CN113861337B - High-temperature-resistant acrylamide copolymer and preparation method and application thereof - Google Patents
High-temperature-resistant acrylamide copolymer and preparation method and application thereof 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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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
Abstract
The invention relates to the field of research on improving the recovery efficiency of oil fields, and discloses a high-temperature-resistant acrylamide copolymer and a preparation method and application thereof. The high-temperature resistant acrylamide copolymer comprises a structural unit A shown in a formula (1), a structural unit B shown in a formula (2) and a structural unit C shown in a formula (3); based on the total weight of the high-temperature resistant acrylamide copolymer, the content of the structural unit A is 83-94wt%, the content of the structural unit B is 5-12wt%, and the content of the structural unit C is 1-5wt%;
Description
Technical Field
The invention relates to the field of research on improving the recovery ratio of an oil field, in particular to a high-temperature-resistant acrylamide copolymer and a preparation method and application thereof.
Background
The high-permeability oil reservoir in the victory oil field is in a development stage of high extraction degree (35.5%) and ultra-high water content (96.9%), the proportion of ineffective oil wells is increased day by day, and the operation cost per ton of oil is higher than 2500 yuan. How to change a large number of inefficient and ineffective wells into effective wells is an important issue facing the field. Meanwhile, a water layer and an oil layer in an oil reservoir stratum are mutually interwoven, the flooding is serious, the oil reservoir conditions are complex, the heterogeneity is serious, the two reservoirs are difficult to be effectively isolated by the existing construction technology, but in order to stabilize the yield of crude oil, a certain amount of water plugging materials are injected into an oil well, the oil-water ratio of produced liquid can be effectively adjusted, the productivity of the oil well is increased, and the method becomes a key technology for water injection development of the oil field. Indoor digital-analog and physical-analog researches also show that the saturation of the residual oil near the oil well is higher than that near the water well, the residual oil is easier to spread when the water is blocked in the oil well, and the characteristics of short, frequent and quick plugging can be realized. Although the existing water-based, oil-based, polymer gel and other water-blocking systems have certain selectivity, the water-blocking and oil-blocking systems have poor temperature resistance and salt resistance, so that the liquid volume of produced liquid is greatly reduced, and the popularization and application range is relatively small. Although the water-soluble polymer water shutoff agent can preferentially enter a stratum with higher water saturation, part of the water-soluble polymer water shutoff agent can enter an oil layer in stratum migration, and the water-soluble polymer water shutoff agent is very difficult to discharge because the water shutoff agent has no self-plugging removal capability. Although the oil-based cement water shutoff agent can also improve the crude oil recovery to a greater extent, the oil-based cement water shutoff agent has great disadvantages, for example, when the oil-based cement water shutoff agent flows into an oil-water mixed stratum, even if only a small part of stratum water is mixed in the oil layer, the oil-based cement water shutoff agent reacts with the stratum water to solidify the cement, which indicates that the water shutoff selectivity of the oil-based cement water shutoff agent is also greatly poor. The polymer gel plugging agent enables the oil-water phase permeability to be reduced unevenly by means of the change of the effective movable volume under the action of oil and water, but the oil-water channel physical plugging can be caused by the treatment mode, so that the seepage capability of a porous medium is reduced, the oil production capability is also reduced while the water production of an oil well is greatly reduced, the liquid production capacity is too low due to improper treatment, and the production of crude oil is reduced.
In summary, most of the water plugging materials used for plugging the water of the oil well are water-soluble polymers such as polyacrylamide and derivatives thereof, and other oil-based water plugging materials, but due to poor selectivity, the oil phase permeability can be greatly reduced while the water is plugged, so that low liquid is generated after plugging, and the application of the water plugging technology of the oil well is restricted. Therefore, the novel phase permeation regulator is developed, the water-plugging and oil-plugging prevention effects of complex oil reservoirs are realized, and the novel phase permeation regulator has important significance for improving the productivity of high-temperature oil reservoir oil wells. The development of a novel phase permeation regulator has important significance and wide application prospect for improving the storage capacity and the utilization rate of an oil-water transition zone, improving the oil yield of a high-water-content oil field and the water yield of the high-water-content oil field.
Disclosure of Invention
The invention aims to overcome the problem of poor selectivity of the water shutoff agent for the oil well in the prior art, and provides a high-temperature-resistant acrylamide copolymer and a preparation method and application thereof. The high-temperature resistant acrylamide copolymer as a water plugging material has excellent temperature resistance, salt resistance and plugging effect, and can significantly improve the oil phase/water phase permeability in an oil reservoir stratum under the stratum conditions of high temperature (above 100 ℃) and high salt (the mineralization is 100,000g/mL), so as to achieve the effect of plugging water and not plugging oil, and has wide application prospect in the field of oil field recovery factor improvement.
In order to achieve the above object, a first aspect of the present invention provides a high temperature resistant acrylamide copolymer, comprising a structural unit a represented by formula (1), a structural unit B represented by formula (2), and a structural unit C represented by formula (3);
based on the total weight of the high-temperature resistant acrylamide copolymer, the content of the structural unit A is 83-94wt%, the content of the structural unit B is 5-12wt%, and the content of the structural unit C is 1-5wt%;
wherein R is 1 、R 2 、R 3 And R 4 Each independently is H or-CH 3 。
The second aspect of the present invention provides a method for preparing a high temperature resistant acrylamide copolymer, wherein the method comprises the following steps:
under the condition of solution polymerization reaction, in the presence of an initiator and a chain transfer agent, carrying out polymerization reaction on a monomer X, a monomer Y and a cross-linking agent M in water to obtain the high-temperature-resistant acrylamide copolymer; wherein the monomer X has a structure shown in a formula (4), the monomer Y has a structure shown in a formula (5), and the crosslinking agent M has a structure shown in a formula (6); based on the total weight of the monomer X, the monomer Y and the cross-linking agent M, the using amount of the monomer X is 83-94wt%, the content of the structural unit B is 5-12wt%, and the content of the structural unit C is 1-5wt%;
wherein R is 1 ’、R 2 ’、R 3 ' and R 4 ' each independently is H or-CH 3 。
The third aspect of the present invention provides a high temperature resistant acrylamide copolymer obtained as described above.
The fourth aspect of the invention provides the application of the high-temperature resistant acrylamide copolymer as a water plugging material in an oil well.
Through the technical scheme, the high-temperature resistant acrylamide copolymer and the preparation method and application thereof have the following beneficial effects:
the invention introduces a functional monomer and an oil-soluble cross-linking agent into an acrylamide polymer macromolecular chain, initiates polymerization to obtain polymer colloid, and obtains the high-temperature resistant acrylamide copolymer after granulation and drying. The introduction of the functional monomer can greatly improve the temperature resistance and salt resistance of the polymer, the introduction of the oil-soluble cross-linking agent can obtain a weak gel system in the polymerization process, and the weak gel system can continuously perform cross-linking reaction in a high-temperature oil reservoir water phase after being injected into a stratum to form a dendritic space network containing a large benzene ring structure, so that a strong gel system is obtained, and the oil reservoir water phase plugging strength is greatly improved. That is to say, after the high-temperature resistant acrylamide copolymer is injected into an oil reservoir stratum, the high-temperature resistant acrylamide copolymer can preferentially enter a water phase layer, and under the synergistic action of the high temperature (more than 100 ℃) of the oil reservoir and a chain transfer agent, a cross-linking effect can be further generated by the cross-linking agent, so that super-strong gel is formed, the water phase permeability is effectively reduced, and the water phase plugging effect is enhanced; after the high-temperature resistant acrylamide copolymer meets the oil phase, the oil-soluble cross-linking agent can be released and dissolved in the crude oil, so that the formation of gel and the influence on the oil phase permeability are avoided.
The high-temperature resistant acrylamide copolymer provided by the invention can obviously improve the oil/water permeability in an oil reservoir stratum, achieves the effects of water plugging and oil non-plugging, provides measures for the development and the efficiency increase of low-efficiency wells at low oil prices, provides technical support for the improvement of the oil well productivity in an ultra-high water-cut period, and has wide application prospects in the field of oil field recovery efficiency improvement.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these 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.
The first aspect of the present invention provides a high temperature resistant acrylamide copolymer, characterized in that the high temperature resistant acrylamide copolymer comprises a structural unit a represented by formula (1), a structural unit B represented by formula (2), and a structural unit C represented by formula (3);
based on the total weight of the high-temperature resistant acrylamide copolymer, the content of the structural unit A is 83-94wt%, the content of the structural unit B is 5-12wt%, and the content of the structural unit C is 1-5wt%;
wherein R is 1 、R 2 、R 3 And R 4 Each independently is H or-CH 3 。
In the invention, the oil-soluble structural unit B and the crosslinkable structural unit C are introduced into the molecular chain of the polyacrylamide, so that the temperature resistance and salt resistance of the polyacrylamide can be obviously improved; furthermore, due to the introduction of the structural unit C, the polyacrylamide is in a weak gel system in the polymerization process, and the cross-linking reaction is continuously carried out in the water phase of the high-temperature oil reservoir to form a strong gel system, so that the blocking strength of the water phase of the oil reservoir can be remarkably improved.
According to the invention, the content of the structural unit A is 83-94wt%, the content of the structural unit B is 5-12wt%, and the content of the structural unit C is 1-5wt% based on the total weight of the high-temperature resistant acrylamide copolymer.
In the present invention, the total content of the structural unit A, the structural unit B and the structural unit C is 100wt%.
In the present invention, the content of each structural unit in the copolymer can be measured by a conventional method in the prior art, such as infrared spectroscopy, nuclear magnetism, and the charge amount of the monomer in the polymerization process.
In the invention, the content of each structural unit in the polymer is determined by adopting the monomer feeding amount, and specifically, the feeding ratio of each monomer actually participating in polymerization is determined by testing the content of the unreacted monomer, so that the content of each structural unit in the polymer is determined.
Further, in the present invention, when the content of each unreacted monomer in the tested polymer is 0.02% by weight or less, it is indicated that substantially all the monomer participates in the polymerization reaction. Specifically, the content of the residual monomer is measured by liquid chromatography.
According to the invention, the high-temperature resistant acrylamide copolymer has an apparent viscosity of greater than 35mPa · s, preferably 40 to 60mPa · s, at high temperatures (above 100 ℃) and under conditions of high salt content (degree of mineralization of 100,000g/mL).
In the present invention, the apparent viscosity of the high temperature resistant acrylamide copolymer is measured by using a Brookfield viscometer, specifically, the apparent viscosity of the acrylamide copolymer (with the mass concentration of 2000 mg/L) is measured under the specified test temperature and mineralization degree.
The second aspect of the present invention provides a method for preparing a high temperature resistant acrylamide copolymer, which is characterized in that the method comprises the following steps:
under the condition of solution polymerization reaction, in the presence of an initiator and a chain transfer agent, carrying out polymerization reaction on a monomer X, a monomer Y and a cross-linking agent M in water to obtain the high-temperature-resistant acrylamide copolymer; wherein the monomer X has a structure shown in a formula (4), the monomer Y has a structure shown in a formula (5), and the crosslinking agent M has a structure shown in a formula (6); the total weight of the monomer X, the monomer Y and the cross-linking agent M is taken as a reference, the dosage of the monomer X is 83-94wt%, and the dosage of the monomer Y is 5-12wt%; the dosage of the cross-linking agent M is 1-5wt%;
wherein R is 1 ’、R 2 ’、R 3 ' and R 4 ' each independently is H or-CH 3 。
According to the invention, a monomer X with a structure shown in a formula (4), a monomer Y with a structure shown in a formula (5) and a cross-linking agent M with a structure shown in a formula (6) are copolymerized to obtain a high-temperature resistant acrylamide copolymer, and the obtained high-temperature resistant acrylamide copolymer not only has excellent salt resistance and salt tolerance, but also can be further subjected to cross-linking action under the condition of a high-temperature oil reservoir (higher than 85 ℃), so that super gel is formed, the water phase permeability is effectively reduced, and the water phase plugging action is enhanced; after the high-temperature resistant acrylamide copolymer meets the oil phase, the oil-soluble cross-linking agent can be released and dissolved in the crude oil, so that the formation of gel and the influence on the oil phase permeability are avoided, and the selective water plugging effect is realized.
In the invention, in the polymerization process of the cross-linking agent M with the structure shown in the formula (6) and the monomer X and the monomer Y, under the condition of the polymerization temperature of the invention, due to the existence of a large side group benzene ring structure in the formula (6), after the double bond at one end initiates polymerization, the chain segment at the other end is hindered from moving, and the probability of encountering active free radicals is reduced, so that the double bond at one end in the cross-linking agent M can be subjected to copolymerization reaction with the monomer X and the monomer Y. When the acrylamide terpolymer is tested by nuclear magnetism, the existence of carbon-carbon double bonds in the copolymer can be confirmed, and the fact that all the double bonds of the crosslinking agent M do not participate in the reaction is confirmed.
According to the invention, the amount of the monomer X is 86-92wt% and the amount of the monomer Y is 6-10wt% based on the total weight of the monomer X, the monomer Y and the cross-linking agent M; the amount of the cross-linking agent M is 2-4wt%.
In a preferred embodiment of the present invention, the monomer X represented by the formula (4) is acrylamide (R) 1 ' is H) or methacrylamide (R) 1 ' is CH 3 ) (ii) a The monomer Y shown as the formula (5) is 4- (acrylamide) methyl benzoate (R) 2 ' is H) or methyl 4- (methacrylamide) benzoate (R) 2 ' is CH 3 ) (ii) a The crosslinking agent M shown as the formula (6) is N- (2, 3, 4-trihydroxy-5-acrylamide methylbenzyl) acrylamide (R) 3 ' and R 4 Both' are H).
In the present invention, the monomer X, the monomer Y and the crosslinking agent M are all commercially available.
In the present invention, the amount of water used is such that the total mass concentration of the monomer X, the monomer Y and the crosslinking agent M in the solution polymerization reaction system is 10 to 30% by weight.
According to the present invention, the conditions of the solution polymerization reaction include: the initiator is an oxidation-reduction system initiator, and the chain transfer agent is tetramethyl thiourea; the reaction temperature is 30-60 ℃, and the reaction time is 6-8h.
According to the present invention, the initiator is used in an amount of 0.15 to 0.75wt% and the chain transfer agent is used in an amount of 0.5 to 2wt%, based on the total weight of the monomer X, the monomer Y and the crosslinking agent M.
In the present invention, the oxidation-reduction system initiator may be a conventional oxidation-reduction system initiator in the art, and is preferably a persulfate oxidizer and a sulfite reducer.
Specifically, the persulfate oxidizer may be, for example, potassium persulfate, ammonium persulfate, or the like. The sulfite reducing agent may be, for example, potassium bisulfite, sodium bisulfite, or the like.
Specifically, the use amount of the persulfate oxidizer is 0.1-0.5wt% based on the total weight of the monomer X, the monomer Y and the crosslinking agent M; the amount of the sulfite reducing agent is 0.05 to 0.25wt%.
According to the present invention, the solution polymerization conditions further comprise: in the presence of an emulsifier.
According to the invention, the emulsifier can emulsify the monomer X, the monomer Y and the cross-linking agent M to form stable emulsion, and the existence of the cross-linking agent enables the high-temperature resistant acrylamide copolymer to be further cross-linked at high temperature (more than 85 ℃) of an oil reservoir, so that a weak gel system is changed into super-strong gel, the water phase permeability is effectively reduced, and the water phase plugging effect is enhanced.
According to the invention, the emulsifiers are used in an amount of from 1 to 5% by weight, based on the total weight of monomers X, monomers Y and crosslinking agents M.
According to the invention, the emulsifier is selected from at least one of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80.
In the present invention, the high-temperature resistant acrylamide copolymer obtained by polymerization is preferably granulated and dried.
In a preferred embodiment of the present invention, the preparation method of the high temperature resistant acrylamide copolymer comprises:
step 1, weighing a monomer X to prepare an aqueous solution;
step 2, weighing a monomer Y, a cross-linking agent M and an emulsifying agent, adding the monomer Y, the cross-linking agent M and the emulsifying agent into the solution, and uniformly stirring to form a stable micelle;
the emulsifier is at least one of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80;
and 3, adding a chain transfer agent and an initiator into the micelle solution obtained in the step 2, uniformly stirring, raising the temperature to 30-60 ℃, initiating polymerization for 6-8 hours to obtain polymer colloid, and granulating and drying to obtain the high-temperature resistant acrylamide copolymer.
In a third aspect, the present invention provides a high temperature resistant acrylamide copolymer prepared by the above method.
The fourth aspect of the invention provides the application of the high-temperature resistant acrylamide copolymer as a water plugging material in an oil well.
The present invention will be described in detail below by way of examples. In the following examples of the present invention, the following examples,
a monomer X represented by the formula (4) (in X1, R) 1 ' is H; in X2, R 1 ' is CH 3 ) And a monomer Y represented by the formula (5) (in Y1, R 2 ' is H, in Y2, R 2 ' is CH 3 ) And a crosslinking agent M represented by the formula (6) (in M1, R 3 ' and R 4 ' both H) from Shanghai Allantin Biotechnology, inc.;
examples and comparative examples all other raw materials were commercially available;
the plugging rate is measured on a rock core flow test device according to the plugging rate test steps in SY/T5840-2007 in the indoor test method of bridging plugging materials for drilling fluid. Specifically, the method comprises the following steps:
and (3) measuring the water plugging rate: loading the artificial core into core holder, saturating with water, and measuring its pore volume PV and water phase permeability (K) w1 ) Then injecting 1.0PV water plugging material, curing at high temperature for 24h, and measuring the permeability (K) of the mixture after adding the water plugging agent by using water w2 )，1-(K w2 /K w1 ) And multiplying 100 percent to obtain the water plugging rate.
And (3) measuring the oil plugging rate: loading the artificial core into core holder, saturating with oil, and measuring its pore volume PV and oil phase permeability (K) o1 ) Then injecting 1.0PV water plugging material, curing at high temperature for 24h, and measuring the permeability (K) of the mixture after adding the water plugging agent by using oil o2 )，1-(K o2 /K o1 ) And multiplying 100 percent to obtain the oil plugging rate.
Wherein the artificial core is obtained by filling quartz sand of 40-60 meshes in a mould.
The apparent viscosity of the high-temperature-resistant acrylamide copolymer is measured by using a Brookfield viscometer, and specifically, the apparent viscosity of the water-plugging material (with the mass concentration of 2000 mg/L) is measured at a specified test temperature and mineralization degree.
Example 1
1. Weighing 28.2g of acrylamide (monomer X1) and adding the acrylamide into a polymerization kettle filled with 150mL of water, and fully stirring and dissolving to obtain a stable aqueous solution;
2. weighing 1.5g of 4- (acrylamide) methyl benzoate (monomer Y1), 0.3g of oil-soluble cross-linking agent (cross-linking agent M1) and 0.8g of emulsifier span 80, adding into the solution, and fully stirring to form stable micelles;
3. and (3) adding 0.45g of chain transfer agent into the micelle in the step (2), then sequentially adding 0.08g of potassium persulfate and 0.04g of sodium bisulfite, fully stirring to ensure that the mixture enters the micelle, raising the temperature to 30 ℃ to initiate polymerization for 7 hours to obtain colloid, and granulating and drying to obtain the high-temperature resistant polyacrylamide copolymer water plugging material W1.
According to the calculation of the material charging amount, based on the total weight of the high temperature resistant polyacrylamide copolymer W1, the content of the structural unit provided by the monomer X is 94 weight percent, the content of the structural unit provided by the monomer Y is 5 weight percent, and the content of the structural unit C provided by the cross-linking agent M is 1 weight percent.
Tests show that under the conditions of high temperature (115 ℃) and high salt (the mineralization degree is 100,000mg/L), the viscosity of the polyacrylamide copolymer is 50.6mPa & s, no delamination occurs after more than 30 days, and the water plugging rate of the water plugging material W1 is 96.5 percent and the oil plugging rate is 9.3 percent.
Example 2
1. Weighing 24.9g of acrylamide (monomer X1) and adding the acrylamide into a polymerization kettle filled with 150mL of water, and fully stirring and dissolving to obtain a stable aqueous solution;
2. weighing 3.6g of 4- (acrylamide) methyl benzoate (monomer Y1), 1.5g of oil-soluble cross-linking agent (cross-linking agent M1) and 1.1g of emulsifier Tween 80, adding into the solution, and fully stirring to form stable micelles;
3. and (3) adding 0.2g of chain transfer agent into the micelle in the step (2), sequentially adding 0.11g of potassium persulfate and 0.055g of sodium bisulfite, fully stirring to ensure that the mixture enters the micelle, raising the temperature to 40 ℃ after the mixture enters the micelle, initiating polymerization for 7 hours to obtain colloid, and granulating and drying to obtain the high-temperature resistant polyacrylamide copolymer water plugging material W2.
According to the calculation of the charging amount, based on the total weight of the high-temperature resistant polyacrylamide copolymer W2, the content of the structural unit provided by the monomer X is 83 weight percent, the content of the structural unit provided by the monomer Y is 12 weight percent, and the content of the structural unit C provided by the crosslinking agent M is 5 weight percent.
Tests show that under the conditions of high temperature (120 ℃) and high salt (the mineralization degree is 100,000mg/L), the viscosity of the polyacrylamide copolymer is 47.3mPa & s, no delamination occurs after more than 30 days, and the water plugging rate of the water plugging material W2 is 95.9 percent and the oil plugging rate is 8.8 percent.
Example 3
1. Weighing 27g of acrylamide (monomer X1) and adding the acrylamide into a polymerization kettle filled with 150mL of water, and fully stirring and dissolving to obtain a stable aqueous solution;
2. weighing 2.1g of 4- (acrylamide) methyl benzoate (monomer Y1), 0.9g of oil-soluble cross-linking agent (cross-linking agent M1) and 1g of emulsifier Tween 40, adding into the solution, and fully stirring to form stable micelles;
3. and (3) adding 0.32g of chain transfer agent into the micelle in the step (2), then sequentially adding 0.06g of potassium persulfate and 0.03g of sodium bisulfite, fully stirring to ensure that the mixture enters the micelle, raising the temperature to 55 ℃ to initiate polymerization for 7 hours to obtain colloid, and granulating and drying to obtain the high-temperature resistant polyacrylamide copolymer water plugging material W3.
According to the calculation of the charging amount, based on the total weight of the high-temperature resistant polyacrylamide copolymer W3, the content of the structural unit provided by the monomer X is 90 wt%, the content of the structural unit provided by the monomer Y is 7 wt%, and the content of the structural unit C provided by the crosslinking agent M is 3 wt%.
Tests show that under the conditions of high temperature (125 ℃) and high salt (the mineralization degree is 100,000mg/L), the viscosity of the polyacrylamide copolymer is 55.9mPa & s, no delamination occurs after more than 30 days, and the water plugging rate of the water plugging material W3 is 98.2 percent and the oil plugging rate is 5.8 percent.
Example 4
1. Weighing 20.5g of acrylamide (monomer X1) and adding into a polymerization kettle filled with 150mL of water, and fully stirring and dissolving to obtain a stable aqueous solution;
2. weighing 2.0g of 4- (acrylamide) methyl benzoate (monomer Y1), 0.6g of oil-soluble cross-linking agent (cross-linking agent M1) and 0.5g of emulsifier span 40, adding the mixture into the solution, and fully stirring the mixture to form a stable micelle;
3. and (3) adding 0.28g of chain transfer agent into the micelle in the step 2, sequentially adding 0.09g of potassium persulfate and 0.045g of sodium bisulfite, fully stirring to ensure that the mixture enters the micelle, raising the temperature to 45 ℃ to initiate polymerization for 7 hours to obtain colloid, and granulating and drying to obtain the high-temperature resistant polyacrylamide copolymer water plugging material W4.
According to the calculation of the charging amount, based on the total weight of the high-temperature resistant polyacrylamide copolymer W3, the content of the structural unit provided by the monomer X is 88 weight percent, the content of the structural unit provided by the monomer Y is 8 weight percent, and the content of the structural unit C provided by the crosslinking agent M is 4 weight percent.
According to tests, under the conditions of high temperature (130 ℃) and high salt (the degree of mineralization is 100,000mg/L), the viscosity of the polyacrylamide copolymer is 53.7mPa & s, the polyacrylamide copolymer is not delaminated after more than 30 days, and the water plugging rate of the water plugging material W4 is 98.9%, and the oil plugging rate is 4.6%.
Example 5
A high-temperature resistant polyacrylamide copolymer water shutoff material W5 was prepared as in example 1, except that: monomer X was replaced by methacrylamide (monomer X2).
Tests show that the viscosity of the polyacrylamide copolymer is 45.4 mPa.s under the conditions of high temperature (115 ℃) and high salt (the degree of mineralization is 100,000mg/L), the polyacrylamide copolymer is not layered after more than 30 days, and the water plugging rate of the water plugging material W5 as a water plugging material is 93.8 percent and the oil plugging rate is 10.2 percent.
Example 6
A high-temperature resistant polyacrylamide copolymer water shutoff material W6 was prepared as in example 1, except that: monomer Y was replaced by methyl 4- (methacrylamide) benzoate (monomer Y2).
Tests show that under the conditions of high temperature (115 ℃) and high salt (the mineralization degree is 100,000mg/L), the viscosity of the polyacrylamide copolymer is 42.7mPa & s, no delamination occurs after more than 30 days, and the water plugging rate of the water plugging material W6 as a water plugging material is 91.7%, and the oil plugging rate is 12.3%.
Comparative example 1
A high temperature resistant polyacrylamide copolymer water blocking material was prepared as in example 1, except that: and (3) preparing the high-temperature resistant polyacrylamide copolymer water plugging material D1 without adding a cross-linking agent M.
According to the calculation of the feeding amount, based on the total weight of the high-temperature resistant polyacrylamide copolymer water plugging material D1, the content of the structural unit provided by the monomer X is 94.95 wt%, and the content of the structural unit provided by the monomer Y is 5.05 wt%.
Tests show that under the conditions of high temperature (115 ℃) and high salt (the mineralization degree is 100,000mg/L), the viscosity of the polyacrylamide copolymer is 26.3mPa & s, obvious layering appears after 3 days, and the water plugging rate of the water plugging material D1 as a water plugging material is 65.3%, and the oil plugging rate is 15.4%.
Comparative example 2
A high temperature resistant polyacrylamide copolymer water blocking material was prepared as in example 1, except that: and (3) not adding the monomer Y to prepare the high-temperature resistant polyacrylamide copolymer water plugging material D2.
According to the calculation of the material charging amount, based on the total weight of the high-temperature resistant polyacrylamide copolymer water plugging material D1, the content of the structural unit provided by the monomer X is 98.95 wt%, and the content of the structural unit provided by the monomer Y is 1.05 wt%.
Tests show that under the conditions of high temperature (115 ℃) and high salt (the degree of mineralization is 100,000mg/L), the viscosity of the polyacrylamide copolymer is 29.1 mPa.s, obvious layering appears after 5 days, and the water plugging rate of the water plugging material D2 as a water plugging material is 52.9 percent, and the oil plugging rate is 40.3 percent.
Comparative example 3
A high-temperature resistant polyacrylamide copolymer water shutoff material D3 was prepared as in example 1, except that: the amounts of monomer X, monomer Y and crosslinking agent M were different from those of example 1.
According to the calculation of the material amount and the raw material allowance, based on the total weight of the high-temperature resistant polyacrylamide copolymer water plugging material D3, the content of the structural unit provided by the monomer X is 75wt%, the content of the structural unit provided by the monomer Y is 15 wt%, and the content of the structural unit C provided by the crosslinking agent M is 10 wt%.
Tests show that under the conditions of high temperature (115 ℃) and high salt (the mineralization degree is 100,000mg/L), the viscosity of the polyacrylamide copolymer is 20.6mPa & s, obvious layering occurs after 7 days, and the water plugging rate of the water plugging material D3 as a water plugging material is 48.6%, and the oil plugging rate is 16.8%.
As can be seen from the above examples and comparative data, the controllable water plugging material provided by the invention can obtain excellent water plugging and oil non-plugging effects.
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 (12)
1. A high-temperature resistant acrylamide copolymer is characterized by comprising a structural unit A shown in a formula (1), a structural unit B shown in a formula (2) and a structural unit C shown in a formula (3);
based on the total weight of the high-temperature resistant acrylamide copolymer, the content of the structural unit A is 83-94wt%, the content of the structural unit B is 5-12wt%, and the content of the structural unit C is 1-5wt%;
wherein R is 1 、R 2 、R 3 And R 4 Each independently is H or-CH 3 。
2. The high temperature resistant acrylamide copolymer according to claim 1, wherein the content of the structural unit a is 86-92wt%, the content of the structural unit B is 6-10wt%, and the content of the structural unit C is 2-4wt%, based on the total weight of the high temperature resistant acrylamide copolymer.
3. A method of preparing a high temperature resistant acrylamide copolymer, comprising the steps of:
under the condition of solution polymerization reaction, in the presence of an initiator and a chain transfer agent, carrying out polymerization reaction on a monomer X, a monomer Y and a cross-linking agent M in water to obtain the high-temperature resistant acrylamide copolymer; wherein the monomer X has a structure shown in a formula (4), the monomer Y has a structure shown in a formula (5), and the crosslinking agent M has a structure shown in a formula (6); based on the total weight of the monomer X, the monomer Y and the cross-linking agent M, the using amount of the monomer X is 83-94wt%, and the using amount of the monomer Y is 5-12wt%; the dosage of the cross-linking agent M is 1-5wt%;
wherein R is 1 ’、R 2 ’、R 3 ' and R 4 ' each independently is H or-CH 3 。
4. The method of claim 3, wherein monomer X is present in an amount of 86 to 92wt% and monomer Y is present in an amount of 6 to 10wt%, based on the total weight of monomer X, monomer Y, and crosslinker M; the amount of the cross-linking agent M is 2-4wt%.
5. The method of claim 3, wherein the conditions of the solution polymerization reaction comprise: the initiator is an oxidation-reduction system initiator, and the chain transfer agent is tetramethyl thiourea; the reaction temperature is 30-60 ℃, and the reaction time is 6-8h.
6. The process according to any one of claims 3 to 5, wherein the initiator is used in an amount of from 0.15 to 0.75% by weight, based on the total weight of the monomers X, Y and the crosslinking agent M; the amount of the chain transfer agent is 0.5-2wt%.
7. The method of any of claims 3-5, wherein the solution polymerization conditions further comprise: in the presence of an emulsifier.
8. The process according to claim 7, wherein the emulsifier is used in an amount of 1 to 5wt%, based on the total weight of the monomer X, the monomer Y and the crosslinking agent M.
9. The method according to claim 5, wherein the oxidation-reduction system initiator is a persulfate oxidizer and a sulfite reducer.
10. The method according to claim 7, wherein the emulsifier is selected from at least one of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80.
11. A high temperature resistant acrylamide copolymer prepared by the method of any one of claims 3-10.
12. Use of the high temperature resistant acrylamide copolymer according to any one of claims 1-2 and 11 as a water plugging material in an oil well.
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| CN102834426A (en) * | 2010-02-12 | 2012-12-19 | 罗地亚管理公司 | Rheology modifier polymer |
| CN109384889A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Polymer and its preparation method and application with selective water plugging function |
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| CN102834426A (en) * | 2010-02-12 | 2012-12-19 | 罗地亚管理公司 | Rheology modifier polymer |
| CN109384889A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Polymer and its preparation method and application with selective water plugging function |
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