CN113185630A - Biodegradable salt-tolerant thickening system and preparation method and application thereof - Google Patents
Biodegradable salt-tolerant thickening system and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a biodegradable salt-tolerant thickening system and a preparation method and application thereof. Compared with the existing fracturing system, the thickening system has better salt tolerance when being applied to the fracturing system; the biodegradability is good, and the damage to the surrounding environment and the stratum permeability can be reduced; the viscosity can be formed in a short time during field preparation, the operation is simple, and the use is convenient; the slippery water and the linear glue solution can be flexibly prepared by controlling the addition amount, and the preparation method has the advantage of one dose with multiple purposes.
Description
Technical Field
The invention relates to the field of acidizing and fracturing agents, in particular to a biodegradable salt-tolerant thickening system and a preparation method and application thereof.
Background
The application of the hydraulic fracturing technology in oil fields starts in the last 40 th century, and gradually becomes one of important yield increasing measures for improving the productivity of oil and gas wells and the recovery ratio of oil reservoirs after the development of more than 70 years. In particular, in recent years, low permeability reservoirs face the situation of low oil recovery rate, low recovery ratio, low reserve utilization rate and difficult energy supplement, and the hydraulic fracturing technology is increasingly regarded as a main technical means for improving the energy production of the low permeability reservoirs. With the increase of oil and gas exploration and development time, the conventional oil and gas yield is continuously reduced, and low-permeability and ultra-low-permeability oil and gas resources have become new hotspots for current oil and gas development, and are paid attention by various countries and oil companies. China has abundant oil and gas resources of low-permeability reservoirs, and the development of the low-permeability oil and gas can form industrial productivity only by carrying out large-scale fracturing, so that high-efficiency development is realized.
The development of hydraulic fracturing for many years gradually forms a slickwater fracturing system and a linear gel fracturing system which take a polymer as a thickening resistance-reducing agent and a clean fracturing fluid system which takes a viscoelastic surfactant as a thickening agent. The clean fracturing fluid uses the micromolecule surfactant as the thickening agent, so that gel breaking is thorough, even the residual surfactant has little damage to the stratum, and meanwhile, the flowback fluid is easy to treat. But the use amount of the thickening agent is relatively high (generally more than 5 wt%), and the temperature resistance and salt tolerance are relatively poor, so that the application in oil and gas fields is relatively less. The polymer-based slickwater and linear gel fracturing system has the advantages of simplicity in preparation, convenience in application, low use cost and the like, is applied in a large scale in the fracturing process of an oil and gas field, but the used polymer is difficult to break gel thoroughly, the molecular weight of the residual polymer after gel breaking is still large, stratum damage can be caused, flowback liquid is difficult to treat and the like, and great problems are brought to the subsequent treatment of the fracturing construction of the oil and gas field.
Therefore, the existing thickening product is difficult to protect the stratum while ensuring better temperature resistance and salt resistance. Therefore, the thickener product with good operation performance and environment friendliness is developed, and the method has important significance for green low-damage development of unconventional oil and gas reservoirs.
Disclosure of Invention
The invention mainly solves the technical problem of providing a biodegradable salt-tolerant thickening system which is biodegradable and has little damage to the stratum.
In order to solve the above technical problems, the inventors tried to modify the polyacrylamide-based polymer in the thickener by introducing some second monomer, and copolymerizing with the monomer of acrylamide structure, in order to obtain a biodegradable polyacrylamide-based polymer.
The invention provides a biodegradable polyacrylamide-based polymer, which comprises a first monomer unit and a second monomer unit, wherein the first monomer unit is selected from one or more of acrylamide and acrylamide with substituted amino, and the second monomer unit is selected from one or more of maleic anhydride, vinyl acetate, epsilon-caprolactone, acrylate, vinyl acetoacetate and p-vinylaniline.
When the second monomer is polymerized, the double bonds in the molecules are broken into single bonds, the single bonds are embedded into the main chain of the polymer to jointly form the main chain structure of the polymer, and the rest groups form the side chain structure of the polymer. The epsilon-caprolactone without double bonds in the molecular structure is broken by single bonds between acyl and oxygen in ester bonds to form two connecting ends to participate in polymerization.
The structure of the acetoacetic acid vinyl ester is as follows:
further, the first monomer is selected from one or more of acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and carboxyl betaine methacrylic acid.
The structure of carboxybetaine methacrylic acid is as follows:
further, the mole percentage content of the second monomer unit in the polyacrylamide-based polymer is 20.0-60.0%.
In a specific embodiment of the present invention, the molar percentage content of the second monomer unit in the polyacrylamide-based polymer is 25 to 60%.
The mole percent of the second monomer unit in the polyacrylamide-based polymer is the ratio of the molar amount of the second monomer unit to the total molar amount of all monomer units in the polymer, i.e., the mole amount of the second monomer participating in the polymerization reaction to the molar amount of all monomers (the second monomer and acrylamide) participating in the polymerization.
Further, the molecular weight of the biodegradable polyacrylamide-based polymer is 1500 to 4000 ten thousand, preferably 3500 ten thousand.
The invention also provides a preparation method of the biodegradable polyacrylamide-based polymer, which comprises the following steps: the monomer raw material is mixed with water and then mixed with an initiator under the atmosphere of inert gas and/or nitrogen to carry out copolymerization reaction.
Further, after the monomer raw material is mixed with water, the mass fraction of the monomer raw material in the mixed solution is 20-40%.
Further, the copolymerization reaction time is 4-10 h, preferably 4-8 h.
Further, the initiator is selected from one or more of azobisisobutyronitrile, ammonium persulfate and sodium bisulfite, preferably azobisisobutyronitrile, or ammonium persulfate and sodium bisulfite.
Further, the mass amount of the initiator is 0.01-0.2%, preferably 0.01-0.1%, and more preferably 0.04-0.1% of the total mass of the monomer raw materials.
Further, the temperature of the copolymerization reaction is 2 to 50 ℃, preferably 5 to 45 ℃.
Furthermore, after the copolymerization reaction is completed, the product obtained by the reaction is washed and dried.
Through continuous research and experiments, the inventor obtains a copolymerization product by polymerizing a biodegradable monomer and acrylamide together, but the copolymerization product does not have a biodegradation function when applied to a thickening agent after polymerization, and even if the copolymerization product has the biodegradation function, the inventor cannot determine whether the copolymerization product has good operation performances such as thickening, resistance reduction, salt tolerance, temperature tolerance and the like under the condition that a main chain and a side chain of polyacrylamide are greatly changed.
In order to verify the operation performance and degradation performance of the biodegradable polyacrylamide-based polymer in a fracturing system when the biodegradable polyacrylamide-based polymer is applied to a thickening agent product, the inventor prepares the biodegradable polyacrylamide-based polymer into fracturing fluids with different concentrations for detection, and finds that the thickening agent using the biodegradable polyacrylamide-based polymer has good biodegradability and the degradation effect is generally influenced by the concentration of the molar content of a second monomer; meanwhile, the coating still has good resistance reduction, salt resistance and the like, and has excellent operation performance.
The invention provides a biodegradable salt-tolerant thickening system comprising a biodegradable polyacrylamide-based polymer of the invention.
The polymer used in the invention has better biodegradability, and the regulation of the molecular weight of the degradation product of the biodegradable polymer and the required degradation time can be realized by adjusting the content of the second monomer.
Further, the mass fraction of the biodegradable polyacrylamide-based polymer in the thickening system is 20.0-60.0%, preferably 30.0-50.0%, and more preferably 40%.
Further, the biodegradable salt-resistant thickening system also comprises a thixotropic agent.
Further, the mass fraction of the thixotropic agent in the thickening system is 0.5 to 3.0%, preferably 2.0 to 3.0%, and more preferably 2.0%.
Further, the thixotropic system is selected from one or more of montmorillonite, modified bentonite, modified nano-silica, carboxymethyl cellulose, polyurethane resin and polyamide wax.
Further, the biodegradable salt-tolerant thickening system also comprises a cleanup additive.
The introduced cleanup additive not only has the functions of reducing surface and interfacial tension, improving resistance reduction rate and facilitating the flowback of the gel breaking liquid, but also can stabilize structural viscosity through the synergistic effect with the thixotropic agent, and in addition, the polar part of the cleanup additive can generate the effect with polymer particles, thereby enhancing the suspension performance of the polymer in a system.
Furthermore, the mass fraction of the cleanup additive in the thickening system is 0.5-2.5%, preferably 1.0-2.5%, and more preferably 1.5%.
Further, the cleanup additive is selected from one or more of sodium dodecyl sulfate, sodium oleate, sodium palmitate, erucamidopropyldimethyl betaine, oleamidopropyldimethyl betaine, dodecyl sulfobetaine, octyl phenol polyoxyethylene ether, Tween-20, Tween-80, Span-60 and Span-80.
Further, the biodegradable salt-tolerant thickening system also comprises a solvent.
According to the conventional technology in the field, the solvent mainly has the function of dissolving each component in the thickening system, the content of the solvent is the mass remained after subtracting the components such as the polymer, the thixotropic agent, the cleanup additive and the like, and the specific content of the solvent is changed along with the change of the added component, and is not limited to a specific range.
Further, the solvent is an organic solvent;
further, the organic solvent is selected from one or more of polyethylene glycol, diethylene glycol dimethyl ether, propylene glycol, condensed glycerol, N-dimethylformamide, white oil and kerosene.
In the invention, the biodegradable salt-tolerant thickening system comprises the following components in percentage by weight: the biodegradable polyacrylamide-based polymer is 30.0-50.0% of biodegradable polyacrylamide-based polymer, 0.5-3.0% of thixotropic agent, 0.5-2.5% of cleanup additive and the balance solvent.
Further, the biodegradable salt-tolerant thickening system comprises the following components in percentage by weight: 30.0 to 50.0% of the biodegradable polyacrylamide-based polymer according to any one of claims 1 to 3, 2.0 to 3.0% of a thixotropic agent, 1.0 to 2.5% of a cleanup additive, and the balance being a solvent.
The invention also provides a preparation method of the biodegradable salt-tolerant thickening system, which comprises the following steps: mixing all the components;
further, the solvent, the thixotropic agent, the biodegradable polyacrylamide-based polymer and the cleanup additive are mixed in sequence.
The sequential mixing refers to mixing the solvent and the thixotropic agent, then mixing the solvent and the thixotropic agent together, and then mixing the solvent and the thixotropic agent together with the polymer and mixing the solvent and the polymer together with the cleanup additive.
The invention also provides application of the biodegradable salt-tolerant thickening system in development of medium-low permeability, ultra-low permeability oil-gas reservoirs or medium-high salinity oil-gas reservoirs.
The application of the salt-tolerant biodegradable thickening system as described above can be carried out by the following steps: adding 0.05-0.2 wt% of a salt-resistant biodegradable fracturing system into tap water or mineralized water, stirring at the speed of 50-100 r/min for 0.5-10 minutes to obtain the biodegradable slickwater fracturing system. Adding 0.5-2.0 wt% of a salt-resistant biodegradable fracturing system into tap water or mineralized water, stirring at the speed of 200-1500 r/min for 5-30 minutes to obtain the biodegradable linear glue fracturing system.
The mineralization degree of the mineralized water in the application method is less than or equal to 10.0 wt%, and the mineralized water comprises high-mineralization-degree water such as oil field flowback fluid, formation water and the like.
The invention has the beneficial effects that:
(1) compared with the existing fracturing system, the thickening system has better salt tolerance when being applied to the fracturing system, can be directly prepared by using high salinity water, and does not need to carry out pretreatment on the water; the flowback fluid and the residual polymers in the stratum after the fracturing operation are degraded under the action of microorganisms, so that the damage to the surrounding environment and the permeability of the stratum can be reduced.
(2) The thickening system can form viscosity in a short time during field preparation, and is simple to operate and convenient to use; the slippery water and the linear glue solution can be flexibly prepared by controlling the addition amount, and the preparation method has the advantage of one dose with multiple purposes.
Drawings
FIG. 1 is the nuclear magnetic spectrum of the biodegradable salt-tolerant polymer in example 1;
FIG. 2 is the nuclear magnetic spectrum of the biodegradable salt-tolerant polymer in example 6.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. 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
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
1.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and vinyl acetate in a molar ratio of 38:20:2:40, dissolving the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid and the vinyl acetate in a certain amount of deionized water, wherein the mass concentration of monomers is 30%, placing the mixture into a 250mL three-neck flask, and continuously stirring the mixture to dissolve the monomers. Placing the three-neck flask in a constant-temperature water bath, and introducing N2And stirred for 0.5 hour until the solution is clear. The initiator Azobisisobutyronitrile (AIBN) was injected with a syringe in an amount of 0.1% by mass of the total monomer. Heating to 43 ℃, and continuously introducing N2Continuously stirring, sealing and placing the three-neck flask for 6 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product. The nuclear magnetic spectrum is shown in figure 1, and the chemical shift delta: 8.07(s,1H), 7.36(s,4H), 5.08(s,1H), 3.65(s,1H), 3.27(s,9H), 2.44(s,2H), 2.07(d,12H), 1.65(m, 4H).
1.2 thickening system raw materials:
the raw materials are as shown in the following table 1 in percentage by weight:
table 1 example 1 raw material table
1.3 preparation method of thickening system:
and (2) placing the organic solvent into a reaction container, controlling the stirring speed at 2000r/min, sequentially adding the thixotropic agent, the biodegradable polymer and the cleanup additive, adjusting the stirring speed to 1000r/min after the addition is finished, and stirring for 30 minutes to finish the preparation of the salt-resistant biodegradable fracturing system.
Example 2
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
2.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing propylene in a molar ratio of 47:15:3:35The enamide, the acrylic acid, the carboxyl betaine methacrylic acid and the acrylic ester are dissolved in a certain amount of deionized water, the mass concentration of the monomers is 20%, and then the monomers are placed in a 250mL three-neck flask and are continuously stirred to be dissolved. Placing the three-neck flask in a constant-temperature water bath, and introducing N2Stirring for 0.5 hr until the solution is clear, and cooling to 5 deg.C for stabilization. Injecting the initiator ammonium persulfate/sodium bisulfite mixed solution by a syringe, wherein the dosage of the initiator is 0.05 percent of the total mass of the monomers. Maintaining the temperature at 5 ℃, and continuously introducing N2Continuously stirring, sealing and placing the three-neck flask for 7 hours to finally obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product.
2.2 thickening system raw materials:
the raw materials are shown in the following table 2 in percentage by weight:
table 2 example 2 raw material table
2.3 preparation method of thickening system:
the same as in example 1.
Example 3
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
3.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, acrylic acid, carboxyl betaine methacrylic acid and maleic anhydride in a molar ratio of 63:10:2:25, dissolving the acrylamide, the acrylic acid, the carboxyl betaine methacrylic acid and the maleic anhydride in a certain amount of deionized water, wherein the mass concentration of a monomer is 40%, placing the monomer into a 250mL three-neck flask, and continuously stirring to dissolve the monomer. Placing the three-neck flask in a constant-temperature water bath, and introducing N2Stirring for 0.5 hr until the solution is clear, and cooling to 10 deg.C for stabilization. Injecting an initiator which is a mixed solution of ammonium persulfate and sodium bisulfite by using a syringe, wherein the dosage of the initiator is 0.07 percent of the total mass of the monomers. Maintaining the temperature at 5 ℃, and continuously introducing N2Stirring continuously, sealing the three-neck flask and standing for 5 hr to obtain transparent colloidal product, taking out, and cutting into small piecesAnd precipitating and purifying the salt-tolerant polymer product by using ethanol for three times, and performing vacuum drying and granulation on the salt-tolerant polymer product.
3.2 thickening system raw materials:
the raw materials are shown in the following table 3 in percentage by weight:
table 3 example 3 table of raw materials
3.3 preparation method of thickening system:
the same as in example 1.
Example 4
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
4.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and vinyl acetoacetate in a molar ratio of 48:20:2:30, dissolving the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid and the vinyl acetoacetate in a certain amount of deionized water, wherein the mass concentration of a monomer is 35%, placing the monomer into a 250mL three-neck flask, and continuously stirring the monomer to dissolve the monomer. Placing the three-neck flask in a constant-temperature water bath, and introducing N2And stirred for 0.5 hour until the solution is clear. The initiator Azobisisobutyronitrile (AIBN) was injected by syringe in an amount of 0.04% by mass of the total monomer. Heating to 45 deg.C, and introducing N2Continuously stirring, sealing and placing the three-neck flask for 8 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product.
4.2 thickening system raw materials:
the raw materials are shown in the following table 4 in percentage by weight:
table 4 example 4 raw material table
4.3 preparation method of thickening system:
the same as in example 1.
Example 5
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
5.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, acrylic acid, carboxyl betaine methacrylic acid and vinyl acetate in a molar ratio of 77:10:3:10, dissolving the acrylamide, the acrylic acid, the carboxyl betaine methacrylic acid and the vinyl acetate in a certain amount of deionized water, wherein the mass concentration of a monomer is 30%, placing the mixture into a 250mL three-neck flask, and continuously stirring to dissolve the monomer. Placing the three-neck flask in a constant-temperature water bath, and introducing N2Stirring for 0.5 hr until the solution is clear, and cooling to 5 deg.C for stabilization. Injecting an initiator which is a mixed solution of ammonium persulfate and sodium bisulfite by using a syringe, wherein the dosage of the initiator is 0.1 percent of the total mass of the monomers. Maintaining the temperature at 8 ℃, and continuously introducing N2Continuously stirring, sealing and placing the three-neck flask for 6 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product.
5.2 thickening system raw materials:
the raw materials are shown in the following table 5 in percentage by weight:
table 5 example 5 table of raw materials
5.3 preparation method of thickening system:
the same as in example 1.
Example 6
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
6.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, acrylic acid, p-vinylaniline, 2-acrylamide-2-methylpropanesulfonic acid and acrylic ester in a molar ratio of 53:15:5:2:25, dissolving the acrylamide, acrylic acid, p-vinylaniline, 2-acrylamide-2-methylpropanesulfonic acid and acrylic ester in a certain amount of deionized water, wherein the mass concentration of monomers is 35%, placing the mixture into a 250mL three-neck flask, and continuously stirring the mixture to dissolve the monomers. Placing the three-neck flask in a constant-temperature water bath, and introducing N2Stirring for 0.5 hr until the solution is clear, and cooling to 5 deg.C for stabilization. Injecting an initiator which is a mixed solution of ammonium persulfate and sodium bisulfite by using a syringe, wherein the dosage of the initiator is 0.05 percent of the total mass of the monomers. Maintaining the temperature at 5 ℃, and continuously introducing N2Continuously stirring, sealing and placing the three-neck flask for 6 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product. The nuclear magnetic spectrum is shown in figure 2, and the chemical shift delta: 8.16(s,1H), 7.67-7.53(s,3H), 7.08(s,3H), 5.07(s,2H), 3.81(s,1H), 3.64(s,1H), 2.67-2.31(s,12H), 2.03(d,1H), 1.79-1.35(m,15H), 1.22(m, 2H).
6.2 thickening system raw materials:
the raw materials are shown in the following table 6 in percentage by weight:
table 6 example 6 raw material table
6.3 preparation method of thickening system:
the same as in example 1.
Example 7
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
7.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, epsilon-caprolactone and methyl acrylate in a molar ratio of 63:10:2:15:10, dissolving the monomers with the mass concentration of 40% in a certain amount of deionized water, placing the mixture into a 250mL three-neck flask, and continuously stirring to dissolve the monomers. Placing the three-neck flask in a constant-temperature water bath, and introducing N2And stirred for 0.5 hour until the solution is clear. The initiator Azobisisobutyronitrile (AIBN) was injected by a syringe in an amount of 0.1% by mass based on the total mass of the monomers. Heating to 42 deg.C, and introducing N2Continuously stirring, sealing and standing the three-neck flask for 5 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small pieces, precipitating and purifying the transparent colloidal product with ethanol for three times, and performing vacuum drying and granulation on the obtained product to obtain the biodegradable productA salt-tolerant polymeric product.
7.2 thickening system raw materials:
the raw materials are shown in the following table 7 in percentage by weight:
table 7 example 7 raw material table
7.3 preparation method of thickening system:
the same as in example 1.
Example 8
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
8.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, maleic anhydride and acrylic ester in a molar ratio of 47:15:3:10:25, dissolving the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid, the maleic anhydride and the acrylic ester in a certain amount of deionized water, wherein the mass concentration of monomers is 35%, placing the mixture into a 250mL three-neck flask, and continuously stirring the mixture to dissolve the monomers. Placing the three-neck flask in a constant-temperature water bath, and introducing N2And stirred for 0.5 hour until the solution is clear. The initiator Azobisisobutyronitrile (AIBN) was injected by a syringe in an amount of 0.1% by mass based on the total mass of the monomers. Heating to 45 deg.C, and introducing N2Continuously stirring, sealing and placing the three-neck flask for 6 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product.
8.2 thickening system raw materials:
the raw materials are shown in the following table 8 in percentage by weight:
table 8 example 8 raw material table
8.3 preparation method of thickening system:
the same as in example 1.
Example 9
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
9.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, vinyl acetate and acrylic ester in a molar ratio of 78:2:5:15, dissolving the acrylamide, the 2-acrylamide-2-methylpropanesulfonic acid, the vinyl acetate and the acrylic ester in a certain amount of deionized water, wherein the mass concentration of monomers is 35%, placing the mixture into a 250mL three-neck flask, and continuously stirring the mixture to dissolve the monomers. Placing the three-neck flask in a constant-temperature water bath, and introducing N2Stirring for 0.5 hr until the solution is clear, and cooling to 5 deg.C for stabilization. Injecting an initiator which is a mixed solution of ammonium persulfate and sodium bisulfite by using a syringe, wherein the dosage of the initiator is 0.1 percent of the total mass of the monomers. Maintaining the temperature at 5 ℃, and continuously introducing N2Continuously stirring, sealing and placing the three-neck flask for 6 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product.
9.2 thickening system raw materials:
the raw materials are shown in the following table 9 in percentage by weight:
table 9 example 9 raw material table
9.3 preparation method of thickening system:
the same as in example 1.
Example 10
The preparation of the biodegradable salt-tolerant thickening system of the invention comprises the following steps:
10.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, maleic anhydride, carboxyl betaine methacrylic acid, acrylic ester and vinyl acetate with the molar ratio of 73:5:2:10:10, dissolving in a certain amount of deionized water, and obtaining the monomerThe mass concentration was 40%, and the mixture was placed in a 250mL three-necked flask and dissolved by stirring. Placing the three-neck flask in a constant-temperature water bath, and introducing N2Stirring for 0.5 hr until the solution is clear, and cooling to 5 deg.C for stabilization. Injecting an initiator which is a mixed solution of ammonium persulfate and sodium bisulfite by using a syringe, wherein the dosage of the initiator is 0.1 percent of the total mass of the monomers. Maintaining the temperature at 5 ℃, and continuously introducing N2Continuously stirring, sealing and placing the three-neck flask for 6 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product.
10.2 thickening system raw materials:
the raw materials are shown in the following table 10 in percentage by weight:
table 10 example 10 raw material table
10.3 preparation method of thickening system:
the same as in example 1.
Comparative example 1
1.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, carboxyl betaine methacrylic acid, maleic anhydride, acrylic ester and vinyl acetate in a molar ratio of 28:2:20:15:35, dissolving the materials in a certain amount of deionized water, wherein the mass concentration of the monomers is 35%, placing the materials in a 250mL three-neck flask, and continuously stirring to dissolve the materials. Placing the three-neck flask in a constant-temperature water bath, and introducing N2Stirring for 0.5 hr until the solution is clear, and cooling to 5 deg.C for stabilization. Injecting an initiator which is a mixed solution of ammonium persulfate and sodium bisulfite by using a syringe, wherein the dosage of the initiator is 0.1 percent of the total mass of the monomers. Maintaining the temperature at 5 ℃, and continuously introducing N2Continuously stirring, sealing and placing the three-neck flask for 6 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product.
1.2 thickening system raw materials:
the raw materials are shown in the following table 11 in percentage by weight:
table 11 comparative example 1 raw material table
1.3 preparation method of thickening system:
the same as in example 1.
Comparative example 2
2.1 preparation of biodegradable salt-tolerant polymers
Accurately weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and vinyl acetate in a molar ratio of 83:10:2:5, dissolving the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid and the vinyl acetate in a certain amount of deionized water, wherein the mass concentration of monomers is 35%, placing the mixture into a 250mL three-neck flask, and continuously stirring the mixture to dissolve the monomers. Placing the three-neck flask in a constant-temperature water bath, and introducing N2Stirring for 0.5 hr until the solution is clear, and cooling to 5 deg.C for stabilization. Injecting an initiator which is a mixed solution of ammonium persulfate and sodium bisulfite by using a syringe, wherein the dosage of the initiator is 0.1 percent of the total mass of the monomers. Maintaining the temperature at 5 ℃, and continuously introducing N2Continuously stirring, sealing and placing the three-neck flask for 6 hours to obtain a transparent colloidal product, taking out and cutting the transparent colloidal product into small blocks, precipitating and purifying the transparent colloidal product by using ethanol for three times, and carrying out vacuum drying and granulation to obtain the biodegradable salt-resistant polymer product.
2.2 thickening system raw materials:
the raw materials are shown in the following table 12 in percentage by weight:
table 12 comparative example 2 raw material table
2.3 preparation method of thickening system:
the same as in example 1.
The beneficial effects of the biodegradable salt-resistant thickener of the invention are verified by the following test examples:
the salt-tolerant biodegradable fracturing systems prepared in examples 1 to 10 and comparative examples 1 to 2 were subjected to performance tests, and the salt-tolerant biodegradable fracturing systems prepared in examples 1 to 11 were sequentially labeled as: sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 8, sample 9, sample 10, sample 11, sample 12; the following performance tests were performed:
(ii) stability to rest
The test method comprises the following steps: the salt-tolerant biodegradable fracturing system samples prepared in examples 1 to 10 and comparative examples 1 to 2 were respectively placed at a constant temperature of 25 ℃ and the appearance of the resistance reducing agent sample was observed.
Viscosity of the body
The test method comprises the following steps: 500mL of the salt-resistant biodegradable fracturing system samples prepared in examples 1 to 10 and comparative examples 1 to 2 were respectively used to measure the sample viscosity by using a six-speed rotational viscometer.
The results of the experiment are shown in table 11 below:
TABLE 11 sample Performance test results
As can be seen from table 11, the salt-tolerant biodegradable fracturing systems prepared in examples 1 to 10 of the present invention and comparative examples 1 to 2 all have good product stability.
Further taking salt-resistant biodegradable fracturing systems with different masses and adding 10% of CaCl2The highly mineralized water is used as a solvent, solution samples 13 to 24 are prepared by different methods, and the apparent viscosity is measured. Further using bacillus badius JHW-1 to perform polymer degradation experiments on 100mL samples 13-24, determining degradation liquid, and calculating degradation rate, wherein the experimental results are shown in table 12:
(ii) apparent viscosity
The test method comprises the following steps: taking samples 13-24 prepared from the highly mineralized water, measuring with capillary viscometer or six-speed viscosity meter at 60 deg.C for 170s-1Lower viscosity.
② degradation of polymers
The test method comprises the following steps: taking 13-24 mL of sample solution, adding 0.2g of glucose and cultured bacillus badius JHW-1 to make the concentration reach 0.5 multiplied by 108Uniformly stirring the mixture per mL, and placing the mixture in a constant temperature incubator at 40 ℃ for 72 hours.
③ viscosity of degradation liquid
The test method comprises the following steps: respectively taking samples 13-24, using 50mL of biodegradable solution at 60 deg.C for 170s with Antopa MCR301 rheometer-1And (3) measuring the viscosity of the gel breaking solution, removing the viscosity standard of pure water by combining the difference value of the viscosities of the samples before and after the microbial biodegradation, and calculating the ratio of the viscosities of the samples before and after the degradation to obtain the viscosity reduction rate of the samples.
TABLE 13 sample degradation Performance test results
As can be seen from table 13, the salt-tolerant biodegradable fracturing systems prepared in examples 1 to 10 of the present invention have good biodegradability, the viscosity reduction rate can reach as high as 92.0%, and the molar content of the degradable monomers in the polymer has a certain influence on the degradation rate. However, in the salt-resistant biodegradable fracturing systems prepared in comparative examples 1 to 2, when the content of the degradable monomer is too high (sample 23), although the viscosity reduction rate can reach 98.5%, the apparent viscosity is only 7.6mPa · s, which is much lower than that of sample 16 at the same concentration, and the systems cannot be used in operation; when the content of the degradable monomer is too low (sample 24), the viscosity-reducing agent has good viscosity-increasing performance, but the viscosity-reducing rate is only 33.5 percent, and the degradability is poor.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A biodegradable polyacrylamide-based polymer characterized by comprising a first monomer unit and a second monomer unit; wherein the first monomer is selected from one or more of acrylamide and acrylamide with substituted amino, and the second monomer is selected from one or more of maleic anhydride, vinyl acetate, epsilon-caprolactone, acrylate, vinyl acetoacetate, p-vinylaniline and acrylic acid;
further, the first monomer is selected from one or more of acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and carboxyl betaine methacrylic acid.
2. The polyacrylamide-based polymer according to claim 1, wherein the molar percentage of the second monomer unit in the polyacrylamide-based polymer is 20.0 to 60.0%, preferably 25 to 60%.
3. Polyacrylamide-based polymer according to claim 1 or 2, characterised in that the molecular weight of the biodegradable polyacrylamide-based polymer is 1500 to 4000 ten thousand, preferably 3500 ten thousand.
4. A process for producing a polyacrylamide-based polymer according to any one of claims 1 to 3, wherein a monomer raw material is mixed with water and then mixed with an initiator in an inert gas and/or nitrogen atmosphere to carry out copolymerization;
further, after the monomer raw material is mixed with water, the mass fraction of the monomer raw material in the mixed solution is 20-40%;
further, the copolymerization reaction time is 4-10 h, preferably 4-8 h;
further, the initiator is selected from one or more of azobisisobutyronitrile, ammonium persulfate and sodium bisulfite, preferably azobisisobutyronitrile, or ammonium persulfate and sodium bisulfite; further, the mass amount of the initiator is 0.01-0.2%, preferably 0.01-0.1%, more preferably 0.04-0.1% of the total mass of the monomer raw materials;
further, the temperature of the copolymerization reaction is 2-50 ℃, preferably 5-45 ℃;
furthermore, after the copolymerization reaction is completed, the product obtained by the reaction is washed and dried.
5. A biodegradable, salt-tolerant thickening system comprising a biodegradable polyacrylamide-based polymer according to any one of claims 1 to 3; further, the mass fraction of the biodegradable polyacrylamide-based polymer is 20.0-60.0%, preferably 30.0-50.0%, and more preferably 40%.
6. The thickening system of claim 5, further comprising a thixotropic agent; furthermore, the mass fraction of the thixotropic agent is 0.5-3.0%, preferably 2.0-3.0%, and more preferably 2.0%;
further, the thixotropic agent is selected from one or more of montmorillonite, modified bentonite, modified nano-silica, carboxymethyl cellulose, polyurethane resin and polyamide wax.
7. The thickening system of claim 5, further comprising a drainage aid; furthermore, the mass fraction of the cleanup additive is 0.5-2.5%, preferably 1.0-2.5%, and more preferably 1.5%;
further, the cleanup additive is selected from one or more of sodium dodecyl sulfate, sodium oleate, sodium palmitate, erucamidopropyldimethyl betaine, oleamidopropyldimethyl betaine, dodecyl sulfobetaine, octyl phenol polyoxyethylene ether, Tween-20, Tween-80, Span-60 and Span-80.
8. The thickening system of claim 5, further comprising a solvent; further, the solvent is an organic solvent;
further, the organic solvent is selected from one or more of polyethylene glycol, diethylene glycol dimethyl ether, propylene glycol, condensed glycerol, N-dimethylformamide, white oil and kerosene.
9. A process for preparing a thickening system according to any one of claims 5 to 8, comprising: mixing all the components;
further, the solvent, the thixotropic agent, the biodegradable polyacrylamide-based polymer and the cleanup additive are mixed in sequence.
10. Use of the viscosified system of any one of claims 5 to 8 in the development of medium-low permeability, ultra-low permeability or medium-high salinity reservoirs.
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| WO2023199855A1 (en) * | 2022-04-13 | 2023-10-19 | 東レ株式会社 | Copolymer, medical composition and coated medical device, and methods respectively for producing those |
| CN115820238A (en) * | 2022-11-12 | 2023-03-21 | 陕西绿尚新材料有限公司 | Degradable thickening agent for emulsion type slickwater fracturing fluid |
| CN115991846A (en) * | 2023-02-14 | 2023-04-21 | 重庆市泓择石油科技有限公司 | Clean residue-free acid liquor thickener and preparation method thereof |
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