CN116064015A - Salt-sensitive self-crosslinking gel foam system and preparation method and application thereof - Google Patents
Salt-sensitive self-crosslinking gel foam system and preparation method and application thereof Download PDFInfo
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- CN116064015A CN116064015A CN202310359869.4A CN202310359869A CN116064015A CN 116064015 A CN116064015 A CN 116064015A CN 202310359869 A CN202310359869 A CN 202310359869A CN 116064015 A CN116064015 A CN 116064015A
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- salt
- gel foam
- foam system
- stirring
- sensitive self
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- 239000006260 foam Substances 0.000 title claims abstract description 125
- 150000003839 salts Chemical class 0.000 title claims abstract description 62
- 238000004132 cross linking Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 50
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000661 sodium alginate Substances 0.000 claims abstract description 45
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 45
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 22
- -1 cation sulfate Chemical class 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 49
- 239000008398 formation water Substances 0.000 claims description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 159000000007 calcium salts Chemical class 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- 238000005187 foaming Methods 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000033558 biomineral tissue development Effects 0.000 claims description 8
- 239000003570 air Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 24
- 239000002480 mineral oil Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000011575 calcium Substances 0.000 description 21
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 11
- 229910001424 calcium ion Inorganic materials 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004088 foaming agent Substances 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000015784 hyperosmotic salinity response Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical compound OCNCO OTJFQRMIRKXXRS-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- FVRSVYZRCZZKJT-UHFFFAOYSA-N OOS(=O)(=O)CCC.[Na] Chemical compound OOS(=O)(=O)CCC.[Na] FVRSVYZRCZZKJT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- UZQPWASKVYDSRV-UHFFFAOYSA-N dodecoxymethylbenzene Chemical compound CCCCCCCCCCCCOCC1=CC=CC=C1 UZQPWASKVYDSRV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
-
- 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
-
- 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
- C09K8/514—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
-
- 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
- C09K8/518—Foams
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention belongs to the technical field of oil and gas field development engineering, and particularly relates to a salt-sensitive self-crosslinking gel foam system, and a preparation method and application thereof. The gel foam system comprises the following raw materials: a hydroxysulfobetaine surfactant, a soluble monovalent metal cation sulfate, a soluble trivalent metal salt, sodium alginate and deionized water. The preparation method of the gel foam system comprises the following steps: (1) Adding sodium alginate into deionized water to form a mixed solution; (2) Adding a hydroxysulfobetaine surfactant into the obtained mixed solution to form a compound solution; (3) Adding soluble monovalent metal cation sulfate into stratum water, and uniformly mixing with the compound solution obtained in the step (2) to generate gel foam; (4) Adding a soluble trivalent metal salt solution to the obtained gel foam to form the gel foam system. The gel foam system can be applied to a fracture-cavity oil reservoir and a high-mineral oil reservoir.
Description
Technical Field
The invention belongs to the technical field of oil and gas field development engineering, and particularly relates to a salt-sensitive self-crosslinking gel foam system, and a preparation method and application thereof.
Background
The foam flooding which is one of the tertiary oil recovery technical series has the characteristics of large and small plugging, water plugging, oil plugging and adjustable density, and has wide application in oil fields, however, in carbonate oil reservoirs, the oil reservoirs have complex environments such as high temperature, high ore and the like due to sea phase deposition, especially in certain oil fields in northwest regions, the ground temperature is above 100 ℃, and the total mineralization degree is as high as 11 multiplied by 10 4 ~26×10 4 mg/L, wherein Ca 2+ The mass concentration is as high as 1.1 multiplied by 10 4 mg/L，Mg 2+ 650mg/L, is a typical high temperature, high calcium, hypersalinity formation. Ca (Ca) 2+ 、Mg 2+ Too high a divalent ion content can seriously affect the stabilization ability of the foam, which results in a significant limitation of foam flooding in the field of hydrocarbon production.
In recent years, various studies have been made on temperature-resistant and salt-resistant foaming agents at home and abroad, and on the one hand, related groups are introduced into chain segments of surfactant molecules to form a compound surfactant, so that the temperature-resistant and salt-resistant properties of the compound surfactant are improved.
Chinese patent document CN202210678659.7 discloses a surfactant for temperature-resistant and salt-resistant oil displacement and a preparation method thereof, wherein the salt resistance of the surfactant is improved by introducing a maleic polyether monoester monomer, and the oil displacement requirement of sandstone under the condition of high-temperature oil water can be metThe cost is low, the operation is easy, but the salt tolerance index of the surfactant can only reach 5 multiplied by 10 4 mg/L。
Chinese patent document CN202210725236.6 discloses a novel temperature-resistant salt-tolerant pentacationic quaternary viscoelastic surfactant and a synthesis method thereof, wherein the salt tolerance index of the surfactant can be improved to 1.4X10 by introducing quaternary amine cations and hydrophobic chains 5 mg/L, but the synthesis process is complex, and the application of the method in the field of oil fields is limited.
On the other hand, some foam stabilizer is added into the surfactant to improve the salt resistance. The Chinese patent document CN202211145795.6 discloses a temperature-resistant and salt-resistant foam gel system and a preparation method thereof, the main components of the foam gel system are nano silicon dioxide, polymer, a first cross-linking agent, a second cross-linking agent and a foaming agent, the foaming agent in the foam gel system is compounded by three salt-resistant foaming agents, and the foam gel system is formed by introducing a terpolymer with temperature resistance and salt resistance and the cross-linking agent, thereby achieving the dual temperature resistance and salt resistance, being capable of resisting the temperature of 105-160 ℃ and the mineralization resistance of 20 multiplied by 10 4 mg/L, has wide application prospect in high-temperature and high-salt oil reservoirs. However, the nano silicon dioxide in the system is expensive, the foaming agent needs to be compounded by three surfactants, the polymer needs to be polymerized by three monomers, and the cross-linking agent needs to be two kinds of the foaming gel system capable of forming the temperature-resistant and salt-resistant foam gel system, so that the cost is high, the manufacturing process is complex, and the foaming gel system cannot be applied to oil fields on a large scale.
The Chinese patent document CN202110425127.8 describes a high-temperature and high-salt resistant reinforced foam plugging agent and an oil reservoir injection method thereof, wherein the components of the reinforced foam plugging agent comprise lignin, urotropine, a foaming agent HZ-1 type and methylcellulose, the reinforced foam plugging agent can improve formation heterogeneity, increase sweep efficiency and improve oil washing efficiency, but lignin in the reinforced foam plugging agent is a complex phenolic polymer, exists in higher plants, is unevenly distributed in wood, and has a chemical structure which is different from cellulose and protein due to lack of regularity and order of repeated units, so that lignin is different from manufacturer to manufacturer, and finally the effect of stabilizing foam synergistically with the foaming agent is difficult to control.
The Chinese patent document CN201911310718.X relates to a phosphonic acid structure-containing temperature-resistant salt-resistant gel foam, and a preparation method and application thereof, wherein the preparation raw materials comprise: the system has strong temperature resistance, can resist high temperature of 80-160 ℃, and can maintain good selective water shutoff under the stratum condition of high mineralization degree. However, phenol and aldehyde compounds used in the system belong to toxic solvents, the operation is complicated, and potential safety hazards exist in field application.
In summary, the salt tolerance of the surfactant can be enhanced by introducing the salt tolerance monomer, but the cost is higher and the enhancement degree is weaker; although the reinforcing degree is remarkable by introducing the foam stabilizer, the process is complex, potential safety hazards exist, large-area popularization cannot be realized, and the application of the foam in carbonate reservoirs is limited. Therefore, there is a need to develop a foam system which is temperature resistant, salt resistant, low in cost and environment friendly.
Disclosure of Invention
The invention aims to provide a salt-sensitive self-crosslinking gel foam system which has the advantages of low cost, stable performance, simple preparation method and environmental protection, and has the dual characteristics of high calcium salt resistance and salt-sensitive self-crosslinking.
The technical scheme of the invention is as follows:
a salt-sensitive self-crosslinking gel foam system, comprising the following raw materials: a hydroxysulfobetaine surfactant, a soluble monovalent metal cation sulfate, a soluble trivalent metal salt, sodium alginate and deionized water; wherein the dosage of the sodium alginate is more than or equal to the dosage of the soluble monovalent metal cation sulfate.
In the gel foam system, the hydroxysulfobetaine surfactant has strong rejection characteristic to salt positive ions in the formation water, and CaCl in the formation water 2 Can dissociate Ca 2+ Forming calcium sulfate micro-solubles with sulfate ions of soluble monovalent metal cation sulfate in the foam system, calcium sulfate releasing Ca at a relatively slow rate in formation water 2+ Part of Ca 2+ Tend to adsorb to the molecular surface of the surfactant, thereby destroying the molecular structure of the surfactant, while hydroxysulfobetaine surfactant vs. Ca 2+ Plays a certain role of 'isolation', and sodium alginate can combine with the repelled Ca at the same speed 2+ Thereby producing a uniform, firm gel foam.
In order to ensure that the speed of absorbing calcium ions by sodium alginate is consistent with the speed of releasing calcium ions by calcium sulfate, the invention needs to ensure that the dosage of sodium alginate is more than or equal to the dosage of soluble monovalent metal cation sulfate.
Finally, because the binding capacity of trivalent metal ions and gel is stronger, on one hand, the trivalent metal ions in the soluble trivalent metal salt and calcium ions on the surface of the sodium alginate gel foam are replaced by utilizing an ion exchange mechanism, and a small amount of replaced Ca 2+ The gel foam surface enters stratum water from the foam surface to be crosslinked with sodium alginate again, trivalent metal ions can interact with carboxylate radicals on gel foam side groups to generate strong ions, molecular chains on the gel foam surface can be stretched and locked to form polymer chains with anisotropic structures, and the anisotropic structures can enable the tensile strength and the elastic modulus of gel to reach megapascal level, so that the gel foam surface has better anti-interference capability. On the other hand, the water absorption of the soluble trivalent metal salt is utilized, so that the liquid discharge speed of the foam can be further slowed down, the liquid separation half life of the foam is enhanced, and the stability of the foam is greatly improved.
In the invention, the molecular structural formula of the hydroxysulfobetaine surfactant in the salt-sensitive self-crosslinking gel foam system is as follows:
wherein R is a compound having C 5 -C 11 Is a linear structure of (a).
The synthesis of the hydroxysulfobetaine surfactant adopts the following three-step synthesis method in the prior art: firstly, fully dissolving sodium sulfate and sodium bisulphite, dropwise adding epichlorohydrin, and carrying out recrystallization and purification to obtain an intermediate sodium hydroxy propane sulfonate; secondly, preparing another intermediate product dodecyl benzyl dimethanol amine by heating, filtering, drying and refluxing by using dimethanol amine and dodecyl benzyl oxide; finally, the two intermediate products are distilled and extracted under reduced pressure under the catalysis of potassium iodide to prepare the final product hydroxysulfobetaine surfactant.
The sulfonic acid group in the adopted hydroxysulfobetaine surfactant molecule can generate electrostatic repulsion to positive ions of calcium ions and the like in formation water, plays a role in isolating the calcium ions in the formation water, and is convenient for the sodium alginate to further absorb the calcium ions; the surfactant molecule also contains quaternary ammonium nitrogen structure, so that the surfactant can always maintain amphoteric state in stratum water, has good mildness and dispersibility, and can resist acid, alkali and salt, thereby achieving salt resistance in the whole.
In the invention, the soluble monovalent metal cation sulfate in the salt-sensitive self-crosslinking gel foam system is at least one of potassium sulfate and sodium sulfate.
Preferably, the soluble monovalent metal cation sulfate is sodium sulfate, which is soluble in water, and the solution is mostly neutral, colorless and transparent in appearance, and provides sufficient sulfate ions in the solution.
In the invention, the soluble trivalent metal salt in the salt-sensitive self-crosslinking gel foam system is one or more of ferric chloride, aluminum chloride or chromium chloride.
Preferably, the soluble metal salt is ferric chloride. Ferric chloride is in a black brown crystalline form, is easy to dissolve in water and has strong water absorbability, and plays roles of strengthening the anti-interference capability of a liquid film and reducing the liquid separation speed.
In the invention, the sodium alginate in the salt-sensitive self-crosslinking gel foam system is a commercial product, is a natural chain-locked high molecular polysaccharide polymer, and contains a large amount of-COOH on the surface, and is dissociated to generate-COO - Weak stability, but strong attraction to salt positive ions, especially calcium ions, so that a large amount of Ca in formation water 2+ Easy to enter-COO - In the hydration layer of (2), a gel network structure with a certain space structure is formed, so that the local salt-sensitive gel forming characteristic of the sodium alginate is enhanced.
In the invention, the salt-sensitive self-crosslinking gel foam system comprises the following raw materials in proportion: the gel foam system comprises the following raw materials in proportion: the hydroxysulfobetaine type surfactant is based on the mass of calcium salt in formation water: the mass ratio of calcium salt in the stratum water is 0.3-0.7:1,
the soluble monovalent metal cation sulfate: the mass ratio of calcium salt in the stratum water is 0.2-1:1,
the soluble trivalent metal salt: the mass ratio of calcium salt in the stratum water is 1.0-1.5:1,
the sodium alginate comprises the following components: the mass ratio of calcium salt in the stratum water is 0.5-1.0:1.
The foaming property, stability and economic benefit of the surfactant are combined, and the hydroxysulfobetaine type surfactant is determined in the above dosage range; the soluble monovalent metal cation sulfate reacts with calcium ions in the formation water according to a ratio of 1:1, and the calcium ions react with sodium alginate in a ratio of 1:1, but part of calcium ions can fall off after ion exchange, so the use amounts of the sodium alginate and the soluble monovalent metal cation sulfate are selected in the range.
The foaming volume of the salt-sensitive self-crosslinking gel foam system is 300-500mL; the half-life of the separating liquid is 1500-2400s; the temperature resistance is 90-120 ℃; mineralization resistance of 1 x 10 5 -21×10 4 mg/L; the bearing capacity of the gel foam system is more than or equal to 20g.
The preparation method of the salt-sensitive self-crosslinking gel foam system comprises the following steps:
(1) Adding sodium alginate into deionized water, and uniformly stirring to form a uniform mixed solution.
(2) Adding a hydroxysulfobetaine surfactant into the obtained mixed solution, and uniformly stirring and mixing at a low speed to form a compound solution; in this step, low-speed stirring is used in order to prevent premature foaming.
(3) Adding soluble monovalent metal cation sulfate into stratum water with a certain mineralization degree, stirring at a high speed for a certain time, uniformly mixing with the compound solution obtained in the step (2), and continuing stirring until uniform gel foam is generated; in order to prevent the foaming effect from being reduced due to overlarge foam viscosity, an air source is introduced in the whole stirring process.
(4) Adding a soluble trivalent metal salt solution into the obtained gel foam, and adopting low-speed stirring to enable trivalent metal ions to replace calcium ions in the surface layer of the gel to form the high-strength gel foam system. The low-speed stirring in this step is to prevent breakage of the macromolecular chains due to high-speed stirring.
In the invention, the rotating speed of uniform stirring in the step (1) of the preparation method of the salt-sensitive self-crosslinking gel foam system is 1000rpm, and the stirring time is 0.5-1h; the rotating speed of low-speed stirring in the step (2) is 600rpm, and the stirring time is 0.5-1h; the rotating speed of high-speed stirring in the step (3) is 6000rpm, and the stirring time is 0.5-1h; the rotating speed of low-speed stirring in the step (4) is 600rpm, and the stirring time is 0.5-1h; the air source in the step (3) is air, nitrogen or carbon dioxide.
The salt-sensitive self-crosslinking gel foam system or the salt-sensitive self-crosslinking gel foam system prepared by the preparation method is applied to fracture-cavity oil reservoirs and high-mineral oil reservoirs.
For example, the large fracture-cavity size of the Western fracture-cavity oil deposit results in weak shearing action, so that the regeneration capability of the foam is poor, the deformation difference of the foam is large, the conventional gel foam system is difficult to be applied to the Western fracture-cavity oil deposit, and the gel foam system can be applied to the Western fracture-cavity oil deposit. The gel foam system of the invention can also be applied to reservoirs with high mineralization caused by the deposition of the sea phase for many years.
The beneficial effects of the invention are as follows:
1. the invention prepares the salt-sensitive self-crosslinking gel foam system with high calcium salt resistance by using sodium alginate and hydroxysulfobetaine surfactant, and the sodium alginate is combined with Ca by utilizing the characteristic of ion rejection of the surfactant 2+ Is characterized by the speed of calcium sulfate to release Ca 2+ Velocity phase of (2)And the gel can fully react to form a uniform gel network structure, and finally, a macromolecular chain with an anisotropic structure is generated on the surface of the gel foam by utilizing a soluble trivalent metal salt solution through ion exchange, so that the disturbance resistance of the foam is enhanced, and on the other hand, the liquid separation speed of the foam can be slowed down through the water absorption of the trivalent metal salt, so that the half life of the foam is greatly improved. And with Ca 2+ The concentration is increased, the surface structure of the formed gel foam is more compact, collapse of the foam in a high-temperature environment is effectively inhibited, and the high-temperature and high-salt-resistant requirement of a fracture-cavity oil reservoir is met.
2. The invention takes sodium alginate as a gel agent and Ca in stratum water 2+ The calcium sulfate which is the product of the injection is used as a cross-linking agent, and Ca does not need to be additionally added 2+ Can effectively prevent the insufficient mixing of plugs during the adding of the cross-linking agent to cause uneven gel formation, and utilizes Ca in the formation water 2+ Can effectively reduce the production cost.
3. Ca in formation water 2+ The sodium alginate adopted by the invention forms gel and simultaneously can form Ca in a local range 2+ Adsorption of free Ca 2+ The concentration is reduced, which is beneficial to the stability of the foam.
4. The sodium alginate used as a raw material is a natural chain-locked high molecular polysaccharide polymer, has stability, solubility, viscosity and safety, gel foam is dehydrated at about 120 ℃ to be changed into alginate fibers, and the fibers can enhance the shearing capacity of base solution after liquid separation in stratum, realize foam shearing regeneration and meet the requirement of environmental protection.
5. The invention adopts low-cost sodium alginate to enhance the salt tolerance of the surfactant, and greatly reduces the gel cost while forming gel to enhance the foam stability, and compared with the existing gel foam system, the cost can be reduced by 10-20%.
6. The sodium alginate adopted by the invention can be glued after encountering calcium sulfate for about 5-10min, and the process is irreversible, so that adverse influence of dilution effect of the sodium alginate by injected water can be reduced, and the profile control characteristic of the gel in a fracture-cavity oil reservoir is ensured.
7. The sodium alginate gel foam system has strong regeneration capability and dynamic stability, not only can selectively block the high-permeability layer and the air channeling layer, but also has selectivity in the high-ore layer, and can sweep the unused residual oil.
8. The sodium alginate gel foam is simple to operate, and can be degraded by microorganisms after being dehydrated, so that the formation is not permanently damaged.
Detailed Description
The present invention will be described in detail with reference to examples.
1. The hydroxysulfobetaine type surfactant used in examples and comparative examples has a molecular structural formula of:
wherein R is C 7 H 15 。
2. Sodium alginate was purchased from Shanghai Xintai industries, inc.
3. Sodium dodecyl sulfate surfactant is available from Shanghai Meilin Biochemical technology Co., ltd and has the molecular formula of C 12 H 25 O 4 NaS。
4. The foamability and stability of the products of the examples and comparative examples were evaluated using the conventional laboratory method Waring Blender method.
5. Ca in formation Water used in examples and comparative examples 2+ The content is up to 0.7X10 4 ~1×10 4 mg/L。
Example 1
The salt-sensitive self-crosslinking gel foam system comprises the following raw materials in parts by weight: 0.5g of hydroxysulfobetaine surfactant, 0.7g of sodium alginate, 0.5g of sodium sulfate, 1.0g of ferric chloride and 100g of deionized water.
The preparation method of the salt-sensitive self-crosslinking gel foam system comprises the following specific steps:
(1) Adding 0.7g of sodium alginate into 100g of deionized water, and uniformly stirring for 1h at 1000rpm by using a magnetic stirrer to form a uniform mixed solution;
(2) Adding 0.5g of hydroxysulfobetaine surfactant into the obtained mixed solution, and stirring at a low speed of 600rpm for 0.5h to uniformly mix the mixed solution to form a compound solution;
(3) In the presence of 0.7g CaCl 2 Adding 0.5g of sodium sulfate into the stratum aqueous solution of the step (2), stirring at a high speed of 6000rpm for 0.5h until the mixture is uniformly mixed, then adding the solution into the compound solution obtained in the step (2), continuously stirring at a high speed of 6000rpm for 3min, and continuously introducing nitrogen into a stirring vessel during stirring to obtain the stable gel foam.
(4) To the obtained gel foam, a salt solution containing 1.0g of ferric chloride was added, and the mixture was stirred at a low speed of 600rpm for 0.5 hours, thereby forming a high-strength gel foam.
Example 2
The salt-sensitive self-crosslinking gel foam system comprises the following raw materials in parts by weight: 0.5g of hydroxysulfobetaine surfactant, 1.0g of sodium alginate, 1.0g of sodium sulfate, 1.2g of ferric chloride and 100g of deionized water.
The aqueous formation solution of step (3) of the gel foam system preparation method of this example contained 1.0g CaCl 2 The other steps are the same as in example 1.
Example 3
The salt-sensitive self-crosslinking gel foam system comprises the following raw materials in parts by weight: 0.3g of hydroxysulfobetaine surfactant, 0.5g of sodium alginate, 0.2g of sodium sulfate, 1.0g of ferric chloride and 100g of deionized water.
The aqueous formation solution of step (3) of the gel foam system preparation method of this example contained 1.0g CaCl 2 The other steps are the same as in example 1.
Example 4
The salt-sensitive self-crosslinking gel foam system comprises the following raw materials in parts by weight: 0.7g of hydroxysulfobetaine surfactant, 1.0g of sodium alginate, 1.0g of sodium sulfate, 1.2g of ferric chloride and 100g of deionized water.
Gel foam System of this exampleThe aqueous solution of the stratum in the step (3) of the preparation method contains 1.0g CaCl 2 The other steps are the same as in example 1.
Comparative example 1
The foam system of the comparative example consists of the following components in parts by weight: 0.5g of hydroxysulfobetaine type surfactant, 0.7g of sodium alginate and 100g of deionized water.
The preparation method of the gel foam system comprises the following steps:
(1) Adding 0.7g of sodium alginate into 100g of deionized water, and uniformly stirring for 1h at 1000rpm by using a magnetic stirrer to form a uniform mixed solution;
(2) Adding 0.5g of hydroxysulfobetaine surfactant into the obtained mixed solution, and stirring at a low speed of 600rpm for 0.5h to uniformly mix the mixed solution to form a compound solution;
(3) The obtained compound solution is stirred for 3min at a high speed of 6000rpm by using a Waring Blender method to generate stable foam.
The foam system of this comparative example was used with formation water containing 0.7g CaCl 2 。
Comparative example 2
The foam system of this comparative example is the same as that of comparative example 1.
The preparation method of the foam system of the comparative example is different from that of comparative example 1 in that nitrogen is introduced as a gas source during stirring by using the Waring Blender method, and other steps are the same as those of comparative example 1. The foam system of this comparative example was used with formation water containing 0.7g CaCl 2 。
Comparative example 3
The foam system of the comparative example consists of the following components in parts by weight: 0.5g of hydroxysulfobetaine surfactant, 0.7g of sodium alginate, 0.5g of sodium sulfate and 100g of deionized water.
The preparation method of the foam system comprises the following specific steps:
(1) Adding 0.7g of sodium alginate into 100g of deionized water, and uniformly stirring for 1h at 1000rpm by using a magnetic stirrer to form a uniform mixed solution;
(2) Adding 0.5g of hydroxysulfobetaine surfactant into the obtained mixed solution, and stirring at a low speed of 600rpm for 0.5h to uniformly mix the mixed solution to form a compound solution;
(3) In the presence of 0.7g CaCl 2 Adding 0.5g of sodium sulfate into the stratum aqueous solution of the step (2), stirring at a high speed of 6000rpm for 0.5h until the mixture is uniformly mixed, then adding the solution into the compound solution obtained in the step (2), continuously stirring at a high speed of 6000rpm for 3min, and continuously introducing nitrogen into a stirring vessel during stirring to obtain the stable colloid foam.
Comparative example 4
The foam system of the comparative example consists of the following components in parts by weight: 0.5g of hydroxysulfobetaine type surfactant, 1.0g of sodium alginate and 100g of deionized water.
The foam system was prepared in the same manner as in comparative example 1. The foam system of this comparative example was used with formation water containing 1.0g CaCl 2 。
Comparative example 5
The foam system of the comparative example consists of the following components in parts by weight: 0.5g of hydroxysulfobetaine surfactant, 1.0g of sodium alginate, 1.0g of sodium sulfate and 100g of deionized water.
The preparation method of the foam system comprises the following specific steps:
(1) Adding 1.0g of sodium alginate into 100g of deionized water, and uniformly stirring for 1h at 1000rpm by using a magnetic stirrer to form a uniform mixed solution;
(2) Adding 0.5g of hydroxysulfobetaine surfactant into the obtained mixed solution, and stirring at a low speed of 600rpm for 0.5h to uniformly mix the mixed solution to form a compound solution;
(3) In the presence of 1.0g CaCl 2 Adding 1.0g of sodium sulfate into the stratum aqueous solution of the step (2), stirring at a high speed of 6000rpm for 0.5h until the mixture is uniformly mixed, then adding the solution into the compound solution obtained in the step (2), continuously stirring at a high speed of 6000rpm for 3min, and continuously introducing nitrogen into a stirring vessel during stirring to obtain the stable colloid foam.
Comparative example 6
The foam system of the comparative example consists of the following components in parts by weight: 0.5g of dodecyl sodium sulfate surfactant, 1.0g of sodium alginate, 1.0g of sodium sulfate and 100g of deionized water.
The foam system was prepared in the same manner as in comparative example 5.
The data of the foaming volume and the half-life of the liquid for the foam systems prepared in examples 1 to 4 and comparative examples 1 to 6 are shown in Table 1.
Table 1 comparison of foam properties of different systems
From table 1 above, the salt-sensitive self-crosslinking gel foam system based on synergistic stabilization of sodium alginate provided by the invention has excellent foaming performance and half-life period, and can meet the requirement of complex oil-gas fields on high foam stability.
Claims (9)
1. A salt-sensitive self-crosslinking gel foam system, which is characterized by comprising the following raw materials: a hydroxysulfobetaine surfactant, a soluble monovalent metal cation sulfate, a soluble trivalent metal salt, sodium alginate and deionized water; wherein the dosage of the sodium alginate is more than or equal to the dosage of the soluble monovalent metal cation sulfate.
2. The salt-sensitive self-crosslinking gel foam system of claim 1, wherein the hydroxysulfobetaine surfactant has a molecular structural formula of:
wherein R is a compound having C 5 -C 11 Is a linear structure of (a).
3. The salt-sensitive self-crosslinking gel foam system of claim 1, wherein the soluble monovalent metal cation sulfate salt is at least one of potassium sulfate and sodium sulfate.
4. The salt-sensitive self-crosslinking gel foam system of claim 1, wherein the soluble trivalent metal salt is one or more of ferric chloride, aluminum chloride, or chromium chloride.
5. The salt-sensitive self-crosslinking gel foam system according to claim 1, wherein the gel foam system comprises the following raw materials in proportion: the hydroxysulfobetaine type surfactant is based on the mass of calcium salt in formation water: the mass ratio of calcium salt in the stratum water is 0.3-0.7:1,
the soluble monovalent metal cation sulfate: the mass ratio of calcium salt in the stratum water is 0.2-1:1,
the soluble trivalent metal salt: the mass ratio of calcium salt in the stratum water is 1.0-1.5:1,
the sodium alginate comprises the following components: the mass ratio of calcium salt in the stratum water is 0.5-1.0:1.
6. The salt-sensitive self-crosslinking gel foam system of any one of claims 1-5, wherein the foaming volume is 450-500mL; the half-life of the separating liquid is 1550-2400s; the temperature resistance is 90-120 ℃; mineralization resistance of 1 x 10 5 -21×10 4 mg/L; the bearing capacity of the gel foam system is more than or equal to 20g.
7. A method of preparing a salt-sensitive self-crosslinking gel foam system as claimed in any one of claims 1 to 5, comprising the steps of:
(1) Adding sodium alginate into deionized water, and uniformly stirring to form a uniform mixed solution;
(2) Adding a hydroxysulfobetaine surfactant into the obtained mixed solution, and uniformly stirring and mixing at a low speed to form a compound solution;
(3) Adding soluble monovalent metal cation sulfate into the stratum water containing mineralization degree, stirring at a high speed, uniformly mixing with the compound solution obtained in the step (2), and continuing stirring until uniform gel foam is generated; introducing an air source during the whole stirring process;
(4) And adding a soluble trivalent metal salt solution into the obtained gel foam, and stirring at a low speed to form the gel foam system.
8. The method for preparing a salt-sensitive self-crosslinking gel foam system as claimed in claim 7, wherein the rotation speed of uniform stirring in the step (1) is 1000rpm, and the stirring time is 0.5-1h; the rotating speed of low-speed stirring in the step (2) is 600rpm, and the stirring time is 0.5-1h; the rotating speed of high-speed stirring in the step (3) is 6000rpm, and the stirring time is 0.5-1h; the rotating speed of low-speed stirring in the step (4) is 600rpm, and the stirring time is 0.5-1h; the air source in the step (3) is air, nitrogen or carbon dioxide.
9. Use of a salt-sensitive self-crosslinking gel foam system according to any one of claims 1 to 5 or a salt-sensitive self-crosslinking gel foam system produced by a method of production according to any one of claims 7 to 8 in a fracture-cave reservoir, a high-mineral reservoir.
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