, fluid loss control in an oil field and/or plugging in a drilling process and well completion.
The application method of the intelligent gel particles capable of being re-crosslinked according to the invention comprises the following steps:
preparing the re-crosslinkable intelligent gel particles into a suspension by using water, so that the mass percentage content of the gel particles is 0.01-10.0%, and pumping the suspension into a stratum; under the action of stratum conditions, re-crosslinking is generated among the intelligent gel particles capable of being re-crosslinked to form gel with high strength, so that profile control and/or plugging of the stratum are realized.
The water for preparing the suspension can be clear water, injected water or reinjected water.
The intelligent gel particles capable of being crosslinked again generate re-crosslinking among the gel particles under the condition of a stratum to form integral gel with high strength, and the mechanism description is as follows: (1) during the preparation of the gel particles, the crosslinker I moderately crosslinks the monomeric polymer to form a gel. After the gel particles are injected into the stratum, the stratum water is absorbed to swell, part of the polymer is liberated, or hydrophilic groups in chain links of part of the polymer extend into the water. (2) The cross-linking agent II in the gel particles is free from the interior of the gel particles to the surface or free water under the action of the formation temperature; in the case of a coated crosslinker, the coating ruptures to release the crosslinker compound. (3) Crosslinker II plays two roles under formation conditions: firstly, gel particles are crosslinked again through chemical bonds, and free polymers or active groups of the polymers extending into water are crosslinked into a three-dimensional network structure to form integral gel with high strength; and secondly, the hydrophilic groups on the surfaces of the gel particles are crosslinked with the hydroxyl groups on the surfaces of the rocks, so that the gel particles are firmly combined with the surfaces of the rocks, and the scouring resistance is improved. These two actions combine to form an effective occlusion.
The invention has the technical characteristics and excellent effects that:
1. the intelligent gel particles capable of being crosslinked again form gel particles on the ground, can be crosslinked again underground, and are gathered among particles of large pore canals, cracks or crevices to form integral gel with high strength by crosslinking again at the formation temperature, so that the intelligent gel particles capable of being crosslinked again can generate more effective plugging effect on high permeable layers, crevices and the like.
2. After the intelligent gel particles capable of being crosslinked are injected into a stratum, if the intelligent gel particles enter a high-permeability layer, a large pore path and a crack, a large amount of particles are accumulated and crosslinked again to form high-strength integral gel, the large pore path, the crack or the fissure are intelligently blocked, and hydrophilic groups on the surfaces of the particles and hydroxyl on the surface of a rock are crosslinked under the action of a crosslinking agent, so that the particles and the surface of the rock are firmly combined, the scouring resistance is improved, the two effects are combined, effective blocking is formed, the blocking capability of the fissure is improved, and the flow resistance to water is increased; if the particles enter small pores and microcracks, the pores are occupied by single particles, and under the action of a cross-linking agent, groups on the surfaces of the particles and hydroxyl on the surfaces of rocks are cross-linked to form firm chemical bonds, so that the particles and the surfaces of the rocks form firm combination to form effective plugging.
3. The intelligent gel particles capable of being crosslinked again contain chemical agents required by crosslinking and re-crosslinking, are injected into and transported in a stratum in one form of solid particles, and all components are contained in the particles, so that the components are prevented from being separated and the content of the components is not changed in all stages of injection and plugging, the polymer is prevented from being degraded, and the phenomena of no gelling or low gelling quality caused by component separation and shear degradation due to chromatographic separation in the process of transporting a conventional underground crosslinked system in the stratum are avoided. The plugging capability to the slot is improved, the flow resistance to water is increased, and the effects of improving the heterogeneity of the stratum and increasing oil and water precipitation are obvious.
4. The intelligent gel particles capable of being crosslinked again in the stratum form a large gel with high strength, and the defect that the mechanical strength is reduced after the general pre-crosslinked gel particles absorb water and expand to a certain multiple in the stratum is overcome, so that the intelligent gel particles capable of being crosslinked again can be used for profile control and water shutoff of high-permeability layers and crevices.
5. In the component of the intelligent gel particles capable of being re-crosslinked, the nano particle material is preferably added, and because the nano particles have high surface energy and mechanical strength, the strength and rheological property of the system after being gelled are further enhanced.
6. The re-crosslinkable intelligent gel particles can contain AMPS, N-vinyl pyrrolidone and other monomers, and improve the temperature resistance and salt resistance of products.
7. The re-crosslinkable intelligent gel particles can be adjusted in particle size according to oil reservoir conditions, are in nanoscale, micron-scale or millimeter-scale, and have strong adaptability. It can also be used for profile control, deep liquid flow diversion, fluid loss control and well drilling and completion plugging.
Drawings
Fig. 1 is a re-crosslinkable smart gel particle prepared in example 1.
FIG. 2 is a graph of the overall gel formed after 5 days of treatment at 80 ℃ for the re-crosslinkable smart gel particles of example 1.
FIG. 3 is an electron micrograph of the overall gel formed after treatment of the re-crosslinkable smart gel particles of example 1 at 80 ℃ for 5 days.
Fig. 4 is a diagram of an experimental device for plugging ability. In the figure, 1, distilled water, 2, an injection pump, 3, an intermediate container, 4, a piston, 5, an expanded gel particle sample, 6, saline, 7, an injection pump, 8, a pressure gauge, 9, a hollow round tube, 10 and a production liquid.
Detailed Description
The present invention is described in detail below by way of specific embodiments. The invention is further illustrated, but is not to be construed as being limited, by the following examples. All percentages in the examples are by mass, unless otherwise specified, and all raw materials used are commercially available materials. The particle size of the nano-particle material is 2nm-500 nm.
The coated zirconium oxychloride, coated aluminum chloride used in the examples was prepared as follows:
zirconium oxychloride or aluminum chloride is dissolved in water to saturation, and 20% by mass of acrylamide and 0.0.5% by mass of K are added based on the total mass of the solution2S2O8With NaHSO3Heating the mixture according to the mass ratio of 2:1 to 50 ℃, polymerizing the mixture into rubber blocks after 4 hours, drying, crushing and sieving the rubber blocks to obtain the coated zirconium oxychloride or the coated aluminum chloride.
Example 1, a re-crosslinkable intelligent gel particle, the raw materials comprise the following components by mass percent:
30% of acrylamide, 10% of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 5% of methacryloyloxyethyl trimethyl ammonium chloride, 3% of N, N-vinyl pyrrolidone, 0.15% of azodiisobutyronitrile, a proper amount of sodium hydroxide, 0.1% of N, N-methylene diacryloyl, 0.1% of N-butyl titanate, 0.1% of EDTA, 3.5% of nano bentonite (500nm), and the balance of water.
The preparation method comprises the following steps:
introducing nitrogen into deionized water for 30min, then adding 3.5% of nano bentonite, ultrasonically dispersing for 30min by using an ultrasonic cleaner (300W) at normal temperature, adding 30% of acrylamide, 5% of methacryloyloxyethyl trimethyl ammonium chloride and 3% of N, N-vinyl pyrrolidone, stirring and dissolving completely, adjusting the pH value of the solution to 7.0-8.5 by using a 25% sodium hydroxide aqueous solution, then sequentially adding 0.1% of EDTA, 0.15% of azobisisobutyronitrile, 0.1% of N, N-methylene bisacrylamide, 0.1% of N-butyl titanate and 0.05% of aluminum citrate, stirring to form a uniform solution, standing and polymerizing for 10h at 50 ℃ to obtain a polymer colloid, drying at 60 ℃, crushing and sieving to obtain particles of 20 meshes, thus obtaining the intelligent gel particles capable of being crosslinked.
Example 2
As described in example 1, except that the mass percentage of nano-bentonite was 8%.
Example 3
As described in example 1, except that the mass percentage of nano-bentonite was 0%.
Example 4
As described in example 1, except that the mass percentage of N, N-methylenebisacrylamide was 0.05%.
Example 5, a re-crosslinkable intelligent gel particle, the raw materials comprise the following components by mass percent:
20% of acrylamide, 15% of Acrylic Acid (AA), 8% of dimethylaminoethyl methacrylate, 3% of N, N-vinyl pyrrolidone, 0.3% of benzoyl peroxide, 0.1% of polyethylene glycol diacrylate, a proper amount of sodium hydroxide, 0.2% of coated zirconium oxychloride, 0.3% of sodium citrate, 5% of nano silicon dioxide (50nm) and the balance of water.
The preparation is as described in example 1.
Example 6, a re-crosslinkable intelligent gel particle, the raw materials comprise the following components by mass percent:
30% of acrylamide, 15% of divinyl sulfonic acid, 8% of methacryloyloxyethyl trimethyl ammonium chloride, 3% of N, N-vinyl pyrrolidone, 0.2% of azodiisobutyronitrile, 0.1% of aluminum citrate, a proper amount of sodium hydroxide, 0.2% of isopropyl titanate, 0.3% of sodium citrate, 4% of nano titanium oxide (100nm) and the balance of water.
The preparation is as described in example 1.
Example 7, a re-crosslinkable intelligent gel particle, the raw materials composition mass percentage is as follows:
20% of acrylamide, 15% of Acrylic Acid (AA), 6% of dimethyl diallyl ammonium chloride, 5% of N, N-vinyl pyrrolidone, 0.3% of benzoyl peroxide, 0.1% of diethylene glycol diacrylate, a proper amount of triethanolamine, 0.1% of isopropyl titanate, 0.1% of coated aluminum chloride, 0.3% of sodium lactate, 3.5% of nano calcium oxide (200nm) and the balance of water.
The preparation is as described in example 1.
Example 8 Pre-crosslinked gel particles (comparative example)
The composition by mass percentage and preparation of the pre-crosslinked gel particles were as described in example 1, except that the mass percentage of the crosslinking agent II was 0 and the mass percentage of the nanoparticle material was 0.
Example 9 comparison of plugging Effect
1. Experimental apparatus: according to the prior art, as shown in FIG. 4;
2. particle samples for experiments: the smart gel particles were the particles prepared in examples 1-7, respectively, and the conventional pre-crosslinked gel particles were the particles prepared according to example 8.
3. The plugging test procedure was as follows:
1) a sample of 20g of the particles (to an accuracy of 0.01g) was weighed on an electronic balance and placed in a 1000mL flask.
2) 900mL of standard saline was measured with a measuring cylinder, added to the flask already containing the pellet sample, capped, and left at room temperature for 24h to swell the pellets.
3) The swollen soaked particles were sampled and filtered through a screen to remove the remaining free water.
4) The expanded particles with free water filtered off are placed in the intermediate container 3 of the core displacement device and the device is adjusted to seal it.
5) Injecting the swollen gel particles from the intermediate container 3 into the hollow round tube 9(1/4 inches in inner diameter) at a constant rate (0.0.05-1m/min, depending on the tube inner diameter) with a constant pressure constant rate pump until particles are produced and the injection pressure is balanced;
6) the hollow round tube 9 filled with the particles is taken down, and the two sides are sealed and put into a constant temperature box with set temperature until the particles are crosslinked again. The time for re-crosslinking can be judged from a reference sample (free water-swollen particles filtered) placed in a glass test tube or vial.
7) After the particles are completely cross-linked, the hollow round tube 9 injected with the particles is remounted to a rock core displacement device, and water is used for a displacement test.
8) And (3) injecting distilled water 1 in a constant pressure mode, and observing the extraction conditions of the gel and the injected water in the hollow circular tube 9. Firstly, injecting water at a lower pressure, for example, at a pressure of 5MPa, such as no gel or water extraction within 5 minutes, then increasing by 1-2MPa, and continuously observing the pressure and the output condition until the pressure is suddenly reduced or gel is produced, wherein the pressure at the moment is defined as breakthrough pressure, and the higher the breakthrough pressure is, the better the plugging effect is.
The breakthrough pressure of the re-crosslinkable smart gel particles of the present invention is significantly higher than that of conventional pre-crosslinked gel particles, and the comparative experimental results are shown in table 1.
TABLE 1 comparison of breakthrough pressures for pre-crosslinked gel particles and re-crosslinkable smart gel particles

Claims (10)

1. The intelligent crosslinking gel particle capable of being crosslinked again is characterized by being prepared from the following components in percentage by mass:
the pH value regulator is proper, the pH value of the solution is regulated to 5.0-8.5,
the balance of water.
The anionic monomer is one of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid or divinyl sulfonic acid;
the cationic monomer is one of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, octadecyl dimethyl allyl ammonium chloride, dimethylaminoethyl methacrylate or diethyl diallyl ammonium chloride;
the cross-linking agent I is one of or the combination of N, N-methylene bisacrylamide, diallylamine, trialkylamine, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, chromium acetate and aluminum citrate;
the cross-linking agent II is a compound of the following cross-linking agents: one or the combination of N, N-methylene bisacrylamide, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, formaldehyde, glutaraldehyde, phenolic resin, urea resin, polyethyleneimine, chromium acetate, chromium malonate, aluminum citrate, aluminum chloride, zirconium oxychloride, zirconium acetate, zirconium tetrachloride, N-butyl titanate or isopropyl titanate; alternatively, the crosslinking agent II is one of the above crosslinking agent compounds which is coated, and is referred to as a coated crosslinking agent.
2. The re-crosslinkable smart crosslinked gel particles of claim 1 wherein the initiator is one or a combination of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, ammonium persulfate, potassium persulfate, benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, dicumyl hydroperoxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide.
3. The re-crosslinkable smart crosslinked gel particles of claim 1 wherein the stabilizer is EDTA, sodium citrate, sodium lactate or resorcinol.
4. The re-crosslinkable smart crosslinked gel particles of claim 1 wherein the nanoparticle material is nano-bentonite, nano-silica, nano-titania, nano-alumina, nano-calcium carbonate, carbon nanotubes or graphene.
5. The re-crosslinkable smart crosslinked gel particles of claim 1 wherein the pH adjusting agent is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethanolamine, ethylenediamine or triethylamine.
6. The intelligent re-crosslinkable crosslinked gel particles according to claim 1, prepared from the following components in percent by mass:
the pH value regulator is proper, and the pH value of the solution is regulated to 5.0-8.5;
the balance of water.
7. The re-crosslinkable smart crosslinked gel particles of claim 1, wherein the mass percent composition is one of:
a. 30% of acrylamide, 10% of 2-acrylamido-2-methylpropanesulfonic acid, 5% of methacryloyloxyethyltrimethyl ammonium chloride, 3% of N, N-vinyl pyrrolidone, 0.15% of azobisisobutyronitrile, a proper amount of sodium hydroxide, 0.1% of N, N-methylene bisacrylamide, 0.1% of N-butyl titanate, 0.1% of EDTA, 3.5% of nano bentonite and the balance of water; or,
b. 20% of acrylamide, 15% of acrylic acid, 8% of dimethylaminoethyl methacrylate, 3% of N, N-vinyl pyrrolidone, 0.3% of benzoyl peroxide, 0.1% of polyethylene glycol diacrylate, a proper amount of sodium hydroxide, 0.2% of coated zirconium oxychloride, 0.3% of sodium citrate, 5% of nano silicon dioxide and the balance of water; or,
c. 30% of acrylamide, 15% of divinyl sulfonic acid, 8% of methacryloyloxyethyl trimethyl ammonium chloride, 3% of N, N-vinyl pyrrolidone, 0.2% of azodiisobutyronitrile, 0.1% of aluminum citrate, a proper amount of sodium hydroxide, 0.1% of isopropyl titanate, 0.3% of sodium citrate, 4% of nano titanium oxide and the balance of water; or,
d. 20% of acrylamide, 15% of Acrylic Acid (AA), 6% of dimethyl diallyl ammonium chloride, 5% of N, N-vinyl pyrrolidone, 0.3% of benzoyl peroxide, 0.1% of diethylene glycol diacrylate, a proper amount of triethanolamine, 0.1% of isopropyl titanate, 0.1% of coated aluminum chloride, 0.3% of sodium lactate, 3.5% of nano calcium oxide and the balance of water.
8. A method of preparing re-crosslinkable smart gel particles according to any one of claims 1 to 7, comprising the steps of:
introducing nitrogen into water for at least 30min, adding a nano-particle material according to a formula, ultrasonically dispersing for 30-50min at normal temperature by using an ultrasonic cleaner, adding acrylamide, an anionic monomer, a cationic monomer and N, N-vinyl pyrrolidone, stirring and dissolving completely, adjusting the pH value of the solution by using a pH value regulator, then sequentially adding a stabilizer, an initiator, a cross-linking agent I and a cross-linking agent II, stirring to form a uniform solution, standing and polymerizing for 3-12h at 5-80 ℃ to obtain a colloid, drying at 40-80 ℃, and crushing to obtain the nano-particle material; preferably, the re-crosslinkable smart gel particles have a particle size of the order of nanometers, micrometers, or millimeters.
9. Use of the re-crosslinkable smart gel particles of any one of claims 1-7 for profile control water shutoff, profile control, fluid loss control in oil fields and/or for lost circulation and lost circulation in drilling.
10. Use of the intelligent re-crosslinkable gel particles according to claim 9, characterized in that the method of use is as follows:
preparing the intelligent gel particles capable of being re-crosslinked into suspension by water, wherein the mass percentage of the gel particles is 0.01-10.0%, and pumping the suspension into a stratum; under the action of stratum conditions, re-crosslinking is generated among the intelligent gel particles capable of being re-crosslinked to form high-strength gel, so that profile control and/or plugging of the stratum are realized.
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CN106010485A (en) * 2016-05-23 2016-10-12 中国石油集团渤海钻探工程有限公司 Self-cementing leaking stoppage agent and leaking stoppage method
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6569968B1 (en) * 1999-08-19 2003-05-27 Kurita Water Industries Ltd. Polymer of a water-soluble radical-polymerizable monomer, process for producing the polymer and flocculant comprising the polymer
CN101270173A (en) * 2007-11-27 2008-09-24 中国科学院长春应用化学研究所 High gel strength, salt-tolerant zwitterionic nanocomposite hydrogel and preparation method thereof
CN101759838A (en) * 2009-12-30 2010-06-30 中国石油大学(华东) Preparation method of profile control and oil displacement system of polyacrylamide nanometer microsphere with low interfacial tension
CN102399345A (en) * 2010-09-14 2012-04-04 中国科学院理化技术研究所 Preparation method of emulsion deep regulating and displacing agent containing core-shell structure gel microspheres and emulsion deep regulating and displacing agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6569968B1 (en) * 1999-08-19 2003-05-27 Kurita Water Industries Ltd. Polymer of a water-soluble radical-polymerizable monomer, process for producing the polymer and flocculant comprising the polymer
CN101270173A (en) * 2007-11-27 2008-09-24 中国科学院长春应用化学研究所 High gel strength, salt-tolerant zwitterionic nanocomposite hydrogel and preparation method thereof
CN101759838A (en) * 2009-12-30 2010-06-30 中国石油大学(华东) Preparation method of profile control and oil displacement system of polyacrylamide nanometer microsphere with low interfacial tension
CN102399345A (en) * 2010-09-14 2012-04-04 中国科学院理化技术研究所 Preparation method of emulsion deep regulating and displacing agent containing core-shell structure gel microspheres and emulsion deep regulating and displacing agent

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