CN114790264A - Spherical gel particles and preparation method and application thereof - Google Patents
Spherical gel particles and preparation method and application thereof Download PDFInfo
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- CN114790264A CN114790264A CN202210519213.XA CN202210519213A CN114790264A CN 114790264 A CN114790264 A CN 114790264A CN 202210519213 A CN202210519213 A CN 202210519213A CN 114790264 A CN114790264 A CN 114790264A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 29
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- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 27
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
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- 238000006386 neutralization reaction Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 229920002545 silicone oil Polymers 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 abstract description 36
- 239000007788 liquid Substances 0.000 abstract description 16
- 239000003999 initiator Substances 0.000 abstract description 12
- 239000003431 cross linking reagent Substances 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 10
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- 230000006835 compression Effects 0.000 abstract description 3
- 238000007906 compression Methods 0.000 abstract description 3
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- 230000008859 change Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- 238000004566 IR spectroscopy Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum ions Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- 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
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
Abstract
The invention provides spherical gel particles and a preparation method and application thereof, belonging to the field of polymer microsphere materials. The invention combines a dripping method and a free radical polymerization method, takes acrylamide and acrylic acid as functional monomers, takes methacrylic acid-beta-hydroxyethyl ester as an auxiliary agent, takes aluminum nitrate as a cross-linking agent, and takes potassium persulfate as an initiator to prepare the spherical gel particles with high compressive strength and strong gelling capacity. The results of the examples show that spherical gel particles prepared according to the inventionThe gel particles have approximately the same size, uniform texture and good balling performance, and the water absorption rate of the gel particles reaches the highest under the conditions of 40 ℃ and 50 ℃; when the mass fraction of the methacrylic acid-beta-hydroxyethyl ester in the precursor liquid is 20 percent at the temperature of 30 ℃, the compression strength of the gel particles is as high as 8.768 multiplied by 10 4 Pa。
Description
Technical Field
The invention relates to the field of polymer microsphere materials, in particular to spherical gel particles and a preparation method and application thereof.
Background
Nowadays, energy determines the comprehensive strength of a country, and under the rapid development of society, the energy becomes the target of competition of various countries, especially the non-renewable energy such as petroleum, the demand is far greater than the actual supply, so the exploitation of petroleum resources is always a research hotspot. And for some developed oil fields, the technical limit is adopted, the technical process in the early stage of exploitation is not perfect, so that further exploitation is still difficult, and the cost is increased continuously. As the development of oil fields enters the later stage of excavation, the water outlet of oil and gas wells becomes increasingly serious, and the improvement of the recovery ratio of crude oil is limited to a great extent. Under the condition, the recovery of old oil fields and the use of excavated oil and gas resources are improved, and the yield of crude oil is stabilized, which becomes a problem to be solved most urgently at present.
The method realizes stable and increased yield in the exploitation of oil fields, and can be widely applied to a series of means such as hydraulic fracturing, acidizing fracturing, water plugging and profile control, tertiary oil recovery and the like. In the implementation of this series of means, the temporary plugging agent plays a very important role. The traditional temporary plugging agent still has the problems of low underground compressive strength and weak gelling capability. Therefore, the research of a temporary plugging agent with high compressive strength and strong gelling capacity is a problem to be solved urgently in the prior art.
Disclosure of Invention
The invention aims to provide spherical gel particles and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of spherical gel particles, which comprises the following steps:
(1) mixing acrylic acid, water and alkali, and carrying out neutralization reaction to obtain a mixed solution; the neutralization degree of acrylic acid in the mixed solution is 55-85%;
(2) mixing the mixed solution obtained in the step (1) with methacrylic acid-beta-hydroxyethyl ester, acrylamide, potassium persulfate and aluminum nitrate to obtain a precursor solution;
(3) dripping the precursor obtained in the step (2) into silicone oil, and carrying out free radical polymerization reaction to obtain spherical gel particles;
the temperature of the silicone oil is 80-100 ℃.
Preferably, the base in step (1) is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide.
Preferably, the temperature of the neutralization reaction in the step (1) is-5-3 ℃, and the time of the neutralization reaction is 25-45 min.
Preferably, the mass ratio of the acrylic acid in the step (1) to the acrylamide in the step (2) is (1-1.8): (0.4 to 1).
Preferably, the mass fraction of the methacrylic acid-beta-hydroxyethyl ester in the precursor solution in the step (2) is 4-26%.
Preferably, the mass ratio of the acrylamide to the potassium persulfate to the aluminum nitrate in the step (2) is (1.5-2.5): (0.04-0.07) and (0.04-0.07).
Preferably, the device used in the step (3) is a dropper, and the diameter of the mouth of the dropper is 2-6 mm.
Preferably, the time of the free radical polymerization reaction in the step (3) is 2-14 min.
The invention also provides the spherical gel particles prepared by the preparation method in the technical scheme.
The invention also provides application of the spherical gel particles in the technical scheme in oilfield exploitation.
The invention provides a preparation method of spherical gel particles, which comprises the steps of firstly, carrying out neutralization reaction on acrylic acid and alkali to form acrylate, obtaining a mixed solution with the neutralization degree of 55-85% of acrylic acid, controlling the activity of monomer acrylic acid participating in free radical polymerization reaction by controlling the neutralization degree, so as to adjust the crosslinking density of the gel particles formed by the free radical polymerization reaction, namely the compactness of a three-dimensional network structure of the gel particles, improve the network pores of the gel particles, enable water molecules to freely pass through the gel particles, improve the water absorption and water retention capacity of the gel particles, increase the viscosity of a gel particle water solution by the three-dimensional network structure, achieve the thickening effect, namely improve the gelling capacity of the gel particles, then adding auxiliary agents of methacrylic acid-beta-hydroxyethyl, monomer acrylamide, initiator potassium and crosslinking agent aluminum persulfate into the mixed solution, obtaining a precursor solution, dripping the precursor solution into silicon oil at a certain temperature by using a dripping method to ensure that an initiator potassium persulfate is decomposed into persulfate by heating, persulfate reacts with acrylic acid and acrylamide to form monomer free radicals, then chain expansion is initiated, free radical polymerization reaction is carried out, and spherical gel particles (acrylamide polymer) with good regularity are formed, wherein water molecules are drilled into the gel particles through surface pores of the gel particles to promote ionization of-COONa existing during neutralization and ionize-COO - And Na + The two particles have opposite charges, a repulsion effect can be generated, the distance between molecular chains can be promoted to be increased, on one hand, the water absorption rate of the gel particles is accelerated, the gel particles have obvious water swelling phenomenon, namely water swelling property, on the other hand, the molecular chains are in a relaxation state, and the molecular chains are respectively dispersed, so that the volume ratio in the water solution is large, the thickening effect is achieved, and the water absorption capacity is improvedHydrophobic group-CONH introduced by water-soluble monomer acrylamide and having gelling ability 2 A hydrophilic group-COO introduced by a monomer acrylic acid - and-COONa, further improving the water absorption and retention capacity of the gel particles, and ester groups and hydroxyl groups on the structure of the auxiliary agent methacrylic acid-beta-hydroxyethyl ester are further crosslinked under the action of a crosslinking agent aluminum nitrate, so that the interaction force among molecular chains is enhanced, the crosslinking degree of the gel particles is further improved, and the compressive strength of the gel particles is further improved, the preparation method has the advantages of easy control of heat transfer, mild reaction conditions and simple operation in the reaction process, and the prepared spherical gel particles contain amide groups, carboxylic groups, vat groups and other hydrophilic groups on the molecular chain, and have a three-dimensional cross-linked network structure in cooperation with the amide groups, the carboxylic groups, the vat groups and other hydrophilic groups, so that the spherical gel particles have the advantages of good water absorption and water retention, controllable microsphere size, good dispersibility and the like, and have wide application prospects in the field of oil fields. The results of the examples show that the spherical gel particles prepared by the method provided by the application have approximately the same size, are approximately maintained at about 3mm, have uniform texture and have good balling property; the mass fraction of the beta-hydroxyethyl methacrylate in the precursor liquid is 5-25%, the content of the beta-hydroxyethyl methacrylate has little influence on the water absorption rate of the gel particles, and the water absorption rate of the gel particles reaches the highest under the conditions of 40 ℃ and 50 ℃; when the mass fraction of the methacrylic acid-beta-hydroxyethyl ester in the precursor liquid is 20 percent at the temperature of 30 ℃, the compression strength of the gel particles is as high as 8.768 multiplied by 10 4 Pa。
Drawings
FIG. 1 is an infrared spectrum of spherical gel particles prepared in example 4 of the present invention;
FIG. 2 is a pictorial representation of spherical gel particles prepared in example 4 of the present invention;
FIG. 3 is a graph showing the change of water absorption rate of spherical gel particles with different methacrylic acid-beta-hydroxyethyl ester contents at 20 ℃ with time, which are prepared in examples 1 to 5 of the present invention;
FIG. 4 is a graph showing the change of water absorption rate of spherical gel particles with different methacrylic acid-beta-hydroxyethyl ester contents at 30 ℃ with time, which are prepared in examples 1 to 5 of the present invention;
FIG. 5 is a graph showing the change of water absorption multiplying power of spherical gel particles with different methacrylic acid-beta-hydroxyethyl ester contents at 40 ℃ along with time, which are prepared in examples 1 to 5 of the invention;
FIG. 6 is a graph showing the change of water absorption rate of spherical gel particles with different methacrylic acid-beta-hydroxyethyl ester contents at 50 ℃ with time, which are prepared in examples 1 to 5 of the present invention;
FIG. 7 is a graph showing the change of water absorption rate of spherical gel particles with different methacrylic acid-beta-hydroxyethyl ester contents at 60 ℃ with time, which are prepared in examples 1 to 5 of the present invention;
FIG. 8 is a graph showing the change of water absorption rate of spherical gel particles with different methacrylic acid-beta-hydroxyethyl ester contents at 70 ℃ with time, which are prepared in examples 1 to 5 of the present invention;
FIG. 9 is a model diagram of a gel particle strength measuring apparatus according to the present invention, in which a first is an iron stand, a second is a pressure bar apparatus, and a third is a sample;
FIG. 10 is a longitudinal sectional view of the gel particle strength measuring instrument of the present invention, in which 1 is a support plate, 2 is a pressure rod, 3 is a connection rod, 4 is a fixing nut, 5 is a sleeve, and 6 is a weight table;
FIG. 11 is a graph of compressive strength of spherical gel particles of different contents of beta-hydroxyethyl methacrylate prepared in examples 1 to 5 of the present invention at different temperatures.
Detailed Description
The invention provides a preparation method of spherical gel particles, which comprises the following steps:
(1) mixing acrylic acid, water and alkali, and carrying out neutralization reaction to obtain a mixed solution; the neutralization degree of acrylic acid in the mixed solution is 55-85%;
(2) mixing the mixed solution obtained in the step (1) with methacrylic acid-beta-hydroxyethyl ester, acrylamide, potassium persulfate and aluminum nitrate to obtain a precursor solution;
(3) dripping the precursor obtained in the step (2) into silicone oil, and carrying out free radical polymerization reaction to obtain spherical gel particles;
the temperature of the silicone oil is 80-100 ℃.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
The invention mixes acrylic acid, water and alkali to carry out neutralization reaction to obtain mixed solution.
In the present invention, the water is preferably distilled water. In the present invention, the base is preferably one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide.
In the invention, the mass ratio of the acrylic acid to the water is preferably (3-4): (3-6), more preferably (3.4-3.8): (3.5-5). The invention controls the mass ratio of the acrylic acid to the water in the range, avoids the problems of too little water, insufficient solute dissolution, difficult free radical polymerization and difficult formation of gel particles; meanwhile, the excessive water is avoided, and the gel particles prepared from the formed solution are soft and have low elasticity and compressive strength.
In the present invention, the mixing manner of the acrylic acid, the water and the alkali is preferably to mix the acrylic acid and the water under stirring to obtain an acrylic acid aqueous solution; mixing the aqueous acrylic acid solution with a base.
The stirring rate is not particularly limited in the present invention, and may be a rate conventional in the art.
In the present invention, the neutralization reaction is preferably carried out under stirring. The stirring rate is not particularly limited in the present invention, and may be any rate that is conventional in the art. In the invention, the temperature of the neutralization reaction is preferably-5-3 ℃, and more preferably-3-1 ℃; the time of the neutralization reaction is preferably 25-45 min, and more preferably 30-40 min. The present invention controls the temperature and time of the neutralization reaction within the above range to ensure complete reaction of acrylic acid and the added base.
In the present invention, the neutralization degree of acrylic acid in the mixed solution is 55 to 85%, and more preferably 60 to 80%. The method controls the neutralization degree of acrylic acid in the mixed solution within the range to control the activity of monomer acrylic acid participating in the free radical polymerization reaction, thereby adjusting the crosslinking density of the gel particles formed by the free radical polymerization reaction, namely the compactness of the three-dimensional network structure, improving the network pores, enabling water molecules to pass through freely and improving the water absorption and retention capacity of the gel particles.
After a mixed solution is obtained, the mixed solution is mixed with methacrylic acid-beta-hydroxyethyl ester, acrylamide, potassium persulfate and aluminum nitrate to obtain a precursor solution.
In the present invention, the mass ratio of acrylic acid to acrylamide is preferably (1 to 1.8): (0.4 to 1), more preferably (1.1 to 1.5): (0.5-0.9). The present invention controls the mass ratio of acrylic acid and acrylamide to be within the above range to adjust the number of hydrophilic groups and hydrophobic groups in the prepared gel particles, and utilizes a water-soluble monomer acrylamide to introduce hydrophobic groups-CONH 2 Hydrophilic group-COO introduced by monomer acrylic acid - and-COONa is used for synergistic action, the water absorption and water retention capacity of the gel particles is further improved, the phenomenon that the dosage of acrylamide is too low and intermolecular reaction tends to self-polymerization reaction among acrylic acid is avoided, molecular chains of polymers are gradually lengthened and the degree of crosslinking is gradually increased, the formed crosslinking density of the gel particles, namely the compactness of a three-dimensional network structure of the gel particles is higher, the water absorption and water retention capacity of the gel particles is reduced, and meanwhile, the viscosity of the gel particle aqueous solution is increased by the three-dimensional network structure, so that the thickening effect is achieved, namely the gelling capacity of the gel particles is improved.
In the invention, the mass fraction of the methacrylic acid-beta-hydroxyethyl ester in the precursor liquid is preferably 4-26%, and more preferably 5-25%. According to the invention, the mass fraction of the beta-hydroxyethyl methacrylate in the precursor liquid is controlled within the above range, on one hand, ester groups and hydroxyl groups on the beta-hydroxyethyl methacrylate structure are further crosslinked under the action of a crosslinking agent aluminum nitrate, so that the interaction force between molecular chains is enhanced, the crosslinking degree of the gel particles is properly improved, and further the compressive strength of the gel particles is improved, and on the other hand, the excessive use amount of the beta-hydroxyethyl methacrylate is avoided, and the prepared gel particles have excessive crosslinking strength and no water-absorbing expansibility.
In the present invention, the acrylamide, potassium persulfate and aluminum nitrateThe mass ratio of (1.5-2.5): (0.04-0.07): (0.04-0.07), more preferably (1.8-2.2): (0.05-0.065): (0.05-0.065). According to the invention, the mass ratio of acrylamide to potassium persulfate to aluminum nitrate is controlled within the above range, the spherical gel particles are beneficial to being regular in shape, good in water absorption capacity and high in strength, the dosage of the initiator is a main factor for determining the length of a polymer chain, when the concentration of the initiator is too low, the amount of formed active free radicals is small, the polymerization reaction rate is slow, so that a large amount of oligomers are formed, but with the increase of the concentration of the initiator, the molecular weight of the polymer is gradually increased, the water retention capacity and the compressive strength are enhanced, and when the concentration of the initiator is too high, the molecular chain of the polymer is gradually shortened, so that the compressive strength is weakened; when the concentration of the cross-linking agent is low, the coordination mode among the molecular chains of the polymer is out-of-plane chelation to form a three-dimensional network structure, the compressive strength is high, the coordination mode is gradually changed from out-of-plane to in-plane along with the increase of the concentration of the cross-linking agent, but due to the chelation competition effect, when the concentration of the cross-linking agent reaches a certain value, the compressive strength of the polymer reaches the minimum value, then the concentration of the cross-linking agent is increased, and the Al content is increased 3+ The concentration of (B) is increased, so that the crosslinking degree is gradually increased and the compressive strength is enhanced.
In the invention, the mixed solution is preferably mixed with beta-hydroxyethyl methacrylate, acrylamide, potassium persulfate and aluminum nitrate in a manner that the beta-hydroxyethyl methacrylate and the acrylamide are sequentially added into the mixed solution to obtain a mixture; sequentially adding potassium persulfate and aluminum nitrate into the mixture under the condition of stirring.
The stirring rate is not particularly limited in the present invention, and may be any rate that is conventional in the art.
In the present invention, the potassium persulfate is preferably added in the form of an aqueous potassium persulfate solution; the mass concentration of the potassium persulfate aqueous solution is preferably 0.40-0.6%. In the present invention, the aluminum nitrate is preferably added in the form of an aqueous aluminum nitrate solution; the mass concentration of the aluminum nitrate aqueous solution is preferably 0.40-0.6%.
After the precursor solution is obtained, the precursor is added into silicone oil in a dropwise manner to carry out free radical polymerization reaction, so that spherical gel particles are obtained.
In the invention, the diameter of the pipe orifice of the equipment used for dripping is preferably 2-6 mm. In the invention, a dripping mode is adopted, so that the liquid drops of the precursor liquid can be slowly dripped into the silicone oil, the dripping speed is easy to control, and the gel particles with regular shapes and uniform sizes can be obtained.
In the invention, silicone oil is used as a reaction medium of free radical polymerization reaction, the boiling point is high, and a water-in-oil emulsion model is utilized in a reaction system of the free radical polymerization reaction to stabilize the droplet form of the precursor liquid so as to finally form the gel particles with uniform form.
In the invention, the temperature of the silicone oil is 80-100 ℃, and preferably 85-95 ℃. According to the invention, the temperature of the silicone oil is controlled within the range, so that the initiator potassium persulfate is heated and decomposed into persulfate, persulfate reacts with acrylic acid and acrylamide to form monomer free radicals, then chain expansion is initiated, free radical polymerization reaction is generated, the rate of the free radical polymerization reaction is controlled, the conditions that the higher the temperature is, the faster the decomposition rate of the initiator is, the too fast the polymerization rate is, or the initiator can be decomposed and failed, the conditions that the temperature is too low, the initiation rate of the initiator is too slow, and the formation of a polymer formed by the free radical polymerization reaction is not facilitated to obtain the gel particles are avoided.
In the present invention, the radical polymerization reaction is preferably carried out under stirring. The stirring rate is not particularly limited in the present invention, and may be a rate conventional in the art. In the present invention, the time for the radical polymerization reaction is preferably 2 to 14min, and more preferably 3 to 12 min. The invention controls the time of free radical polymerization reaction in the range, is favorable for promoting each component to completely generate the free radical polymerization reaction, and is easy to form to obtain the gel particles with better regularity and absorption performance.
After the free radical polymerization reaction is finished, the product of the free radical polymerization reaction is preferably separated, cleaned and dried in sequence to obtain spherical gel particles.
The invention has no special limitation on the separation mode, and the purpose of separating the gel particles is realized. In the present invention, the agent for washing is preferably petroleum ether. In the invention, the drying temperature is preferably 60-80 ℃, and more preferably 65-75 ℃. The drying time is not particularly limited, and the aim of removing moisture and solvent is fulfilled.
The invention also provides the spherical gel particles prepared by the preparation method of the technical scheme. In the invention, the particle size of the spherical gel particles is preferably 2-6 mm, and more preferably 3-5 mm.
The invention also provides application of the spherical gel particles in the technical scheme. In the invention, the spherical gel particles can be used as a temporary plugging agent for oilfield exploitation.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation method of spherical gel particles
(1) Adding 3.6g of acrylic acid and 4g of water into a 50mL beaker under the stirring condition, slowly adding 1.6g of sodium hydroxide, and carrying out neutralization reaction to obtain a mixed solution with the neutralization degree of 80% of acrylic acid; the mass ratio of the acrylic acid to the water is 3.6: 4;
(2) adding 0.517g of beta-hydroxyethyl methacrylate and 2.1g of acrylamide into the mixed solution obtained in the step (1), and then adding a potassium persulfate aqueous solution (containing 0.057g of potassium persulfate) with the mass concentration of 0.5% and an aluminum nitrate aqueous solution (containing 0.057g of aluminum nitrate) with the mass concentration of 0.5% in sequence under the condition of stirring to mix to obtain a precursor solution;
the mass ratio of the acrylic acid in the step (2) to the acrylamide in the step (2) is 1.2: 0.7;
the mass fraction of methacrylic acid-beta-hydroxyethyl in the precursor liquid in the step (2) is 5%;
in the step (2), the mass ratio of acrylamide to potassium persulfate to aluminum nitrate is 2.1: 0.057: 0.057;
(3) and (3) dropwise adding the precursor liquid obtained in the step (2) into 90 ℃ silicone oil by using a dropper with the diameter of 3-5 mm, carrying out free radical polymerization for 4min, separating a product of the free radical polymerization, cleaning the silicone oil on the surface by using petroleum ether, and drying in a 70 ℃ drying oven to obtain spherical gel particles.
Example 2
Spherical gel particles were prepared according to the method of example 1
Different from the embodiment 1, the mass of the beta-hydroxyethyl methacrylate in the step (2) is 1.035g, and the mass fraction of the beta-hydroxyethyl methacrylate in the precursor liquid is 10%.
Example 3
Spherical gel particles were prepared according to the method of example 1
Unlike example 1, the mass of β -hydroxyethyl methacrylate in step (2) was 1.552g, and the mass fraction of β -hydroxyethyl methacrylate in the precursor liquid was 15%.
Example 4
Spherical gel particles were prepared according to the method of example 1
Unlike example 1, the mass of β -hydroxyethyl methacrylate in the step (2) was 2.069g, and the mass fraction of β -hydroxyethyl methacrylate in the precursor liquid was 20%.
Example 5
Spherical gel particles were prepared according to the method of example 1
Unlike example 1, the mass of β -hydroxyethyl methacrylate in the step (2) was 2.586g, and the mass fraction of β -hydroxyethyl methacrylate in the precursor liquid was 25%.
First, infrared spectrometry
The spherical gel particles prepared in example 4 were analyzed using an infrared spectrometer by first drying the drug product sufficiently, grinding into a fine powder, mixing with potassium bromide particles in a certain ratio, grinding twice in an agate mortar, grinding into a finer powder, tabletting with a tabletting machine, placing into a fourier transform infrared analyzer for infrared spectroscopy and analysis.
FIG. 1 is an infrared spectrum of spherical gel particles prepared in example 4, which is shown in FIG. 1 at 3426cm -1 And 3189cm -1 In the form of free-NH on Acrylamide (AM) 2 Characteristic peak of (2), 2954cm -1 Is a characteristic peak of-CH in methylene at 1725cm -1 The peak is a characteristic peak of-C-CO-O-in beta-hydroxyethyl methacrylate (HEMA), because the cross-linking agent aluminum nitrate has trivalent aluminum ions, and 1673cm under the induction of the trivalent aluminum ions -1 The characteristic peak of carbonyl (C ═ O) at (A) and 1407cm -1 The characteristic peaks of the ester groups (COO-) are close to each other, 1407cm -1 The peak is the characteristic peak of the ester group (COO-) -and 1407cm -1 The characteristic peaks of hydroxyl (-OH) at the position are mutually overlapped, and the absorption intensity is higher at 1162cm -1 The peak is the characteristic peak of the ester group (COO-), and is 1083cm -1 And (b) is a characteristic peak at O-H. This indicates that spherical gel particles have been successfully prepared.
Second, appearance
The spherical gel particles prepared in example 4 were subjected to appearance observation, and the degree of uniformity of the spherical polyacrylamide was judged by the naked eye and recorded by a mobile phone.
FIG. 2 is a schematic diagram showing the spherical gel particles prepared in example 4, and it can be seen from FIG. 2 that the spherical gel particles prepared in example 4 have a spherical shape, substantially the same size, substantially maintained at about 3mm, uniform texture, and good sphericity.
Third, determination of water absorption multiplying power
One sample is taken randomly from each of the spherical gel particles prepared in examples 1 to 5 in sequence, six samples are taken respectively, then the samples are placed into beakers containing deionized water respectively, the beakers are placed into constant-temperature water baths at 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃ respectively in sequence to be soaked, the time intervals are set to be 10min, 30min, 60min, 120min and 120min for observation, the gel particles are fished out, and the spherical polyacrylamide is observed and analyzed by photographing and recording the moisture on the surface of the gel particles through a mobile phone and fishing out the particles to measure the diameter. The water absorption rate calculation formula is as follows:
wherein W is the water absorption of spherical polyacrylamide in mm.mm -1 (ii) a D is the diameter of the spherical polyacrylamide after absorbing water for corresponding time, and the unit is mm; do is the initial diameter of the spherical polyacrylamide in mm.
FIGS. 3 to 8 are graphs showing the change of water absorption rates of the spherical gel particles with different contents of beta-hydroxyethyl methacrylate prepared in examples 1 to 5 at 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃ along with time, as can be seen from FIGS. 3 to 8, the water absorption rate of the gel particles is not greatly influenced by the content of beta-hydroxyethyl methacrylate, the gel particles rapidly absorb water and swell within the first 50min under different temperature conditions, the water absorption rate of the gel particles reaches a peak value and then tends to decrease along with the increasing soaking time, and finally a stable state is maintained, so that the water absorption rate of the gel particles reaches the highest under the conditions of 40 ℃ and 50 ℃, and the water absorption rate of the gel particles tends to decrease at the temperature of 70 ℃ because the molecular chains of the gel particles break at high temperature, leading to poor water retention and reduced water absorption capacity; according to principle analysis, the surface of the gel particles has pore gaps, so that water molecules can freely pass through the surface of the gel particles, and the water molecules are drilled into the spherical polyacrylamide to promote the ionization of-COONa existing during neutralization and ionize-COO - And Na + The ions can generate repulsion effect due to the same charges of the two generated particles, so that the distance between molecular chains can be increased, the water absorption rate of the spherical polyacrylamide is increased, and the phenomenon of obvious water absorption swelling is caused; under the influence of osmotic pressure, sodium ions in the spherical polyacrylamide and part of polymers with smaller molecular chains pass through smaller gaps between the molecular chains to be dissociated into the spherical polypropyleneIn a solution system outside the acrylamide, the water absorption rate of the spherical polyacrylamide is further accelerated until osmotic pressure in the whole system reaches a dynamic balance, and the swelling multiplying power of the spherical polyacrylamide reaches a peak value; with the continuous increase of the soaking time, the macromolecular chains gradually start to carry out self-disentanglement reaction, the water-retaining capacity of the spherical polyacrylamide is gradually reduced, and the particle size of the spherical polyacrylamide is continuously reduced until a balance is maintained and the particle size of the spherical polyacrylamide is kept unchanged.
Fourthly, determination of solubility
Sequentially taking one sample from the spherical gel particles prepared in the embodiments 1-5 at random, taking six samples from each sample, placing the samples into beakers filled with deionized water, placing the beakers into constant-temperature water bath pots with the temperatures set to 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃ for soaking, and observing the dissolution conditions of spherical polyacrylamide with different concentrations after long-time soaking, wherein the observation result is as follows: after long-time soaking, the spherical gel particles prepared in examples 1 to 5 are found to be insoluble, shrunk to a certain extent, and remain unchanged, and still have certain strength after soaking. The spherical gel particles prepared in examples 1 to 5 were observed to have water absorption property after being fished out and dried at room temperature and then continuously soaked.
Fifth, viscosity test
The spherical gel particles prepared in example 1 were prepared as a 5% solution by mass and placed in an oven at 90 ℃ and observed at intervals until dissolved. The viscosity of the spherical polyacrylamide was measured by a rotational viscometer using a No. 1 rotor at a rotation speed of 60r/min, and the viscosity was read.
The viscosity test results are: the obtained viscosity value is 9, which is not in accordance with the expected assumption, and the related literature consults to find that because methacrylic acid-beta-hydroxyethyl exists in the system, the hydroxyl groups existing in the molecule can generate esterification reaction, crosslinking reaction and the like with other corresponding groups, the adhesion of the molecular chain is improved, the product is insoluble for a long time, and the strength is higher.
Sixthly, determination of compressive strength
The strength of the gel particles prepared in examples 1 to 5 was tested using a home-made gel particle strength tester. The design of the gel particle strength tester is shown in fig. 9 and 10;
the gel particle strength tester processing should satisfy the following conditions: 1. the surfaces of the pressure rod and the connecting rod and the inner wall of the sleeve are required to be as smooth as possible; 2. the total weight of the weight table, the connecting rod and the pressure rod is ensured to be minimum under the condition of meeting the processability; 3. the diameter D of the pressure rod head is 12 mm.
The strength of the gel particles was calculated according to the following formula:
G 2 ＝m 0 g
wherein S represents the strength of gel particles/Pa; m 0-total initial mass of weight table, connecting rod and pressure rod; m represents the mass per gram of weight; g 1 -weight; g 2 -total weight per gram of weight table, connecting rod and pressure rod; a, the cross section area of a pressure rod head; f, friction force, and when the surfaces of the pressure rod and the connecting rod and the inner wall of the sleeve are smooth enough, the friction force can be ignored; g-acceleration of gravity, 10.0m/s 2 。
The measuring method comprises the following steps: taking one sample from the spherical gel particles prepared in the embodiments 1 to 5, taking six samples from each sample, placing the samples into beakers filled with deionized water, placing the beakers into constant-temperature water bath pots with the temperature set to be 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃ in sequence, soaking for 2 to 3 hours to make the beakers absorb water and expand, placing the gel particle samples into a tester after the water absorption of the gel particle samples is saturated, enabling the lower end surface of a pressure rod to contact with gel, and adding weights into a weight tray until the gel is broken.
FIG. 9 is a schematic diagram of a gel particle strength measuring apparatus, in which the apparatus includes an iron stand, a pressure bar, and a sample.
FIG. 10 is a longitudinal sectional view of a gel particle strength measuring instrument, in which 1 is a support plate, 2 is a pressure rod, 3 is a connection rod, 4 is a fixing nut, 5 is a sleeve, and 6 is a weight table.
FIG. 11 is a graph of the compressive strength of the spherical gel particles with different contents of beta-hydroxyethyl methacrylate prepared in examples 1 to 5 at different temperatures, and it can be seen from FIG. 11 that at the temperature of 50 ℃ and 60 ℃, the compressive strength of the gel particles decreases and then increases with the increase of the content of beta-hydroxyethyl methacrylate, and when the content of beta-hydroxyethyl methacrylate is 20%, the compressive strength of the gel particles is the strongest; at the temperature of 40 ℃ and 70 ℃, the compressive strength of the gel particles shows a tendency of increasing after decreasing with increasing content of beta-hydroxyethyl methacrylate, and a peak appears when the content of beta-hydroxyethyl methacrylate is 15%. And at the temperature of 30 ℃, the compressive strength of the gel particles is increased along with the increase of the content of the beta-hydroxyethyl methacrylate, and the maximum compressive strength is obtained when the content of the beta-hydroxyethyl methacrylate is 20 percent, so that at the temperature of 30 ℃, the molecular chains are intertwined to form physical crosslinking in a three-dimensional space, which is favorable for improving the strength of the gel particles, and ester groups (COO-) and hydroxyl groups (-OH) in the beta-hydroxyethyl methacrylate are crosslinked under the action of a crosslinking agent aluminum nitrate, so that the compressive strength of the gel particles is increased. When the content of the beta-hydroxyethyl methacrylate is 5 percent, the compressive strength is 2.3435 beta 010 4 Pa, the compressive strength is 8.768X 10 when the content of methacrylic acid-beta-hydroxyethyl ester is 20 percent 4 The Pa, the addition of the methacrylic acid-beta-hydroxyethyl ester obviously improves the strength of the gel particles and produces the best effect at 30 ℃; when the content of beta-hydroxyethyl methacrylate is 25%, the gel particles do not swell due to excessive high content and excessive crosslinking strength, and the compressive strength cannot be measured.
In summary, the spherical gel particles prepared by the method provided by the application have approximately the same size, are approximately maintained at about 3mm, have uniform texture and good balling property; the mass fraction of the methacrylic acid-beta-hydroxyethyl ester in the precursor liquid is within the range of 5-25%, and the content of the methacrylic acid-beta-hydroxyethyl ester is relative to the coagulationThe influence of the water absorption of the gel particles is small, and the water absorption of the gel particles reaches the highest at 40 ℃ and 50 ℃; when the mass fraction of the methacrylic acid-beta-hydroxyethyl ester in the precursor liquid is 20 percent at the temperature of 30 ℃, the compression strength of the gel particles is as high as 8.768 multiplied by 10 4 Pa. The invention combines a dripping method and a free radical polymerization method, takes acrylamide and acrylic acid as functional monomers, takes methacrylic acid-beta-hydroxyethyl ester as an auxiliary agent, takes aluminum nitrate as a cross-linking agent and takes potassium persulfate as an initiator to prepare spherical gel particles with high compressive strength and strong gelling capacity
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing spherical gel particles, comprising the steps of:
(1) mixing acrylic acid, water and alkali, and performing neutralization reaction to obtain a mixed solution; the neutralization degree of acrylic acid in the mixed solution is 55-85%;
(2) mixing the mixed solution obtained in the step (1) with methacrylic acid-beta-hydroxyethyl ester, acrylamide, potassium persulfate and aluminum nitrate to obtain a precursor solution;
(3) dripping the precursor obtained in the step (2) into silicone oil, and carrying out free radical polymerization reaction to obtain spherical gel particles;
the temperature of the silicone oil is 80-100 ℃.
2. The method according to claim 1, wherein the base in the step (1) is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide.
3. The preparation method according to claim 1, wherein the temperature of the neutralization reaction in the step (1) is-5 to 3 ℃, and the time of the neutralization reaction is 25 to 45 min.
4. The method according to claim 1, wherein the mass ratio of acrylic acid in the step (1) to acrylamide in the step (2) is (1-1.8): (0.4-1).
5. The method according to claim 1, wherein the mass fraction of β -hydroxyethyl methacrylate in the precursor solution in the step (2) is 4 to 26%.
6. The production method according to claim 1, wherein the mass ratio of acrylamide, potassium persulfate and aluminum nitrate in the step (2) is (1.5 to 2.5): (0.04-0.07) and (0.04-0.07).
7. The preparation method according to claim 1, wherein the diameter of the nozzle of the device used for dropwise addition in the step (3) is 2-6 mm.
8. The method according to claim 1, wherein the time for the radical polymerization in the step (3) is 2 to 14 min.
9. Spherical gel particles obtained by the production method according to any one of claims 1 to 8.
10. Use of the spherical gel particles of claim 9 in oilfield exploitation.
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