CN109666474B - Surfactant binary compound system with ultralow oil-water interfacial tension - Google Patents

Surfactant binary compound system with ultralow oil-water interfacial tension Download PDF

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CN109666474B
CN109666474B CN201710962870.0A CN201710962870A CN109666474B CN 109666474 B CN109666474 B CN 109666474B CN 201710962870 A CN201710962870 A CN 201710962870A CN 109666474 B CN109666474 B CN 109666474B
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betaine
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沈少春
李应成
沙鸥
张卫东
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a surfactant binary compound system with ultralow oil-water interfacial tension, which mainly solves the problem that the surfactant has poor effect of reducing the oil-water interfacial tension. The invention adopts a surfactant binary compound system, which comprises a betaine surfactant and a nonionic surfactant, wherein the molar ratio of the betaine surfactant to the nonionic surfactant is 1 (0.01-100), the structure of the betaine surfactant can be represented by the following molecular formula A, wherein X is any one of acetate, propionate, ethylsulfonate, propylsulfonate and hydroxypropylsulfonate, and R is any one of acetate, propionate, ethylsulfonate, propylsulfonate and hydroxypropylsulfonate1Is C6～C24Any one of aliphatic group or aromatic group of (1), R2，R3Is C1～C4Any one of alkyl groups; the technical scheme that the nonionic surfactant is represented by the following molecular general formula B better solves the problem and can be used in industrial application of an oil field crude oil recovery increasing method.
Figure 1

Description

Surfactant binary compound system with ultralow oil-water interfacial tension
Technical Field
The invention relates to a surfactant binary compound system capable of generating ultralow oil-water interfacial tension, belonging to the technical field of oilfield chemistry.
Background
With the increase of world energy demand, the reasonable development and utilization of petroleum have attracted great attention of people, and the requirements on the production quantity and the production efficiency of petroleum are higher and higher. The method realizes the efficient exploitation of oil and gas resources, and has practical significance and important strategic significance for improving the yield of crude oil. Conventional oil recovery processes (primary and secondary) typically produce only 1/3 from the geological reserves of crude oil, and also fail to produce about 2/3 of crude oil, so increasing oil recovery has become more efficient with increasing energy useThe major topic of oil exploitation research. Many studies over the years have proposed various enhanced oil recovery techniques, which can be divided into four broad categories: the first is thermal flooding, including steam flooding, in-situ combustion and the like; second, miscible flooding, comprising CO2Miscible phase, hydrocarbon miscible phase and other inert gas miscible phase flooding; thirdly, chemical flooding; and fourthly, microbial oil recovery, including biopolymer and microbial surfactant flooding. Chemical flooding is a very important and large-scale technology for enhanced oil recovery, and comprises polymer flooding, surfactant flooding, alkali water flooding and the like, and various combination technologies of polymer, alkali and surfactant.
The chemical flooding effect is the result of physical action, which is the sweeping action of the displacement fluid, and chemical action, which is the microscopic displacement action of the displacement fluid. The core of the chemical action is to reduce the interfacial tension of the displacement fluid and the crude oil. Whether the oil-water interfacial tension can be reduced to be ultra-low (10)-3mN/m) is an important index for screening chemical oil-displacing agents. The oil-water interfacial tension depends on the molecular composition in the interfacial layer, and the stronger the hydrophobicity of the oil phase, the larger the difference with the water phase, the higher the interfacial tension. The surfactant is adsorbed and enriched on an oil-water interface, a hydrophilic group extends to a water phase, and a lipophilic group extends to an oil phase, so that the interfacial energy is greatly reduced, and the interfacial tension is reduced. The reduction of the oil-water interfacial tension means that the surfactant system can overcome the cohesive force among the crude oil and disperse large oil drops into small oil drops, thereby improving the passing rate of the crude oil when the crude oil flows through the pore throat.
At present, the surfactant for tertiary oil recovery mostly adopts a multi-component compound system, simultaneously comprises a non-ionic surfactant and an ionic surfactant, and auxiliary agents such as alkali, alcohol and the like are added into part of the formula. For example, patent CN101024764A provides a surfactant for heavy oil wells in oil fields, which is composed of water, caustic soda flakes, ethanol, oleic acid, alkylphenol ethoxylates and sodium dodecyl benzene sulfonate. For another example, patent CN1458219A discloses a surfactant polymer pure binary ultra-low interfacial tension composite flooding formulation for tertiary oil recovery, wherein the used surfactant is petroleum sulfonate or a composite surfactant prepared by mixing petroleum sulfonate as a main agent, a diluent and other surfactants, and the weight percentages of the components are 50-100% of petroleum sulfonate, 0-50% of alkyl sulfonate, 0-50% of carboxylate, 0-35% of alkyl aryl sulfonate and 0-20% of low carbon alcohol. For another example, patent CN1394935 discloses a chemical oil-displacing agent, which mainly comprises sodium octyl benzene sulfonate anionic surfactant, surfactant adjuvant, surfactant synergist, and surfactant solubilizer. The oil displacement agent can obviously reduce the structural viscosity of the thickened oil and can reduce the oil-water interfacial tension, thereby improving the crude oil recovery rate.
However, the surfactant for tertiary oil recovery still has many problems, mainly including poor activity and low oil displacement efficiency; the oil displacement system contains inorganic base, which causes damage to stratum and oil well and causes corrosion to equipment and pipelines, and the inorganic base can seriously reduce the viscosity of the polymer, so that the use concentration of the polymer can be greatly improved to reach the required viscosity, and the comprehensive cost of oil extraction is improved; surfactants have limited ability to resist high temperatures, high salt, and hypersalinity.
As is well known, anionic surfactants such as petroleum sulfonate, petroleum carboxylate, alkylbenzene sulfonate and the like are currently used in tertiary oil recovery in large quantities, while single cationic surfactants are not generally used in tertiary oil recovery because they are easily adsorbed by the formation or precipitate, and thus have poor ability to reduce the interfacial tension between oil and water. Betaine surfactants are a class of surfactants which are researched more in recent years, and a cationic center and an anionic center exist in a molecular structure simultaneously, so that a solution of the betaine surfactants has different property characteristics from those of conventional surfactants.
Therefore, on the basis of combining the problems, the betaine surfactant and the nonionic surfactant are compounded, and the oil-water interfacial tension is measured, and the result shows that the surfactant binary complex system with a proper structure can reduce the oil-water interfacial tension to be ultra-low under a certain compounding ratio, and shows better interfacial activity.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the effect of reducing the oil-water interfacial tension of the central surfactant in the prior art is poor, and a binary compound system of the surfactant is provided, so that the oil-water interfacial tension can be reduced to be ultra-low, and the surfactant has the advantage of high interfacial activity.
The second technical problem to be solved by the invention is to provide a preparation method of a surfactant binary compound system corresponding to the first technical problem.
The invention aims to solve the technical problem and provides an application method of a surfactant binary complex system in oil extraction of oil fields, which corresponds to the technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a surfactant binary compound system comprises a betaine surfactant and a nonionic surfactant, wherein the molar ratio of the betaine surfactant to the nonionic surfactant is 1 (0.01-100), the structure of the betaine surfactant is represented by the following molecular general formula A, and the nonionic surfactant is represented by the following molecular general formula B:
Figure BDA0001435640510000031
wherein, X is any one of acetate, propionate, ethylsulfonate, propylsulfonate and hydroxypropyl sulfonate, R is1Is C6～C24Any one of aliphatic group or aromatic group of (1), R2，R3Is C1～C4Any one of alkyl groups; wherein R is4Is C6～C24Any one of the aliphatic group and the aromatic group of (1).
In the above technical scheme, X in the betaine surfactant is preferably any one of acetate, propionate, ethanesulfonate, propanesulfonate, and hydroxypropanesulfonate.
In the technical scheme, R in the betaine surfactant1Is selected from C6～C24Wherein the aliphatic or aromatic group may contain acyl, carbonyl, ether, hydroxyl, etc., and may containIt may be a saturated carbon chain or may contain an unsaturated carbon chain, and R is a preferable embodiment1Preferably C14～C22The substituent can be a substituent commonly used in the chemical field, such as hydroxyl, phenyl, halogen and the like.
In the technical scheme, R in the betaine surfactant2，R3Is independently selected from C1～C4Any one of alkyl groups.
In the above technical scheme, R in the nonionic surfactant is4Is selected from C6～C24Wherein the aliphatic group or the aromatic group may contain a group such as an acyl group, a carbonyl group, an ether group, a hydroxyl group, etc., and may contain a saturated carbon chain or an unsaturated carbon chain, as a preferable embodiment R4Preferably C10～C22The substituent group can be a substituent group which is common in the chemical field, such as hydroxyl, phenyl, halogen and the like.
In the technical scheme, the preferable range of the molar ratio of the betaine surfactant to the nonionic surfactant is 1 (0.01-100).
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of any one of the surfactant binary complex system in the technical scheme for solving one of the technical problems comprises the following steps:
(1) dissolving a betaine surfactant in water to obtain a solution I;
(2) dissolving a nonionic surfactant in water to obtain a solution II;
(3) and uniformly mixing the solutions I and II according to the molar ratio of 1: 0.01-100 of the betaine surfactant to the nonionic surfactant to obtain the surfactant binary compound system.
To solve the second technical problem, the invention adopts the following technical scheme: the technical scheme solves the technical problem that any one of the surfactant binary complex systems in the technical scheme is applied to oil recovery in oil fields.
In the above technical scheme, the application method can be utilized by those skilled in the art according to the surfactant flooding method in the prior art, and has no special requirement; in the surfactant binary compound system solution, the system concentration is 0.01-0.5% by the total mass of the betaine surfactant and the nonionic surfactant.
In the technical scheme, the surfactant binary complex system can realize the ultra-low oil-water interfacial tension under the condition of the mineralization degree of 0-150000 mg/L (calculated by NaCl).
The surfactant binary compound system selects the betaine surfactant with good polar end hydrophilicity and strong interface adsorption tendency and the nonionic surfactant with better solubilizing capability, and the betaine surfactant and the nonionic surfactant have synergistic effect to reduce the oil-water interfacial tension. And the two types of surfactants are mature in synthesis process, the components are conventional and easy to obtain, the cost is low, and certain economic benefits are achieved.
By adopting the technical scheme of the invention, the surfactant binary compound system can still form 10 with underground crude oil under the condition that the dosage is 0.01-0.05 wt%-3～10-4An ultra-low interfacial tension of mN/m; the surfactant composition system is simple. Because the system does not contain inorganic base, the problems of damage to the stratum, corrosion to equipment and demulsification difficulty caused by the damage to the stratum and the corrosion to the equipment in field application are solved, and a better technical effect is achieved.
Drawings
FIG. 1 is a time-dependent change curve of oil-water interfacial tension, which is obtained by measuring the time-dependent change of the oil-water interfacial tension using a surfactant binary complex system of example 1a of the present invention and a TEXAS-500 spinning drop interfacial tension apparatus. Crude oil is from domestic oil fields.
The invention is further illustrated by the following examples, but is not limited thereto.
Detailed Description
[ example 1a ]
Dissolving erucic acid propyl betaine and dodecyl diethanol amide surfactant in 20000mg/L NaCl saline respectively, stirringStirring for 30 minutes to prepare 0.1 wt% aqueous solution, and then uniformly mixing the surfactant according to the molar ratio of the zwitterion to the nonionic surfactant of 1:5 to obtain a surfactant binary compound system 1 a. Measuring oil-water interfacial tension of crude oil and the obtained solution at 40 deg.C and rotating speed of 4500r/min with TEXAS-500 rotary drop interfacial tension meter, wherein the interfacial tension curve is shown in figure 1, and the lowest oil-water interfacial tension reaches 4x10-4mN/m, equilibrium interfacial tension after 2 hours 1.6X10-3mN/m。
[ example 2a ]
In 8000mg/L NaCl saline, tetradecyl sulfonic acid betaine and octadecyl diethanol amide surfactant are respectively dissolved and stirred for 30 minutes to prepare 0.15 percent wt aqueous solution, and then the surfactants are uniformly mixed according to the molar ratio of the zwitterion to the nonionic surfactant of 85:15 to obtain a surfactant binary compound system 2 a. Measuring oil-water interfacial tension of crude oil and the obtained solution at 30 deg.C and 4500r/min with TEXAS-500 rotary drop interfacial tension meter, wherein the equilibrium interfacial tension is 3.8x10-3mN/m。
[ example 3a ]
In 60000mg/L NaCl saline, octadecyl betaine and nonylphenol acetic acid diethanolamide surfactants are respectively dissolved and stirred for 30 minutes to prepare 0.2 percent by weight aqueous solution, and then the surfactants are uniformly mixed according to the molar ratio of the zwitterionic surfactant to the nonionic surfactant of 30:70 to obtain a surfactant binary complex system 3 a. Measuring oil-water interfacial tension of crude oil and the obtained solution at 35 deg.C and 4500r/min with TEXAS-500 rotary drop interfacial tension meter, wherein the equilibrium interfacial tension is 2.3x10-3mN/m。
[ example 4a ]
In 110000mg/L NaCl saline, respectively dissolving cetyl betaine and octadecyl diethanolamide surfactants, stirring for 30 minutes to prepare 0.3 percent by weight aqueous solution, and then uniformly mixing the surfactants according to the molar ratio of the zwitterion to the nonionic surfactant of 65:35 to obtain a surfactant binary compound system 4 a. At 50 ℃, the rotating speed is 4500r/miUnder the condition of n, the TEXAS-500 rotating drop interfacial tension meter is used for measuring the oil-water interfacial tension of the crude oil in the oil field and the obtained solution, and the equilibrium interfacial tension is 4.1x10-3mN/m。
[ example 5a ]
In 120000mg/L NaCl saline, octadecyl amide sulfobetaine and octadecyl diethanol amide surfactant are respectively dissolved and stirred for 30 minutes to prepare 0.2 percent by weight aqueous solution, and then the surfactants are uniformly mixed according to the molar ratio of zwitterion to nonionic surfactant of 60:40 to obtain a surfactant binary complex system 5 a. Measuring oil-water interfacial tension of crude oil and the obtained solution at 50 deg.C and 4500r/min with TEXAS-500 rotary drop interfacial tension meter, wherein the equilibrium interfacial tension is 2.1x10-3mN/m。
[ example 6a ]
In 100000mg/L NaCl saline, octadecyl amide sulfonic acid betaine and oleic acid diethanol amide surfactant are respectively dissolved and stirred for 30 minutes to prepare 0.05 percent by weight of aqueous solution, and then the surfactants are uniformly mixed according to the molar ratio of the zwitterion to the nonionic surfactant of 60:40 to obtain a surfactant binary complex system 6 a. Measuring oil-water interfacial tension of crude oil and the obtained solution at 50 deg.C and 4500r/min with TEXAS-500 rotary drop interfacial tension meter, wherein the equilibrium interfacial tension is 4.1x10-4mN/m。
[ COMPARATIVE EXAMPLE 1b ]
Erucic acid propyl betaine is dissolved in 20000mg/L NaCl brine and stirred for 30 minutes to prepare 0.1% wt aqueous solution 1 b. Measuring oil-water interfacial tension of crude oil and the obtained solution at 40 deg.C and rotating speed of 4500r/min with TEXAS-500 rotary drop interfacial tension meter, wherein the equilibrium interfacial tension is 3.2x10-1mN/m。
[ COMPARATIVE EXAMPLE 2b ]
In 40000mg/L NaCl saline, octadecyl diethanolamide surfactant was dissolved and stirred for 30 minutes to prepare 0.15% wt aqueous solution 2 b. Measuring oil-water boundary of crude oil and the obtained solution at 40 deg.C and rotating speed of 4500r/min with TEXAS-500 rotary drop interfacial tensiometerSurface tension, equilibrium interfacial tension 5.2x10-2mN/m。
[ COMPARATIVE EXAMPLE 3b ]
In 120000mg/L NaCl saline, petroleum sulfonate and octadecyl diethanolamide surfactant are respectively dissolved and stirred for 30 minutes to prepare 0.2 percent wt aqueous solution, and then the surfactants are uniformly mixed according to the molar ratio of the zwitterion to the nonionic surfactant of 60:40 to obtain a surfactant binary complex system 3 b. Measuring oil-water interfacial tension of crude oil and the obtained solution at 50 deg.C and 4500r/min with TEXAS-500 rotary drop interfacial tension meter, wherein the equilibrium interfacial tension is 2.8x10-1mN/m。
[ COMPARATIVE EXAMPLE 4b ]
Dissolving three surfactants, namely octadecyl amide sulfobetaine, oleic acid diethanol amide and polyoxyethylene oleic acid amide, in 100000mg/L NaCl saline respectively, stirring for 30 minutes to prepare 0.05 percent by weight of aqueous solution, and then uniformly mixing the surfactants according to the molar ratio of 80:2:18 of the surfactants to obtain a surfactant binary complex system 4 b. Measuring oil-water interfacial tension of crude oil and the obtained solution at 50 deg.C and 4500r/min with TEXAS-500 rotary drop interfacial tension meter, wherein the equilibrium interfacial tension is 4.2x10-2mN/m。

Claims (7)

1. A surfactant binary compound system comprises a betaine surfactant and a nonionic surfactant, wherein the molar ratio of the betaine surfactant to the nonionic surfactant is 1 (0.01-100), the betaine surfactant is represented by the following molecular general formula A, and the nonionic surfactant is represented by the following molecular general formula B:
Figure 517997DEST_PATH_IMAGE001
wherein X is any one of propionate, ethylsulfonate, propylsulfonate and hydroxypropyl sulfonate, and R is1Is C6~C24Alkyl, alkenyl, aryl radicals ofAny one of (1), R2，R3Is C1~C4Any one of the hydrocarbyl or substituted hydrocarbyl of (a); the nonionic surfactant is selected from at least one of nonyl phenol acetic acid diethanolamide, octadecyl diethanolamide and oleic acid diethanolamide; the preparation method of the surfactant binary compound system comprises the following steps:
(1) dissolving a betaine surfactant in NaCl saline to obtain a solution I;
(2) dissolving a nonionic surfactant in NaCl saline to obtain a solution II;
(3) uniformly mixing the solution I and the solution II according to the molar ratio of the betaine surfactant to the nonionic surfactant of 1 (0.01-100) to obtain a surfactant binary compound system;
the concentration of the NaCl brine is 20000-150000 mg/L, and the oil-water interfacial tension between the surfactant binary compound system and the underground crude oil is 3.8 multiplied by 10-3mN/m or 2.1X10-3mN/m or 4.1X10-4mN/m。
2. The surfactant binary complex system according to claim 1, wherein R is2Is C1~C4Any one of alkyl groups.
3. The surfactant binary complex system according to claim 1, wherein R is3Is C1~C4Any one of alkyl groups.
4. A method for preparing the surfactant binary complex system according to any one of claims 1 to 3, comprising the following steps:
(1) dissolving a betaine surfactant in water to obtain a solution I;
(2) dissolving a nonionic surfactant in water to obtain a solution II;
(3) and uniformly mixing the solution I and the solution II according to the molar ratio of the betaine surfactant to the nonionic surfactant of 1 (0.01-100) to obtain the surfactant binary compound system.
5. Use of the surfactant dual complexing system according to any one of claims 1 to 3 in oil field oil recovery.
6. The application of the surfactant binary complex system in oil recovery in oil fields according to claim 5, wherein the solvent used in the surfactant binary complex system is pure water or brine, and the mineralization degree of the aqueous solution is 20000-150000 mg/L calculated by NaCl.
7. The application of the surfactant binary complex system in oil recovery in oil fields according to claim 5, wherein in the surfactant binary complex system solution, the surfactant binary complex system mass concentration is 0.01-0.5% by total mass of the betaine surfactant and the nonionic surfactant.
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