CN116063619B - Acrylamide copolymer containing hydroxyl-terminated long-chain structure, and preparation method and application thereof - Google Patents
Acrylamide copolymer containing hydroxyl-terminated long-chain structure, and preparation method and application thereof Download PDFInfo
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- 229920006322 acrylamide copolymer Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims description 76
- 239000003999 initiator Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 239000007864 aqueous solution Substances 0.000 claims description 32
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000008139 complexing agent Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 230000000977 initiatory effect Effects 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 230000033558 biomineral tissue development Effects 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 238000011161 development Methods 0.000 abstract description 13
- 239000002332 oil field water Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 41
- 239000003921 oil Substances 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 238000007664 blowing Methods 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 12
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 108060003393 Granulin Proteins 0.000 description 1
- UWPAYIRSOCALJW-UHFFFAOYSA-N NC(=S)N.CO.CO Chemical group NC(=S)N.CO.CO UWPAYIRSOCALJW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 102000017941 granulin Human genes 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- YIEDSISPYKQADU-UHFFFAOYSA-N n-acetyl-n-[2-methyl-4-[(2-methylphenyl)diazenyl]phenyl]acetamide Chemical compound C1=C(C)C(N(C(C)=O)C(=O)C)=CC=C1N=NC1=CC=CC=C1C YIEDSISPYKQADU-UHFFFAOYSA-N 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—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 polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of high-temperature high-salt oilfield water flooding development, and discloses an acrylamide copolymer containing a hydroxyl-terminated long-chain structure, and a preparation method and application thereof. The 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), wherein the content of the structural unit A is 79-95 wt%, the content of the structural unit B is 4-20 wt%, the content of the structural unit C is 0.1-2 wt%, and p is an integer of 1-5 based on the weight of the acrylamide copolymer; the copolymer can enter the deep part of the oil reservoir to achieve the purpose of deep profile control;
Description
Technical Field
The invention relates to the technical field of high-temperature high-salt oilfield water injection development, in particular to an acrylamide copolymer containing hydroxyl-terminated long-chain structures, and a preparation method and application thereof.
Background
Along with the entering of the middle and later development stages of the oil fields in China, a plurality of oil fields enter a high water-containing period, and the water control, oil stabilization and the improvement of the recovery ratio become the main problems at present. In the initial stage of profile control and water shutoff, high-strength plugging agents are mainly used, and the action mechanism is mainly physical barriers or blockage in near-wellbore zones. However, with the increase of profile control and water shutoff rounds of oil fields, the difficulty in improving the crude oil recovery ratio by controlling water and stabilizing oil is gradually outstanding, and the conventional shallow profile control and near wellbore area transformation can not meet the requirements of oil field development. The deep profile control technology is taken as a main technical measure for improving development effect and controlling water and stabilizing oil, and has good application effect in a plurality of oil fields at home and abroad.
At present, with the continuous deepening of the development degree of the oil field, the recoverable reserves of the conventional oil field are smaller and smaller, the deep mining value is lower and the people have to throw the eyes to the oil field under unconventional and severe conditions such as high temperature and high salt. However, in the face of high-temperature high-salinity and extra-high water-cut oil reservoirs, the problems of serious flooding of oil wells, complex oil-water relationship and the like are solved, and conventional profile control agents such as high-strength gel plugging agents, inorganic particle plugging agent systems and the like can only act on near-wellbore zones, so that deep profile control is difficult to achieve, and the field implementation effect is poor.
Therefore, the development of the novel deep profile control material has important practical significance and wide application prospect for improving the recovery ratio of the high-temperature high-salt ultra-high water-containing period oil reservoir.
Disclosure of Invention
The invention aims to overcome the problems that in the prior art, aiming at high-temperature high-salt and extra-high water-containing oil reservoirs, the existing profile control agent is difficult to realize deep profile control and poor in effect, and provides an acrylamide copolymer containing hydroxyl-terminated long-chain structures, a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides an acrylamide copolymer containing a hydroxyl-terminated long chain structure, the copolymer containing 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 a structural unit having a structure represented by formula (3); wherein the content of the structural unit A is 79-95 wt%, the content of the structural unit B is 4-20 wt% and the content of the structural unit C is 0.1-2 wt% based on the weight of the acrylamide copolymer;
wherein p is an integer of 1 to 5.
In a second aspect, the present invention provides a method for producing an acrylamide copolymer having a hydroxyl-terminated long chain structure, the method comprising: under the condition of solution polymerization, in the presence of a composite initiation system, carrying out polymerization reaction on a monomer mixture in water, wherein the monomer mixture contains a monomer X, a functional monomer Y and acrylamide, the monomer X is a monomer with a structure shown in a formula (4), and the functional monomer Y is a monomer with a structure shown in a formula (5); the composite initiation system comprises a main initiator and a co-initiator, wherein the main initiator has a structure shown in a formula (6), and the co-initiator has a structure shown in a formula (7); and the content of the acrylamide is 79-95 wt%, the content of the monomer X is 4-20 wt% and the content of the functional monomer Y is.01-2 wt% based on the total amount of the monomer mixture;
wherein p is an integer of 1 to 5, and m is an integer of 1 to 6.
In a third aspect, the present invention provides an acrylamide copolymer containing a hydroxyl-terminated long chain structure prepared by the aforementioned preparation method.
The fourth aspect of the invention provides an application of the acrylamide copolymer containing the hydroxyl-terminated long-chain structure in a high-temperature high-salt ultrahigh water-containing oil reservoir.
Through the technical scheme, the acrylamide copolymer containing the hydroxyl-terminated long-chain structure has higher viscosity under the oil reservoir condition of high temperature, high salt and ultra-high water content period, has good fluidity under certain injection pressure, can enter the deep part of the oil reservoir, plays roles of removing and blocking, and achieves the purpose of deep profile control and flooding.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides an acrylamide copolymer having a hydroxyl-terminated long-chain structure, the copolymer 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 a structural unit having a structure represented by formula (3); wherein the content of the structural unit A is 79-95 wt%, the content of the structural unit B is 4-20 wt% and the content of the structural unit C is 0.1-2 wt% based on the weight of the acrylamide copolymer;
wherein p is an integer of 1 to 5.
The inventors of the present invention unexpectedly found that: the composite initiation system containing the main initiator and the auxiliary initiator is adopted, so that the copolymerization of the acrylamide, the monomer X and the functional monomer Y can be smoothly initiated under the normal temperature condition, and the acrylamide copolymer with high viscosity is obtained. The inventor of the invention discovers that, on one hand, in the composite initiation system, the main initiator and the auxiliary initiator can generate free radicals under the synergistic effect, and can initiate the stable polymerization of acrylamide and comonomer, so that the temperature of the polymerization system is slowly increased; on the other hand, in the polymerization process, the auxiliary initiator is dimethanol thiourea, and has a molecular structure similar to that of the functional monomer Y, so that the free radical polymerization activity of the functional monomer Y can be improved, chain transfer reaction of thiourea groups in the structural unit of the functional monomer Y can be performed, a polyacrylamide copolymer containing hydroxyl-terminated long-chain structures can be formed, and further, the high-viscosity acrylamide copolymer can be obtained, and can be used as an acrylamide deep profile control material.
According to the invention, p is preferably an integer from 1 to 3; according to the invention, by adopting the preferable scheme, the acrylamide copolymer has higher viscosity, can reach the deep part of an oil reservoir, has better water shutoff effect, and is more beneficial to improving the recovery ratio of crude oil.
According to the present invention, the content of the structural unit A is preferably 79 to 95% by weight, the content of the structural unit B is preferably 4 to 20% by weight, and the content of the structural unit C is preferably 0.1 to 2% by weight, based on the weight of the acrylamide copolymer.
According to the invention, the aqueous solution of the acrylamide copolymer has an apparent viscosity of 70.9 to 96.7 mPas, preferably 84.8 to 96.7 mPas, at 90℃with a calcium-magnesium ion concentration of 10000mg/L and a mineralization of 150000 mg/L.
In the invention, the apparent viscosity is obtained by measuring the aqueous solution of the copolymer by using a Brookfield viscometer of Bowler's company in the United states under the conditions that the concentration is 10000mg/L, the mineralization degree is 150000mg/L and the temperature is 90 ℃.
According to the invention, the mineralization degree in the invention is Na in simulated formation water + 、K + 、Ca 2+ 、Mg 2+ 、Cl - 、SO 4 2- 、CO 3 2- Sum of the inorganic ion contents.
According to the invention, the acrylamide residual monomer content is < 0.05 wt.%; the acrylamide residual monomer content in the copolymer was determined using a Waters liquid chromatograph.
In a second aspect, the present invention provides a method for producing an acrylamide copolymer having a hydroxyl-terminated long chain structure, the method comprising: under the condition of solution polymerization, in the presence of a composite initiation system, carrying out polymerization reaction on a monomer mixture in water, wherein the monomer mixture contains a monomer X, a functional monomer Y and acrylamide, the monomer X is a monomer with a structure shown in a formula (4), and the functional monomer Y is a monomer with a structure shown in a formula (5); the composite initiation system comprises a main initiator and a co-initiator, wherein the main initiator has a structure shown in a formula (6), and the co-initiator has a structure shown in a formula (7); and the content of the acrylamide is 79-95 wt%, the content of the monomer X is 4-20 wt% and the content of the functional monomer Y is 0.1-2 wt% based on the total amount of the monomer mixture;
wherein p is an integer of 1 to 5, and m is an integer of 1 to 6.
According to the invention, p is preferably an integer from 1 to 3 and m is an integer from 2 to 5; the prepared acrylamide copolymer has higher viscosity, can reach deep oil reservoir, has better water shutoff effect and is more beneficial to improving the crude oil recovery ratio.
According to the present invention, the acrylamide is preferably contained in an amount of 90 to 95% by weight, the monomer X is preferably contained in an amount of 4 to 8% by weight, and the functional monomer Y is preferably contained in an amount of 1 to 2% by weight, based on the total amount of the monomer mixture.
According to the invention, the monomers are converted approximately completely into the corresponding structural units contained in the acrylamide copolymer, and the amount of the monomers can be identical to the content of the corresponding structural units contained in the acrylamide copolymer.
According to the invention, the monomer mixture is used in an amount of 20 to 40% by weight based on the total amount of monomer mixture and water; in the present invention, the water is preferably deionized water.
According to the invention, the main initiator is used in an amount of 0.02 to 0.2% by weight and the co-initiator is used in an amount of 0.02 to 0.2% by weight, based on the total amount of the monomer mixture; preferably, the main initiator is an aqueous solution with a mass concentration of 1%; the auxiliary initiator is an aqueous solution with the mass concentration of 1%.
According to the present invention, it is preferable to add a complexing agent to prevent the influence of metal ions on the polymerization reaction, and therefore, it is preferable that the polymerization reaction is performed in the presence of the complexing agent.
According to the invention, the complexing agent is preferably used in an amount of 0.01 to 0.1% by weight, relative to the total amount of the monomer mixture; more preferably, the complexing agent is ethylenediamine tetraacetic acid and/or disodium ethylenediamine tetraacetate; still more preferably, the complexing agent is sodium ethylenediamine tetraacetate.
According to the method of the present invention, preferably, the polymerization reaction is carried out under an inert atmosphere, which means an atmosphere of an inert gas which is a gas which does not react with the raw materials and the products, and may be at least one of nitrogen gas or a gas of a group zero element in the periodic table, which is conventional in the art, preferably, nitrogen and/or argon gas.
According to the invention, the introducing time of the complexing agent and the initiator is not limited; preferably, the method comprises the steps of:
(1) Mixing the monomer mixture with water, and regulating the pH value of a polymerization system to be 6-10;
(2) Mixing the material obtained in the step (1) with a complexing agent;
(3) And (3) mixing the material obtained in the step (2) with a composite initiation system under the condition of solution polymerization in an inert atmosphere, and carrying out polymerization reaction.
According to the present invention, the conditions of the solution polymerization include: the temperature is 10-40deg.C, preferably 10-30deg.C; the time is 8-16h, preferably 8-12h; in the present invention, the time of the solution polymerization means a time for continuing to maintain the polymerization after the polymerization system is automatically heated to a high point.
According to the present invention, preferably, the conditions of the solution polymerization further include: the pH of the polymerization system is 6-10. The above pH value may be obtained by adding a pH adjuster to the polymerization system, and the pH adjuster for adjusting the pH value may be various pH adjusters commonly used in the art, and may be, for example, a base and/or a basic salt. Preferably, the base may be an alkali metal element-containing base and/or aqueous ammonia; preferably, the salt may be sodium carbonate and/or potassium carbonate.
According to the invention, the pH of the polymerization system is preferably adjusted with a base. More preferably, the base is selected from NaOH or KOH, preferably NaOH.
According to the present invention, preferably, the method further comprises: granulating the copolymer obtained after the polymerization reaction, and then carrying out hydrolysis, drying, crushing and sieving treatment by using granulesten, wherein the hydrolysis is carried out so that the degree of hydrolysis of the copolymer obtained after the polymerization reaction is 25-29%.
According to the invention, the conditions of the hydrolysis include: the temperature is 70-90 ℃ and the time is 1-4h.
In the present invention, preferably, the mixing in step (2) is preferably performed under stirring so that the respective materials are completely dissolved. In the present invention, it is preferable that the person skilled in the art can blow an inert atmosphere to remove oxygen after the completion of the mixing in the step (2), so that the polymerization in the step (3) is performed under an inert atmosphere. The time for the inert atmosphere to be blown in 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 reintroduced when the desired temperature for the solution polymerization described in 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 copolymer obtained after step (3) is generally gel-like and may be optionally pelletized according to practical requirements.
In the present invention, the apparatus for the polymerization is not limited as long as the polymerization can be carried out; for example, a 5L Dewar polymerization reactor.
According to a particularly preferred embodiment of the present invention, a process for preparing an acrylamide copolymer comprises:
step 1, weighing acrylamide, a monomer X and a functional monomer Y, adding the acrylamide, the monomer X and the functional monomer Y into a polymerization bottle to prepare an aqueous solution, and regulating the pH value of the aqueous solution to be 6-10 by liquid alkali;
the monomer X is trimethylol methacrylamide, and the structural formula is as follows:
the structural formula of the functional monomer Y is as follows:
wherein p is an integer of 1 to 3;
step 2, adding a weighed complexing agent into the aqueous solution, placing the aqueous solution in a water bath at 10-40 ℃, and blowing nitrogen for more than 30 minutes;
step 3, under the protection of nitrogen, sequentially adding a main initiator A and a co-initiator B into the aqueous solution, continuously blowing nitrogen until the solution thickens, namely starting the initiation, and maintaining the polymerization for 8-12 hours after sealing to obtain a copolymer gel block;
the structural formulas of the main initiator A and the auxiliary initiator B are respectively as follows:
(A) Wherein m is an integer of 2 to 5;
step 4, taking out the gel block, granulating, and hydrolyzing with granulin at 70-90 ℃ for 1-4 hours;
and step 5, after hydrolysis, drying, crushing and screening the colloidal particles to obtain a deep profile control material sample for water flooding development.
In a third aspect, the present invention provides an acrylamide copolymer containing a hydroxyl-terminated long chain structure prepared by the aforementioned preparation method.
In the present invention, the copolymer has the same structure and composition as those of the aforementioned copolymer, and is not described herein.
The fourth aspect of the invention provides an application of the acrylamide copolymer containing the hydroxyl-terminated long-chain structure in a high-temperature high-salt ultrahigh water-containing oil reservoir.
According to the invention, the high-temperature high-salt ultra-high water-bearing oil reservoir refers to a reservoir with the temperature of more than 85 ℃, the mineralization degree of more than 100000mg/L and the comprehensive water content of more than 95%.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
the apparent viscosity of the copolymer sample solution at a mineralization degree of 150000mg/L, in which calcium magnesium ions are 10000mg/L (high salt), was measured with a Brookfield viscometer at a specified test temperature (90 ℃); the acrylamide-containing monomer content in the copolymer was determined using a Waters liquid chromatograph.
Example 1
This example is intended to illustrate an acrylamide copolymer prepared by the process of the invention.
(1) 474g of acrylamide (the mass content is 79%), 120g of trimethylol methacrylamide (the mass content is 20%) and 6g of functional monomer Y (p=2 and the mass content is 1%) are added into a polymerization bottle, 1800g of deionized water is added, fully stirred and dissolved to prepare an aqueous solution, and then liquid alkali is added to adjust the pH to 7.0;
(2) Adding 0.2g of complexing agent, placing in a water bath at 15 ℃, and blowing nitrogen for more than 30 minutes;
(3) Under the protection of nitrogen, sequentially adding 40g of a main initiator A (m=2) aqueous solution and 60g of a co-initiator B aqueous solution into the aqueous solution, continuously blowing nitrogen until the solution becomes thick, and performing sealed polymerization for 12 hours to obtain a copolymer gel block;
(4) Taking out the gel block, granulating, adding 84.5g of granulexite, and hydrolyzing at 80 ℃ for 3 hours;
(5) After hydrolysis, the colloidal particles are dried, crushed and screened to obtain the deep profile control material sample ZTQ1 for water flooding development.
Example 2
This example is intended to illustrate an acrylamide copolymer prepared by the process of the invention.
(1) 540g of acrylamide (the mass content is 90%), 48g of trimethylol methacrylamide (the mass content is 8%) and 12g of functional monomer Y (p=1 and the mass content is 2%) are added into a polymerization bottle, 1800g of deionized water is added, fully stirred and dissolved to prepare an aqueous solution, and then liquid alkali is added to adjust the pH to 7.5;
(2) Adding 0.06g of complexing agent, placing in a water bath at 30 ℃, and blowing nitrogen for more than 30 minutes;
(3) Under the protection of nitrogen, sequentially adding 102g of a main initiator A (m=3) aqueous solution and 120g of a co-initiator B aqueous solution into the aqueous solution, continuously blowing nitrogen until the solution becomes thick, and performing sealed polymerization for 9 hours to obtain a copolymer gel block;
(4) Taking out the gel block, granulating, adding 94.6g of granulexite, and hydrolyzing at 85 ℃ for 2 hours;
(5) And after hydrolysis, drying, crushing and screening the colloidal particles to obtain a deep profile control material sample ZTQ2 for water flooding development.
Example 3
This example is intended to illustrate an acrylamide copolymer prepared by the process of the invention.
(1) 570g of acrylamide (the mass content is 95%), 29.4g of trimethylol methacrylamide (the mass content is 4.9%) and 0.6g of functional monomer Y (p=3 and the mass content is 0.1%) are added into a polymerization bottle, 1800g of deionized water is added, fully stirred and dissolved to prepare an aqueous solution, and then liquid alkali is added to adjust the pH to 6.2;
(2) Adding 0.6g of complexing agent, placing in a water bath at 20 ℃, and blowing nitrogen for more than 30 minutes;
(3) Under the protection of nitrogen, sequentially adding 12g of a main initiator A (m=5) aqueous solution and 12g of a co-initiator B aqueous solution into the aqueous solution, continuously blowing nitrogen until the solution becomes thick, and performing sealed polymerization for 8 hours to obtain a copolymer gel block;
(4) Taking out the gel block, granulating, adding 98.03g of granulexite, and hydrolyzing at 90 ℃ for 1 hour;
(5) And after hydrolysis, drying, crushing and screening the colloidal particles to obtain a deep profile control material sample ZTQ3 for water flooding development.
Example 4
This example is intended to illustrate an acrylamide copolymer prepared by the process of the invention.
(1) 570g of acrylamide (the mass content is 95%), 24g of trimethylol methacrylamide (the mass content is 4%) and 6g of functional monomer Y (p=1 and the mass content is 1.0%) are added into a polymerization bottle, 1800g of deionized water is added, fully stirred and dissolved to prepare an aqueous solution, and then liquid alkali is added to adjust the pH to 9.5;
(2) Adding 0.3g of complexing agent, placing in a water bath at 10 ℃, and blowing nitrogen for more than 30 minutes;
(3) Under the protection of nitrogen, sequentially adding 120g of main initiator A (m=2) aqueous solution and 80g of auxiliary initiator B aqueous solution into the aqueous solution, continuously blowing nitrogen until the solution becomes thick, and performing sealed polymerization for 10 hours to obtain a copolymer gel block;
(4) Taking out the gel block, granulating, adding 91.3g of granulexite, and hydrolyzing at 80 ℃ for 4 hours;
(5) And after hydrolysis, drying, crushing and screening the colloidal particles to obtain a deep profile control material sample ZTQ for water flooding development.
Example 5
This example is intended to illustrate an acrylamide copolymer prepared by the process of the invention.
(1) 558g of acrylamide (with the mass content of 93%), 33g of trimethylol methacrylamide (with the mass content of 5.5%) and 9g of functional monomer Y (p=1 and with the mass content of 1.5%) are added into a polymerization bottle, 1800g of deionized water is added, fully stirred and dissolved to prepare an aqueous solution, and then liquid alkali is added to adjust the pH to 7.2;
(2) Adding 0.5g of complexing agent, placing in a water bath at 18 ℃, and blowing nitrogen for more than 30 minutes;
(3) Under the protection of nitrogen, sequentially adding 80g of main initiator A (m=2) aqueous solution and 94g of auxiliary initiator B aqueous solution into the aqueous solution, continuously blowing nitrogen until the solution becomes thick, and performing sealed polymerization for 11 hours to obtain a copolymer gel block;
(4) Taking out the gel block, granulating, adding 86.2g of granulexite, and hydrolyzing at 80 ℃ for 3 hours;
(5) And after hydrolysis, drying, crushing and screening the colloidal particles to obtain a deep profile control material sample ZTQ for water flooding development.
Example 6
This example is intended to illustrate an acrylamide copolymer prepared by the process of the invention.
An acrylamide copolymer was synthesized in the same manner as in example 1 except that: "functional monomer Y (p=2)" is replaced with "functional monomer Y (p=5)".
And obtaining an acrylamide deep profile control material sample ZTQ.
Example 7
This example is intended to illustrate an acrylamide copolymer prepared by the process of the invention.
An acrylamide copolymer was synthesized in the same manner as in example 1 except that: "40g of the main initiator a (m=2)" was replaced with "40g of the main initiator a (m=6)".
And obtaining an acrylamide deep profile control material sample ZTQ.
Comparative example 1
An acrylamide copolymer was synthesized in the same manner as in example 1 except that: the functional monomer Y is not added, and the binary copolymer D1 of the acrylamide and the trimethylol methacrylamide is prepared.
Comparative example 2
An acrylamide copolymer was synthesized in the same manner as in example 1 except that: the composite initiation system of the main initiator A and the auxiliary initiator B is replaced by the composite initiation system composed of potassium persulfate and sodium bisulfite.
As a result, copolymer D2 was produced.
Comparative example 3
An acrylamide copolymer was synthesized in the same manner as in example 1 except that: "474g of acrylamide (mass content: 79%), 120g of trimethylol methacrylamide (mass content: 20%) and 6g of functional monomer Y (p=2, mass content: 1%)" were replaced by "402g of acrylamide (mass content: 67%), 150g of trimethylol methacrylamide (mass content: 25%) and 48g of functional monomer Y (p=2, mass content: 8%)".
As a result, copolymer D3 was produced.
Test case
The injection amount (PV number, maximum injection amount not exceeding 20 PV) and the blocking rate of the copolymer sample solutions prepared in the test examples and comparative examples were tested at 90℃by the in-house core-matrix test at an injection pressure of 8MPa, and the injection property and flowability thereof were studied, and the results are shown in Table 1.
TABLE 1
Remarks: the test conditions for apparent viscosity in the table are: copolymer concentration 2000mg/L, ULA rotor, shear rate 7.34s -1 。
As can be seen from the results in Table 1, the acrylamide copolymer prepared by the invention in examples 1-7 has higher viscosity in high-temperature high-salt and ultra-high water-containing period oil reservoirs, has good fluidity under certain injection pressure, and can enter the deep part of the oil reservoirs to achieve the purpose of deep profile control.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. An acrylamide copolymer containing a hydroxyl-terminated long-chain structure, which comprises a structural unit A, a structural unit B and a structural unit C, and is characterized in that 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 a structural unit with a structure shown in a formula (3); wherein the content of the structural unit A is 79-95 wt%, the content of the structural unit B is 4-20 wt% and the content of the structural unit C is 0.1-2 wt% based on the weight of the acrylamide copolymer;
wherein p is an integer of 1 to 5.
2. The copolymer of claim 1, wherein p is an integer from 1 to 3;
and/or, based on the weight of the acrylamide copolymer, the content of the structural unit A is 90-95 wt%, the content of the structural unit B is 4-8 wt%, and the content of the structural unit C is 1-2 wt%.
3. The copolymer according to claim 1 or 2, wherein the aqueous solution of the acrylamide copolymer has an apparent viscosity of 70.9-96.7 mPa-s and an acrylamide residual monomer content of < 0.05% by weight at 90 ℃ with a calcium magnesium ion concentration of 10000mg/L and a mineralization of 150000 mg/L.
4. A method for preparing an acrylamide copolymer having a hydroxyl-terminated long chain structure, the method comprising: under the condition of solution polymerization, in the presence of a composite initiation system, carrying out polymerization reaction on a monomer mixture in water, wherein the monomer mixture contains a monomer X, a functional monomer Y and acrylamide, the monomer X is a monomer with a structure shown in a formula (4), and the functional monomer Y is a monomer with a structure shown in a formula (5); the composite initiation system comprises a main initiator and a co-initiator, wherein the main initiator has a structure shown in a formula (6), and the co-initiator has a structure shown in a formula (7); and the content of the acrylamide is 79-95 wt%, the content of the monomer X is 4-20 wt% and the content of the functional monomer Y is 0.1-2 wt% based on the total amount of the monomer mixture;
wherein p is an integer of 1 to 5, and m is an integer of 1 to 6.
5. The method of claim 4, wherein p is an integer from 1 to 3 and m is an integer from 2 to 5;
and/or, the content of the acrylamide is 90-95 wt%, the content of the monomer X is 4-8 wt%, and the content of the functional monomer Y is 1-2 wt%, based on the total amount of the monomer mixture.
6. The method of claim 4 or 5, wherein the monomer mixture is used in an amount of 20-40% by weight of the total amount of monomer mixture and water;
and/or the main initiator is used in an amount of 0.02 to 0.2 wt% and the auxiliary initiator is used in an amount of 0.02 to 0.2 wt% based on the total amount of the monomer mixture;
and/or the main initiator is an aqueous solution with the mass concentration of 1%; the auxiliary initiator is an aqueous solution with the mass concentration of 1%.
7. The method of claim 4, wherein the polymerization is performed in the presence of a complexing agent;
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;
the complexing agent is ethylenediamine tetraacetic acid and/or disodium ethylenediamine tetraacetate;
and/or, the polymerization is carried out under an inert atmosphere;
and/or the method comprises the steps of:
(1) Mixing the monomer mixture with water, and regulating the pH value of a polymerization system to be 6-10;
(2) Mixing the material obtained in the step (1) with a complexing agent;
(3) And (3) mixing the material obtained in the step (2) with a composite initiation system under the condition of solution polymerization in an inert atmosphere, and carrying out polymerization reaction.
8. The method of claim 4 or 7, wherein the conditions of the solution polymerization comprise: the temperature is 10-40 ℃; the time is 8-16h;
adjusting the pH value of the polymerization system by adopting alkali;
the base is selected from NaOH and/or KOH;
and/or, the method further comprises: granulating the copolymer obtained after the polymerization reaction, and then carrying out hydrolysis, drying, crushing and screening treatment by using granalkali, wherein the hydrolysis ensures that the hydrolysis degree of the copolymer obtained after the polymerization reaction is 25-29%;
the conditions of the hydrolysis include: the temperature is 70-90 ℃ and the time is 1-4h.
9. The method of claim 8, wherein the conditions of the solution polymerization comprise: the temperature is 10-30 ℃; the time is 8-12h.
10. An acrylamide copolymer containing a hydroxyl-terminated long chain structure produced by the production method according to any one of claims 4 to 9.
11. Use of an acrylamide copolymer containing hydroxyl-terminated long chain structures according to any one of claims 1-3 and 10 in high temperature high salt extra-high water phase reservoirs.
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