CN111909306A - Double-aqueous-phase PAM/AMPS nano microsphere latex as well as preparation method and application thereof - Google Patents
Double-aqueous-phase PAM/AMPS nano microsphere latex as well as preparation method and application thereof Download PDFInfo
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Abstract
A double-aqueous-phase PAM/AMPS nano-microsphere latex and a preparation method and application thereof are disclosed, wherein a cross-linking agent is added into a polyethylene glycol aqueous solution to obtain a mixed solution; uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and distilled water, adjusting the pH value, adding the mixture into the mixed solution, dropwise adding an initiator solution, and reacting for 1-3 hours at 50-60 ℃ in a nitrogen environment after dropwise adding. The invention prepares the double-aqueous-phase PAM/AMPS copolymer nano-microsphere latex with a certain concentration by using clean water and saline water, and then injects the double-aqueous-phase PAM/AMPS copolymer nano-microsphere latex into the stratum under the action of an injection pump. And the PAM/AMPS copolymer nano microspheres are subjected to gradual water absorption expansion, block and match the stratum, deform to break through pore throats under the action of injected medium pressure, enter deep parts of the stratum, realize multistage blocking, profile control and flooding, improve the heterogeneity of low-permeability and medium-low-permeability oil reservoirs and improve the crude oil recovery ratio.
Description
Technical Field
The invention relates to the fields of chemistry and oilfield chemistry, in particular to double-aqueous-phase PAM/AMPS nano microsphere latex and a preparation method and application thereof.
Background
The polyacrylamide microsphere has good plugging performance, can change the flow direction of injected water, improves the sweep coefficient of the injected water, improves the recovery ratio of crude oil, and is a novel deep plugging control technology developed in the field of oil field exploitation in recent years by applying polyacrylamide microsphere profile control and flooding. Polyacrylamide microspheres are mostly prepared by inverse suspension polymerization and inverse (micro) emulsion polymerization. The reversed phase suspension polymerization is to disperse reactants in an oil-soluble medium, take a monomer aqueous solution as a water phase, initiate polymerization by a water-soluble initiator, have mild reaction conditions and few side reactions, and are suitable for preparing micron-sized large-particle-size polymer microspheres, but a polymerization system is thermodynamically unstable, and is easy to generate a caking phenomenon, and the product purity is lower. The inverse (micro) emulsion polymerization is carried out by taking nonpolar solvent as continuous phase, dissolving polymerization monomer in water and dispersing in oil phase by emulsifier to form water-in-oil (W/O) type (micro) emulsion, and is suitable for preparing micron-scale to nanometer-scale polymer microspheres. Besides acrylamide, in order to improve the salt and temperature resistance of the polyacrylamide microspheres, monomers such as 2-acrylamide-2-methylpropanesulfonic acid, sodium styrene sulfonate, sodium acrylate, methacryloyloxyethyl trimethyl ammonium chloride and the like are added, and the prepared polyacrylamide microspheres are used as a profile control agent for improving the crude oil recovery ratio. Such as: CN107814874A discloses a nano-scale polymer microsphere prepared by taking acrylamide, acrylic acid and 2-acrylamide-2-methyl sodium propanesulfonate as reaction monomers and adopting inverse emulsion polymerization, which has the advantages of temperature resistance, salt resistance and good plugging effect and can be used for improving the crude oil recovery ratio. The cationic crosslinked swelling functional microsphere with the particle size of 1-50 mu m, which is disclosed in CN101029109 and is prepared by reversed-phase suspension polymerization of cationic monomer methacryloyloxyethyl trimethyl ammonium chloride and acrylamide, has the advantages of gradual swelling after water absorption, and controllable swelling rate and swelling multiplying power. The CN105315403A temperature-resistant and salt-resistant active microsphere with the particle size of 0.5-200 mu m, which is prepared from acrylamide and/or anionic hydrophilic monomers, cationic hydrophilic monomers, hydrophobic monomers, a cross-linking agent and the like, has good thermal stability and injectability, expands when meeting water, and blocks a large pore throat by bridging, and is suitable for tertiary oil recovery water shutoff profile control operation of a medium-high permeability oil reservoir. CN107417863A discloses a water-swellable thermosensitive polymer microsphere prepared from acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, sodium styrenesulfonate, methacryloyloxyethyl dimethyl hexadecyl ammonium bromide, a cross-linking agent and the like, which hardly swells in the early injection process, starts to slowly swell under the influence of temperature after reaching a certain depth, and does not rapidly hydrate and dissolve, so that the microsphere can enter the deep part of a stratum to achieve the purpose of deep profile control and flooding in the injection process. However, both the inverse suspension polymerization and the inverse emulsion polymerization use organic solvents, so that the production cost is relatively high, the problems of solvent pollution, recovery, production safety and the like exist, and the application of the method in the application field with high requirement on the residual quantity of the solvent is limited.
Disclosure of Invention
In order to realize the purpose, the invention provides aqueous two-phase PAM/AMPS nano microsphere latex, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the double-aqueous-phase PAM/AMPS nano microsphere latex comprises the following steps:
(1) adding a cross-linking agent into the polyethylene glycol aqueous solution, and uniformly stirring to obtain a mixed solution;
(2) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and distilled water, adjusting the pH value to 6.0-7.0, adding the mixture into the mixed solution, dropwise adding an initiator solution at 50-60 ℃, and reacting for 1-3 hours at 50-60 ℃ in a nitrogen environment after dropwise adding is finished to obtain the PAM/AMPS nano microsphere latex.
The invention has the further improvement that the PAM/AMPS nano microsphere latex comprises, by mass, 7.0-9.0% of polyethylene glycol, 0.0005-0.00015% of a cross-linking agent, 8.0-10.0% of acrylamide, 1.0-3.0% of 2-acrylamide-2-methylpropanesulfonic acid, 0.0020-0.0030% of an initiator and the balance of water.
In a further development of the invention, the crosslinking agent is N, N-methylenebisacrylamide.
In a further development of the invention, the initiator is 2,2' -azobisisobutylamidine dihydrochloride.
The aqueous two-phase PAM/AMPS nano microsphere latex prepared by the method comprises, by mass, 7.0-9.0% of polyethylene glycol, 0.0005-0.0015% of a cross-linking agent, 8.0-10.0% of acrylamide, 1.0-3.0% of 2-acrylamido-2-methylpropanesulfonic acid, 0.0020-0.0030% of an initiator, and the balance of water.
The application of the double-aqueous-phase PAM/AMPS nano microsphere latex prepared by the method in profile control and flooding of oil fields.
The invention has the further improvement that after the double-water-phase PAM/AMPS nano microsphere latex is prepared from clear water and saline water, the double-water-phase PAM/AMPS nano microsphere latex is injected into the stratum under the action of an injection pump.
Compared with the prior art, the invention has the following beneficial effects: the aqueous two-phase PAM/AMPS nano microsphere latex provided by the invention contains polyethylene glycol and PAM/AMPS copolymer microspheres, wherein the polyethylene glycol can increase the viscosity of injected liquid, the initial particle size of the PAM/AMPS nano microsphere is small, the elasticity is good, the fluidity is strong, the particle size is only dozens of nanometers at the initial injection stage, and after the PAM/AMPS nano microsphere latex is injected into a stratum, the PAM/AMPS microsphere gradually absorbs water and expands, so that the high-permeability pore canal is blocked, and the polymer microsphere which absorbs water and expands breaks through the pore throat at the deep part of the stratum to the deep part under the action of the pressure of an injection medium, so that the aim of multi-level blocking, profile control. The double-aqueous-phase PAM/AMPS nano-microsphere is suitable for improving the heterogeneity of low-permeability and medium-low-permeability oil reservoirs, improving the volume sweep coefficient of injected liquid and increasing the recovery ratio of crude oil.
Further, Acrylamide (AM) and 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) are used as polymerization monomers, N, N-Methylene Bisacrylamide (MBA) is used as a cross-linking agent, 2,2' -azobisisobutylamidine dihydrochloride (V-50) is used as an initiator, polyethylene glycol is used as a thickening stabilizer, and a double-water-phase polymerization technology is adopted to synthesize the double-water-phase polyacrylamide/2-acrylamide-2-methylpropanesulfonic acid (PAM/AMPS) nano-microsphere emulsion, wherein the double-water-phase PAM/AMPS nano-microsphere has good salt resistance, temperature resistance, water absorption swelling property and viscoelasticity; the double-aqueous-phase PAM/AMPS nano microsphere emulsion has low viscosity and good stability, can be prepared and diluted by clear water and saline water, can smoothly enter the deep part of a stratum under the action of a pump under lower pressure, and blocks the matched stratum after swelling in water, and can be used as a chemical agent for deep profile control and flooding of low-permeability and medium-low-permeability oil reservoirs to effectively adjust and improve the heterogeneity of the oil reservoirs, improve the volume wave and coefficient of injected liquid, change the deep liquid flow diversion of the oil reservoirs and improve the application of crude oil recovery ratio.
The method for preparing the aqueous two-phase polymer microspheres overcomes the problems of relatively high production cost, solvent pollution, production and transportation safety and the like caused by using an organic solvent in inverse suspension polymerization and inverse emulsion polymerization, and meets the requirements of water quality and the like in the aspect of preparation and use of the inverse emulsion polymer microspheres as profile control materials for oil fields.
The invention prepares the double-aqueous-phase PAM/AMPS copolymer nano-microsphere latex with a certain concentration by using clean water and saline water, and then injects the double-aqueous-phase PAM/AMPS copolymer nano-microsphere latex into the stratum under the action of an injection pump. And the PAM/AMPS copolymer nano microspheres are subjected to gradual water absorption expansion, block and match the stratum, deform to break through pore throats under the action of injected medium pressure, enter deep parts of the stratum, realize multistage blocking, profile control and flooding, improve the heterogeneity of low-permeability and medium-low-permeability oil reservoirs and improve the crude oil recovery ratio.
Drawings
FIG. 1 shows the swelling of PAM/AMPS nanospheres.
FIG. 2 shows the morphology of PAM/AMPS nanospheres after swelling.
FIG. 3 is a viscosity temperature curve of PAM/AMPS nanosphere latex.
FIG. 4 shows the water flooding pressure changes before and after plugging with PAM/AMPS nanosphere latex.
Fig. 5 is a schematic diagram of a simulated core flooding experimental device.
FIG. 6 shows the result of a PAM/AMPS nanosphere emulsion oil displacement simulation experiment.
In the figure, 1, a constant flow pump, 2, an oil container, 3, a first displacement fluid container, 4, a second displacement fluid container, 5, a pressure gauge, 6, a core holder, and 7, a measuring device.
Detailed Description
The invention is exemplified and further understood by combining the preparation of the double-aqueous-phase PAM/AMPS copolymer nano microspheres and the specific implementation case of the profile control and flooding application of the double-aqueous-phase PAM/AMPS copolymer nano microspheres in low and medium permeability oil reservoirs, but the implementation case is given by way of example only, is not regarded as the whole technical scheme of the invention, is not limited to the general technical scheme of the invention, and all the nano-microspheres with the same or similar technical characteristics, simple changes or substitutions belong to the protection scope of the invention.
The invention provides a method for synthesizing double-aqueous-phase PAM/AMPS copolymer nano microspheres, which comprises the following steps:
(1) weighing a certain amount of polyethylene glycol, placing the polyethylene glycol in a beaker, adding fresh distilled water in a certain proportion, stirring to fully dissolve the polyethylene glycol to prepare a polyethylene glycol aqueous solution, then adding a trace amount of N, N-methylene bisacrylamide, stirring to dissolve, transferring the mixture into a four-neck flask, introducing nitrogen to remove oxygen, adjusting the stirring speed to 500r/min, and stirring uniformly to obtain a mixed solution.
(2) Weighing a certain amount of acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, placing the acrylamide and the 2-acrylamide-2-methylpropanesulfonic acid into a beaker, adding a certain proportion of fresh distilled water, stirring to completely dissolve the acrylamide and the 2-acrylamide-2-methylpropanesulfonic acid, adjusting the pH value to 6.0-7.0, then adding the mixture into the mixed solution, and heating the water bath temperature from room temperature to 50-60 ℃.
(3) And then dropwise adding a 2,2' -azobisisobutylamidine dihydrochloride (V-50) solution, finishing the dropwise adding within about 30min, observing the change of the reading on a thermometer, controlling the reaction temperature to be 50-60 ℃ (preferably 55 ℃), keeping the stirring speed at 300r/min, continuously reacting for 1-3h (preferably 1.5h) in a nitrogen environment, and then stopping to obtain a stable, uniform and viscous flowable emulsion, namely the PAM/AMPS nano microsphere emulsion.
The aqueous two-phase PAM/AMPS nano microsphere latex provided by the invention comprises, by mass, 8.0% -10.0% of acrylamide, 1.0% -3.0% of 2-acrylamide-2-methylpropanesulfonic acid, 7.0% -9.0% of polyethylene glycol, 0.0020% -0.0030% of an initiator (V-50), and 0.0005% -0.0015% of a cross-linking agent (MBA).
The application method of the double aqueous phase PAM/AMPS copolymer nano microsphere latex in profile control and flooding of the oil field comprises the following steps:
the double water phase PAM/AMPS copolymer nanometer microsphere latex with a certain concentration (1-11%) is injected into the stratum under the action of an injection pump. And the PAM/AMPS copolymer nano microspheres are subjected to gradual water absorption expansion, block and match the stratum, deform to break through pore throats under the action of injected medium pressure, enter deep parts of the stratum, realize multistage blocking, profile control and flooding, improve the heterogeneity of low-permeability and medium-low-permeability oil reservoirs and improve the crude oil recovery ratio.
The following are specific examples.
Example 1
The preparation method of the double-aqueous-phase PAM/AMPS nano microsphere latex comprises the following specific steps:
(1) 16.0g of polyethylene glycol is weighed and placed in a beaker, then 0.002g N g of N-methylene bisacrylamide is added, 114.0g of fresh distilled water is added, the mixture is stirred to be fully dissolved to prepare an aqueous solution, the aqueous solution is transferred to a four-neck flask, and nitrogen is introduced to remove oxygen.
(2) Weighing 20.0g of acrylamide and 4.0g of 2-acrylamido-2-methylpropanesulfonic acid, placing the acrylamide and the 2-acrylamido-2-methylpropanesulfonic acid into a beaker, adding 36.0g of fresh distilled water, stirring to completely dissolve the distilled water, adjusting the pH value to 7.0 by using a sodium hydroxide solution with the mass fraction of 40%, then adding the solution into a four-neck flask, adjusting the stirring speed to 300r/min, introducing nitrogen to remove oxygen, and raising the water bath temperature from room temperature to 55 ℃.
(3) After the temperature is stabilized to 55 ℃, dropwise adding 10.0g of 2,2' -azobisisobutylamidine dihydrochloride aqueous solution with the mass fraction of 0.05 percent under the protection of nitrogen, finishing dropwise adding for about 30min, controlling the reaction temperature to be 55 ℃, reacting for 1.5h, and stopping the reaction to obtain stable, uniform and viscous flowable emulsion, namely the double-aqueous-phase PAM/AMPS nano microsphere latex.
Under the preparation condition, the conversion rate of the prepared aqueous two-phase PAM/AMPS nano microsphere latex monomer is 92.6 percent, and the initial particle size of the PAM/AMPS nano microsphere is 65.9 nm. FIG. 1 shows the degree of mineralization of PAM/AMPS nanospheres in distilled water, tap water and water being 1.0 × 104mg/L、5.0×104mg/L、1.0×105The relationship between swelling multiplying power and swelling time in mg/L simulated mineralized water, and FIG. 2 shows the appearance of PAM/AMPS nano microspheres after water absorption and swelling. FIG. 3 shows the degree of mineralization being 1X 104PAM/AMPS nano microsphere latex system with 10% mass fraction prepared from mg/L simulated water sample and using Haake viscometer at shear rate of 170s-1The viscosity temperature curve was measured. Table 1 shows the apparent viscosities of solutions with different mass fractions and standing time, which were obtained by testing the aqueous two-phase PAM/AMPS nanosphere latex prepared with distilled water with an NDJ-1 digital rotational viscometer at a temperature of 25 ℃.
TABLE 1 relationship between PAM/AMPS nanosphere viscosity and concentration
Example 2
Plugging experiment of the two-water-phase PAM/AMPS nano microsphere latex: uniformly mixing quartz sand with different thicknesses according to a proportion, filling the mixture into a sand filling pipe with the caliber of 2.5cm and the length of 20cm, filling the sand filling pipe with water after compaction, recording the water drive pressure, and measuring the pore volume of the sand filling pipe; and then injecting the double-aqueous-phase PAM/AMPS nano-microsphere latex into a sand filling pipe, standing for 24h, performing water drive again, and recording the water drive pressure, wherein the change situation of the two-time drive pressure is shown in figure 4. As can be seen from FIG. 4, the water-driving pressure before the PAM/AMPS nanosphere latex is injected is 0.12 MPa; and after PAM/AMPS nano microsphere latex is injected and stands for 12 hours in a sand filling pipe, the water drive pressure is rapidly increased to 1.07MPa, and when the injection amount of water drive is 0.4PV, the water drive pressure is slightly increased, and finally the pressure is increased to 1.38 MPa. The double-aqueous-phase PAM/AMPS nano microsphere latex shows good plugging property.
Example 3
Oil displacement experiment of the double-aqueous-phase PAM/AMPS nano microsphere emulsion: uniformly mixing quartz sand with different thicknesses according to a proportion, filling the mixture into a sand filling pipe with the caliber of 2.5cm and the length of 20cm, filling water into the sand filling pipe after compaction, and measuring the pore volume of the sand filling pipe; vacuumizing to remove saturated water, and sucking simulated crude oil to saturate. Fig. 5 is a schematic diagram of a simulated core flooding experimental device. The experimental device comprises a constant flow pump 1, an oil container 2, a first displacement fluid container 3, a second displacement fluid container 4, a pressure gauge 5, a rock core holder 6 and a measuring device 7. Wherein, the outlet of the constant flow pump 1 is divided into two paths, one path is communicated with the inlet of the oil container 2 through a valve, the outlet of the oil container 2 is divided into two paths, one path is communicated with the inlet at the bottom of the first displacement liquid container 3 through the valve, the other path is communicated with the inlet at the bottom of the second displacement liquid container 4 through the valve, the outlet at the top of the first displacement liquid container 3 is divided into two paths after passing through the valve, one path is communicated with the inlet at the top of the second displacement liquid container 4, the other path is communicated with the inlet of the rock core holder 6, and the outlet of the rock core holder 6 is communicated with the measuring device 7. The other path of the outlet of the constant flow pump 1 is communicated with the inlet of the core holder 6.
FIG. 6 is a graph showing oil displacement experimental recovery and variation of aqueous two-phase PAM/AMPS nanosphere latex. As can be seen from FIG. 6, in the first stage of crude oil water flooding, when the water content is 99.5%, the recovery rate is 42.4%; in the second stage, PAM/AMPS nano microsphere emulsion solution flooding is injected, and the recovery rate is increased to 51.8%; and in the third stage, the sand filling pipe injected with the PAM/AMPS nano microsphere latex is placed for 12 hours, and then water is again driven until the water content is 99.5%, so that the recovery rate is increased to 59.3%. Namely, the total recovery ratio of the simulated oil displacement by using the PAM/AMPS nano microsphere emulsion is improved by 16.9 percent compared with the recovery ratio of water displacement.
Preferably, the invention takes Acrylamide (AM) and 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) as polymerization monomers, N, N-methylene bisacrylamide as a cross-linking agent, 2' -azobisisobutylamidine dihydrochloride (V-50) as an initiator, and polyethylene glycol as a thickening stabilizer, and adopts a two-aqueous phase polymerization technology to synthesize the polyacrylamide/2-acrylamido-2-methylpropanesulfonic acid (PAM/AMPS) nano-microsphere latex, which comprises the components in percentage, the control of reaction temperature, reaction time, reaction link and the like, and provides an application and a technical implementation method of the double-aqueous-phase PAM/AMPS) nano microsphere emulsion as a chemical agent for tertiary oil recovery in the deep profile control and profile control of low-permeability and medium-permeability oil reservoirs and the improvement of crude oil recovery.
Example 4
The preparation method of the double-aqueous-phase PAM/AMPS nano microsphere latex comprises the following steps:
(1) 16.0g of polyethylene glycol was added to water to obtain an aqueous polyethylene glycol solution. Adding N, N-methylene bisacrylamide into a polyethylene glycol aqueous solution, and uniformly stirring to obtain a mixed solution;
(2) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and distilled water, adjusting the pH value to 6.0, adding the mixture into the mixed solution, dropwise adding 2,2' -azobisisobutylamidine dihydrochloride solution at 50 ℃, and reacting for 3 hours at 50 ℃ in a nitrogen environment after dropwise adding to obtain the PAM/AMPS nano microsphere latex.
The PAM/AMPS nano microsphere latex comprises, by mass, 7.0% of polyethylene glycol, 0.0005% of N, N-methylene bisacrylamide, 9.0% of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2,2' -azobisisobutylamidine dihydrochloride, and the balance of water.
The application of the double-aqueous-phase PAM/AMPS nano microsphere latex in profile control and flooding of an oil field is as follows: the double-aqueous-phase PAM/AMPS nano-microsphere latex is prepared into the double-aqueous-phase PAM/AMPS nano-microsphere latex with the mass concentration of 1% by clear water, and then is injected into a stratum under the action of an injection pump.
Example 5
The preparation method of the double-aqueous-phase PAM/AMPS nano microsphere latex comprises the following steps:
(1) 16.0g of polyethylene glycol was added to water to obtain an aqueous polyethylene glycol solution. Adding N, N-methylene bisacrylamide into a polyethylene glycol aqueous solution, and uniformly stirring to obtain a mixed solution;
(2) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and distilled water, adjusting the pH value to 7.0, adding the mixture into the mixed solution, dropwise adding 2,2' -azobisisobutylamidine dihydrochloride solution at 60 ℃, and reacting for 1h at 60 ℃ in a nitrogen environment to obtain the PAM/AMPS nano microsphere latex.
The PAM/AMPS nano microsphere latex comprises, by mass, 8.0% of polyethylene glycol, 0.001% of N, N-methylene bisacrylamide, 10.0% of acrylamide, 1.0% of 2-acrylamido-2-methylpropanesulfonic acid, 0.0025% of 2,2' -azobisisobutylamidine dihydrochloride and the balance of water.
The application of the double-aqueous-phase PAM/AMPS nano microsphere latex in profile control and flooding of an oil field is as follows: the double-aqueous-phase PAM/AMPS nano-microsphere latex is prepared into the double-aqueous-phase PAM/AMPS nano-microsphere latex with the mass concentration of 11% by clear water, and then is injected into a stratum under the action of an injection pump.
Example 6
The preparation method of the double-aqueous-phase PAM/AMPS nano microsphere latex comprises the following steps:
(1) 16.0g of polyethylene glycol was added to water to obtain an aqueous polyethylene glycol solution. Adding N, N-methylene bisacrylamide into a polyethylene glycol aqueous solution, and uniformly stirring to obtain a mixed solution;
(2) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and distilled water, adjusting the pH value to 6.0, adding the mixture into the mixed solution, dropwise adding 2,2' -azobisisobutylamidine dihydrochloride solution at 55 ℃, and reacting for 2 hours at 55 ℃ in a nitrogen environment after dropwise adding to obtain the PAM/AMPS nano microsphere latex.
The PAM/AMPS nano microsphere latex comprises, by mass, 9.0% of polyethylene glycol, 0.0015% of N, N-methylene bisacrylamide, 8.0% of acrylamide, 3.0% of 2-acrylamido-2-methylpropanesulfonic acid, 0.003% of 2,2' -azobisisobutylamidine dihydrochloride and the balance of water.
The application of the double-aqueous-phase PAM/AMPS nano microsphere latex in profile control and flooding of an oil field is as follows: the double-aqueous-phase PAM/AMPS nano-microsphere latex is prepared into the double-aqueous-phase PAM/AMPS nano-microsphere latex with the mass concentration of 5% by saline water, and then is injected into a stratum under the action of an injection pump.
Example 7
The preparation method of the double-aqueous-phase PAM/AMPS nano microsphere latex comprises the following steps:
(1) 16.0g of polyethylene glycol was added to water to obtain an aqueous polyethylene glycol solution. Adding N, N-methylene bisacrylamide into a polyethylene glycol aqueous solution, and uniformly stirring to obtain a mixed solution;
(2) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and distilled water, adjusting the pH value to 6.5, adding the mixture into the mixed solution, dropwise adding 2,2' -azobisisobutylamidine dihydrochloride solution at 52 ℃, and reacting for 2 hours at 52 ℃ in a nitrogen environment to obtain the PAM/AMPS nano microsphere latex.
The PAM/AMPS nano microsphere latex comprises, by mass, 7.0% of polyethylene glycol, 0.0007% of N, N-methylene bisacrylamide, 8.0% of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2,2' -azobisisobutylamidine dihydrochloride, and the balance of water.
The application of the double-aqueous-phase PAM/AMPS nano microsphere latex in profile control and flooding of an oil field is as follows: the double-aqueous-phase PAM/AMPS nano-microsphere latex is prepared into the double-aqueous-phase PAM/AMPS nano-microsphere latex with the mass concentration of 8% by clear water, and then is injected into a stratum under the action of an injection pump.
Claims (7)
1. The preparation method of the double-aqueous-phase PAM/AMPS nano microsphere latex is characterized by comprising the following steps:
(1) adding a cross-linking agent into the polyethylene glycol aqueous solution, and uniformly stirring to obtain a mixed solution;
(2) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and distilled water, adjusting the pH value to 6.0-7.0, adding the mixture into the mixed solution, dropwise adding an initiator solution at 50-60 ℃, and reacting for 1-3 hours at 50-60 ℃ in a nitrogen environment after dropwise adding is finished to obtain the PAM/AMPS nano microsphere latex.
2. The preparation method of the aqueous two-phase PAM/AMPS nanosphere latex according to claim 1, wherein the PAM/AMPS nanosphere latex comprises, by mass, 7.0-9.0% of polyethylene glycol, 0.0005-0.0015% of a cross-linking agent, 8.0-10.0% of acrylamide, 1.0-3.0% of 2-acrylamido-2-methylpropanesulfonic acid, 0.0020-0.0030% of an initiator, and the balance water.
3. The method for preparing the aqueous two-phase PAM/AMPS nanosphere latex according to claim 1, wherein the cross-linking agent is N, N-methylene bisacrylamide.
4. The method for preparing the aqueous two-phase PAM/AMPS nanosphere latex of claim 1, wherein the initiator is 2,2' -azobisisobutylamidine dihydrochloride.
5. The aqueous two-phase PAM/AMPS nanosphere latex prepared by the method of claim 1, wherein the PAM/AMPS nanosphere latex comprises, by mass, 7.0-9.0% of polyethylene glycol, 0.0005-0.0015% of a cross-linking agent, 8.0-10.0% of acrylamide, 1.0-3.0% of 2-acrylamido-2-methylpropanesulfonic acid, 0.0020-0.0030% of an initiator, and the balance water.
6. The application of the aqueous two-phase PAM/AMPS nano microsphere latex prepared by the method of claim 1 in profile control and flooding of oil fields.
7. The use of claim 6, wherein the aqueous PAM/AMPS nanosphere emulsion is prepared from clear water and saline water, and then injected into the formation under the action of an injection pump.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341570A (en) * | 2020-11-28 | 2021-02-09 | 西安石油大学 | Double-aqueous-phase polyacrylamide terpolymer nano microsphere emulsion and preparation method thereof |
| CN115073673A (en) * | 2021-03-12 | 2022-09-20 | 中国石油天然气股份有限公司 | Polymer and double aqueous phase preparation method and application thereof |
| CN116217791A (en) * | 2021-12-03 | 2023-06-06 | 中国石油天然气集团有限公司 | Water-based polymer nano microsphere high-temperature-resistant filtrate reducer and preparation method and application thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006152143A (en) * | 2004-11-30 | 2006-06-15 | Dainippon Ink & Chem Inc | Preparation method of liquid-absorbing resin |
| CN101029109A (en) * | 2007-02-01 | 2007-09-05 | 江南大学 | Production of cationic microsphere with crosslinked swelling function |
| CN103408698A (en) * | 2013-08-28 | 2013-11-27 | 江苏博特新材料有限公司 | In-situ redox initiation for preparing polyacrylamide water-drum water dispersion |
| US20140326457A1 (en) * | 2012-01-20 | 2014-11-06 | S.P.C.M. Sa | Process For The Enhanced Recovery Of Oil By Injection Of A Polymer Solution |
| CN104449617A (en) * | 2014-11-26 | 2015-03-25 | 胜利油田胜利化工有限责任公司 | Anionic polyacrylamide water-in-water emulsion water shutoff profile control agent, and preparation method and using method thereof |
| CN105315403A (en) * | 2014-07-24 | 2016-02-10 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant active microsphere, and preparation method and applications thereof |
| CN105482033A (en) * | 2014-09-19 | 2016-04-13 | 中国石油化工股份有限公司 | Polymer microsphere and preparation method and application thereof |
| CN105524215A (en) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | Heatproof salt-resistant acrylamide polymer microsphere dispersed system and preparation method and use thereof |
| CN106146730A (en) * | 2015-03-25 | 2016-11-23 | 中国石油天然气股份有限公司 | Acrylamide polymer thickener, preparation method thereof and fracturing fluid |
| CN106220782A (en) * | 2016-08-29 | 2016-12-14 | 浙江大川新材料股份有限公司 | A kind of polyacrylamide water-in-water emulsion and preparation method thereof |
| CN106589225A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Polymer gel particle for profile control and water plugging of deep parts as well as preparation method thereof |
| CN106749885A (en) * | 2015-11-19 | 2017-05-31 | 北京熠海能源科技有限公司 | A kind of preparation method and applications of nano-micro level water-in-water type microballoon profile control agent |
| CN106832111A (en) * | 2017-01-18 | 2017-06-13 | 西安石油大学 | A kind of multi-functional smooth hydraulic pressure splits the preparation method of liquid drag reducer |
| CN107417863A (en) * | 2017-07-14 | 2017-12-01 | 西安长庆化工集团有限公司 | A kind of thermosensitive type polymer microballoon of water swelling and its preparation method and application |
| CN107814874A (en) * | 2017-11-01 | 2018-03-20 | 南阳理工学院 | A kind of nanoscale temperature-salty resisting cross-linked polymer microballoon and preparation method thereof |
-
2020
- 2020-08-14 CN CN202010819429.9A patent/CN111909306B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006152143A (en) * | 2004-11-30 | 2006-06-15 | Dainippon Ink & Chem Inc | Preparation method of liquid-absorbing resin |
| CN101029109A (en) * | 2007-02-01 | 2007-09-05 | 江南大学 | Production of cationic microsphere with crosslinked swelling function |
| US20140326457A1 (en) * | 2012-01-20 | 2014-11-06 | S.P.C.M. Sa | Process For The Enhanced Recovery Of Oil By Injection Of A Polymer Solution |
| CN103408698A (en) * | 2013-08-28 | 2013-11-27 | 江苏博特新材料有限公司 | In-situ redox initiation for preparing polyacrylamide water-drum water dispersion |
| CN105315403A (en) * | 2014-07-24 | 2016-02-10 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant active microsphere, and preparation method and applications thereof |
| CN105482033A (en) * | 2014-09-19 | 2016-04-13 | 中国石油化工股份有限公司 | Polymer microsphere and preparation method and application thereof |
| CN105524215A (en) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | Heatproof salt-resistant acrylamide polymer microsphere dispersed system and preparation method and use thereof |
| CN104449617A (en) * | 2014-11-26 | 2015-03-25 | 胜利油田胜利化工有限责任公司 | Anionic polyacrylamide water-in-water emulsion water shutoff profile control agent, and preparation method and using method thereof |
| CN106146730A (en) * | 2015-03-25 | 2016-11-23 | 中国石油天然气股份有限公司 | Acrylamide polymer thickener, preparation method thereof and fracturing fluid |
| CN106589225A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Polymer gel particle for profile control and water plugging of deep parts as well as preparation method thereof |
| CN106749885A (en) * | 2015-11-19 | 2017-05-31 | 北京熠海能源科技有限公司 | A kind of preparation method and applications of nano-micro level water-in-water type microballoon profile control agent |
| CN106220782A (en) * | 2016-08-29 | 2016-12-14 | 浙江大川新材料股份有限公司 | A kind of polyacrylamide water-in-water emulsion and preparation method thereof |
| CN106832111A (en) * | 2017-01-18 | 2017-06-13 | 西安石油大学 | A kind of multi-functional smooth hydraulic pressure splits the preparation method of liquid drag reducer |
| CN107417863A (en) * | 2017-07-14 | 2017-12-01 | 西安长庆化工集团有限公司 | A kind of thermosensitive type polymer microballoon of water swelling and its preparation method and application |
| CN107814874A (en) * | 2017-11-01 | 2018-03-20 | 南阳理工学院 | A kind of nanoscale temperature-salty resisting cross-linked polymer microballoon and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| JIN-HUA HUO，等: "Preparation, characterization, and investigation of poly(AMPS/AM/SSS) on application performance of water-based drilling fluid", 《J. APPL. POLYM. SCI.》 * |
| KUANXIANG SHANG，等: "Unusual Soluble-Insoluble-Soluble Phase Transition in Two-Phase Copolymerization of Acrylamide and an Anionic Comonomer in a Poly(ethylene glycol) Aqueous Solution", 《IND. ENG. CHEM. RES.》 * |
| S. DURMAZ，等: "Acrylamide/2-acrylamido-2-methylpropane sulfonic acid sodium salt-based hydrogels: synthesis and characterization", 《POLYMER》 * |
| 单国荣，等: "水体系相图及丙烯酰胺单体在两相中的分配", 《高等学校化学学报》 * |
| 呼早霞，等: "高稳定性双水相共聚物PAM-AMPS的合成与表征", 《精细化工》 * |
| 柏少玲: "阴离子型聚丙烯酰胺微球的水分散聚合法制备", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341570A (en) * | 2020-11-28 | 2021-02-09 | 西安石油大学 | Double-aqueous-phase polyacrylamide terpolymer nano microsphere emulsion and preparation method thereof |
| CN115073673A (en) * | 2021-03-12 | 2022-09-20 | 中国石油天然气股份有限公司 | Polymer and double aqueous phase preparation method and application thereof |
| CN115073673B (en) * | 2021-03-12 | 2023-08-22 | 中国石油天然气股份有限公司 | Polymer and double water phase preparation method and application thereof |
| CN116217791A (en) * | 2021-12-03 | 2023-06-06 | 中国石油天然气集团有限公司 | Water-based polymer nano microsphere high-temperature-resistant filtrate reducer and preparation method and application thereof |
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