CN107686534B - Polymer with selective water plugging function and preparation method and application thereof - Google Patents
Polymer with selective water plugging function and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of crude oil recovery, and discloses a polymer with a selective water plugging function, a preparation method and an application thereof, wherein the polymer comprises a structural unit A, a structural unit B and a structural unit C, the structural unit A is a structural unit with a structure shown in a formula (1), the structural unit B is a structural unit with a structure shown in a formula (2), and the structural unit C is at least one selected from the structural unit with a structure shown in a formula (3-1), the structural unit with a structure shown in a formula (3-2) and the structural unit with a structure shown in a formula (3-3). The polymer has a high-selectivity water plugging function, and a water plugging material formed by using the polymer can achieve the effect of high-selectivity water plugging without oil plugging.
Description
Technical Field
The invention relates to the field of crude oil recovery, in particular to a polymer with a selective water plugging function, a method for preparing the polymer with the selective water plugging function, the polymer with the selective water plugging function prepared by the method and application of the polymer with the selective water plugging function as a selective water plugging agent.
Background
The polymer water shutoff agent is a water shutoff agent applied in large scale at present and is mainly divided into a polymer relative permeability regulator (also called a phase permeation regulator) and a polymer gel water shutoff agent. The main difference between the two is that the phase permeation regulator is mainly long-chain polymer molecules, and the polymer molecular chains stretch in the water phase and shrink in the oil phase to form a dragging effect on the water phase, so that the water phase permeability is reduced, and the system cannot cause physical blocking of the pore volume; the polymer gel water shutoff agent enables the oil-water phase permeability to be reduced unevenly by means of the change of effective movable volume under the action of oil and water, but the processing mode can cause physical blockage of an oil-water channel, 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 amount is too low due to improper processing, and the production of crude oil is reduced.
The polymer water shutoff agent has good practical effect, but a corresponding injection process must be formulated according to the actual conditions of each oil field in the use process, otherwise, the injection of the water shutoff agent cannot achieve the water shutoff effect, the water yield can be increased, and the crude oil yield is reduced.
The thickened oil water shutoff agent is composed of high-viscosity crude oil and surfactant, i.e. thickened oil with certain viscosity added with W/O type emulsifier, the thickened oil is pumped into the stratum of an oil well under high pressure, the thickened oil entering an oil flow channel is dissolved in the stratum crude oil and is extracted from the oil well, the thickened oil entering a water flow channel is mixed with seepage formation water or injected water to be emulsified to form water-in-oil emulsion, the viscosity of the water-in-oil emulsion is greatly increased, the mechanism of the water shutoff action mainly comprises the following aspects that ① emulsified thickened oil is cut into a spherical shape by water flow to cause physical blockage at the pore throat part of the water flow channel, ② thickened oil is adsorbed on the wall of the water flow channel to change wall rock from hydrophilic to lipophilic, the pore channel is reduced, the flow of water is hindered, ③ the surfactant component in the thickened oil emulsifies the thickened oil into oil drops in water to generate Jamin effect in pores, the permeability of water is reduced, however, the emulsified oil is a water shutoff agent with obvious water shutoff and the research and the application of the research and the controllability of the water shutoff agent is limited.
The composite water shutoff agent is a composite selective water shutoff agent which is formed by adding an inorganic water shutoff agent with low price and a polymerization solution and has certain strength and certain selectivity, such as a sodium silicate-polymer blocking selection agent, a terpolymer blocking selection agent and the like.
At present, selective water shutoff agents and deep profile control technologies at home and abroad are improved day by day, and the selective water shutoff agent has been developed greatly on the technologies of research development, construction process and the like of selective water shutoff materials, but with the development of oil fields, the characteristics of oil layers and the environment are changed constantly, particularly in the later development period, the contradiction of oil reservoir development is more prominent by adopting the water shutoff materials for a long time, the practical development experience of the oil fields is summarized according to the characteristics of the selective water shutoff materials, the technical problem which needs to be overcome by the current selective water shutoff agent is provided, and the specific research and development of new technologies to adapt to the water shutoff effect of a special oil field for improving a selective system is particularly important.
The research of the selective water shutoff agent is the result of the development of the material technology, and the material microstructure recognition and the synthesis modification technology based on the molecular level are the key points of the research of the selective water shutoff agent; the interaction mechanism of the plugging agent and rock is researched under the real oil reservoir condition, and the deduction of the water plugging effect from the molecular level is the basis of the research and evaluation of the selective plugging agent.
In summary, most of the selective plugging agents used for water plugging of oil wells at present are gels or jelly generated by water-soluble polymers such as polyacrylamide and derivatives thereof in the stratum to plug the stratum water, or oil-based plugging agents are gelled or solidified to plug water channeling passages when meeting water, but due to poor selectivity, the oil phase permeability can be greatly reduced while water is plugged, so that low liquid after plugging is caused, and the application of the water plugging technology of the oil wells is restricted.
Therefore, a novel high-selectivity water plugging material is developed, so that water plugging and oil plugging of an oil layer are realized, and the method has important significance for improving the productivity of an oil well in an ultrahigh water cut period.
Disclosure of Invention
The water plugging material with high oil-water selectivity provided by the invention has excellent temperature resistance, salt resistance and expansibility, so that the water phase permeability can be reduced, the water phase plugging effect can be enhanced, and the effects of selectively plugging water and not plugging oil can be achieved.
In order to achieve the above object, in a first aspect, the present invention provides a polymer having a selective water shutoff function, the 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), the structural unit B is a structural unit having a structure represented by formula (2), and the structural unit C is at least one selected from the group consisting of a structural unit having a structure represented by formula (3-1), a structural unit having a structure represented by formula (3-2) and a structural unit having a structure represented by formula (3-3); wherein, based on the weight of the polymer, the content of the structural unit A is 30-90 wt%, the content of the structural unit B is 5-50 wt%, the content of the structural unit C is 1-30 wt%, and the expansion multiple of the polymer is 75-110;
wherein R is1And R2Each independently is H or C1-C4 alkyl; r3Is C1-C14 alkylene; r4And R5Each independently is H or C1-C4 alkyl, and R4And R5Not H at the same time; m is H, Na or K; r6Is H or C1-C4 alkyl; t is an integer of 1 to 10, and n is an integer of 1 to 6.
In a second aspect, the present invention provides a method for preparing a polymer having a selective water shutoff function, the method comprising: in the presence of an initiator, a crosslinking agent and water as a solvent, carrying out solution polymerization reaction on a monomer D, a monomer E and a monomer F, wherein the monomer D is a monomer with a structure shown in a formula (4), the monomer E is a monomer with a structure shown in a formula (5), the monomer F is at least one selected from the group consisting of a monomer having a structure represented by formula (6-1), a monomer having a structure represented by formula (6-2) and a monomer having a structure represented by formula (6-3), wherein the monomers D, E and F are used in amounts such that the content of the structural unit A in the prepared polymer is 30-90 wt%, the content of the structural unit B is 5-50 wt%, the content of the structural unit C is 1-30 wt%, and the expansion factor of the prepared polymer is 75-110; the structural unit A is a structural unit with a structure shown in a formula (1), the structural unit B is a structural unit with a structure shown in a formula (2), the structural unit C is at least one selected from the structural unit with a structure shown in a formula (3-1), the structural unit with a structure shown in a formula (3-2) and the structural unit with a structure shown in a formula (3-3),
wherein R is1And R2Each independently is H or C1-C4 alkyl; r3Is C1-C14 alkylene; r4And R5Each independently is H or C1-C4 alkyl, and R4And R5Not H at the same time; m is H, Na or K; r6Is H or C1-C4 alkyl; t is an integer of 1 to 10, and n is an integer of 1 to 6.
In a third aspect, the invention provides a polymer with selective water plugging function prepared by the method.
In a fourth aspect, the invention provides an application of the polymer with the selective water plugging function as a selective water plugging agent.
The invention obtains the polymer water plugging material with high-selectivity water plugging function by introducing a vinylpyridine type zwitterionic monomer into a macromolecular chain. The polymer provided by the invention has a high-selectivity water plugging function, a water plugging material formed by using the polymer can achieve the effect of high-selectivity water plugging without oil plugging, and the polymer has excellent temperature resistance and salt resistance and expansibility, so that the water phase permeability can be reduced, and the water phase plugging effect can be enhanced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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.
In the invention, the alkyl of C1-C4 refers to the alkyl with 1-4 carbon atoms; the alkylene group having C1-C14 means an alkylene group having 1-14 carbon atoms. Integers from 1 to 10 include 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. Integers from 1 to 6 include 1, 2, 3, 4, 5 and 6.
According to the present invention, the C1-C4 alkyl groups may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
According to the invention, the C1-C14 alkylene group may be linear or branched, and the C1-C14 alkylene group may include, but is not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene, neopentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene and n-tetradecylene, preferably methylene. The alkylene group refers to a residue of an alkane which has been deprived of two hydrogen atoms, which may be two hydrogen atoms on the same carbon atom or two hydrogen atoms on different carbon atoms, and which may be linear or branched, for example, the ethylene group may be-CH2CH2-or-CH(CH3)-。
First aspectThe invention provides a polymer with a selective water plugging function, which 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), the structural unit B is a structural unit with a structure shown in a formula (2), and the structural unit C is at least one selected from the structural unit with a structure shown in a formula (3-1), the structural unit with a structure shown in a formula (3-2) and the structural unit with a structure shown in a formula (3-3); wherein, based on the weight of the polymer, the content of the structural unit A is 30-90 wt%, the content of the structural unit B is 5-50 wt%, the content of the structural unit C is 1-30 wt%, and the expansion multiple of the polymer is 75-110;
wherein R is1And R2Each independently is H or C1-C4 alkyl; r3Is C1-C14 alkylene; r4And R5Each independently is H or C1-C4 alkyl, and R4And R5Not H at the same time; m is H, Na or K; r6Is H or C1-C4 alkyl; t is an integer of 1 to 10, and n is an integer of 1 to 6.
Preferably, the content of the structural unit A is 40 to 85 wt%, the content of the structural unit B is 10 to 40 wt%, the content of the structural unit C is 5 to 20 wt%, and the polymer has an expansion ratio of 80 to 100, based on the weight of the polymer.
In the present invention, the expansion factor of the polymer is the ratio of the weight of the polymer after the completion of water absorption to the weight of the polymer before the water absorption.
According to the present invention, in a first preferred aspect, R is represented by formula (1), formula (2) and formula (3)1And R2Each independently is H, methyl, ethyl, n-propyl, isopropyl, n-butyl; r3Is methyleneEthylene, n-propylene, n-butylene, n-pentylene, n-hexylene; r4And R5Each independently is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, and R4And R5Not H at the same time; m is H, Na or K; r6H, methyl, ethyl, n-propyl, isopropyl and n-butyl; t is an integer of 1 to 8, and n is an integer of 1 to 5.
According to the present invention, in a second preferred aspect, R is in a structural unit having a structure represented by formula (1), a structural unit having a structure represented by formula (2), and a structural unit having a structure represented by formula (3)1And R2Each independently is H, methyl, ethyl, n-propyl; r3Is methylene, ethylene, n-propylene, n-butylene; r4And R5Each independently is H, methyl, ethyl, n-propyl, and R4And R5Not H at the same time; m is Na or K; r6H, methyl, ethyl, n-propyl; t is an integer of 2 to 6, and n is an integer of 1 to 5.
According to the present invention, in a third preferred aspect, R is in a structural unit having a structure represented by formula (1), a structural unit having a structure represented by formula (2), and a structural unit having a structure represented by formula (3)1And R2Each independently is H, methyl; r3Is methylene; r4And R5Each independently is H, methyl, ethyl, and R4And R5Not H at the same time; m is Na or K; r6H, methyl, ethyl; t is an integer of 3 to 5, and n is an integer of 1 to 4.
The inventors of the present invention have found, in their studies, that the selectivity of the water shutoff function for a polymer composed of the following specific structural unit a, structural unit B and structural unit C is higher. The structural unit A is a structural unit having a structure represented by formula (7), the structural unit B is a structural unit having a structure represented by formula (8), and the structural unit C is at least one selected from the group consisting of a structural unit having a structure represented by formula (9-1), a structural unit having a structure represented by formula (9-2), and a structural unit having a structure represented by formula (9-3),
second aspect of the inventionThe invention provides a method for preparing a polymer with a selective water plugging function, which comprises the following steps: in the presence of an initiator, a crosslinking agent and water as a solvent, carrying out solution polymerization reaction on a monomer D, a monomer E and a monomer F, wherein the monomer D is a monomer with a structure shown in a formula (4), the monomer E is a monomer with a structure shown in a formula (5), the monomer F is at least one selected from the group consisting of a monomer having a structure represented by formula (6-1), a monomer having a structure represented by formula (6-2) and a monomer having a structure represented by formula (6-3), wherein the monomers D, E and F are used in amounts such that the content of the structural unit A in the prepared polymer is 30-90 wt%, the content of the structural unit B is 5-50 wt%, the content of the structural unit C is 1-30 wt%, and the expansion factor of the prepared polymer is 75-110; the structural unit A is a structural unit with a structure shown in a formula (1), the structural unit B is a structural unit with a structure shown in a formula (2), the structural unit C is at least one selected from the structural unit with a structure shown in a formula (3-1), the structural unit with a structure shown in a formula (3-2) and the structural unit with a structure shown in a formula (3-3),
wherein R is1And R2Each independently is H or C1-C4 alkyl; r3Is C1-C14 alkylene; r4And R5Each independently is H or C1-C4 alkyl, and R4And R5Not H at the same time; m is H, Na or K; r6Is H or C1-C4 alkyl; t is an integer of 1 to 10, and n is an integer of 1 to 6.
The monomer F can be obtained commercially or synthesized by methods known in the art. For example, monomers F used in the examples section of this invention are all commercially available. And the polymerization reaction involved in the method for preparing the polymer with the selective water shutoff function is carried out in a random copolymerization mode.
In the present invention, the relevant definitions and species of the substituents in the structural unit of the structure represented by formula (1), the structural unit of the structure represented by formula (2), the structural unit of the structure represented by formula (3-1), the structural unit of the structure represented by formula (3-2), the structural unit of the structure represented by formula (3-3), the monomer of the structure represented by formula (4), the monomer of the structure represented by formula (5), the monomer of the structure represented by formula (6-1), the monomer of the structure represented by formula (6-2) and the monomer of the structure represented by formula (6-3) are the same as those described above in the present invention, and the present invention is not described herein again, and those skilled in the art should not be construed as a limitation to the technical solution of the present invention.
In the present invention, it should be noted that the monomer is approximately completely converted into the corresponding structural unit contained in the polymer with selective water shutoff function, and the amount of the monomer may be consistent with the content of the corresponding structural unit contained in the polymer with selective water shutoff function.
Preferably, the monomers D, E and F are used in amounts such that the polymer produced has a content of structural unit A of 40 to 85% by weight, a content of structural unit B of 10 to 40% by weight and a content of structural unit C of 5 to 20% by weight, and such that the polymer produced has a multiple of expansion of 80 to 100.
Preferably, monomer D, monomer E and monomer F form an aqueous solution in the presence of water; more preferably, the total concentration of monomer D, monomer E and monomer F in the aqueous solution is from 20 to 40% by weight.
According to the process of the present invention, the solution polymerization is preferably carried out at a pH of from 6 to 10. The pH may be obtained by adding a pH adjuster, which may be various pH adjusters conventional in the art, to the polymerization system, and may be, for example, at least one of sodium hydroxide, sodium carbonate, potassium carbonate, and ammonia, preferably sodium hydroxide and/or sodium carbonate.
According to the method of the present invention, the addition of the chelating agent can prevent the metal ions from affecting the polymerization reaction, and therefore, it is preferable that the solution polymerization reaction is carried out in the presence of the chelating agent. The chelating agent may be disodium ethylenediaminetetraacetate, nitrilotriacetic acid or ammonium citrate, preferably disodium ethylenediaminetetraacetate. The amount of the chelating agent used in the present invention is not particularly limited and may vary within a wide range, and may be 0.01 to 0.1% by weight based on the total amount of the monomer D, the monomer E and the monomer F.
The crosslinking agent is preferably N, N' -methylenebisacrylamide, which is used in an amount of 0.02 to 0.1% by weight based on the total amount of the monomers D, E and F.
The solution polymerization reaction of the present invention further comprises carrying out in the presence of tetramethylethylenediamine, which is used in an amount of 0.02 to 0.2% by weight based on the total amount of the monomer D, the monomer E and the monomer F.
The solution polymerization reaction may also be carried out in the presence of a protective gas, which may preferably be nitrogen.
In order to obtain the polymer finished product with the selective water plugging function, the method can also comprise the steps of granulating, drying, crushing and screening the obtained polymer colloid to obtain the polymer finished product with the selective water plugging function.
Preferably, the monomer D is a monomer having a structure represented by formula (10); the monomer E is a monomer with a structure shown in a formula (11); the monomer F is at least one selected from the group consisting of a monomer having a structure represented by formula (12-1), a monomer having a structure represented by formula (12-2) and a monomer having a structure represented by formula (12-3),
preferably, the conditions of the solution polymerization reaction include: the temperature is 0-30 ℃, preferably 0-20 ℃; the time is 2-15h, preferably 5-10 h.
Preferably, the initiator includes at least one of an azo-type initiator, a peroxide-type initiator, and a redox-type initiator; 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 persulfate-sulfite, persulfate-thiourea, persulfate-organic salt and ammonium persulfate-fatty amine.
Preferably, the initiator is a redox initiator; more preferably, the redox initiator is an oxidation-reduction initiation system consisting of a persulfate oxidizer and a sulfite reducer. In this preferred case, the persulfate oxidizer is used in an amount of from 0.01 to 0.1% by weight of the total amount of monomer D, monomer E and monomer F; the amount of the sulfite reducing agent is 0.005-0.05% of the total amount of the monomer D, the monomer E and the monomer F. For example, the oxidizing agent in the redox initiator may be a 0.2 wt% aqueous solution of potassium persulfate and/or a 0.2 wt% aqueous solution of ammonium persulfate; the reducing agent in the redox initiator may be 0.1 wt% aqueous potassium bisulfite solution and/or 0.1 wt% aqueous sodium bisulfite solution.
According to a preferred embodiment, the preparation method of the polymer with the selective water plugging function comprises the following steps:
step 1: adding the monomer D, the monomer E and the monomer F into a polymerization reaction bottle to prepare an aqueous solution, and adjusting the pH value of the aqueous solution to 6-10 by using alkali;
step 2: adding a chelating agent, a cross-linking agent and tetramethylethylenediamine into the aqueous solution obtained in the step 1, and uniformly stirring;
and 3, step 3: blowing nitrogen for 5-60min at the temperature of 0-30 ℃, adding an initiator into the aqueous solution obtained in the step 2, blowing nitrogen to uniformly mix the initiator and the aqueous solution, and carrying out sealed polymerization for 2-15h to obtain a polymer colloid;
and 4, step 4: and taking out the colloid, and then granulating, drying, crushing and screening to obtain a polymer finished product with the selective water plugging function.
Third aspect of the inventionThe invention provides a polymer with selective water plugging function prepared by the method.
Fourth aspect of the inventionThe invention provides application of the polymer with the selective water plugging function as a selective water plugging agent.
In the application of the polymer with the selective water plugging function as the selective water plugging agent, a specific application method is well known by the technical personnel in the field.
The polymer with the selective water plugging function, the preparation method and the application thereof have the following specific advantages:
1) by introducing a vinylpyridine type zwitterionic monomer into the acrylamide copolymer, the temperature resistance and salt resistance of the water plugging agent material are greatly improved, and the expansion factor of the material is also greatly increased;
2) the polymer particles prepared by the method are firstly swelled in a NaCl aqueous solution containing 10 wt%, fully stirred to be uniformly suspended in a system, and pressed into a stratum oil reservoir at an oil production well through an injection pump, and the suspended colloidal particles can further expand when meeting stratum water to block a water phase passage, so that the water phase permeability is greatly reduced; the suspended colloidal particles can shrink when meeting the oil phase, so that the oil/water selectivity of the water plugging material is obviously improved, the effect of plugging water and not plugging oil is achieved, convenience is provided for the benefit and benefit increase of low-efficiency wells at low oil price, and technical support is provided for the improvement of the oil well productivity in an ultra-high water-cut period.
The present invention will be described in detail below by way of examples.
The zwitterionic monomers used below were all available from Aladdin reagents (Shanghai) Inc.
In the following examples, the test methods involved are as follows:
the plugging rate is carried out on a rock core flow test device according to the plugging rate test procedure in SY/T5840-2007 bridge plugging material indoor test method 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 water phase permeability (K)w1) Then 10mL of water plugging agent is extruded, and after curing for 24h at 80 ℃, the permeability (K) of the mixture after adding the water plugging agent is measured by waterw2)，Kw2And Kw1Ratio (K)w2/Kw1) Namely the water plugging rate.
And (3) measuring the oil plugging rate: loading the artificial core into core holder, saturating with oil, and measuring oil phase permeability (K)o1) Then 10mL of water shutoff agent is extruded, and after curing for 24h at 80 ℃, the permeability (K) of the water shutoff agent added is measured by oilo2)，Ko2And Ko1Of (K)o2/Ko1) Namely the oil plugging rate.
Wherein the artificial core is obtained by filling quartz sand of 40-60 meshes in a mould.
Example 1: preparation of polymer with selective water plugging function
1. Adding 14.0g of acrylamide (accounting for 70 wt% of the total amount of the monomers), 2.0g of 2-acrylamido-2-methylpropanesulfonic acid (accounting for 10 wt% of the total amount of the monomers) shown in a formula (11) and 4.0g of zwitterionic monomer (accounting for 20 wt% of the total amount of the monomers) shown in a formula (12-1) into a heat-preservation polymerization reaction bottle (namely a polymerization bottle), adding 60.0g of deionized water, dissolving to prepare an aqueous solution, and adding sodium hydroxide to adjust the pH to 7.0;
2. sequentially adding 1.0g of EDTA-2Na aqueous solution with the weight percent of 1, 10mg of N, N' -methylene bisacrylamide and 10.0mg of tetramethyl ethylenediamine, and uniformly stirring;
3. controlling the temperature of the aqueous solution at 5 ℃, introducing nitrogen to drive oxygen for 20 minutes, then adding 2.0g of 0.2 weight percent potassium persulfate aqueous solution and 2.0g of 0.1 weight percent sodium bisulfite aqueous solution to initiate reaction, continuing introducing nitrogen for 5 minutes, stopping, and carrying out polymerization reaction for 6 hours after sealing;
4. and taking out the rubber block, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain a white granular selective water plugging polymer sample.
And (3) testing results: the polymer sample had a water blocking rate of 96.8%, an oil blocking rate of 10.1%, and an expansion factor of 100. This shows that the selective water plugging polymer prepared in this example has a significant selective plugging rate for oil/water.
Example 2: preparation of polymer with selective water plugging function
1. Adding 13.0g of acrylamide (accounting for 65 weight percent of the total amount of the monomers), 4.0g of 2-acrylamido-2-methylpropanesulfonic acid (accounting for 20 weight percent of the total amount of the monomers) shown in a formula (11) and 3.0g of zwitterionic monomer (accounting for 15 weight percent of the total amount of the monomers) shown in a formula (12-2) into a heat-preservation polymerization reaction bottle (namely a polymerization bottle), adding 60.0g of deionized water, dissolving to prepare an aqueous solution, and adding sodium hydroxide to adjust the pH to 6.0;
2. sequentially adding 1.0g of EDTA-2Na aqueous solution with the weight percent of 1, 10mg of N, N' -methylene bisacrylamide and 10.0mg of tetramethyl ethylenediamine, and uniformly stirring;
3. controlling the temperature of the aqueous solution at 0 ℃, introducing nitrogen to drive oxygen for 20 minutes, then adding 3.0g of 0.2 weight percent potassium persulfate aqueous solution and 3.0g of 0.1 weight percent sodium bisulfite aqueous solution to initiate reaction, continuing introducing nitrogen for 5 minutes, stopping, and carrying out polymerization reaction for 8 hours after sealing;
4. and taking out the rubber block, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain a white granular selective water plugging polymer sample.
And (3) testing results: the polymer sample had a water blocking ratio of 99.3%, an oil blocking ratio of 7.6%, and an expansion factor of 99.5. This shows that the selective water plugging polymer prepared in this example has a significant selective plugging rate for oil/water.
Example 3: preparation of polymer with selective water plugging function
1. Adding 11.0g of acrylamide (accounting for 55 wt% of the total amount of the monomers), 8.0g of 2-acrylamido-2-methylpropanesulfonic acid (accounting for 40 wt% of the total amount of the monomers) shown in formula (11) and 1.0g of zwitterionic monomer (accounting for 5 wt% of the total amount of the monomers) shown in formula (12-3) into a heat-preservation polymerization reaction bottle (namely a polymerization bottle), adding 60.0g of deionized water, dissolving to prepare an aqueous solution, and adding sodium hydroxide to adjust the pH to 8.0;
2. sequentially adding 1.0g of EDTA-2Na aqueous solution with the weight percent of 1, 20mg of N, N' -methylene bisacrylamide and 10.0mg of tetramethyl ethylenediamine, and uniformly stirring;
3. controlling the temperature of the aqueous solution at 10 ℃, introducing nitrogen to drive oxygen for 20 minutes, then adding 4.0g of 0.2 weight percent potassium persulfate aqueous solution and 4.0g of 0.1 weight percent sodium bisulfite aqueous solution to initiate reaction, continuing introducing nitrogen for 5 minutes, stopping, and carrying out polymerization reaction for 7 hours after sealing;
4. and taking out the rubber block, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain a white granular selective water plugging polymer sample.
And (3) testing results: the polymer sample had a water blocking rate of 94.2%, an oil blocking rate of 9.5%, and an expansion factor of 99.8. This shows that the selective water plugging polymer prepared in this example has a significant selective plugging rate for oil/water.
Example 4: preparation of polymer with selective water plugging function
This example was carried out in a similar manner to example 1, except that the zwitterionic monomer in this example had a structure represented by formula (6-1), and R6Is H and t is 2.
That is, the present embodiment adopts the structure shown in the formula (6-1) with equal weight, and R6The zwitterionic monomer of example 1 was replaced with a zwitterionic monomer of H, t is 2.
The rest is the same as in example 1. A white granular selective water-plugging polymer sample is obtained.
And (3) testing results: the polymer sample had a water blocking ratio of 95.3%, an oil blocking ratio of 9.1%, and an expansion factor of 99.4. This shows that the selective water plugging polymer prepared in this example has a significant selective plugging rate for oil/water.
Example 5: preparation of polymer with selective water plugging function
This example was carried out in a similar manner to example 2, except that the zwitterionic monomer in this example had a structure represented by formula (6-2), and R6Is H, and t is 4.
That is, the present embodiment adopts the structure shown by the formula (6-2) with equal weight, and R6The zwitterionic monomer of example 2 was replaced with a zwitterionic monomer of H, t 4.
The rest is the same as in example 2. A white granular selective water-plugging polymer sample is obtained.
And (3) testing results: the polymer sample had a water blocking ratio of 97.9%, an oil blocking ratio of 9.8%, and an expansion factor of 98.9. This shows that the selective water plugging polymer prepared in this example has a significant selective plugging rate for oil/water.
Example 6: preparation of polymer with selective water plugging function
This example was carried out in a similar manner to example 3, except that the zwitterionic monomer in this example had a structure represented by formula (6-3), and R6Is H, n is 2 and t is 3.
That is, the present embodiment adopts the structure shown in the formula (6-3) with equal weight, and R6The zwitterionic monomer of example 3 was replaced with a zwitterionic monomer of H, n is 2 and t is 3.
The rest is the same as in example 3. A white granular selective water-plugging polymer sample is obtained.
And (3) testing results: the polymer sample had a water blocking rate of 94.0%, an oil blocking rate of 10.6%, and an expansion factor of 99.2. This shows that the selective water plugging polymer prepared in this example has a significant selective plugging rate for oil/water.
Example 7: preparation of polymer with selective water plugging function
This example was carried out in a similar manner to example 1, except that:
the monomers used in this example were varied, and specifically, acrylamide was used in an amount of 13g (65 wt% based on the total amount of the monomers), 2-acrylamido-2-methylpropanesulfonic acid represented by formula (11) was used in an amount of 6.4g (32 wt% based on the total amount of the monomers), and a zwitterionic monomer represented by formula (12-1) (3 wt% based on the total amount of the monomers) was used in an amount of 0.6 g.
The rest of the process was the same as in example 1, and a white granular selective water-plugging polymer sample was obtained.
And (3) testing results: the polymer sample had a water blocking ratio of 90.1%, an oil blocking ratio of 17.0%, and an expansion factor of 94.2. This shows that the selective water plugging polymer prepared in this example has a significant selective plugging rate for oil/water.
Example 8: preparation of polymer with selective water plugging function
This example was carried out in a similar manner to example 1, except that:
the monomers used in this example were different, specifically, acrylamide was used in an amount of 10g (50 wt% based on the total amount of the monomers), 2-acrylamido-2-methylpropanesulfonic acid represented by formula (11) was used in an amount of 5g (25 wt% based on the total amount of the monomers), and a zwitterionic monomer represented by formula (12-1) (25 wt% based on the total amount of the monomers) was used in an amount of 5 g.
The rest of the process was the same as in example 1, and a white granular selective water-plugging polymer sample was obtained.
And (3) testing results: the polymer sample had a water blocking ratio of 91.0%, an oil blocking ratio of 17.6%, and an expansion factor of 95.8. This shows that the selective water plugging polymer prepared in this example has a significant selective plugging rate for oil/water.
Comparative example 1
This comparative example was conducted in a similar manner to example 1 except that the zwitterionic monomer represented by the formula (12-1) was not added in this comparative example and the amount of 2-acrylamido-2-methylpropanesulfonic acid represented by the formula (11) was adjusted to 6.0 g. Specifically, the method comprises the following steps:
1. adding 14.0g of acrylamide (accounting for 70 weight percent of the total amount of the monomers) and 6.0g of 2-acrylamido-2-methylpropanesulfonic acid (accounting for 30 weight percent of the total amount of the monomers) into a heat-preservation polymerization reaction bottle (namely a polymerization bottle), adding 60.0g of deionized water, dissolving to prepare an aqueous solution, and adding sodium hydroxide to adjust the pH value to 7.0;
2. sequentially adding 1.0g of EDTA-2Na aqueous solution with the weight percent of 1, 10mg of N, N' -methylene bisacrylamide and 10.0mg of tetramethyl ethylenediamine, and uniformly stirring;
3. controlling the temperature of the aqueous solution at 5 ℃, introducing nitrogen to drive oxygen for 20 minutes, then adding 2.0g of 0.2 weight percent potassium persulfate aqueous solution and 2.0g of 0.1 weight percent sodium bisulfite aqueous solution to initiate reaction, continuing introducing nitrogen for 5 minutes, stopping, and carrying out polymerization reaction for 6 hours after sealing;
4. and taking out the rubber block, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain a white granular polymer sample.
And (3) testing results: the polymer sample had a water blocking ratio of 80.9%, an oil blocking ratio of 65.8%, and an expansion factor of 65.2. This shows that the polymer prepared in this comparative example is not highly selective in terms of oil/water blocking rate.
From the results of the above examples and comparative examples, it can be seen that the polymer having selective water plugging function prepared by the method of the present invention has excellent selective water plugging and oil non-plugging function.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A polymer with a selective water blocking function is characterized by comprising 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), the structural unit B is a structural unit with a structure shown in a formula (2), and the structural unit C is at least one selected from the structural unit with a structure shown in a formula (3-1), the structural unit with a structure shown in a formula (3-2) and the structural unit with a structure shown in a formula (3-3); wherein, based on the weight of the polymer, the content of the structural unit A is 30-90 wt%, the content of the structural unit B is 5-50 wt%, the content of the structural unit C is 1-30 wt%, and the expansion multiple of the polymer is 75-110;
wherein R is1And R2Each independently is H or C1-C4 alkyl; r3Is C1-C14 alkylene; r4And R5Each independently is H or C1-C4 alkyl, and R4And R5Not H at the same time; m is H, Na or K; r6Is H or C1-C4 alkyl; t is an integer of 1 to 10, and n is an integer of 1 to 6.
2. The polymer of claim 1, wherein the amount of structural unit a is from 40 to 85 wt%, the amount of structural unit B is from 10 to 40 wt%, the amount of structural unit C is from 5 to 20 wt%, and the polymer has a multiple expansion of from 80 to 100, based on the weight of the polymer.
3. The polymer according to claim 1 or 2, wherein the structural unit A is a structural unit having a structure represented by formula (7), the structural unit B is a structural unit having a structure represented by formula (8), and the structural unit C is at least one selected from the group consisting of a structural unit having a structure represented by formula (9-1), a structural unit having a structure represented by formula (9-2), and a structural unit having a structure represented by formula (9-3),
4. a method for preparing the polymer having the selective water shutoff function according to any one of claims 1 to 3, comprising: in the presence of an initiator, a crosslinking agent and water as a solvent, carrying out solution polymerization reaction on a monomer D, a monomer E and a monomer F, wherein the monomer D is a monomer with a structure shown in a formula (4), the monomer E is a monomer with a structure shown in a formula (5), the monomer F is at least one selected from the group consisting of a monomer having a structure represented by formula (6-1), a monomer having a structure represented by formula (6-2) and a monomer having a structure represented by formula (6-3), wherein the monomers D, E and F are used in amounts such that the content of the structural unit A in the prepared polymer is 30-90 wt%, the content of the structural unit B is 5-50 wt%, the content of the structural unit C is 1-30 wt%, and the expansion factor of the prepared polymer is 75-110; the structural unit A is a structural unit with a structure shown in a formula (1), the structural unit B is a structural unit with a structure shown in a formula (2), the structural unit C is at least one selected from the structural unit with a structure shown in a formula (3-1), the structural unit with a structure shown in a formula (3-2) and the structural unit with a structure shown in a formula (3-3),
wherein R is1And R2Each independently is H or C1-C4 alkyl; r3Is C1-C14 alkylene; r4And R5Each independently is H or C1-C4 alkyl, and R4And R5Not H at the same time; m is H, Na or K; r6Is H or C1-C4 alkyl; t is an integer of 1 to 10, and n is an integer of 1 to 6.
5. The process according to claim 4, wherein the monomers D, E and F are used in amounts such that the polymer produced has a content of the structural unit A of from 40 to 85% by weight, a content of the structural unit B of from 10 to 40% by weight and a content of the structural unit C of from 5 to 20% by weight, and such that the polymer produced has a multiple expansion of from 80 to 100.
6. The process according to claim 4 or 5, wherein the crosslinking agent is N, N' -methylenebisacrylamide in an amount of 0.02 to 0.1% by weight based on the total amount of monomer D, monomer E and monomer F.
7. The method according to claim 4 or 5, wherein the monomer D is a monomer having a structure represented by formula (10); the monomer E is a monomer with a structure shown in a formula (11); the monomer F is at least one selected from the group consisting of a monomer having a structure represented by formula (12-1), a monomer having a structure represented by formula (12-2) and a monomer having a structure represented by formula (12-3),
8. the method of claim 4 or 5, wherein the conditions of the solution polymerization reaction comprise: the temperature is 0-30 ℃; the time is 2-15 h.
9. The method of claim 4 or 5, wherein the conditions of the solution polymerization reaction comprise: the temperature is 0-20 ℃; the time is 5-10 h.
10. The method of claim 4 or 5, wherein the initiator comprises at least one of an azo-type initiator, a peroxide-type initiator, and a redox-type initiator; 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 persulfate-sulfite, persulfate-thiourea, persulfate-organic salt and ammonium persulfate-fatty amine.
11. Use of the polymer with selective water plugging function according to any one of claims 1 to 3 as a selective water plugging agent.
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| WO2000053815A1 (en) * | 1999-03-10 | 2000-09-14 | Nalco Chemical Company | A detectable cationic flocculant and method of using same in industrial food processes |
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| CN105086962A (en) * | 2014-05-12 | 2015-11-25 | 中国石油化工股份有限公司 | Drilling fluid with high inhibition property and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2826015A1 (en) * | 2001-06-18 | 2002-12-20 | Schlumberger Services Petrol | Shear viscosifying or gelling fluid for well drilling operations, comprises polymer containing hydrosoluble non-ionic, ionic and hydrophobic or low critical solution temperature functional groups |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0156030A1 (en) * | 1981-12-15 | 1985-10-02 | Calgon Corporation | Aqueous drilling fluid |
| WO2000053815A1 (en) * | 1999-03-10 | 2000-09-14 | Nalco Chemical Company | A detectable cationic flocculant and method of using same in industrial food processes |
| CN104926991A (en) * | 2014-03-19 | 2015-09-23 | 中国石油化工股份有限公司 | Preparation method for amphoteric ion copolymer for well drilling fluid |
| CN103923254A (en) * | 2014-04-17 | 2014-07-16 | 中国海洋石油总公司 | Salt-thickened water-soluble branched polymer as well as preparation method and application thereof |
| CN105086962A (en) * | 2014-05-12 | 2015-11-25 | 中国石油化工股份有限公司 | Drilling fluid with high inhibition property and preparation method and application thereof |
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