CN114437294A - Surface active polymer, preparation method thereof and application of surface active polymer as polymer oil displacement agent - Google Patents
Surface active polymer, preparation method thereof and application of surface active polymer as polymer oil displacement agent Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
Abstract
The invention relates to the field of petrochemical industry, and particularly discloses a surface active polymer, a preparation method thereof and application of the surface active polymer as a polymer oil displacement agent, wherein the polymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit with a structure shown in a formula (1) and/or a formula (2), the structural unit B is a structural unit with a structure shown in a formula (3), and the structural unit C is a structural unit with a structure shown in a formula (4);
wherein M is 1 to 8, n is 1 to 9, p1 and p2 are each independently 1 to 6, M1And M2Each independently an alkali metal. The polymer disclosed by the invention has excellent viscosity increasing property and emulsifying property on the basis of excellent temperature resistance and salt resistance, reduces the surface interfacial tension, and has good oil displacement and oil washing capabilities.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a surface active polymer, a preparation method thereof and application of the surface active polymer as a polymer oil displacement agent.
Background
The chemical flooding is the most direct and effective technical means for improving the crude oil recovery ratio in the tertiary oil recovery technology. Chemical flooding mainly comprises surfactant flooding, polymer flooding, binary or ternary combination flooding, foam flooding and the like. The method has already formed the industrialized application of chemical flooding in Daqing oil field, Shengli oil field and Henan oil field in China, and obtains remarkable economic benefit.
The field application result shows that the chromatographic separation phenomenon can occur in the migration process of the oil reservoir porous medium in the binary or ternary combination flooding, and the performance of the combination flooding effect is seriously influenced. The surfactant has the capacity of reducing the oil-water interfacial tension and emulsifying oil carrying, can improve the oil washing efficiency, but cannot increase the viscosity of a water phase and cannot improve the swept volume. The polymer flooding has the effects of increasing the viscosity of a water phase and improving swept volume, but cannot reduce the tension of an oil-water interface, has no capacity of emulsifying and washing oil, cannot improve the oil washing efficiency, and is limited to be applied to low-permeability and ultra-low-permeability oil reservoirs.
The surface active polymer is from the perspective of polymer design, functional groups such as active groups, temperature-resistant salt-resistant groups and the like are introduced into a copolymer chain structural unit, the molecular weight of the copolymer can be effectively controlled through a synthesis process, and the temperature-resistant salt-resistant performance and activity of the polymer are improved, so that the polymer has good tackifying property, emulsifying property, temperature-resistant salt-resistant property and good oil washing capacity, and the phenomenon of chromatographic separation in an oil reservoir porous medium is avoided.
According to the recent exploration and research data of China and in view of the matching of the molecular size of the surfactant polymer and the low permeability reservoir, the surfactant polymer flooding method becomes an important technical means for further improving the crude oil recovery rate in the exploration and development of oil fields in China.
Compared with the traditional polymer oil displacement agent and plugging agent, the surface active polymer is a polymer with better water solubility and has greater application advantages. On one hand, the surface active polymer has the viscosity increasing property of a common polymer oil displacement agent, and can enter the deep part of an oil reservoir under certain pressure to carry out deep oil displacement; on the other hand, the surface active polymer has the characteristics of good surface interfacial activity, emulsification and the like, and can reduce the oil-water interfacial tension, thereby increasing the oil washing capacity of the surface active polymer in the deep part of an oil reservoir. In a word, the surfactant polymer oil displacement agent can achieve the function of one agent with multiple effects, and the site construction equipment and operation cost are reduced.
Therefore, the development of the surface active polymer is an important way for realizing deep oil displacement and oil washing of the ultra-low permeability reservoir, and meanwhile, measures are provided for creating and increasing the low-efficiency well of the low oil field, and technical support is provided for improving the productivity of the oil well in the ultra-high water-cut period.
However, the oil displacement and washing capabilities of the current surface active polymers need to be further improved.
Disclosure of Invention
The invention aims to overcome the defect that the oil displacement and washing capacity of the surface active polymer in the prior art needs to be further improved, and provides the surface active polymer, a preparation method thereof and application of the surface active polymer as a polymer oil displacement agent, wherein the polymer has excellent viscosity increasing property and emulsifying property on the basis of excellent temperature resistance and salt resistance, reduces surface interfacial tension and has good oil displacement and washing capacity; and the viscosity-average molecular weight of the polymer is low, and deep oil displacement and oil washing under the conditions of a low-permeability reservoir and an ultra-low-permeability reservoir can be realized.
In order to achieve the above object, a first aspect of the present invention provides a surface active polymer comprising a structural unit a, a structural unit B and a structural unit C, wherein the structural unit a is a structural unit having a structure represented by formula (1) and/or formula (2), the structural unit B is a structural unit having a structure represented by formula (3), and the structural unit C is a structural unit having a structure represented by formula (4); wherein, based on the weight of the surface active polymer, the content of the structural unit A is 65-99 wt%, the content of the structural unit B is 0.5-25 wt%, and the content of the structural unit C is 0.5-15 wt%;
wherein M is 1 to 8, n is 1 to 9, p1 and p2 are each independently 1 to 6, M1And M2Each independently an alkali metal.
Preferably, m is 1 to 4, n is 1 to 6, and p1 and p2 are each independently 1 to 4.
In a second aspect, the present invention provides a process for preparing a surface active polymer, the process comprising: carrying out polymerization reaction on a monomer mixture in water under the solution polymerization condition in the presence of an initiator, wherein the monomer mixture contains a monomer X and a monomer Y, the monomer X is a monomer with a structure shown in a formula (5), and the monomer Y is a monomer with a structure shown in a formula (6); based on the total amount of the monomer mixture, the content of acrylamide is 65-99 wt%, the content of the monomer X is 0.5-25 wt%, and the content of the monomer Y is 0.5-15 wt%;
wherein m is 1 to 8, n is 1 to 9, and p1 and p2 are each independently 1 to 6; m3Is an alkali metal and/or H.
In a third aspect, the present invention provides a surface active polymer prepared by the method of the second aspect.
In a fourth aspect, the present invention provides the use of a surface active polymer as described in the first or third aspects above as a polymer oil-displacing agent.
According to the invention, the specific monomer X is introduced into a macromolecular chain structure of polyacrylamide, and the monomer X contains a long-chain structure of a benzene ring, so that the tackifying property, the temperature resistance and the salt resistance of the polymer can be improved, the surface interface activity is reduced, and the oil displacing and washing capacities of the surface active polymer are improved; and a specific monomer Y is introduced, the monomer Y not only participates in copolymerization reaction, but also two secondary amine groups in a molecular unit can generate chain transfer reaction in different degrees, the size of the molecular chain of the polymer can be effectively adjusted, and the thiourea group in the molecular unit can increase the water solubility and the dissolution speed of the polymer, so that the surface active polymer can be effectively injected into a low-permeability reservoir and an extra-low-permeability reservoir, thereby realizing oil displacement and oil washing of a deep reservoir and further improving the oil recovery rate of crude oil.
In addition, compared with the common polymer flooding, the polymer provided by the invention can reduce the investment of on-site injection equipment and facilities, and greatly reduce the oil production cost. More importantly, in view of the matching property of the molecular size of the surface active polymer and the stratum permeability, the molecular weight and the dissolution time of the surface active polymer can be adjusted according to the geological conditions of an oil reservoir and the properties of crude oil so as to meet deep oil displacement and oil washing under the conditions of a low-permeability oil reservoir and an ultra-low-permeability oil reservoir.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a surfactant polymer comprising a structural unit a, a structural unit B and a structural unit C, wherein the structural unit a is a structural unit having a structure represented by formula (1) and/or formula (2), the structural unit B is a structural unit having a structure represented by formula (3), and the structural unit C is a structural unit having a structure represented by formula (4); wherein, based on the weight of the surface active polymer, the content of the structural unit A is 65-99 wt%, the content of the structural unit B is 0.5-25 wt%, and the content of the structural unit C is 0.5-15 wt%;
wherein M is 1 to 8, n is 1 to 9, p1 and p2 are each independently 1 to 6, M1And M2Each independently an alkali metal.
Preferably, the content of the structural unit A is 74 to 96 wt%, the content of the structural unit B is 2 to 18 wt%, and the content of the structural unit C is 2 to 8 wt%, based on the weight of the surface active polymer. By adopting the optimal scheme, the oil washing effect and the oil displacement performance of the surface active polymer can be improved, and the oil recovery rate of crude oil can be further improved.
According to the invention, preferably m is 1 to 4, n is 1 to 6, and p1 and p2 are each independently 1 to 4. By adopting the optimal scheme, the oil washing effect and the oil displacement performance of the surface active polymer can be improved, and the oil recovery rate of crude oil can be further improved.
In the formula (4) of the present invention, p1 and p2 may be the same or different, and preferably, p1 and p2 are the same.
In the present invention, said M1And M2When each is independently an alkali metal, M1And M2May be the same or different. In the present invention, preferably, the alkali metal is selected from at least one of lithium (Li), sodium (Na), and potassium (K). More preferably, the alkali metal is selected from sodium or potassium.
According to the present invention, it is preferable that the structural unit a is a structural unit having a structure represented by formula (1) and formula (2), and the content of the structural unit having a structure represented by formula (2) is 10 to 30% by weight based on the weight of the surface active polymer.
In the present invention, it is preferable that the structural unit having the structure represented by formula (2) is obtained by hydrolyzing a part of the acrylamide structural unit. The process of hydrolysis comprises reacting a hydrolysis agent with the surface active polymer, preferably in an amount such that the degree of hydrolysis of the surface active polymer is from 10 to 30%, as will be appreciated by those skilled in the art. In the present invention, the conditions of the hydrolysis are not particularly limited, and preferably, the conditions of the hydrolysis include: the temperature is 50-100 ℃, and the optimal temperature is 70-90 ℃; the time is 0.5-6h, preferably 1-4 h. In the present invention, the drying conditions are not limited as long as they can be dried. In the present invention, the hydrolyzing agent is various inorganic alkaline substances commonly used in the art to achieve the above-mentioned purpose, and may be selected from one or more of sodium hydroxide, potassium hydroxide and sodium carbonate, and more preferably sodium hydroxide (preferably introduced in the form of granular alkali). The amount of the hydrolysis agent may be appropriately selected according to the degree of hydrolysis of the surface active polymer, so that the degree of hydrolysis of the acrylamide copolymer satisfies the use requirements. As will be appreciated by those skilled in the art, by adjusting the amount of inorganic alkaline material used, surface active polymers of varying degrees of hydrolysis can be obtained. In the present invention, the number of moles of the inorganic basic substance is equal to the number of moles of the acrylate structural unit having the structure represented by formula (2).
According to the present invention, preferably the polymer has a viscosity average molecular weight of from 500 to 1200 ten thousand, more preferably from 600 to 1000 ten thousand. The polymer can be applied to low-permeability oil reservoirs and ultra-low-permeability oil reservoirs under the condition of low viscosity average molecular weight; in the prior art, the common polymer with the viscosity-average molecular weight of less than 1000 ten thousand has no oil washing capacity and poor temperature resistance and salt resistance.
The polymer of the invention has good solubility while having the low viscosity average molecular weight, can be completely dissolved, and has the dissolving time of less than or equal to 50 minutes.
According to the invention, the apparent viscosity of the aqueous solution of the polymer is preferably from 30 to 56 mPas at a concentration of 1500mg/L, a degree of mineralization of 20000mg/L and 60 ℃.
In the present invention, the apparent viscosity is measured by using a Brookfield viscometer of Bohler Federation, USA, at a concentration of 1500mg/L, a degree of mineralization of 20000mg/L and 60 ℃.
According to the invention, the mineralization degree is Na in simulated formation water+、K+、Ca2+、Mg2+、Cl-、SO4 2-、CO3 2-And the sum of the inorganic ion contents.
According to the invention, an aqueous solution of the polymer at a concentration of 1500mg/L preferably has a surface tension of 30 to 36mN/m at 25 ℃.
According to the invention, an aqueous solution of the polymer having a concentration of 1500mg/L preferably has an interfacial tension of 4X 10 at 60 ℃-2-10×10-2mN/m。
In the present invention, the surface tension was measured at a concentration of 1500mg/L using a Datophysics DCAT-21 surface tension meter at 25 ℃ on an aqueous solution of the polymer in pure water (i.e., deionized water), and the interfacial tension was measured at 60 ℃ on an aqueous solution of the polymer using a TX500C interfacial tension meter from Corno, USA.
The surface active polymer provided by the invention has excellent tackifying property, temperature resistance, salt resistance and emulsibility, and reduces surface interfacial tension, thereby improving the oil displacing and washing capacities of the polymer; and the viscosity-average molecular weight of the polymer is low, so that deep oil displacement and oil washing under the conditions of a low-permeability reservoir and an ultra-low-permeability reservoir can be realized.
As previously mentioned, a second aspect of the present invention provides a method for preparing a surface active polymer, the method comprising: carrying out polymerization reaction on a monomer mixture in water under the solution polymerization condition in the presence of an initiator, wherein the monomer mixture contains a monomer X and a monomer Y, the monomer X is a monomer with a structure shown in a formula (5), and the monomer Y is a monomer with a structure shown in a formula (6); based on the total amount of the monomer mixture, the content of acrylamide is 65-99 wt%, the content of the monomer X is 0.5-25 wt%, and the content of the monomer Y is 0.5-15 wt%;
wherein m is 1 to 8, n is 1 to 9, and p1 and p2 are each independently 1 to 6; m3Is an alkali metal and/or H.
Preferably, the acrylamide is present in an amount of 74 to 96 wt%, the monomer X is present in an amount of 2 to 18 wt%, and the monomer Y is present in an amount of 2 to 8 wt%, based on the total amount of the monomer mixture.
According to the invention, it is to be noted that the monomers are converted approximately completely into the corresponding structural units contained in the surface-active polymer, and the amount of monomers used can be matched to the content of the corresponding structural units contained in the surface-active polymer.
According to the invention, preferably m is 1 to 4, n is 1 to 6, and p1 and p2 are each independently 1 to 4.
According to the invention, p1 and p2 may be the same or different; preferably, p1 and p2 are the same.
According to the invention, preferably M3Is H.
According to the invention, preferably M3When it is an alkali metal, M is the same as that in the first aspect2The selectable ranges are the same, and are not described in detail herein.
According to the present invention, preferably, the monomer mixture is used in an amount of 20 to 40 wt% based on the total amount of the monomer mixture and water; the amount of initiator is 0.02 to 0.2% by weight, relative to the total amount of the monomer mixture. In the present invention, the water is preferably deionized water.
According to the present invention, the initiator may be various initiators commonly used in the art, for example, may be selected from any two of radical polymerization initiators; the free radical polymerization initiator comprises azo initiators, peroxide initiators and redox initiators; the azo initiator is selected from at least one of azobisisobutyric acid dimethyl ester, azobisisobutyramidine hydrochloride, azobisformamide, azobisisopropylimidazoline hydrochloride, azobisisobutyronitrile formamide, azobisdicyclohexyl carbonitrile, azobiscyanovaleric acid, azobisdiisopropylimidazoline, azobisisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile; the peroxide initiator is selected from at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, benzoyl peroxide and benzoyl peroxide tert-butyl ester; the redox initiator is at least one selected from sulfate-sulfite, persulfate-thiourea, persulfate-organic salt and ammonium persulfate-fatty amine. In the present invention, it should be noted that: in the present invention, the initiator may be selected from any two of radical polymerization initiators, and means that it may be selected from any two of azo initiators, may be selected from any two of peroxide initiators, may be selected from any two of redox initiators, and may be selected from any two of azo initiators, peroxide initiators, and redox initiators.
More preferably, the initiator is a redox initiation system comprising a persulfate oxidizer and a sulfite reducer. The present invention is not limited to the kind of the persulfate oxidizer and the sulfite reducer, and those skilled in the art can freely select them according to actual requirements, for example, preferably, the persulfate oxidizer may be selected from potassium persulfate and/or ammonium persulfate, and the sulfite reducer may be selected from potassium bisulfite and/or sodium bisulfite.
The amount of the persulfate oxidizer and the sulfite reducer used is not limited in the present invention, and those skilled in the art can freely select them according to actual requirements as long as the polymerization reaction can be carried out to obtain the desired polymer; preferably, the persulfate oxidizer is used in an amount of 0.01 to 0.1 wt% and the sulfite reducer is used in an amount of 0.005 to 0.05 wt% with respect to the total amount of the monomer mixture.
In the present invention, preferably, the persulfate oxidizer and the sulfite reducer are each independently introduced in the form of an aqueous solution; further preferably, the aqueous persulfate oxidizer solution has a concentration of from 1 to 5 wt.%; preferably, the concentration of the aqueous sulfite reducing agent solution is 1 to 5 wt%.
In the invention, the monomer X and the monomer Y can be prepared independently by the existing method or can be obtained commercially; for example, the monomer X may be prepared by the following method or a similar method: in a saline bath at the temperature of between 20 ℃ below zero and 0 ℃, tetrahydrofuran and p-benzene are put intoMixing divinyl, and introducing SO3After the reaction is completed, a Grignard reagent (for example, p-ethylbenzylmagnesium chloride, which can be prepared by a conventional method such as a method of reacting a corresponding halogenated hydrocarbon with magnesium powder in anhydrous ether or Tetrahydrofuran (THF)) is introduced, the reaction is maintained, n-hexane is added to precipitate the product, and finally, the product is washed (preferably, three times or more) with a detergent (preferably, n-hexane). The amount of each raw material used is such that the monomer X produced has the structure represented by formula (5).
According to the method of the present invention, it is preferable that a complexing agent is added to prevent the influence of metal ions on the polymerization reaction, and therefore, it is preferable that the polymerization reaction is carried out in the presence of the complexing agent.
Preferably, the complexing agent is used in an amount of 0.01 to 0.1 wt.%, relative to the total amount of the monomer mixture.
Preferably, the complexing agent is ethylenediaminetetraacetic acid and/or disodium ethylenediaminetetraacetate, more preferably disodium ethylenediaminetetraacetate. In the present invention, preferably, the complexing agent is introduced in the form of an aqueous complexing agent solution, and the concentration of the complexing agent in the aqueous complexing agent solution is 1 to 5 wt%.
According to the process of the present invention, it is preferred that the polymer solubilizer be added to improve the solubility of the polymer, and therefore, it is preferred that the polymerization reaction be carried out in the presence of the polymer solubilizer.
Preferably, the polymeric solubilizer is used in an amount of 0.5 to 5% by weight relative to the total amount of the monomer mixture.
Preferably, the polymeric solubilizer is urea. Under the preferred scheme, the method is more favorable for improving the solubility of the polymer and can save the cost.
According to the method of the present invention, preferably, the polymerization reaction is performed under an inert gas atmosphere, which means an atmosphere of an inert gas that is a gas that does not react with the raw materials and the product, and may be at least one of nitrogen gas or a gas of a group zero element in the periodic table of elements, which is conventional in the art, preferably nitrogen gas and argon gas.
According to the present invention, there is no limitation on the introduction timing of the complexing agent, the initiator and the polymer solubilizer, and preferably, the method comprises the steps of:
(1) mixing the monomer mixture with water, and adjusting the pH value to 6-10;
(2) mixing the material obtained in the step (1) with a complexing agent (preferably an aqueous solution of the complexing agent) and a polymer solubilizer;
(3) and (3) mixing the material obtained in the step (2) with an initiator under the solution polymerization condition in an inert atmosphere to carry out polymerization reaction. Under the optimized scheme, the oil washing efficiency and the oil displacement performance of the prepared polymer are improved.
According to the present invention, preferably, the solution polymerization conditions include: the temperature is 0-30 ℃, preferably 10-20 ℃; the time is 4-10h, preferably 6-8 h. In the present invention, the time of the solution polymerization is a time for continuing the polymerization after the polymerization system is automatically heated to a high point.
Preferably, the solution polymerization conditions further comprise: the pH value of the polymerization system is 6-10. The above pH may be obtained by adding a pH adjusting agent to the polymerization system, and the pH adjusting agent for adjusting the pH may be various pH adjusting agents commonly used in the art, and may be, for example, an alkali and/or an alkali salt. Preferably, the base may be an alkali containing an alkali metal element and/or aqueous ammonia; preferably, the salt may be sodium carbonate and/or potassium carbonate.
Preferably, the pH of the polymerization system is adjusted with a base. More preferably, the base is selected from NaOH or KOH, preferably NaOH.
According to the present invention, it is preferred that acrylamide is contained in the monomer mixture. Under this scheme, preferably, the method further comprises: the polymer obtained after the polymerization is subjected to hydrolysis so that the degree of hydrolysis of the polymer obtained after the polymerization is 10 to 30%, that is, the content of the acrylic acid salt having the structure represented by formula (2) is 10 to 30% by weight based on the total amount of the polymer, and optionally dried. In this preferred embodiment, the polymer obtained is one having a structural unit of the formula (2) by hydrolysis of a portion of the acrylamide structural units and optionally drying. The hydrolysis and drying are the same as those in the foregoing first aspect, and will not be described in detail here.
In the present invention, preferably, the mixing in step (2) is preferably performed under stirring to completely dissolve the respective materials. In the present invention, preferably, after the mixing in step (2) is completed, a person skilled in the art may blow an inert atmosphere to remove oxygen, so that the polymerization reaction in step (3) is performed under an inert atmosphere. The time for blowing the inert gas atmosphere is not limited in the present invention, and may be, for example, 20 to 30 minutes.
In the present invention, it is preferable that the initiator is introduced again when the desired temperature for the solution polymerization described in the step (3) is reached. Preferably, after the initiator is introduced, nitrogen is continuously introduced for 2-10 minutes, the system is automatically heated, and polymerization is continuously maintained after the temperature is raised to a high point. In the present invention, the polymer prepared after step (3) is generally in the form of a gel, which may be optionally pelletized according to practical requirements.
In the present invention, the apparatus for the polymerization reaction is not limited as long as the polymerization reaction can be achieved; for example, a dewar flask.
As mentioned above, a third aspect of the present invention provides a surface active polymer obtainable by the process of the second aspect. The polymer has the same structure and composition as the polymer of the first aspect described above and will not be described in detail herein.
As mentioned previously, a fourth aspect of the present invention provides the use of a surface-active polymer as described in the first or third aspects above as a polymer oil-displacing agent. The surfactant polymer can be used as a polymer oil displacement agent and used in the field of enhanced oil recovery.
Preferably, the surface active polymer is used as a polymer oil displacement agent in low-permeability oil reservoirs and ultra-low-permeability oil reservoirs. The surface active polymer can realize deep oil displacement and oil washing under the conditions of low-permeability reservoir and ultra-low-permeability reservoir.
The present invention will be described in detail below by way of examples. In the following examples and preparations, the starting materials are, unless otherwise indicated, commercially available, in which the monomer X is a monomer having the formulaA monomer having a structure represented by formula (5) (wherein M3All H), prepared by the method of the following preparation example; the monomer Y is a monomer having a structure represented by the formula (6) and is commercially available.
In the following examples, the apparent viscosity of an aqueous solution of a surface-active polymer having a concentration of 1500mg/L at a mineralization degree of 20000mg/L was measured at 60 ℃ using a Brookfield viscometer from Boehler fly, USA.
The surface tension of an aqueous solution of the polymer (1500 mg/L concentration) in pure water was measured at 25 ℃ using a Datophysics DCAT-21 surface tension meter; the interfacial tension of the aqueous solution was measured at 60 ℃ using a TX500C interfacial tensiometer from koro, usa.
Viscosity average molecular weight according to formula Mη＝145.8[η]1.515And (4) calculating.
The molecular structural formula is determined by an infrared spectrogram.
The dissolution time of the polymer was determined according to the method specified in GB 12005.8-89.
According to the literature: exploration of an oil washing capacity test method, petrochemical engineering, 2012, 41 (supplement), 1060-.
The following preparation examples were used to prepare monomer X. Among them, the following grignard reagents were prepared by reacting the corresponding halogenated hydrocarbon with magnesium powder in Tetrahydrofuran (THF) in such amounts that the corresponding halogenated hydrocarbon was prepared with magnesium powder and THF in such molar amounts as to obtain the corresponding grignard reagents.
Preparation example 1
Adding 100mL of tetrahydrofuran into a 250mL three-neck flask, placing in a saline bath at-10 deg.C, adding 0.1mol of p-divinyl (i.e. p-divinyl benzene, the same below) while stirring, and then introducing 0.1mol of SO3After the reaction is completed, 0.1mol of Grignard reagent of p-ethylbenzylmagnesium chloride is dripped, the reaction is kept for 1 hour after the dripping is completed, then n-hexane is added to separate out the product, finally the product is washed for more than three times by the n-hexane, and the product obtained by nuclear magnetic testing is the monomer X (m is 1, n is 2) with the structure shown in the formula (5).
Preparation example 2
Adding 100mL of tetrahydrofuran into a 250mL three-neck flask, placing the three-neck flask in a salt water bath at the temperature of-10 ℃, adding 0.1mol of p-phenylenediethylene and 0.1mol of sodium chloromethane sulfonate (purchased from carbofuran technologies, Inc.) under stirring, then adding 0.2g of boron trichloride as a catalyst to perform an addition reaction, after the reaction is completed, dropwise adding 0.1mol of Grignard reagent of p-hexylbenzylmagnesium chloride, using cuprous chloride as a catalyst, after the dropwise adding is completed, performing heat preservation reaction for 1h, then adding n-hexane to precipitate a product, finally washing the product for more than three times by using n-hexane, and verifying that the obtained product is a monomer X (m is 2, n is 6) with the structure shown in formula (5) through a nuclear magnetic test.
Preparation example 3
The procedure of preparation example 2 was followed, except that sodium 3-chloropropanesulfonate (available from huge dragon hall of Hubei, Co., Ltd.) was used in place of the sodium chloromethanesulfonate in the same amount, and the grignard reagent for p-propylbenzylmagnesium chloride was used in place of the grignard reagent for p-hexylbenzylmagnesium chloride in the same amount, and otherwise the procedure of preparation example 2 was repeated, to prepare a monomer X having a structure represented by formula (5) (m ═ 4, n ═ 3); the product obtained by nuclear magnetic test was confirmed to be a monomer X having a structure represented by formula (5) (m ═ 4, n ═ 3).
Preparation example 4
The procedure of preparation 2 was followed, except that the grignard reagent of p-hexylbenzylmagnesium chloride was replaced with the grignard reagent of p-ethylbenzylmagnesium chloride in the same amount as in preparation 2, to prepare a monomer X having a structure represented by formula (5) (m ═ 2, n ═ 2); the product obtained by nuclear magnetic test was confirmed to be a monomer X having a structure represented by formula (5) (m ═ 2, n ═ 2).
The following examples serve to illustrate the surface-active polymers according to the invention, their preparation and their use.
Example 1
(1) 80.0g of acrylamide, 18.0g of monomer X (prepared as described in preparation example 1 above), 2.0g of monomer Y (p1 and p2 are both 1, available from carbofuran technologies Inc.) were added sequentially to a Dewar flask (i.e., a polymerization flask), 400.0g of deionized water was added and stirred sufficiently to dissolve completely to form an aqueous solution, and sodium hydroxide was added to adjust the pH to 7.2;
(2) adding 3.0g of EDTA-2Na aqueous solution with the concentration of 1 weight percent and 3.0g of urea into the aqueous solution, stirring the mixture to completely dissolve the mixture, and blowing nitrogen for 25 minutes to remove oxygen;
(3) controlling the temperature of the aqueous solution obtained in the step (2) to be 10 ℃, adding 10.0g of 0.2 weight percent potassium persulfate aqueous solution and 10.0g of 0.1 weight percent sodium bisulfite aqueous solution under the protection of nitrogen, continuously introducing nitrogen for 3 minutes, automatically heating the polymerization system, and continuously maintaining the polymerization for 7 hours after heating to a high point;
(4) and (4) taking out the gel block (namely the surface active polymer, the same applies below) obtained in the step (3), after granulation, hydrolyzing the gel block with sodium hydroxide granular alkali (the dosage of the granular alkali is 4 wt% relative to the gel block, so that the hydrolysis degree is 20%) at 85 ℃ for 2 hours, drying, crushing and sieving to obtain a hydrolyzed surface active polymer sample H1.
The polymer H1 was purified and subjected to structural determination: in the infrared spectrum, 1675cm-1The peak of absorption of stretching vibration of the carbonyl group C ═ O of the amide group in the structural unit A appeared at 1204cm-1A stretching vibration absorption peak of 3025cm, which is an absorption peak of O in the sulfonic acid group S ═ O in the structural unit B-1The stretching vibration absorption peak of the benzene ring C-H in the structural unit B is 1359cm-1A stretching vibration absorption peak of thiourea group C ═ S in the structural unit C appeared, and it was confirmed that the obtained polymer molecule had the structural unit a, the structural unit B, and the structural unit C. The content of the unreacted monomer in each group was less than 0.1% by weight as measured by liquid chromatography, and it was confirmed that the content of the structural unit B was 18% by weight, the content of the structural unit C was 2% by weight, and the content of the structural unit A was 80% by weight.
The polymer samples obtained above were tested correspondingly, the dissolution time of the polymer being 50 minutes; the viscosity-average molecular weight of the polymer was 960 ten thousand, the apparent viscosity was 52.4 mPas, the surface tension was 31.2mN/m, and the interfacial tension was 5.6X 10- 2mN/m, and the oil washing capacity of 82.6 percent, and the high-temperature-resistant high-salt-resistance high-performance high-temperature-resistant high-salt-resistance high-performance high-temperature-resistant high-oil-washing capacity.
Example 2
(1) 96.0g of acrylamide, 2.0g of monomer X (prepared as described in preparation example 2 above), 2.0g of monomer Y (p1 and p2 both equal to 4, available from carbofuran technologies ltd.) were added sequentially to a dewar (i.e. a polymerization flask), 400.0g of deionized water was added and stirred thoroughly to dissolve completely to form an aqueous solution, and sodium hydroxide was added to adjust the pH to 7.0;
(2) to this aqueous solution, 1.0g of an aqueous EDTA-2Na solution (same concentration as in example 1) and 5g of urea were added, and the mixture was stirred to completely dissolve the urea, and then nitrogen gas was blown into the mixture for 30 minutes to remove oxygen;
(3) controlling the temperature of the aqueous solution obtained in the step (2) to be 15 ℃, adding 20g of 0.2 weight percent potassium persulfate aqueous solution and 20g of 0.1 weight percent sodium bisulfite aqueous solution under the protection of nitrogen, continuously introducing nitrogen for 3 minutes, automatically heating the polymerization system, and continuously maintaining the polymerization for 7 hours after the temperature is raised to a high point;
(4) and (3) taking out the rubber block obtained in the step (3), granulating, hydrolyzing for 2H at 85 ℃ by using sodium hydroxide granular alkali (the amount is the same as that in example 1), drying, crushing and sieving to obtain a hydrolyzed surface active polymer sample H2. The IR spectrum of the polymer sample was determined to be similar to that of example 1; the determination by liquid chromatography of the unreacted monomer content of each group was less than 0.1% by weight, indicating that each monomer was converted almost completely into the corresponding structural unit contained in the surface-active polymer.
The polymer samples obtained above were tested correspondingly, the dissolution time of the polymer being 45 minutes; the polymer had a viscosity-average molecular weight of 880 ten thousand, an apparent viscosity of 47.3 mPas, a surface tension of 34.5mN/m and an interfacial tension of 9.9X 10- 2mN/m, and the oil washing capacity is 75.6%, and the high-temperature-resistant high-salt-resistance high-performance high-temperature-resistant high-salt-resistance high-oil-washing capacity is shown.
Example 3
(1) Adding 88.0g of acrylamide, 9.0g of monomer X (prepared in preparation example 3), and 3.0g of monomer Y (p1 and p2 both equal to 2, from the same source as in example 2) to a Dewar flask (i.e., a polymerization flask) in sequence, adding 400.0g of deionized water, stirring thoroughly to dissolve completely to form an aqueous solution, and adding sodium hydroxide to adjust the pH to 8.0;
(2) to this aqueous solution, 8.0g of an aqueous EDTA-2Na solution (same concentration as in example 1) and 2.0g of urea were added, and the mixture was stirred to completely dissolve the urea, and then nitrogen gas was blown into the mixture for 30 minutes to remove oxygen;
(3) controlling the temperature of the aqueous solution obtained in the step (2) to be 15 ℃, adding 25.0g of 0.2 weight percent potassium persulfate aqueous solution and 25.0g of 0.1 weight percent sodium bisulfite aqueous solution under the protection of nitrogen, continuously introducing nitrogen for 3 minutes, automatically heating the polymerization system, and continuously maintaining the polymerization for 8 hours after heating to a high point;
(4) and (3) taking out the rubber block obtained in the step (3), granulating, hydrolyzing for 2H at 85 ℃ by using sodium hydroxide granular alkali (the amount is the same as that in example 1), drying, crushing and sieving to obtain a hydrolyzed surface active polymer sample H3. The infrared spectrum of the polymer sample was determined to be similar to that of example 1; the determination by liquid chromatography of the unreacted monomer content of each group was less than 0.1% by weight, indicating that each monomer was converted almost completely into the corresponding structural unit contained in the surface-active polymer.
The polymer sample prepared above was tested accordingly, and the dissolution time of the polymer was 50 minutes; the polymer had a viscosity-average molecular weight of 980 ten thousand, an apparent viscosity of 55.6 mPas, a surface tension of 31.3mN/m and an interfacial tension of 4.8X 10-2mN/m, and the oil washing capacity is 85.3%, and the high-temperature-resistant high-salt-resistance high-performance high-temperature-resistant high-salt-resistance high-oil-washing capacity is shown.
Example 4
(1) 92.0g of acrylamide, 5.5g of monomer X (prepared as described in preparation example 4 above), 2.5g of monomer Y (p1 and p2 both equal to 1, from the same source as in example 2) were added sequentially to a Dewar flask (i.e., a polymerization flask), 257.0g of deionized water was added and stirred sufficiently to dissolve completely, forming an aqueous solution, and sodium hydroxide was added to adjust the pH to 9;
(2) to this aqueous solution, 6.0g of an EDTA-2Na aqueous solution (same concentration as in example 1) and 0.5g of urea were added, and the mixture was stirred to completely dissolve the urea, and then nitrogen gas was blown into the mixture for 30 minutes to remove oxygen;
(3) controlling the temperature of the aqueous solution obtained in the step (2) to be 20 ℃, adding 40.0g of 0.2 weight percent potassium persulfate aqueous solution and 40.0g of 0.1 weight percent sodium bisulfite aqueous solution under the protection of nitrogen, continuously introducing nitrogen for 3 minutes, automatically heating the polymerization system, and continuously maintaining the polymerization for 7.0 hours after the temperature is raised to a high point;
(4) and (3) taking out the rubber block obtained in the step (3), granulating, hydrolyzing for 2H at 85 ℃ by using sodium hydroxide granular alkali (the amount is the same as that in example 1), drying, crushing and sieving to obtain a hydrolyzed surface active polymer sample H4. The IR spectrum of the polymer sample was determined to be similar to that of example 1; the determination by liquid chromatography of the unreacted monomer content of each group was less than 0.1% by weight, indicating that each monomer was converted almost completely into the corresponding structural unit contained in the surface-active polymer.
The polymer sample prepared above was tested accordingly, and the dissolution time of the polymer was 40 minutes; the polymer had a viscosity-average molecular weight of 850 ten thousand, an apparent viscosity of 45.8 mPas, a surface tension of 33.8mN/m, and an interfacial tension of 7.6X 10-2mN/m, and the oil washing capacity of 76.4 percent, and the high-temperature-resistant high-salt-resistance high-performance high-temperature-resistant high-salt-resistance high-performance high-temperature-resistant high-oil-washing capacity.
Example 5
The procedure is as in example 1, except that the structure of the monomer Y differs in the values of p1 and p2 from example 1, in particular the same amount of monomer Y (p1 and p2 both equal to 6, from carbofuran technologies) is used instead of said monomer Y (p1 and p2 both equal to 1, from example 1). The infrared spectrum of the polymer sample obtained was determined to be similar to that of example 1; the determination by liquid chromatography of the unreacted monomer content of each group was less than 0.1% by weight, indicating that each monomer was converted almost completely into the corresponding structural unit contained in the surface-active polymer.
The polymer property test results are shown in table 1.
Example 6
The procedure is as in example 1, except that the total amount of monomers X and Y is the same, but the respective amounts of monomers X and Y are different; specifically, 8g of monomer X (prepared for preparation example 1 above) and 12g of monomer Y (p1 and p2 are both 1, from the same source as in example 1) were used. The infrared spectrum of the polymer sample obtained was determined to be similar to that of example 1; the determination by liquid chromatography of the unreacted monomer content of each group was less than 0.1% by weight, indicating that each monomer was converted almost completely into the corresponding structural unit contained in the surface-active polymer.
The polymer property test results are shown in table 1.
Comparative example 1
The procedure of example 1 was followed, except that the composition of the monomer mixture was varied, and specifically, in step (1), 80.0g of acrylamide and 20g of monomer X (prepared for preparation 1 above) were added without adding said monomer Y (p1 and p2 both equal to 1, and the source was the same as in example 1), otherwise the same as in example 1.
The polymer property test results are shown in table 1.
TABLE 1
As can be seen from the results of Table 1 and the above examples, the polymer with a specific structure prepared by the examples of the invention has a significantly better oil washing effect; the viscosity-average molecular weight of the polymer is 600-1000 ten thousand, and the polymer shows excellent solubility, surface activity, high-temperature and high-salt resistance and oil washing capacity. Among them, the polymers prepared by examples 1 to 4 according to the preferred embodiment of the present invention have better solubility, surface activity, high temperature and high salt resistance and oil washing ability.
In addition, the comparative example is not a prior art, is only set for comparison with the present invention, and is not a limitation of the present invention.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A surface active polymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit with a structure shown in a formula (1) and/or a formula (2), the structural unit B is a structural unit with a structure shown in a formula (3), and the structural unit C is a structural unit with a structure shown in a formula (4); wherein, based on the weight of the surface active polymer, the content of the structural unit A is 65-99 wt%, the content of the structural unit B is 0.5-25 wt%, and the content of the structural unit C is 0.5-15 wt%;
wherein M is 1 to 8, n is 1 to 9, p1 and p2 are each independently 1 to 6, M1And M2Each independently an alkali metal.
2. The polymer of claim 1, wherein the amount of structural unit a is 74 to 96 wt%, the amount of structural unit B is 2 to 18 wt%, and the amount of structural unit C is 2 to 8 wt%, based on the weight of the surface active polymer;
preferably, m is 1 to 4, n is 1 to 6, p1 and p2 are each independently 1 to 4;
preferably, p1 and p2 are the same;
preferably, the alkali metal is selected from sodium or potassium;
preferably, the structural unit A is a structural unit having a structure represented by formula (1) and formula (2), and the content of the structural unit having a structure represented by formula (2) is 10 to 30% by weight based on the weight of the surface active polymer.
3. The polymer of claim 1 or 2, wherein the polymer has a viscosity average molecular weight of 500 to 1200 ten thousand;
preferably, the apparent viscosity of the aqueous solution of the polymer is 30-56 mPas under the conditions of the concentration of 1500mg/L, the mineralization degree of 20000mg/L and the temperature of 60 ℃;
preferably, the surface tension of an aqueous solution of the polymer at a concentration of 1500mg/L at 25 ℃ is 30-36 mN/m;
preferably, the interfacial tension of an aqueous solution of said polymer at a concentration of 1500mg/L at 60 ℃ is 4X 10-2-10×10-2mN/m。
4. A method of preparing a surface active polymer, the method comprising: carrying out a polymerization reaction of a monomer mixture in water under a solution polymerization condition in the presence of an initiator, wherein the monomer mixture contains a monomer X, a monomer Y and acrylamide, the monomer X is a monomer with a structure shown in a formula (5), and the monomer Y is a monomer with a structure shown in a formula (6); and based on the total amount of the monomer mixture, the content of acrylamide is 65-99 wt%, the content of the monomer X is 0.5-25 wt%, and the content of the monomer Y is 0.5-15 wt%;
wherein m is 1 to 8, n is 1 to 9, and p1 and p2 are each independently 1 to 6; m3Is an alkali metal and/or H.
5. The process of claim 4 wherein the acrylamide is present in an amount of 74 to 96 wt.%, the monomer X is present in an amount of 2 to 18 wt.%, and the monomer Y is present in an amount of 2 to 8 wt.%, based on the total amount of monomer mixture;
preferably, m is 1 to 4, n is 1 to 6, p1 and p2 are each independently 1 to 4;
preferably, p1 and p2 are the same;
preferably, M3Is H.
6. The method according to claim 4 or 5, wherein the monomer mixture is used in an amount of 20-40 wt% based on the total amount of monomer mixture and water; the amount of initiator is 0.02-0.2% by weight relative to the total amount of the monomer mixture;
preferably, the initiator is selected from any two of free radical polymerization initiators; preferably, the radical polymerization initiator includes azo-type initiators, peroxide-type initiators, and redox-type initiators;
more preferably, the initiator is a redox initiation system comprising a persulfate oxidizer and a sulfite reducer;
further preferably, the persulfate oxidizer is used in an amount of 0.01 to 0.1 wt% and the sulfite reducer is used in an amount of 0.005 to 0.05 wt% with respect to the total amount of the monomer mixture.
7. The process according to any one of claims 4-6, wherein the polymerization reaction is carried out in the presence of a complexing agent;
preferably, the complexing agent is used in an amount of 0.01 to 0.1% by weight relative to the total amount of the monomer mixture;
preferably, the complexing agent is ethylene diamine tetraacetic acid and/or disodium ethylene diamine tetraacetic acid;
preferably, the polymerization reaction is carried out in the presence of a polymeric solubilizer;
preferably, the polymeric solubilizer is used in an amount of 0.5 to 5% by weight relative to the total amount of the monomer mixture;
preferably, the polymeric solubilizer is urea;
preferably, the method comprises the steps of:
(1) mixing the monomer mixture with water, and adjusting the pH value to 6-10;
(2) mixing the material obtained in the step (1) with a complexing agent and a polymer solubilizer;
(3) and (3) mixing the material obtained in the step (2) with an initiator under the condition of solution polymerization in an inert atmosphere to carry out polymerization reaction.
8. The method of any of claims 4-7, wherein the conditions of the solution polymerization comprise: the temperature is 0-30 ℃, preferably 10-20 ℃; the time is 4 to 10 hours, preferably 6 to 8 hours;
preferably, the solution polymerization conditions further comprise: the pH value of the polymerization system is 6-10;
preferably, the pH of the polymerization system is adjusted with a base;
preferably, the base is selected from NaOH or KOH;
preferably, the polymerization reaction is carried out under an inert atmosphere;
preferably, the method further comprises: hydrolyzing and optionally drying the polymer obtained after the polymerization reaction, wherein the hydrolysis ensures that the degree of hydrolysis of the polymer obtained after the polymerization reaction is 10-30%;
preferably, the conditions of the hydrolysis include: the temperature is 50-100 ℃ and the time is 0.5-6 h.
9. A surface-active polymer prepared by the process of any one of claims 4 to 8.
10. Use of a surface active polymer as claimed in any one of claims 1 to 3 and 9 as a polymeric oil-displacing agent.
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