CN113943564A - Compound ultra-low interfacial tension surfactant and preparation method thereof - Google Patents
Compound ultra-low interfacial tension surfactant and preparation method thereof Download PDFInfo
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- CN113943564A CN113943564A CN202111244465.8A CN202111244465A CN113943564A CN 113943564 A CN113943564 A CN 113943564A CN 202111244465 A CN202111244465 A CN 202111244465A CN 113943564 A CN113943564 A CN 113943564A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Abstract
The invention discloses a compound surfactant with ultra-low interfacial tension, which comprises the following raw materials by weight percent of 100%, 0.1% -2% of fluorine-containing gemini surfactant, 10% -30% of alpha-alkenyl sulfonate, 1% -5% of peregal O-20, 10% -20% of hexadecyl/octadecyl betaine and the balance of water. The ultra-low interfacial tension surfactant is mutually soluble with water, has high dissolving speed and strong mineralization resistance, and can reduce the surface tension of the water from 73.4 mN.m < -1 > to 15.3 mN.m < -1 > by using the content of 0.1 percent; the interfacial tension of the crude oil and the water is reduced to below 0.008 mN.m < -1 >, and the ultralow interfacial tension is achieved. In addition, the ultra-low interfacial tension surfactant is neutral, has good compatibility with bactericides, flocculating agents and other medicaments, and has no corrosion to equipment and pipelines.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to a compound surfactant with ultralow interfacial tension and a preparation method thereof.
Background
As oil fields are exploited, water-flooding oil recovery has become difficult, and because the recovery rate of water flooding is low, the use of chemical flooding to increase the recovery rate of crude oil has become the main research direction for oil field development. The surfactant flooding in the chemical flooding is more favored by people, and has great application prospect in tertiary oil recovery application of oil fields.
The gemini surfactant is a novel surfactant, the molecule of which at least contains 2 hydrophilic groups and 2 hydrophobic groups, and the hydrophilic groups or the positions close to the hydrophilic groups are linked together through chemical bonds by linking groups. The hydrophilic group may be a cationic, anionic, zwitterionic or polar group; the linking group is various and can be a hydrocarbon chain or a polar group; the hydrophobic moiety is typically a hydrocarbon chain, a fluorocarbon chain, or the like. Compared with the traditional surfactant, the gemini surfactant has the advantages of strong micelle forming capability, low critical micelle concentration, high efficiency of reducing surface tension, low Kraft point, good water solubility, good compatibility with other surfactants and the like, and is called as a new-generation surfactant.
The fluorine-containing surfactant is a surfactant in which hydrogen atoms in a hydrophobic group of a hydrocarbon chain are partially or completely replaced by fluorine atoms, and is one of surfactants having the highest surface activity so far. The fluorine surfactant has unique properties of three high and two hydrophobic (high surface activity, high thermal stability, high chemical stability, hydrophobic and oleophobic).
The fluorine-containing gemini surfactant has the advantages of both hydrocarbon gemini surfactants and common fluorine-containing surfactants, can overcome the defects of the hydrocarbon gemini surfactants and the common fluorine-containing surfactants, has higher surface activity, and is receiving more and more extensive attention.
At present, the research on the fluorine-containing gemini surfactant is more, but the practical application group of the fluorine-containing gemini surfactant in oil field development is less. Therefore, based on the special performance of the fluorine-containing gemini surfactant, the invention provides the composite surfactant which has ultralow interfacial tension and can be applied to oilfield exploitation.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides the surfactant with the ultralow interfacial tension, which can greatly reduce the surface tension of water and the oil-water interfacial tension, reduce the water injection pressure, start the displacement of residual oil and improve the oil recovery rate.
In order to realize the purpose, the invention discloses a compound ultra-low interfacial tension surfactant, which adopts the following technical scheme:
a compound surfactant with ultra-low interfacial tension comprises the following raw materials by weight percentage of 100%,
specifically, the structural formula of the fluorine-containing gemini surfactant is as follows,
wherein Rf is C8F17And n is 2 or 5.
Specifically, the hexadecyl/octadecyl betaine is hexadecyl dimethyl hydroxypropyl sulfobetaine and octadecyl dimethyl hydroxypropyl sulfobetaine, and the ratio of the hexadecyl dimethyl hydroxypropyl sulfobetaine to the octadecyl dimethyl hydroxypropyl sulfobetaine is 1: 7.
Compared with the prior art, the invention has the beneficial effects that:
the ultra-low interfacial tension surfactant is mutually soluble with water, has high dissolving speed and strong mineralization resistance, and can ensure that the surface tension of the water is from 73.4 mN.m.-1Reduced to 15.3 mN.m-1(ii) a The interfacial tension of the crude oil and the water is reduced to 0.008 mN.m-1In the following, an ultra-low interfacial tension is achieved. In addition, the ultra-low interfacial tension surfactant is neutral, has good compatibility with bactericides, flocculating agents and other medicaments, and has no corrosion to equipment and pipelines.
H in C-H in the fluorocarbon surfactant is replaced by F, the bond energy between C and F is larger, the fluorocarbon surfactant is not easy to polarize, and the radius of fluorine ions is larger than that of hydrogen ions, so that the C-C bond is protected due to the shielding effect of fluorine atoms, and the fluorocarbon surfactant has extremely high surface activity and can more effectively reduce the surface tension of liquid than a hydrocarbon surfactant. Gemini surfactants have CMC values that are 1-3 orders of magnitude lower than conventional surfactants, and thus have much higher surface tension lowering efficiency than conventional surfactants. The invention adopts the fluorocarbon gemini surfactant, has the advantages of common fluorocarbon surfactant and gemini surfactant, two ion head groups are connected by a connecting group through a chemical bond, thereby causing the tight connection of the two surfactant ion head groups, leading the hydrocarbon chains to generate strong interaction more easily, namely strengthening the hydrophobic bonding force between the hydrocarbon chains, and the repulsion tendency between the ion head groups is greatly weakened by the chemical bond force to form ultrahigh surfactant. Therefore, the addition of a very small amount is effective for reducing the surface tension. After the fluorocarbon gemini surfactant and the hydrocarbon surfactant are compounded, a coordination effect is generated, so that the surface tension of the system is further reduced.
Improving the oil washing efficiency of crude oil is one of the main approaches for improving the recovery efficiency by surfactant flooding. This is usually achieved by increasing the capillary number, which is inversely related to the oil-water interfacial tension. In the oil displacement process, the oil-water interfacial tension is reduced to an ultra-low level, the number of capillaries is increased by several orders of magnitude, the retained crude oil starts to flow, and the oil displacement efficiency of the crude oil is improved.
After residual oil in rock pores meets injected surfactant, the surfactant is adsorbed on the oil surface, so that the oil-water interfacial tension is effectively reduced, the elasticity of an oil-water interfacial film is enhanced, oil drops are easy to deform, the Jamin effect is weakened, the oil drops in the rock pores are easy to migrate and aggregate into an oil zone, and the oil displacement efficiency is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a compound surfactant with ultralow interfacial tension, which is mainly applied to the technical field of oil fields, and particularly improves the stratum wettability, reduces the oil-water interfacial tension, peels off an oil film on a pore channel, and enlarges an effective water injection channel, thereby improving the seepage environment, improving the water phase permeability, reducing the water injection pressure and achieving the purpose of increasing the injection.
The compound ultra-low interfacial tension surfactant comprises the following raw materials by weight percentage of 100 percent,
wherein the structural formula of the fluorine-containing gemini surfactant is as follows,
wherein Rf is C8F17And n is 2 or 5.
Preferably, the cetyl/stearyl betaine is cetyl dimethylhydroxypropyl sulfobetaine and stearyl dimethylhydroxypropyl sulfobetaine in a ratio of 1: 7.
The preparation method of the compound ultra-low interfacial tension surfactant comprises the following steps,
in the case of the example 1, the following examples are given,
firstly, adding 72Kg of water into a reaction kettle, heating to 50 ℃, starting stirring, keeping the stirring speed at 100-inch and 200rpm, sequentially adding 15Kg of alpha-alkenyl sulfonate, 1Kg of peregal O-20, 6Kg of hexadecyl dimethyl hydroxypropyl sulfobetaine and 6Kg of octadecyl dimethyl hydroxypropyl sulfobetaine, uniformly stirring, and cooling to 30 ℃ to obtain the surfactant with ultra-low interfacial tension.
In the case of the example 2, the following examples are given,
firstly adding 71.8Kg of water into a reaction kettle, heating to 50 ℃, starting stirring, keeping the stirring speed at 100-200rpm, sequentially adding 0.2Kg of fluorine-containing gemini surfactant, 15Kg of alpha-alkenyl sulfonate, 1Kg of peregal O-20, 6Kg of hexadecyl dimethyl hydroxypropyl sulfobetaine and 6Kg of octadecyl dimethyl hydroxypropyl sulfobetaine, uniformly stirring, and cooling to 30 ℃ to obtain the ultra-low interfacial tension surfactant.
In the case of the example 3, the following examples are given,
adding 68.8Kg of water into a reaction kettle, heating to 50 ℃, starting stirring, keeping the stirring speed at 100-200rpm, sequentially adding 0.2Kg of fluorine-containing gemini surfactant, 20Kg of alpha-olefin sulfonate, 3Kg of peregal O-20, 1Kg of hexadecyl dimethyl hydroxypropyl sulfobetaine and 7Kg of octadecyl dimethyl hydroxypropyl sulfobetaine, uniformly stirring, and cooling to 30 ℃ to obtain the ultra-low interfacial tension surfactant.
In the case of the example 4, the following examples are given,
firstly, adding 60.5Kg of water into a reaction kettle, heating to 50 ℃, starting stirring, keeping the stirring speed at 100-200rpm, sequentially adding 0.5Kg of fluorine-containing gemini surfactant, 20Kg of alpha-alkenyl sulfonate, 3Kg of peregal O-20, 2Kg of hexadecyl dimethyl hydroxypropyl sulfobetaine and 8Kg of octadecyl dimethyl hydroxypropyl sulfobetaine, uniformly stirring, and cooling to 30 ℃ to obtain the ultra-low interfacial tension surfactant.
In the case of the example 5, the following examples were conducted,
firstly, adding 64Kg of water into a reaction kettle, heating to 50 ℃, starting stirring, keeping the stirring speed at 100-inch and 200rpm, sequentially adding 1Kg of fluorine-containing gemini surfactant, 15Kg of alpha-alkenyl sulfonate, 4Kg of peregal O-20, 2Kg of hexadecyl dimethyl hydroxypropyl sulfobetaine and 8Kg of octadecyl dimethyl hydroxypropyl sulfobetaine, uniformly stirring, and cooling to 30 ℃ to obtain the ultra-low interface tension surfactant.
The ultra-low interfacial tension surfactants prepared in examples 1-5 above were tested for surface tension and oil-water interfacial tension using the hanging piece method, and for oil-water interfacial tension using the rotating drop method. The surface tension and the oil-water interfacial tension are tested by preparing 0.1 percent solution from the field water of Jiangsu oil field.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (5)
1. A compound surfactant with ultra-low interfacial tension is characterized in that: comprises the following raw materials by weight percentage of 100 percent,
the balance of water.
2. The compound ultra-low interfacial tension surfactant as claimed in claim 1, wherein: the structural formula of the fluorine-containing gemini surfactant is as follows,
wherein Rf is C8F17And n is 2 or 5.
3. The compound ultra-low interfacial tension surfactant as claimed in claim 1, wherein: the hexadecyl/octadecyl betaine is hexadecyl dimethyl hydroxypropyl sulfobetaine and octadecyl dimethyl hydroxypropyl sulfobetaine, and the ratio of the hexadecyl/octadecyl betaine to the octadecyl dimethyl hydroxypropyl sulfobetaine is 1: 7.
4. A preparation method for preparing the compound ultra-low interfacial tension surfactant as described in any one of claims 1 to 3, which is characterized in that: the method comprises the following steps of putting water into a reaction kettle, stirring and heating, then sequentially adding a fluorine-containing gemini surfactant, alpha-alkenyl sulfonate, peregal O-20 and hexadecyl/octadecyl betaine, uniformly stirring, and cooling to obtain the product.
5. The preparation method for preparing the compound ultra-low interfacial tension surfactant as defined in any one of claims 1 to 3, according to claim 4, is characterized in that: the heating temperature is 50 ℃, and the cooling temperature is 30 ℃.
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