CN113372498B - Nano profile control and flooding material, and preparation method and application thereof - Google Patents
Nano profile control and flooding material, and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a nano profile control and flooding material which is a core-shell structure formed by wrapping an oil-soluble material with a water-soluble material; the oil-soluble material is prepared by a material I polymerization reaction I containing an olefinic acid ester compound, a styrene compound, a cross-linking agent, an emulsifier and an initiator I; the water-soluble material is prepared by a material II polymerization reaction II containing a water-soluble monomer and an initiator II. The nano profile control and flooding material can release oil-soluble core material in the process of transferring to the deep part of a reservoir, block water when meeting water and wash oil when meeting oil, thereby playing the role of deep profile control and flooding.
Description
Technical Field
The application relates to a nano profile control and flooding material and a preparation method and application thereof, belonging to the field of low-permeability profile control and flooding.
Background
With the development of oil and gas exploration and development technology, particularly since the 21 st century, the proportion of low-permeability oil reservoirs in the geology reserves of the crude oil explored in China is larger and larger, the oil reservoirs with low production and closed before are included, the world energy crisis is aggravated, and people pay more and more attention to the development of the low-permeability oil reservoirs.
The low permeability, the severe fractured heterogeneity, the severe water lock and the slow energy transfer are the prominent characteristics of the low permeability reservoir, and the displacement pressure required by the reservoir is also higher. In recent years, the development degree of oil fields is further increased, the water injection development period is prolonged, geological heterogeneity is increased, injected water is rapidly pushed along a relative high-permeability layer or a high-permeability strip, the water content of a part of corresponding oil wells is increased rapidly, the liquid yield of the other part of oil wells is low due to the fact that energy cannot be supplied timely, and therefore the liquid yield, the water content and other parameters of the oil wells forming the same block or sand body are greatly different, finally, the utilization degree of reserves is low, the utilization of the reserves is uneven, and the further improvement of the recovery ratio is seriously influenced.
The research and application of the technology of profile control and water shutoff in China can be traced back to the end of the last 50 years of the last century, and the water shutoff of an oil well is mainly carried out in the sixty-seven decades. The profile control technology of the water injection well is rapidly developed along with the appearance of polymer gel in the early 80 s, and profile control and water shutoff are mainly performed by using a plugging agent with higher strength and mainly performed by using physical plugging as a main action mechanism. As the oil field begins to enter the development stage of the high water-cut period in the 90 s, the profile control and water plugging technology reaches the peak period. In the 21 st century, the problem of high water content becomes one of the problems which need to be solved in the oil field, the heterogeneity of an oil reservoir is further intensified by long-term water injection development, a large pore passage and a high-permeability passage in the oil reservoir are ubiquitous, injected water directly flows to the position near the bottom of an oil well, the effect of water injection development is seriously reduced, and the conventional profile control and water shutoff technology cannot meet the requirements of water injection development. At the moment, the deep profile control technology has a new breakthrough, and mainly effectively combines the deep fluid diversion technology with the oil reservoir engineering technology, and the whole oil reservoir is taken as a processing target, so that the scale change is larger, and the effect is more obvious.
Compared with the conventional profile control and water shutoff agents, the deep profile control agent has better use effect and more obvious performance in the aspect of improving the recovery efficiency. The reason for this is that, the deep profile control agent migrates in the stratum through the driving of water after entering the stratum, and under the condition that the deep profile control agent receives water drive pressure and is greater than its breakthrough pressure, the deep profile control agent can move to the deeper position of stratum all the time, can stop when meetting littleer pore throat, pore and produce the shutoff effect, makes the water drive scope grow, and the rivers direction obtains automatic adjustment. Compared with the conventional plugging agent, the deep plugging agent is a polymer which is injected into a stratum and has higher viscosity, so that the stress of the residual oil is changed, the residual oil can be separated from the sandstone surface, and the oil field exploitation effect is better.
The main profile control and flooding technologies which are widely applied in recent years are: gel deep profile control and flooding technology, foam deep profile control and flooding technology, microorganism deep profile control and flooding technology, oil-containing sludge deep profile control (flooding) technology, combined profile control and flooding technology, microspheres and the like
Although various deep profile control technologies achieve certain mine field effects, they also have certain disadvantages: (1) underground cross-linked gel profile control and flooding system: the gelling condition is harsh, the blocking degree is low, the oil reservoir is not suitable for large pore and crack oil reservoirs, the temperature resistance is below 90 ℃, the mineralization degree of injected water is not more than 50000mg/L, the crosslinking time is slow, and the long-time migration of a crosslinking system in a stratum pore causes diffusion, dilution, shearing, degradation and the like, so that the gelling condition of the crosslinking system which is harsh under the ground gelling condition is worse in the underground, and even a part of the crosslinking system can not be crosslinked. (2) Pre-crosslinked gel particles: surface blockage is easy to form to a certain degree, certain requirements are required on the construction process, and in addition, the particles have certain limits on the permeability. (3) Microbial deep profile control and flooding agent: overgrowth of microorganisms can cause clogging of the wells. (4) Precipitation type inorganic salt deep profile control agent: not suitable for severely heterogeneous formations. (5) Foam deep profile control agent: the validity period is short and the construction process is complex. (6) Clay gum polymer flocculation deep profile control agent: the natural selectivity is poor, special equipment is needed for field construction, the injection property is poor, and the large-dose injection is limited. (7) Oil-containing sludge deep profile control agent: is limited by the production area and the yield of raw materials, and is not easy to popularize and use on a large scale; (8) anionic and cationic polymer deep profile control agent: the profile control effect is greatly influenced by the sequence of alternate injection, injection concentration and injection proportion, and the large-scale popularization of the profile control effect is limited. (9) Polymer microspheres have been widely used in oilfield profile control, but with the gradual development of high-temperature and high-salinity oil reservoirs and CO 2 The popularization and application of the flooding technology put higher requirements on the temperature resistance, salt resistance, acid resistance and shear resistance of the polymer microsphere, as shown in the following: a. with CO 2 The driving is vigorously promoted by CO 2 After flooding, the high-temperature and high-pressure oil reservoir environment is generally acidic, and the microspheres are unstable and easy to degrade under the acidic condition, so that the effective period is short, and the deep profile control effect is limited; b. along with the drilling development of deep wells and ultra-deep wells, the deep oil reservoir conditions are more complex, higher requirements are provided for the temperature resistance and salt tolerance of the polymer microspheres, and the polymer microspheres can reach the deep part of the oil reservoir only by long-distance migration, which also provides higher requirements for the shear resistance of the polymer microspheres; c. at present, most of polymer microspheres are synthesized by inverse polymerization, so that the production process is high in requirement, low in yield and uncontrollable in cost.
Disclosure of Invention
In order to solve the problems, the application provides a nano profile control material, a nano core-shell material is synthesized by a one-step or multi-step polymerization method, and a core material with a certain size is designed by regulating and controlling the molecular structure and the molecular weight distribution of a core oil-soluble nano material by means of a molecular design theory; the water-soluble monomer is used as an external shell, and the shell has good temperature resistance and salt resistance and has the functions of protecting and supporting the core. In the process that the water-soluble shell material carries the core to move to the deep part of the reservoir, the water-soluble shell material releases oil-soluble core material due to the influence of factors such as stratum shearing, adsorption or swelling and the like; by the migration of the oil-soluble core in the reservoir, water is blocked when meeting water, and oil is washed when meeting oil, so that the intelligent profile control and flooding function is realized.
According to one aspect of the application, a nano profile control and flooding material is provided, wherein the nano profile control and flooding material is a core-shell structure formed by wrapping an oil-soluble material with a water-soluble material; the oil-soluble material is prepared by a material I polymerization reaction I containing an olefinic acid ester compound, a styrene compound, a cross-linking agent, an emulsifier and an initiator I; the water-soluble material is prepared by a material II polymerization reaction II containing a water-soluble monomer and an initiator II.
Optionally, the alkenoic acid ester compound is selected from at least one of stearyl acrylate and stearyl methacrylate.
Preferably, the olefinic acid ester compound is selected from octadecyl acrylate.
Optionally, the styrene compound is selected from at least one of styrene, methyl styrene, dimethyl styrene, and phenyl propylene.
Preferably, the styrenic compound is selected from styrene.
Optionally, the cross-linking agent is selected from at least one of N-N methylene bisacrylamide, methylene acrylamide, and N-N vinyl bisacrylamide.
Preferably, the crosslinking agent is selected from N-N methylene bisacrylamide.
Optionally, the emulsifier is selected from at least one of tween 80, tween 60 and tween 20.
Preferably, the emulsifier is selected from tween 80.
Optionally, the initiator I is selected from at least one of potassium persulfate, sodium persulfate and ammonium persulfate.
Optionally, the water-soluble monomer is selected from at least one of acrylamide, acrylic acid, sodium acrylate and 2-acrylamido-2-methylpropanesulfonic acid.
Optionally, the initiator II is selected from at least one of potassium sulfate, sodium persulfate and ammonium persulfate.
Optionally, the molecular weight of the nano profile control material is 30 to 50 ten thousand.
Optionally, the oil-soluble material has a molecular weight of 3 to 5 ten thousand.
Optionally, the contact angle of the oil-soluble material is 100 to 125 °.
Optionally, the contact angle of the nano profile control and flooding material is 40-60 °.
Optionally, the contact angle is measured by: dissolving a material to be measured in ethanol, dripping the solution on a glass sheet, and reading the angle formed by the liquid drops by using a goniometer, wherein the angle is a contact angle.
According to another aspect of the present application, there is provided a method for preparing the nano profile control material, the method comprising: (1) Polymerizing a material I containing an olefinic acid ester compound, a styrene compound, a cross-linking agent, an emulsifying agent and an initiator I to obtain an oil-soluble material; (2) And (3) carrying out polymerization reaction on a material II containing a water-soluble monomer, the oil-soluble material and an initiator to obtain the nano profile control material.
Optionally, the step (1) comprises:
(i) Dissolving a raw material I containing an olefinic acid ester compound, a styrene compound, a cross-linking agent and an emulsifying agent in water to obtain a mixture I;
(ii) Dissolving a raw material II containing an initiator in water, and deoxidizing to obtain a mixture II;
(iii) And adding the mixture II into the mixture I, and carrying out polymerization reaction I to obtain the oily material.
Optionally, the raw material I further comprises a solvent; the solvent is selected from water.
Optionally, the water is deionized water.
Optionally, the mass ratio of the olefinic acid ester compound, the styrene compound, the cross-linking agent, the emulsifier and the initiator I is 3-5: 5 to 9:0.01 to 0.03:8 to 12:0.05 to 0.2.
Preferably, the mass ratio of the olefinic ester compound to the styrene compound is 3:7.
preferably, the mass ratio of the olefinic ester compound, the styrene compound, the crosslinking agent, the emulsifying agent and the initiator I is (3).
Alternatively, the conditions of the polymerization reaction I are: the reaction temperature is 60-70 ℃, and the reaction time is 4-6 h.
Optionally, the mass ratio of the water-soluble monomer, the oil-soluble material and the initiator II is 6-8.
Preferably, the mass ratio of the water-soluble monomer, the oil-soluble material and the initiator II is 7.5.
Alternatively, the conditions of the polymerization reaction II are: the reaction temperature is 70-90 ℃, and the reaction time is 2-4 h.
Preferably, the reaction temperature is 80 ℃ and the reaction time is 3h.
Optionally, the step (2) comprises: a. dissolving at least two water-soluble monomers in water, and adjusting the pH value to 6-7 to obtain a mixture A; b. mixing the mixture A and the oily material, stirring at room temperature, and deoxidizing to obtain a mixture B; c. dissolving raw materials containing an initiator in water, and deoxidizing to obtain a mixture C; d. and adding the mixture C into the mixture B, and carrying out polymerization reaction II to obtain the nano profile control material.
Alternatively, the mixture a includes a water-soluble monomer A1 and a water-soluble monomer A2.
Preferably, the water-soluble monomer A1 is selected from acrylamide; the water-soluble monomer A2 is selected from 2-acrylamide-2-methylpropanesulfonic acid.
Alternatively, the mass ratio of the water-soluble monomer A1 to the water-soluble monomer A2 is 6.
According to a further aspect of the application, an oil displacement agent is provided, wherein the oil displacement agent comprises at least one of the nano material as described in any one of the above and the nano material prepared by the method as described in any one of the above.
According to yet another aspect of the application, there is provided the use of an oil displacement agent as described above in low permeability oil fields.
The beneficial effects that this application can produce include:
1. the nanometer profile control and flooding material is a core-shell structure formed by wrapping an oil-soluble material with a water-soluble material, and the shell has good temperature resistance and salt resistance and has the functions of protecting and supporting a core. The water-soluble shell material carries the inner core to move to the deep part of the reservoir, then the oil-soluble inner core material is released, water is blocked when the water-soluble inner core material meets water, oil is washed when the water-soluble inner core material meets oil, and therefore the intelligent oil displacement and displacement function is achieved.
2. The nano profile control and flooding material has better dispersibility in water and kerosene, and has smaller contact angle.
3. The preparation method of the nano profile control and flooding material is simple, simple and easy to operate, and has good application.
Drawings
FIG. 1 is a schematic diagram of a nano profile control material structure and a process for releasing an oil-soluble core according to an embodiment of the present disclosure;
FIG. 2 is a schematic view of a low permeability oil-containing passage according to an embodiment of the present application;
fig. 3 is a schematic diagram illustrating a profile control mechanism of a nano profile control material according to an embodiment of the present disclosure.
FIG. 4 is a graph showing the dissolution of an inner core oil-soluble material prepared in example 1 of the present application in water and kerosene, respectively;
FIG. 5 is a schematic illustration of the contact angle of the core oil-soluble material prepared in example 1 of the present application;
FIG. 6 is a schematic view showing the contact angle of an oil-soluble material of an inner core prepared in comparative example 1 of the present application;
FIG. 7 is a graph showing contact angles of an oil-soluble material of an inner core prepared in comparative example 2 of the present application;
FIG. 8 is a diagram showing the dissolution of the nano profile control material prepared in comparative example 2 of the present application in water and kerosene, respectively;
FIG. 9 is an optical microscope photograph of the nano profile control material prepared in example 4 of the present application; (a) a scale of 10um; (b) 100nm as a scale.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially. If not stated, the test method adopts the conventional method, and the instrument setting adopts the setting recommended by the manufacturer.
Contact angle instrument: DSA25, koro.
The nano profile control and flooding material is a core-shell structure formed by wrapping an oil-soluble material with a water-soluble material.
The water-soluble monomer is used as an external shell, and the shell has good temperature resistance and salt resistance and has the functions of protecting and supporting the core. In the process that the water-soluble shell material carries the inner core to move to the deep part of the reservoir, the oil-soluble core material (shown in figure 1) is released from the water-soluble shell material due to the influence of factors such as stratum shearing, adsorption or swelling and the like, so that the effect of depth profile control is achieved.
The viscoelasticity and flexibility of the core-shell particles can be transferred in a low-permeability reservoir, and after the oil-soluble core is released, the core plays a role in blocking a water flow channel of a high-permeability layer by utilizing the principle of similarity and intermiscibility; however, in the low-permeability oil-containing channel, the oil-soluble core body material can emulsify and disperse crude oil to achieve an oil displacement effect. The size of the oil-soluble core body is designed by regulating the molecular structure and molecular weight of the core body, so that the pore throat is blocked, as shown in figures 2 and 3.
Example 1 preparation of core oil soluble Material # 1 of Nano Profile control Material
1. Weighing 90g of deionized water, adding 10g of Tween 80, heating at 500rpm and 55 ℃, magnetically stirring until the Tween 80 is dissolved, and adding 0.01g of N-N methylene bisacrylamide;
2. weighing 3g of octadecyl acrylate, adding 7g of styrene, magnetically stirring at 500rpm and 55 ℃, and heating for dissolving;
3. pouring the mixture dissolved in the step 2 into the mixture in the step 1 at one time, magnetically stirring at the temperature of 55 ℃ and the speed of 500rpm for 30min to form stable emulsion, and introducing N 2 20min；
4. Weighing 0.1g of potassium persulfate, adding 10g of deionized water, shaking for dissolution, and introducing N 2 15min；
5. And (3) starting stirring the stable emulsion in the step (3) at the rotation speed of 350rpm, heating to 70 ℃, pouring the initiator potassium persulfate solution obtained in the step (4) after 10min, and reacting for 5h.
The molecular weight of the oil-soluble material is 3.8-4.2 ten thousand. The obtained kernel oily material is well dispersed in kerosene but cannot be dispersed in water, and precipitation and delamination phenomena occur, as shown in figure 4; the inner core oily material was subjected to a contact angle test and the contact angle was measured to be 122 °, as shown in fig. 5.
Example 2 preparation of core oil soluble Material # 2 of Nano Profile control Material
1. Weighing 90g of deionized water, adding 8g of Tween 80, heating at 500rpm and 55 ℃, magnetically stirring until the Tween 80 is dissolved, and adding 0.01g of N-N methylene bisacrylamide;
2. weighing 4g of octadecyl acrylate, adding 8g of styrene, magnetically stirring at 500rpm and 55 ℃, and heating for dissolving;
3. pouring the mixture dissolved in the step 2 into the mixture in the step 1 at one time, magnetically stirring at the temperature of 55 ℃ and the rpm of 500 for 30min to form stable emulsion, and introducing N 2 20min；
4. 0.1g of potassium persulfate is weighed, 10g of deionized water is added, and N is introduced after shaking and dissolving 2 15min；
5. And (3) starting stirring the stable emulsion in the step (3) at the rotation speed of 350rpm, heating to 70 ℃, pouring the initiator potassium persulfate solution obtained in the step (4) after 10min, and reacting for 6h.
The molecular weight of the oil-soluble material is 4.3-4.6 ten thousand. The obtained kernel oily material is well dispersed in kerosene but can not be dispersed in water, and precipitation and delamination phenomena occur; the inner core oily material was subjected to a contact angle test, and the contact angle was measured to be 118 °.
Example 3 preparation of core oil soluble Material # 3 of Nano Profile control Material
1. Weighing 90g of deionized water, adding 10g of Tween 80, heating at 500rpm and 55 ℃, magnetically stirring until the Tween 80 is dissolved, and adding 0.02g of N-N methylene-bisacrylamide;
2. weighing 3g of octadecyl acrylate, adding 7g of styrene, magnetically stirring at 500rpm and 55 ℃, and heating for dissolving;
3. pouring the mixture dissolved in the step 2 into the mixture in the step 1 at one time, magnetically stirring at the temperature of 55 ℃ and the rpm of 500 for 30min to form stable emulsion, and introducing N 2 20min；
4. 0.2g of potassium persulfate is weighed, 10g of deionized water is added, and N is introduced after shaking and dissolving 2 15min；
5. And (3) starting stirring the stable emulsion in the step (3) at the rotation speed of 350rpm, heating to 80 ℃, pouring the initiator potassium persulfate solution obtained in the step (4) after 10min, and reacting for 7h.
The molecular weight of the oil-soluble material is 4.8-5.1 ten thousand. The obtained kernel oily material is well dispersed in kerosene but cannot be dispersed in water, and precipitation and delamination phenomena occur; the inner core oily material was subjected to a contact angle test, and the contact angle was measured to be 109 °.
Comparative example 1 preparation of core oil-soluble Material of Nano Profile flooding Material
1. Weighing 90g of deionized water, adding 10g of Tween 80, heating at 500rpm and 55 ℃, and magnetically stirring until the Tween 80 is dissolved;
2. weighing 1g of octadecyl acrylate, adding 9g of styrene, magnetically stirring at 500rpm and 55 ℃, and heating for dissolving;
3. pouring the mixture dissolved in the step 2 into the mixture in the step 1 at one time, magnetically stirring at the temperature of 55 ℃ and the speed of 500rpm for 30min to form stable emulsion, and introducing N 2 20min；
4. 0.1g of potassium persulfate is weighed, 10g of deionized water is added, and N is introduced after shaking and dissolving 2 15min；
5. And (4) starting stirring the stable emulsion obtained in the step (3) at the rotation speed of 350rpm, heating to 70 ℃, pouring the initiator potassium persulfate solution obtained in the step (4) after 10min, and reacting for 5h.
The molecular weight of the oil-soluble material is 8-9 ten thousand. The inner core oily material was subjected to a contact angle test and the contact angle measured was 108 ° as shown in fig. 6. However, the oil-soluble material has poor dispersibility in water and kerosene, and a white substance is precipitated on the upper layer of the stock solution after standing overnight.
Comparative example 2 preparation of core oil-soluble Material of Nano flooding and Profile control Material
1. Weighing 90g of deionized water, adding 10g of Tween 80, heating at 500rpm and 55 ℃, and magnetically stirring until the Tween 80 is dissolved;
2. weighing 3g of octadecyl acrylate, adding 7g of styrene, magnetically stirring at 500rpm and 55 ℃, and heating for dissolving;
3. pouring the mixture dissolved in the step 2 into the mixture in the step 1 at one time, magnetically stirring at the temperature of 55 ℃ and the speed of 500rpm for 30min to form stable emulsion, and introducing N 2 20min；
4. 0.1g of potassium persulfate is weighed, 10g of deionized water is added, and N is introduced after shaking and dissolving 2 15min；
5. And (4) starting stirring the stable emulsion obtained in the step (3) at the rotation speed of 350rpm, heating to 70 ℃, pouring the initiator potassium persulfate solution obtained in the step (4) after 10min, and reacting for 5h.
The molecular weight of the oil-soluble material is 5-7 ten thousand. The inner core oily material was subjected to a contact angle test and the contact angle was measured to be 127 ° as shown in fig. 7. However, the white substance precipitated on the upper layer when the stock solution was left standing overnight, and it was preliminarily concluded that stearyl acrylate and styrene were in an aqueous solution and were not sufficiently reactive for polymerization of the monomers to provide sufficient radicals to provide the reaction, as shown in FIG. 8.
Comparative example 3 preparation of core oil-soluble Material of Nano Profile flooding Material
1. Weighing 90g of deionized water and 10g of Tween 80, heating at 500rpm and 55 ℃, magnetically stirring until the Tween 80 is dissolved, and adding 0.01g of N-N methylene bisacrylamide;
2. weighing 10g of styrene, magnetically stirring at 500rpm and 55 ℃, and heating for dissolving;
3. pouring the mixture dissolved in the step 2 into the mixture in the step 1 at one time, magnetically stirring at the temperature of 55 ℃ and the speed of 500rpm for 30min to form stable emulsion, and introducing N 2 20min；
4. 0.1g of potassium persulfate is weighed, 10g of deionized water is added, and N is introduced after shaking and dissolving 2 15min；
5. And (3) starting stirring the stable emulsion in the step (3) at the rotation speed of 350rpm, heating to 70 ℃, pouring the initiator potassium persulfate solution obtained in the step (4) after 10min, and reacting for 5h.
The resulting oil-soluble material did not disperse in both water and kerosene. Aqueous solution polymerization of styrene monomer, oil solubility of polystyrene is insufficient; in addition, in consideration of crude oil components, more components except aromatic hydrocarbons in the crude oil components are straight-chain or branched alkanes, so that the core material is synthesized by copolymerizing styrene and a long-chain alkyl monomer (octadecyl acrylate).
Comparative example 4 preparation of core oil-soluble Material of Nano flooding and Profile control Material
1. Weighing 90g of deionized water, adding 10g of Tween 80, heating at 500rpm and 55 ℃, magnetically stirring until the Tween 80 is dissolved, and adding 0.01g of N-N methylene-bisacrylamide;
2. weighing 2g of octadecyl acrylate, adding 8g of styrene, magnetically stirring at 500rpm and 55 ℃, and heating for dissolving;
3. pouring the mixture dissolved in the step 2 into the mixture in the step 1 at one time, magnetically stirring at the temperature of 55 ℃ and the rpm of 500 for 30min to form stable emulsion, and introducing N 2 20min；
4. Weighing 0.1g of potassium persulfate, adding 10g of deionized water, shaking for dissolution, and introducing N 2 15min；
5. And (3) starting stirring the stable emulsion in the step (3) at the rotation speed of 350rpm, heating to 70 ℃, pouring the initiator potassium persulfate solution obtained in the step (4) after 10min, and reacting for 5h.
The obtained oil-soluble material was better dispersed in kerosene than water with a contact angle of 108 °, but the effect of dispersion in kerosene was still insufficient.
Example 4 preparation of nano profile control material 1
1. Weighing 6g of acrylamide monomer and 1.5g of AMPS monomer, adding 40g of deionized water for dissolving, and adjusting the pH of the solution to about 6-7 by using NaOH;
2. mixing the mixed solution of the oil-soluble material prepared in the example 1 with the shell solution of which the pH is adjusted in the step 1, stirring at 500rpm at room temperature for 30min, and introducing N 2 20min；
3. Weighing 0.075g of potassium persulfate, adding 10g of deionized water, shaking for dissolution, and introducing N 2 15min；
4. And (3) heating the mixed solution obtained in the step (2) to 80 ℃, adding the potassium persulfate solution obtained in the step (3) after rotating at the speed of 200rpm for 10min, and reacting for 3h.
The structure of the prepared nano profile control and flooding material is shown in fig. 9 and is a two-layer coated core-shell structure. The outer part is a water-soluble shell; the inner part is an oil-soluble inner core; the water-soluble shell coats the oil-soluble core. The molecular weight of the nano profile control material is 44-46 ten thousand, and the contact angle is 49 degrees.
Example 5 preparation of nano profile control material 2
1. Weighing 7g of acrylamide monomer and 1g of AMPS monomer, adding 40g of deionized water for dissolution, and adjusting the pH of the solution to about 6-7 by using NaOH;
2. mixing the mixed solution of the oil-soluble material prepared in the example 1 with the shell solution of which the pH is adjusted in the step 1, stirring at 500rpm at room temperature for 30min, and introducing N 2 20min；
3. Weighing 0.1g of potassium persulfate, adding 10g of deionized water, shaking for dissolution, and introducing N 2 15min；
4. And (3) heating the mixed solution obtained in the step (2) to 70 ℃, adding the potassium persulfate solution obtained in the step (3) after the rotation speed of 200rpm is 10min, and reacting for 6h.
The prepared nano profile control and flooding material is of a two-layer coated core-shell structure. The outer part is a water-soluble shell; the inner part is an oil-soluble inner core; the water-soluble shell coats the oil-soluble core. The molecular weight of the nano profile control material is 48-50 ten thousand, and the contact angle is 40 degrees.
Example 6 preparation of nano profile control material 3
1. Weighing 5g of acrylamide monomer and 3g of AMPS monomer, adding 40g of deionized water for dissolution, and adjusting the pH of the solution to about 6-7 by using NaOH;
2. mixing the mixed solution of the oil-soluble material prepared in the example 1 with the shell solution of which the pH is adjusted in the step 1, stirring at 500rpm at room temperature for 30min, and introducing N 2 20min；
3. Weighing 0.08g of potassium persulfate, adding 10g of deionized water, shaking for dissolution, and introducing N 2 15min；
4. And (3) heating the mixed solution obtained in the step (2) to 80 ℃, adding the potassium persulfate solution obtained in the step (3) after rotating at the speed of 200rpm for 10min, and reacting for 5h.
The prepared nano profile control and flooding material is of a two-layer coated core-shell structure. The outer part is a water-soluble shell; the inner part is an oil-soluble inner core; the water-soluble shell coats the oil-soluble core. The molecular weight of the nano profile control and flooding material is 30-32 ten thousand, and the contact angle is 58 degrees.
Comparative example 5 preparation of Nano profile control Material
1. Weighing 10g of acrylamide monomer and 5g of AMPS monomer, adding 40g of deionized water for dissolution, and adjusting the pH of the solution to about 6-7 by using NaOH;
2. mixing the mixed solution of the oil-soluble material prepared in example 1 with the shell solution of which the pH is adjusted in the step 1, stirring at 500rpm for 30min at room temperature, and introducing N 2 20min；
3. 0.075g of potassium persulfate is weighed, 10g of deionized water is added, and the mixture is shaken to dissolveRear-through N 2 15min；
4. And (3) heating the mixed solution obtained in the step (2) to 80 ℃, adding the potassium persulfate solution obtained in the step (3) after the rotation speed of 200rpm is 10min, and reacting for 3h.
The product produced in this comparative example, was too concentrated and had too high a molecular weight; the polymerization degree of the shell material is too high, so that the viscosity is too high; after the reaction is finished, a serious pole climbing phenomenon occurs, which is not allowed in the production process.
Comparative example 6 preparation of Nano profile control and flooding Material
1. Weighing 3g of acrylamide monomer and 1g of AMPS monomer, adding 40g of deionized water for dissolving, and then adjusting the pH of the solution to about 6-7 by using NaOH;
2. mixing the mixed solution of the oil-soluble material prepared in the embodiment 1 with the shell solution of which the pH is adjusted in the step 1, stirring at 500rpm at room temperature for 30min, and introducing N for 20min;
3. weighing 0.075g of potassium persulfate, adding 10g of deionized water, shaking for dissolution, and introducing N for 15min;
4. and (3) heating the mixed solution obtained in the step (2) to 80 ℃, adding the potassium persulfate solution obtained in the step (3) after the rotation speed of 200rpm is 10min, and reacting for 3h.
The reaction solution is layered, and the concentration is too low to coat the core material. Due to the too low concentration, the core material was not completely coated after the reaction, so that the liquid was stratified and a clear white float appeared on the upper layer of the liquid.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A nanometer profile control and flooding material is characterized in that the nanometer profile control and flooding material is a core-shell structure formed by wrapping an oil-soluble material with a water-soluble material;
the oil-soluble material is prepared by carrying out polymerization reaction I on a material I containing an olefinic acid ester compound, a styrene compound, a cross-linking agent, an emulsifier and an initiator I;
the water-soluble material is prepared by carrying out polymerization reaction II on a material II containing a water-soluble monomer and an initiator II;
the preparation method of the nano profile control and flooding material comprises the following steps:
(1) Polymerizing a material I containing an olefinic ester compound, a styrene compound, a cross-linking agent, an emulsifying agent and an initiator I to obtain an oil-soluble material;
(2) Polymerizing a material II containing a water-soluble monomer, the oil-soluble material and an initiator II to obtain the nano profile control material;
the alkenoic acid ester compound is selected from at least one of octadecyl acrylate and octadecyl methacrylate;
the water-soluble monomer is at least one selected from acrylamide, acrylic acid, sodium acrylate and 2-acrylamido-2-methylpropanesulfonic acid.
2. A nano profile control material according to claim 1,
the styrene compound is selected from at least one of styrene, methyl styrene, dimethyl styrene and phenyl propylene;
the cross-linking agent is selected from at least one of N-N methylene bisacrylamide, methylene acrylamide and N-N vinyl bisacrylamide;
the emulsifier is at least one selected from Tween 80, tween 60 and Tween 20;
the initiator I is at least one of potassium persulfate, sodium persulfate and ammonium persulfate;
the initiator II is at least one selected from potassium persulfate, sodium persulfate and ammonium persulfate.
3. The nano profile control and flooding material according to any one of claims 1 to 2, characterized in that the contact angle of the oil-soluble material is 100 ° -125 °; the contact angle of the nano profile control and flooding material is 40-60 degrees.
4. The nanotopography material of claim 1, wherein the step (1) comprises:
(i) Dissolving a raw material I containing an olefinic ester compound, a styrene compound, a cross-linking agent and an emulsifying agent in water to obtain a mixture I;
(ii) Dissolving a raw material II containing an initiator in water, and deoxidizing to obtain a mixture II;
(iii) And adding the mixture II into the mixture I, and carrying out polymerization reaction I to obtain the oil-soluble material.
5. The nano profile control material according to claim 1, wherein the mass ratio of the olefinic acid ester compound, the styrene compound, the cross-linking agent, the emulsifier and the initiator I is 3-5: 5 to 9:0.01 to 0.03:8 to 12:0.05 to 0.2.
6. The nano profile-control material according to claim 1, wherein the conditions of the polymerization reaction I are as follows: the reaction temperature is 60-70 ℃, and the reaction time is 4-6 h.
7. The nano profile-control material according to claim 1, wherein the mass ratio of the water-soluble monomer, the oil-soluble material and the initiator II is 6-8.
8. The nano profile-control material according to claim 1, wherein the conditions of the polymerization reaction II are as follows: the reaction temperature is 70-90 ℃, and the reaction time is 2-4 h.
9. An oil-displacing agent, characterized in that it comprises at least one of the nano profile control and flooding materials according to any one of claims 1 to 8.
10. Use of the oil-displacing agent of claim 9 in low permeability oil fields.
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