CN114478897B - Slow-expansion type pre-crosslinked gel particles and preparation method thereof - Google Patents
Slow-expansion type pre-crosslinked gel particles and preparation method thereof Download PDFInfo
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- CN114478897B CN114478897B CN202111403511.4A CN202111403511A CN114478897B CN 114478897 B CN114478897 B CN 114478897B CN 202111403511 A CN202111403511 A CN 202111403511A CN 114478897 B CN114478897 B CN 114478897B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007863 gel particle Substances 0.000 title abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 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 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- XAMCLRBWHRRBCN-UHFFFAOYSA-N 5-prop-2-enoyloxypentyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCOC(=O)C=C XAMCLRBWHRRBCN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 16
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 13
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 16
- VNVPAXTWPXRLSZ-UHFFFAOYSA-N [NH4+].[Na].OS([O-])(=O)=O Chemical compound [NH4+].[Na].OS([O-])(=O)=O VNVPAXTWPXRLSZ-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- SATQNYRZLIROHO-UHFFFAOYSA-N [NH4+].[Na].OS([O-])=O Chemical compound [NH4+].[Na].OS([O-])=O SATQNYRZLIROHO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000010779 crude oil Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 11
- 230000008961 swelling Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 229920006037 cross link polymer Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 125000001165 hydrophobic group Chemical group 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000008398 formation water Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003334 secondary amides Chemical class 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 sodium carboxylate Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of oil field enhanced crude oil recovery, and discloses a slow-swelling pre-crosslinked gel particle and a preparation method thereof. The raw materials of the pre-crosslinked gel particles comprise: acrylic acid, sodium dodecyl sulfate, N' -methylene bisacrylamide, 1, 5-pentanediol diacrylate, an initiator, a pH regulator and deionized water; the initiator is a redox system consisting of an oxidant and a reducing agent. The beneficial effects of the invention are as follows: can enhance the slow expansion performance of the pre-crosslinked gel particles and improve the plugging strength of the pre-crosslinked gel particles.
Description
Technical Field
The invention relates to the technical field of enhanced oil recovery of oil fields, in particular to slow-swelling pre-crosslinked gel particles and a preparation method thereof.
Background
The oil reservoir in China is mainly developed by natural water flooding or artificial water flooding, is influenced by factors such as cementing degree, heterogeneity, water flooding system and the like of the reservoir, and gradually forms an dominant seepage channel after the reservoir is subjected to long-term flushing of side water, bottom water or injected water, and the side water, the bottom water or the injected water can flow to an oil well along the dominant seepage channel, so that the oil yield of the oil well is reduced, the water yield is increased, and the oil reservoir development effect is seriously influenced.
At present, in order to improve the development effect of natural water flooding or artificial water flooding, the scope of water flooding is enlarged, and the dominant seepage channels in the reservoir are blocked by mainly adopting a blocking regulator such as crosslinked polymer gel, pre-crosslinked gel particles and the like, so that deep liquid flow diversion is realized. The cross-linked polymer gel is prepared by adding a cross-linking agent into a polymer solution, injecting the polymer solution into a reservoir before gel formation, and cross-linking the polymer solution in the reservoir to form gel so as to realize the plugging of a dominant seepage channel of the reservoir. During the application process, the dilution effect of formation water and the shearing effect of the porous medium can influence the plugging effect of the crosslinked polymer gel. In addition, because of the difference in polarity between the polymer solution and the cross-linking agent, chromatographic separation of the injected polymer solution added with the cross-linking agent occurs, and the polymer solution is separated from the cross-linking agent, so that the gel forming effect is poor or not, and the phenomenon is more obvious when the polymer solution is moved to the deep part of the reservoir. So the crosslinked polymer gel cannot well meet the deep plugging and deep flow diversion requirements of the water-flooding development oil reservoir. The pre-crosslinked gel particles are plugging agents capable of absorbing water and expanding after being injected into a reservoir, and the water expansion formed by expansion can plug a dominant seepage channel. Compared with crosslinked polymer gel, the pre-crosslinked gel particles have little influence by shearing action, stratum water dilution action and chromatographic separation action, and have great application potential in blocking dominant seepage channels and realizing liquid flow diversion. However, the existing pre-crosslinked gel particles are quick in water absorption expansion under the reservoir condition, so that the pre-crosslinked gel particles are expanded completely before being transported to the deep part of the reservoir, and therefore, only the dominant seepage channels in the near-wellbore zone can be plugged, and the dominant seepage channels in the deep part of the reservoir cannot be effectively plugged.
Currently, the prior art mainly delays the expansion of pre-crosslinked gel particles by adding formaldehyde crosslinking agent into the system or introducing monomer with hydrophobic group into the system. The formaldehyde cross-linking agent is added into the system to increase the toxicity of the pre-cross-linked gel particles, which is unfavorable for protecting the environment, and the slow expansion effect is limited. The monomer with hydrophobic group is introduced into the system, and although the expansion time can be prolonged to a certain extent, the expansion performance of the prepared pre-crosslinked gel particles in oil is enhanced and the expansion performance in water is weakened along with the increase of the content of the hydrophobic group, so that the phenomenon of oil shutoff and water non-shutoff occurs. In addition, the main limitation of the prior art is that the main raw material used for preparing the pre-crosslinked gel particles is acrylamide, an amide base band in the acrylamide has two hydrogen atoms, and can form a strong hydrogen bond with water molecules, so that the water molecules can easily enter the pre-crosslinked gel particles to quickly expand.
Therefore, in order to effectively block the dominant seepage channel at the deep part of the reservoir, realize the deep liquid flow diversion and improve the development effect of the water displacement reservoir, the slow-swelling pre-crosslinked gel particles and the preparation method thereof are provided, so that the slow-swelling performance of the pre-crosslinked gel particles can be enhanced, and the strength of the pre-crosslinked gel particles can be improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a slow-swelling pre-crosslinked gel particle and a preparation method thereof, which can enhance the slow-swelling performance of the pre-crosslinked gel particle and improve the strength of the pre-crosslinked gel particle.
The aim of the invention is realized by the following technical scheme:
the slow swelling pre-crosslinked gel particle is prepared from the following raw materials:
acrylic acid, sodium dodecyl sulfate, N' -methylene bisacrylamide, 1, 5-pentanediol diacrylate, an initiator, a pH regulator and deionized water;
the initiator is a redox system consisting of an oxidant and a reducing agent.
Further, the redox system is a sodium bisulphite-ammonium persulfate system.
Further, the slow-swelling pre-crosslinked gel particles are prepared from the following components: 25-30 parts of acrylic acid, 0.025-0.15 part of sodium dodecyl sulfate, 0.025-0.09 part of N, N' -methylene bisacrylamide, 0.025-0.15 part of 1, 5-pentanediol diacrylate, 0.05-0.18 part of sodium bisulfate-ammonium persulfate, and a pH regulator, wherein the dosage of the pH regulator is required to meet the pH value requirement of the solution after adjustment, and the balance of deionized water.
Further, the pH regulator is sodium hydroxide.
Further, in the sodium bisulphite-ammonium persulfate system, the molar ratio of the sodium bisulphite to the ammonium persulfate is 1:1.
a preparation method of slow-swelling pre-crosslinked gel particles comprises the following steps:
step a, adding deionized water and acrylic acid into a round-bottom flask, and regulating the pH value to 7.0-7.5 by sodium hydroxide to obtain a solution with the pH value regulated;
b, adding sodium dodecyl sulfate, N' -methylenebisacrylamide and 1, 5-pentanediol diacrylate into the solution obtained in the step a, fully stirring, and then adding deionized water to prepare an aqueous solution with the mass concentration of 25% -30% of acrylic acid;
step c, introducing nitrogen into an aqueous solution with the mass concentration of 25% -30% of acrylic acid to remove oxygen, then placing the aqueous solution in a constant-temperature water bath at 45 ℃ to heat, adding a sodium bisulfate-ammonium persulfate initiator after the temperature of the aqueous solution reaches 45 ℃, and reacting for 6 hours under the condition of maintaining the reaction temperature at 45 ℃ to obtain a reaction product;
and d, drying and crushing the reaction product to obtain the slow-swelling pre-crosslinked gel particles.
The pH value in step a is controlled between 7 and 7.5, which is beneficial to the polymerization reaction.
The network structure of the polymer gel has great influence on water absorption, and the existing gel particles utilize a crosslinked network formed among gel molecules to fix water molecules in the molecular network so as to enhance the water absorption of the gel. The method has the advantages that on one hand, the crosslinking strength of the slow-swelling pre-crosslinked gel particles can be improved, the entry speed of water molecules can be reduced to a certain extent, and meanwhile, under the action of formation water and temperature, two ester bonds of the 1, 5-pentanediol diacrylate are slowly hydrolyzed, the ester bonds are hydrolyzed, the network structure of gel molecules is further expanded, the effect of improving the crosslinking strength of the slow-swelling pre-crosslinked gel particles is gradually lost, and the slow-swelling pre-crosslinked gel particles are correspondingly and slowly swelled, so that the 1, 5-pentanediol diacrylate plays a role in delaying swelling. Meanwhile, the charge distribution of the whole molecule of the 1, 5-pentanediol diacrylate is uniform and symmetrical, the whole polarity is weak, the hydrophilicity is weak, the expansion is delayed, and further, a hydrophobic group is not required to be introduced into a system, and the phenomenon that oil is blocked and water is not blocked due to the introduction of the hydrophobic group in the prior art is avoided.
The beneficial effects of the invention are as follows:
(1) The sodium acrylate is generated by the reaction of acrylic acid and sodium hydroxide, and the sodium acrylate is used as a main raw material to prepare slow-swelling pre-crosslinked gel particles, so that compared with amido, the slow-swelling pre-crosslinked gel particles have better slow-swelling performance because the hydrogen bond formed by sodium carboxylate and water molecules is weaker and the speed of water molecules entering the slow-swelling pre-crosslinked gel particles is slower; (2) The addition of the 1, 5-pentanediol diacrylate can improve the crosslinking strength of the slow-swelling pre-crosslinked gel particles, reduce the entry speed of water molecules to a certain extent, and simultaneously slowly hydrolyze two ester bonds of the 1, 5-pentanediol diacrylate under the action of formation water and temperature, so that the effect of improving the crosslinking strength of the slow-swelling pre-crosslinked gel particles is gradually lost, and the slow-swelling pre-crosslinked gel particles correspondingly slowly expand, so that the 1, 5-pentanediol diacrylate plays a role in delaying expansion; (3) N, N' -methylene bisacrylamide is used as a cross-linking agent to improve the strength of the slow-swelling pre-cross-linked gel particles; (4) The surfactant sodium dodecyl sulfate is favorable for the solubility of the 1, 5-pentanediol diacrylate and realizes the aqueous solution polymerization.
Drawings
FIG. 1 is an infrared spectrogram of slow-swelling pre-crosslinked gel particles;
FIG. 2 is a graph showing the change of the expansion coefficient of water absorption with time of the slow swelling pre-crosslinked gel particles prepared in examples 1, 2 and 3;
FIG. 3 is a graph showing the variation of injection pressure with time during the plugging performance test of the slow swelling pre-crosslinked gel particles prepared in examples 1, 2 and 3.
Detailed Description
The technical scheme of the present invention is described in further detail below with reference to specific embodiments, but the scope of the present invention is not limited to the following description.
Example 1
The slow-swelling pre-crosslinked gel particles are prepared from the following components in parts by weight:
30g of acrylic acid, 0.15g of sodium dodecyl sulfate, 0.07g of N, N' -methylene bisacrylamide, 0.12g of 1, 5-pentanediol diacrylate, 0.13g of initiator and a pH regulator, wherein the dosage of the pH regulator is required to meet the pH value requirement of the solution after regulation, and the balance of deionized water, and the weight part of the pH regulator in the scheme is 16.65g.
The initiator is an oxidation-reduction system consisting of an oxidant and a reducing agent, and is preferably a sodium bisulfate-ammonium persulfate system; the pH regulator is sodium hydroxide.
A preparation method of slow-swelling pre-crosslinked gel particles comprises the following steps:
firstly, 50g of deionized water and 30g of acrylic acid are added into a round-bottom flask, and the pH value is adjusted by 16.65g of sodium hydroxide to obtain a solution with the pH value adjusted;
then adding 0.15g of sodium dodecyl sulfate, 0.07g of N, N' -methylene bisacrylamide and 0.12g of 1, 5-pentanediol diacrylate into the solution obtained after the pH value is regulated, fully stirring, and then adding deionized water to prepare an aqueous solution with the mass concentration of 30 percent of acrylic acid;
then introducing nitrogen into the aqueous solution with the mass concentration of 30% of acrylic acid to remove oxygen, then placing the aqueous solution in a constant-temperature water bath at 45 ℃ to heat, adding 0.13g of sodium bisulfate-ammonium persulfate initiator after the temperature of the aqueous solution reaches 45 ℃, and reacting for 6 hours at the temperature of 45 ℃ to obtain a reaction product;
finally, the reaction product is dried and crushed to prepare the slow-swelling pre-crosslinked gel particles.
Example 2
A preparation method of slow-swelling pre-crosslinked gel particles comprises the following steps:
firstly, weighing the following raw materials in parts by weight:
25g of acrylic acid, 0.15g of sodium dodecyl sulfate, 0.09g of N, N' -methylenebisacrylamide, 0.15g of 1, 5-pentanediol diacrylate, 0.16g of initiator, 13.88g of pH regulator and the balance of deionized water; wherein the initiator is sodium bisulfate-ammonium persulfate, and the pH regulator is sodium hydroxide;
then, 50g of deionized water and 25g of acrylic acid are added into a round-bottom flask, and the pH value is adjusted by 13.88g of sodium hydroxide, so as to obtain a solution with the pH value adjusted;
then adding 0.15g of sodium dodecyl sulfate, 0.09g of N, N' -methylenebisacrylamide and 0.15g of 1, 5-pentanediol diacrylate into the solution obtained after the pH value is regulated, fully stirring, and then adding deionized water to prepare an aqueous solution with the mass concentration of acrylic acid of 25%;
then introducing nitrogen into the aqueous solution with 25% of acrylic acid mass concentration to remove oxygen, then placing the aqueous solution in a constant-temperature water bath at 45 ℃ to heat, adding 0.16g of sodium bisulfate-ammonium persulfate initiator after the temperature of the aqueous solution reaches 45 ℃, and reacting for 6 hours at the temperature of 45 ℃ to obtain a reaction product;
finally, the reaction product is dried and crushed to prepare the slow-swelling pre-crosslinked gel particles.
Example 3
28g of acrylic acid, 0.14g of sodium dodecyl sulfate, 0.08g of N, N' -methylenebisacrylamide, 0.13g of 1, 5-pentanediol diacrylate, 0.12g of initiator, 15.55g of pH regulator and the balance of deionized water.
In the scheme, the initiator is a redox system consisting of an oxidant and a reducing agent, and is preferably a sodium bisulfate-ammonium persulfate system; the pH regulator is sodium hydroxide.
A preparation method of slow-swelling pre-crosslinked gel particles comprises the following steps:
firstly, 50g of deionized water and 28g of acrylic acid are added into a round-bottom flask, and the pH value is adjusted by 15.55g of sodium hydroxide to obtain a solution with the pH value adjusted;
then adding 0.14g of sodium dodecyl sulfate, 0.08g of N, N' -methylenebisacrylamide and 0.13g of 1, 5-pentanediol diacrylate into the solution obtained after the pH value is regulated, fully stirring, and then adding deionized water to prepare an aqueous solution with the mass concentration of 28 percent of acrylic acid;
then introducing nitrogen into the aqueous solution with the mass concentration of 28% of acrylic acid to remove oxygen, then placing the aqueous solution in a constant-temperature water bath at 45 ℃ to heat, adding 0.12g of sodium bisulfate-ammonium persulfate initiator after the temperature of the aqueous solution reaches 45 ℃, and reacting for 6 hours at the temperature of 45 ℃ to obtain a reaction product;
finally, the reaction product is dried and crushed to prepare the slow-swelling pre-crosslinked gel particles.
Wherein, the initiator is an oxidation-reduction system composed of an oxidant and a reducing agent, and is preferably a sodium bisulfate-ammonium persulfate system; the pH regulator is sodium hydroxide.
Experimental example
The slow swelling pre-crosslinked gel particles prepared in example 2 were subjected to infrared spectrogram analysis, and the slow swelling pre-crosslinked gel particles prepared in examples 1, 2 and 3 were subjected to measurement of water absorption expansion coefficient and blocking performance.
(1) Characterization of slow-swelling pre-crosslinked gel particles:
as shown in FIG. 1, the infrared spectrogram of the slow swelling pre-crosslinked gel particles synthesized by example 2 has N-H stretching vibration absorption peak at 3438cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H antisymmetric telescopic vibration absorption peak is positioned at 2922cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H symmetrical telescopic vibration absorption peak is 2851cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C=o stretching vibration absorption peak at 1631cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The N-H bending vibration absorption peak in the secondary amide is 1567cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H in-plane bending vibration absorption peak at 1455cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-O symmetrical telescopic vibration absorption peak in acrylic acid is 1407cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The C-N telescopic vibration absorption peak in the secondary amide is 1323cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-O-C telescopic vibration absorption peak is located at 1175cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-C telescopic vibration absorption peak is 1127cm -1 。
Therefore, the product had infrared absorption peaks of the groups contained in acrylic acid, N' -methylenebisacrylamide, and 1, 5-pentanediol diacrylate, indicating that the objective product was obtained.
The slow-swelling pre-crosslinked gel particles prepared by the scheme have the following structural formula:
wherein x, y, a, b, c is the degree of polymerization, and the infrared spectrum is shown in FIG. 1.
(2) The swelling time and the water absorption times of the slow swelling pre-crosslinked gel particles prepared in examples 1, 2 and 3 were measured respectively:
10g of each of the slow-swelling pre-crosslinked gel particles prepared in examples 1, 2 and 3 is added into three reagent bottles containing 1000g of deionized water, the reagent bottles are respectively sealed and then placed into a 60 ℃ incubator, the three reagent bottles are taken out periodically, and the slow-swelling pre-crosslinked gel particles after water absorption are weighed. The expansion performance of the slow-swelling pre-crosslinked gel particles is characterized by adopting the water absorption multiple, wherein the water absorption multiple is the ratio of the mass of the slow-swelling pre-crosslinked gel particles after water absorption to the mass of the slow-swelling pre-crosslinked gel particles before water absorption. The experimental results are shown in FIG. 2. As is clear from FIG. 2, the swelling time of the slow swelling pre-crosslinked gel particles was about 10 days, and the water absorption capacity was 15 times or more.
(3) Blocking performance of slow-swelling pre-crosslinked gel particles:
200g of each of the slow-swelling pre-crosslinked gel particles prepared in examples 1, 2 and 3 is uniformly mixed with 800g of quartz sand with the particle size of 60-80 meshes to obtain three parts of quartz sand mixed with the slow-swelling pre-crosslinked gel particles, and the quartz sand mixed with the slow-swelling pre-crosslinked gel particles is filled into a sand filling pipe (with the diameter of 20cm and the inner diameter of 2 cm) with the filling pressure of 5MPa; deionized water was injected from the inlet end of the sand filling pipe at 60 degrees celsius with a constant flow pump at a constant flow rate of 1ml/min, and the injection pressure was recorded, and the results of three sets of experiments are shown in fig. 3. The experimental result shows that the injection pressure is lower in the initial stage of water injection, the injection pressure gradually rises along with the time extension, the injection pressure can reach more than 1MPa after 10 days, and then the injection pressure is basically kept stable. Under the condition that the injection speed of deionized water is unchanged, the injection pressure is increased to indicate that the permeability of quartz sand in the sand filling pipe is reduced, so that the expansion of the slow-swelling pre-crosslinked gel particles plays a role in blocking the quartz sand. The higher the injection pressure rise, the stronger the corresponding plugging performance. The experimental results show that the slow-swelling pre-crosslinked gel particles have good plugging performance.
The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (3)
1. The plugging agent for the dominant seepage channel in the deep part of the reservoir is characterized in that the plugging agent is prepared from the following raw materials:
25-30 parts of acrylic acid, 0.025-0.15 part of sodium dodecyl sulfate, 0.025-0.09 part of N, N' -methylene bisacrylamide, 0.025-0.15 part of 1, 5-pentanediol diacrylate, 0.05-0.18 part of sodium bisulfate-ammonium persulfate, a pH regulator, wherein the dosage of the pH regulator should meet the requirement of the pH value of the solution after the regulation, and the balance of deionized water;
the preparation method of the plugging agent comprises the following steps:
a. adding deionized water and acrylic acid into a round-bottom flask, and regulating the pH value to 7.0-7.5 to obtain a solution with the pH value regulated;
b. adding sodium dodecyl sulfate, N' -methylenebisacrylamide and 1, 5-pentanediol diacrylate into the solution obtained in the step a, fully stirring, and then adding deionized water to prepare an aqueous solution with the mass concentration of 25% -30% of acrylic acid;
c. introducing nitrogen into an aqueous solution with the mass concentration of 25% -30% of acrylic acid to remove oxygen, then placing the aqueous solution in a constant-temperature water bath at 45 ℃ to heat, adding a sodium bisulfate-ammonium persulfate initiator after the temperature of the aqueous solution reaches 45 ℃, and maintaining the reaction temperature at 45 ℃ to react for 6 hours to obtain a reaction product;
and (3) drying and crushing the reaction product to obtain the plugging agent.
2. A plugging agent for a dominant seepage path in a deep portion of a reservoir according to claim 1, wherein the pH adjusting agent is sodium hydroxide.
3. The plugging agent for the dominant seepage channel of the deep part of a reservoir according to claim 2, wherein the molar ratio of sodium bisulphite to ammonium persulfate in the sodium bisulphite-ammonium persulfate system is 1:1.
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