CN106590589B - Oil displacement method - Google Patents
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Abstract
The invention relates to an oil displacement method, which mainly solves the problems of poor high-temperature resistance and salt resistance performance and poor oil displacement efficiency of an oil displacement agent in the prior art, and the oil displacement method comprises the following steps of 1) mixing the oil displacement agent with water to obtain an oil displacement system, 2) contacting the oil displacement system with an oil-bearing stratum under the conditions that the oil displacement temperature is 25-120 ℃ and the total mineralization is more than 500 mg/L of stratum water to displace crude oil in the oil-bearing stratum, wherein the oil displacement agent comprises the following components, by mass, 1)1 part of surfactant, 2) 0-50 parts of polymer, and 3) 0-50 parts of alkali, wherein in the oil displacement system, the concentration of the surfactant is 0.001-2.0 wt%, the concentration of the polymer is 0-1.8 wt%, and the concentration of the alkali is 0-2.0 wt%, and the problem is better solved, and the oil displacement agent is used in the enhanced oil recovery of an oil field R 1 O (CH 2 CH 3578O) 357 (CH 357) 357 (CH 5639O) 36 2 3, CH 3623 (CH 3) 3R 364934) R3623).
Description
Technical Field
The invention relates to an oil displacement method.
Background
The technology of increasing recovery ratio, namely strengthening (EOR) and Improving (IOR) recovery ratio technology commonly referred to abroad, can be summarized as improving water drive, chemical flooding, heavy oil thermal recovery, gas drive, microbial oil recovery and physical oil recovery, at present, the technology of increasing recovery ratio entering the large-scale application of mines focuses on three categories of thermal recovery, gas drive and chemical flooding, wherein the chemical flooding yield is more than 5.18 x 10 4 m 3/d and accounts for about 14.7% of the total EOR output in the world, chemical flooding is a strengthening measure for increasing recovery ratio by adding chemical agents into aqueous solution and changing the physicochemical property and rheological property of injected fluid and the interaction characteristic with reservoir rocks, and is developed rapidly in China, and the main reason is that the reservoir is strong in terrestrial sedimentary property, the viscosity of terrestrial heterogeneous crude oil is high, and the technology is more suitable for chemical flooding in an EOR method.
The surfactant oil displacement technology is a method for improving the oil displacement efficiency by adding a surfactant into injected water and reducing the oil-water interfacial tension to improve the oil washing capacity. Compared with general water flooding, the polymer flooding mainly increases the viscosity of a water phase, controls the fluidity ratio of a flooding system, plays a role in enlarging swept volume, and has lower cost compared with a surfactant. The addition of the alkali mainly reduces the adsorption quantity of the surfactant and increases the interfacial activity of the surfactant. As an important technology in chemical flooding, surfactant active water flooding, micellar solution flooding and microemulsion flooding technologies, polymer surfactant formed binary composite flooding technologies and polymer surfactant alkali formed ternary composite flooding technologies have been subjected to some mine field tests at home and abroad, and good flooding effects are obtained. In 2002, the Daqing oil field develops an active water injection pressure reduction and injection increase test in a peripheral low-permeability oil field, and in 2003, develops an active water injection oil displacement test in a peripheral low-permeability oil field and a reservoir outside the surface of a loudspeaker, a pizza and an apricot oil field, and aims to greatly reduce the oil-water interfacial tension, reduce the action of interphase surfaces, activate and disperse retained oil blocks or strip adhered oil films, improve the flow permeability of an oil layer by means of the increase of the flow porosity, and achieve the effects of reducing the starting pressure, improving the water injection wave and volume and improving the oil displacement efficiency. Practice proves that the active water flooding can greatly improve the recovery ratio of crude oil in a development block, and effectively develop part of reserves which cannot be used under the current economic and technical conditions. Since 1994, Daqing oil field adopts the heavy alkylbenzene sulfonate imported from abroad to carry out 5 ternary combination flooding tests, and the crude oil recovery rate is increased by 20% on the basis of the water flooding recovery rate, thereby defining the dominant tertiary oil recovery technology after the ternary combination flooding is polymer flooding. After the ternary combination flooding pilot field test of the oil field succeeds, the problems of scaling and difficult demulsification are considered, a technical route of binary combination flooding is adopted, petroleum sulfonate surfactant synthesized by using victory crude oil as a raw material is used as a main agent, nonionic surface activity is used as an auxiliary agent, ultralow interfacial tension can be achieved under the alkali-free condition, a pilot test of the mine field is carried out in southwest of the seven regions of eastern soliton in 2003, the recovery ratio is improved by 12%, and the problems of scaling and difficult demulsification are solved.
In the oil displacement technology implemented above, the use of the high-activity surfactant is one of the key factors, but the surfactant suitable for oil displacement in China is few in types, poor in product performance stability and not strong in universality. The screening of the surfactant for oil displacement in China is mainly based on the capability of reducing the oil-water interfacial tension, and the selection of the surfactant for oil displacement and the cosurfactant in foreign countries is based on the phase behavior of an oil displacement system and crude oil: (1) forming large middle-phase micro-emulsion; (2) high solubilization parameters at optimal salinity; (3) no viscous phase such as lamellar liquid crystal, etc. can be produced. In 1973, Healy and Reed firstly studied the microemulsion system by using a three-phase diagram, and then through the work of Healy, Reed, Nelson, Pope and Huh, the correlation between the oil displacement efficiency and the phase characteristics, and the correlation between the solubilization parameters and the interfacial tension are established. Although the phase behavior is based on the research of concentrated surfactant flooding such as microemulsion flooding, the theoretical system is complete, so the screening of the foreign high-efficiency surfactant oil flooding system is still based on the theoretical system.
The surfactant used in the tertiary oil recovery research is most anionic, then nonionic and zwitterionic, and the least used is cationic, the patents of US3927716, US4018281 and US4216097 of Mobil Petroleum company successively report the results of adopting alkaline water for displacement of reservoir oil, surfactant or alkaline water for displacement of reservoir oil and using zwitterionic surfactant for displacement of reservoir oil, the zwitterionic surfactant used is carboxylic acid or sulfonate betaine surfactant with different chain lengths, the patent of US4370243 of Mobil Petroleum company reports that a displacement system consisting of oil-soluble alcohol, sulfonate betaine and quaternary ammonium salt is used in a simulated saline solution with total mineralized 62000-16000 mg/L, which has the interface tension of 10 -1 -10 mN/m for Texas south crude oil, and a displacement system consisting of oil-soluble alcohol, sulfonate and quaternary ammonium salt, which can play the role of surfactant and also play the role of fluidity of high-temperature adsorption of surfactant, and high-mobility of ionic surfactant, wherein the quaternary ammonium salt is 16% of carbon chain length, the surfactant is 16% of alkyl sulfate, the surfactant is used as a cationic surfactant, the surfactant is used as a linear surfactant, the surfactant used is used as a linear surfactant for displacement of a linear surfactant, the displacement of crude oil, the high-oil field-oil-water-oil-field-oil-water-oil-water-oil-water-oil-water surfactant, the surfactant is used for which has the high-oil-water surfactant, the surfactant of which has the high-oil.
The use of temperature and salt resistant polymers is another key factor. Early commercial products of polymer flooding, commonly used for Enhanced Oil Recovery (EOR), were only partially Hydrolyzed Polyacrylamides (HPAMs), which relied on the exclusion of high molecular weight and ionic and strongly polar side groups on the polymer molecular chain to achieve viscosifying effects. However, high molecular weight polymers are susceptible to mechanical degradation and loss of viscosity when subjected to high tensile and shear stresses, particularly when injected into low permeability formations. Cations, especially divalent ions, in the aqueous solution can shield ionic groups in the polymer, so that polymer molecular chains are curled, the hydrodynamic volume is reduced, even the polymer is precipitated, and the tackifying property is greatly reduced. When the temperature of a stratum oil layer is higher (more than 93 ℃), amide groups in Polyacrylamide (PAM) are easy to hydrolyze in a high-temperature aqueous solution, so that the salt resistance of a polymer solution is reduced rapidly. In recent years, the research on temperature and salt resistant polyacrylamide mainly improves the thermal stability of the polymer by introducing large side groups or rigid side groups to the main chain of the polymer, improves the hydrolysis resistance and salt resistance of the polymer by introducing monomers inhibiting hydrolysis or copolymerizing monomers insensitive to salt, or improves the temperature and salt resistance of the polymer by hydrophobic association of hydrophobic groups.
Therefore, aiming at high-temperature medium-high-permeability or low-permeability oil reservoirs, the oil displacement agent which has stable structure at the formation temperature, can form low interfacial tension of 10 -2 -10 -4 mN/m with crude oil and effectively improves the recovery ratio of the crude oil is invented.
Disclosure of Invention
The invention aims to solve the technical problem that an oil displacement agent in the prior art is poor in oil displacement efficiency, and provides a novel oil displacement method. The oil displacement method uses an aqueous solution containing a surfactant, or an aqueous solution of the surfactant and a polymer, or an aqueous solution containing the surfactant, the polymer and an alkali as an oil displacement agent in the oil displacement process, and has the advantages of good temperature resistance and salt tolerance and high oil displacement efficiency under high temperature conditions.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: an oil displacement method comprises the following steps:
(1) Mixing an oil displacement agent with water to obtain an oil displacement system;
(2) Contacting the oil displacement system with an oil-bearing stratum under the conditions that the oil displacement temperature is 25-120 ℃ and the total salinity is more than 500 mg/L stratum water, and displacing the crude oil in the oil-bearing stratum;
the oil displacement agent comprises the following components in parts by weight:
1)1 part of a surfactant;
2)0 to 50 parts of a polymer;
3) 0-50 parts of alkali;
The amounts of the polymer and the base are not 0 at the same time; the surfactant is an anionic surfactant; the polymer is a polymer suitable for oil extraction in oil fields; the alkali is at least one of inorganic alkali or organic amine; in the oil displacement system, the concentration of the anionic surfactant is 0.001-2.0 wt%, the concentration of the polymer is 0-1.8 wt%, and the concentration of the alkali is 0-2.0 wt% based on the total mass of the oil displacement system.
In the above technical solution, the anionic surfactant preferably has a structure represented by the general molecular formula (1):
R 1 O (CH 2 CH 2 O) m1 (CH 3) CH 2 O) n (CH 2 CH 2 O) m2 R 2 Y, formula (1);
Wherein R 1 is C 8 -C 30 aliphatic alkyl or aryl substituted by C 4 -C 20 straight chain or branched chain saturated and unsaturated alkyl, M1 is 1-30, M2 is 1-50, N is 1-30, R 2 is C 1 -C 5 alkylene or hydroxyl substituted alkylene, Y is COOM or SO 3 N, M and N are independently selected from hydrogen, alkali metal or at least one of groups represented by formula NR 3 (R 4) (R 5) (R 6), R 3 and R 4, R 5, R 6 are independently selected from H, (CH 2) p OH or (CH 2) q CH 3, p is any integer of 2-4, q is 0-5, the polymer is a polymer suitable for oil field, and the alkali is at least one of inorganic alkali or organic amine.
In the technical scheme, R 1 is preferably C 12 -C 24 alkyl or phenyl substituted by C 8 -C 12 alkyl, and R 2 is preferably C 1 -C 3 alkylene or hydroxy substituted propylene.
In the technical scheme, p is preferably 2, and q is preferably 0-1; m1 is 2-10, m2 is 1-20, and n is 2-15.
In the above technical solution, the polymer is not strictly limited, and may be various polymers for oil field oil recovery known to those skilled in the art, such as but not limited to at least one selected from xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, anionic polyacrylamide, modified polyacrylamide, hydrophobically associating polymer, and polymer microsphere.
In the technical scheme, the hydrophobic association polymer is preferably copolymerized by acrylamide, a temperature-resistant salt-resistant monomer or a hydrophobic monomer; the modified polyacrylamide is preferably copolymerized by acrylamide and a temperature-resistant salt-resistant monomer; the temperature-resistant and salt-resistant monomer or hydrophobic monomer may be at least one of monomers having a large side group or a rigid side group (e.g., styrenesulfonic acid, N-alkylmaleimide, acrylamido long-chain alkylsulfonic acid, long-chain alkylallyl dimethylammonium halide, 3-acrylamido-3-methylbutyric acid, etc.), monomers having a salt-resistant group (e.g., 2-acrylamido-2-methylpropanesulfonic acid), monomers having a hydrolysis-resistant group (e.g., N-alkylacrylamide), monomers having a group that inhibits hydrolysis of an amide group (e.g., N-vinylpyrrolidone), monomers having a hydrophobic group, etc.), which are well known to those skilled in the art, the temperature-resistant and salt-resistant monomer is preferably 2-acrylamido-2-methylpropanesulfonic acid, and the hydrophobic monomer is preferably 2-acrylamidododecyl sulfonic acid.
in the above technical scheme, the mole ratio of acrylamide to the temperature-resistant salt-resistant monomer to the hydrophobic monomer in the hydrophobic association polymer is 1: (0.1-40): (0.001 to 0.05) and a viscosity average molecular weight of 500 to 2500 ten thousand; more preferably, the molar ratio of the acrylamide to the temperature-resistant salt-resistant monomer to the hydrophobic monomer is 1 to (0.1-20) to (0.001-0.01), and the viscosity average molecular weight is more 1200-2200 ten thousand.
In the technical scheme, the mol optimal ratio of acrylamide to the temperature-resistant and salt-resistant monomer in the modified polyacrylamide is (0.1-40) to 1.
In the above technical scheme, the hydrophobic association polymer is preferably formed by copolymerizing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamidododecyl sulfonic acid, and the molar ratio of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamidododecyl sulfonic acid is preferably 1: (0.1-40): (0.001 to 0.05), more preferably 1: (0.1 to 20): (0.001 to 0.01).
In the technical scheme, the modified polyacrylamide is preferably prepared by copolymerizing acrylamide and 2-acrylamido-2-methylpropanesulfonic acid, the molar ratio of the acrylamide to the 2-acrylamido-2-methylpropanesulfonic acid is preferably (0.1-40) to 1, and the viscosity average molecular weight of the modified polyacrylamide is preferably 800-2500 ten thousand.
In the above technical solution, the inorganic base is preferably at least one selected from alkali metal hydroxide, alkaline earth metal hydroxide, and alkali metal carbonate, and more preferably from sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate; the organic amine is preferably selected from short carbon chain organic amines, and is further preferably selected from at least one of ethanolamine, diethanolamine, triethanolamine or triethylamine.
In the technical scheme, the mass ratio of the surfactant to the polymer to the alkali in the oil displacement agent is preferably 1 to (0-2): (0-5); the oil displacement temperature is preferably 50-100 ℃.
In the technical scheme, the total mineralization of the formation water is preferably 20000-300000 mg/L, and the concentration of Ca 2+ is preferably 1000-15000 mg/L, Mg 2+ and 400-8000 mg/L.
The component represented by the formula (1) of the present invention can be synthesized by a known Williamson reaction using a substance represented by the formula (1), and the substance represented by the formula (1) can be obtained from a commercially available source or synthesized by a technique known in the art, and the synthesis step comprises:
a. In the presence of a basic catalyst, R 1 OH sequentially reacts with required amount of ethylene oxide, propylene oxide and ethylene oxide to obtain R 1 O (CH 2 CH 2 O) m1 (CHCH 3 CH 2 O) n (CH 2 CH 2 O) m2 H
b. and c, in the presence of alkali metal hydroxide or alkali metal alkoxide, reacting the product obtained in the step a with XR 2 Y 1 in a solvent at the reaction temperature of 50-120 ℃ for 3-15 hours to generate polyether carboxylic acid or polyether sulfonic acid alkali metal with the following structure:
R1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2R2Y1；
Wherein Y 1 is COOM 1 or SO 3 N 1, M 1 and N 1 are alkali metals, and X is Cl, Br or I.
In the above technical scheme, the alkaline catalyst can be selected from alkali metal hydroxide (such as sodium hydroxide or potassium hydroxide) and alkali metal alkoxide (such as sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide).
In the technical scheme, in the step b, the molar ratio of R 1 O (CH 2 CH 2 O) m1 (CHCH 3 CH 2 O) n (CH 2 CH 2 O) m2 H to XR 2 Y 1 to alkali metal hydroxide is preferably 1 to (1-6).
As long as the reaction of step b is carried out, one skilled in the art can obtain the surfactant containing salt and excess basic catalyst by removing the solvent by distillation without complicated separation. Step b can be carried out without any inventive step by a person skilled in the art in order to obtain a pure product comprising only formula (1).
For example, in order to obtain an anionic surfactant described by formula (1) free of salt and excess alkaline catalyst, the product when M 1 or N 1 is H may further comprise steps c and d:
c. B, adding an acid into the reaction mixture obtained in the step b to adjust the pH value of the water phase to be 1-3, and separating to obtain an organic phase;
d. The resulting organic phase is concentrated to give the desired product.
for another example, in order to obtain a product of the anionic surfactant of formula (1) free of salt and excess basic catalyst when M 1 or N 1 is an alkali metal or a group of formula NR 3 (R 4) (R 5) (R 6), it is sufficient to neutralize on the basis of step c with a base corresponding to the desired alkali metal or a group of formula NR 3 (R 4) (R 5) (R 6) and then remove the solvent from the organic phase.
the alkali metal or base corresponding to the group of formula NR 3 (R 4) (R 5) (R 6) as described in the above embodiment is, for example, a base corresponding to an alkali metal selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal oxides, alkali metal alkoxides and the like, and a base corresponding to the group of formula NR 3 (R 4) (R 5) (R 6) selected from the group consisting of ammonia, ethanolamine, diethanolamine, triethanolamine, triethylamine, quaternary ammonium bases and the like.
Examples of XR 2 Y 1 include, but are not limited to, alkali metal salts of chloroacetic acid (e.g., sodium chloroacetate), alkali metal salts of 3-chloro-2-hydroxypropanesulfonic acid, alkali metal salts of 2-chloroethanesulfonic acid, and the like.
In the technical scheme, the modified polyacrylamide is prepared from two monomers of acrylamide and 2-acrylamide-2-methylpropanesulfonic acid by an aqueous solution polymerization method, can be purchased from the market, and can also be prepared by conventional free radical copolymerization. The resulting products, whether block or random, are useful in and meet the objectives of the present invention. The modified polyacrylamide in the embodiment of the invention is prepared by mixing acrylamide and 2-acrylamido-2-methylpropanesulfonic acid according to a molar ratio of (0.5-5) to 1, and initiating a free radical polymerization reaction by using water as a solvent and using a conventional free radical initiator.
In the technical scheme, the hydrophobic association polymer is prepared from three monomers, namely acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamido dodecylsulfonic acid, by an aqueous solution polymerization method, can be obtained from the market, and can also be prepared by conventional free radical copolymerization. The resulting products, whether block or random, are useful in and meet the objectives of the present invention. The hydrophobic association polymer in the embodiment of the invention is prepared by mixing three monomers, namely acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamidododecylsulfonic acid, according to a molar ratio of 1: (0.5-5): (0.001-0.01) and then initiating a free radical polymerization reaction by using water as a solvent and a conventional free radical initiator.
The key active ingredients of the oil-displacing agent of the present invention are the components 1), 2) and 3), and those skilled in the art know that various supply forms such as a non-aqueous solid form, an aqueous paste form, or an aqueous solution form can be adopted for convenience of transportation and storage or field use; the water solution form comprises a form of preparing a concentrated solution by using water and a form of directly preparing an oil displacement agent with the concentration required by on-site oil displacement; the water is not particularly required, and can be deionized water or water containing inorganic mineral substances, and the water containing the inorganic mineral substances can be tap water, oil field formation water or oil field injection water.
The oil displacement agent of the invention can also contain oil recovery aids such as foaming agents, small molecular organic matters (such as isopropanol, ethylene glycol monobutyl ether, DMSO and the like) and the like which are commonly used in the field.
In the technical scheme, the oil-displacing agent can be obtained by mixing the components according to required amount by adopting various conventional mixing methods, and is dissolved by water according to required concentration when used for displacing oil to obtain the oil-displacing agent for displacing oil; and according to the concentration of the needed oil displacement agent, the components in the oil displacement agent are respectively dissolved in water to obtain the oil displacement agent for oil displacement. The water used in the preparation can be tap water, river water, seawater and oil field formation water; preferred water is: the total mineralization degree of the simulated oil field formation water is preferably 20000-300000 mg/L.
The oil displacement method can also comprise steam flooding, gas flooding and the like commonly used in the field.
The invention adopts a physical simulation displacement evaluation method to evaluate the effect, and the specific evaluation method comprises the following steps:
Drying the core at constant temperature to constant weight, and measuring the gas logging permeability of the core; calculating the pore volume of the simulated oil field stratum water saturated core, recording the volume of saturated crude oil by using the crude oil saturated core at the oil displacement temperature, pumping the stratum water at the speed of 0.1ml/min, driving until the water content reaches 100%, calculating the recovery ratio of the crude oil improved by water drive, then transferring the oil displacement agent obtained in the step c at the speed of 0.1ml/min to 0.1-1 PV (core pore volume), driving the water to 100% at the speed of 0.1ml/min, and calculating the percentage of the recovery ratio of the crude oil improved on the basis of the water drive.
the anionic surfactant prepared by the invention has the temperature resistance of the anionic surfactant and the salt tolerance of the nonionic surfactant due to the polyether and the carboxylate or sulfonate anionic groups, so that the surfactant has excellent temperature resistance and salt tolerance; the polyether carboxylic acid or sulfonate surfactant has lower critical micelle concentration (cmc) which is 1-2 orders of magnitude lower than that of the traditional anionic surfactant, so that the use concentration window of the surfactant is wider, the problem of interface tension rise caused by gradual reduction of the concentration of the surfactant in the field use process of an oil field can be solved, and the ultra-low oil-water interface tension can be still maintained even if the concentration is lower in the underground migration process of the surfactant, so that the oil displacement efficiency can be improved.
The anionic surfactant containing polyether group in the invention is composed of EO-PO-EO chain segment structure, the inventor surprisingly discovers that under the condition of other same structures and same EO number and PO number, the oil displacement effect of the composition obtained by adopting the arrangement mode is far better than that of EO-PO arrangement or PO-EO arrangement.
the oil displacement method is used for simulating oil field formation water and crude oil with the formation temperature of 50-100 ℃ and the mineralization degree of 20000-300000 mg/L, the surfactant with the amount of 0.005-0.6 wt% and the hydrophobic association polymer with the amount of 0-0.3 wt% and the alkali with the amount of 0-1.2 wt% form an oil displacement agent according to the mass percentage, the apparent viscosity of the oil displacement agent composition aqueous solution is measured, the dynamic interfacial tension value between the oil displacement agent composition aqueous solution and dehydrated crude oil of victory oil fields and dehydrated crude oil of the original oil fields can reach 10 -2 -10 -4 mN/m, the oil displacement agent can improve the crude oil recovery ratio on the basis of water displacement and can reach 18.03 percent through evaluation in a physical simulation displacement test room, and a better technical effect is obtained.
Drawings
FIG. 1 is an infrared spectrum of a hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether.
FIG. 2 is an infrared spectrum of hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether acetic acid.
Fig. 3 is a flow chart of a simulated core displacement test. Wherein, 1 is a constant flow pump, 2 is a six-way valve, 3 is an intermediate container, 4 is a medicament tank, 5 is a pressure pump, 6 is a six-way valve, 7 is a sand filling pipe, and 8 is a measuring cylinder.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
a. The structural formula of the prepared anionic surfactant is as follows:
C16H33O(CH2CH2O)3(CHCH3CH2O)8(CH2CH2O)4CH2COOH.NH3
Adding 374 g (1 mol) of cetyl polyoxyethylene (3) ether and 5.6 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 469.8 g (8.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, 1008.9 g of hexadecanol polyoxyethylene (3), polyoxypropylene (8) and polyoxyethylene (4) ether are obtained, and the yield is 99.5%.
507 g (0.5 mol) of hexadecanol polyoxyethylene (3), polyoxypropylene (8), polyoxyethylene (4) ether, 112.2 g (2 mol) of potassium hydroxide, 116.5 g (1 mol) of sodium chloroacetate and 700 ml of toluene are mixed in a 2000 ml reaction kettle equipped with a mechanical stirrer, a thermometer and a reflux condenser, and heated to 90 ℃ for 6 hours. Cooling, acidifying with 25 wt% sulfuric acid, separating water and inorganic salts, evaporating to remove solvent to obtain 494.7 g of carboxylic acid product, and analyzing by High Performance Liquid Chromatography (HPLC), the content of cetyl polyoxyethylene (3), polyoxypropylene (8), polyoxyethylene (4) ether acetic acid in the product is 92.3%.
the synthesized hexadecanol polyoxyethylene (3), polyoxypropylene (8), polyoxyethylene (4) ether and the synthesized hexadecanol polyoxyethylene (3), polyoxypropylene (8), polyoxyethylene (4) ether acetic acid are subjected to infrared spectroscopy (scanning range is 4000-400 cm -1) by a liquid film method by using an American Nicolet-5700 infrared spectrometer, and infrared spectrograms are respectively shown in a figure 1 and a figure 2.
494.7 g of the above-synthesized carboxylic acid product was mixed with 500 g of water, and the pH of the system was adjusted to 8.5 with 25% aqueous ammonia to obtain the desired hexadecyl polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) etherammonium acetate anionic surfactant S-1.
b. The specific compositions of the simulated formation water of the oil field with different divalent cations and total mineralization are shown in table 1.
Respectively preparing the S-1 surfactant, the hydrophobically associating polymer (P1, the molar ratio of the copolymer AM/AMPS/2-acrylamido dodecyl sulfonic acid is 1/0.5/0.001, and the viscosity average molecular weight is 1930 ten thousand) and the aqueous solution of sodium carbonate prepared in the step a by using oilfield simulated formation water A, stirring for 3 hours, mixing the three to obtain a uniform polyepizkyrine ternary system oil displacement agent, measuring the viscosity and the oil-water interfacial tension of the system, and comparing the system with S-1, P1 and S-1+ P1 systems, which are shown in Table 2. S-1 aqueous solutions with different concentrations are prepared respectively from simulated formation water of different oil fields, and the oil-water interfacial tension of the S-1 aqueous solutions on dehydrated crude oil (I) of the victory oil field is measured and is shown in Table 3. The viscosity of the dehydrated crude oil in the victory oil field is 9.8 mPa.s. The apparent viscosity was measured by BroodFilld model III viscometer from Brookfield corporation, USA, and the interfacial tension was measured by TX500 type rotary drop interfacial tensiometer from Texas university, USA.
c. And drying the artificial core at constant temperature to constant weight, measuring the average diameter and the length of the core, weighing the dry weight of the core, and measuring the gas logging permeability of the core. And testing the pore volume of the stratum water saturated core. And (4) the saturated core of the dehydrated crude oil in the oil field is favored, and the volume of the saturated crude oil is recorded. And c, at the temperature of 85 ℃, simulating the formation water A of the oil field to drive the produced fluid to contain 100 percent of water, calculating the recovery ratio of the crude oil improved by water drive, injecting the polyepichia pastoris ternary system oil displacement agent synthesized in the step b with 0.3PV (core pore volume), driving the water to contain 100 percent of water, calculating the percent of the crude oil improved on the basis of the water drive, and simultaneously comparing the percent with a single or binary oil displacement agent injected with the same PV, wherein the percent is shown in the table 2. The gas permeability of the core is measured by an HKGP-3 type compact core gas permeability porosity measuring instrument, and the flow of the adopted simulated core displacement test is shown in figure 3.
[ example 2 ]
a. The structural formula of the prepared anionic surfactant is as follows:
C16H33O(CH2CH2O)3(CHCH3CH2O)8(CH2CH2O)4CH2COOH.N(CH2CH2OH)3
In the same manner as in example 1, 494.7 g of cetylenepolyoxyethylene (3) polyoxypropylene (n-8) polyoxyethylene (4) etheracetic acid was synthesized, and mixed with 500 g of water, and the pH of the system was adjusted to 8 with 98% triethanolamine to obtain the desired cetylenepolyoxyethylene (3) polyoxypropylene (n-8) polyoxyethylene (4) etherethanoicacid triethanolamine salt anionic surfactant S-2.
b. S-2 prepared in the step a, a hydrophobically associating polymer (P1, the molar ratio of the copolymer AM/AMPS/2-acrylamidododecyl sulfonic acid is 1/0.5/0.001, and the viscosity average molecular weight is 1930 ten thousand) and a sodium carbonate aqueous solution are prepared respectively by using the simulated formation water A of the Shengli oil field, and the stirring is carried out for 4 hours, and the rest is the same as the example 1 b, and the results are shown in Table 4. S-2 aqueous solutions with different concentrations are prepared respectively from simulated formation water of different oil fields, and the oil-water interfacial tension is measured and is shown in Table 3.
c. The indoor simulated oil displacement test was carried out in the same manner as in example 1, and the results are shown in table 4.
[ example 3 ]
a. The structural formula of the prepared anionic surfactant is as follows:
308 g (1 mol) of nonylphenol polyoxyethylene (2) ether, 1.5 g of potassium hydroxide and 4.6 g of anhydrous potassium carbonate are added into a 2L pressure reactor provided with a stirring device, dehydration and nitrogen replacement are carried out in the same way as in example 1, the reaction temperature of the system is adjusted to 160 ℃, 638 g (11 mol) of propylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, after the propylene oxide reaction is finished, the temperature is reduced, 134.2 g (3.05 mol) of ethylene oxide is slowly introduced at 140 ℃, and the pressure is controlled to be less than or equal to 0.50 MPa. After the reaction, the reaction mixture was worked up in the same manner as in example 1 to obtain 1006.7 g of nonylphenol polyoxyethylene (2) polyoxypropylene (10) polyoxyethylene (3) ether in a yield of 98.7%.
nonylphenol polyoxyethylene (2) polyoxypropylene (10) polyoxyethylene (3) ether 510 g (0.5 mol), 40 g (1 mol) sodium hydroxide, 145.6 g (1.25 mol) sodium chloroacetate and 500 ml acetone were mixed in a 2000 ml reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser, and heated to reflux for 12 hours. Cooling, acidifying with 10 wt% hydrochloric acid, separating water and inorganic salts, evaporating to remove solvent to obtain 523.4 g of carboxylic acid product, and analyzing by High Performance Liquid Chromatography (HPLC), wherein the content of nonylphenol polyoxyethylene (2), polyoxypropylene (10), polyoxyethylene (3) ether acetic acid in the product is 97.1%.
523.4 g of the synthesized carboxylic acid product is mixed with 500 g of water, and the pH value of the system is adjusted to 12 by 10% triethylamine aqueous solution, so that the required nonylphenol polyoxyethylene (2) polyoxypropylene (10) polyoxyethylene (3) ether acetic acid triethylamine salt anionic surfactant S-3 is obtained.
b. S-3 prepared in the step a, a hydrophobically associating polymer (P1, the molar ratio of the copolymer AM/AMPS/2-acrylamidododecyl sulfonic acid is 1/0.5/0.001, and the viscosity average molecular weight is 1930 ten thousand) and a sodium carbonate aqueous solution are prepared respectively by using the simulated formation water A of the Shengli oil field, and the stirring is carried out for 4 hours, and the rest is the same as the example 1 b, and the results are shown in Table 5. S-3 aqueous solutions with different concentrations are prepared respectively by using simulated formation water of different oil fields, and the oil-water interfacial tension is measured and is shown in Table 3.
c. The indoor simulated oil displacement test was carried out in the same manner as in example 1, and the results are shown in table 5.
[ example 4 ]
a. The structural formula of the prepared anionic surfactant is as follows:
254 g (0.5 mol) of isomeric tridecanol polyoxyethylene (7) ether (tradename: TO 7, basf) and 2.5 g of potassium hydroxide were charged into a 2L pressure reactor equipped with a stirrer, and water removal and nitrogen substitution were carried out in the same manner as in example 1. the reaction temperature of the system was adjusted TO 160 ℃ and 88.2 g (1.52 mol) of propylene oxide was slowly introduced under a controlled pressure of 0.60MPa or less, after the completion of the propylene oxide reaction, the temperature was lowered, 44.9 g (1.02 mol) of ethylene oxide was slowly introduced under a controlled pressure of 0.40MPa or less at 120 ℃ and after the completion of the reaction in the same manner as in example 1, the isomeric tridecanol polyoxyethylene (7) polyoxypropylene (3) polyoxyethylene (2) ether 376.9 g was obtained at a yield of 97.9%.
The isotridecanol polyoxyethylene (7) polyoxypropylene (3) polyoxyethylene (2) ether 231.0 g (0.3 mol) was mixed with 42 g (0.75 mol) potassium hydroxide, 114.9 g (0.69 mol) sodium 2-chloroethanesulfonate and 700 ml toluene in a 2000 ml three-neck flask equipped with a mechanical stirrer, thermometer and reflux condenser and heated to 105 ℃ for 6 hours. Cooling, acidifying with 35 wt% sulfuric acid, separating water and inorganic salts, evaporating to remove solvent to obtain 450.0 g sulfonic acid product, and analyzing by High Performance Liquid Chromatography (HPLC), wherein the content of isotridecanol polyoxyethylene (7), polyoxypropylene (3), polyoxyethylene (2) ether ethanesulfonic acid in the product is 95.9%.
450.0 g of the sulfonic acid product synthesized above is mixed with 500 g of water, and the pH value of the system is adjusted to 13 by 15% of sodium hydroxide aqueous solution, so as to obtain the required isomeric tridecanol polyoxyethylene (7) polyoxypropylene (3) polyoxyethylene (2) ether sodium ethanesulfonate anionic surfactant S-4.
b. S-4 prepared in the step a, a hydrophobically associating polymer (P1, the molar ratio of the copolymer AM/AMPS/2-acrylamidododecyl sulfonic acid is 1/0.5/0.001, and the viscosity average molecular weight is 1930 ten thousand) and a sodium carbonate aqueous solution are prepared respectively by using the simulated formation water A of the Shengli oil field, and the stirring is carried out for 4 hours, and the rest is the same as the example 1 b, and the results are shown in Table 6. S-4 aqueous solutions with different concentrations are prepared respectively from simulated formation water of different oil fields, and the oil-water interfacial tension is measured and is shown in Table 3.
c. The results of the indoor simulated oil displacement test conducted in the same manner as in example 1 are shown in Table 6.
[ example 5 ]
a. the structural formula of the prepared anionic surfactant is as follows:
R1O(CH2CH2O)5(CHCH3CH2O)4(CH2CH2O)20CH2COONa
Wherein, the carbon chain distribution of R 1 is C 12 72.3.3 percent and C 14 27.7.7 percent.
414.9 g (1 mol) of mixed dodeca/tetradecyl (C 12~14) alcohol polyoxyethylene (5) ether and 14.5 g of anhydrous potassium carbonate are added into a 2.5L pressure reactor provided with a stirring device, water removal and nitrogen replacement are carried out in the same way as in example 1, the reaction temperature of the system is adjusted to 150 ℃, 234.9 g (4.05 mol) of propylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.50MPa, the temperature is reduced after the propylene oxide reaction is finished, 924 g (21 mol) of ethylene oxide is slowly introduced at 130 ℃, the pressure is controlled to be less than or equal to 0.40MPa, after the reaction is finished, the aftertreatment is carried out in the same way as in example 1, and 1513.3 g of mixed dodeca/tetradecyl (C 12~14) alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20) ether is obtained, and the yield is 99.1%.
763.5 g (0.5 mol) of dodeca/tetradecyl (C 12~14) alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20) ether, 70.1 g (1.25 mol) of potassium hydroxide, 64.1 g (0.55 mol) of sodium chloroacetate and 400 ml of benzene were mixed in a 2000 ml reaction kettle equipped with a mechanical stirrer, a thermometer and a reflux condenser, heated to 70 ℃ for reaction for 9 hours, cooled, acidified with 15 wt% sulfuric acid, and then water and inorganic salts were removed, and the solvent was distilled off to obtain 740.9 g of carboxylic acid product, in which the acetic acid content of the mixed dodeca/tetradecyl (C 12~14) alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20) ether was 93.5% by High Performance Liquid Chromatography (HPLC).
740.9 g of the carboxylic acid product synthesized above was mixed with 900 g of water, and the pH of the system was adjusted to 10 with a 40% aqueous solution of sodium hydroxide to obtain the desired mixed dodeca/tetradecyl (C 12~14) ol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20) ether sodium acetate anionic surfactant S-5.
b. aqueous solutions of S-5 and hydrophobically associating polymer (P2, molar ratio of copolymer AM/AMPS/2-acrylamidododecylsulfonic acid 1/0.5/0.002, viscosity average molecular weight 1800 ten thousand) prepared in step a were prepared from virgin oilfield simulated formation waters C and D, respectively, and stirred for 4 hours, as in example 1 b, with the results shown in tables 7 and 8. S-5 aqueous solutions with different concentrations are prepared respectively from the simulated formation water of the original oilfield, and the interfacial tension of the S-5 aqueous solutions on the dehydrated crude oil (II) of the original oilfield in oil and water is measured and shown in Table 3. The viscosity of the dehydrated crude oil in the original oilfield is 2.9 mPa.s.
c. The results of the indoor simulated oil displacement test conducted in the same manner as in example 1 are shown in tables 7 and 8.
[ example 6 ]
The oil displacing compositions prepared in [ example 1 ] and [ example 5 ] were filled in 50 ml ampoules, vacuum deoxygenated and sealed, placed in an oven for thermal stability testing and compared with the same concentration of polymer as shown in table 9; the oil-water interfacial tension of the flooding composition on the oil field dewatered crude oil after different aging times was measured and compared to the same concentration of surfactant as shown in table 10.
[ COMPARATIVE EXAMPLE 1 ]
A certain amount of comparative surfactant was dissolved in simulated saline A-D of different degrees of mineralization, the oil-water interfacial tension of the solutions of the comparative surfactants of different concentrations on crude oil was measured and compared with the surfactants prepared in the corresponding examples, and the results are shown in Table 11. The interfacial tension was measured by a rotary drop interfacial tensiometer model TX500, produced by texas university, usa.
In Table 11, S-6 is ceteth-3, polyoxypropylene (8), polyoxyethylene (4) ether, S-7 is ammonium cetoacetate, S-8 is the isomeric trideceth-7, polyoxypropylene (3), polyoxyethylene (2) ether, S-9 is the isomeric sodium trideceth-sulfonate, S-10 is the mixed dodeca/tetradecyl (C 12~14) alcohol polyoxyethylene (5), polyoxypropylene (4), polyoxyethylene (20) ether, and S-11 is the mixed sodium dodeca/tetradecyl (C 12~14) acetate.
[ COMPARATIVE EXAMPLE 2 ]
an anionic/zwitterionic complex surfactant S-12 formed by Sodium Dodecyl Sulfate (SDS) as an anionic surfactant and lauramidopropyl betaine (LMB) as a zwitterionic surfactant studied in Zhanguqin et al (2002, volume 3, 20: colloid and polymer, P1-5) was subjected to an interfacial property measurement test as in example 1, and the results are shown in Table 12 in comparison with S-1 and S-5.
[ COMPARATIVE EXAMPLE 3 ]
The same as in example 1, except that the reaction with propylene oxide and ethylene oxide was not carried out stepwise one after another, but was carried out in one step after mixing both. Namely, slowly introducing a mixture of 469.8 g (8.1 mol) of propylene oxide and 178.2 g (4.05 mol) of ethylene oxide at the temperature of 140-150 ℃, controlling the pressure to be less than or equal to 0.60MPa, and obtaining the anionic surfactant S-13 with the rest being the same. Interfacial properties were measured as in [ example 1 ] and compared with S-1, and the results are shown in Table 13.
[ COMPARATIVE EXAMPLE 4 ]
the same as in example 4, except that the reaction with propylene oxide and ethylene oxide was not carried out stepwise one after another, but was carried out in one step after mixing both. Namely, a mixture of 88.2 g (1.52 mol) of propylene oxide and 44.9 g (1.02 mol) of ethylene oxide is slowly introduced at 120-160 ℃, and the rest is the same, so as to obtain the anionic surfactant S-14. The interfacial properties were measured as in example 1 and compared with S-4, and the results are shown in Table 13.
[ COMPARATIVE EXAMPLE 5 ]
The same as in example 5, except that the reaction with propylene oxide and ethylene oxide was not carried out stepwise one after another, but was carried out in one step after mixing both. Namely, a mixture of 234.9 g (4.05 mol) of propylene oxide and 924 g (21 mol) of ethylene oxide is slowly introduced at 120-160 ℃, and the rest is the same, so as to obtain the anionic surfactant S-15. The interfacial properties were measured as in example 1 and compared with S-5, and the results are shown in Table 13.
[ COMPARATIVE EXAMPLE 6 ]
The same as [ example 1 ] except that the hydrophobically associative polymer P1 was replaced with a high molecular weight anionic polyacrylamide P3 (having a viscosity average molecular weight of 1500 ten thousand), and the results were as shown in FIG. 14.
TABLE 1
| Simulated salt water | Ca2+(mg/L) | Mg2+(mg/L) | TDS(mg/L) |
| A | 1200 | 400 | 32000 |
| B | 20 | 12 | 8000 |
| C | 15000 | 8000 | 180000 |
| D | 4000 | 1250 | 250000 |
TABLE 2
TABLE 3
| Surface active agent | Simulated salt water | temperature (. degree.C.) | Crude oil | Concentration (%) | IFT(mN/m) |
| S-1 | A | 85 | I | 0.6 | 0.0385 |
| S-1 | A | 85 | I | 0.3 | 0.0042 |
| S-1 | A | 85 | I | 0.1 | 0.00075 |
| S-1 | A | 85 | I | 0.05 | 0.0024 |
| S-1 | A | 85 | I | 0.025 | 0.0042 |
| S-1 | A | 85 | I | 0.01 | 0.0271 |
| S-1 | A | 85 | I | 0.005 | 0.0885 |
| S-1 | A | 85 | I | 0.001 | 0.1312 |
| S-1 | B | 85 | I | 0.1 | 0.5247 |
| S-1 | D | 85 | I | 0.1 | 0.0583 |
| S-2 | A | 85 | I | 0.3 | 0.0021 |
| S-2 | A | 85 | I | 0.05 | 0.0054 |
| S-2 | A | 85 | I | 0.01 | 0.0079 |
| S-2 | A | 85 | I | 0.005 | 0.0411 |
| S-2 | B | 85 | I | 0.3 | 0.1217 |
| S-3 | A | 85 | I | 0.6 | 0.00852 |
| S-3 | A | 85 | I | 0.3 | 0.0041 |
| S-3 | A | 85 | I | 0.05 | 0.00052 |
| S-3 | A | 85 | I | 0.025 | 0.0034 |
| S-3 | A | 85 | I | 0.01 | 0.0428 |
| S-3 | C | 85 | I | 0.05 | 0.0852 |
| S-3 | D | 85 | I | 0.05 | 0.0439 |
| S-4 | A | 85 | I | 0.3 | 0.00058 |
| S-4 | A | 85 | I | 0.2 | 0.0016 |
| S-4 | A | 85 | I | 0.1 | 0.00076 |
| S-4 | A | 85 | I | 0.05 | 0.0034 |
| S-4 | A | 85 | I | 0.01 | 0.0069 |
| S-4 | A | 85 | I | 0.005 | 0.0463 |
| S-5 | C | 95 | II | 0.3 | 0.0056 |
| S-5 | C | 95 | II | 0.1 | 0.00042 |
| S-5 | C | 95 | II | 0.025 | 0.0013 |
| S-5 | C | 95 | II | 0.01 | 0.0076 |
| S-5 | C | 95 | II | 0.005 | 0.0233 |
| S-5 | C | 95 | II | 0.001 | 0.3221 |
| S-5 | D | 95 | II | 0.3 | 0.0032 |
| S-5 | D | 95 | II | 0.1 | 0.00053 |
| S-5 | D | 95 | II | 0.01 | 0.0011 |
TABLE 4
TABLE 5
TABLE 6
Table 7 (simulated salt water C)
Table 8 (simulated salt water D)
TABLE 9
Watch 10
TABLE 11
| Surface active agent | simulated salt water | Temperature (. degree.C.) | Crude oil | concentration (%) | IFT(mN/m) |
| S-1 | A | 85 | I | 0.3 | 0.0042 |
| S-1 | A | 85 | I | 0.05 | 0.0024 |
| S-6 | A | 85 | I | 0.3 | 0.0232 |
| S-6 | A | 85 | I | 0.05 | 0.0872 |
| S-7 | A | 85 | I | 0.3 | 0.0566 |
| S-7 | A | 85 | I | 0.05 | 0.1455 |
| S-4 | A | 85 | I | 0.3 | 0.00058 |
| S-8 | A | 85 | I | 0.3 | 0.0464 |
| S-9 | A | 85 | I | 0.3 | 0.0352 |
| S-5 | D | 95 | II | 0.3 | 0.0056 |
| S-10 | D | 95 | II | 0.3 | 0.0732 |
| S-11 | D | 95 | II | 0.3 | 0.0299 |
TABLE 12
| Surface active agent | simulated salt water | Temperature (. degree.C.) | Crude oil | Concentration (%) | IFT(mN/m) |
| S-1 | A | 85 | I | 0.3 | 0.0042 |
| S-1 | A | 85 | I | 0.05 | 0.0024 |
| S-12 | A | 85 | I | 0.3 | 0.0787 |
| S-12 | A | 85 | I | 0.05 | 0.5333 |
| S-5 | D | 95 | II | 0.1 | 0.00042 |
| S-5 | D | 95 | II | 0.025 | 0.0013 |
| S-12 | D | 95 | II | 0.1 | 0.0254 |
| S-12 | D | 95 | II | 0.025 | 0.0189 |
Watch 13
| Surface active agent | Simulated salt water | Temperature (. degree.C.) | crude oil | Concentration (%) | IFT(mN/m) |
| S-1 | A | 85 | I | 0.3 | 0.0042 |
| S-1 | A | 85 | I | 0.05 | 0.0024 |
| S-13 | A | 85 | I | 0.3 | 0.0087 |
| S-13 | A | 85 | I | 0.05 | 0.0065 |
| S-4 | A | 85 | I | 0.3 | 0.00058 |
| S-4 | A | 85 | I | 0.1 | 0.00076 |
| S-14 | A | 85 | I | 0.3 | 0.0067 |
| S-14 | A | 85 | I | 0.1 | 0.0023 |
| S-5 | C | 95 | II | 0.1 | 0.00042 |
| S-5 | D | 95 | II | 0.1 | 0.00053 |
| S-15 | C | 95 | II | 0.1 | 0.0076 |
| S-15 | D | 95 | II | 0.1 | 0.0087 |
TABLE 14
Claims (6)
1. An oil displacement method comprises the following steps:
(1) Mixing an oil displacement agent with water to obtain an oil displacement system;
(2) Contacting the oil displacement system with an oil-bearing stratum under the conditions that the oil displacement temperature is 25-120 ℃ and the total salinity is more than 500 mg/L stratum water, and displacing the crude oil in the oil-bearing stratum;
The oil displacement agent comprises the following components in parts by weight:
1)1 part of a surfactant;
2)0 to 50 parts of a polymer;
3) 0-50 parts of alkali;
Wherein the amounts of the polymer and the base are not 0 at the same time; the surfactant is an anionic surfactant; the polymer is a polymer suitable for oil extraction in oil fields; the alkali is at least one of inorganic alkali or organic amine; in the oil displacement system, the concentration of the anionic surfactant is 0.001-2.0 wt%, the concentration of the polymer is 0-1.8 wt%, and the concentration of the alkali is 0-2.0 wt% based on the total mass of the oil displacement system;
The anionic surfactant has a structure shown as a molecular general formula (1):
R 1 O (CH 2 CH 2 O) m1 (CH 3) CH 2 O) n (CH 2 CH 2 O) m2 R 2 Y, formula (1);
wherein R 1 is an aliphatic alkyl group of C 8 -C 30 or an aryl group substituted by a C 4 -C 20 straight chain or branched chain saturated or unsaturated alkyl group, M1 is 1-30, M2 is 1-50, N is 1-30, R 2 is an alkylene group or hydroxyl substituted alkylene group of C 1 -C 5, Y is COOM or SO 3 N, M and N are independently selected from hydrogen, alkali metal or at least one of groups represented by NR 3 (R 4) (R 5) (R 6), R 3, R 4, R 5 and R2200 6 are independently selected from one of H, (CH 2) p OH or (CH 2) q CH 3, p is 2-4, q is any integer of 0-5, the hydrophobic polymer is hydrophobic polyacrylamide, the molar ratio of acrylamide and anti-salt monomer to the hydrophobic association monomer is 1.001-1.01, and the molecular weight is 0.1200-1200.
2. the oil displacement method of claim 1, wherein R 1 is C 12 -C 24 alkyl or phenyl substituted by C 8 -C 12 alkyl, R 2 is C 1 -C 3 alkylene or hydroxy-substituted propylene, p is 2, q is 0-1, m1 is 2-10, m2 is 1-20, and n is 2-15.
3. The oil displacement method according to claim 1, wherein the base is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, and short carbon chain organic amines.
4. The oil displacement method of claim 1, wherein the organic amine is a short carbon chain organic amine.
5. the oil displacement method according to claim 1, wherein the mass ratio of the surfactant to the polymer to the alkali in the oil displacement agent is 1: 0-2: (0-5).
6. The oil displacement method according to claim 1, characterized in that the oil displacement temperature is 50-100 ℃, the total mineralization degree of the formation water is 20000-300000 mg/L, and the Ca 2+ is 1000-15000 mg/L, Mg 2+ is 400-8000 mg/L.
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