CN116064010B - Raw material composition of high-temperature-resistant high-salt plugging agent, preparation method and application - Google Patents
Raw material composition of high-temperature-resistant high-salt plugging agent, preparation method and application Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000002994 raw material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 20
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 15
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000013557 residual solvent Substances 0.000 claims abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 20
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006136 alcoholysis reaction Methods 0.000 claims description 7
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 7
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 235000010350 erythorbic acid Nutrition 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229940026239 isoascorbic acid Drugs 0.000 claims description 3
- ZWRLWJAFBLTMSQ-UHFFFAOYSA-N Docosa-7,10,14-triensaeure Natural products C1C(C)=C2CC(C)(C)CC2C(O)C2=COC=C21 ZWRLWJAFBLTMSQ-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003623 enhancer Substances 0.000 claims description 2
- YKASHPSKFYVZRC-UHFFFAOYSA-M furan-2-ylmethyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CC1=CC=CO1 YKASHPSKFYVZRC-UHFFFAOYSA-M 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 230000005465 channeling Effects 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 46
- 239000002981 blocking agent Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000009815 Momordica Nutrition 0.000 description 1
- 241000218984 Momordica Species 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
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Abstract
The invention relates to a raw material composition of a high-temperature-resistant high-salt plugging agent, a preparation method and application. The raw material composition of the high-temperature-resistant high-salt plugging agent comprises a salt-resistant acrylamide polymer, a cross-linking agent, an deoxidizer and a reinforcing agent; a solvent may be further included. When the plugging agent is prepared, firstly, adding the reinforcing agent into part of the solvent, and fully dissolving to obtain reinforcing agent solution; adding a salt-resistant acrylamide polymer into the residual solvent, and fully dissolving to obtain a salt-resistant acrylamide polymer solution; then adding the reinforcing agent solution for mixing to obtain a mixed solution; and fully mixing the mixed solution with a cross-linking agent and an deoxidizing agent to obtain the high-temperature-resistant high-salt plugging agent. The high-temperature-resistant high-salt plugging agent has good application in oil reservoir exploitation, in particular in carbonate oil reservoir exploitation, and can effectively plug a water channeling passage in a longer time range under the environments of higher temperature, higher mineralization degree and high calcium and magnesium ions, in particular to plug a high water-containing well of an ultra-deep well.
Description
Technical Field
The invention relates to the technical field of petroleum exploitation, in particular to a raw material composition of a high-temperature-resistant high-salt plugging agent, a preparation method and application.
Background
Carbonate reservoirs are widely distributed worldwide, and the oil gas ascertained recoverable reserves of the carbonate reservoirs account for 50.6% of the total reserves of the world, so that the carbonate reservoirs have important significance for increasing oil gas production and storage of the world. The carbonate rock oil gas distribution in China is mainly located in a Tarim basin, an Erdos basin and the like. Compared with sandstone oil reservoirs, carbonate oil reservoirs can quickly meet water, and oil and gas yield can be quickly reduced after water flooding. The water control and oil stabilization by using the water shutoff technology is the most common technological measure at present, and has a certain effect in the middle east oil field. However, for carbonate reservoirs, the reservoir conditions are more severe, and the reservoir is generally buried in ultra-deep and high-temperature and high-salinity. Taking a Tahe oil field as an example, most oil reservoirs have burial depths of more than 4000m, main reservoir temperature of more than 125 ℃, stratum water mineralization degree of up to 200000mg/L and high calcium-magnesium ion content (Ca 2+,Mg2+ is 5-8 g/L).
The conventional plugging agent mainly comprises resins, precipitates, foams and gels, wherein the conventional plugging agent is widely applied to the gels. The plugging agent is mainly prepared by taking polyacrylamide aqueous solution as a thickening agent, phenolic resin or metallic chromium as a crosslinking agent, compounding and injecting the plugging agent into a stratum, and in-situ crosslinking to form gel in the depth of the stratum so as to plug water. The plugging agent has good oil-water selectivity and toughness, but has poor temperature resistance and salt resistance, and especially has the problems of poor tolerance, short plugging validity period and the like because of rapid syneresis under the influence of high mineralization degree and high calcium and magnesium ions.
Therefore, the preparation of the plugging agent with high temperature resistance and high salt resistance has important significance.
Disclosure of Invention
In order to solve the problem that the existing gel plugging agent cannot be effectively applied to environments with higher temperature, higher mineralization degree and higher calcium and magnesium ions and realize long-time water plugging, the invention provides a raw material composition of a high-temperature-resistant high-salt plugging agent, a preparation method and application. The raw material composition or the plugging agent of the high-temperature and high-salt resistant plugging agent can effectively plug a water channeling passage in a longer time range under the environments of higher temperature, higher mineralization degree and high calcium and magnesium ions, and particularly aims at plugging ultra-deep wells and high-water-content wells.
One of the purposes of the invention is to provide a raw material composition of a high-temperature-resistant high-salt plugging agent, which comprises a salt-resistant acrylamide polymer, a cross-linking agent, an oxygen scavenger and a reinforcing agent;
the reinforcing agent is polyvinyl alcohol;
The mass ratio of the salt-tolerant acrylamide polymer to the cross-linking agent to the deoxidizing agent to the reinforcing agent is (0.4-1.5): (0.6-3): (0.01-0.5): (0.02-0.8), preferably (0.6-1.2): (0.8-2): (0.05-0.3): (0.05-0.5). The weight ratio of the components may be any ratio of the values of points in the range.
The components in the raw material composition of the high-temperature-resistant high-salt plugging agent can be stored independently or in a mixed mode. The high-temperature-resistant high-salt plugging agent raw material composition needs to have a solvent when in use, but can be sold as a product when not containing the solvent, and can be matched with a preset amount of solvent when in use.
The plugging agent raw material composition for profile control and water plugging of the high-temperature and high-salt oil reservoir can be added with conventional substances in the field according to the use requirement and the conventional dosage.
In the present invention, the kind of the salt-tolerant acrylamide polymer may be selected with reference to the prior art. For the present invention, the salt-tolerant acrylamide polymer is preferably at least one selected from the group consisting of an acrylamide homopolymer, an N, N-dimethylacrylamide homopolymer, an acrylamide/2-acrylamide-2-methylpropanesulfonic acid copolymer (AM/AMPS copolymer), an acrylamide/N, N-dimethylacrylamide copolymer, an acrylamide/N-vinylpyrrolidone copolymer, an N, N-dimethylacrylamide/N-vinylpyrrolidone copolymer, and an acrylamide/N, N-dimethylacrylamide/N-vinylpyrrolidone copolymer.
In the present invention, the salt-tolerant acrylamide polymer preferably has a viscosity average molecular weight of 600 to 1500 tens of thousands, more preferably 800 to 1200 tens of thousands.
Preferably, the method comprises the steps of,
The cross-linking agent comprises a cross-linking agent I and a cross-linking agent II;
the cross-linking agent is at least one selected from phenolic substances; preferably at least one selected from catechol, resorcinol and hydroquinone;
The cross-linking agent II is at least one selected from aldehydes, amines or alcohols; preferably at least one from among formaldehyde, glyoxal, hexamethylenetetramine and furanol
According to the invention, the crosslinking agent can further improve the gel strength and the blocking performance of the high-temperature-resistant high-salt-resistant high-calcium magnesium ion blocking agent.
In the present invention, phenolic, aldehyde, amine or alcohol materials refer to materials that provide phenols, aldehydes, amines or alcohols, respectively.
Preferably, the method comprises the steps of,
The mass ratio of the first cross-linking agent to the second cross-linking agent is 1:0.5-1.5.
In the present invention, the kind and amount of the oxygen scavenger can be selected with reference to the prior art. For the present invention, preferably, the oxygen scavenger is at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium dithionite, isoascorbic acid and thiourea.
Preferably, the method comprises the steps of,
The alcoholysis degree of the polyvinyl alcohol is 84-99%;
The average molecular weight of the polyvinyl alcohol is 2 ten thousand to 13 ten thousand.
In the present invention, one or more of polyvinyl alcohol type 0588, 1788, 1795, 1799, 2099, 2488, 2499, 2688 or 2699 is included, preferably 1795.
It is another object of the present invention to provide a high temperature and high salt resistant plugging agent comprising the raw material composition and solvent of the high temperature and high salt resistant plugging agent of one of the objects of the present invention.
In the present invention, the solvent is a solvent commonly used in the prior art as a blocking agent, and the choice thereof is not particularly limited.
Preferably, the method comprises the steps of,
The solvent comprises water; the water can be natural water and artificial water, the natural water can be river, lake, atmospheric water, seawater, underground water and the like, and the artificial water can be tap water, distilled water, deionized water or heavy water.
In the present invention, water is used as a solvent and reaction medium for the blocking agent. Generally, in practical applications, the water used is often water at the oilfield location or its corresponding simulated brine. Preferably, the mineralization degree of the water is below 200000mg/L, especially suitable for water with the mineralization degree of 500-200000mg/L, more suitable for water with the mineralization degree of 40000-200000mg/L, the content of calcium and magnesium ions is below 10000mg/L, especially suitable for water with the content of calcium and magnesium ions of 100-10000mg/L, and more suitable for water with the content of calcium and magnesium ions of 2000-10000 mg/L.
In the invention, the content of calcium and magnesium ions refers to the sum of the content of calcium ions and magnesium ions in water, and can be measured by an ICP-MS method.
It will be appreciated that the high temperature and high salt resistant plugging agent material composition will contain impurities derived from water depending on the degree of mineralization of the water, but will be calculated as a whole with the water during the calculation.
Preferably, the method comprises the steps of,
Based on 100 percent of the total weight of the plugging agent,
The content of the salt-resistant acrylamide polymer is 0.4-1.5wt%;
the content of the cross-linking agent is 0.6-3wt%;
The content of the deoxidizer is 0.01-0.5wt%;
The content of the reinforcing agent is 0.02-0.8wt%.
In the present invention, based on 100% by weight of the total blocking agent,
The salt-tolerant acrylamide polymer may be present in an amount of 0.4 to 1.5wt%, such as 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.5wt%, and any range between any two values.
The first cross-linking agent contains 0.3-1.5wt% of phenolic raw material, such as 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.5wt% and any range between any two values, and the second cross-linking agent contains 0.3-1.5wt% of aldehyde, amine or alcohol raw material, such as 0.3, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.4, 1.5wt% and any range between any two values.
The oxygen scavenger may be present in an amount of 0.01 to 0.5wt%, such as 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5wt% and any range between any two values.
The reinforcing agent may be present in an amount of 0.02 to 0.8wt%, for example, 0.02,0.04,0.06,0.08,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8wt% and any range between any two values.
More preferably, the method further comprises the steps of,
Based on 100 percent of the total weight of the plugging agent,
The content of the salt-resistant acrylamide polymer is 0.6-1.2wt%;
The content of the cross-linking agent is 0.8-2wt%;
The content of the deoxidizer is 0.05-0.3wt%;
The content of the reinforcing agent is 0.05-0.5wt%.
In the preferred range, the gel strength and the blocking performance of the high-temperature-resistant high-salt blocking agent can be further improved.
The third object of the present invention is to provide a method for preparing the high temperature and high salt resistant plugging agent of the second object of the present invention, the method comprising the steps of:
(1) Adding reinforcing agent into part of solvent, and fully dissolving to obtain polyvinyl alcohol solution;
(2) Adding a salt-resistant acrylamide polymer into the residual solvent, and fully dissolving to obtain a salt-resistant acrylamide polymer solution; then adding the enhancer solution and mixing to obtain a mixed solution;
(3) And fully mixing the mixed solution with a cross-linking agent and an deoxidizing agent to obtain the high-temperature-resistant high-salt plugging agent.
In the invention, the partial solvent and the residual solvent have no special proportioning requirement, so that the dissolution of the dissolved components can be realized, and the sum of the partial solvent and the residual solvent is the total amount of the solvents.
In the present invention, the conditions and manner of the dissolution in the steps (1) and (2) are not particularly limited as long as the material can be sufficiently dissolved. The dissolution can be carried out at normal temperature and normal pressure, and can be determined according to the specific environment when the high-temperature and high-salt resistant plugging agent is prepared; in order to accelerate dissolution and mixing in the mixing process, the mixing can be assisted by stirring, ultrasonic and other modes, so that each material is dissolved more quickly and is uniformly distributed.
It is a fourth object of the present invention to provide the use of the raw material composition of the high temperature and high salt resistant plugging agent according to one of the objects of the present invention or the high temperature and high salt resistant plugging agent according to the second object of the present invention in oil reservoir exploitation, in particular in carbonate oil reservoir exploitation.
The high temperature and high salt resistant plugging agent is injected into the stratum so that the high temperature and high salt resistant plugging agent is crosslinked in situ in the stratum to form gel.
The high-temperature-resistant high-salt plugging agent can be glued at the high temperature of 120-140 ℃ for 6-15 hours to form a plug, and the plugging agent is kept at the temperature for 60 days.
The high-temperature-resistant high-salt plugging agent is suitable for exploitation of carbonate oil reservoir ultra-deep well region oil reservoir, preferably, the mineralization degree of water in the region is below 200000mg/L, and the content of calcium and magnesium ions is below 10000 mg/L.
Polyvinyl alcohol is a water-soluble high polymer with wide application, which is obtained by alcoholysis, hydrolysis or ammonolysis of polyvinyl acetate. The molecular main chain is a carbon chain, and each repeating unit contains a hydroxyl. The hydrogen bond between molecules makes the polymer have good chemical stability and thermal stability, and simultaneously, a large number of hydroxyl groups on the molecular chain make the polymer have stronger hydrophilicity, film forming property and cohesive force. In the invention, the polyvinyl alcohol is used as a strength supporting material, interpenetrating is formed in the original polyacrylamide gel network, and meanwhile, the hydroxyl group rich in the polyvinyl alcohol is utilized to strengthen the hydrogen bond action with the polyacrylamide gel network, so that the polyvinyl alcohol has stronger plugging capability and profile improvement capability through synergistic interaction, improves the salt-resistant calcium-magnesium-resistant performance of the existing acrylamide gel at high temperature, and inhibits the network collapse under high salt and high calcium magnesium.
Compared with the prior art, the technical scheme of the invention has at least the following advantages:
the high-temperature-resistant high-salt plugging agent provided by the invention has the advantages that the preparation method is simple, the formed gel has good stability and high strength, and can effectively plug a water channeling passage for a long time within 60 days under the environment that the total mineralization degree is up to 200000mg/L and the calcium-magnesium ion concentration is up to 10000mg/L at a higher temperature of 120-140 ℃.
Compared with the existing gel plugging agent, the high-temperature and high-salt resistant plugging agent provided by the invention has higher plugging rate and longer plugging time, and can be suitable for large pore canal plugging operation in an ultra-deep well of a carbonate oil reservoir (such as a tower and river oil field).
According to the invention, the reinforcing agent polyvinyl alcohol is introduced into the polyacrylamide gel network, and the stability of the existing gel plugging material in a high-temperature, high-salt and high-calcium magnesium ion environment can be enhanced through physical and chemical synergy.
The gelling time of the plugging agent is controlled to be more than 6 hours, so that the plugging agent is sufficient in time for site construction and has high practical value.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In the following examples, salt-tolerant acrylamide polymers were purchased from Shandong Bao Momordica biochemistry;
Polyvinyl alcohol 0588 is available from Shanghai Ala Biochemical technology Co., ltd;
Polyvinyl alcohol 1795, 2488 is available from national pharmaceutical group chemical company, inc.
Reagents and materials used in the following examples were all commercially available without specific explanation.
In the following examples, simulated brine was formulated according to the applicable reservoir environment, the degree of mineralization of the simulated brine was 200000mg/L, and the calcium magnesium ion content was 10000mg/L (it should be understood that the degree of mineralization and the calcium magnesium ion content were about values).
In the following examples, the test of plugging performance applies darcy's principle, and the test method is as follows:
Filling a simulated rock core (diameter d=25 mm, length L=200 mm), vacuumizing, filling water into the rock core at a flow rate of 2 milliliters/minute (injection rate Q), and measuring permeability (k 0) before blocking the rock core; and then injecting a high-temperature and high-salt resistant plugging agent with the concentration of 1.0-1.5PV into the core model, plugging two ends of the core by using plugs, placing the core into a constant temperature oven for standing for a certain number of days, and injecting water again until the pressure is stable, so as to obtain the permeability (k') of the core after plugging, thereby calculating the plugging rate.
The plugging rate (eta) is used as a parameter for representing the plugging performance of the plugging agent, and the calculation formula is as follows:
In the following examples and comparative examples, the polymer gel blocking agent was gelled at 120-140℃for a gel strength code method, and the time elapsed for converting the gel system from a solution to the strength code G was defined as the gel time.
In the following examples and comparative examples, the thermal stability was expressed in terms of dehydration rate, and stability was examined by measuring dehydration rate at various times. The measuring method comprises the following steps: the polymer gel blocking agent is placed into a closed stainless steel reaction kettle to react in a constant temperature box, the polymer gel blocking agent is taken out of the constant temperature box at fixed intervals, the mass of the gel dehydrated water is weighed by a balance, and the ratio of the mass to the mass of the initial gel forming agent is the dehydration rate.
Colloid strength test: the colloid strength is tested by adopting a breakthrough vacuum degree method, and the specific operation is as follows: the gel is put into a test bottle of a breaking vacuum degree experiment device, a 1mL pipette tip part is inserted into a position 1cm below the surface of the gel, a vacuum pump is started, a knob is slowly adjusted to increase the system vacuum degree, when air breaks through the gel, the maximum reading of the vacuum degree on a vacuum meter, namely the breaking vacuum degree of the gel, is repeatedly measured for 3 times, and the arithmetic average value is taken as the final strength value.
Example 1
This example is illustrative of the high temperature and high salt resistant plugging agent of the present invention and its preparation method.
Firstly, 90g of deionized water is heated to more than 80 ℃, 10g of polyvinyl alcohol (0588 type, average molecular weight 22000 and alcoholysis degree 86.0-89.0%) is added, and the mixture is stirred until the mixture is uniformly dissolved, so as to obtain 10wt% of polyvinyl alcohol solution, and the solution is cooled to room temperature.
15G of acrylamide/N-vinylpyrrolidone copolymer powder (viscosity average molecular weight: 600 ten thousand) is added into 900g of simulated saline, stirred at 600rpm/min until the mixture is completely dissolved, 2g of 10wt% polyvinyl alcohol solution (0588 type) is added, stirred until the mixture is completely dissolved, 15g of catechol, 15g of glyoxal and 5g of sodium bisulphite are added, the total weight is 1kg after the mixture is complemented by the simulated saline, and the mixture is uniformly stirred to obtain the high-temperature-resistant high-salt plugging agent.
And recording the gel forming time of the high-temperature-resistant high-salt plugging agent at 130 ℃ by adopting a gel strength code method.
The gel strength of the high-temperature-resistant high-salt plugging agent is measured by adopting a breakthrough vacuum degree method.
After the high-temperature and high-salt resistant plugging agent is gelled, the plugging agent is stably maintained at 130 ℃ for 60 days, and then the dehydration rate and the plugging performance of the plugging agent are measured, and the results are shown in table 1.
Example 2
This example is illustrative of the high temperature and high salt resistant plugging agent of the present invention and its preparation method.
Firstly, 90g of deionized water is heated to more than 80 ℃,10 g of polyvinyl alcohol (1795 type, average molecular weight 77000 and alcoholysis degree 94.0% -95.0%) is added, and the mixture is stirred until the mixture is uniformly dissolved, so as to obtain 10wt% of polyvinyl alcohol solution, and the solution is cooled to room temperature.
7.5G of acrylamide/2-acrylamide-2-methylpropanesulfonic acid copolymer (AM/AMPS copolymer) powder (viscosity average molecular weight 870 ten thousand) is added into 900g of simulated saline, after stirring at 600rpm/min until the powder is completely dissolved, 12g of 10wt% polyvinyl alcohol solution is added, after stirring until the powder is completely dissolved, 8g of hydroquinone, 8g of hexamethylenetetramine and 0.6g of sodium thiosulfate are added, the simulated saline is used for supplementing to the total weight of 1kg, and the high-temperature-resistant high-salt plugging agent is obtained after stirring uniformly.
And recording the gel forming time of the high-temperature-resistant high-salt plugging agent at 140 ℃ by adopting a gel strength code method.
The gel strength of the high-temperature-resistant high-salt plugging agent is measured by adopting a breakthrough vacuum degree method.
After the high-temperature and high-salt resistant plugging agent is gelled, the plugging agent is stably maintained at 140 ℃ for 60 days, and then the dehydration rate and the plugging performance of the plugging agent are measured, and the results are shown in table 1.
Example 3
This example is illustrative of the high temperature and high salt resistant plugging agent of the present invention and its preparation method.
Firstly, 80g of deionized water is heated to more than 80 ℃, 20g of polyvinyl alcohol (2488 type, average molecular weight 121000 and alcoholysis degree 86.0-90.0%) is added, and the mixture is stirred until the mixture is uniformly dissolved, thus obtaining 20wt% of polyvinyl alcohol solution, and the solution is cooled to room temperature.
4G of acrylamide copolymer (viscosity average molecular weight: 1500 ten thousand) is added into 900g of simulated saline, stirred at 600rpm/min until the copolymer is completely dissolved, 40g of 20wt% polyvinyl alcohol solution is added, stirred until the copolymer is completely dissolved, 3g of resorcinol, 4g of hexamethylenetetramine and 0.1g of sodium bisulfite are added, the total weight is 1kg after the copolymer is complemented by the simulated saline, and the mixture is uniformly stirred to obtain the high-temperature-resistant high-salt plugging agent.
And recording the gel forming time of the high-temperature-resistant high-salt plugging agent at 120 ℃ by adopting a gel strength code method.
The gel strength of the high-temperature-resistant high-salt plugging agent is measured by adopting a breakthrough vacuum degree method.
After the high-temperature and high-salt resistant plugging agent is gelled, the plugging agent is stably maintained for 60 days at 120 ℃, and then the dehydration rate and the plugging performance of the plugging agent are measured, and the results are shown in Table 1.
Example 4
This example is illustrative of the high temperature and high salt resistant plugging agent of the present invention and its preparation method.
The preparation of example 4 was identical to that of example 2, except that the acrylamide/AMPS copolymer powder was replaced with an N, N-dimethylacrylamide homopolymer powder (viscosity average molecular weight: 850 ten thousand); and replacing sodium thiosulfate with isoascorbic acid to obtain the high-temperature-resistant high-salt plugging agent.
And recording the gel forming time of the high-temperature-resistant high-salt plugging agent at 140 ℃ by adopting a gel strength code method.
The gel strength of the high-temperature-resistant high-salt plugging agent is measured by adopting a breakthrough vacuum degree method.
After the high-temperature-resistant high-salt plugging agent is gelled, the high-temperature-resistant high-salt plugging agent is stably maintained at 140 ℃ for 60 days, and then the dehydration rate and the plugging performance of the high-temperature-resistant high-salt plugging agent are measured, and the results are shown in Table 1.
Comparative example 1
This comparative example is illustrative of a reference blocking agent and method of making the same.
7.5G of acrylamide/N-vinylpyrrolidone copolymer (viscosity average molecular weight 870 ten thousand) is dissolved in 900g of simulated saline, 8g of hydroquinone, 8g of hexamethylenetetramine and 0.6g of sodium thiosulfate are added, the simulated saline is used for supplementing to the total weight of 1Kg, and the plugging agent is obtained after stirring uniformly.
The gel time of the blocking agent at 140℃was recorded by gel strength code.
The gel strength of the plugging agent is measured by adopting a breakthrough vacuum degree method.
After the blocking agent was gelled, it was kept at 140℃for 30 days, and then the dehydration rate and blocking performance were measured, and the results are shown in Table 1.
Comparative example 2
This comparative example is illustrative of a reference blocking agent and method of making the same.
75G of 10wt% polyvinyl alcohol solution (1795 type, average molecular weight 77000, alcoholysis 94.0% -95.0%) are dissolved in 908.4g of simulated brine, 8g of hydroquinone, 8g of hexamethylenetetramine, 0.6g of sodium thiosulfate are added, and after stirring well at 130℃no gel formation is observed within 48 hours.
TABLE 1
In the present invention, the gel forming time of example 3 was longer and the gel strength was lower than in the other examples, because the copolymer and the crosslinking agent content were relatively low in example 3 and the gel forming temperature was also lower.
As can be seen from the results in Table 1, the polyvinyl alcohol is introduced into the system to form an interpenetrating network structure with the original acrylamide gel network, and the prepared high-temperature and high-salt-resistant plugging agent has good thermal stability and plugging rate at 120-140 ℃ and has good plugging effect on ultra-deep well large pore canals of carbonate reservoirs with high temperature, high mineralization and high calcium and magnesium ions through synergistic effect.
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 (15)
1. A raw material composition of a high-temperature-resistant high-salt plugging agent is characterized in that,
The raw material composition comprises a salt-resistant acrylamide polymer, a cross-linking agent, an oxygen scavenger and a reinforcing agent;
the reinforcing agent is polyvinyl alcohol; the average molecular weight of the polyvinyl alcohol is 2 ten thousand to 13 ten thousand;
the mass ratio of the salt-tolerant acrylamide polymer to the cross-linking agent to the deoxidizing agent to the reinforcing agent is (0.4-1.5): (0.6-3): (0.01-0.5): (0.02-0.8);
the cross-linking agent comprises a cross-linking agent I and a cross-linking agent II;
the cross-linking agent is at least one selected from phenolic substances;
the cross-linking agent II is at least one selected from aldehydes, amines or alcohols;
The salt-resistant acrylamide polymer is at least one selected from acrylamide homopolymer, N-dimethylacrylamide homopolymer, acrylamide/2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylamide/N, N-dimethylacrylamide copolymer, acrylamide/N-vinylpyrrolidone copolymer, N-dimethylacrylamide/N-vinylpyrrolidone copolymer and acrylamide/N, N-dimethylacrylamide/N-vinylpyrrolidone copolymer;
The viscosity average molecular weight of the salt-resistant acrylamide polymer is 600-1500 ten thousand.
2. The raw material composition of the high-temperature and high-salt plugging agent according to claim 1, wherein,
The mass ratio of the salt-tolerant acrylamide polymer to the cross-linking agent to the deoxidizing agent to the reinforcing agent is (0.6-1.2): (0.8-2): (0.05-0.3): (0.05-0.5).
3. The raw material composition of the high-temperature and high-salt plugging agent according to claim 1, wherein,
The viscosity average molecular weight of the salt-resistant acrylamide polymer is 800-1200 ten thousand.
4. The raw material composition of the high-temperature and high-salt plugging agent according to claim 1, wherein,
The cross-linking agent I is at least one selected from catechol, resorcinol and hydroquinone;
The cross-linking agent II is at least one selected from formaldehyde, glyoxal, hexamethylenetetramine and furanol.
5. The raw material composition of the high-temperature and high-salt plugging agent according to claim 1, wherein,
The mass ratio of the first cross-linking agent to the second cross-linking agent is 1:0.5-1.5.
6. The raw material composition of the high-temperature and high-salt plugging agent according to claim 1, wherein,
The deoxidizer is at least one selected from sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium dithionite, isoascorbic acid and thiourea.
7. The raw material composition of the high-temperature and high-salt plugging agent according to claim 1, wherein,
The alcoholysis degree of the polyvinyl alcohol is 84-99%.
8. A high-temperature and high-salt resistant plugging agent is characterized in that,
The plugging agent comprises the raw material composition of the high-temperature-resistant high-salt plugging agent as defined in any one of claims 1 to 7 and a solvent.
9. The high-temperature and high-salt-resistant plugging agent according to claim 8, wherein,
The solvent comprises water.
10. The high-temperature and high-salt-resistant plugging agent according to claim 9, wherein,
The mineralization degree of the water is below 200000mg/L, and the content of calcium and magnesium ions is below 10000 mg/L.
11. The high-temperature and high-salt-resistant plugging agent according to claim 8, wherein,
Based on 100 percent of the total weight of the plugging agent,
The content of the salt-resistant acrylamide polymer is 0.4-1.5wt%;
The content of the cross-linking agent is 0.6-3wt%;
the content of the deoxidizer is 0.01-0.5wt%;
the content of the reinforcing agent is 0.02-0.8wt%.
12. The high-temperature and high-salt-resistant plugging agent according to claim 11, wherein,
Based on 100 percent of the total weight of the plugging agent,
The content of the salt-resistant acrylamide polymer is 0.6-1.2wt%;
the content of the cross-linking agent is 0.8-2wt%;
the content of the deoxidizer is 0.05-0.3wt%;
the content of the reinforcing agent is 0.05-0.5wt%.
13. A method for preparing a high temperature and high salt resistant plugging agent according to any one of claims 8-12, wherein said method comprises the steps of:
(1) Adding the reinforcing agent into part of the solvent, and fully dissolving to obtain reinforcing agent solution;
(2) Adding a salt-resistant acrylamide polymer into the residual solvent, and fully dissolving to obtain a salt-resistant acrylamide polymer solution; then adding the enhancer solution and mixing to obtain a mixed solution;
(3) And fully mixing the mixed solution with a cross-linking agent and an deoxidizing agent to obtain the high-temperature-resistant high-salt plugging agent.
14. Use of the high temperature and salt resistant plugging agent according to any one of claims 1 to 7 or according to any one of claims 8 to 12 in oil reservoir exploitation.
15. The use according to claim 14, in carbonate reservoir production.
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