CN105368428B - Anionic-nonionic mixed oil-displacing surfactant and preparation method and application thereof - Google Patents
Anionic-nonionic mixed oil-displacing surfactant and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an anionic-nonionic mixed oil displacement surfactant, a preparation method and application thereof, and mainly solves the problems of high cost and poor high temperature and high salt resistance of a surfactant used as an oil displacement agent system in the prior art, the invention adopts a nonionic surfactant shown in a formula (1), a single hydrophilic head-based anionic surfactant shown in a formula (2), a double hydrophilic head-based anionic surfactant shown in a formula (3), R 1, R 2 and R 3 are aliphatic hydrocarbon groups of C 4 -C 40 or aryl substituted by saturated and unsaturated hydrocarbon groups of C 4 -C 30 linear chain or branched chain, Z 1, Z 2 and Z 3 are respectively-R 01 Y 1, -R 02 Y9, -R 03 Y 3, R 4, R 5, R 6, R 7 are respectively selected from H, (CH 2) p OH or (CH p) p CH p, p is equal to q2, q, and the oil displacement rate can be improved compared with the oil displacement technology scheme, and the oil displacement problem can be improved by the oil displacement technology
Description
Technical Field
The invention relates to a negative-non mixed oil displacement surfactant and a preparation method thereof.
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 used in the current tertiary oil recovery research is most anionic, then nonionic and zwitterionic, and least cationic, the amphoteric ionic surfactant used is the cationic betaine surfactant with different chain lengths, the surfactant used is the carboxylic acid or sulfonate betaine surfactant with excellent anionic displacement by using alkali water, surfactant or alkali water, and the oil displacement by using zwitterionic surfactant, the surfactant used is the oil displacement agent with different chain lengths, the surfactant used is the oil displacement agent with total mineralized surfactant 62000-160000 mg/L, calcium magnesium ions 1500-18000 mg/L simulated saline, the surfactant system composed of high-temperature alcohol, sulfonate betaine and quaternary ammonium salt has the function of 10 -1 -10 mN 243/m crude oil, the surfactant used is the oil displacement agent with high interfacial tension of oil-soluble alcohol, sulfonate betaine and quaternary ammonium salt, the surfactant system has the function of 10 -1 -10 mN 243/m, the surfactant used is the surfactant used as a linear surfactant with high-linear surfactant, the cationic surfactant, the surfactant used is the surfactant used as a linear surfactant with the linear surfactant used as a linear surfactant with high-linear surfactant, the anionic surfactant, the high-linear surfactant, the linear surfactant used is the surfactant used under the conditions of anionic surfactant used as a high-linear surfactant of no-linear surfactant, the high-linear surfactant under the conditions of no-linear surfactant, the high-linear surfactant of No. 7-10 alkyl-10 alkyl-10-2 surfactant, the high-10-2-linear surfactant-10-2-linear surfactant-2 linear surfactant-2-linear surfactant-2 linear surfactant-2 surfactant-linear surfactant-2 high-linear surfactant-2 linear surfactant-2 high-linear surfactant-2-linear surfactant-2 high-linear surfactant-2-linear surfactant-2-linear surfactant-2.
The research results show that the cost is an important factor influencing the application of the oil displacement surfactant, the anionic-nonionic mixed surfactant formed by the nonionic surfactant and the anionic surfactants with the single hydrophilic head group and the double hydrophilic head group is obtained by reacting the carboxylation agent or the sulfonating agent with lower molar weight with the polyether, the high-temperature stability of the nonionic surfactant is improved by improving the polymerization degree of the polyether, the product can be used without complex separation, the preparation cost is saved, and the synergistic effect of the multi-component surfactant is exerted, so that the mixed surfactant has excellent temperature resistance and salt resistance, and has good oil displacement application prospect. The invention relates to a negative-non mixed oil displacement surfactant with stable structure under oil reservoir conditions and a preparation method thereof.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the surfactant mainly composed of an oil displacement agent system in the prior art has the problems of high preparation cost and poor temperature and salt resistance, and provides a novel anionic-nonionic mixed oil displacement surfactant, wherein the aqueous solution of the anionic-nonionic mixed oil displacement surfactant can form low interfacial tension of 10 -2 -10 -4 milli-newtons per meter with crude oil within the range of 0.005-0.6%.
The second technical problem to be solved by the invention is to provide a preparation method of the anionic-nonionic mixed oil-displacing surfactant for solving the first technical problem.
The invention aims to solve the third technical problem and provides another preparation method of the anionic-nonionic mixed oil-displacing surfactant for solving one of the technical problems.
The fourth technical problem to be solved by the invention is to provide the application of the anionic-nonionic mixed oil-displacing surfactant for oil displacement in oil fields, which solves one of the technical problems.
in order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: an anionic-nonionic mixed oil-displacing surfactant comprises a nonionic surfactant shown as a formula (1) and anionic surfactants shown as formulas (2) and (3), wherein the surfactant (1): (2): (3) the mass ratio of (0.01-5): 1: (0.1-5); more preferably (0.03 to 3): 1: (1-3).
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 linear or branched saturated and unsaturated 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 0-50 but p3 and p3 are not selected from 0-M, p3 and p3 are not selected from 0-M, n 3 and n 3 are independently selected from n 3 and n 3 are selected from 0, or n 3 and n 3 are independently selected from n 3 and n 3 are selected from an integer selected from n 3 and n 3 (wherein n) are independently selected from n) and n are selected from n 3 and n) and n 3 and n are selected from n 3 and n are independently selected from n 3 and n 72 and n 3 and n are selected from n 3 and n 72 and n are selected from n 3 and n are selected from n and n are selected.
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 2-10, m3+ m4 is 2-20, and n1+ n2 is 5-40; and/or r1+ r2 is 2-10, r3+ r4 is 2-20, s1+ s2 is 5-40 and/or p1+ p2 is 2-10, p3+ p4 is 2-20, and q1+ q2 is 5-40.
The key of the anionic and non-mixed oil-displacing surfactant 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 technical personnel in the field know that the anionic and non-mixed oil-displacing surfactant can adopt various supply forms for the convenience of transportation, storage, field use and the like, such as a non-aqueous solid form, an aqueous paste form or an aqueous solution form; 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 anionic and non-mixed oil-displacing surfactant can be obtained by mixing the nonionic surfactant, the single hydrophilic head-based anionic surfactant and the single hydrophilic head-based anionic surfactant according to a required proportion, and is preferably obtained by the following technical scheme for solving the second technical problem or the technical scheme for solving the third technical problem.
To solve the second technical problem, the technical solution adopted by the present invention is as follows: the preparation method of the anionic-nonionic mixed oil-displacing surfactant, which is one of the technical problems, 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 alkali metal hydroxide or alkali metal alkoxide 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), the single hydrophilic head-based anionic surfactant shown in the formula (4) and the double hydrophilic head-based 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 COOW 1, M 1 and W 1 are alkali metals, and X 1 is selected from chlorine, bromine or iodine.
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 in the step b is preferably 1 (1-2) to (1-3).
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 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).
as long as the reaction of the step b is carried out, a person skilled in the art can obtain the anionic-nonionic mixed oil-displacing surfactant containing the salt and the excessive basic catalyst by only removing the solvent by distillation without complicated separation. 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 an anionic non-hybrid type oil-displacing surfactant free of salt and an excess amount of alkaline catalyst, which is composed of the nonionic surfactant of formula (1) and the mono-hydrophilic head-based anionic surfactant of formula (4) and the bis-hydrophilic head-based anionic surfactant of formula (6), when M 1 or W 1 is H, the product may further include 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 an anionic-nonionic hybrid type oil-displacing surfactant free of salt and an excessive amount of basic catalyst, which is composed of the nonionic surfactant of formula (1), the single-hydrohead-based anionic surfactant of formula (4) and the double-hydrohead-based anionic surfactant of formula (6), when M 1 or W 1 is an alkali metal or a product of a group of 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 of formula NR 4 (R 5) (R 6) (R 7) on the basis of step c, 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 order to solve the third technical problem, the technical scheme of the invention is as follows: one of the technical problems is that the preparation method of the anionic-nonionic mixed oil-displacing surfactant comprises the following steps:
(b) reacting the product obtained in the step a of claim 5 with 1, 3-propane sultone and alkali metal hydroxide or alkali metal alkoxide 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 represented by the formula (1) and a mono-hydrophilic head-based anionic surfactant represented by the formula (6) and a bi-hydrophilic head-based anionic surfactant represented by the formula (7);
Wherein Z' 01 is-CH 2 CH 2 CH 2 SO 3 M 2, and M 2 is alkali metal.
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 1, 3-propanesultone to alkali metal hydroxide or alkali metal alkoxide in the step (b) is preferably 1 (1-2) to (1-4).
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 1, 3-propanesultone to alkali metal hydroxide or alkali metal alkoxide in step b is preferably 1 (1-2) to (1-3).
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, xylene, trimethylbenzene, ethylbenzene and diethylbenzene.
As long as the reaction of the step (b) is carried out, a person skilled in the art can obtain the anionic-nonionic mixed oil-displacing surfactant containing the salt and the excessive alkaline catalyst by only removing the solvent by distillation without complicated separation. 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 an anionic non-hybrid type oil-displacing surfactant free of salt and an excess amount of alkaline catalyst, which is composed of the nonionic surfactant of formula (1) and the mono-hydrophilic head-based anionic surfactant of formula (6) and the bis-hydrophilic head-based anionic surfactant of formula (7), when M 1 or W 1 is H, the product may further include step (c) and step (d):
(c) 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;
(d) The resulting organic phase is concentrated to give the desired product.
for another example, in order to obtain an anionic-nonionic hybrid type oil-displacing surfactant free of salts and an excessive amount of basic catalysts, which is composed of the nonionic surfactant of formula (1), the single-hydrohead-based anionic surfactant of formula (6) and the double-hydrohead-based anionic surfactant of formula (7), when M 1 or W 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 (c), 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 order to solve the fourth technical problem, the technical scheme of the invention is that the anionic-nonionic mixed oil displacement surfactant is applied to oil displacement of an oil field, the oil displacement is high-temperature high-salt oil reservoir oil displacement, the total salinity of stratum brine of the high-temperature high-salt oil reservoir is 50000-250000 mg/L, wherein the Ca 2+ is 1500-5000 mg/L, Mg 2+ and is 500-1500 mg/L, the viscosity of crude oil is 1-10 mPa.s, and the stratum temperature is 75-95 ℃.
The dosage or concentration of the anionic and non-mixed oil displacement surfactant is calculated by the total amount of 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).
the anionic-nonionic mixed oil-displacing surfactant prepared by the invention can form low interfacial tension of 10 -2 -10 -4 mN/m with underground crude oil under the condition that the dosage is 0.005-0.6 wt% in percentage by mass, and the interfacial tension can still keep a low value after the surfactant is aged for 90 days under the condition of stable oil deposit, so that a good technical effect is obtained.
Drawings
FIG. 1 is a graph of interfacial tension of aqueous solutions of surfactants S-1 to S-3 of different concentrations prepared with a simulated brine A against oilfield dewatered crude oil at 85 ℃;
FIG. 2 is a graph of the interfacial tension of simulated brine B solution (95 deg.C), S-5 simulated brine A solution (85 deg.C) for various concentrations of S-1, S-4 and S-5 versus oilfield dewatered crude;
FIG. 3 is a graph of the interfacial tension of a simulated brine A solution (85 ℃) and a simulated brine B solution (95 ℃) of S-6 and S-8 with different concentrations on oilfield dehydrated crude oil;
FIG. 4 is a graph of interfacial tension of a 0.3 wt% aqueous solution of S-1, S-3, S-5, S-6, and S-8 surfactants formulated in brine A after aging for various periods of time at 85 deg.C on oil field dewatered crude;
FIG. 5 is a graph of interfacial tension of oil field dewatered crude oil aged at different times in 0.3 wt% aqueous solutions of S-1, S-4, and S-6 surfactants made with brine B at 95 deg.C.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
(1) Z 1 ═ H, Z 2 ═ H, nonionic surfactant, (2) Z 1 ═ H, Z 2 ═ -CH 2 COONa, monohydrophilic head-based ionic surfactant, (3) Z 1 ═ Z 2 ═ -CH 2 COONa, amphiphilic head-based ionic surfactant, (m 1 + m 2 ═ 4, n 1 + n 2 ═ 35, m 3 + m 4 ═ 3.
Adding 261 g (1 mol) of dodecylaniline, 5.2 g of sodium hydroxide and 13.1 g of anhydrous potassium carbonate 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 with nitrogen, adjusting the reaction temperature of the system to 110 ℃, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.50MPa, after the reaction of the ethylene oxide is finished, slowly introducing 2053.2 g (35.4 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, and after the reaction of the propylene oxide is finished, adjusting the temperature to 140 ℃, and slowly introducing 134.2 g (3.05 mol) of ethylene oxide. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, 2515.8 g of dodecylaniline polyoxyethylene (4), polyoxypropylene (35) and polyoxyethylene (3) ether are obtained, and the yield is 96.8%.
Dodecylaniline polyoxyethylene (4) polyoxypropylene (35) polyoxyethylene (3) ether 1299.5 g (0.5 mol), 24 g (0.6 mol) sodium hydroxide, 58.3 g (0.5 mol) sodium chloroacetate and 1000 ml toluene/benzene (v/v ═ 1) were mixed in a 5000 ml four-neck flask equipped with a mechanical stirrer, thermometer and reflux condenser, and the mixture was heated to reflux reaction for 7 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric 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 the dodecylaniline polyoxyethylene (4) polyoxypropylene (35) polyoxyethylene (3) ether, the dodecylaniline polyoxyethylene (4) polyoxypropylene (35) polyoxyethylene (3) ether acetic acid and the dodecylaniline polyoxyethylene (4) polyoxypropylene (35) polyoxyethylene (3) ether diacetic acid is 49.2:20.0: 30.8. Distilling the residual untreated reaction solution to remove the solvent, adding water and uniformly mixing to obtain the mixed surfactant S-1 containing sodium chloride and sodium hydroxide.
[ example 2 ]
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 12 with a 30 wt% aqueous solution of sodium hydroxide to obtain the desired mixed surfactant S-2.
[ example 3 ]
(1) Z 1 ═ H, Z 2 ═ H, nonionic surfactant, (2) Z 1 ═ H, Z 2 ═ -CH 2 cooh.hn (CH 2 CH 2 OH) 2, mono-hydrophilic head group ionic surfactant, (3) Z 1 ═ Z 2 ═ -CH 2 cooh.hn (CH 2 CH 2 OH) 2, bis-hydrophilic head group ionic surfactant, m 1 + m 2 ═ 4, n 1 + n 2 ═ 35, m 3 + m 4 ═ 3.
The same as [ example 2 ] except that the pH of the system was adjusted to 12 by replacing 30 wt% aqueous sodium hydroxide solution with 95% diethanolamine to obtain the desired mixed surfactant S-3.
[ example 4 ]
(1) Z 1 H, Z 2 H, nonionic surfactant, (2) Z 1 H, Z 2 CH 2 CH 2 CH 2 SO 3 Na, single hydrophilic head group ionic surfactant, (3) Z 1 Z 2 CH 2 CH 2 CH 2 SO 3 Na, double hydrophilic head group ionic surfactant, (m 1 + m 2 3, n 1 + n 2 10, 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 reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, neutralization and dehydration are carried out after cooling, 1126.2 g of the icosapolyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether are obtained, and the yield is 96.3%.
Icosamethylenediamine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether 584.5 g (0.5 mol), 81.0 g (1.5 mol) sodium methoxide, 122 g (1.0 mol) 1, 3-propanesultone and 800 ml cyclopentanone were mixed in a 5000 ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and after the addition, the temperature was raised to reflux for 5 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 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 1.2:27.8: 71.0. The product was mixed with water, and the pH of the system was adjusted to 13 with a 15% aqueous solution of sodium hydroxide to obtain the desired mixed surfactant S-4.
[ example 5 ]
The same as in example 4, except that the amount of sodium methoxide charged was changed to 1.25mol, the amount of 1, 3-propanesultone charged was changed to 0.8mol, and the obtained mixture was analyzed by High Performance Liquid Chromatography (HPLC), and the mass percentages of the behenyl amine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether, the behenyl amine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether propanesulfonic acid, and the behenyl amine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether dipropylsulfonic acid were 17.6:29.2: 53.2. The product was mixed with water, and the pH of the system was adjusted to 13 with a 15% aqueous solution of sodium hydroxide to obtain the desired mixed surfactant S-5.
[ example 6 ]
(1) Z 1 ═ H, Z 2 ═ H, nonionic surfactant, (2) Z 1 ═ H, Z 2 ═ -CH 2 CH 2 SO 3 Na, mono-hydrophilic head-based ionic surfactant, (3) Z 1 ═ -Z 2 ═ -CH 2 CH 2 SO 3 Na, amphiphilic head-based ionic surfactant, (m 1 + m 2 ═ 6, n 1 + n 2 ═ 25, m 3 + m 4 ═ 15.
199 g (1 mol) of tridecylamine and 4.8 g of potassium hydroxide were added into a 2L pressure reactor equipped with a stirring device, the reaction temperature of the system was adjusted to 110 ℃ and 266.2 g (6.05 mol) of ethylene oxide was slowly introduced with water and nitrogen substitution as in example 1, the pressure was controlled to be less than or equal to 0.60MPa, 1467.4 g (25.3 mol) of propylene oxide was slowly introduced at 130 ℃ after the reaction of ethylene oxide was completed, the pressure was controlled to be less than or equal to 0.60MPa, and 668.8 g (15.2 mol) of ethylene oxide was slowly introduced with temperature adjusted to 140 ℃ after the reaction of propylene oxide was completed. After completion of the reaction, the reaction mixture was worked up in the same manner as in example 1 to obtain 2421.2 g of tridecylamine polyoxyethylene (6) polyoxypropylene (25) polyoxyethylene (15) ether, yield 94.1%.
Tridecylamine polyoxyethylene (6) polyoxypropylene (25) polyoxyethylene (15) ether 1286.5 g (0.5 mol) was mixed with 50 g (1.25 mol) sodium hydroxide, 83.3 g (0.5 mol) sodium 2-chloroethanesulfonate and 800 ml toluene in a 5000 ml four-neck flask equipped with a mechanical stirrer, thermometer and reflux condenser and heated to reflux for 6 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 35 wt% sulfuric acid, separating water and inorganic salt, evaporating the solvent, and analyzing the obtained mixture by High Performance Liquid Chromatography (HPLC), wherein the mass percent of the tridecylamine polyoxyethylene (6) polyoxypropylene (25) polyoxyethylene (15) ether, the tridecylamine polyoxyethylene (6) polyoxypropylene (25) polyoxyethylene (15) ether ethanesulfonic acid, the tridecylamine polyoxyethylene (6) polyoxypropylene (25) polyoxyethylene (15) ether diethylsulfonic acid is 48.5:25.1: 26.4. Distilling the residual untreated reaction solution to remove the solvent, adding water and uniformly mixing to obtain the mixed surfactant S-6 containing sodium chloride and sodium hydroxide.
[ example 7 ]
The same as in example 6, 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 mixed surfactant S-7.
[ example 8 ]
(1) z 1 H, Z 2 H, nonionic surfactant, (2) Z 1 H, Z 2 CH 2 CH 2 SO 3 H.N (CH 2 CH 3) 3, single hydrophilic head group ionic surfactant, (3) Z 1 Z 2 CH 2 CH 2 SO 3 H.N (CH 2 CH 3) 3, double hydrophilic head group ionic surfactant, m 1 + m 2 6, n 1 + n 2 H25, m 3 + m 4 15.
The same as [ example 7 ] except that the pH of the system was adjusted to 13 by replacing 30 wt% aqueous sodium hydroxide solution with 90% triethylamine to obtain the desired mixed surfactant S-8.
[ example 9 ]
The specific compositions of the oil field simulated water with different divalent cations and total mineralization are shown in table 1.
oil-water interfacial tension measurement was performed on crude oil supplied to an oil field, and the crude oil was dehydrated and used, and the viscosity of the crude oil was 2.5 mpa.s. The oil-water interfacial tension was measured by a rotary drop interfacial tension meter model TX500, produced by the university of Texas, USA.
A certain amount of surfactants S-1 to S-8 are dissolved in simulated saline A and B, and the oil-water interfacial tension of the surfactant solutions with different concentrations on crude oil is measured, and the results are shown in figures 1 to 3.
And (2) filling the surfactant simulated saline solution into a 20 ml Ampere bottle, sealing the Ampere bottle, putting the Ampere bottle into an oven, measuring the oil-water interfacial tension of the surfactant simulated saline to the crude oil after different aging times, and finding that the oil-water interfacial tension can still keep the ultralow value of 10 -3 -10 -4 mN/m after aging, wherein the values are shown in figures 4-5.
[ COMPARATIVE EXAMPLE 1 ]
0.1 wt% of a comparative surfactant was dissolved in a simulated saline, and an interfacial property measurement test was performed as in [ example 9 ] and the concentration of the surfactant was such that the results are shown in Table 2, in comparison with the corresponding surfactant prepared in example.
In Table 2, S-9 is dodecylanilinoethylene (4) polyoxypropylene (35) polyoxyethylene (3) ether; s-10 is behenyl diamine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (3) ether; s-11 tridecylamine polyoxyethylene (6) polyoxypropylene (25) polyoxyethylene (15) ether.
[ COMPARATIVE EXAMPLE 2 ]
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, a mixture of 2053.2 g (35.4 mol) of propylene oxide and 312.4 g (7.1 mol) of ethylene oxide is slowly introduced at the temperature of 110-150 ℃, and the rest is the same, so as to obtain the mixed surfactant S-12. The interfacial property measurement test was performed in the same manner as in example 9, and the concentration of the surfactant was 0.1 wt% as compared with the surfactant prepared in the corresponding example, and the results are shown in Table 3.
[ COMPARATIVE EXAMPLE 3 ]
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. Slowly introducing a mixture of 585.8 g (10.1 mol) of propylene oxide and 268.4 g (6.1 mol) of ethylene oxide at the temperature of 110-150 ℃, controlling the pressure to be less than or equal to 0.60MPa, and keeping the pressure the same, thus obtaining the mixed surfactant S-13. The interfacial property measurement test was performed in the same manner as in example 9, and the concentration of the surfactant was 0.1 wt% as compared with the surfactant prepared in the corresponding example, and the results are shown in Table 3.
[ COMPARATIVE EXAMPLE 4 ]
The same as in example 6, 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 1467.4 g (25.3 mol) of propylene oxide and 935 g (21.3 mol) of ethylene oxide is slowly introduced at 110-150 ℃, and the rest is the same, so as to obtain the mixed surfactant S-14. The interfacial property measurement test was performed in the same manner as in example 9, and the concentration of the surfactant was 0.1 wt% as compared with the surfactant prepared in the corresponding example, and the results are shown in Table 3.
[ COMPARATIVE EXAMPLE 5 ]
The same as in example 2, except that the amount of sodium chloroacetate was changed to 349.5 g (3 mol) and the amount of sodium hydroxide was changed to 100 g (2.5 mol), and the other was the same, and the mass ratio of dodecylanilinepolyoxyethylene (4) polyoxypropylene (35) polyoxyethylene (3) ether diacetic acid to dodecylanilinepoxyethylene (4) polyoxypropylene (35) polyoxyethylene (3) ether was 1:0.013 by (HPLC) analysis of the product obtained after evaporation of the solvent. The pH of the system was adjusted to 12 with 30 wt% sodium hydroxide and mixed well to obtain surfactant S-15. The interfacial properties measurement test was conducted in the same manner as in [ example 9 ], and the concentration of the surfactant was 0.1% by weight as compared with S-2, and the results are shown in Table 3.
TABLE 1
| Simulated salt water | Ca2+(mg/L) | Mg2+(mg/L) | TDS(mg/L) |
| A | 1500 | 525 | 75000 |
| B | 5000 | 1500 | 255000 |
TABLE 2
| Surface active agent | Salt water | Temperature (. degree.C.) | IFT(mN/m) |
| S-1 | A | 85 | 0.00077 |
| S-2 | A | 85 | 0.00053 |
| S-3 | A | 85 | 0.00112 |
| S-9 | A | 85 | 2.3455 |
| S-4 | B | 95 | 0.00129 |
| S-10 | B | 95 | 3.5512 |
| S-5 | A | 85 | 0.00071 |
| S-10 | A | 85 | 2.7796 |
| S-6 | A | 85 | 0.00056 |
| S-7 | A | 85 | 0.00087 |
| S-8 | A | 85 | 0.00145 |
| S-11 | A | 85 | 1.04522 |
TABLE 3
| Surface active agent | Salt water | temperature (. degree.C.) | IFT(mN/m) |
| S-1 | A | 85 | 0.00077 |
| S-12 | A | 85 | 0.00898 |
| S-4 | B | 95 | 0.00129 |
| S-13 | B | 95 | 0.01255 |
| S-6 | A | 85 | 0.00056 |
| S-14 | A | 85 | 0.00733 |
| S-15 | A | 85 | 3.7764 |
Claims (10)
1. an anionic-non-mixed oil-displacing surfactant comprises a nonionic surfactant shown as a formula (1), an anionic surfactant I shown as a formula (2), and an anionic surfactant II shown as a formula (3), wherein the nonionic surfactant: anionic surfactant i: the mass ratio of the anionic surfactant II is (0.01-5): 1: (0.1-5);
Wherein 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 linear or branched saturated and unsaturated hydrocarbon groups, M1, M2, M3 and M4 are independently selected from 0 to 50 but M1 and M2, M3 and M4 cannot be 0 simultaneously, n1 and n2 are independently selected from 0 to 100 but n1 and n2 cannot be 0 simultaneously, R1, R2, R3 and R4 are independently selected from 0 to 50 but R1 and R2, R3 and R3 cannot be 0 simultaneously, s3 and s3 are independently selected from 0 to 100 but s3 and s3 cannot be 0 simultaneously, p3 and p3 are independently selected from 3650 but p3 and p3 are independently selected from 0 to 3 and p3 are not selected from 0 and p3 and n 3 are independently selected from an integer of a hydrogen, a hydrogen atom.
2. The anionic non-mixed oil-displacing surfactant as claimed in claim 1, wherein at least one of R 1, R 2 or R 3 is C 6 -C 20 alkyl or phenyl substituted by C 8 -C 16 alkyl.
3. The anionic-nonionic mixed oil-displacing surfactant according to claim 1, wherein p is 2 and q is 0-1.
4. The anionic-nonionic mixed oil-displacing surfactant as claimed in claim 1, wherein m1+ m2 is 2-10, m3+ m4 is 2-20, and n1+ n2 is 5-40; and/or r1+ r2 is 2-10, r3+ r4 is 2-20, s1+ s2 is 5-40 and/or p1+ p2 is 2-10, p3+ p4 is 2-20, and q1+ q2 is 5-40.
5. A preparation method of the anionic-nonionic mixed oil-displacing surfactant as claimed in any one of claims 1 to 4, comprising 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 alkali metal hydroxide or alkali metal alkoxide 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), the single hydrophilic head-based anionic surfactant shown in the formula (4) and the double hydrophilic head-based 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 COOW 1, M 1 and W 1 are alkali metals, and X 1 is selected from chlorine, bromine or iodine.
6. The preparation method of the anionic-nonionic mixed oil-displacing surfactant 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) to X 1 R 01 Y 01: alkali metal hydroxide or alkali metal alkoxide in step b is 1 (1-2) to (1-3).
7. The method for preparing the anionic-nonionic mixed oil-displacing surfactant as claimed in claim 5, wherein the solvent in step b is at least one selected from C 3 -C 8 ketone and C 6 -C 9 aromatic hydrocarbon.
8. A preparation method of the anionic-nonionic mixed oil-displacing surfactant as claimed in any one of claims 1 to 4, comprising the following steps:
(b) Reacting the product obtained in the step a of claim 5 with 1, 3-propane sultone and alkali metal hydroxide or alkali metal alkoxide 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 represented by the formula (1) and a mono-hydrophilic head-based anionic surfactant represented by the formula (6) and a bi-hydrophilic head-based anionic surfactant represented by the formula (7);
Wherein Z' 01 is-CH 2 CH 2 CH 2 SO 3 M 2, and M 2 is alkali metal.
9. The preparation method of the anionic-nonionic mixed oil-displacing surfactant according to claim 8, 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 is 1 (1-2) to (1-3) in step (b).
10. The application of the anionic-nonionic mixed oil-displacing surfactant in oil displacement of an oil field according to any one of claims 1 to 4 is characterized in that the oil displacement is high-temperature high-salt oil reservoir oil displacement, the total salinity of formation brine of the high-temperature high-salt oil reservoir is 50000-250000 mg/L, wherein the Ca 2+ is 1500-5000 mg/L, Mg 2+ is 500-1500 mg/L, the viscosity of crude oil is 1-10 mPa.s, and the formation temperature is 75-95 ℃.
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