CN112279963B - Temperature-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles and preparation method and application thereof - Google Patents
Temperature-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles and preparation method and application thereof Download PDFInfo
- Publication number
- CN112279963B CN112279963B CN202011600021.9A CN202011600021A CN112279963B CN 112279963 B CN112279963 B CN 112279963B CN 202011600021 A CN202011600021 A CN 202011600021A CN 112279963 B CN112279963 B CN 112279963B
- Authority
- CN
- China
- Prior art keywords
- reaction
- temperature
- resistant
- crosslinked gel
- gel particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
Abstract
The invention provides a temperature-resistant and salt-resistant multi-copolymerization pre-crosslinked gel particle, and a preparation method and application thereof, and belongs to the technical field of oil exploitation, transportation and chemical engineering. The pre-crosslinked gel particles provided by the invention are formed by copolymerizing acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, the copolymer has a stable structure and good high-temperature aging resistance, is not easy to hydrolyze, has good compatibility with polymers, greatly improves the viscosity of the system, improves the suspension performance of the pre-crosslinked gel particles in the system, and enables the oil displacement capacity of the system to be stronger and the oil displacement efficiency to be higher.
Description
Technical Field
The invention belongs to the technical field of petroleum exploitation, transportation and chemical engineering, and relates to a temperature-resistant salt-resistant multi-component copolymerization pre-crosslinked gel particle, and a preparation method and application thereof.
Background
Polymer flooding is one of the first developed tertiary oil recovery technologies, and is now used as the most mature technology of chemical flooding tertiary oil recovery, and is widely applied to foreign and domestic oil fields. The final recovery ratio of the oil reservoir after the polymer flooding can reach 40% -50%, more than 50% of residual oil still needs to be developed, and the oil reservoir exploitation potential is still very large.
The pre-crosslinked material is one new kind of polymer material, which is insoluble in water and expands into micron particle with certain viscoelasticity. In recent years, the plugging agent is widely applied to plugging a fracture development stratum, a high-permeability stratum and an ultrahigh-permeability stratum by matching with other plugging technologies. Although the pre-crosslinked body has the characteristics of deformation property, selective entry and the like in the stratum, the viscosity is not high due to the influence of temperature and mineralization degree, the improvement on the sweep efficiency is limited, and the requirement of different oil reservoirs on fully expanding the sweep volume is difficult to meet.
Patent application CN105368422A discloses a pre-crosslinked bulk-expanded particle profile control agent and a preparation method thereof, the pre-crosslinked bulk-expanded particle profile control agent is synthesized by 2-acrylamido octadecyl sulfonic acid or 2-acrylamido hexadecyl sulfonic acid, the synthesized pre-crosslinked bulk-expanded particle profile control agent is a body type high polymer with extremely high crosslinking degree, the content and the molecular weight of an internal free high polymer chain are very low, and the tackifying effect is poor. Patent CN102585093B discloses pre-crosslinked gel particles for profile control and polymer flooding, and a preparation method and application thereof, but the adopted pre-crosslinked gel particle crosslinking agent has unstable structure, and is easy to cause the network structure to be easily degraded and lose efficacy at the oil reservoir temperature. Therefore, a pre-crosslinked gel particle which has better temperature resistance and salt resistance, is easy to inject, can move in a stratum and has a dynamic profile control effect is not provided.
Disclosure of Invention
The invention provides a temperature-resistant salt-resistant multicomponent copolymerization pre-crosslinked gel particle, a preparation method and an application thereof, the pre-crosslinked gel particle adopts acrylamide and 2-acrylamide-2-methylpropanesulfonic acid as reaction raw materials, is matched with a preferred process, has stable reaction and is beneficial to chain growth, and the obtained product not only has high molecular weight, but also shows higher viscosity of an aqueous dispersion system in saline water with a certain temperature and mineralization degree.
In order to achieve the aim, the invention provides a preparation method of temperature-resistant and salt-resistant pre-crosslinked gel particles, which comprises the following steps:
adding deionized water into a reaction kettle, sequentially adding acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, and after completely dissolving, keeping the reaction system at 25-30 ℃ and stirring to be fully and uniformly mixed;
adding a cross-linking agent N, N-dimethylacrylamide into the reaction system, fully and uniformly mixing, adjusting the pH value in the reaction kettle under the protection of nitrogen, slowly adding a potassium persulfate-ionic liquid initiation system into the reaction system to initiate aqueous solution prepolymerization, and sealing the reaction kettle;
adding nano clay into the reaction system, and reacting for 3-4 hours at the final reaction temperature of 50 +/-1 ℃;
and after the polymerization reaction is finished, introducing hot water into the jacket of the reaction kettle for circulation, introducing steam into a steam heater of the reaction kettle for heating, raising the temperature of the gel in the reaction kettle to 80-85 ℃ for hydrolysis reaction, wherein the hydrolysis reaction is carried out for 1.5-2h, and after the reaction is finished, taking out a polymerization sample, drying and crushing to obtain the pre-crosslinked gel particles.
Preferably, the acrylamide added: 2-acrylamido-2-methylpropanesulfonic acid: the mass ratio of the deionized water is (0.15-0.5): (0.01-0.05): 1. it is understood that the acrylamide added: 2-acrylamido-2-methylpropanesulfonic acid: the mass ratio of deionized water may be adjusted within the above-mentioned range according to the actual circumstances, and may be, for example, 0.15:0.01:1, 0.15:0.02:1, 0.15:0.03:1, 0.15:0.04:1, 0.15:0.05:1, 0.2:0.01:1, 0.2:0.02:1, 0.2:0.03:1, 0.2:0.04:1, 0.2:0.05:1, 0.3:0.01:1, 0.3:0.02:1, 0.3:0.03:1, 0.3:0.04:1, 0.3:0.05:1, 0.4:0.01:1, 0.4:0.02:1, 0.4:0.03:1, 0.4:0.04:1, 0.4:0.05:1, 0.01:1, 0.5:0.02:1, 0.5: 1, 0.02:1, 0.5: 1, or any of the above-0.5: 1.
Preferably, the mass of the added cross-linking agent accounts for 2-3% of the total mass of the reaction system.
Preferably, the pH value in the reaction kettle is adjusted to 7-8. It will be appreciated that a suitable pH of the solution is effective in increasing the molecular weight of the polymer, and that if the pH is too high, the higher the reaction rate, meaning the concentration of active radicals in the solution increases, the molecular chain length of the pre-crosslinked gel particles will decrease accordingly, and if the pH is too low, the initiation rate of the monomer molecules will decrease, thereby decreasing the production efficiency.
Preferably, the mass ratio of the potassium persulfate to the ionic liquid in the initiation system is (7-9):1, and the initiation system accounts for 0.1-0.5% of the total mass of the reaction system. It is understood that the mass ratio of potassium persulfate to ionic liquid may be adjusted within the above range depending on the actual situation, and may also be, for example, 7.5:1, 8:1, 8.5:1, or any ratio within the above range. The initiator system may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5% or any value within the above range based on the total mass of the reaction system.
Preferably, the ionic liquid in the initiation system is at least one selected from 1-ethyl acetate-3-allyl imidazole tetrafluoroborate, 1-ethyl acetate-3-allyl imidazole hexafluorophosphate and 1-ethyl acetate-3-allyl imidazole bis (trifluoromethanesulfonyl) imide salt. It is understood that the ionic liquid is selected because it contains double bonds which can be copolymerized with acrylamide and incorporated into the main chain, and the peroxide can also react with free radicals in single electron transfer with the ionic liquid to form an initiation active site on the secondary carbon adjacent to the nitrogen, so as to initiate free radical polymerization to form a long-chain branch, and the chain-end free radicals can be terminated by coupling to form crosslinking, so as to generate a network structure of pre-crosslinked gel particles with a quantum amount of coexistent crosslinking network and long-chain branch.
Preferably, the mass of the added nano clay accounts for 2-2.5% of the total mass of the reaction system.
The invention provides a temperature-resistant salt-resistant multi-component copolymerization pre-crosslinked gel particle prepared by the preparation method according to any one of the technical schemes.
The invention provides application of the temperature-resistant and salt-resistant multi-copolymerization pre-crosslinked gel particles in oil field exploitation at the temperature of less than or equal to 90 ℃ and the mineralization degree of less than or equal to 19334mg/L according to the technical scheme. It can be understood that the pre-crosslinked gel particles have higher viscosity and viscoelasticity in oilfield exploitation, and can be helpful for improving the oil-water fluidity ratio and enlarging the swept area of the displacement phase, thereby improving the recovery ratio.
Preferably, the temperature-resistant and salt-resistant multicomponent copolymerization pre-crosslinked gel particles have a dispersion system stability time of more than or equal to 6 hours and a swollen particle size median of more than or equal to 781 μm at room temperature and a saline salinity of 19334 mg/L; under the conditions of high temperature of 90 ℃ and salinity of saline water of 19334mg/L, the viscosity of the water dispersion system is more than or equal to 166.2 mPa.s, and the elastic modulus of the water dispersion system is more than or equal to 1.7 Pa.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the pre-crosslinked gel particles provided by the invention are formed by copolymerizing acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, the copolymer has a stable structure, good high-temperature aging resistance and difficult hydrolysis, has high viscosity and viscoelasticity in oilfield exploitation, can improve the oil-water fluidity ratio, expand the swept area of a displacement phase and effectively improve the recovery ratio. The introduction of the N, N-dimethylacrylamide functional monomer further improves the temperature resistance and salt resistance, and can meet the preparation requirement of the oil field sewage.
2. The initiation system provided by the invention can excite a plurality of active points, not only can rapidly initiate reaction, but also can effectively control reaction rate, can greatly reduce byproducts generated by implosion, and has high relative molecular weight and easy separation between the polymer and the initiation system.
3. The nano clay provided by the invention not only effectively restrains polymer molecular chains in gaps of a layered structure, but also can uniformly disperse nano clay particles in a polymer network structure, and the synergistic effect between the nano clay particles and the polymer network structure further improves the stability of the temperature-resistant and salt-resistant multi-copolymerization pre-crosslinked gel particles.
4. The temperature-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles provided by the invention have good compatibility with polymers, greatly improve the viscosity of a system, and improve the suspension performance of the pre-crosslinked gel particles in the system, so that the oil displacement capacity of the system is stronger, and the oil displacement efficiency is higher.
Detailed Description
In order to more clearly and specifically describe the synthesis and application of the temperature-resistant and salt-tolerant multi-copolymerization pre-crosslinked gel particles provided by the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, but not all of the 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.
The method for measuring the product performance comprises the following steps:
1 solid content
1.1 weigh clean and dried to constant weight bottle mass to an accuracy of 0.0001g, recorded as m1。
1.2 Add about 2g viscoelastic particle displacement agent sample into constant weight weighing bottle, make sample evenly spread in weighing bottle, accurate to 0.0001g, mark as m2。
1.3 placing the weighing bottle with the sample in the 1.2 into a constant temperature drying box, and drying for 2 hours at the constant temperature of (105 +/-2) DEG C.
1.4 taking out the weighing bottle, putting the weighing bottle into a dryer, cooling for 30min, weighing until the weight is accurate to 0.0001g, and recording as m3。
1.5 three replicates of one sample were taken and the arithmetic mean was used as the measurement. When the individual values deviate from the arithmetic mean by more than 0.5%, a resampling measurement is required.
1.6 the solids S is calculated as follows:
S=(m 3 -m 1 )/(m 2 -m 1 )ⅹ100%—（1）
in the formula: s-solid content,%;
m1-weighing the bottle mass, g;
m2-sample mass before drying, g;
m3-sample mass after drying, g.
2 settling time of the Dispersion
2.1 accurately weighing (5/S) g of a temperature-resistant and salt-resistant multicomponent copolymer sample (S is solid content) to be accurate to 0.0001 g. Weighing (1000-5/S) g of victory brine II into a 1000mL wide-mouth bottle, starting a constant speed stirrer to slowly add a sample along the vortex wall for 30S at (400 +/-20) r/min, then stirring for 2h at the stirring speed of (500 +/-20) r/min, and then stopping stirring the wide-mouth bottle and sealing the wide-mouth bottle with a bottle cap.
2.2 starting timing when the stirring of the 2.1 sample is stopped, standing and observing the liquid level, and recording the time from the uniform dispersion to the clear interface of the dispersion, thereby determining the stable time of the dispersion.
3 median particle diameter after swelling
3.1 accurately weighing (5/S) g of viscoelastic particle oil displacement agent sample (S is solid content) to be accurate to 0.0001 g. Weighing (1000-5/S) g of victory saline II into a 1000mL wide-mouth bottle, starting a constant speed stirrer to slowly add a sample along the vortex wall for 30S at (400 +/-20) r/min, and then stirring for 2h at the stirring speed of (500 +/-20) r/min to obtain a solution with the concentration of 5000 mg/L.
3.2 taking a proper amount of the test solution prepared in the step 3.1, and measuring the median particle size (D50) on a laser particle distribution measuring instrument according to the operation steps.
4 modulus of elasticity of aqueous dispersion
4.1 taking temperature-resistant and salt-resistant multi-copolymerization pre-crosslinked gel particles, preparing a proper amount of test solution for the test by 3.1 using the victory saline II.
4.2 starting up and setting conditions according to the rheometer operation instruction, setting the measurement temperature to be 90 ℃, transferring the solution to be measured into a measuring cylinder, keeping the temperature for 3 min, selecting a coaxial cylinder mode and a rotor model CC27, and carrying out the elastic modulus test of the temperature-resistant and salt-resistant multi-copolymerization pre-crosslinked gel particle water dispersion system under the conditions of the set stress of 0.1Pa and the frequency of 1.0 Hz.
4.3 each sample should be 3 replicates according to 3.1-3.2, the relative error of each measured value and the arithmetic mean value is not more than 10%, and the arithmetic mean value is taken as the measured result.
5 viscosity of aqueous Dispersion
5.1 taking 2.1 moderate temperature resistant and salt resistant multi-copolymerization pre-crosslinked gel particles rather than saline II to prepare a proper amount of test solution.
5.2 starting up and setting conditions according to the rheometer operation instruction, setting the measurement temperature to be 90 ℃, moving the solution to be measured into a measuring cylinder, keeping the temperature for 3 min, selecting a coaxial cylinder mode, setting the rotor model number CC27 and the shear rate to be 7.34 s-1And measuring the viscosity of the dispersion system within 1 min according to the operation instruction of the rheometer, and taking the average value of the viscosity to obtain the viscosity of the dispersion system.
5.3 each sample should be processed into 3 parallel samples according to 4.1-4.2, the relative error of each measured value and the arithmetic mean value is not more than 10%, and the arithmetic mean value is taken as the measured result.
Example 1
Adding 100Kg of deionized water into a reaction kettle, sequentially adding 15Kg of AM and 1Kg of AMPS, adding the next substance after the former substance is completely dissolved, simultaneously keeping the temperature of the reaction system at 25 ℃, stirring for 1h, and finally fully stirring and uniformly mixing. 2.32Kg of N, N-dimethylacrylamide is added into the reaction system, and after the N, N-dimethylacrylamide is dissolved and uniformly mixed, nitrogen is introduced into a nitrogen port at the bottom of the reaction kettle for 30min to the reaction solution, so that oxygen in the reaction system can be removed sufficiently. Adjusting the pH value in the reaction kettle, and slowly adding 0.1015Kg of potassium persulfate and 0.0145Kg of 1-ethyl acetate-3-allyl imidazole tetrafluoroborate composite initiation system aqueous solution into the reaction system under the protection of nitrogen for prepolymerization.
And (3) sealing the reaction kettle, adding 2.32Kg of nano clay in the process, reacting for 3 hours, and recording the temperature change in the process, wherein the final reaction temperature is about 50 ℃.
And after the polymerization reaction is finished, introducing hot water into a jacket of the reaction kettle for circulation, introducing steam into a steam heater in the reaction kettle for heating at the same time, raising the temperature of the rubber body in the kettle to 80 ℃, carrying out hydrolysis reaction, wherein the hydrolysis reaction period is 1.5h, taking out the polymerization sample after the hydrolysis reaction is finished, shearing the polymerization sample into pieces, drying the polymerization sample in a vacuum drying oven at 100 ℃, and screening the pieces by using a standard screen to obtain the pre-crosslinked gel particles JX-1.
Example 2
Adding 100Kg of deionized water into a reaction kettle, sequentially adding 15Kg of AM and 5Kg of AMPS, adding the next substance after the former substance is completely dissolved, simultaneously keeping the temperature of the reaction system at 30 ℃, stirring for 1h, and finally fully stirring and uniformly mixing. Adding 3.12Kg of N, N-dimethylacrylamide into the reaction system, and after the N, N-dimethylacrylamide is dissolved and uniformly mixed, introducing nitrogen into the reaction solution for 30min at a nitrogen port at the bottom of the reaction kettle, so as to be convenient for fully removing oxygen in the reaction system. Adjusting the pH value in the reaction kettle, and slowly adding 0.54Kg of potassium persulfate and 0.06Kg of 1-ethyl acetate-3-allyl imidazole bis (trifluoromethanesulfonyl) imide salt composite initiation system aqueous solution into the reaction system under the protection of nitrogen for prepolymerization.
And (3) sealing the reaction kettle, adding 2.6Kg of nano clay in the process, reacting for 4 hours, wherein the final reaction temperature is about 50 ℃, and recording the temperature change in the process.
And after the polymerization reaction is finished, introducing hot water into a jacket of the reaction kettle for circulation, introducing steam into a steam heater in the reaction kettle for heating at the same time, raising the temperature of colloid in the kettle to 85 ℃, carrying out hydrolysis reaction for 2h, taking out the polymerization sample after the hydrolysis reaction is finished, shearing the polymerization sample into pieces, drying the polymerization sample in a vacuum drying oven at 100 ℃, and screening the crushed polymerization sample by a standard screen to obtain the pre-crosslinked gel particles JX-2.
Example 3
Adding 100Kg of deionized water into a reaction kettle, sequentially adding 50Kg of AM and 1Kg of AMPS, adding the next substance after the former substance is completely dissolved, simultaneously keeping the temperature of the reaction system at 27 ℃, stirring for 1h, and finally fully stirring and uniformly mixing. 1.609Kg of N, N-dimethylacrylamide is added into the reaction system, after the N, N-dimethylacrylamide is dissolved and mixed fully and uniformly, nitrogen is introduced into the reaction liquid for 30min from a nitrogen port at the bottom of the reaction kettle, so that oxygen in the reaction system can be removed fully. Adjusting the pH value in the reaction kettle, and slowly adding 0.4027Kg of potassium persulfate and 0.0503Kg of 1-ethyl acetate-3-allyl imidazole hexafluorophosphate compounded initiation system aqueous solution into the reaction system under the protection of nitrogen for prepolymerization.
The reaction kettle is sealed, 3.322Kg of nano clay is added in the process, the reaction time is 3.5h, the final reaction temperature is about 50 ℃, and the temperature change in the process is recorded.
And after the polymerization reaction is finished, introducing hot water into a jacket of the reaction kettle for circulation, introducing steam into a steam heater in the reaction kettle for heating at the same time to raise the temperature of the glue in the kettle to 82 ℃, carrying out hydrolysis reaction, wherein the hydrolysis reaction period is 1.8h, taking out the polymerization sample after the hydrolysis reaction is finished, shearing the polymerization sample into pieces, drying the polymerization sample in a vacuum drying oven at 100 ℃, and screening the pieces by using a standard screen to obtain the pre-crosslinked gel particles JX-3.
Example 4
Adding 100Kg of deionized water into a reaction kettle, sequentially adding 50Kg of AM and 5Kg of AMPS, adding the next substance after the former substance is completely dissolved, simultaneously keeping the temperature of the reaction system at 25 ℃, stirring for 1h, and finally fully stirring and uniformly mixing. Adding 3.1Kg of N, N-dimethylacrylamide into the reaction system, and after the N, N-dimethylacrylamide is dissolved and uniformly mixed, introducing nitrogen into the reaction solution for 30min at a nitrogen port at the bottom of the reaction kettle, so as to be convenient for fully removing oxygen in the reaction system. Adjusting the pH value in the reaction kettle, and slowly adding 0.1356Kg of potassium persulfate and 0.0194Kg of 1-ethyl acetate-3-allyl imidazole tetrafluoroborate composite initiation system aqueous solution into the reaction system under the protection of nitrogen for prepolymerization.
And (3) sealing the reaction kettle, adding 3.1Kg of nano clay in the process, reacting for 3 hours, wherein the final reaction temperature is about 50 ℃, and recording the temperature change in the process.
And after the polymerization reaction is finished, introducing hot water into a jacket of the reaction kettle for circulation, introducing steam into a steam heater in the reaction kettle for heating at the same time, raising the temperature of the rubber body in the kettle to 80 ℃, carrying out hydrolysis reaction, wherein the hydrolysis reaction period is 1.5h, taking out the polymerization sample after the hydrolysis reaction is finished, shearing the polymerization sample into pieces, drying the polymerization sample in a vacuum drying oven at 100 ℃, and screening the pieces by using a standard screen to obtain the pre-crosslinked gel particles JX-4.
Example 5
Adding 100Kg of deionized water into a reaction kettle, sequentially adding 50Kg of AM and 5Kg of AMPS, adding the next substance after the former substance is completely dissolved, simultaneously keeping the temperature of the reaction system at 30 ℃, stirring for 1h, and finally fully stirring and uniformly mixing. 4.65Kg of N, N-dimethylacrylamide is added into the reaction system, and after the N, N-dimethylacrylamide is dissolved and uniformly mixed, nitrogen is introduced into a nitrogen port at the bottom of the reaction kettle for 30min to the reaction solution, so that oxygen in the reaction system can be removed sufficiently. Adjusting the pH value in the reaction kettle, and slowly adding 0.6975Kg of potassium persulfate and 0.0775Kg of 1-ethyl acetate-3-allyl imidazole bis (trifluoromethanesulfonyl) imide salt composite initiation system aqueous solution into the reaction system under the protection of nitrogen for prepolymerization.
And (3) sealing the reaction kettle, adding 3.875Kg of nano clay in the process, reacting for 4 hours, keeping the reaction final temperature at about 50 ℃, and recording the temperature change in the process.
And after the polymerization reaction is finished, introducing hot water into a jacket of the reaction kettle for circulation, introducing steam into a steam heater in the reaction kettle for heating at the same time, raising the temperature of colloid in the kettle to 85 ℃, carrying out hydrolysis reaction for 2h, taking out the polymerization sample after the hydrolysis reaction is finished, shearing the polymerization sample into pieces, drying the polymerization sample in a vacuum drying oven at 100 ℃, and screening the crushed polymerization sample by a standard screen to obtain the pre-crosslinked gel particles JX-5.
Comparative example 1
Adding a proper amount of 100Kg of deionized water into a reaction kettle, sequentially adding 15Kg of Acrylic Acid (AA) and 1Kg of AMPS, adding the next substance after the former substance is completely dissolved, simultaneously keeping the temperature of the reaction system at 25 ℃, stirring for 1h, and finally fully stirring and uniformly mixing. 2.32Kg of N, N-dimethylacrylamide is added into the reaction system, and after the N, N-dimethylacrylamide is dissolved and uniformly mixed, nitrogen is introduced into a nitrogen port at the bottom of the reaction kettle for 30min to the reaction solution, so that oxygen in the reaction system can be removed sufficiently. Adjusting the pH value in the reaction kettle, and slowly adding 0.1015Kg of potassium persulfate and 0.0145Kg of 1-ethyl acetate-3-allyl imidazole tetrafluoroborate composite initiation system aqueous solution into the reaction system under the protection of nitrogen for prepolymerization.
And (3) sealing the reaction kettle, adding 2.32Kg of nano clay in the process, reacting for 3 hours, and recording the temperature change in the process, wherein the final reaction temperature is about 50 ℃.
And after the polymerization reaction is finished, introducing hot water into a jacket of the reaction kettle for circulation, introducing steam into a steam heater in the reaction kettle for heating at the same time, raising the temperature of the rubber body in the kettle to 80 ℃, carrying out hydrolysis reaction, wherein the hydrolysis reaction period is 1.5h, taking out the polymerization sample after the hydrolysis reaction is finished, shearing the polymerization sample into pieces, drying the polymerization sample in a vacuum drying oven at 100 ℃, and screening the pieces by using a standard screen to obtain the pre-crosslinked gel particles JX-6.
Comparative example 2
Adding a proper amount of 100Kg of deionized water into a reaction kettle, then sequentially adding 50Kg of AM and 1Kg of AMPS, adding the next substance after the former substance is completely dissolved, simultaneously keeping the temperature of the reaction system at 27 ℃, stirring for 1h, and finally fully stirring and uniformly mixing. 1.609Kg of N, N-dimethylacrylamide is added into the reaction system, after the N, N-dimethylacrylamide is dissolved and mixed fully and uniformly, nitrogen is introduced into the reaction liquid for 30min from a nitrogen port at the bottom of the reaction kettle, so that oxygen in the reaction system can be removed fully. Adjusting the pH value in the reaction kettle, and slowly adding 0.4027Kg of potassium persulfate and 0.0503Kg of 1-ethyl acetate-3-allyl imidazole hexafluorophosphate compounded initiation system aqueous solution into the reaction system under the protection of nitrogen for prepolymerization.
And sealing the reaction kettle, reacting for 3.5h, wherein the final reaction temperature is about 50 ℃, and recording the temperature change in the process.
And after the polymerization reaction is finished, introducing hot water into a jacket of the reaction kettle for circulation, introducing steam into a steam heater in the reaction kettle for heating at the same time to raise the temperature of the rubber body in the kettle to 82 ℃ for hydrolysis reaction, wherein the hydrolysis reaction period is 1.8h, taking out the polymerization sample after the hydrolysis reaction is finished, shearing the polymerization sample into pieces, drying the polymerization sample in a vacuum drying oven at 100 ℃, and screening the pieces by using a standard screen to obtain the pre-crosslinked gel particles JX-7.
Comparative example 3
Adding 100Kg of deionized water into a reaction kettle, sequentially adding 50Kg of AM and 5Kg of AMPS, adding the next substance after the former substance is completely dissolved, simultaneously keeping the temperature of the reaction system at 25 ℃, stirring for 1h, and finally fully stirring and uniformly mixing. Adding 3.1Kg of N, N-dimethylacrylamide into the reaction system, and after the N, N-dimethylacrylamide is dissolved and uniformly mixed, introducing nitrogen into the reaction solution for 30min at a nitrogen port at the bottom of the reaction kettle, so as to be convenient for fully removing oxygen in the reaction system. Adjusting the pH value in the reaction kettle, and slowly adding 0.1356Kg of potassium persulfate initiator aqueous solution into the reaction system for prepolymerization under the protection of nitrogen.
And (3) sealing the reaction kettle, adding 3.1Kg of nano clay in the process, reacting for 3 hours, wherein the final reaction temperature is about 50 ℃, and recording the temperature change in the process.
And after the polymerization reaction is finished, introducing hot water into a jacket of the reaction kettle for circulation, introducing steam into a steam heater in the reaction kettle for heating at the same time, raising the temperature of the rubber body in the kettle to 80 ℃, carrying out hydrolysis reaction, wherein the hydrolysis reaction period is 1.5h, taking out the polymerization sample after the hydrolysis reaction is finished, shearing the polymerization sample into pieces, drying the polymerization sample in a vacuum drying oven at 100 ℃, and screening the pieces by using a standard screen to obtain the pre-crosslinked gel particles JX-8.
Performance testing
In order to further verify that the obtained product has good temperature and salt resistance effects, when the median particle size after swelling, the elastic modulus of a water dispersion system, the viscosity of the water dispersion system and the stability time of the dispersion system are measured according to a product performance test method, the experiment is performed based on the existing technical requirement Q/SH 102023742020 of viscoelastic particle oil displacement agents, under the premise that other conditions are not changed, the specified test temperature is only increased from (70 +/-0.5) DEG C to (90 +/-0.5) DEG C, and the simulated water mineralization degree for the experiment is increased from 5727mg/L to 19334mg/L (aiming at proving the temperature and salt resistance of the product), and the results are shown in Table 1.
TABLE 1 Performance test results for various examples/comparative examples
As can be seen from the above table 1, when the technical requirements specified by the product performance measuring method are tested, the technical indexes JX-1, JX-2, JX-3, JX-4 and JX-5 are all obviously higher than the technical requirements specified in the technical requirement Q/SH 102023742020 of the viscoelastic particle oil displacement agent of the existing standard, and the test value is also measured under the conditions of raising the test temperature and experimentally simulating the water mineralization degree. Unlike the examples, comparative example 1, in which the activation energy required for the reaction substrate AA to generate radicals is low, when an initiator is added, the conversion rate of polymerization reaction is too high, the product is sufficiently crosslinked, the molecular chain is difficult to extend, the length of the branch chain generated at the end of the polymer network is limited, and the JX-6 aqueous dispersion has a low viscosity due to the complete granular feeling. Comparative example 2 no nanoclay was added and the polymer molecular chain could not act synergistically with the nanoclay particles, thus the temperature-resistant salt-resistant multicomponent copolymerization pre-crosslinked gel particles JX-7 were less stable. In addition, in comparative example 3, when only potassium persulfate was used for the initiation system, the amount of the initiated soluble components in the polymer increased, the degree of crosslinking decreased, and the granular feel of the dispersion decreased, so that the median particle diameter and the elastic modulus of the dispersion after swelling of the temperature-resistant salt-resistant multicomponent copolymerized pre-crosslinked gel particles JX-8 were both greatly decreased.
Claims (8)
1. The preparation method of the temperature-resistant and salt-resistant multi-copolymerization pre-crosslinked gel particles is characterized by comprising the following steps:
adding deionized water into a reaction kettle, sequentially adding acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, and after completely dissolving, keeping the reaction system at 25-30 ℃ and stirring to be fully and uniformly mixed;
adding a cross-linking agent N, N-dimethylacrylamide into the reaction system, fully and uniformly mixing, adjusting the pH value in the reaction kettle under the protection of nitrogen, slowly adding a potassium persulfate-ionic liquid initiation system into the reaction system to initiate aqueous solution prepolymerization, and sealing the reaction kettle;
adding nano clay into the reaction system, and reacting for 3-4h, wherein the final reaction temperature is 50 +/-1 ℃;
after the polymerization reaction is finished, introducing hot water into a jacket of the reaction kettle for circulation, introducing steam into a steam heater of the reaction kettle for heating at the same time, raising the temperature of the gel in the reaction kettle to 80-85 ℃ for hydrolysis reaction, wherein the hydrolysis reaction is carried out for 1.5-2h, and after the reaction is finished, taking out a polymerization sample, drying and crushing to obtain pre-crosslinked gel particles;
the ionic liquid in the initiation system is selected from at least one of 1-ethyl acetate-3-allyl imidazole tetrafluoroborate, 1-ethyl acetate-3-allyl imidazole hexafluorophosphate and 1-ethyl acetate-3-allyl imidazole bis (trifluoromethanesulfonyl) imide salt;
the mass ratio of potassium persulfate to ionic liquid in the initiation system is (7-9):1, and the initiation system accounts for 0.1-0.5% of the total mass of the reaction system.
2. The method according to claim 1, wherein the ratio of acrylamide: 2-acrylamido-2-methylpropanesulfonic acid: the mass ratio of the deionized water is (0.15-0.5): (0.01-0.05): 1.
3. the method according to claim 1, wherein the mass of the crosslinking agent added is 2 to 3% of the total mass of the reaction system.
4. The method according to claim 1, wherein the pH in the reaction vessel is adjusted to 7 to 8.
5. The method according to claim 1, wherein the amount of the nanoclay added is 2 to 2.5% by mass based on the total mass of the reaction system.
6. The temperature-resistant and salt-resistant multi-copolymerization pre-crosslinked gel particles prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the temperature and salt tolerant multicomponent copolymeric pre-crosslinked gel particles of claim 6 in oil field mining at a temperature of 90 ℃ or less and a degree of mineralization of 19334mg/L or less.
8. The application of the heat-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles as claimed in claim 7, wherein the dispersion system of the temperature-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles has a stable time of not less than 6h and a median value of particle sizes after swelling of not less than 781 μm at room temperature and a salinity of saline solution of 19334 mg/L; under the conditions of high temperature of 90 ℃ and salinity of saline water of 19334mg/L, the viscosity of the water dispersion system is more than or equal to 166.2 mPa.s, and the elastic modulus of the water dispersion system is more than or equal to 1.7 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011600021.9A CN112279963B (en) | 2020-12-30 | 2020-12-30 | Temperature-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011600021.9A CN112279963B (en) | 2020-12-30 | 2020-12-30 | Temperature-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112279963A CN112279963A (en) | 2021-01-29 |
| CN112279963B true CN112279963B (en) | 2021-03-09 |
Family
ID=74426948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011600021.9A Active CN112279963B (en) | 2020-12-30 | 2020-12-30 | Temperature-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112279963B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213594B (en) * | 2021-10-12 | 2022-06-14 | 山东聚星石油科技有限公司 | Preparation method and application of heterogeneous oil displacement system based on temperature-resistant and salt-resistant viscoelastic particle oil displacement agent |
| CN115677905B (en) * | 2022-10-13 | 2023-06-27 | 兰州理工大学 | Preparation method of polyacrylamide gel particles |
| CN117050231A (en) * | 2023-09-25 | 2023-11-14 | 山东聚星石油科技有限公司 | Amphiphilic hyperbranched polymer emulsion for oil displacement as well as preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8163834B2 (en) * | 2009-03-18 | 2012-04-24 | Dublin City University | Photoresponsive ionogel |
| CN102585093B (en) * | 2012-02-24 | 2014-09-24 | 中国石油天然气股份有限公司 | Pre-crosslinked gel granulate for profile control and polymer flooding as well as preparation method and application of pre-crosslinked gel granulates |
| CN103570867B (en) * | 2012-07-27 | 2015-12-16 | 中国石油化工股份有限公司 | A kind of Acrylamide terpolymer and its preparation method and application |
| CN106008804B (en) * | 2016-06-04 | 2017-09-01 | 王金明 | A kind of method that post-crosslinking method prepares oil-well cement filtrate reducer |
-
2020
- 2020-12-30 CN CN202011600021.9A patent/CN112279963B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112279963A (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112279963B (en) | Temperature-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles and preparation method and application thereof | |
| CN109705834B (en) | Composition, temperature-resistant salt-resistant fracturing fluid thickening agent prepared from composition and preparation method of thickening agent | |
| CN107771191B (en) | Water-soluble or water-swellable polymers as fluid loss agents in cement slurries | |
| CN103666433B (en) | Oil-displacing agent composition used for improving recovery ratio of high-temperature reservoir and preparation method of composition | |
| CN101691485A (en) | High temperature resistant amphoteric ion polymer fluid loss agent used for drilling fluid and preparation method thereof | |
| CN113214809B (en) | Environment-friendly profile control water plugging system, preparation method thereof and application thereof in medium-low-temperature high-water-content oil reservoir | |
| WO2013138156A1 (en) | Synthesis and application of high pressure high temperature fluid loss additive and rheology stabilizer | |
| CN104449636B (en) | Oil displacement agent of recovery ratio and preparation method thereof is improved suitable for high temperature and high salt harshness oil reservoir | |
| El-Hoshoudy et al. | Investigation of optimum polymerization conditions for synthesis of cross-linked polyacrylamide-amphoteric surfmer nanocomposites for polymer flooding in sandstone reservoirs | |
| CN102181010A (en) | Preparation method of high-temperature-resistant high-salt polymer oil-replacement agent | |
| CN104151574B (en) | A kind of cement additive with temperature sensitive thickening power and preparation method thereof | |
| CN114213594B (en) | Preparation method and application of heterogeneous oil displacement system based on temperature-resistant and salt-resistant viscoelastic particle oil displacement agent | |
| CN112321764B (en) | Temperature-resistant salt-resistant viscoelastic particle oil displacement agent and preparation method and application thereof | |
| CN103788295B (en) | A kind of two-step method prepares the method for acrylamide based copolymer | |
| CN104892837A (en) | Preparation method of fluid loss agent for well-cementing cement slurry | |
| CN113549438A (en) | Water plugging agent and preparation method and application thereof | |
| CN104774287A (en) | Polyacrylate emulsion microgel and preparation method thereof | |
| CN102391849A (en) | Imidazole polymer oil displacement agent and synthesizing method thereof | |
| CN110790862B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN104744623B (en) | A kind of concrete workability conditioning agent and preparation method thereof | |
| CN110790859B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN104403052A (en) | Acrylamide copolymer oil-dispelling agent with sulfitobetaine structure and synthesis method | |
| CN102898665B (en) | Method for preparing adsorptive double cross-linked amphoteric cassava starch | |
| CN105154054B (en) | A kind of tertiary amine participates in crosslinking polymer oil displacement agent of synthesis and preparation method thereof | |
| CN117720698B (en) | Temperature-resistant salt-resistant nano-crosslinked polymer microsphere and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 208, Nan'er Road, Dongying District, Dongying City, Shandong Province 257067 Patentee after: Shandong Juxing Petroleum Technology Co.,Ltd. Address before: 257087 No.208, Nan'er Road, Dongying District, Dongying City, Shandong Province Patentee before: Dongying Juxing Petroleum Technology Co.,Ltd. |