CN115819676A - Self-assembled nano-particles for oil reservoir deep profile control and preparation method and application thereof - Google Patents
Self-assembled nano-particles for oil reservoir deep profile control and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses self-assembled nanoparticles for oil reservoir deep profile control and a preparation method and application thereof, and belongs to the field of profile control and water shutoff of oil fields. The self-assembled nano particles are prepared by an emulsion polymerization method, and the self-assembled nano particles comprise the following raw materials in percentage by mass: 10 to 30 percent of styrene monomer, 0.5 to 3 percent of acrylamide monomer, 0.01 to 0.5 percent of N, N' -methylene-bisacrylamide monomer, 0.05 to 1 percent of emulsifier, 0.1 to 1 percent of main functional monomer, 0.1 to 1 percent of object functional monomer, 0.01 to 0.05 percent of initiator and the balance of water. The self-assembled nano particles are dispersed in injected water to form a nano particle profile control system with the concentration of 500-4000 mg/L, and then are injected into a water channeling channel to form particle clusters matched with the size of the water channeling channel through self-assembly, so that the deep part of the water channeling channel is blocked strongly.
Description
Technical Field
The invention relates to the technical field of profile control and water shutoff in oil and gas field development, in particular to self-assembled nanoparticles for oil reservoir deep profile control and a preparation method and application thereof.
Background
Most blocks enter the high-water-content and ultra-high-water-content exploitation period in the later exploitation stage of the oil field, and the demand for the deep profile control technology of the oil reservoir aiming at treating water channeling is more and more common and urgent. Profile control is one of important means for improving the heterogeneity of the oil reservoir and realizing high efficiency and stable yield of the oil reservoir. The method is a novel oil reservoir deep profile control technology formed by combining the actual conditions of the oil reservoir at present on the basis of an inorganic particle profile control and water shutoff technology, and the plugging mechanism is bridging plugging and elastic deformation. Although the viscoelastic particle profile control agent has ideal application effect in medium-high permeability reservoirs, in low-permeability reservoirs, the contradiction between the injection property of the viscoelastic particles and deep plugging is particularly prominent, the profile control agent is difficult to inject, and pollution plugging is easy to form near the injection end. Therefore, the inventor of the application develops an oil reservoir deep aggregation plugging control method (Chinese patent CN 114922586A), and nanoparticles are injected into an oil reservoir firstly, and then a nanoparticle self-aggregation control agent is injected, so that the nanoparticles are aggregated to form a nanoparticle cluster matched with the size of a water channeling channel, a hypertonic area is plugged, and deep profile control is realized. Although the method disclosed by the patent can realize deep plugging of a low-permeability reservoir, the prepared nanoparticles do not have aggregation performance, a regulating agent is required to be used for aggregation, the operation is troublesome in practical application, and the nanoparticles and the regulating agent are subjected to chromatographic separation, so that the utilization rate of the nanoparticles is low, the using amount is large, and the method is uneconomical.
Disclosure of Invention
In order to solve the technical problems, the invention provides self-assembled nanoparticles for oil reservoir deep profile control and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a self-assembled nano-particle for oil reservoir deep profile control is prepared by the following raw materials through an emulsion polymerization method; 10 to 30 percent of styrene monomer; 0.5 to 3 percent of acrylamide monomer; 0.01 to 0.5 percent of N, N' -methylene bisacrylamide monomer; 0.1 to 1 percent of main functional monomer; 0.1 to 1 percent of object functional monomer; 0.05 to 1 percent of emulsifier; 0.01 to 0.05 percent of initiator; the balance of water.
Preferably, the host functional monomer comprises: any one of allyl-beta-cyclodextrin and acrylamide-beta-cyclodextrin.
Preferably, the guest functional monomer comprises: any one of hexadecyl dimethyl allyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride.
Preferably, the emulsifier is one or more of sodium fatty alcohol-polyoxyethylene ether sulfate, sodium dodecyl benzene sulfonate or sodium dodecyl sulfate.
Preferably, the initiator is one or more of potassium persulfate, ammonium persulfate and sodium persulfate.
Preferably, the water is deionized water.
The preparation method of the self-assembled nanoparticles for the oil reservoir deep profile control comprises the following steps: adding acrylamide monomer, N' -methylene bisacrylamide monomer, host functional monomer, object functional monomer, emulsifier and initiator into deionized water in turn, and mixing uniformly; then adding styrene monomer and mixing uniformly; heating to 60-70 ℃ under the stirring condition, and reacting for 4-6 h to prepare the self-assembled nano particles.
Further, the particle size of the self-assembly nano-particles is 50-400 nm. For a low permeability reservoir (permeability less than 50 mD), the permeability of a high permeability channel of water channeling is hundreds, even thousands of millidarcies, according to the J.Kozeny formula, the average pore throat radius of the water channeling channel is 1-20 μm, the nano particles are too large, and the water channeling channel is not easy to inject.
In the application of any self-assembled nano-particles for oil reservoir deep profile control, the self-assembled nano-particles are dispersed in injection water to form a nano-particle profile control system with the concentration of 500-4000 mg/L, and then the nano-particle profile control system is injected into a water channeling channel. The plugging effect is poor due to too low concentration, the concentration is too high, the injection pressure is too large, the energy consumption is high, and the problem that the section is blocked by the nanoparticles easily occurs at the injection end, so that the subsequent nanoparticles cannot be injected.
Further, the injection speed of the nanoparticle profile control system is 0.01-3 mL/min. The injection speed is too small, the injection time is too long, the injection speed is too large, the injection pressure is large, and the injection speed within the range of 0.01-3 mL/min can take efficiency and energy consumption into consideration.
The invention has the beneficial effects that:
1. the surface of the nano-particle prepared by the invention contains cyclodextrin and long-chain hydrophobic groups, and the nano-particle can be self-assembled into an aggregate through the interaction of a host and an object, and a regulating agent is not required to be added during use, so that the operation is simple, the utilization rate of the nano-particle is high, the using amount is small, and the economic benefit is good.
2. Because the nano particles have the self-assembly characteristic, in pore throats with different sizes and different shapes, the nano particles can be self-assembled to form particle clusters matched with the pore throats according to the pore throat structures, so that the nano particles can be effectively blocked, and the self adaptability is strong.
3. The nano particles are prepared by an emulsion polymerization method, and have a core-shell structure, wherein the core is formed by polymerizing styrene, and the shell is formed by crosslinking and polymerizing acrylamide, N' -methylene bisacrylamide, a main functional monomer and an object functional monomer.
Drawings
FIG. 1 is a transmission electron micrograph of the self-assembled nanoparticles obtained in example 1 of the present invention.
FIG. 2 is a transmission electron microscope image of the self-assembled nanoparticles obtained in example 2 of the present invention.
FIG. 3 is a transmission electron micrograph of the self-assembled nanoparticles obtained in example 3 of the present invention.
FIG. 4 is a transmission electron micrograph of the self-assembled nanoparticles obtained in example 4 of the present invention.
FIG. 5 is a transmission electron micrograph of the self-assembled nanoparticles obtained in example 5 of the present invention.
FIG. 6 is a transmission electron micrograph of the self-assembled nanoparticles obtained in example 6 of the present invention.
FIG. 7 is a transmission electron micrograph of the self-assembled nanoparticles obtained in comparative example 1 of the present invention.
FIG. 8 is a diagram showing the dispersion state of the nanoparticles obtained in comparative example 1 of the present invention in deionized water.
FIG. 9 is a diagram of the dispersion state of the nanoparticles obtained in example 1 of the present invention in deionized water.
FIG. 10 is a transmission electron microscope image of the self-assembly of nanoparticles into clusters obtained in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to specific examples to facilitate the understanding of the invention, but the invention is not limited thereby.
Example 1
The embodiment provides a self-assembled nanoparticle for oil reservoir deep profile control and a preparation method thereof, and the preparation method comprises the following specific implementation steps: 0.5g of acrylamide, 0.01g of N, N' -methylene bisacrylamide, 0.05g of sodium fatty alcohol polyoxyethylene ether sulfate, 0.1g of acrylamide-beta-cyclodextrin, 0.1g of hexadecyl dimethyl allyl ammonium chloride and 0.01g of potassium persulfate are sequentially added into 89.23g of water, uniformly stirred, 10g of styrene is added, the temperature is raised to 60 ℃ under the stirring condition, the reaction is carried out for 4 hours, the self-assembled nano-particles can be prepared, the average particle size of the obtained nano-particles is 75nm, and the projection electron microscope image of the nano-particles is shown as figure 1.
Example 2
The embodiment provides a self-assembled nanoparticle for oil reservoir deep profile control and a preparation method thereof, and the preparation method comprises the following specific implementation steps: 1g of acrylamide, 0.05g of N, N' -methylene bisacrylamide, 0.05g of sodium fatty alcohol polyoxyethylene ether sulfate, 0.2g of acrylamide-beta-cyclodextrin, 0.2g of hexadecyl dimethyl allyl ammonium chloride and 0.01g of ammonium persulfate are sequentially added into 83.49g of water, uniformly stirred, then 15g of styrene is added, the temperature is raised to 60 ℃ under the stirring condition, the reaction is carried out for 4 hours, and the self-assembled nano-particles can be prepared, wherein the average particle size of the obtained nano-particles is 115nm, and the projection electron microscope image of the nano-particles is shown in figure 2.
Example 3
The embodiment provides a self-assembled nanoparticle for oil reservoir deep profile control and a preparation method thereof, and the preparation method comprises the following specific implementation steps: 2g of acrylamide, 0.1g of N, N' -methylene bisacrylamide, 0.1g of sodium fatty alcohol polyoxyethylene ether sulfate, 0.2g of acrylamide-beta-cyclodextrin, 0.2g of hexadecyl dimethyl allyl ammonium chloride and 0.01g of sodium persulfate are sequentially added into 77.39g of water, uniformly stirred, then 20g of styrene is added, the temperature is raised to 60 ℃ under the stirring condition, the reaction is carried out for 4 hours, and the self-assembled nanoparticles can be prepared, wherein the average particle size of the obtained nanoparticles is 185nm, and the projection electron microscope image of the nanoparticles is shown in figure 3.
Example 4
The embodiment provides a self-assembled nanoparticle for oil reservoir deep profile control and a preparation method thereof, and the preparation method comprises the following specific implementation steps: adding 3g of acrylamide, 0.2g of N, N' -methylene bisacrylamide, 0.2g of sodium fatty alcohol polyoxyethylene ether sulfate, 0.3g of acrylamide-beta-cyclodextrin, 0.3g of hexadecyl dimethyl allyl ammonium chloride and 0.02g of potassium persulfate into 70.98g of water sequentially, stirring uniformly, then adding 25g of styrene, heating to 70 ℃ under the condition of stirring, and reacting for 4 hours to prepare the self-assembled nanoparticles, wherein the average particle size of the obtained nanoparticles is 255nm, and the projection electron microscope image of the nanoparticles is shown in figure 4.
Example 5
The embodiment provides a self-assembled nanoparticle for oil reservoir deep profile control and a preparation method thereof, and the preparation method comprises the following specific implementation steps: 3g of acrylamide, 0.4g of N, N' -methylene bisacrylamide, 0.3g of sodium dodecyl benzene sulfonate, 0.5g of allyl-beta-cyclodextrin, 0.5g of octadecyl dimethyl allyl ammonium chloride and 0.03g of potassium persulfate are sequentially added into 65.27g of water, uniformly stirred, then 30g of styrene is added, the temperature is raised to 65 ℃ under the stirring condition, the reaction is carried out for 5 hours, and the self-assembled nano-particles can be prepared, wherein the average particle size of the obtained nano-particles is 323nm, and the projection electron microscope image of the nano-particles is shown in figure 5.
Example 6
The embodiment provides a self-assembled nanoparticle for oil reservoir deep profile control and a preparation method thereof, and the preparation method comprises the following specific implementation steps: 3g of acrylamide, 0.5g of N, N' -methylene bisacrylamide, 0.4g of sodium dodecyl sulfate, 0.8g of allyl-beta-cyclodextrin, 0.8g of octadecyl dimethyl allyl ammonium chloride and 0.04g of sodium persulfate are sequentially added into 60.86g of water, stirred uniformly, then 30g of styrene is added, the temperature is raised to 70 ℃ under the stirring condition, the reaction is carried out for 6 hours, and the self-assembled nano-particles can be prepared, wherein the average particle size of the obtained nano-particles is 348nm, and the projection electron microscope image of the nano-particles is shown in figure 6.
Comparative example 1
The embodiment provides a self-assembled nanoparticle for oil reservoir deep profile control and a preparation method thereof, which are different from embodiment 4 in that a host functional monomer and an object functional monomer are not added during preparation of the nanoparticle, and the specific implementation steps are as follows: adding 3g of acrylamide, 0.2g of N, N' -methylene bisacrylamide, 0.2g of sodium fatty alcohol polyoxyethylene ether sulfate and 0.02g of potassium persulfate into water, stirring uniformly, adding 25g of styrene, heating to 70 ℃ under the stirring condition, and reacting for 4 hours to prepare the nano-particles, wherein the average particle size of the obtained nano-particles is 245nm, and a projection electron microscope picture of the nano-particles is shown in figure 7.
Plugging Performance test
And (3) characterization of the properties of the nanoparticles:
the nanoparticles in example 1 and comparative example 1 were prepared into sample solutions with a mass concentration of 2000mg/L using deionized water, respectively, and then sealed and placed in a 60 ℃ incubator, and the dispersion state of the nanoparticles in the deionized water was observed, and the experimental results are shown in fig. 8 and fig. 9.
FIG. 8 is a dispersion state of nanoparticles in comparative example 1, the nanoparticles being uniformly dispersed in water regardless of the standing time; while fig. 9 shows the state of the nanoparticles in example 1 after aging for 20h, it can be seen from fig. 9 that the nanoparticles are aggregated and settled at the bottom of the bottle, which is caused by the self-assembly of the host-guest groups on the surface of the nanoparticles under the interaction. By electron microscope observation, as shown in fig. 10, it can be clearly seen that the nanoparticles in example 1 are agglomerated together.
Evaluation of plugging performance:
in order to investigate the injectability and plugging performance of the nanoparticles prepared in the present invention, examples 1, 2, 3, 4 and 1 were used, and the length was 30cm, the diameter was 2.5cm, the average permeability was 200X 10 ～3 μm 2 The core model having a porosity of 27.2% and an average throat radius of 2.43 μm was subjected to a performance evaluation test in which the average throat radius of the core was calculated according to the j.kozeny formula.
In the experimental process, firstly, vacuumizing the rock core, injecting saturated water at an injection speed of 1mL/min until the injection pressure is stable, and then respectively injecting 0.5PV nanoparticle profile control systems with mass concentration of 4000mg/L, of example 1, example 2, example 3, example 4 and comparative example 1 at the same injection speed; aging at 60 ℃ for 24h, performing subsequent water drive after the nanoparticles are self-assembled, stopping the experiment until the pressure at the pressure measuring point is balanced, wherein the resistance coefficient and the residual resistance coefficient are respectively calculated by a formula 1 and a formula 2,
in the formula: p 0 Is an initial water-drive stable pressure value, P c Is the pressure value in the process of injecting the profile control agent, and P is the water drive pressure value after plugging.
The results of the experiment are shown in table 1.
As can be seen from table 1, when the examples and comparative examples were injected with nanoparticles, the injection pressure did not change much compared to the increase in injection pressure, and the coefficient of resistance was around 2.0 because the nanoparticles were small in size; when water flooding is subsequently performed, the subsequent water flooding pressure of the embodiments 1 to 4 is obviously increased, the residual resistance coefficient reaches over 3.0, and the plugging rate is about 70%, which indicates that the particle cluster after self-assembly of the nanoparticles can effectively plug a water channeling channel; while the subsequent water-driving pressure of the comparative example 1 is basically kept unchanged, the residual resistance coefficient is only 1.10, because the profile control system has no plugging effect when the nano particles cannot form self-assembly. The combination of the resistance coefficient and the residual resistance coefficient shows that the nano-particles prepared by the method have good injection characteristics and strong plugging capability.
TABLE 1 Profile control System injectability and plugging Effect results
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and the improvements and modifications are also within the protection scope of the present invention.
Claims (10)
1. The self-assembled nano particles for oil reservoir deep profile control are characterized by being prepared from the following raw materials by an emulsion polymerization method;
10 to 30 percent of styrene monomer;
0.5 to 3 percent of acrylamide monomer;
0.01 to 0.5 percent of N, N' -methylene bisacrylamide monomer;
0.1 to 1 percent of main functional monomer;
0.1 to 1 percent of object functional monomer;
0.05 to 1 percent of emulsifier;
0.01 to 0.05 percent of initiator;
the balance of water.
2. The self-assembled nanoparticle for deep profile control of oil reservoirs of claim 1, wherein the main functional monomer comprises: any one of allyl-beta-cyclodextrin and acrylamide-beta-cyclodextrin.
3. The self-assembled nanoparticles for deep profile control of oil reservoirs of claim 1, wherein the guest functional monomer comprises: any one of hexadecyl dimethyl allyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride.
4. The self-assembled nanoparticle for deep profile control of oil reservoirs of claim 1, wherein the emulsifier is one or more of sodium fatty alcohol-polyoxyethylene ether sulfate, sodium dodecyl benzene sulfonate or sodium dodecyl sulfate.
5. The self-assembled nanoparticles for deep profile control of oil reservoirs of claim 1, wherein the initiator is one or more of potassium persulfate, ammonium persulfate and sodium persulfate.
6. The self-assembled nanoparticles for deep profile control of oil reservoirs of claim 1, wherein the water is deionized water.
7. The method for preparing the self-assembled nanoparticles for the deep profile control of the oil reservoir according to any one of claims 1 to 6, which comprises the following steps: adding acrylamide monomer, N' -methylene bisacrylamide monomer, host functional monomer, object functional monomer, emulsifier and initiator into deionized water in turn, and mixing uniformly; then adding styrene monomer and mixing uniformly; under the condition of stirring, the temperature is raised to 60-70 ℃, and the self-assembled nano-particles can be prepared after 4-6 h of reaction.
8. The method for preparing the self-assembled nanoparticles for the deep profile control of the oil reservoir as claimed in claim 7, wherein the particle size of the self-assembled nanoparticles is 50-400 nm.
9. The use of the self-assembled nanoparticles for deep profile control of oil reservoirs according to any one of claims 1 to 6, wherein the self-assembled nanoparticles are dispersed in injection water to form a nanoparticle profile control system with a concentration of 500 to 4000mg/L, and then the nanoparticle profile control system is injected into a water channeling channel.
10. The use of the self-assembled nanoparticles for deep profile control of oil reservoirs according to claim 9, wherein the injection speed of the nanoparticle profile control system is 0.01-3 mL/min.
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| CN117304429A (en) * | 2023-11-29 | 2023-12-29 | 大庆市唯品科技开发有限公司 | Composite high-temperature-resistant and salt-resistant water shutoff agent and preparation method thereof |
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| CN117304429A (en) * | 2023-11-29 | 2023-12-29 | 大庆市唯品科技开发有限公司 | Composite high-temperature-resistant and salt-resistant water shutoff agent and preparation method thereof |
| CN117304429B (en) * | 2023-11-29 | 2024-02-02 | 大庆市唯品科技开发有限公司 | Composite high-temperature-resistant and salt-resistant water shutoff agent and preparation method thereof |
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