CN112708410B - Composite surfactant containing aryl alcohol polyether anionic nonionic surfactant - Google Patents
Composite surfactant containing aryl alcohol polyether anionic nonionic surfactant Download PDFInfo
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Abstract
The invention relates to a composite surfactant containing aryl alcohol polyether anionic nonionic surfactant. Principal solutionThe problem that the compound oil displacement agent in the prior art is difficult to effectively improve the recovery ratio under the condition of high-temperature and high-salinity oil reservoir is solved. The invention adopts a composite surfactant which comprises the following components in parts by weight: (1) 0.01-1.0 part of alkyl polyether quaternary ammonium salt surfactant; (2) 0.02-1.0 part of aryl alcohol polyether acid salt surfactant; wherein the molecular general formula of the alkyl polyether quaternary ammonium salt surfactant is shown as a formula (I); the molecular general formula of the aryl alcohol polyether acid salt surfactant is shown in a formula (II), so that the problem is solved well, and the aryl alcohol polyether acid salt surfactant can be used in tertiary oil recovery production of an oil field.
Description
Technical Field
The invention relates to a composite surfactant containing aryl alcohol polyether anionic nonionic surfactant.
Background
Petroleum is an important non-regenerative strategic resource, plays an important role in the energy structure of China, is also an important raw material in chemical industry, and has important significance for national economic construction. Because of the severe situation of yield decrement of developed main oil fields in China, the complex types of oil and gas reservoirs without using reserves are proved, particularly the proportion of high-temperature high-salt oil reservoirs, heavy oil extra-heavy oil and low-permeability extra-low-permeability oil reservoirs (which are collectively called as severe oil reservoirs) which are already used and are about to be used is gradually increased, and the development by utilizing the prior art is very difficult, so that the development of a new exploitation technology is urgently needed, the recovery ratio of old oil fields is greatly improved, and the utilization ratio of proved resources is greatly improved, so that the requirements of economic development and national safety are met.
Surfactant flooding is one of the main current research directions for enhanced oil recovery from tertiary recovery. The surfactant can effectively reduce the oil-water interfacial tension, change the oil reservoir wettability, solubilize the crude oil and reduce the crude oil viscosity, and plays an important role in tertiary oil recovery. The anion and cation compound surfactant is used as a novel surfactant mixed system and shows special performance in many fields. The strong electrostatic interaction exists between the cationic surfactant and the anionic surfactant, so that the complex system has lower critical micelle concentration, limited occupied area and better interfacial activity, has good capability of forming microemulsion, and is beneficial to obtaining and stabilizing ultra-low interfacial tension. Meanwhile, the formation of the cation-anion pairs greatly enhances the adsorption resistance and calcium-magnesium ion resistance of the cation-anion compound surfactant, and improves the oil displacement effect of the system in high-temperature and high-salinity oil reservoirs.
At present, the anion-cation compound surfactant is less applied in the third mining. Patent CN103773347A reports a composite surfactant composition composed of alkyl polyoxyethylene ether anionic surfactant containing aromatic ring and tetraalkyl quaternary ammonium salt, and the composition has good interfacial properties for the oil field in south of Henan; korea xia et al (physical chemistry report, 2012, 28 (1), 146-153) have demonstrated the effect of oil-water distribution balance of surfactant molecules on ultra-low interfacial tension by studying a binary formulation system composed of alkyl ethoxy sulfonate and tetraalkyl ammonium bromide or bromohexadecyl pyridine. Patent CN107573916A reports a flooding composition consisting of anionic surfactant, cationic surfactant and cosurfactant, which can be used for flooding at a very low use concentration, but the system is complex, the use temperature is not higher than 65 ℃, and the mineralization degree is less than 2000mg/L. Patent CN104650841A reports that an anion-cation composite surfactant oil displacement agent has ultralow oil-water interfacial tension and good emulsification stability to crude oil, but the use temperature is room temperature and the universality is not high. Patent CN104099077A reports a composition formed by compounding xanthan gum, a negative nonionic surfactant and a negative and positive amphoteric surfactant, which is called to be capable of tolerating 32000-36000mg/L of total mineralization degree, but the oil-water interfacial tension of the composition cannot be ultra-low and is only 10 -2 An order of magnitude. Patent CN102161883A reports a compound chemical oil displacement agent for tertiary oil recovery in an oil field, which comprises an anionic surfactant, a cationic surfactant and a nonionic surfactant, wherein the formation of cation and anion pairs enables the compound chemical oil displacement agent to form a compact interface adsorption film instead of an ionThe addition of the sub-type surfactant improves the stability of the surfactant in high-salinity water, so that the surfactant is not easy to precipitate. Patent CN109652048A provides a composite oil displacement agent and a preparation method and application thereof, and the composite oil displacement agent comprises a symmetric alkyl alcohol polyoxyethylene ether sulfonate anionic-nonionic surfactant, a cationic surfactant and the balance of water, and can remarkably reduce the oil-water interfacial tension, especially can generate ultralow interfacial tension for low-permeability oil reservoirs, but the temperature resistance of the composite oil displacement agent needs to be improved.
In order to solve the problem that the recovery ratio of the composite oil displacement agent is difficult to effectively improve under the conditions of high-temperature and high-salt oil reservoirs in the prior art and further improve the temperature resistance and salt resistance performance and the oil displacement efficiency of the surfactant, the cationic quaternary ammonium salt containing polyether nonionic segments and the anionic nonionic are compounded, compared with the cationic surfactant without nonionic segments, the cationic nonionic surfactant shows more excellent salt resistance, is more favorable for accurately regulating and controlling the hydrophilic, oleophilic, temperature resistance and salt resistance performance of the composite surfactant, and obtains the composite oil displacement agent with wider application range and higher oil displacement efficiency.
Disclosure of Invention
The invention aims to solve the technical problems that the composite oil displacement agent in the prior art is poor in temperature resistance and salt resistance, high in use concentration and low in oil displacement efficiency, and provides the composite surfactant containing the aryl alcohol polyether anionic and nonionic surfactant and the alkyl polyether quaternary ammonium salt surfactant, which can greatly improve the recovery ratio under the condition of high-temperature and high-salt oil reservoir. The composite surfactant can form 10 with crude oil under the conditions of wide concentration range, high temperature and high salinity oil reservoir -2 ～10 -4 mN/m low interfacial tension, thereby improving the oil displacement efficiency of the oil displacement agent.
The invention also provides a preparation method of the composite surfactant capable of improving the recovery ratio, which is used for solving the technical problem.
The invention aims to solve the third technical problem of the application of the composite surfactant capable of improving the recovery ratio in oil field oil recovery corresponding to one of the technical problems.
In order to solve one of the technical problems, the technical scheme adopted by the invention is as follows: the composite surfactant for improving the recovery efficiency of crude oil comprises the following components in parts by mass:
(1) 0.01 to 1.0 portion of alkyl polyether quaternary ammonium salt surfactant;
(2) 0.02-1.0 part of aryl alcohol polyether acid salt surfactant;
wherein the molecular general formula of the alkyl polyether quaternary ammonium salt surfactant is shown in a formula (I):
the molecular general formula of the aryl alcohol polyether acid salt surfactant is shown in a formula (II):
in the formula, R 1 Is C 1 ～C 50 Alkyl groups of (a); r is 2 、R 3 、R 4 Is independently selected from C 1 ～C 4 Alkyl or substituted alkyl of (a); r 5 Is C 1 ～C 30 Alkyl, aryl, SO 3 M or COON; r is 6 Is selected from C 1 ～C 4 An alkylene group or a substituent-containing alkylene group of (a); r is 7 、R 8 Is independently selected from C 1 ～C 10 An alkylene group or a substituent-containing alkylene group of (a); x is selected from anions which render the molecule of formula (I) electrically neutral, j is the reciprocal of the absolute value of the valence of X; y is selected from-SO 3 Any of M or-COON; m and N are selected from cations or cationic groups; a. m is the addition number of the propoxy groups, a = 0-10, m = 0-20; b. n is the sum of ethoxy groups, b = 1-10, n = 0-20.
In the above technical scheme, when X is preferably a-1 valent anion, the molecular general formula of the alkyl polyether quaternary ammonium salt surfactant is represented by formula (III):
in the above technical scheme, R 1 Preferably C 1 ～C 20 Alkyl groups of (a); r is as described 2 、R 3 、R 4 Independently selected as C 1 、C 2 、C 3 Alkyl or hydroxy-substituted alkyl of (a); further preferred is R 1 Is C 8 、C 9 、C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 Or C 18 Alkyl of (2), R 2 、R 3 Is methyl and/or ethyl, R 4 Is C 1 、C 2 、C 3 Alkyl or hydroxy-substituted alkyl. .
In the above technical scheme, R 5 Preferably C 1 ～C 20 Alkyl, aryl, COON or SO of 3 M，R 6 Is C 1 ～C 4 Alkylene or hydroxy-substituted alkylene of (A), R 7 、R 8 Is C 1 ～C 10 Alkylene or hydroxy-substituted alkylene of (2), further preferably R 5 Is C 8 、C 9 、C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 、C 18 Alkyl, COON or SO 3 M；R 6 、R 7 、R 8 Is C 1 、C 2 、C 3 An alkylene group of (a).
In the above technical solution, the X is preferably a halogen ion, and more preferably-Cl — 、-Br — 、-I — At least one of (1).
In the above technical solution, a =0 to 5, b =5 to 8, m =0 to 10, n =2 to 10 are more preferable.
In the above embodiment, the mass ratio of the aryl alcohol polyether acid salt surfactant to the alkyl polyether quaternary ammonium salt surfactant is preferably 25 to 1, more preferably 15 to 1, still more preferably 10 to 1, even more preferably 8 to 1, still more preferably 5 to 1, and most preferably 2.5 to 1.
In the above technical solution, M and N are preferably at least one selected from ammonium ions and alkali metal ions.
In the technical scheme, the composite surfactant for improving the crude oil recovery rate further comprises 98.0-99.98 parts by mass of injected water.
In the above technical scheme, the total mineralization degree of the injected water is preferably 100000-300000 mg/L, ca 2+ +Mg 2+ Preferably 0 to 7000mg/L.
In the above technical solution, X is — Is preferably-Cl — 。
In order to solve the second technical problem, the invention adopts the technical scheme that: a method for preparing an enhanced oil recovery composite surfactant according to any one of the above technical solutions to solve the technical problems, comprising the steps of:
(a) Preparation of aryl alcohol polyether acid salt
HO- [ CH (CH) 3 )CH 2 O]-[CH 2 CH 2 O]-R 6 Y and
reacting at 100-180 ℃ in the presence of a catalyst, then adding water for dilution, performing oil-water separation, and obtaining aryl alcohol polyether acid salt from a water phase;
(b) Preparation of alkyl polyoxyethylene polyoxypropylene ether
R is to be 4 Carrying out alkoxylation reaction on OH and required amount of propylene oxide and ethylene oxide in the presence of an alkaline catalyst to obtain the alkyl polyoxyethylene polyoxypropylene ether;
(c) Halogenation of alkylpolyoxyethylene polyoxypropylene ethers
Mixing the alkyl polyoxyethylene polyoxypropylene ether synthesized in the step (c) with a halogenating reagent for halogenating reaction to obtain halide of the alkyl polyoxyethylene polyoxypropylene ether;
(d) Preparation of alkyl polyether quaternary ammonium salt
Will (R) 1 R 2 R 3 ) N and step (c) SynthesisCarrying out quaternization reaction on the halogenated alkyl polyoxyethylene polyoxypropylene ether; after the reaction is finished, evaporating the solvent to obtain the product alkyl polyether quaternary ammonium salt;
(e) And (3) mixing the aryl alcohol polyether acid salt synthesized in the step (a), the alkyl polyether quaternary ammonium salt synthesized in the step (d) and injected water according to the required proportion, stirring, and adjusting the pH value to be = 7-10 to obtain the required composite surfactant.
In the above technical solution, in the step (a), wherein the HO- [ CH (CH) 3 )CH 2 O]-[CH 2 CH 2 O]-R 6 Y and
the molar ratio is preferably 1 (2-5), the catalyst is preferably an alkaline catalyst, more preferably an alkali metal hydroxide, most preferably sodium hydroxide, and the amount of the catalyst is 1
1-3 wt% of the mass.
In the above technical scheme, in the step (b), the propylene oxide and the ethylene oxide are preferably added in sequence by adding the propylene oxide first and then adding the ethylene oxide; the basic catalyst is preferably used in an amount R 4 1-3 wt% of OH; the reaction conditions of the alkoxylation reaction are preferably: the reaction temperature is preferably 100 to 180 ℃ and the reaction pressure is preferably less than 0.60MPa gauge.
In the above technical scheme, in the step (c), the halogenation temperature is preferably 25 to 80 ℃; the halogenating agent is preferably triphenylphosphine and carbon tetrachloride.
In the above technical solution, in the step (d), the solvent is preferably at least one selected from ethanol and isopropanol; the quaternization reaction is preferably carried out in a solvent, and the pH value of the reaction is = 9-10; the reaction temperature is preferably 60-80 ℃, and the reaction time is preferably 10-16 hours; said (R) 1 R 2 R 3 ) The molar ratio of N to alkylpolyoxyethylene polyoxypropylene ether halide is preferably (1-1.2): 1, more preferably 1.1.
In the above technical solution, in the step (e), the stirring time is preferably 1 to 30 minutes, and the pH =8 to 9.5.
In the above technical scheme, in the step (e), the preferable range of the aryl alcohol polyether acid salt is 0.1 to 0.3wt%, and the preferable range of the alkyl polyether quaternary ammonium salt surfactant is 0.02 to 0.15wt%, based on the total system mass percentage.
In order to solve the third technical problem, the invention adopts the technical scheme that: the use of the enhanced oil recovery composite surfactant according to any one of the above technical solutions to solve the technical problems in oil recovery in an oil field.
In the above technical solution, the application method can be used by those skilled in the art according to the prior art, for example, but not limited to, injecting the composite surfactant solution into an oil reservoir to contact with the underground crude oil, and displacing the underground crude oil; or be used together with other oil production agents.
In the above technical scheme, the application method comprises the following steps that the preferred range of the dosage of the aryl alcohol polyether acid salt is 0.1-0.3 wt%, and the preferred range of the alkyl polyether quaternary ammonium salt surfactant is 0.02-0.15 wt%.
According to the invention, the anion-nonionic and cation-nonionic composite surfactants are adopted, and after the anion-nonionic and cation-nonionic surfactants are compounded, the problems of loose arrangement of an interface film and the like caused by electrostatic repulsion among the same charges of the traditional surfactants can be avoided, so that the interfacial activity of the compounded agent is enhanced, and the oil displacement efficiency is improved. Meanwhile, the adsorption resistance and calcium and magnesium ion resistance of the composite surfactant are enhanced, so that the composite surfactant has the possibility of being applied to high-salinity oil reservoirs.
The composite surfactant capable of improving the recovery efficiency can be used for the formation with the temperature of 90 ℃ and the mineralization degree of 20 multiplied by 10 4 The dynamic interfacial tension between the oil displacement agent aqueous solution and the Jianghan crude oil is measured to be 10 by using 0.1-0.3 wt% of aryl alcohol polyether acid salt and 0.02-0.15 wt% of alkyl polyether quaternary ammonium salt to form the composite surfactant oil displacement agent of mg/L Jianghan formation water and crude oil -3 ～10 -4 Ultra mN/mLow interfacial tension, good technical effect and can be used for improving the recovery ratio of tertiary oil recovery.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
(1) HO- [ CH (CH) 3 )CH 2 O]-[CH 2 CH 2 O]-R 6 Y and
adding catalyst sodium hydroxide into a reaction kettle, introducing nitrogen to the reaction kettle until the pressure is 20kg/L, and reacting at 150-180 ℃, wherein HO- [ CH (CH) 3 )CH 2 O]-[CH 2 CH 2 O]-R 6 Y、
The catalyst molar ratio is 1:2:1.5, adding water for dilution, performing oil-water separation, and obtaining aryl alcohol polyoxyethylene polyoxypropylene etherate from a water phase;
(2) Adding a certain amount of R into a polymerization reaction kettle 4 OH and with R 4 KOH by weight of OH, heating the system temperature to 80-90 ℃ with stirring, starting the vacuum system, dehydrating under high vacuum for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then adjusting the reaction temperature of the system to 130 ℃ and slowly introducing a calculated amount of propylene oxide to control the reaction pressure<And (3) carrying out propoxylation alkylation reaction at 0.40MPa, continuing to slowly introduce a calculated amount of ethylene oxide after the reaction is finished, purging the system by using nitrogen after the reaction is finished (the reaction pressure is unchanged), removing unreacted ethylene oxide, cooling, neutralizing, decolorizing, filtering and dehydrating to obtain the alkyl polyoxyethylene polyoxypropylene ether with different polymerization degrees.
(3) Adding the alkyl polyoxyethylene polyoxypropylene ether synthesized in the step (2) and triphenylphosphine (the molar ratio is 1.5).
(4) Preparation of alkyl polyether quaternary ammonium salt
Will (R) 1 R 2 R 3 ) Dissolving N in solvent, adding potassium hydroxide to regulate pH to 9-10. Slowly adding the halogenated alkyl polyoxyethylene polyoxypropylene ether synthesized in the step (3) into the mixture at the temperature of between 60 and 80 ℃ according to the mol ratio of 1.1. After the reaction is finished, the solvent is evaporated to obtain the product alkyl polyether quaternary ammonium salt. Wherein the solvent is selected from one of ethanol and isopropanol;
(5) And (3) uniformly mixing the aryl alcohol polyoxypropylene polyoxyethylene ether sulfonic acid product synthesized in the step (1), the alkyl polyether quaternary ammonium salt synthesized in the step (4), calculated amount of alkali liquor and water at a temperature of between 50 and 60 ℃ according to the required proportion to obtain the surfactant product with the required content.
[ example 2 ] A method for producing a polycarbonate
Aryl alcohol polyoxypropylene polyoxyethylene ether sodium sulfonate (R) 5 ＝CH 3 (CH 2 ) 14 ，R 6 ＝CH 2 ，R 7 ＝CH 2 ，R 8 ＝C 9 H 18 M =9, n = 6) and tetradecylpolyoxypropylene polyoxyethylene hydroxyethylammonium chloride (R) 1 ＝C 14 H 30 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A =2, b = 6) the surfactants were dissolved in formation water having a degree of mineralization of 200000mg/L, respectively, and stirred for 30 minutes to prepare an aqueous solution having a weight of 0.1 to 0.5%, respectively, and then the ratio of the anionic to cationic surfactants was adjusted in a molar ratio of 1:0.2 mixing the above surfactants uniformly to obtain the surfactant composition product solution 1a.
[ example 3 ] A method for producing a polycarbonate
Sodium aryl alcohol polyoxypropylene Polyoxyethylene Ether sulfonate (R) 5 ＝CH 3 (CH 2 ) 7 ，R 6 ＝C 5 H 10 ，R 7 ＝C 2 H 4 ，R 8 ＝C 6 H 12 M =7, n = 5) and dodecyl polyoxypropylene polyoxyethylene ether hydroxyethyl ammonium chloride (R) 1 ＝C 12 H 26 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A =0, b = 7) surfactants, respectivelyDissolving in formation water having a mineralization of 200000mg/L, stirring for 30 minutes to prepare an aqueous solution of 0.1-0.5% by weight, and then mixing the aqueous solution according to a molar ratio of 1:0.54 the above surfactants were mixed well to obtain a surfactant composition product solution 2a.
[ example 4 ]
Aryl alcohol polyoxypropylene polyoxyethylene ether sodium sulfonate (R) 5 ＝CH 3 (CH 2 ) 4 ，R 6 ＝C 5 H 10 ，R 7 ＝C 5 H 10 ，R 8 ＝C 4 H 8 M =6,n = 2) and cetylpolyoxypropylene polyoxyethylene ether hydroxyethyl ammonium chloride (R) 1 ＝C 16 H 34 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A =3, b = 5) the surfactants were dissolved in formation water having a degree of mineralization of 200000mg/L, respectively, and stirred for 30 minutes to prepare 0.1 to 0.5% wt aqueous solution, and then the ratio of the anionic to cationic surfactant was adjusted in a molar ratio of 1:0.8 mixing the above surfactants uniformly to obtain the surfactant composition product solution 3a.
[ example 5 ]
Aryl alcohol polyoxypropylene polyoxyethylene ether sodium sulfonate (R) 5 ＝COONa，R 6 ＝C 3 H 6 ，R 7 ＝C 10 H 20 ，R 8 ＝CH 2 M =9,n = 10) and octadecyl polyoxypropylene polyoxyethylene ether hydroxyethylammonium chloride (R) 1 ＝C 18 H 38 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A =0, b = 5) the surfactants were dissolved in the formation water having a mineralization of 200000mg/L, respectively, stirred for 30 minutes to prepare 0.1 to 0.5% by weight of an aqueous solution, and then the ratio was adjusted in accordance with the anionic to cationic surfactant molar ratio of 1:0.6 mixing the surfactants evenly to obtain the surfactant composition product solution 4a.
[ example 6 ]
Aryl alcohol polyoxypropylene polyoxyethylene ether sodium sulfonate (R) 5 ＝CH 3 ，R 6 ＝C 4 H 8 ，R 7 ＝C 9 H 18 ，R 8 = CH2, m =10, n = 6) and dodecyl polyoxypropylene polyoxyethylene ether hydroxyethyl ammonium chloride (R) 1 ＝C 12 H 26 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 And, a =0, b = 7) the surfactants were dissolved in formation water having a degree of mineralization of 200000mg/L, respectively, and stirred for 30 minutes to prepare 0.1 to 0.5% by weight aqueous solution, and then the ratio of the anionic to cationic surfactant was adjusted in a molar ratio of 1:0.9 mixing the above surfactants uniformly to obtain the surfactant composition product solution 5a.
[ example 7 ]
Aryl alcohol polyoxypropylene polyoxyethylene ether sodium sulfonate (R) 5 ＝SO 3 Na，R 6 ＝CH 2 ，R 7 ＝C 3 H 6 ，R 8 ＝C 3 H 6 M =6,n = 6) and octadecyl polyoxypropylene polyoxyethylene ether ammonium chloride (R) 1 ＝C 18 H 38 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH 2 CH 3 A =0, b = 5) the surfactants were dissolved in formation water having a mineralization of 200000mg/L, respectively, and stirred for 30 minutes to prepare 0.1 to 0.5% wt aqueous solution, and then the ratio of the surfactant to the surfactant was adjusted in accordance with the anion: cationic surfactant molar ratio 1:1.9 mixing the surface active agents evenly to obtain a surface active agent composition product solution 6a.
[ example 8 ]
Aryl alcohol polyoxypropylene polyoxyethylene ether sodium carboxylate (R) 5 ＝CH 3 (CH 2 ) 4 ，R 6 ＝CH 2 ，R 7 ＝C 5 H 10 ，R 8 ＝C 4 H 8 M =4,n = 5) and dodecyl polyoxypropylene polyoxyethylene ether hydroxyethyl ammonium chloride (R) 1 ＝C 12 H 26 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A =0, b = 7) surfactant is dissolved in formation water having a degree of mineralization of 200000mg/L, and the mixture is stirred for 30 minutes to prepare 0.1 to 0.5%wt aqueous solution, then according to the anion: cationic surfactant molar ratio 1:2.2 mixing the surface active agents evenly to obtain a surface active agent composition product solution 7a.
[ example 9 ]
Aryl alcohol polyoxypropylene polyoxyethylene ether sodium carboxylate (R) 5 ＝SO 3 Na，R 6 ＝C 2 H 4 ，R 7 ＝CH 2 ，R 8 ＝CH 2 M =5,n = 7) and octadecyl polyoxypropylene polyoxyethylene ether ammonium chloride (R) 1 ＝C 18 H 38 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH 2 CH 3 A =0, b = 5) the surfactants were dissolved in formation water having a mineralization of 200000mg/L, respectively, and stirred for 30 minutes to prepare 0.1 to 0.5% wt aqueous solution, and then the ratio of the surfactant to the surfactant was adjusted in accordance with the anion: cationic surfactant molar ratio 1:0.2 mixing the above surfactants uniformly to obtain the surfactant composition product solution 8a.
[ example 10 ]
Preparing sodium aryl alcohol polyoxypropylene polyoxyethylene ether carboxylate (R) 5 ＝CH 3 (CH 2 ) 7 ，R 6 ＝C 5 H 10 ，R 7 ＝C 2 H 4 ，R 8 ＝C 6 H 12 M =4,n = 7) and cetylpolyoxypropylene polyoxyethylene ether hydroxyethylammonium chloride (R) 1 ＝C 16 H 34 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A =3, b = 5) surfactants were dissolved in formation water having a degree of mineralization of 200000mg/L, respectively, stirred for 30 minutes to prepare 0.1 to 0.5% by weight of an aqueous solution, and then the water was concentrated in terms of an anion: cationic surfactant molar ratio 1:0.5 mixing the above surfactants uniformly to obtain the surfactant composition product solution 9a.
[ example 11a ] interfacial Property test of surfactant composition
The oil-water interfacial tension of the surfactant composition solutions of examples 2-10 and Jianghan crude oil was measured using a TX-500C spinning drop interfacial tension apparatus, and the results are shown in Table 1:
and (3) testing temperature: 85 ℃; the mineralization degree of the formation water is 20000mg/L.
TABLE 1 oil-water interfacial tension of composite surfactant compositions
[ example 11b ] ultra-low interfacial tension window test for surfactant compositions
The surfactant composition described in example 3 was selected, samples of different concentrations of surfactant were prepared with formation water, and oil-water interfacial tension concentration window tests were performed at 85 ℃ (heated by an external oil bath) using a TX-500C spinning drop interfacial tensiometer (rotating speed 4500 rpm), the results of which are shown in table 2.
TABLE 2 oil-water interfacial tension of different concentrations of surfactant
| Concentration wt% | 0.010 | 0.025 | 0.05 | 0.1 | 0.3 | 0.5 |
| Interfacial tension mN/m | 0.0065 | 0.0039 | 0.0025 | 0.0022 | 0.0020 | 0.0024 |
The results show that the surfactant composition has high oil-water interfacial activity on crude oil in Jianghan oil field
[ example 12 ] oil-washing ability test of surfactant composition
The method comprises the steps of cleaning stratum sand of the Jianghan oil field, grinding and sieving for later use, uniformly mixing the stratum sand with target crude oil according to the saturation of residual oil, aging the mixture for 7 days at the oil reservoir temperature, taking out 5 g of aged oil sand, and then performing oil sand treatment according to the following steps: and (2) adding 0.5% of a surfactant composition solution according to the proportion of the solution = 1.
TABLE 3 oil wash results for surfactant compositions
| Examples | Oil washing rate% |
| 2 | 53.3 |
| 3 | 71.4 |
| 4 | 65.4 |
| 5 | 75.2 |
| 6 | 60.0 |
| 7 | 51.7 |
| 8 | 63.9 |
| 9 | 55.5 |
| 10 | 66.8 |
[ COMPARATIVE EXAMPLE 1 ]
According to the method of patent CN109652048A, symmetric alkyl alcohol polyoxyethylene ether sulfonate anionic-nonionic surfactant and hexadecyl trimethyl ammonium bromide surfactant are respectively dissolved in formation water to prepare 0.1-wt% aqueous solution, and the molar ratio of anionic-nonionic surfactant to cationic surfactant is 0.25. And stirred for 30 minutes to mix well to give reference surfactant composition 1b.
[ COMPARATIVE EXAMPLE 2 ]
Sodium aryl alcohol polyoxypropylene Polyoxyethylene Ether sulfonate (R) 5 ＝CH 3 (CH 2 ) 7 ，R 6 ＝C 5 H 10 ，R 7 ＝C 2 H 4 ，R 8 ＝C 6 H 12 M =7, n = 5) surfactant and cetyltrimethylammonium chloride surfactant were dissolved in formation water having a degree of mineralization of 200000mg/L, respectively, stirred for 30 minutes, to prepare a 0.1-wt% aqueous solution, and then the water was concentrated in terms of an anion: cationic surfactant molar ratio 1:0.54 the above surfactants were mixed well to obtain a surfactant composition product solution 2b.
[ COMPARATIVE EXAMPLE 3 ]
Aryl alcohol polyoxypropylene polyoxyethylene ether sodium sulfonate (R) 5 ＝CH 3 (CH 2 ) 7 ，R 6 ＝C 5 H 10 ，R 7 ＝C 2 H 4 ，R 8 ＝C 6 H 12 M =7, n = 5) the surfactant was dissolved in formation water having a degree of mineralization of 200000mg/L, and stirred for 30 minutes to prepare a 0.1% wt aqueous solution, thereby obtaining a reference surfactant solution 3b.
[ COMPARATIVE EXAMPLE 4 ] interfacial Property test for different surfactant compositions
The oil-water interfacial tension of the surfactant composition solutions of examples 2-10 and Jianghan crude oil was measured using a TX-500C rolling-drop interfacial tension apparatus, and the results are shown in Table 4:
and (3) testing temperature: 85 ℃; the mineralization degree of the formation water is 20000mg/L.
TABLE 4 surfactant composition oil-water interfacial tension
| Sample(s) | Interfacial tension (mN/m) |
| Example 3 | 0.0022 |
| Comparative example 1b | 0.033 |
| Comparative example 2b | 0.026 |
| Comparative example 3b | 0.057 |
As shown in table 4, example 3 has a more significant property of reducing the interfacial tension between oil and water than the comparative examples, and the anionic and cationic surfactants have a higher interfacial performance after being compounded than the single surfactant.
Claims (33)
1. The composite surfactant comprises the following components in parts by weight:
(1) 0.01 to 1.0 part of alkyl polyether quaternary ammonium salt surfactant;
(2) 0.02 to 1.0 part of aryl alcohol polyether acid salt surfactant;
wherein the molecular general formula of the alkyl polyether quaternary ammonium salt surfactant is shown in a formula (I):
the molecular general formula of the aryl alcohol polyether acid salt surfactant is shown in the formula (A)
) Shown in the figure:
in the formula, R 1 Is C 1 ～C 50 Alkyl groups of (a); r is 2 、R 3 、R 4 Is independently selected from C 1 ~C 4 Alkyl or substituted alkyl of (a); r 5 Is C 1 ～C 30 Alkyl, aryl, SO 3 M or COON; r 6 Is selected from C 1 ~C 4 An alkylene group or a substituent-containing alkylene group of (a); r 7 、R 8 Is independently selected from C 1 ~C 10 An alkylene group or a substituent-containing alkylene group of (a); x is selected from anions which render the molecule of formula (I) electrically neutral, j is the reciprocal of the absolute value of the valence of X; y is selected from-SO 3 Any one of M or-COON;m and N are selected from cations or cationic groups; a. m is the addition number of the propoxy groups, a =0 to 10, m =0 to 20; b. n is the sum of the ethoxy groups, b =1 to 10, n =2 to 20.
2. The composite surfactant according to claim 1, wherein R is 1 Is C 1 ～C 20 Alkyl groups of (a); said R 2 、R 3 、R 4 Independently selected as C 1 、C 2 、C 3 Alkyl or hydroxy-substituted alkyl.
3. The composite surfactant according to claim 2, characterized in that
Said R is 1 Is C 8 、C 9 、C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 Or C 18 Alkyl of R 2 、R 3 Each independently selected from methyl, ethyl, R 4 Is C 1 、C 2 、C 3 Alkyl or hydroxy substituted alkyl.
4. The composite surfactant according to claim 1, characterized in that
Said R 5 Is C 1 ～C 20 Alkyl, aryl, COON or SO of 3 M，R 6 Is C 1 ~C 4 Alkylene or hydroxy-substituted alkylene of (2), R 7 、R 8 Is C 1 ~C 10 Alkylene or hydroxy-substituted alkylene of (a).
5. The composite surfactant according to claim 1, wherein R is 5 Is C 1 ～C 20 Alkyl, aryl, SO 3 M or COON; r is 6 Is C 1 、C 2 Or C 3 An alkylene group of (a); r is 7 、R 8 Independently selected as C 2 、C 3 Or C 4 An alkylene group of (2).
6. The composite surfactant according to claim 5, characterized in that
R 5 Is C 8 、C 9 、C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 、C 18 Alkyl, COON or SO 3 M。
7. The composite surfactant according to claim 1, wherein a =0 to 5,b =5 to 8.
8. The composite surfactant according to claim 1, wherein m =0 to 10.
9. The composite surfactant according to claim 1, wherein the mass ratio of the aryl alcohol polyether acid salt surfactant to the alkyl polyether quaternary ammonium salt surfactant is 25 to 1.
10. The composite surfactant according to claim 9, wherein the mass ratio of the aryl alcohol polyether acid salt surfactant to the alkyl polyether quaternary ammonium salt surfactant is 15 to 1.
11. The composite surfactant according to claim 10, wherein the mass ratio of the aryl alcohol polyether acid salt surfactant to the alkyl polyether quaternary ammonium salt surfactant is 10 to 1.
12. The composite surfactant according to claim 11, wherein the mass ratio of the aryl alcohol polyether acid salt surfactant to the alkyl polyether quaternary ammonium salt surfactant is 8 to 1.
13. The composite surfactant according to claim 12, wherein the mass ratio of the aryl alcohol polyether acid salt surfactant to the alkyl polyether quaternary ammonium salt surfactant is 5 to 1.
14. The composite surfactant according to claim 13, wherein the mass ratio of the aryl alcohol polyether acid salt surfactant to the alkyl polyether quaternary ammonium salt surfactant is 2.5 to 1.
15. The composite surfactant according to claim 1, characterized by further comprising 98.0 to 99.98 parts by mass of injected water.
16. The composite surfactant according to claim 15, wherein the total mineralization of the injected water is 100000 to 300000mg/L and Ca 2+ +Mg 2+ The concentration is 0 to 7000mg/L.
17. The composite surfactant according to claim 1, characterized in that
When X is negative ion with a valence of-1, the molecular general formula of the alkyl polyether quaternary ammonium salt surfactant is shown in a formula (III):
18. The composite surfactant according to claim 17, wherein the surfactant is a nonionic surfactant
And X is a halogen ion.
19. The composite surfactant of claim 18, wherein the surfactant is a mixture of a surfactant and a water-soluble surfactant
X is-Cl — 、-Br — 、-I — At least one of (a).
20. The composite surfactant according to claim 1, characterized in that
And M and N are selected from at least one of ammonium ions or alkali metal ions.
21. A method for preparing the composite surfactant of any one of claims 1 to 20, comprising the steps of:
(a) Preparation of aryl alcohol polyether acid salt
HO- [ CH (CH) 3 )CH 2 O]-[CH 2 CH 2 O]-R 6 Y and
reacting at 100-180 ℃ in the presence of a catalyst, then adding water for dilution, carrying out oil-water separation, and obtaining aryl alcohol polyether acid salt from a water phase;
(b) Preparation of alkyl polyoxyethylene polyoxypropylene ether
R is to be 4 Performing alkoxylation reaction on OH and required amount of propylene oxide and ethylene oxide in the presence of an alkaline catalyst to obtain the alkyl polyoxyethylene polyoxypropylene ether;
(c) Halogenation of alkylpolyoxyethylene polyoxypropylene ethers
Mixing the alkyl polyoxyethylene polyoxypropylene ether synthesized in the step (b) with a halogenating reagent, and carrying out halogenation reaction to obtain halogenated alkyl polyoxyethylene polyoxypropylene ether;
(d) Preparation of alkyl polyether quaternary ammonium salt
Will (R) 1 R 2 R 3 ) N and the halogenated alkyl polyoxyethylene polyoxypropylene ether synthesized in the step (c) are subjected to quaternization reaction; after the reaction is finished, evaporating the solvent to obtain the product alkyl polyether quaternary ammonium salt;
(e) And (3) mixing the aryl alcohol polyether acid salt synthesized in the step (a), the alkyl polyether quaternary ammonium salt synthesized in the step (d) and injected water according to the required proportion, stirring, and adjusting the pH value to be =7 to 10 to obtain the required composite surfactant.
22. The method for preparing a composite surfactant according to claim 21, wherein the surfactant is a surfactant having a specific structure
In step (a), the HO- [ CH (CH) 3 )CH 2 O]-[CH 2 CH 2 O]-R 6 Y and
the molar ratio is 1 (2 to 5), the catalyst is an alkaline catalyst, and the dosage of the catalyst is
1 to 3wt% of the mass.
23. The method for preparing the composite surfactant according to claim 22, wherein the surfactant is a surfactant having a specific structure
The catalyst is an alkali metal hydroxide.
24. The method for preparing a composite surfactant according to claim 23, wherein the surfactant is a surfactant having a specific structure
The catalyst is sodium hydroxide.
25. The method for preparing a composite surfactant according to claim 21, wherein the surfactant is a surfactant having a specific structure
In the step (b), the dosage of the basic catalyst is R 4 1 to 3wt% of OH mass; the reaction conditions of the alkoxylation reaction are as follows: the reaction temperature is 100 to 180 ℃, and the reaction pressure is less than 0.60MPa gauge pressure.
26. The method for preparing the composite surfactant according to claim 21, wherein the surfactant is a surfactant having a specific structure
In the step (c), the halogenation temperature is 25-80 ℃; the halogenating agent is triphenylphosphine and carbon tetrachloride.
27. The method for preparing a composite surfactant according to claim 21, wherein the surfactant is a surfactant having a specific structure
In the step (d), the solvent is at least one selected from ethanol and isopropanol; the quaternization reaction is carried out in a solvent, and the pH value of the reaction is =9 to 10; the reaction temperature is 60 to 80 ℃, and the reaction time is 10 to 16 hours; said (R) 1 R 2 R 3 ) The molar ratio of N to the haloalkylpolyoxyethylene polyoxypropylene ether is (1 to 1.2) 1.
28. The method for preparing a composite surfactant according to claim 27, wherein the surfactant is a surfactant having a surfactant-containing group
In step (d), the (R) 1 R 2 R 3 ) The molar ratio of N to haloalkylpolyoxyethylene polyoxypropylene ether was 1.1:1.
29. The method for preparing the composite surfactant according to claim 21, wherein the surfactant is a surfactant having a specific structure
In the step (e), the stirring time is 1 to 30 minutes, and the pH value is =8 to 9.5.
30. The method for preparing the composite surfactant according to claim 21, wherein the surfactant is a surfactant having a specific structure
In the step (e), the dosage of the aryl alcohol polyether acid salt is 0.1 to 0.3wt%, and the dosage of the alkyl polyether quaternary ammonium salt surfactant is 0.02 to 0.15wt%.
31. Use of the composite surfactant of any one of claims 1 to 20 or the composite surfactant prepared by the method of any one of claims 21 to 30 in oil recovery in oil fields.
32. The use according to claim 31, characterized in that the complex surfactant is injected in the form of an aqueous solution into the reservoir formation in contact with the crude oil and displaces the crude oil from the reservoir formation.
33. Use according to claim 31, characterized by the use in tertiary oil recovery.
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