CN115216284B - Three-phase foam system suitable for regulation and control of deep clastic rock oil reservoir gas channeling - Google Patents
Three-phase foam system suitable for regulation and control of deep clastic rock oil reservoir gas channeling Download PDFInfo
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- CN115216284B CN115216284B CN202110422625.7A CN202110422625A CN115216284B CN 115216284 B CN115216284 B CN 115216284B CN 202110422625 A CN202110422625 A CN 202110422625A CN 115216284 B CN115216284 B CN 115216284B
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- 239000006260 foam Substances 0.000 title claims abstract description 81
- 230000005465 channeling Effects 0.000 title claims abstract description 27
- 239000011435 rock Substances 0.000 title claims abstract description 20
- 239000004088 foaming agent Substances 0.000 claims abstract description 29
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 28
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 28
- 238000005886 esterification reaction Methods 0.000 claims abstract description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000004666 short chain fatty acids Chemical class 0.000 claims abstract description 20
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 230000001276 controlling effect Effects 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 9
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 8
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 9
- 238000005187 foaming Methods 0.000 description 62
- 239000007789 gas Substances 0.000 description 40
- 239000007788 liquid Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000033558 biomineral tissue development Effects 0.000 description 21
- 230000000087 stabilizing effect Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 238000000605 extraction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
Landscapes
- 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)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention provides a three-phase foam system suitable for regulating and controlling gas channeling of a deep clastic rock oil reservoir, which comprises the following components: 0.4wt% to 0.8wt% of foaming agent, 0.8wt% to 1.2wt% of foam stabilizer, and the balance of water; wherein the foaming agent comprises short-chain hydroxysulfobetaine with 8-16 carbon atoms and long-chain hydroxysulfobetaine with 18-24 carbon atoms, and the foam stabilizer comprises an esterification product generated by esterification reaction of polyethylene glycol and short-chain fatty acid with 4-6 carbon atoms. The three-phase foam system has the characteristics of good high temperature resistance, salt resistance and the like, and can improve the gas driving efficiency.
Description
Technical Field
The invention relates to the field of petroleum exploitation, in particular to a three-phase foam system suitable for regulating and controlling gas channeling of deep clastic rock oil reservoirs and application thereof.
Background
In the gas-driven oil extraction process of oil field development, the gas channeling problem is usually generated under the influence of factors such as reservoir (stratum) heterogeneity, oil-gas fluidity difference, gravity difference and the like, so that the gas driving wave and efficiency are low, and the recovery ratio is reduced, therefore, the gas channeling channel in the stratum is blocked, the occurrence of the gas channeling phenomenon is restrained, and the gas-driven recovery ratio is necessary to be improved.
Foam can easily enter the gas channeling passage, the gas channeling phenomenon can be inhibited by generating foam with a foaming agent, and related researches and reports for inhibiting the gas channeling phenomenon by using the foaming agent are currently carried out, for example, patent document CN102212348A discloses a salt-resistant and methanol-resistant foam discharging agent which can resist 18 multiplied by 10 4 The mineralization degree of mg/L, while the components of the composition contain fluorocarbon surfactant, the composition has the defects of high cost, great harm to the environment and the like; patent document CN102660251A discloses a temperature-resistant and salt-resistant foaming agent for carbon dioxide flooding profile control, and the system is suitable for sealing channeling profile control of carbon dioxide flooding under the address condition that the temperature is not higher than 110 ℃ and the mineralization degree is not higher than 150000 ppm; patent document CN102399548A discloses a foaming agent for complex foam oil displacement, which consists of hydroxysulfobetaine, 1227 and dodecanol, and has the temperature resistance of 50 ℃ and the salt resistance of 8 multiplied by 10 4 mg/L; patent document CN103881683a discloses a method for CO 2 The foaming agent for blocking gas channeling in oil displacement comprises anionic surfactant, imidazole type amphoteric surfactant, betaine type amphoteric surfactant, foam stabilizer and water, wherein the foaming agent has a temperature resistance of 80 ℃ and a salt resistance of 10 multiplied by 10 4 mg/L; patent document CN103952132B discloses a salt synergistic heat-resistant salt-resistant foam system which is suitable for the mineralization degree of 20 multiplied by 10 at the temperature of below 90 DEG C 4 A mg/L or less reservoir; patent document CN104109520B discloses a foaming agent suitable for high-temperature and high-salt oil reservoirs, which is suitable for the oil reservoirs with the temperature of not higher than 95 ℃ and the mineralization degree of 10 multiplied by 10 4 ～15×10 4 mg/L and calcium-magnesium ion concentration lower than 10×10 4 mg/L reservoir; patent CN106318362B discloses a novel carbon dioxide foaming agent for oil displacement, which is suitable for oil reservoir with the temperature not higher than 150 ℃ and the mineralization degree lower than 80000mg/L and the calcium and magnesium ion concentration lower than 1000mg/L reservoir; patent document CN109777393B discloses a foam oil displacement agent which has the temperature resistance of 130 ℃ and the mineralization resistance of 22 multiplied by 10 4 mg/L, the polyethylene glycol gradually loses the foam stabilizing capability due to thermal degradation at 130 ℃, so that the foaming system is not suitable for oil reservoir environments in severe environments such as higher temperature, mineralization degree and the like.
However, the reservoir environment is complex, the foaming capacity and the foam stabilizing capacity of the existing foaming agent are poor, and especially, the effect of the existing foaming agent on inhibiting the gas channeling phenomenon is limited for reservoirs with severe conditions such as deep clastic rock reservoirs and the like, such as high temperature, high mineralization degree and the like. Wherein, the foam stabilizer is introduced into the foaming system to improve the stability of the foam generated by the foaming system to a certain extent, and the common foam stabilizer generally comprises inorganic particles such as clay, fly ash, cement and the like, and nano SiO 2 However, these foam stabilizers have many drawbacks, such as difficulty in injecting into the foaming system and easiness in sedimentation, and the nano SiO 2 And the materials such as sol, gel dispersion and the like have the defects of poor stability, complex production process and the like.
Therefore, how to improve the foaming capacity, foam stabilizing capacity and other performances of foaming agents used in the oilfield gas-driven oil extraction process, especially the foaming capacity, foam stabilizing capacity and other performances under severe conditions such as high temperature, hypersalinity and the like, and improve the gas channeling prevention effect are important problems faced by the technicians in the field.
Disclosure of Invention
The invention provides a three-phase foam system suitable for regulating and controlling gas channeling of deep clastic rock oil reservoirs, which has good foaming capacity and foam stabilizing capacity, can be particularly applied to high-temperature and high-mineralization environments, has excellent gas channeling prevention effect under the high-temperature and high-mineralization environments, improves gas flooding recovery ratio, and can effectively overcome the defects existing in the prior art.
In one aspect of the invention, a three-phase foam system suitable for regulation and control of gas channeling of deep clastic rock reservoirs is provided, comprising the following components: 0.4wt% to 0.8wt% of foaming agent, 0.8wt% to 1.2wt% of foam stabilizer, and the balance of water; wherein the foaming agent comprises short-chain hydroxysulfobetaine with 8-16 carbon atoms and long-chain hydroxysulfobetaine with 18-24 carbon atoms, and the foam stabilizer comprises an esterification product generated by esterification reaction of polyethylene glycol and short-chain fatty acid with 4-6 carbon atoms.
According to one embodiment of the invention, the mass ratio of the short-chain hydroxysulfobetaine to the long-chain hydroxysulfobetaine is 1.5:1 to 1:1.5.
According to one embodiment of the invention, the short chain hydroxysulfobetaine comprises cetyl hydroxysulfobetaine.
According to an embodiment of the invention, the long chain hydroxysulfobetaine comprises behenyl hydroxysulfobetaine.
According to one embodiment of the invention, the foam stabilizer is solid phase particles with a particle size of 80nm to 200 nm.
According to one embodiment of the present invention, the polyethylene glycol has a molecular weight of 2000 to 20000.
According to one embodiment of the present invention, the polyethylene glycol has a molecular weight of 6000 to 10000.
According to an embodiment of the invention, the short chain fatty acid comprises at least one of n-butyric acid, n-valeric acid, n-caproic acid.
According to an embodiment of the present invention, the esterification reaction conditions are: the esterification reaction temperature is 100-120 ℃, and the mol ratio of the short chain fatty acid to the polyethylene glycol is 1 (1.1-1.3).
In another aspect, the invention provides an application of the foaming system in a gas-driven oil extraction process of an oil reservoir.
The three-phase foam system provided by the invention has good foaming capacity and foam stabilizing capacity, can effectively inhibit the phenomenon of gas channeling in the gas-driven oil extraction process, and can be especially applied to high temperature (up to 150 ℃ or even more) and high mineralization (25 multiplied by 10) 4 mg/L or even above), the research shows that under the high-temperature and hypersalinity environment, the foaming volume of the foaming system reaches more than 400mL, and the half-life of the foam reaches more than 4.3hThe half-life of the separated liquid reaches more than 4.3min, the resistance factor reaches more than 140, and the excellent gas channeling prevention capability is shown.
Detailed Description
The present invention will be described in further detail below for the purpose of better understanding of the aspects of the present invention by those skilled in the art.
The three-phase foam system (or referred to as a foam system) suitable for regulating and controlling the gas channeling of deep clastic rock oil reservoirs comprises the following components: 0.4wt% to 0.8wt% of foaming agent, 0.8wt% to 1.2wt% of foam stabilizer, and the balance of water; wherein the foaming agent comprises short-chain hydroxysulfobetaine with 8-16 carbon atoms and long-chain hydroxysulfobetaine with 18-24 carbon atoms, and the foam stabilizer comprises an esterification product generated by esterification reaction of polyethylene glycol and short-chain fatty acid with 4-6 carbon atoms.
Specifically, the above-mentioned short-chain hydroxysulfobetaine and long-chain hydroxysulfobetaine are alkyl hydroxysulfobetaine amphoteric surfactants, which have the properties of temperature resistance, salt resistance, etc., and the inventors have found that from the viewpoint of molecular structure, the foam stability has a great relationship with the cohesion between the molecules of the surfactants, when the cohesion between the molecules of the surfactants is greater, the foam liquid film is more stable, the macro-appearance is better, and the cohesion between the molecules of the surfactants and the carbon chain length in the molecular structure thereof are normally positively correlated, i.e., the longer the carbon chain, the greater the cohesion between the molecules of the surfactants, the more stable the foam liquid film, and therefore, the introduction of the above-mentioned long-chain hydroxysulfobetaine of a specific carbon number in the foaming system is advantageous for ensuring the foam stability of the foaming system; from the viewpoint of Critical Micelle Concentration (CMC), the lower the CMC, the higher the foaming efficiency of the surfactant, in the foaming system of the invention, the short-chain hydroxysulfobetaine and the long-chain hydroxysulfobetaine with specific carbon numbers are compounded, and the synergistic effect of the two occurs, so that the CMC of the mixed system is lower than that of any CMC, thereby the excellent foaming efficiency is shown, and simultaneously, the compounding of the two also ensures that the surfactant molecules are compacter in the gas-liquid interface of the foam, the strength of the foam liquid film is higher, and the macroscopically shows that the liquid film is more stable. And compared with other surfactants such as carboxybetaine, the adsorption amount of the hydroxysulfobetaine on the surface (generally electronegativity) of reservoir rock such as clastic rock is smaller, so that the propagation of a foaming system in the reservoir is facilitated, and the gas channeling prevention effect is further ensured.
In addition, in the foaming system of the invention, the esterified product generated by esterification reaction of polyethylene glycol and C4-C6 short chain fatty acid is used as the foam stabilizer matched with the long chain hydroxysulfobetaine and the short chain hydroxysulfobetaine, thus further ensuring the foam stabilizing capability of the foaming system, the esterified product has good temperature resistance and salt tolerance, further ensuring the application effect of the foaming system in a high-temperature and high-mineralization environment, and especially ensuring that the foaming system is applied to the environment with the temperature of about 150 ℃ and even higher and the mineralization degree of 25 multiplied by 10 4 In a reservoir environment (such as a deep clastic rock oil reservoir environment) with mg/L or even higher, the gas-flooding recovery ratio is improved, and the gas-flooding recovery ratio is effectively inhibited.
The short-chain hydroxysulfobetaine can be adsorbed on a gas-liquid interface rapidly and is easy to foam, but because the short lipophilic group of the short-chain hydroxysulfobetaine has relatively poor foam stabilizing capability, the long-chain hydroxysulfobetaine has long lipophilic group, has low adsorption speed on the gas-liquid interface and weaker foam stabilizing capability, but the short-chain hydroxysulfobetaine generally has good foam stabilizing capability once being adsorbed on the gas-liquid interface, so that the short-chain hydroxysulfobetaine and the long-chain hydroxysulfobetaine are compounded to be used as the foaming functional components of the foaming system, and the foaming capability, the foam stabilizing capability and other performances of the foaming system can be guaranteed. Further optimization of the performance of the foaming system shows that the mass ratio of short chain hydroxysulfobetaine to long chain hydroxysulfobetaine described above can generally be in the range of 1.5:1 to 1:1.5, e.g., 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1:1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, or any two of these.
The foaming agent has good temperature resistance and salt resistance, foaming capacity, foam stabilizing capacity and propagation performance in reservoir rocks such as clastic rocks compared with common foaming agents such as conventional alpha-olefin sulfonate, alkyl diphenyl disulfonate, carboxymethyl polyoxyethylene alkylphenol (or alcohol) ether, tertiary amine oxide surfactants, alkyl betaine surfactants and the like. According to a further development of the invention, in some preferred embodiments, the short chain hydroxysulfobetaine may comprise cetyl hydroxysulfobetaine and the long chain hydroxysulfobetaine may comprise behenyl hydroxysulfobetaine.
In the above-mentioned foaming system, the mass content of the foaming agent is, for example, in the range of 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt% or any two thereof, the mass content of the foam stabilizer is, for example, in the range of 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt% or any two thereof, and the balance is water.
In the invention, the foaming system can be prepared by uniformly mixing the foaming agent, the foam stabilizer and the water according to the proportion. The water in the foaming system can be mineral water with a certain mineralization degree, and in the specific implementation, the mineralization degree of the mineral water used for preparing the foaming system is basically the same as or is close to the mineralization degree of the oil reservoir environment suitable for the foaming system, and according to the research of the invention, the mineralization degree of the water in the foaming system can be more than or equal to 25 multiplied by 10 4 The salt water with the high mineralization degree is compounded with the foaming agent and the foam stabilizer of the specific types, and the formed three-phase foam system has good stability and foaming performance and can be applied to the salt water with the mineralization degree not less than 25 multiplied by 10 4 mg/L, high mineralization environment with temperature not lower than 150 ℃.
The esterified product obtained by esterification of polyethylene glycol and short chain fatty acid is generally solid-phase granular, and the foaming system of the invention is particularly a three-phase foaming system. The esterification product is easy to gather at the gas-liquid interface, and the soft particles adsorbed on the gas-liquid interface greatly reduce the liquid discharge speed of the bubble liquid film, enhance the strength of the bubble liquid film and make the bubbles more stable; the foam stabilizing system has the advantages of good dispersion performance in the foaming system, difficult occurrence of sedimentation and other phenomena, difficult damage to a reservoir, good thermal stability, simple preparation process and the like. In some embodiments, the foam stabilizer may be solid phase particles having a particle size of 80nm to 200nm, for example, in the range of 80nm, 100nm, 120nm, 150nm, 180nm, 200nm, or any two thereof, which may be advantageous for further improving the performance of the foaming system.
In some embodiments, the polyethylene glycol has a molecular weight of 2000 to 20000, e.g., 2000, 4000, 6000, 8000, 10000, 12000, 14000, 16000, 18000, 20000, or any two thereof, and generally preferably 6000 to 10000, which facilitates the combination of the foam stabilizer with the foaming agent and improves the foaming and foam stabilizing properties of the foaming system.
The number of carboxyl groups (-COOH) in the above short chain fatty acid is preferably 1, which may include at least one of n-butyric acid, n-valeric acid, and n-caproic acid. The esterification product can specifically comprise at least one of polyethylene glycol n-butyrate generated by esterification reaction of polyethylene glycol and n-butyric acid, polyethylene glycol n-valerate generated by esterification reaction of polyethylene glycol and n-valeric acid and polyethylene glycol n-caproate generated by esterification reaction of polyethylene glycol and n-caproic acid.
In general, the esterification conditions are as follows: the esterification reaction temperature is 100-120 ℃, such as 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ or any two of them, the mol ratio (acid-alcohol ratio) of short chain fatty acid to polyethylene glycol is 1 (1.1-1.3), such as 1:1.1, 1:1.2, 1:1.3 or any two of them, and the esterified product prepared by the conditions is favorable for further improving the performance of the foaming system.
In order to further improve the esterification reaction efficiency, polyethylene glycol and short chain fatty acid can be subjected to esterification reaction under the action of a catalyst to prepare an esterification product, and the catalyst can comprise p-toluenesulfonic acid. In the specific implementation, polyethylene glycol and short-chain fatty acid are refluxed at 100-120 ℃ in the presence of a catalyst for esterification reaction, the reaction time is generally about 8+/-1 hours, after the reaction is finished, the reaction product is placed in methanol to prepare a methanol solution with the mass fraction of 50% of the reaction product, and then the methanol solution is dripped into saline water with the temperature of about 90 ℃ and the mineralization degree (salt content) of 250000ml/L, and soft particles with the particle size of 80-200 nm are formed by stirring, so that the foam stabilizer is prepared. Optionally in brine (simulated brine) usedDivalent metal ions mainly containing Ca 2+ And Mg (magnesium) 2+ ，Ca 2+ Is 11273Mg/L, mg 2+ Is 1519mg/L.
Specifically, the above foam stabilizer is an esterified product of polyethylene glycol and a short chain fatty acid, which is in a highly mineralized brine having a salt content of about 250000ml/L, and when the temperature is sufficiently large (e.g., 90 ℃ as above), hydrogen bonds between the esterified product and water molecules are broken, and the water solubility thereof is lowered, whereby the molecular weight is contracted to form soft particles. The introduction of the short-chain fatty acid enables the soft particles to have weak oil affinity, so that the soft particles are easy to gather at the gas-liquid interface of bubbles generated by a foaming system, the soft particles adsorbed on the gas-liquid interface greatly reduce the liquid discharge speed of the bubble liquid film, the strength of the bubble liquid film is enhanced, and the bubbles are more stable.
As an extension of the idea of the invention, the invention also provides application of the foaming system in the oil reservoir gas-driven oil extraction process, so as to inhibit the gas channeling phenomenon in the gas-driven oil extraction process and improve the recovery ratio. The gas-driven oil extraction process is, for example, a carbon dioxide-driven oil extraction process, but not limited thereto, and may be a gas-driven oil extraction process using other gases. The research result shows that the foaming system of the invention can be applied to deep clastic rock or other high-temperature (up to 150 ℃ or even more) high-mineralization (25 multiplied by 10) 4 mg/L or even above) and shows excellent gas channeling prevention effect, and the recovery ratio is remarkably improved.
For the purpose of promoting an understanding of the principles of the invention, reference will now be made in detail to specific examples, some but not all of which are illustrated in the accompanying drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples, the foam stabilizer (esterification product) used was prepared as follows, unless otherwise specified: reflux-reacting polyethylene glycol and short-chain fatty acid for 8 hours at 110 ℃ under the catalysis of p-toluenesulfonic acid; placing the obtained reaction product into methanol to prepare a methanol solution with the mass concentration of 50% of the reaction product, then dripping the methanol solution into saline water with the temperature of about 90 ℃ and the mineralization degree (salt content) of 250000ml/L, and stirring to form soft particles; wherein, the mol ratio of the short chain fatty acid to the polyethylene glycol is 1:1.2; the molecular weight of polyethylene glycol, short chain fatty acid, and particle size of soft particles are shown in Table 1.
In the following examples, the foaming system is prepared by mixing a foaming agent, a foam stabilizer and simulated saline with the mineralization degree of 250000mg/L according to the corresponding proportion.
In the following examples and comparative examples, the static properties and blocking properties of the foaming system were evaluated according to the following procedures:
(1) Static Performance evaluation
Static performance evaluation is carried out in a high-temperature high-pressure foam meter, and experimental conditions are as follows: the temperature is 150 ℃ and the pressure is 3MPa; the experimental procedure was as follows: 100ml of the foaming system was injected into a high temperature and high pressure foamer and then stirred at a speed of 3000r/min for 1min, after stirring was completed (the foaming system was substantially completely converted into foam), the initial foam volume produced was designated as foam volume V f And begin recording the change in the bubbling volume and the volume of the effluent over time; the time period from the beginning of recording to the time when the volume of the precipitated liquid reaches 50mL is the half-life T of the precipitated liquid l The duration from the beginning of the recording to the time when the foam volume was reduced to half the initial foam volume was the foam half-life T f 。
(2) Evaluation of blocking Property
The foam plugging performance represents the gas channeling prevention capability of the foam, and the relative resistance factor R of a foaming system is measured through a core displacement experiment F ，R F ＝ΔP 1 /ΔP 0 Δp was measured according to the following core displacement experiment 1 and core displacement experiment 2, respectively 1 、ΔP 0 (permeability of core used see table 1):
core displacement experiment 1 (liquid injected into the core is a foaming system): under the condition of back pressure of 3MPa and temperature of 150 ℃, injecting nitrogen and a foaming system into the rock core according to the volume ratio of gas to liquid (the volume ratio of the nitrogen to the foaming system) of 9:1 for gas driving and foamingThe injection speed of the system is 0.5mL/min, after the injection pressure is stable (i.e. when the core migration reaches balance), the pressure difference value at two ends of the core is recorded, namely the plugging pressure difference delta P 1 ；
Core displacement experiment 2 (the liquid injected into the core is water): at 150 ℃, injecting nitrogen and water into the rock core according to the volume ratio of gas to liquid (the volume ratio of nitrogen to water) of 9:1 for gas driving, wherein the injection speed of water is 0.5mL/min, and after the injection pressure is stable (namely when the migration of the rock core reaches balance), recording the differential pressure value of two ends of the rock core, namely the plugging differential pressure delta P 0 。
The foaming system composition (mass fraction of foaming agent in the foaming system, foaming agent composition, molecular weight of polyethylene glycol and short chain fatty acid to be made into foam stabilizer, particle size of foam stabilizer in solid phase particle) of each example and comparative example, performance evaluation result of foaming system (foaming volume V f Half-life of analysis solution T l Half-life T of foam f Resistance factor R F ) Test R F The permeability of the cores used in the core displacement experiments of (2) are summarized in table 1; the mass fractions of the components in Table 1 refer to the mass content of the components in the foaming system, unless otherwise specified.
TABLE 1
* The foaming agent consists of hexadecyl hydroxysulfobetaine and docosyl hydroxysulfobetaine, and the "mass ratio (short chain: long chain)" refers to the mass ratio of hexadecyl hydroxysulfobetaine to docosyl hydroxysulfobetaine.
As can be seen from Table 1, the resistance factor of the foaming systems of examples 1 to 8 is as high as 146 or more at 150 ℃ and 25000mg/L, which is far higher than that of the foaming systems of comparative examples 1 to 3, the foaming volume is 400mL or more, the foam half-life is 4.33h or more, and the liquid separation half-life is 4.35min or more, showing excellent channeling blocking capability, indicating that the foaming system of the invention can be especially applied to deep clastic rock and other high temperatures (up to 150 ℃ or even more) and high mineralization(25×10 4 mg/L or even above), the occurrence of gas channeling phenomenon in the gas flooding process of the oil deposit is inhibited, and the recovery ratio is improved.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The three-phase foam system suitable for regulating and controlling the gas channeling of deep clastic rock oil reservoirs is characterized by comprising the following components: 0.4wt% to 0.8wt% of foaming agent, 0.8wt% to 1.2wt% of foam stabilizer, and the balance of water;
wherein the foaming agent comprises hexadecyl hydroxysulfobetaine and docosyl hydroxysulfobetaine, and the mass ratio of the hexadecyl hydroxysulfobetaine to the docosyl hydroxysulfobetaine is (1-1.5): 1, a step of;
the foam stabilizer comprises an esterification product generated by esterification reaction of polyethylene glycol and short-chain fatty acid with carbon number of C4-C6, wherein the molecular weight of the polyethylene glycol is 2000-20000, the short-chain fatty acid comprises at least one of n-butyric acid, n-valeric acid and n-caproic acid, and the mol ratio of the short-chain fatty acid to the polyethylene glycol is 1 (1.1-1.3).
2. The three-phase foam system according to claim 1, wherein the foam stabilizer is solid phase particles having a particle size of 80nm to 200 nm.
3. The three-phase foam system according to claim 1, wherein the polyethylene glycol has a molecular weight of 6000 to 10000.
4. The three-phase foam system according to claim 1, wherein the esterification reaction conditions are: the esterification reaction temperature is 100-120 ℃.
5. Use of the three-phase foam system according to any one of claims 1 to 4 in a gas-driven oil recovery process of an oil reservoir.
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