CN113755144A - A kind of gel water blocking agent and preparation method thereof - Google Patents
A kind of gel water blocking agent and preparation method thereof Download PDFInfo
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- CN113755144A CN113755144A CN202111012893.8A CN202111012893A CN113755144A CN 113755144 A CN113755144 A CN 113755144A CN 202111012893 A CN202111012893 A CN 202111012893A CN 113755144 A CN113755144 A CN 113755144A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002981 blocking agent Substances 0.000 title abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 71
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 63
- 239000003381 stabilizer Substances 0.000 claims abstract description 58
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 53
- 125000000129 anionic group Chemical group 0.000 claims abstract description 41
- 150000001768 cations Chemical class 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229940069428 antacid Drugs 0.000 claims abstract description 10
- 239000003159 antacid agent Substances 0.000 claims abstract description 10
- 230000001458 anti-acid effect Effects 0.000 claims abstract description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 8
- YWMAPNNZOCSAPF-UHFFFAOYSA-N Nickel(1+) Chemical group [Ni+] YWMAPNNZOCSAPF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940006444 nickel cation Drugs 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical group OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 230000033558 biomineral tissue development Effects 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- FEBUJFMRSBAMES-UHFFFAOYSA-N 2-[(2-{[3,5-dihydroxy-2-(hydroxymethyl)-6-phosphanyloxan-4-yl]oxy}-3,5-dihydroxy-6-({[3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy}methyl)oxan-4-yl)oxy]-3,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl phosphinite Chemical group OC1C(O)C(O)C(CO)OC1OCC1C(O)C(OC2C(C(OP)C(O)C(CO)O2)O)C(O)C(OC2C(C(CO)OC(P)C2O)O)O1 FEBUJFMRSBAMES-UHFFFAOYSA-N 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 9
- 229920002305 Schizophyllan Polymers 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical group OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 description 91
- 239000000243 solution Substances 0.000 description 72
- 239000003921 oil Substances 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000011780 sodium chloride Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 8
- 239000008398 formation water Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003129 oil well Substances 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000004579 marble Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002332 oil field water Substances 0.000 description 2
- -1 phenolic aldehyde Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 235000020681 well water Nutrition 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
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- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 238000012795 verification Methods 0.000 description 1
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- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明提供了一种凝胶堵水剂及其制备方法。以凝胶堵水剂的原料质量为基准，该凝胶堵水剂的原料组成包括：阴非离子型聚丙烯酰胺0.5‑0.7％，阴离子型聚丙烯酰胺0.5‑0.7％，交联剂A 0.9‑1.1％，交联剂B 0.9‑1.1％，抗酸稳定剂0.1‑0.3％，金属阳离子稳定剂0.1‑0.3％、无机盐类纳米稳定剂0.1‑0.3％和水；其中，所述交联剂A为醛类交联剂和醛类衍生物交联剂中的一种或两种以上的组合；所述交联剂B为苯酚类交联几种的一种或两种以上的组合；其中，所述金属阳离子稳定剂为镍阳离子稳定剂。
The invention provides a gel water blocking agent and a preparation method thereof. Based on the raw material quality of the gel water plugging agent, the raw material composition of the gel water plugging agent includes: anionic and nonionic polyacrylamide 0.5-0.7%, anionic polyacrylamide 0.5-0.7%, cross-linking agent A 0.9% -1.1%, cross-linking agent B 0.9-1.1%, antacid stabilizer 0.1-0.3%, metal cation stabilizer 0.1-0.3%, inorganic salt nano-stabilizer 0.1-0.3% and water; wherein, the cross-linking agent Agent A is a combination of one or more of aldehyde cross-linking agents and aldehyde derivatives cross-linking agents; the cross-linking agent B is a combination of one or more of phenolic cross-linking agents; Wherein, the metal cation stabilizer is a nickel cation stabilizer.
Description
Technical Field
The invention belongs to the technical field of chemical water plugging of oil wells for improving recovery ratio, and particularly relates to a self-repairing pre-crosslinked gel water plugging agent with high-salt and ultrahigh-temperature resistance, which is suitable for high-temperature and high-salt oil field fracture-cavity type oil reservoir ultra-deep wells.
Background
At present, the onshore main oil fields at home and abroad enter the medium and high water content exploitation period, and the profile control and water shutoff is more and more emphasized as an important measure for improving the water drive effect and improving the recovery ratio, and becomes one of the core technologies for increasing the storage and excavation potential of the high water content oil fields.
For example, when a certain oil field is taken as a typical high-temperature high-salt fracture-cavity type oil reservoir, the oil reservoir burial depth (5000 + 7000 m) is different from 130 + 160 ℃, the temperature of part of ultra-deep wells can reach 170 ℃, the mineralization degree of formation water is more than 20 ppm, the reservoir space comprises large holes, large seams and corrosion holes, the size difference is large, the scale is from micron level to meter level, the heterogeneity is strong, the recovery ratio is generally low, and the average rate in 2017 is only about 16.1 percent and is less than half of that of clastic rock oil reservoirs. Along with the development of the water plugging process, various organic and inorganic chemical water plugging agents, cement paste, casing and other process means are applied to the pilot experiment of the oil field and mine field; through continuous trial and screening, the mode of the immobile pipe column chemical gel water adjusting and plugging agent mainly adopted at present is finally formed. However, in view of the severe geological conditions of the oil field, most of the common gel water adjusting and plugging agents are difficult to be applied to the oil field due to the difficulty in meeting the requirements of high temperature resistance and high salinity, and the problem of short dehydration period usually occurs when the gel water adjusting and plugging agents are used for plugging the oil field.
At present, the common chemical water shutoff agent mainly comprising crosslinked polymer particles is prepared by polymerizing acrylamide or hydrolyzing polyacrylamide and then adding a phenolic resin crosslinking agent; under the condition of high temperature and high mineralization, partial amide groups can be hydrolyzed and react with calcium and magnesium ions in the stratum, so that the product is dehydrated, even hardened and loses deformability, the profile control and plugging effects on the deep stratum cannot be realized, and the failure rate of the chemical water plugging process of the immobile pipe column is greatly increased.
Therefore, a high-strength chemical water plugging formula system which can simultaneously meet the requirements of a high-temperature high-salt stratum, ensures good injection performance of a medicament system and excellent shearing and adsorption resistance is required to be researched, provides medicament support for profile control and water plugging of an ultra-deep ultra-high temperature reservoir of a high-temperature high-salt oil field, and solves the problem of oil well water outlet which troubles the high-temperature oil reservoir of the high-temperature high-salt oil field at present.
Disclosure of Invention
The invention aims to provide a gel water shutoff agent suitable for water shutoff of a high-salinity ultrahigh-temperature oil reservoir, which can be well suitable for water shutoff construction of a high-salinity fracture-cavity oil reservoir ultra-deep well in a high-temperature high-salinity oil field.
In order to achieve the purpose, the invention provides a gel water shutoff agent, wherein the gel water shutoff agent comprises the following raw materials:
negative non-ionic polyacrylamide, anionic polyacrylamide, a cross-linking agent A, a cross-linking agent B, an antacid stabilizer, a metal cation stabilizer, an inorganic salt nano-stabilizer and water; wherein, the cross-linking agent A is one or the combination of more than two of aldehyde cross-linking agents and aldehyde derivative cross-linking agents; the crosslinking agent B is one or the combination of more than two of phenol crosslinking agents; wherein the metal cation stabilizer is a nickel cation stabilizer;
based on the mass of the raw materials of the gel water plugging agent, the mass percentage of the negative non-ionic polyacrylamide is 0.5-0.7%, the mass percentage of the cross-linking agent A is 0.9-1.1%, the mass percentage of the cross-linking agent B is 0.9-1.1%, the mass percentage of the antacid stabilizer is 0.1-0.3%, the mass percentage of the metal cation stabilizer is 0.1-0.3%, and the mass percentage of the inorganic salt nano stabilizer is 0.1-0.3%.
The gel water shutoff agent provided by the invention realizes the improvement of the strength, the salt resistance, the temperature resistance and the stability of a polymer gel system by utilizing a high-content organic phenolic aldehyde crosslinking system and simultaneously using three types of stabilizers. The high-content cross-linking agent A and the high-content cross-linking agent B enhance the thermal stability of a high-temperature polymer gel system and reduce the separation effect of a polymer main agent and the cross-linking agent; on the basis, the acid-resistant stabilizer, the metal cation stabilizer and the inorganic salt nano stabilizer are added into the high-temperature polymer gel system at the same time, so that more water locking points are provided for the three-dimensional grid-shaped cross-linked polymer solution, the thermal stability is improved, meanwhile, the hypersalinity water corrosion is effectively inhibited, and a more stable structure is formed (as shown in figure 1).
In the above gel plugging agent, preferably, the raw material composition of the gel plugging agent further comprises 0.7-0.9% of an oxygen scavenger based on the raw material mass of the gel plugging agent; more preferably, the oxygen scavenger is selected from urea and/or thiourea;
in a specific embodiment, the gel water shutoff agent comprises the following raw materials in percentage by mass:
0.5-0.7% of negative non-ionic polyacrylamide, 0.5-0.7% of anionic polyacrylamide, 0.9-1.1% of cross-linking agent A, 0.9-1.1% of cross-linking agent B, 0.7-0.9% of deoxidant, 0.1-0.3% of antacid stabilizer, 0.1-0.3% of metal cation stabilizer, 0.1-0.3% of inorganic salt nano stabilizer and the balance of water;
wherein, the cross-linking agent A is one or the combination of more than two of aldehyde cross-linking agents and aldehyde derivative cross-linking agents; the crosslinking agent B is one or the combination of more than two of phenol crosslinking agents; wherein the metal cation stabilizer is a nickel cation stabilizer.
In the above gel blocking agent, preferably, the average molecular weight of the anionic or nonionic polyacrylamide is 700000-800000 daltons.
In the above gel blocking agent, preferably, the average molecular weight of the anionic polyacrylamide is 400000-500000 daltons.
In the above gel water shutoff agent, preferably, the crosslinking agent a is formaldehyde and/or urotropine. When urotropine is used as the crosslinking agent A, the urotropine slowly releases formaldehyde and ammonia gas at the formation temperature, the formaldehyde reacts with the crosslinking agent B to form a phenolic aldehyde pre-polymerization crosslinking body, the gelling time of a polymer gel system is prolonged, the thermal stability of the polymer gel system is further improved, and the separation effect of a polymer main agent and the crosslinking agent is effectively reduced.
In the above gel water shutoff agent, preferably, the crosslinking agent B is catechol, hydroquinone and/or resorcinol.
In the above gel water shutoff agent, preferably, the antacid stabilizer is scleroglucan.
In the above gel blocking agent, preferably, the metal cation stabilizer is nickel chloride.
In the above gel water shutoff agent, preferably, the inorganic salt nano stabilizer is selected from nano silica.
In the above gel water shutoff agent, the water may be distilled water or saline water (e.g., formation water, simulated formation water, etc.); preferably, the degree of mineralization of said water does not exceed 25 x 104mg/L。
The invention also provides a preparation method of the gel water shutoff agent, wherein the method comprises the following steps:
adding an antacid stabilizer to water to obtain a first solution;
respectively dissolving anionic polyacrylamide and anionic polyacrylamide in the first solution to obtain an anionic polyacrylamide solution and an anionic polyacrylamide solution;
mixing a negative non-ionic polyacrylamide solution and an anionic polyacrylamide solution, and adding a cross-linking agent A and a cross-linking agent B to obtain a second solution;
and dissolving inorganic salt nano stabilizer and metal cation stabilizer in the second solution in sequence to prepare the gel water shutoff agent.
In the above preparation method, preferably, when the raw material composition of the gel water shutoff agent contains an oxygen scavenger, the oxygen scavenger is added simultaneously with the crosslinking agent a and the crosslinking agent B.
In one embodiment, the preparation method of the gel water shutoff agent comprises the following steps:
the method comprises the following steps: taking a certain amount of water, adding an antacid stabilizer into the water, and stirring the mixture for at least 0.5h at the stirring speed of 800-;
step two: taking part of the first solution, slowly adding the anionic and nonionic polyacrylamide under the stirring condition of 200-300rpm, and continuously stirring for 1-1.5h at the stirring speed of 200-300rpm until the anionic and nonionic polyacrylamide is completely dissolved to obtain an anionic and nonionic polyacrylamide solution; the obtained anionic and nonionic polyacrylamide solution is a homogeneous solution which is as transparent as possible and has no fish eye blocking substances;
step three: taking the other part of the first solution, slowly adding the anionic polyacrylamide under the stirring condition of 200-300rpm, and continuously stirring at the stirring speed of 200-300rpm for 1-1.5h until the anionic polyacrylamide is completely dissolved to obtain an anionic polyacrylamide solution; the obtained anionic polyacrylamide solution is as transparent as possible and is a homogeneous solution without fish eye blocking substances;
step four: mixing the anionic polyacrylamide solution and the nonionic polyacrylamide solution prepared in the second step and the third step, and stirring for 0.5-1h at a stirring speed of not more than 200rpm to ensure that the anionic polyacrylamide solution and the nonionic polyacrylamide solution are fully dissolved;
step five: on the basis of the fourth step, adding a cross-linking agent A, a cross-linking agent B and an oxygen scavenger into the mixed solution, and stirring at the stirring speed of 200-300rpm for 20-30min until all the powder is completely dissolved to obtain a second solution;
step six: on the basis of the fifth step, adding the inorganic salt nano stabilizer into the second solution, and stirring for 30-45min at the stirring speed of 200-300rpm until all the powder is completely dissolved; then, continuing to add the metal cation stabilizer, and stirring for 5-10min at the stirring speed of 200-300rpm until all the powder is completely dissolved to obtain the gel water plugging agent.
The gel water shutoff agent provided by the invention is a self-repairing pre-crosslinked gel system, and the shear stress is basically kept unchanged at a constant shear rate. Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
1. can be directly used with a mineralization value lower than 25 × 104Preparation of mg/L formation water, greatly reducingThe construction cost of the mine field is low, and the final gelling performance of the rubber composition comprises a stable period and the colloid strength and the like are not influenced.
2. The gel can tolerate the high temperature of not less than 170 ℃, has good thermal stability, can still effectively gel under the conditions of ultrahigh temperature and high salt, has low dehydration rate after gelling, and can be suitable for the water plugging requirement of high-temperature and high-salt oil fields (such as Tahe oil fields) with well depth of more than 6000m and ultrahigh reservoir temperature.
3. After being gelatinized, the colloid has high strength and good plugging performance.
Drawings
Fig. 1 is a schematic diagram of a gelling mechanism of the gel water plugging agent provided by the invention.
Fig. 2A is a gel SEM image of the gel water shutoff agent salt-carrying particle provided in example 2 of the present invention.
Fig. 2B is a gel SEM image of the gel water shutoff agent salt-carrying particle provided in example 2 of the present invention.
FIG. 3 is a graph showing production data in Experimental example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described in detail and completely with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment of the invention, the dehydration rate is determined by the following formula:
wherein S is dehydration rate,%; v is the gel volume at the onset of the gel; vt is the gel volume after the aging time t.
Example 1
The embodiment provides a gel plugging agent SPG1, wherein the gel plugging agent is prepared by:
the method comprises the following steps: taking 100mL of simulated saltWater (16 g NaCl, 7g CaCl per 100ml deionized water)2And 1g of MgCl2Prepared to obtain the product with the total mineralization degree of 24 multiplied by 104mg/L) is put into a beaker, 0.2g of acid-fast stabilizer scleroglucan is added into the simulated saline under the stirring condition of a magnetic stirrer (the stirring speed is 800-;
step two: taking part of the first solution, stirring by a magnetic stirrer under the stirring condition of the magnetic stirrer (the stirring speed is 200-;
step three: taking the other part of the first solution, stirring the first solution by a magnetic stirrer, slowly adding 0.6g of anionic polyacrylamide (with the average molecular weight of 400000-;
step four: mixing the anionic polyacrylamide solution and the nonionic polyacrylamide solution prepared in the second step and the third step, and stirring for 0.5-1h by using a magnetic stirrer at a stirring speed of not more than 200rpm to ensure that the anionic polyacrylamide solution and the nonionic polyacrylamide solution are fully mutually soluble;
step five: on the basis of the fourth step, adding 1.0g of urotropine, 1.0g of hydroquinone and 0.8g of thiourea into the mixed solution, and stirring for 20-30min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved to obtain a second solution;
step six: on the basis of the fifth step, 0.2g of nano silicon dioxide is added into the second solution, and a magnetic stirrer is used for stirring for 30-45min at the stirring speed of 200-300rpm until all the powder is completely dissolved; then, 0.2g of nickel chloride is continuously added, and the mixture is stirred for 5-10min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved, so as to obtain the gel water plugging agent.
The gel water shutoff agent prepared in the embodiment is kept stand in a high-temperature oven at 170 ℃ for about 2-4H to gelatinize, the colloid strength of the formed colloid reaches H-I grade through evaluation by a visual code method, and the dehydration rate of 120 days at 170 ℃ is less than 30%.
Example 2
The embodiment provides a gel plugging agent SPG2, wherein the gel plugging agent is prepared by:
the method comprises the following steps: taking 100mL of formation water (a water sample is provided by a Tahe oilfield oil extraction second factory, the mineralization degree is 240g/L), putting the formation water into a beaker, adding 0.2g of acid-resistant stabilizer scleroglucan into the simulated saline water under the stirring condition of a magnetic stirrer (the stirring speed is 900rpm), and continuing stirring for 0.5h until the acid-resistant stabilizer scleroglucan is completely dissolved to obtain a first solution;
step two: taking part of the first solution, stirring by a magnetic stirrer under the stirring condition of the magnetic stirrer (the stirring speed is 200-;
step three: taking the other part of the first solution, stirring the first solution by a magnetic stirrer, slowly adding 0.6g of anionic polyacrylamide (with the average molecular weight of 400000-;
step four: mixing the anionic polyacrylamide solution and the nonionic polyacrylamide solution prepared in the second step and the third step, and stirring for 0.5-1h by using a magnetic stirrer at a stirring speed of not more than 200rpm to ensure that the anionic polyacrylamide solution and the nonionic polyacrylamide solution are fully mutually soluble;
step five: on the basis of the fourth step, adding 1.0g of urotropine, 1.0g of hydroquinone and 0.8g of thiourea into the mixed solution, and stirring for 20-30min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved to obtain a second solution;
step six: on the basis of the fifth step, 0.2g of nano silicon dioxide is added into the second solution, and a magnetic stirrer is used for stirring for 30-45min at the stirring speed of 200-300rpm until all the powder is completely dissolved; then, 0.2g of nickel chloride is continuously added, and the mixture is stirred for 5-10min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved, so as to obtain the gel water plugging agent.
The gel water shutoff agent prepared in the embodiment is kept stand in a high-temperature oven at 170 ℃ for about 2-4H to gelatinize (as shown in fig. 2A and fig. 2B), the colloid strength of the formed colloid reaches H-I grade by adopting a visual code method, and the dehydration rate of 105 days at 170 ℃ is less than 30%.
Experimental example 1
The experimental example provides a series of gel water shutoff agent performance tests, wherein the gel water shutoff agents are only different in that the addition amounts of the metal cation stabilizer nickel chloride are respectively as follows: 0%, 0.02%, 0.04%, 0.06%, 0.08%, 0.1%. The preparation method of the gel specifically comprises the following steps:
the method comprises the following steps: 100mL of simulated saline (16 g NaCl, 7g CaCl per 100mL of deionized water)2And 1g of MgCl2Prepared to obtain the product with the total mineralization degree of 24 multiplied by 104mg/L) is put into a beaker, 0.2g of acid-fast stabilizer scleroglucan is added into the simulated saline under the stirring condition of a magnetic stirrer (the stirring speed is 800-;
step two: taking 50mL of the first solution, stirring the first solution by a magnetic stirrer under the stirring condition of the magnetic stirrer (the stirring speed is 200-;
step three: taking 50mL of the first solution, stirring the first solution by a magnetic stirrer under the stirring condition of the magnetic stirrer (the stirring speed is 200-;
step four: mixing the anionic polyacrylamide solution and the nonionic polyacrylamide solution prepared in the second step and the third step, and stirring for 0.5-1h by using a magnetic stirrer at a stirring speed of not more than 200rpm to ensure that the anionic polyacrylamide solution and the nonionic polyacrylamide solution are fully mutually soluble;
step five: on the basis of the fourth step, adding 1.0g of urotropine, 1.0g of hydroquinone and 0.8g of thiourea into the mixed solution, and stirring for 20-30min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved to obtain a second solution;
step six: on the basis of the fifth step, 0.2g of nano silicon dioxide is added into the second solution, and a magnetic stirrer is used for stirring for 30-45min at the stirring speed of 200-300rpm until all the powder is completely dissolved; and then, continuously adding nickel chloride according to the addition amount of the metal cation stabilizer nickel chloride, and stirring for 5-10min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved to obtain the gel water plugging agent.
The properties of these gel water-blocking agents are shown in Table 1.
TABLE 1
Experimental example 2
The experimental example is used for testing the plugging capability of the gel plugging agent provided in example 1, and a one-dimensional core plugging experiment under different crack opening degrees is performed by specifically adopting the following method:
1. preparing three one-dimensional fracture simulation rock cores F1, F2 and F3 with different fracture openness, wherein the fracture openness is 1mm, 3mm and 5mm respectively;
selecting two marble plates A, B with the same size, cutting the marble A into 3 blocks with the same size, namely A1, A2 and A3, and cutting the marble B into 3 blocks with the same size, namely B1, B2 and B3; bonding A1 and B1 by using epoxy resin, drilling holes at the outlet end and the inlet end, cleaning, connecting pipelines, and manufacturing a one-dimensional fracture simulation rock core F1 with the fracture size of 30cm in length, 4.5cm in width and 1mm in opening degree; bonding A2 and B2 by using epoxy resin, drilling holes at the outlet end and the inlet end, cleaning, connecting pipelines, and manufacturing a one-dimensional fracture simulation rock core F2 with the fracture size of 30cm in length, 4.5cm in width and 3mm in opening degree; bonding A3 and B3 by using epoxy resin, drilling holes at the outlet end and the inlet end, cleaning, connecting pipelines, and manufacturing a one-dimensional fracture simulation rock core F3 with the fracture size of 30cm in length, 4.5cm in width and 5mm in opening degree;
2. in an oven, 2PV formation water injection (outlet end is driven by water) is carried out at the speed of 0.5ml/min on one-dimensional fracture simulation cores F1, F2 and F3 respectively to record the injection pressure delta p1Then, the injection pressure Δ p of the gel blocking agent SPG1 of 0.52PV was recorded at a rate of 0.5ml/min2Adjusting the temperature of the oven to 150 ℃, standing for 3 hours, injecting water again to record the injection pressure delta p3And calculating the plugging rate. The results are shown in Table 2.
TABLE 2
| Core numbering | Core opening (mm) | Δp1(kPa) | Δp2(kPa) | Δp3(kPa) | Plugging rate |
| F1 | 1 | 0.81 | 100.82 | 103.85 | 82.46％ |
| F2 | 3 | 0.46 | 96.42 | 96.86 | 90.27％ |
| F3 | 5 | 0.21 | 92.05 | 96.17 | 87.69％ |
Experimental example 3
The experimental example provides the field application verification of the gel water shutoff agent provided by the invention.
Before the gel water shutoff agent system is used for water shutoff, a certain oil well of the Tahe oil field is subjected to water shutoff for many times, and the oil increment for 3 months is difficult to achieve. The well belongs to a typical high-salt high-temperature fracture-cave carbonate reservoir well, the reservoir body of the oil well develops in a fracture mode, the well depth is 5703m, the salinity of saline water is 207608mg/L, and the formation temperature is as high as 125-. Injecting 50m from 6 months, 20 days to 24 days in 20203After the gel water shutoff agent provided by the invention is used for stewing for one week, under the condition of not changing the liquid production amount, the well water content is reduced from 90 percent to 50 percent, the crude oil yield is increased from 5t/d to 15t/d, the later record shows that the oil well stably produces for 3 months, and the accumulated yield is increased by 1000 t. As shown in fig. 3.
In the experimental example, the gel plugging agent provided by the invention is prepared in the following manner:
adding oil field water into an on-site stirring tank, adding 0.2 wt% of scleroglucan into the oil field water, then adding 0.6 wt% of polyacrylamide A and 0.6 wt% of polyacrylamide B according to the percentage, then adding 1.0 wt% of hydroquinone, 1.0 wt% of urotropine, 0.8 wt% of thiourea, 0.2 wt% of nano silicon dioxide and 0.1 wt% of metal cation stabilizer, and fully stirring and dissolving.
Experimental example 4
The experimental example provides a series of gel water shutoff agent performance tests, wherein the gel water shutoff agents are only different in the addition amount of the acid-resistant stabilizer concentration: 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, 0.20%. The preparation method of the gel specifically comprises the following steps:
the method comprises the following steps: 100mL of simulated saline (16 g NaCl, 7g CaCl per 100mL of deionized water)2And 1g of MgCl2Prepared to obtain the product with the total mineralization degree of 24 multiplied by 104mg/L) is put into a beaker, the acid-resistant stabilizer scleroglucan is added into the simulated saline according to the addition amount of the acid-resistant stabilizer under the stirring condition of a magnetic stirrer (the stirring speed is 800-;
step two: taking 50mL of the first solution, stirring the first solution by a magnetic stirrer under the stirring condition of the magnetic stirrer (the stirring speed is 200-;
step three: taking 50mL of the first solution, stirring the first solution by a magnetic stirrer under the stirring condition of the magnetic stirrer (the stirring speed is 200-;
step four: mixing the anionic polyacrylamide solution and the nonionic polyacrylamide solution prepared in the second step and the third step, and stirring for 0.5-1h by using a magnetic stirrer at a stirring speed of not more than 200rpm to ensure that the anionic polyacrylamide solution and the nonionic polyacrylamide solution are fully mutually soluble;
step five: on the basis of the fourth step, adding 1.0g of urotropine, 1.0g of hydroquinone and 0.8g of thiourea into the mixed solution, and stirring for 20-30min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved to obtain a second solution;
step six: on the basis of the fifth step, 0.2g of nano silicon dioxide is added into the second solution, and a magnetic stirrer is used for stirring for 30-45min at the stirring speed of 200-300rpm until all the powder is completely dissolved; then, 0.2g of nickel chloride is added continuously, and the mixture is stirred for 5-10min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved, so as to obtain the gel water plugging agent.
The properties of these gel water-blocking agents are shown in Table 3.
TABLE 3
Experimental example 5
The experimental example provides a series of gel water shutoff agent performance tests, wherein the gel water shutoff agents are only different in the addition amount of the inorganic salt nano stabilizer, and the addition amount is respectively as follows: 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, 0.20%. The preparation method of the gel specifically comprises the following steps:
the method comprises the following steps: 100mL of simulated saline (16 g NaCl, 7g CaCl per 100mL of deionized water)2And 1g of MgCl2Prepared to obtain the product with the total mineralization degree of 24 multiplied by 104mg/L) is put into a beaker, 0.2g of acid-fast stabilizer scleroglucan is added into the simulated saline under the stirring condition of a magnetic stirrer (the stirring speed is 800-;
step two: taking 50mL of the first solution, stirring the first solution by a magnetic stirrer under the stirring condition of the magnetic stirrer (the stirring speed is 200-;
step three: taking 50mL of the first solution, stirring the first solution by a magnetic stirrer under the stirring condition of the magnetic stirrer (the stirring speed is 200-;
step four: mixing the anionic polyacrylamide solution and the nonionic polyacrylamide solution prepared in the second step and the third step, and stirring for 0.5-1h by using a magnetic stirrer at a stirring speed of not more than 200rpm to ensure that the anionic polyacrylamide solution and the nonionic polyacrylamide solution are fully mutually soluble;
step five: on the basis of the fourth step, adding 1.0g of urotropine, 1.0g of hydroquinone and 0.8g of thiourea into the mixed solution, and stirring for 20-30min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved to obtain a second solution;
step six: on the basis of the fifth step, adding nano silicon dioxide into the second solution according to the addition of the inorganic salt nano stabilizer, and stirring for 30-45min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved; then, 0.2g of nickel chloride is added continuously, and the mixture is stirred for 5-10min by using a magnetic stirrer at the stirring speed of 200-300rpm until all the powder is completely dissolved, so as to obtain the gel water plugging agent.
The properties of these gel water-blocking agents are shown in Table 4.
TABLE 4
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The gel water shutoff agent comprises the following raw materials:
negative non-ionic polyacrylamide, anionic polyacrylamide, a cross-linking agent A, a cross-linking agent B, an antacid stabilizer, a metal cation stabilizer, an inorganic salt nano-stabilizer and water; wherein, the cross-linking agent A is one or the combination of more than two of aldehyde cross-linking agents and aldehyde derivative cross-linking agents; the crosslinking agent B is one or the combination of more than two of phenol crosslinking agents; wherein the metal cation stabilizer is a nickel cation stabilizer;
based on the total mass of the raw materials of the gel water plugging agent, the mass percentage of the negative non-ionic polyacrylamide is 0.5-0.7%, the mass percentage of the cross-linking agent A is 0.9-1.1%, the mass percentage of the cross-linking agent B is 0.9-1.1%, the mass percentage of the acid-resistant stabilizer is 0.1-0.3%, the mass percentage of the metal cation stabilizer is 0.1-0.3%, and the mass percentage of the inorganic salt nano stabilizer is 0.1-0.3%.
2. The gel plugging agent according to claim 1, wherein the raw material composition of the gel plugging agent further comprises 0.7-0.9% of an oxygen scavenger;
preferably, the oxygen scavenger is selected from urea and/or thiourea.
3. The gel water shutoff agent according to claim 1 or 2, wherein the anionic or nonionic polyacrylamide has an average molecular weight of 700000-; the average molecular weight of the anionic polyacrylamide is 400000 and 500000 daltons.
4. The gel water shutoff agent according to claim 1 or 2, wherein the crosslinking agent A is selected from formaldehyde and/or urotropine.
5. The gel water shutoff agent according to claim 1 or 2, wherein the crosslinking agent B is catechol, hydroquinone and/or resorcinol.
6. The gel water shutoff agent according to claim 1 or 2, wherein the antacid stabilizer is scleroglucan.
7. The gel water shutoff agent according to claim 1 or 2, wherein the metal cation stabilizer is nickel chloride.
8. The gel water shutoff agent according to claim 1 or 2, wherein the inorganic salt nano stabilizer is selected from nano silicon dioxide.
9. A gel water shutoff agent according to claim 1 or 2 wherein the degree of mineralization of the water is not more than 25 x 104mg/L。
10. The method of preparing a gel water shutoff agent according to any one of claims 1 to 9, wherein the method comprises:
adding an antacid stabilizer to water to obtain a first solution;
respectively dissolving anionic polyacrylamide and anionic polyacrylamide in the first solution to obtain an anionic polyacrylamide solution and an anionic polyacrylamide solution;
mixing a negative non-ionic polyacrylamide solution and an anionic polyacrylamide solution, and adding a cross-linking agent A and a cross-linking agent B to obtain a second solution;
sequentially dissolving inorganic salt nano stabilizer and metal cation stabilizer in the second solution to prepare the gel plugging agent;
preferably, when the raw material composition of the gel water shutoff agent contains an oxygen scavenger, the oxygen scavenger is added simultaneously with the crosslinking agent A and the crosslinking agent B.
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