CN114058354A - Foam oil displacement agent suitable for high-salinity low-permeability reservoir and preparation method and application thereof - Google Patents
Foam oil displacement agent suitable for high-salinity low-permeability reservoir and preparation method and application thereof Download PDFInfo
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- CN114058354A CN114058354A CN202111476384.0A CN202111476384A CN114058354A CN 114058354 A CN114058354 A CN 114058354A CN 202111476384 A CN202111476384 A CN 202111476384A CN 114058354 A CN114058354 A CN 114058354A
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- 239000006260 foam Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006073 displacement reaction Methods 0.000 title claims description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 21
- 239000007983 Tris buffer Substances 0.000 claims abstract description 17
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 229960004025 sodium salicylate Drugs 0.000 claims abstract description 11
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 11
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229960003237 betaine Drugs 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 claims 1
- 150000008040 ionic compounds Chemical class 0.000 claims 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 13
- 238000005187 foaming Methods 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 3
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000005185 salting out Methods 0.000 abstract 1
- 238000010408 sweeping Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 72
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 16
- 239000000693 micelle Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000002131 composite material Substances 0.000 description 11
- 239000010779 crude oil Substances 0.000 description 11
- 238000011049 filling Methods 0.000 description 11
- 239000008398 formation water Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000004576 sand Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 230000033558 biomineral tissue development Effects 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000001338 self-assembly Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000005465 channeling Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- -1 ion compound Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—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
-
- 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
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- 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
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/164—Injecting CO2 or carbonated water
-
- 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
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/166—Injecting a gaseous medium; Injecting a gaseous medium and a liquid medium
- E21B43/168—Injecting a gaseous medium
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Lubricants (AREA)
Abstract
本发明提供一种适合高矿化度低渗油藏泡沫驱油剂由如下重量百分比的组分组成：三[(N‑十二烷基‑N‑乙基‑N‑羧甲基钠)‑2‑溴化铵乙撑基]胺：0.4‑0.6％，十二烷基二甲基氧化胺：0.1‑0.35％，水杨酸钠：0.02‑0.07％，螯合剂：0.04‑0.14％，无机盐：6‑10％，余量为水。本发明专利还提供该超低界面张力自组装二氧化碳泡沫驱油剂的制备方法和应用。该自组装二氧化碳泡沫驱油剂，抗盐抗酸碱性好，起泡液有较高粘度，提高泡沫界面膜强度和稳定性，使油水界面张力达到10‑3mN/m数量级及以下，实验产生的泡沫细腻丰富，在低渗油藏中注入性好，能改善油水流度比，显著扩大波及效率和提高洗油效率；该泡沫剂不会产生盐析现象而失去界面活性，也不与钙镁离子发生化学反应生成沉淀而失去界面活性。The invention provides a foam oil-displacing agent suitable for high-salinity and low-permeability oil reservoirs, which is composed of the following components by weight: tris[(N-dodecyl-N-ethyl-N-carboxymethyl sodium)- 2-Ammonium Bromide Ethyl] Amine: 0.4-0.6%, Dodecyl Dimethylamine Oxide: 0.1-0.35%, Sodium Salicylate: 0.02-0.07%, Chelating Agent: 0.04-0.14%, Inorganic Salt: 6‑10%, balance water. The patent of the present invention also provides the preparation method and application of the ultra-low interfacial tension self-assembled carbon dioxide foam oil-displacing agent. The self-assembled carbon dioxide foam oil displacing agent has good salt resistance, acid and alkali resistance, high viscosity of the foaming liquid, improves the strength and stability of the foam interface film, and makes the oil-water interfacial tension reach the order of magnitude of 10-3 mN/m or below. The foam produced is fine and rich, and has good injectability in low-permeability reservoirs. It can improve the oil-water mobility ratio, significantly expand the sweeping efficiency and improve the oil washing efficiency; the foam agent will not cause salting out and lose interfacial activity. Calcium and magnesium ions undergo chemical reaction to form precipitation and lose interfacial activity.
Description
Technical Field
The invention belongs to the field of chemical oil displacement, and particularly relates to a foam oil displacement agent suitable for a high-salinity low-permeability reservoir, and a preparation method and application thereof.
Background
The gas drive is selected for the low-permeability oil reservoir because the migration capacity of gas in the low-permeability oil reservoir is weakened, the gas channeling time is greatly delayed, the volume of the accessible pore in the low-permeability oil reservoir and even a compact oil reservoir is increased, the gas injection of the low-permeability oil reservoir in an oil field is prolonged, such as the injection of carbon dioxide, and a certain effect is achieved.
The low-permeability reservoir is prolonged to have the characteristics of low porosity, low permeability and low yield, the development effect of the low-permeability reservoir can be improved by adopting the conventional water injection and gas injection method, but the low-permeability reservoir is low in exploitation degree and recovery ratio due to the fact that 'no injection', or water channeling and gas channeling are easy to occur in the middle and later stages of development and the injection fluid wave and efficiency are low. The currently common methods are: polymer flooding, surfactant flooding, alkali water flooding, foam flooding. The alkali water flooding can reduce the viscoelasticity of the system and increase the treatment difficulty of the produced liquid; polymer flooding is not suitable for low permeability fields with small injection gaps, which are difficult to inject.
The foam flooding can improve the recovery ratio of the low-permeability reservoir by improving the fluidity ratio, reducing the tension of an oil-water interface, improving the oil washing efficiency, increasing the formation energy, reducing the starting pressure and the water injection pressure and improving the seepage capability of the mixed fluid. The main reason that the foam has the functions of profile control and oil displacement is the seepage characteristic of the foam in a porous medium, namely the characteristics of large foam plugging, small foam plugging and water plugging and oil plugging, so that the foam is uniformly propelled at high and low permeability; meanwhile, the foam also has the function of reducing the interfacial tension to a certain extent. Therefore, the foam can improve the recovery rate remarkably, the foam flooding can improve the recovery rate by more than 25% in general conditions, and the polymer flooding can improve the recovery rate by 10-20%. For the extended low-permeability reservoir with low-permeability and low-pressure characteristics, most pore throats belong to slender pore throats, the pore diameter is too small, polymer flooding is not injected because of large molecular weight and large hydraulic radius of random coils, and the water flooding effect is not good, so that foam flooding is considered.
The fluidity control capability of the foam system is stronger than that of a polymer, the flow front edge is more stable, the volume sweep coefficient is higher, the foam oil washing capability is stronger, the dosage of a surfactant can be saved, and meanwhile, the foam oil washing agent has better foam performance and ultralow interfacial tension, reduces ineffective water circulation, does not contain strong alkali or weak alkali, avoids corrosion and scaling, and improves economic benefits.
At present, although some foam oil-displacing agents have been developed on the market, there still remain problems such as poor foamability of foam in saline, low viscosity, insufficient reduction of interfacial tension, low foam combination index, insufficient foam stability, and the like. For example, patent ZL201710864250.3 'a self-assembly ultramicro foam oil displacement agent, and a preparation method and application thereof' has the practical problems of low interfacial tension under the condition of high salinity, low viscosity of foaming liquid, insufficient foam strength, relatively high cost, and expansion and insufficient volume of a low-permeability reservoir with good reservoir permeability and strong performance. In addition, while some foaming systems have reduced interfacial tension and high strength, the surfactant concentrations used are too high, resulting in too high a cost to be used in the field. For example, in the invention patent CN110776893A 'an ultra-low interfacial tension strong foam oil displacement agent', the minimum concentration of the used surfactant reaches 30%, the oil displacement efficiency is between 16 and 21%, and the oil displacement efficiency is not high, so that the surfactant is difficult to be applied to oil fields on a large scale. Aiming at the actual problems and the characteristics of the low-permeability reservoir, through molecular structure design and repeated experiments, under the same experimental conditions as patent ZL201710864250.3, the ultralow interfacial tension self-assembly oil displacement agent suitable for the low-permeability reservoir, disclosed by the invention, has the advantages that the oil-water interfacial tension is reduced to be lower and reaches an ultralow value or even lower, the viscosity of a composite worm-shaped micelle formed by self-assembly under the same dosage condition is higher, the formed foam has longer stable time, and the spreading efficiency is more remarkable.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a foam oil displacement agent suitable for a high-salinity low-permeability reservoir and application thereof, wherein each component of the foam can be self-assembled to form a composite worm-shaped micelle, so that the viscosity of the system is increased, the foam oil displacement agent has the characteristics of no alkali and no corrosion, has the salt and acid resistance capability, can ensure that the oil-water interfacial tension is ultra-low, and the generated foam is fine, stable and rich.
A foam oil displacement agent suitable for a high-salinity low-permeability oil reservoir comprises the following components in percentage by weight:
tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine: 0.4 to 0.6 percent of,
nonionic surfactant dodecyl dimethyl amine oxide: 0.1 to 0.35 percent of,
counter-ionic compound sodium salicylate: 0.02 to 0.07 percent of the total weight of the mixture,
chelating agent: 0.04-0.14 percent of the total weight of the mixture,
inorganic salts: 5 to 7 percent of the total weight of the mixture,
the balance of water,
wherein the structural formula of the tri [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine is shown in the specification
The tri [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine is a trimeric betaine surfactant.
The tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine is a surfactant in the prior art, and the preparation method is shown in a paper of synthesis and performance evaluation of tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine, a chemical reagent and 2016, published by Zhou Ming subject group of southwestern university of Petroleum.
Preferably, the nonionic surfactant is dodecyl dimethyl amine oxide (0B-2).
Preferably, the counter-ionic compound is sodium salicylate.
Preferably, the chelating agent is EDTA.
Preferably, the inorganic salt is any one or more of sodium chloride, magnesium chloride, sodium sulfate, sodium bisulfate, sodium carbonate, potassium chloride and calcium chloride. When the inorganic salt is any of sodium chloride, magnesium chloride, sodium sulfate, sodium bisulfate, sodium carbonate, potassium chloride and calcium chloride, the components of any of the components are mixed in any proportion.
The preparation method of the ultralow interfacial tension self-assembly carbon dioxide foam oil displacement agent suitable for the low-permeability oil reservoir comprises the following steps:
(1) heating water to 70 ℃, adding inorganic salt, adding tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine, and stirring for dissolving;
(2) and (2) sequentially adding a nonionic surfactant dodecyl dimethyl amine oxide and a chelating agent into the mixed solution obtained in the step (1), and stirring and dissolving.
(3) And (3) adding sodium salicylate into the mixed solution obtained in the step (2), and stirring for dissolving.
And (4) measuring the viscosity of the high-salinity low-permeability reservoir foam oil displacement agent by using a Brookfield VIII viscometer for the mixed solution obtained in the step (3), and measuring the interfacial tension by using a Tax500 ultralow-rotation interfacial tension meter.
The foam oil displacement agent suitable for the high-salinity low-permeability oil reservoir and the application thereof are as follows: adding a low-permeability reservoir foam oil displacement agent solution into a stirring cup by adopting an OWC-9360 constant-speed stirrer, and introducing CO2Stirring the gas for 60s at a constant rotating speed of 10000r/min, and immediately detecting the gas, wherein the specific detection is as follows:
reading the firstInitial foam volume V0And start timing; the time t required for half of the foam to disappear was recorded1/2Namely, the foam half-life is obtained, and finally, the foam comprehensive index FCI (FCI is 0.75 multiplied by V)0×t1/2)。
The foam oil displacement agent suitable for the high-salinity low-permeability oil reservoir and the application thereof are as follows: preparing foam by the ultra-low interfacial tension foam oil displacement agent through a sand-packed pipe model, and specifically operating as follows: adding the foam oil displacement agent with ultra-low interfacial tension into a piston container; the lower end of the piston container is connected with the double-cylinder pump, the upper end of the piston container is connected with the inlet end of the sand filling pipe through a three-way valve, and CO2The high-pressure gas cylinder is connected with the inlet end of the sand filling pipe through a three-way valve; the outlet end of the sand filling pipe is sequentially connected with the soap foam flowmeter and the foam test tube; with CO2The high-pressure gas cylinder is connected into the upper space of the piston container and is filled with CO2Gas and CO Retention2The high-pressure gas cylinder has equal pressure; the output flow of the double-cylinder pump is 1mL/min, the gas-liquid ratio is alternately injected by 1.5:1, and after continuous and stable rich and fine foam is generated, the ultralow interfacial tension foam injected into the low-permeability core can be obtained; the sand filling pipe is filled with 80-100 meshes of quartz sand, and the double-cylinder pump is an ISCO constant-pressure constant-flow double-cylinder pump.
The foam oil displacement agent suitable for the high-salinity low-permeability oil reservoir and the application thereof are as follows: carrying out a core oil displacement experiment on a low-permeability core by using an ultra-low interfacial tension foam oil displacement agent, and specifically operating as follows: putting the rock core of the saturated high-salinity formation water into a rock core holder, loading, applying confining pressure, checking the tightness of the system, and continuing the experiment if the tightness is good; injecting crude oil into the rock core through the intermediate container until all crude oil flows out of the outlet, and establishing original oil saturation; water-flooding crude oil to an economic limit (the water content is stabilized to 98%), establishing a water-flooding oil reservoir model, and calculating the water-flooding recovery ratio; and opening a valve, accessing foam prepared by the sand filling pipe in front, injecting 0.5PV ultra-low interfacial tension foam displacement crude oil, after the foam slug is completely injected, subsequently driving water to the economic limit, and calculating the ultra-low interfacial tension foam displacement agent to improve the crude oil recovery ratio.
In the formula of the foam oil displacement agent suitable for the high-salinity low-permeability oil reservoir, the concentration of the surfactant is low, the foam oil displacement agent can be self-assembled to form a composite worm-shaped micelle under the action of a counter ion compound, and the contour length of the composite worm-shaped micelle can be 500 nanometers or even 100 micrometers; in the solution, when the composite wormlike micelles reach a certain length and density, the micelles begin to intertwine and overlap with each other to form a network structure with viscoelasticity. Different from the existing polymer solution, the polymer is a long-chain molecular structure connected together by covalent bonds, and the composite wormlike micelle is a molecular ordered assembly formed by gathering small molecules under the action of intermolecular force. The dissociation and recombination process exists between the compound wormlike micelle formed by the surfactant molecules and the small molecule surfactant, so that the whole system is a dynamic and balanced network structure. Compared with the patent CN110776893A and ZL201710864250.3, the molecular weight of the counter ions of the invention is smaller, the composite wormlike micelles formed by self-assembly are longer, and the viscosity of the composite wormlike micelles is higher under the macroscopically same dosage. The formation of the composite vermicular micelle can effectively prevent the generation of calcium carbonate crystal nucleus and the growth of crystal, the extrusion of calcium and magnesium ions on the composite vermicular micelle causes the thinning of an electric double layer, the hydromechanics of the composite vermicular micelle is reduced, the size is reduced, the generated foam is fine and uniform, the stability is good, and the foam with the diameter of 1-20um is generated after foaming. Meanwhile, due to the synergistic effect of the trimeric betaine surfactant and the amine oxide type nonionic surfactant, the surfactant molecules are arranged more tightly on an oil-water interface, the tension of the oil-water interface is reduced more strongly, and the tension value of the oil-water interface can reach an ultralow value or even lower.
The invention has the advantages that:
(1) the foam oil displacement agent is a trimeric betaine surfactant tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium bromide ethylene group]The amine and the sodium salicylate can form a compound wormlike micelle in saline water, and the compound wormlike micelle has certain viscosity. The viscosity of the system formed by the sodium salicylate is far higher than that of the system formed by the sodium dodecyl sulfate by adding the same amount under the same conditionViscosity. Introducing CO2After foaming, the generated foam is rich and fine, the diameter size is between 1 and 20 mu m, and the half-life period is longer; CO injection in extended oil field reservoirs with high salinity2When in foaming, the foam is acid-resistant and salt-resistant, the foam system does not generate precipitation with calcium and magnesium ions, has good foamability and foam stability, and can ensure that the oil-water interfacial tension reaches 10-3Of the order of mN/m or even lower.
(2) The foam oil displacement agent does not contain alkali and polymer, so that the problems of reduction of viscoelasticity of a system, precipitation of alkali and formation water, increase of injection process and treatment difficulty of produced liquid, increase of cost and the like caused by application of alkali are solved, and the defects that the use of polymer is too large in molecular weight, the hydraulic radius of a non-substituted coil formed after the polymer is dissolved in the formation water is large, and the polymer is difficult to inject into a long and thin pore throat in a low-permeability oil reservoir are overcome;
(3) the foamed foam obviously reduces the oil-water interfacial tension, improves the oil washing efficiency, increases the formation energy and improves the sweep capacity of the fluid by improving the fluidity ratio, thereby improving the recovery ratio of the low-permeability reservoir.
Detailed Description
The formation water mineralization for the specific examples is shown in table 1.
TABLE 1 formation Water mineralization
Example 1
1. A foam oil displacement agent suitable for a high-salinity low-permeability oil reservoir comprises the following components in percentage by weight:
tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine: 0.4 percent of the total weight of the mixture,
nonionic surfactant dodecyl dimethyl amine oxide (0B-2): 0.1 percent of the total weight of the mixture,
sodium salicylate: 0.03 percent of the total weight of the mixture,
the chelating agent is EDTA: 0.14 percent of the total weight of the mixture,
formation water mineralization degree: 89542mg/L of the active carbon,
the balance of water, the total amount is 100 percent,
wherein the structure of the tri [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine is
The tri [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium bromide ethylene ] amine is a hydroxyl sulfobetaine type Gemini surfactant.
The tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine is a surfactant in the prior art, and the preparation method is shown in a paper of synthesis and performance evaluation of tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine, a chemical reagent and 2016, which are published by ZhouMing subject group.
Example 2
2. A foam oil displacement agent suitable for a high-salinity low-permeability oil reservoir comprises the following components in percentage by weight:
tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine: 0.5 percent of the total weight of the mixture,
nonionic surfactant dodecyl dimethyl amine oxide (0B-2): 0.2 percent of the total weight of the mixture,
the chelating agent is EDTA: 0.04 percent of the total weight of the mixture,
formation water mineralization degree: 89542mg/L of the total weight of the powder,
the balance of water, the total amount is 100 percent,
wherein, the structural formula and the preparation method of the tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine are the same as those of the embodiment 1;
example 3
3. A foam oil displacement agent suitable for a high-salinity low-permeability oil reservoir and an application thereof comprise the following components in percentage by weight:
tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine: 0.6 percent of the total weight of the mixture,
nonionic surfactant dodecyl dimethyl amine oxide (0B-2): 0.35 percent of the total weight of the mixture,
the chelating agent is EDTA: 0.10 percent of the total weight of the mixture,
formation water mineralization degree: 89542mg/L of the active carbon,
the balance of water, the total amount is 100 percent,
wherein, the structural formula and the preparation method of the tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine are the same as those of the embodiment 1;
preparation method, performance detection and application
1. Foams suitable for the high-salinity low-permeability oil reservoirs in the examples 1 to 3 are respectively prepared according to the following preparation methods:
(1) heating formation water to 70 ℃ (the concentration of specific cations and anions for the mineralization of the formation water is shown in table 1), adding tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine, and stirring to dissolve;
(2) and (2) sequentially adding a nonionic surfactant dodecyl dimethyl amine oxide and a chelating agent into the mixed solution obtained in the step (1), and stirring and dissolving.
(3) And (3) adding sodium salicylate into the mixed solution obtained in the step (2), and stirring for dissolving.
2. Performance detection and application
(1) The mixed solution obtained in the step (3) was measured for the viscosity of the ultra-low interfacial tension foam oil-displacing agent by means of a Brookfield VIII viscometer, and the interfacial tension was measured by means of a Tax500 ultra-low rotary interfacial tensiometer, and the results are shown in Table 2.
(2) Adding foam oil displacement agent with ultralow interfacial tension into a stirring cup by adopting an OWC-9360 constant speed stirrer, and introducing CO2Gas, stirring for 60s at a constant rotation speed of 10000r/min, and immediately reading the initial foam volume V0And start timing; the time t required for half of the foam to disappear was recorded1/2Namely, the foam half-life is obtained, and finally, the foam comprehensive index FCI (FCI is 0.75 multiplied by V)0×t1/2) The results are shown in Table 2.
TABLE 2 influence of viscosity, interfacial tension, foamability and half-life of foam oil-displacing agent
Compared with the patent ZL201710864250.3, the invention does not use triethanolamine and urea; under the same conditions of other dosage and conditions, two patent examples 1, 2 and 3 are compared one by one: the viscosity of the product in patent example 1 is 5.7mPa.s higher than that of the product in patent ZL201710864250.3, the foaming volume is increased by 8mL, the half-life period is increased by 10min, and the foam comprehensive index FCI is increased by 4398 mL.min; the viscosity of the foam of the embodiment 2 of the patent is improved by 8.2mPa.s, the foaming volume is increased by 25mL, the half-life period is increased by 6min, and the foam comprehensive index FCI is increased by 2408 mL.min; the viscosity of the foam of the patent in example 3 is improved by 13.2mPa.s, the foaming volume is increased by 160mL, the half-life period is increased by 6min, and the foam comprehensive index FCI is increased by 4920 mL.min; compared with the invention patent ZL201710864250.3, the viscosity of the foam oil displacement agent and the foam comprehensive index FCI are obviously increased.
Aiming at the crude oil of the extended oil field, the patent ZL201710864250.3 does not measure the oil-water interfacial tension, and three examples of the patent are measured under the experimental condition of the patent, and the oil-water interfacial tension of all the three examples is less than 10-3mN.m-1Magnitude order (ultra-low value), and the oil-water interfacial tension of patent examples 1 and 2 of the invention reaches 10-3mN.m-1Order of magnitude, while the oil-water interfacial tension of example 3 is lower, reaching 10-4 mN.m-1The oil displacement agent disclosed by the invention has stronger capability of reducing the tension of an oil-water interface.
Under the condition that the surfactant and the assistant used in the invention are far smaller than those in the invention patent CN110776893A, the oil displacement agent of the invention has lower oil-water interfacial tension and better foaming volume than that of the invention patent CN 110776893A.
(3) Preparing foam by using the foam oil displacement agent with ultralow interfacial tension through a sand filling pipe, and specifically operating as follows: adding the foam oil displacement agent with ultra-low interfacial tension into a piston container; the lower end of the piston container is connected with the double-cylinder pump, and the upper end of the piston container is connected with the inlet of the sand filling pipe through a three-way valveEnd-to-end, CO2The high-pressure gas cylinder is connected with the inlet end of the sand filling pipe through a three-way valve; the outlet end of the sand filling pipe is sequentially connected with the soap foam flowmeter and the foam test tube; with CO2The high-pressure gas cylinder is connected into the upper space of the piston container and is filled with CO2Gas and CO Retention2The high-pressure gas cylinder has equal pressure; the output flow of the double-cylinder pump is 1mL/min, the gas-liquid ratio is maintained at 1.5:1, and the low-interfacial tension foam injected into the low-permeability core can be obtained after continuous and stable rich and fine foam is generated; the sand filling pipe is filled with 80-100 meshes of quartz sand, and the double-cylinder pump is an ISCO constant-pressure constant-flow double-cylinder pump.
(4) Carrying out core oil displacement on the ultra-low interfacial tension foam oil displacement agent by the following specific operations: putting the rock core of the saturated high-salinity formation water into a rock core holder, loading, applying confining pressure, checking the tightness of the system, and continuing the experiment if the tightness is good; injecting crude oil into the rock core through the intermediate container until all crude oil flows out of the outlet, and establishing original oil saturation; water-flooding crude oil to an economic limit (the water content is stabilized to 98%), establishing a water-flooding oil reservoir model, and calculating the water-flooding recovery ratio; and opening a valve, accessing foam prepared by the sand filling pipe in front, injecting 0.5PV ultra-low interfacial tension foam to displace crude oil, after the foam is injected, subsequently driving water to the economic limit, and calculating the ultra-low interfacial tension foam oil displacement agent to improve the crude oil recovery ratio. Core parameters of cores used in examples 1-3 are shown in table 3, and displacement experiment results of ultra-low interfacial tension foam displacement agents used in examples 1-3 are shown in table 4.
TABLE 3 basic parameters of the experimental cores
TABLE 4 ultra-low interfacial tension foam flooding test results
Under the condition that the total dosage (0.56-1.16%) of the main agents (including tris [ (N-dodecyl-N-ethyl-N-carboxymethyl sodium) -2-ammonium ethylene bromide ] amine, dodecyl dimethyl amine oxide, sodium salicylate and chelating agent EDTA) used in the invention patent is far less than the total dosage (30-80%) of the main agents (anionic and cationic surfactants, betaine surfactants and nonionic surfactants) of the invention patent CN110776893A, the minimum oil displacement efficiency and the maximum oil displacement efficiency in the invention patent are respectively 26.9% and 32.8%, and are 10.7% and 12.1% higher than the minimum oil displacement efficiency and the maximum oil displacement efficiency in nine embodiments of the invention patent CN110776893A, so that the invention has higher oil displacement capability.
Claims (7)
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