CN106590594B - Method suitable for low-calcium-magnesium oil reservoir enhanced oil recovery - Google Patents

Method suitable for low-calcium-magnesium oil reservoir enhanced oil recovery Download PDF

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CN106590594B
CN106590594B CN201510684090.5A CN201510684090A CN106590594B CN 106590594 B CN106590594 B CN 106590594B CN 201510684090 A CN201510684090 A CN 201510684090A CN 106590594 B CN106590594 B CN 106590594B
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water
oil displacement
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CN106590594A (en
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沈之芹
李应成
何秀娟
何良好
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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China Petrochemical Corp
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    • 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
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    • 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
    • C09K8/588—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 polymers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

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Abstract

The invention relates to an enhanced oil recovery method, which mainly solves the problem of poor oil displacement efficiency of an oil displacement composition in the prior art, and adopts the enhanced oil recovery method, and the method comprises the following steps of 1) mixing the oil displacement composition with oil displacement 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 25-110 ℃ and the total mineralization is more than 100 mg/L of oil field stratum water to displace crude oil in the oil-bearing stratum, wherein the oil displacement composition comprises the following components of 1)1 part of surfactant, 2) 0-50 parts of polymer, 3) 0-50 parts of alkaline substance, 0.001-2.0 wt% of surfactant, 0-1.8 wt% of polymer and more than zero, and 0-2.0 wt% of alkaline substance and more than zero

Description

Method suitable for low-calcium-magnesium oil reservoir enhanced oil recovery
Technical Field
The invention relates to an enhanced oil recovery method, in particular to an enhanced oil recovery method suitable for a low-calcium magnesium oil reservoir.
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-mobility, wherein the quaternary ammonium salt is 16-based carbon chain length, the surfactant is 16-based, the surfactant is used as a cationic surfactant, the loss of the surfactant is 16-20%, the surfactant is reduced by using the same amount of anionic surfactant as a linear surfactant, the surfactant used in situ as a linear surfactant of a linear surfactant, the displacement system of a linear surfactant used in a high-linear surfactant, the displacement of crude oil field, the high-linear surfactant, the application of a high-linear surfactant, the surfactant used for displacement of a high-linear surfactant, the high-linear surfactant is used for displacement of a high-linear surfactant, the high-.
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.
The invention provides an 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, and the invention provides the oil displacement composition, the preparation method and the application thereof in the enhanced oil recovery.
Disclosure of Invention
the invention aims to solve the technical problem that the oil displacement composition in the prior art is poor in oil displacement efficiency, and provides a novel method for enhanced oil recovery. The method uses the water solution containing the surfactant or the water solution of the surfactant, the polymer and the alkaline substance as the oil displacement composition in the oil displacement process, and has the advantages of good temperature resistance and high oil displacement efficiency under the high temperature condition.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method of enhanced oil recovery comprising the steps of:
(1) Mixing the oil displacement composition with oil displacement 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 25-110 ℃ and the total mineralization is more than 100 mg/L of oil field stratum water, and displacing the crude oil in the oil-bearing stratum;
The oil displacement composition 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 and more than 0 part of alkaline substance;
The surfactant is a negative non-mixed surfactant; the alkaline substance is at least one of an inorganic alkaline substance and an organic alkaline substance; the oil displacement system contains 0.001-2.0 wt% of the surfactant, 0-1.8 wt% of the polymer and larger than zero, and the alkaline substance is 0-2.0 wt% and larger than zero.
In the technical scheme, the anionic-nonionic mixed surfactant preferably comprises a nonionic surfactant shown in a formula (1), an anionic surfactant shown in a formula (2) and an anionic surfactant shown in a formula (3), wherein the mass ratio of the nonionic surfactant shown in the formula (1), the anionic surfactant shown in the formula (2) and the anionic surfactant shown in the formula (3) is (0.5-5): 1: (0.2-5);
R 1, R 2 and R 3 are independently selected from C 4 -C 40 aliphatic hydrocarbon groups or aryl groups substituted by C 4 -C 30 hydrocarbon groups, M1, M2, M3 and M4 are independently selected from 0-50, but M1 and M2, M3 and M4 cannot be 0 simultaneously, N1 and N2 are independently selected from 0-100, but N1 and N2 cannot be 0 simultaneously, R1, R2, R3 and R4 are independently selected from 0-50, but R1 and R2, R3 and R3 cannot be 0 simultaneously, s3 and s3 are independently selected from 0-100, but s3 and s3 cannot be 0 simultaneously, p3 and p3 are independently selected from 0-3650, but p3 and p3, p3 and p3 are not selected from 0-M, N3 and N3 are independently selected from N3 and N3 are selected from N3 and N3 (H) or N3 and N3 are independently selected from N3 and N3 are selected from N3 and N3.
In the above-mentioned embodiment, the mass ratio of the nonionic surfactant represented by the formula (1), the anionic surfactant represented by the formula (2), and the anionic surfactant represented by the formula (3) is preferably (0.5 to 5): 1: (0.2-5); more preferably (0.03 to 3): 1: (1-3).
in the above technical means, at least one of R 1, R 2 and R 3 is preferably a C 6 -C 20 alkyl group or a C 8 -C 16 alkyl-substituted phenyl group.
In the above-described embodiment, p is preferably 2 and q is preferably 0 to 1.
In the technical scheme, preferably, m1+ m2 is 2-6, m3+ m4 is 2-6, and n1+ n2 is 10-40; and/or r1+ r2 is 2-6, r3+ r4 is 2-6, s1+ s2 is 10-40 and/or p1+ p2 is 2-6, p3+ p4 is 2-6, and q1+ q2 is 10-40.
The key of the surfactant suitable for the low-calcium magnesium oil deposit is that the effective components are the nonionic surfactant shown in the formula (1), the single hydrophilic head-based anionic surfactant shown in the formula (2) and the double hydrophilic head-based anionic surfactant shown in the formula (3), and the skilled person knows that the surfactant can be supplied in various forms, such as a non-aqueous solid form, an aqueous paste form or an aqueous solution form, for the convenience of transportation, storage, field use and the like; the aqueous solution form comprises a form of preparing a concentrated solution by water, and is directly prepared into a solution form with the concentration required by the on-site oil displacement, for example, a solution with the key active ingredient content of 0.005-0.6 wt% by mass is a form suitable for the 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 surfactant suitable for the low-calcium magnesium oil reservoir can be obtained by mixing the nonionic surfactant, the single hydrophilic head-based anionic surfactant and the double hydrophilic head-based anionic surfactant according to a required proportion, and is preferably obtained by the following preparation method.
In the above technical solution, the amount of the polymer is preferably greater than 0; the polymer is not critical and may be any of various polymers known to those skilled in the art for oil field recovery, such as but not limited to at least one selected from xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, anionic polyacrylamide, modified polyacrylamide, hydrophobically associating polymer, polymeric microspheres.
in the above technical solution, the anionic polyacrylamide is preferably at least one of partially hydrolyzed polyacrylamide, and a copolymer of acrylamide and acrylic acid or acrylate; more preferably partially hydrolyzed polyacrylamide, the degree of hydrolysis is preferably 5 to 30%, and the viscosity average molecular weight is preferably 300 to 3000 ten thousand.
In the technical scheme, the modified polyacrylamide is preferably prepared by copolymerizing acrylamide and a temperature-resistant and salt-resistant monomer, wherein the molar ratio of the acrylamide to the temperature-resistant and salt-resistant monomer is (0.1-40) to 1, and more preferably (5-30) to 1; the temperature-resistant and salt-resistant monomer can be at least one of monomers containing a large side group or a rigid side group (such as styrenesulfonic acid, N-alkylmaleimide, acrylamido long-chain alkylsulfonic acid, 3-acrylamido-3-methylbutyric acid and the like), monomers containing a salt-resistant group (such as 2-acrylamido-2-methylpropanesulfonic acid), monomers containing a hydrolysis-resistant group (such as N-alkylacrylamide), monomers containing a group capable of inhibiting hydrolysis of an amide group (such as N-vinylpyrrolidone), monomers containing a hydrophobic group and the like, which are well known to those skilled in the art, and is preferably 2-acrylamido-2-methylpropanesulfonic acid.
In the technical scheme, the modified polyacrylamide is preferably prepared by copolymerizing acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, wherein the molar ratio of the acrylamide to the 2-acrylamide-2-methylpropanesulfonic acid is (5-30) to 1, more preferably (5-20) to 1, and further preferably (5-10) to 1.
In the technical scheme, the viscosity average molecular weight of the modified polyacrylamide is preferably 500-3000 ten thousand, and more preferably 1500-2500 ten thousand.
In the above technical solution, the inorganic basic substance is preferably at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, and an alkali metal carbonate; it is further preferable that the alkali metal hydroxide is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide, the alkaline earth metal hydroxide is at least one selected from the group consisting of magnesium hydroxide and calcium hydroxide, and the alkali metal carbonate is at least one selected from the group consisting of sodium carbonate and sodium bicarbonate. The organic basic substance preferably contains at least one of a primary amine group, a secondary amine group, a tertiary amine group, and a quaternary ammonium base group in a molecule, and more preferably at least one of ethanolamine, diethanolamine, triethanolamine, and triethylamine.
In the technical scheme, the mass ratio of the surfactant to the polymer to the alkaline substance in the oil displacing composition is preferably 1 (0-2) to 0-5.
In the above technical scheme, one of the preferable schemes of the preparation method of the oil-displacing composition comprises the following steps:
a. In the presence of a basic catalyst, R 1 NH 2 is sequentially reacted with required amounts of ethylene oxide, propylene oxide and ethylene oxide to obtain R 1 N ((CH 2 CH 2 O) m1 (CHCH 3 CH 2 O) n1 (CH 2 CH 2 O) m3 H) ((CH 2 CH 2 O) m2) (CHCH 3 CH 2 O) n2 (CH 2 CH 2 O) m4 H);
b. B, reacting the product obtained in the step a with X 1 R 01 Y 01 and an alkaline catalyst in a solvent according to a molar ratio of 1 (1-2) to (1-4) at a reaction temperature of 50-120 ℃ for 3-15 hours to obtain a mixture containing a nonionic surfactant shown in a formula (1), the single hydrophilic head group anionic surfactant shown in the formula (4) and the double hydrophilic head group anionic surfactant shown in the formula (5);
Wherein Z 01 is-R 02 Y 01, Y 01 is selected from SO 3 M 1 or COON 1, M 1 and N 1 are alkali metals, and X 1 is selected from chlorine, bromine or iodine.
c. And (c) uniformly mixing the surfactant mixture obtained in the step (b) with a polymer and an alkaline substance in parts by mass to obtain the oil displacing composition.
In the technical scheme, the molar ratio of R 1 N ((CH 2 CH 2 O) m1 (CHCH 3 CH 2 O) n1 (CH 2 CH 2 O) m3 H) (CH 2 CH 2 O) m2 (CHCH 3 CH 2 O) n2 (CH 2 CH 2 O) m4 H) to X 1 R 01 Y 01 to alkali metal hydroxide or alkali metal alkoxide is 1 (1-1.5) to (1-2).
In the above technical solution, the solvent in step b is preferably at least one selected from the group consisting of ketones of C 3 -C 8 and aromatic hydrocarbons of C 6 -C 9, such as at least one selected from the group consisting of acetone, butanone, pentanone, benzene, toluene or xylene, trimethylbenzene, ethylbenzene and diethylbenzene.
In the above technical scheme, the alkali catalyst may be selected from alkali metal hydroxide or alkali metal alkoxide, wherein the alkali metal hydroxide may be selected from sodium hydroxide or potassium hydroxide, and the alkali metal alkoxide may be selected from sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.
as long as the reaction of step b is carried out, the skilled person can remove the solvent by distillation without complicated separation, and the surfactant suitable for low-calcium magnesium oil reservoirs containing salt and excessive alkaline catalyst can be obtained. Step b can be carried out without inventive work by a person skilled in the art in order to obtain a product comprising formula (1) and formula (4) and formula (5) free of salts and excess basic catalyst.
For example, in order to obtain a surfactant suitable for low-calcium magnesium reservoirs free of salt and excess alkaline catalyst, which is composed of the nonionic surfactant of formula (1) and the single hydrophilic head-based anionic surfactant of formula (4) and the double hydrophilic head-based anionic surfactant of formula (6), the product when M 1 or N 1 is H may further include step d and step e:
d. 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;
e. The resulting organic phase is concentrated to give the desired product.
for another example, in order to obtain a surfactant suitable for low-calcium magnesium oil reservoirs, which is free of salt and an excess amount of basic catalyst, from the nonionic surfactant represented by formula (1), the single hydrophilic head-based anionic surfactant represented by formula (4), and the double hydrophilic head-based anionic surfactant represented by formula (6), when M 1 or N 1 is an alkali metal or a product represented by formula NR 4 (R 5) (R 6) (R 7), it is sufficient to neutralize with a base corresponding to the desired alkali metal or a group represented by formula NR 4 (R 5) (R 6) (R 7) on the basis of step d, and then remove the solvent from the organic phase.
The alkali metal or base corresponding to the group of formula NR 4 (R 5) (R 6) (R 7) 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 4 (R 5) (R 6) (R 7) selected from the group consisting of ammonia, ethanolamine, diethanolamine, triethanolamine, triethylamine, quaternary ammonium bases and the like.
Examples of X 1 R 01 Y 01 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 above technical scheme, the second preferred method for preparing the flooding composition comprises the following steps:
(b) reacting a product obtained in the step a in the preferred scheme with 1, 3-propane sultone and an alkaline catalyst in a solvent at a reaction temperature of 50-120 ℃ for 3-15 hours according to a molar ratio of 1 (1-2) to (1-4) to obtain a mixture containing a nonionic surfactant shown in a formula (1), a single hydrophilic head group anionic surfactant shown in a formula (6) and a double hydrophilic head group anionic surfactant shown in a formula (7);
Wherein Z' 01 is-CH 2 CH 2 CH 2 SO 3 M 2, and M 2 is alkali metal.
(c) And (c) uniformly mixing the surfactant mixture obtained in the step (b) with a polymer and an alkaline substance in parts by mass to obtain the oil displacing composition.
in the technical scheme, the molar ratio of the R 1 N ((CH 2 CH 2 O) m1 (CHCH 3 CH 2 O) n1 (CH 2 CH 2 O) m3 H) (CH 2 CH 2 O) m2 (CHCH 3 CH 2 O) n2 (CH 2 CH 2 O) m4 H) to the basic catalyst in the step (b) is preferably 1 (1-1.5) to (1-2).
In the above technical scheme, the solvent in step (b) is preferably at least one selected from C 3 -C 8 ketone and C 6 -C 9 aromatic hydrocarbon, such as at least one selected from acetone, butanone, pentanone, benzene, toluene or xylene, trimethylbenzene, ethylbenzene and diethylbenzene, and the alkaline catalyst can be alkali metal hydroxide or alkali metal alkoxide, wherein the alkali metal hydroxide can be sodium hydroxide or potassium hydroxide, and the alkali metal alkoxide can be sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide.
As long as the reaction of step (b) is carried out, the skilled person can remove the solvent by distillation without complicated separation, and the surfactant suitable for low-calcium magnesium oil deposit containing salt and excessive alkaline catalyst can be obtained. Step (b) can be carried out without inventive work by a person skilled in the art in order to obtain a product comprising formula (1) and formula (6) and formula (7) free of salts and excess basic catalyst.
For example, in order to obtain a surfactant suitable for low-calcium magnesium reservoirs free of salt and excess alkaline catalyst, which is composed of the nonionic surfactant of formula (1) and the single hydrophilic head-based anionic surfactant of formula (6) and the double hydrophilic head-based anionic surfactant of formula (7), the product when M 1 or N 1 is H may further include step (d) and step (e):
(d) adding an acid into the reaction mixture obtained in the step (b) to adjust the pH value of the water phase to 1-3, and separating to obtain an organic phase;
(e) The resulting organic phase is concentrated to give the desired product.
For another example, in order to obtain a surfactant suitable for low-calcium magnesium oil reservoirs, which is free of salt and an excess amount of an alkaline catalyst, from the nonionic surfactant represented by formula (1), the single-hydrohead-based anionic surfactant represented by formula (6), and the double-hydrohead-based anionic surfactant represented by formula (7), when M 1 or N 1 is an alkali metal or a product of a group represented by formula NR 4 (R 5) (R 6) (R 7), it is sufficient to neutralize with a base corresponding to the desired alkali metal or a group represented by formula NR 4 (R 5) (R 6) (R 7) on the basis of step (d), and then remove the solvent from the organic phase.
The alkali metal or base corresponding to the group of formula NR 4 (R 5) (R 6) (R 7) 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 4 (R 5) (R 6) (R 7) selected from the group consisting of ammonia, ethanolamine, diethanolamine, triethanolamine, triethylamine, quaternary ammonium bases 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 (5-10) to 1, and initiating a free radical polymerization reaction by using water as a solvent and using 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.
in the present invention, the nonionic surfactant represented by the formula (1), the anionic surfactant represented by the formula (2), and the anionic surfactant represented by the formula (3) have EO-PO-EO arrangement in EO and PO segments, and the inventors have surprisingly found that the oil displacement effect of the composition obtained by using such arrangement is far superior to that of EO-PO arrangement or PO-EO arrangement under the conditions of the same structure and the same EO number and PO number.
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 above technical scheme, the oil-displacing agent obtained in step c or (c) can be obtained by mixing the components according to the required amount by various conventional mixing methods, and is dissolved by water according to the required concentration when used for oil displacement to obtain the oil-displacing agent for oil displacement; 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 1000-20000 mg/L.
In the technical scheme, the oil displacement water can be deionized water or water containing inorganic mineral substances, and can be selected from tap water, river water, sea water, oil field formation water or oil field injection water, preferably simulated oil field formation water, the mass ratio of a surfactant to a polymer to an alkaline substance in an oil displacement system is preferably 1: 0-2: 0-5, the oil displacement temperature is preferably 50-95 ℃, the total salinity (TDS) of the simulated oil field formation water is preferably 1000-20000 mg/L, and the water type is NaHCO 3 type.
In the technical scheme, the total mineralization degree of the oil field formation water is preferably 3000-20000 mg/L, wherein the Ca 2+ is 10-60 mg/L, Mg 2+ and 5-30 mg/L, HCO 3 - and 1000-3000 mg/L, the viscosity of the crude oil is preferably 2-5 mPa.s, and the formation temperature is preferably 70-90 ℃.
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 or (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 mixed surfactant formed by the nonionic surfactant and the anionic surfactant, which is prepared by the invention, has higher polymerization degree and higher cloud point, so that the temperature resistance of the nonionic surfactant is improved, and meanwhile, the nonionic surfactant mixture with different contents is obtained by controlling the molar ratio of polyether, an ionizing reagent and an alkaline catalyst, so that the mixed surfactant has excellent interface performance on oil reservoir crude oils with different properties; the modified polyacrylamide in the composition is endowed with better temperature resistance and salt resistance due to the adoption of a 2-acrylamide-2-methylpropanesulfonic acid polymerization monomer; the addition of the alkali can improve the interfacial activity of the surfactant, reduce the adsorption of the surfactant on the stratum, reduce the using amount of the surfactant, save the cost of the oil displacement agent and have better effect on improving the crude oil recovery ratio.
in the present invention, the nonionic surfactant represented by the formula (1), the anionic surfactant represented by the formula (2), and the anionic surfactant represented by the formula (3) have EO-PO-EO arrangement in EO and PO segments, and the inventors have surprisingly found that the oil displacement effect of the composition obtained by using such arrangement is far superior to that of EO-PO arrangement or PO-EO arrangement under the conditions of the same structure and the same EO number and PO number.
In the examples of the present invention, the concentrations of the surfactants involved in the test were calculated based on the total amount of the nonionic surfactant represented by the formula (1) and the anionic surfactants represented by the formulae (2) and (3) in the test solution.
the enhanced oil recovery method can be used for simulating oil field formation water and crude oil with the formation temperature of 50-95 ℃ and the mineralization degree of 1000-20000 mg/L, the mixed surfactant with the dosage of 0.005-0.6 wt% and the modified polyacrylamide with the dosage of 0-0.3 wt% and the alkali with the dosage 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 the oil field dehydration crude oil can reach 10 -2 -10 -4 mN/m, the oil displacement agent can improve the crude oil recovery rate on the basis of water displacement and can reach 25.25% through evaluation in a physical simulation displacement test room, and a better technical effect is obtained.
drawings
FIG. 1a is a graph of interfacial tension of aqueous solutions of surfactants S-1 to S-5 of different concentrations prepared with brine I at 75 ℃ on oilfield dehydrated crude oil.
FIG. 1b is a graph of interfacial tension of aqueous solutions of surfactants S-1 to S-5 with different concentrations prepared from brine II on oil field dehydrated crude oil at 81 ℃.
FIG. 1c is a graph of interfacial tension of aqueous solutions of surfactants S-6 to S-9 of different concentrations formulated with brine III against oil field dewatered crude at 87 ℃.
Fig. 2 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.
FIG. 3a is a graph of the viscosity of an aqueous saline I solution of 0.15 wt% P1, 0.3 wt% S-1+0.15 wt% P1, 0.3% wtS-1+0.15 wt% P1+0.8 wt% Na 2 CO 3 after aging at 75 deg.C for various times.
FIG. 3b is a viscosity chart of aqueous saline III solution of 0.15 wt% P2, 0.3 wt% S-1+0.15 wt% P2, 0.3% wtS-1+0.15 wt% P2+0.8 wt% Na 2 CO 3 after aging at 87 ℃ for various times.
FIG. 3c is a graph of the viscosity of an aqueous solution of brine II at 81 ℃ after aging for various times of 0.15 wt% P3, 0.3 wt% S-1+0.15 wt% P3, 0.3 wt% wtS-1+0.15 wt% P3+0.8 wt% Na 2 CO 3.
FIG. 3d is a graph of the viscosity of an aqueous saline I solution of 0.15 wt% P4, 0.3 wt% S-1+0.15 wt% P4, 0.3% wtS-1+0.15 wt% P4+0.8 wt% Na 2 CO 3 after aging at 75 deg.C for various times.
FIG. 3e is a viscosity chart of saline I aqueous solution of 0.15 wt% P1, 0.3 wt% S-1+0.15 wt% P1, 0.3 wt% wtS-1+0.15 wt% P1+0.8 wt% DEA after aging at 75 deg.C for various times
FIG. 4a is a graph of the interfacial tension of an aqueous brine I solution of 0.15 wt% P1, 0.3 wt% S-1+0.15 wt% P1, 0.3% wtS-1+0.15 wt% P1+0.8 wt% Na 2 CO 3 after aging at 75 ℃ for various times for oilfield dewatered crude oil.
FIG. 4b is a graph of the interfacial tension of an aqueous brine III solution of 0.15 wt% P2, 0.3 wt% S-1+0.15 wt% P2, 0.3% wtS-1+0.15 wt% P2+0.8 wt% Na 2 CO 3 after aging at 87 ℃ for various times on oilfield dewatered crude oil.
FIG. 4c is a graph of the interfacial tension of an aqueous brine II solution of 0.15 wt% P3, 0.3 wt% S-1+0.15 wt% P3, 0.3% wtS-1+0.15 wt% P3+0.8 wt% Na 2 CO 3 after aging at 81 ℃ for various times for oilfield dewatered crude oil.
FIG. 4d is an interfacial tension plot of brine I aqueous solution of 0.15 wt% P4, 0.3 wt% S-1+0.15 wt% P4, 0.3% wtS-1+0.15 wt% P4+0.8 wt% Na 2 CO 3 after aging at 75 deg.C for various times for oilfield dewatered crude oil.
FIG. 4e is a graph of the interfacial tension of a brine I aqueous solution of 0.15 wt% P1, 0.3 wt% S-1+0.15 wt% P1, 0.3% wtS-1+0.15 wt% P1+0.8 wt% DEA on oil field dewatered crude after aging at 75 deg.C for various times.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
a. The prepared anionic nonionic mixed surfactant has the following structural formula, wherein (1) Z 1 ═ H, Z 2 ═ H and nonionic surfactants, (2) Z 1 ═ H, Z 2 ═ CH 2 CH 2 SO 3 Na and single hydrophilic head group ionic surfactants, (3) Z 1 ═ Z 2 ═ CH 2 CH 2 SO 3 Na and double hydrophilic head group ionic surfactants, the carbon chain distribution of R 1 is C 12 61.9.9 wt%, C 14 21.8.8 wt%, C 16 16.3.3 wt%, m 1 + m 2 ═ 3, n 1 + n 2 ═ 40, and m 3 + m 4 ═ 4.
Adding 200.4 g (1 mol) of mixed carbon chain (C 12~16) amine and 9.5 g of potassium hydroxide into a 5L 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 110 ℃, slowly introducing 132.9 g (3.02 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.50MPa, slowly introducing 2349.0 g (40.5 mol) of propylene oxide at 150 ℃ after the reaction of the ethylene oxide is finished, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 130 ℃ after the reaction of the propylene oxide, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, cooling to 90 ℃, removing low-boiling substances in vacuum, cooling, neutralizing, and dehydrating to obtain 2667.2 g (94.3%) of mixed carbon chain (C 12~16) amine polyoxyethylene (40) polyoxypropylene (40) polyoxyethylene (4) ether.
1414.2 g (0.5 mol) of mixed carbon chain (C 12~16) amine polyoxyethylene (3) polyoxypropylene (40) polyoxyethylene (4) ether, 24 g (0.6 mol) sodium hydroxide, 83.3 g (0.5 mol) sodium 2-chloroethanesulfonate and 1000 ml of toluene/benzene (v/v ═ 1) were mixed in a 5000 ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, heated to reflux for 6 hours, cooled, 50 g of the homogeneous reaction solution was acidified with 20 wt% hydrochloric acid, water and inorganic salts were separated, the solvent was evaporated, the resulting mixture was analyzed by High Performance Liquid Chromatography (HPLC), the mass percent of the mixed carbon chain (C 12~16) amine polyoxyethylene (3) polyoxypropylene (40) polyoxyethylene (4) ether, the mixed carbon chain (C 12~16) amine polyoxyethylene (3) polyoxyethylene (40) ether ethanesulfonic acid, the mixed carbon chain (C 12~16) amine polyoxyethylene (3) polyoxyethylene (40) ether ethanesulfonic acid, the distilled sulfonic acid-containing sodium hydroxide, was added to obtain a homogeneous mixture, the distilled solution containing 20.8.8.8.8.8% sodium hydroxide and the remaining sodium chloride was added.
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 modified polyacrylamide (the molar ratio of a comonomer AM/AMPS is 4/1, and the viscosity average molecular weight is 1500 ten thousand) and the aqueous solution of sodium carbonate prepared in the step a by using the simulated formation water I of the oil field, stirring for 3 hours, mixing the three to obtain a uniform polyepitheline ternary system oil displacement agent, measuring the viscosity and the oil-water interfacial tension of the system, and comparing the system with the systems of S-1, P1 and S-1+ P1, wherein the system is shown in the table 1. S-1 aqueous solutions with different concentrations are prepared respectively by using oilfield simulated formation water I and II, and the oil-water interfacial tension of the aqueous solutions is measured, which is shown in figure 1. The viscosity of the oil field dehydrated crude oil is 2.2 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) recording the volume of the saturated crude oil by using the oil field dehydrated crude oil saturated core. And (b) at the temperature of 75 ℃, using oil field simulated formation water I to drive the produced fluid to contain 100% of water, calculating the recovery ratio of the crude oil improved by water drive, transferring the polyepichia pastoris alkali ternary system oil displacement agent synthesized in the step b of 0.3PV (core pore volume), driving the water to contain 100%, calculating the percentage of the crude oil improved on the basis of water drive, and simultaneously comparing the percentage with a single or binary oil displacement agent injected with the same PV, wherein the percentage is shown in 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 2.
[ example 2 ]
a. The same as in example 1, except that after the completion of the reaction, all the reaction solutions were acidified, washed with water and the solvent was distilled off, the resulting mixture was mixed with water, and the pH of the system was adjusted to 13 with a 40 wt% aqueous solution of sodium hydroxide to obtain the desired surfactant composition S-2.
b. S-2 prepared in step a, modified polyacrylamide (comonomer AM/AMPS molar ratio: 4/1, viscosity average molecular weight 1500 ten thousand) and an aqueous solution of sodium carbonate were prepared from the oil field formation-simulating water I, and stirred for 4 hours, as shown in table 3 for the rest [ example 1 ] b. S-1 aqueous solutions with different concentrations are prepared respectively by using oilfield simulated formation water I and II, and the oil-water interfacial tension of the aqueous solutions is measured, which is shown in figure 1.
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 3.
[ example 3 ]
a. The prepared anionic nonionic mixed surfactant has the following structural formula, wherein (1) Z 1 ═ H, Z 2 ═ H and nonionic surfactant, (2) Z 1 ═ H, Z 2 ═ CH 2 CH 2 SO 3 H.N (CH 2 CH 2 OH) 3 and single hydrophilic head group ionic surfactant, (3) Z 1 ═ Z 2 ═ CH 2 CH 2 SO 3 H.N (CH 2 CH 2 OH) 3 and double hydrophilic head group ionic surfactant, and the carbon chain distribution of R 1 is C 12 61.9.9 wt%, C 14 21.8.8 wt%, C 16 16.3.3 wt%, m 1 + m 2 ═ 3, n 1 + n 2 ═ 40 and m 3 + m 4 ═ 4.
The same as [ example 2 ] a except that the pH of the system was adjusted to 13 by substituting 98% triethanolamine for 40 wt% aqueous sodium hydroxide to give the desired surfactant composition S-3.
b. S-3 prepared in step a, modified polyacrylamide (comonomer AM/AMPS molar ratio: 4/1, viscosity average molecular weight 1500 ten thousand) and an aqueous solution of sodium carbonate were prepared from the oil field formation-simulating water I, and stirred for 4 hours, as shown in table 3 for the rest [ example 1 ] b. S-1 aqueous solutions with different concentrations are prepared respectively by using oilfield simulated formation water I and II, and the oil-water interfacial tension of the aqueous solutions is measured, which is shown in figure 1.
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 4 ]
a. The prepared anionic nonionic mixed surfactant has the following structural formula, wherein (1) Z 1 ═ H, Z 2 ═ H and nonionic surfactants, (2) Z 1 ═ H, Z 2 ═ CH 2 CH (OH) CH 2 SO 3 H.HN (CH 2 CH 3) 2 and single hydrophilic head group ionic surfactants, (3) Z 1 ═ Z 2 ═ CH 2 CH (OH) CH 2 SO 3 H.HN (CH 2 CH 3) 2 and double hydrophilic head group ionic surfactants, m 1 + m 2 ═ 4, n 1 + n 2 ═ 30 and m 3 + m 4 ═ 3.
269 g (1 mol) of octadecylamine and 9.5 g of potassium hydroxide are added into a 2L 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 120 ℃, 178.2 g (4.05 mol) of ethylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, after the reaction of the ethylene oxide is finished, the temperature is adjusted to 130 ℃, 1757.4 g (30.3 mol) of propylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, and after the reaction of the propylene oxide is finished, the temperature is adjusted to 140 ℃, and 134.2 g (3.05 mol) of ethylene oxide is slowly introduced. After the completion of the reaction, the reaction mixture was worked up in the same manner as in example 1 to obtain 2205.8 g of octadecylamine polyoxyethylene (4), polyoxypropylene (30), polyoxyethylene (3) ether in a yield of 95.2%.
Octadecylamine, polyoxyethylene (4), polyoxypropylene (30), polyoxyethylene (3) ether 1158.5 g (0.5 mol), 56.1 g (1 mol) of potassium hydroxide, 147.4 g (0.75 mol) of sodium 3-chloro-2-hydroxypropanesulfonate and 1000 ml of benzene were mixed in a 5000 ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and after completion of the addition, the temperature was raised to reflux for 10 hours. Cooling, acidifying with 30 wt% phosphoric acid, separating water and inorganic salt, evaporating to remove solvent, and analyzing the obtained mixture by High Performance Liquid Chromatography (HPLC), wherein the mass percent of the octadecylamine polyoxyethylene (4) polyoxypropylene (30) polyoxyethylene (3) ether, the octadecylamine polyoxyethylene (4) polyoxypropylene (30) polyoxyethylene (3) ether hydroxypropyl sulfonic acid and the mass percent of the octadecylamine polyoxyethylene (4) polyoxypropylene (30) polyoxyethylene (3) ether dihydroxypropane sulfonic acid are 47.7:20.2: 32.1. The product was mixed with water, and the pH of the system was adjusted to 13 with a 50% aqueous solution of diethylamine to obtain the desired surfactant composition S-4.
b. S-4 prepared in step a, modified polyacrylamide (comonomer AM/AMPS molar ratio: 4/1, viscosity average molecular weight 1500 ten thousand) and an aqueous solution of sodium carbonate were prepared from the oil field formation-simulating water I, and stirred for 4 hours, as shown in table 5, for the remainder of the same procedure as in example 1 b. S-1 aqueous solutions with different concentrations are prepared respectively by using oilfield simulated formation water I and II, and the oil-water interfacial tension of the aqueous solutions is measured, which is shown in figure 1.
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 5 ]
a. The prepared anionic nonionic mixed surfactant has the following structural formula, wherein (1) Z 1 ═ H, Z 2 ═ H and nonionic surfactants, (2) Z 1 ═ H, Z 2 ═ CH 2 CH 2 CH 2 SO 3 K and single hydrophilic head group ionic surfactants, (3) Z 1 ═ Z 2 ═ CH 2 CH 2 CH 2 SO 3 K and double hydrophilic head group ionic surfactants, (m 1 + m 2 ═ 3, n 1 + n 2 ═ 10 and m 3 + m 4 ═ 3.
325 g (1 mol) of icosaediamine and 9.7 g of potassium hydroxide are added into a 2L pressure reactor provided with a stirring device, the dehydration and nitrogen replacement are carried out in the same way as in example 1, the reaction temperature of the system is adjusted to 120 ℃, 134.2 g (3.05 mol) of ethylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, the temperature is adjusted to 130 ℃ after the reaction of the ethylene oxide is finished, 585.8 g (10.1 mol) of propylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, and the temperature is adjusted to 140 ℃ after the reaction of the propylene oxide is finished, 134.2 g (3.05 mol) of ethylene oxide is slowly introduced. After the completion of the reaction, the reaction mixture was worked up in the same manner as in example 1 to obtain 1126.2 g of icosanediamine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether in a yield of 96.3%.
icosamethylenediamine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether 584.5 g (0.5 mol), 32.4 g (0.6 mol) sodium methoxide, 61 g (0.5 mol) 1, 3-propanesultone and 500 ml cyclopentanone were mixed in a 2500 ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and after completion of the addition, the temperature was raised to reflux for 4 hours. Cooling, acidifying with 30 wt% sulfuric acid, separating water and inorganic salts, evaporating to remove solvent, and analyzing the obtained mixture by High Performance Liquid Chromatography (HPLC), wherein the mass percent of the icosapolyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether, the icosapolyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether propanesulfonic acid, and the mass percent of the icosapolyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether dipropylsulfonic acid is 46.1:20.4: 33.5. The product was mixed with water, and the pH of the system was adjusted to 13 with a 15% aqueous solution of potassium hydroxide to obtain the desired surfactant composition S-5.
b. S-5 prepared in step a, modified polyacrylamide (comonomer AM/AMPS molar ratio: 4/1, viscosity average molecular weight 1500 ten thousand) and an aqueous solution of sodium carbonate were prepared from the oil field formation-simulating water I, and stirred for 4 hours, as shown in table 6. S-1 aqueous solutions with different concentrations are prepared respectively by using oilfield simulated formation water I and II, and the oil-water interfacial tension of the aqueous solutions is measured, which is shown in figure 1.
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 6 ]
a. The prepared anionic nonionic mixed surfactant has the following structural formula, wherein (1) Z 1 ═ H, Z 2 ═ H and nonionic surfactants, (2) Z 1 ═ H, Z 2 ═ CH 2 CH 2 SO 3 Na and single hydrophilic head group ionic surfactants, (3) Z 1 ═ Z 2 ═ CH 2 CH 2 SO 3 Na and double hydrophilic head group ionic surfactants, m 1 + m 2 ═ 2, n 1 + n 2 ═ 25 and m 3 + m 4 ═ 2.
233 g (1 mol) of decylaniline and 4.8 g of potassium hydroxide are added into a 2L pressure reactor provided with a stirring device, the dehydration and nitrogen replacement are carried out in the same way as in example 1, the reaction temperature of the system is adjusted to 110 ℃, 90.2 g (2.05 mol) of ethylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, 1467.4 g (25.3 mol) of propylene oxide is slowly introduced at 130 ℃ after the reaction of the ethylene oxide is finished, the pressure is controlled to be less than or equal to 0.60MPa, and 90.2 g (2.05 mol) of ethylene oxide is slowly introduced at 140 ℃ after the reaction of the propylene oxide is finished. After the completion of the reaction, the reaction mixture was worked up in the same manner as in example 1 to obtain 1749.3 g of decylaniline polyoxyethylene (2) polyoxypropylene (25) polyoxyethylene (2) ether in a yield of 94.1%.
Decylaniline polyoxyethylene (2) polyoxypropylene (25) polyoxyethylene (2) ether 929.5 g (0.5 mol), 60 g (1.5 mol) sodium hydroxide, 100.0 g (0.6 mol) sodium 2-chloroethanesulfonate and 800 ml toluene were mixed in a 5000 ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and heated to reflux for 6 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying by 35 wt% sulfuric acid, separating water and inorganic salt, evaporating to remove the solvent, and analyzing the obtained mixture by High Performance Liquid Chromatography (HPLC), wherein the mass percent of decyl aniline polyoxyethylene (2) polyoxypropylene (25) polyoxyethylene (2) ether, decyl aniline polyoxyethylene (2) polyoxypropylene (25) polyoxyethylene (2) ether ethanesulfonic acid and decyl aniline polyoxyethylene (2) polyoxypropylene (25) polyoxyethylene (2) ether diethylsulfonic acid is 46.1:20.4: 33.5. Distilling the residual untreated reaction solution to remove the solvent, adding water and uniformly mixing to obtain the surfactant composition S-6 containing sodium chloride and sodium hydroxide.
b. S-6 prepared in step a, modified polyacrylamide (P2, molar ratio of comonomer AM/AMPS 10/1, viscosity average molecular weight 2300 ten thousand) and an aqueous solution of sodium carbonate were prepared separately from the oil field formation-simulating water III, and stirred for 4 hours, as shown in table 7. The oil-water interfacial tension of S-6 aqueous solutions of different concentrations is shown in FIG. 1.
c. an indoor simulated oil displacement test was carried out in the same manner as in example 1, except that the oil displacement temperature was 87 ℃, and the results are shown in Table 7
[ example 7 ]
a. the same as in example 6 a, except that after the completion of the reaction, all the reaction solutions were acidified, washed with water and the solvent was distilled off, the resulting mixture was mixed with water, and the pH of the system was adjusted to 13 with a 30 wt% aqueous solution of sodium hydroxide to obtain the desired surfactant composition S-7.
b. The results are shown in Table 8, as in example 6 b. The oil-water interfacial tension of S-7 aqueous solutions of different concentrations is shown in FIG. 1.
c. The indoor simulated oil displacement test was carried out in the same manner as in example 6, and the results are shown in table 8.
[ example 8 ]
a. the prepared anionic nonionic mixed surfactant has the following structural formula, wherein (1) Z 1 ═ H, Z 2 ═ H and nonionic surfactants, (2) Z 1 ═ H, Z 2 ═ CH 2 CH 2 SO 3 H.H 2 NCH 2 CH 2 OH and single hydrophilic head group ionic surfactants, (3) Z 1 ═ Z 2 ═ CH 2 CH 2 SO 3 H.H 2 NCH 2 CH 2 OH and double hydrophilic head group ionic surfactants, and m 1 + m 2 ═ 2, n 1 + n 2 ═ 25 and m 3 + m 4 ═ 2.
The same as [ example 7 ] a except that the pH of the system was adjusted to 13 by replacing 30 wt% aqueous sodium hydroxide solution with 95% ethanolamine to give the desired surfactant composition S-8.
b. The results are shown in Table 9, as in example 6 b. The oil-water interfacial tension of S-8 aqueous solutions of different concentrations is shown in FIG. 1.
c. The results of the indoor simulated oil displacement test conducted in the same manner as in example 6 c are shown in Table 9.
[ example 9 ]
a. The prepared anionic nonionic mixed surfactant has the following structural formula, wherein (1) Z 1 ═ H, Z 2 ═ H and nonionic surfactants, (2) Z 1 ═ H, Z 2 ═ CH 2 CH 2 SO 3 H.NH 3 and single hydrophilic head group ionic surfactants, (3) Z 1 ═ Z 2 ═ CH 2 CH 2 SO 3 H.NH 3 and double hydrophilic head group ionic surfactants, m 1 + m 2 ═ 2, n 1 + n 2 ═ 25 and m 3 + m 4 ═ 2.
the same as [ example 7 ] except that the pH of the system was adjusted to 13 by substituting 15% aqueous ammonia for 30% aqueous sodium hydroxide solution by weight to give the desired surfactant composition S-9.
b. The results are shown in Table 10, as in example 6 b. The oil-water interfacial tension of S-9 aqueous solutions of different concentrations is shown in FIG. 1.
c. the results of the indoor simulated oil displacement test conducted in the same manner as in example 6 c are shown in Table 10.
[ example 10 ]
the difference from example 1 is that the results of using P2 (oil displacement temperature 87 ℃), P3 (modified polyacrylamide, comonomer AM/AMPS molar ratio 7/1, viscosity average molecular weight 1800 ten thousand, oil displacement temperature 81 ℃), and P4 (anionic polyacrylamide, viscosity average molecular weight 2500 ten thousand, oil displacement temperature 75 ℃) are shown in tables 11-13.
The same as [ example 1 ] except that Diethanolamine (DEA) was used as a base, the results are shown in Table 14.
[ example 11 ]
The oil displacing compositions prepared in example 1 and example 10 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 fig. 3 a-e; 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 figures 4 a-e.
[ COMPARATIVE EXAMPLE 1 ]
an amount of a comparative surfactant was dissolved in simulated brine of various degrees of mineralization, and the oil-water interfacial tension of the comparative surfactant solution on dehydrated crude oil was measured and compared with the surfactants prepared in the corresponding examples, and the results are shown in Table 15, in which the concentration of the surfactant was 0.1 wt%.
In Table 15, S-10 is mixed carbon chain (C 12~16) amine polyoxyethylene (3) polyoxypropylene (40) polyoxyethylene (4) ether, S-11 is octadecylamine polyoxyethylene (4) polyoxypropylene (30) polyoxyethylene (3) ether, S-12 is behenamine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether, and S-13 is decylaniline polyoxyethylene (2) polyoxypropylene (25) polyoxyethylene (2) ether.
[ COMPARATIVE EXAMPLE 2 ]
The same as in example 1, example 4, example 5 and example 6 except that propylene oxide and ethylene oxide were not reacted in steps one after another, ethylene oxide and propylene oxide were mixed in advance in an amount required for polymerization and reacted in one step, and the rest were the same, to obtain mixed surfactants S-14 to S-16. The interfacial tension of the oil field dehydrated crude oil was measured and the results are shown in Table 16, wherein the surfactant concentration was 0.1 wt%.
[ COMPARATIVE EXAMPLE 3 ]
The same as [ example 2 ] except that the amount of sodium 2-chloroethanesulfonate was changed to 416.5 g (2.5 mol), the amount of sodium hydroxide was changed to 120 g (3 mol), and the balance was the same, the product obtained by distilling off the solvent was analyzed by (HPLC), the mass ratio of mixed carbon chain (C 12~16) amine polyoxyethylene (3) polyoxypropylene (40) polyoxyethylene (4) ether diethylsulfonic acid to mixed carbon chain (C 12~16) amine polyoxyethylene (3) polyoxypropylene (40) polyoxyethylene (4) ether was 1:0.058, the pH of the system was adjusted to 13 with sodium hydroxide at a concentration of 40 wt%, and after mixing uniformly, a surfactant composition S-17 was obtained, the oil-water interfacial tension of the dehydrated crude oil was measured, and the concentration of the surfactant was 0.1 wt% as compared with S-2, and the results are shown in table 16.
[ COMPARATIVE EXAMPLE 4 ]
The same as example 1, except that high molecular weight anionic polyacrylamide P5 (viscosity average molecular weight 1250 ten thousand) was used instead of modified polyacrylamide P1, the results are shown in FIG. 17.
TABLE 1
Simulated salt water Ca2+(mg/L) Mg2+(mg/L) HCO3 -(mg/L) TDS(mg/L)
I 25 10 1150 5000
II 20 7 1875 8000
III 45 22 2455 14900
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
Watch 10
TABLE 11
TABLE 12
Watch 13
TABLE 14
Watch 15
Surface active agent Salt water Temperature (. degree.C.) IFT(mN/m)
S-1 I 75 0.00096
S-2 I 75 0.00112
S-3 I 75 0.00078
S-10 I 75 3.3321
S-4 I 75 0.00211
S-11 I 75 2.5455
S-5 I 75 0.00311
S-12 I 75 3.5645
S-1 II 81 0.00215
S-10 II 81 3.2542
S-4 II 81 0.00277
S-11 II 81 2.8965
S-5 II 81 0.00122
S-12 II 81 1.2113
S-6 III 87 0.00055
S-7 III 87 0.00067
S-8 III 87 0.00266
S-9 III 87 0.00063
S-13 III 87 3.3698
TABLE 16
Surface active agent Salt water Temperature (. degree.C.) IFT(mN/m)
S-1 I 75 0.00096
S-14 I 75 0.00788
S-4 II 81 0.00277
S-15 II 81 0.01909
S-5 II 81 0.00122
S-16 II 81 0.01223
S-6 III 87 0.00055
S-17 III 87 0.00766
S-2 I 75 0.00112
S-18 I 75 2.33346
TABLE 17

Claims (8)

1. A method of enhanced oil recovery comprising the steps of:
(1) Mixing the oil displacement composition with oil displacement water to obtain an oil displacement system;
(2) Contacting the oil displacement system with an oil-bearing stratum under the conditions of oil displacement temperature of 25-110 ℃, total mineralization degree of 100 mg/L and oil field stratum water with Ca 2+ of 10-60 mg/L, Mg 2+ of 5-30 mg/L, and displacing crude oil in the oil-bearing stratum;
The oil displacement composition 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 and more than 0 part of alkaline substance;
The surfactant is a negative non-mixed surfactant; the alkaline substance is at least one of an inorganic alkaline substance and an organic alkaline substance; the oil displacement system contains 0.001-2.0 wt% of the surfactant, 0-1.8 wt% of the polymer and more than zero, and 0-2.0 wt% of the alkaline substance and more than zero by the total mass of the oil displacement system;
The anionic and non-mixed surfactant comprises a nonionic surfactant shown in a formula (1), an anionic surfactant shown in a formula (2) and an anionic surfactant shown in a formula (3), wherein the mass ratio of the nonionic surfactant shown in the formula (1), the anionic surfactant shown in the formula (2) and the anionic surfactant shown in the formula (3) is (0.5-5): 1: (0.2-5);
R 1, R 2 and R 3 are each independently selected from C 4 to C 40 aliphatic hydrocarbon groups or aryl groups substituted with C 4 to C 30 hydrocarbon groups, M1, M2, M3 and M4 are independently selected from 0 to 50, but M1 and M2, M3 and M4 cannot be 0 at the same time, N1 and N2 are independently selected from 0 to 100, but N1 and N2 cannot be 0 at the same time, R1, R2, R3 and R4 are independently selected from 0 to 50, but R1 and R2, R3 and R3 cannot be 0 at the same time, s3 and s3 are independently selected from 0 to 100, but s3 and s3 cannot be 0 at the same time, p3 and p3 are independently selected from 0 to 50, but p3 and p3, p3 and p3 are not selected from 0 to N3, N3 and N3 are independently selected from N3 and N3 are selected from N3 and N3 are independently selected from N3 and N3 are selected from N3 and N3 are selected from N3 and N3;
at least one of R 1, R 2 and R 3 is C 6 -C 20 alkyl or phenyl substituted by C 8 -C 16 alkyl, p is 2, q is 0-1, m1+ m2 is 2-6, m3+ m4 is 2-6, n1+ n2 is 10-40, and/or R1+ R2 is 2-6, R3+ R4 is 2-6, s1+ s2 is 10-40 and/or p1+ p2 is 2-6, p3+ p4 is 2-6, q1+ q2 is 10-40.
2. The method of enhanced oil recovery of claim 1, characterized in that the polymer is at least one of xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, anionic polyacrylamide and modified polyacrylamide;
Wherein the anionic polyacrylamide is at least one of partially hydrolyzed polyacrylamide, a copolymer of acrylamide and acrylic acid, and a copolymer of acrylamide and acrylate; the hydrolysis degree of the partially hydrolyzed polyacrylamide is 5-30%, and the viscosity average molecular weight is 300-3000 ten thousand;
The modified polyacrylamide is prepared by copolymerizing acrylamide and a temperature-resistant and salt-resistant monomer, wherein the molar ratio of the acrylamide to the temperature-resistant and salt-resistant monomer is (0.1-40) to 1; the temperature-resistant and salt-resistant monomer is at least one selected from styrene sulfonic acid, N-alkyl maleimide, acrylamide long-chain alkyl sulfonic acid, 3-acrylamide-3-methyl butyric acid, 2-acrylamide-2-methyl propane sulfonic acid, N-alkyl acrylamide, N-vinyl pyrrolidone and 2-acrylamide-2-methyl propane sulfonic acid.
3. The method for enhanced oil recovery according to claim 1, characterized in that the inorganic basic substance is selected from at least one of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates; the organic alkaline substance is selected from at least one of primary amine group, secondary amine group, tertiary amine group and quaternary ammonium base group contained in the molecule.
4. the method for enhancing oil recovery according to claim 1, wherein the mass ratio of the surfactant to the polymer to the basic substance in the oil displacement agent is 1: 0-2: (0-5).
5. The method for enhanced oil recovery according to any one of claims 1 to 4, wherein the preparation method of the flooding composition comprises the following steps:
a. In the presence of a basic catalyst, R 1 NH 2 is sequentially reacted with required amounts of ethylene oxide, propylene oxide and ethylene oxide to obtain R 1 N ((CH 2 CH 2 O) m1 (CHCH 3 CH 2 O) n1 (CH 2 CH 2 O) m3 H) ((CH 2 CH 2 O) m2) (CHCH 3 CH 2 O) n2 (CH 2 CH 2 O) m4 H);
b. B, reacting the product obtained in the step a with X 1 R 01 Y 01 and an alkaline catalyst in a solvent according to a molar ratio of 1 (1-2) to (1-4) at a reaction temperature of 50-120 ℃ for 3-15 hours to obtain a mixture containing a nonionic surfactant shown in a formula (1), the single hydrophilic head group anionic surfactant shown in the formula (4) and the double hydrophilic head group anionic surfactant shown in the formula (5);
Wherein Z 01 is-R 02 Y 01, Y 01 is selected from SO 3 M 1 or COON 1, M 1 and N 1 are alkali metals, and X 1 is selected from chlorine, bromine or iodine;
c. And (c) uniformly mixing the surfactant mixture obtained in the step (b) with a polymer and an alkaline substance in parts by mass to obtain the oil displacing composition.
6. The method for enhancing oil recovery according to claim 5, wherein the molar ratio of R 1 N ((CH 2 CH 2 O) m1 (CHCH 3 CH 2 O) n1 (CH 2 CH 2 O) m3 H) ((CH 2 CH 2 O) m2) (CHCH 3 CH 2 O) n2 (CH 2 CH 2 O) m4 H) X 1 R 01 Y 01: alkali metal hydroxide or alkali metal alkoxide in step b is 1 (1-1.5) to (1-2).
7. The method for enhanced oil recovery according to claim 5, characterized in that the preparation method of the flooding composition comprises the following steps:
(b) Reacting the product obtained in the step a of claim 6 with 1, 3-propane sultone and a basic catalyst in a molar ratio of 1 (1-2) to (1-4) in a solvent at a reaction temperature of 50-120 ℃ for 3-15 hours to obtain a mixture containing a nonionic surfactant shown in a formula (1), a single hydrophilic head-based anionic surfactant shown in a formula (6) and a double hydrophilic head-based anionic surfactant shown in a formula (7);
Wherein Z' 01 is-CH 2 CH 2 CH 2 SO 3 M 2, and M 2 is an alkali metal;
(c) And (c) uniformly mixing the surfactant mixture obtained in the step (b) with a polymer and an alkaline substance in parts by mass to obtain the oil displacing composition.
8. The method for enhancing oil recovery according to claim 7, wherein the molar ratio of R 1 N ((CH 2 CH 2 O) m1 (CHCH 3 CH 2 O) n1 (CH 2 CH 2 O) m3 H) ((CH 2 CH 2 O) m2) (CHCH 3 CH 2 O) n2 (CH 2 CH 2 O) m4 H) to 1, 3-propanesultone to alkali metal hydroxide or alkali metal alkoxide in step (b) is 1 (1-1.5) to (1-2).
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CN103740345A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Foam sealing channeling composition, preparation method thereof and applications thereof
CN104232044A (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Composite surface active agent composition for tertiary oil recovery and preparation method and application thereof
CN104830302A (en) * 2015-04-29 2015-08-12 中国石油大学(华东) Binary composite oil dispelling system and optimization method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102220119A (en) * 2010-04-15 2011-10-19 中国石油化工股份有限公司 Oil displacing method for reservoirs with high temperature and salinity
CN103421174A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Fatty amine polyoxyethylene ether carboxylate and preparation method thereof
CN103740345A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Foam sealing channeling composition, preparation method thereof and applications thereof
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