CN115010930A - Amphiphilic nano-particle containing sulfonate hydrophilic unit and preparation method and application thereof - Google Patents
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Abstract
The invention discloses amphiphilic nano particles containing a sulfonate hydrophilic unit, and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1: taking ethanol as a solvent, adding a silane coupling agent I, a silane coupling agent II, a catalyst and deionized water, uniformly stirring, and heating to perform hydrolysis co-condensation reaction; the silane coupling agent I is phenyl trimethoxy silane or phenyl triethoxy silane, and the silane coupling agent II is mercaptopropyl trimethoxy silane or mercaptopropyl triethoxy silane; s2: adding hydrogen peroxide into the reaction system of the step S1 to oxidize the mercapto group into a sulfonic group; s3: adding sodium hydroxide into the reaction system of the step S2 to convert the sulfonic acid group into sodium sulfonate; s4: and after the reaction is finished, filtering and drying to obtain white powder, namely the amphiphilic nano-particles containing the sulfonate hydrophilic units. The invention can prepare the nano-particles with the amphiphilic property, and the nano-particles can be used as a foam stabilizer, so that the stability of foam can be obviously improved.
Description
Technical Field
The invention relates to the technical field of foam flooding, in particular to amphiphilic nanoparticles containing a sulfonate hydrophilic unit, and a preparation method and application thereof.
Background
Foams are unstable systems with a liquid as the continuous phase and a gas as the dispersed phase. In the stratum migration process, the Jamin effect generated by the foam can greatly improve the apparent viscosity of the fluid, increase the swept area and obviously improve the crude oil recovery rate. However, the instability of the foam is related to the effective generation and stabilization of the foam, and the practical application effect of the foam flooding is influenced.
In order to improve foam stability, researchers have conducted a great deal of research around the screening of foam systems. The generation and the stabilization of the foam depend on the existence of a surfactant, and the surfactant can be spontaneously adsorbed on the surface of a liquid film, reduce the interfacial tension, enhance the elasticity of the liquid film and reduce the surface free energy, so that the stability of the foam is improved. The single surfactant has poor foam stabilizing effect, and the compounding of different types of surfactants can generate a synergistic effect so as to improve the foam stability. However, the surfactant is reversibly adsorbed on the foam liquid film, and the liquid film has disadvantages such as discontinuity and fluctuation, and has high fluidity and is easily aggregated and defoamed. Research shows that the nano particles can obviously improve the foam stability. The flexible rigid film formed by the nanoparticles which are adsorbed on the gas-liquid interface of the foam in a staggered mode can reduce the drainage speed, the disproportionation speed and the gas diffusion speed of the foam, and therefore the effect of enhancing the stability of the foam is achieved. For example, an anionic surfactant SDS is compounded with aluminum hydroxide nanoparticles, SDS can be adsorbed on the surfaces of the aluminum hydroxide nanoparticles through electrostatic action, so that the surfaces of the particles are covered with a layer of alkyl chains, and the particles are adsorbed on an air-liquid interface in a particle monolayer form after the hydrophilicity is weakened, so that the foam stabilizing effect is good. In aqueous solution, the nano particles and the surfactant are subjected to synergistic association to form a special vesicle structure, so that the foam stability of the foam is enhanced. The nano particles are also arranged between the bubble layers and in the Plateau boundary, and form a three-dimensional network structure in the continuous phase, so that the liquid phase flow resistance is increased, the thinning and subsequent cracking of the foam are delayed, and the foam stability is enhanced. However, the nanoparticles themselves are hydrophilic, resulting in poor stability at the gas-liquid interface. Under high temperature or high salt conditions, this poor stability will cause the particles to break away from the gas-liquid interface and lose the foam stabilizing effect. Further research shows that the amphiphilic nano particles can be spontaneously gathered at a gas-liquid interface to play a good foam stabilizing effect. However, the method of preparing amphiphilic nanoparticles has the following problems: 1) the preparation method is complex, and the process flow is difficult to industrialize; 2) the preparation process is uncontrollable, so that the amphipathy of the nano particles is difficult to effectively regulate.
Disclosure of Invention
In view of the above problems, the present invention aims to provide amphiphilic nanoparticles containing a sulfonate hydrophilic unit, and a preparation method and an application thereof.
The technical scheme of the invention is as follows:
in one aspect, an amphiphilic nanoparticle containing a sulfonate hydrophilic unit is provided, and the structure of the amphiphilic nanoparticle is as follows:
in the formula: r 1 is-C 6 H 5 ；R 2 is-SO 3 - ，R 3 is-CH 2 CH 2 CH 2 -。
Preferably, R 1 And R 2 The molar ratio of (a) to (b) is 1:3 to 3: 1.
In another aspect, there is provided a method for preparing amphiphilic nanoparticles containing sulfonate hydrophilic units, comprising the steps of:
s1: taking ethanol as a solvent, adding a silane coupling agent I, a silane coupling agent II, a catalyst and deionized water, uniformly stirring, and heating to perform hydrolysis co-condensation reaction; the silane coupling agent I is phenyl trimethoxy silane or phenyl triethoxy silane, and the silane coupling agent II is mercaptopropyl trimethoxy silane or mercaptopropyl triethoxy silane;
s2: adding hydrogen peroxide into the reaction system of the step S1 to oxidize the mercapto group into a sulfonic group;
s3: adding sodium hydroxide into the reaction system of the step S2 to convert the sulfonic acid group into sodium sulfonate;
s4: and after the reaction is finished, filtering and drying to obtain white powder, namely the amphiphilic nano-particles containing the sulfonate hydrophilic units.
Preferably, in step S1, the molar ratio of the first silane coupling agent to the second silane coupling agent is 1:3 to 3: 1.
Preferably, in step S1, the catalyst is tetramethylammonium hydroxide, and the amount of the added tetramethylammonium hydroxide is 0.01-0.03 g/mL.
Preferably, in step S1, the molar ratio of the deionized water to the two silane coupling agents is 3: 1.
Preferably, in step S1, the hydrolysis co-condensation reaction is carried out at a reaction temperature of 50-80 ℃ for a reaction time of 18-36 h.
Preferably, in step S2, the amount of hydrogen peroxide added is 2 to 4 g/mL.
Preferably, in step S2, the reaction time of hydrogen peroxide is 12 hours or longer.
On the other hand, the application of the amphiphilic nanoparticles containing the hydrophilic unit of the sulfonate in the foam stabilizer is also provided, and the amphiphilic nanoparticles containing the hydrophilic unit of the sulfonate are the amphiphilic nanoparticles containing the hydrophilic unit of the sulfonate described in any item above, or the amphiphilic nanoparticles containing the hydrophilic unit of the sulfonate prepared by the preparation method described in any item above.
The invention has the beneficial effects that:
the nano-particles have amphipathy by taking a sulfonate group as a hydrophilic unit and taking a benzene ring as a hydrophobic unit; in the preparation process, the hydrophilicity and hydrophobicity of the nano-particles can be effectively adjusted by adjusting the charge ratio of the two coupling agents and the reaction time of the sulfydryl oxidation reaction, so that the amphipathy of the nano-particles is effectively adjusted and controlled; when the amphiphilic nano-particles are used as a foam stabilizer, the stability of the foam for oil displacement can be improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a graph showing the results of IR spectroscopy on nanoparticles of example 2;
FIG. 2 is a graph showing the results of contact angle measurements of the product of example 2 with different reaction times of hydrogen peroxide;
FIG. 3 is a schematic diagram showing the results of the foam stabilizing property test of the amphiphilic nanoparticles of the present invention;
FIG. 4 is a graph showing the results of tests of the effect of different degrees of mineralization on foam properties;
FIG. 5 is a graph showing the results of foam property tests of the examples.
Detailed Description
The invention is further illustrated with reference to the following figures and examples. It should be noted that, in the present application, the embodiments and the technical features of the embodiments may be combined with each other without conflict. It is noted that, unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The use of the terms "comprising" or "including" and the like in the present disclosure is intended to mean that the elements or items listed before that term include the elements or items listed after that term and their equivalents, without excluding other elements or items.
In one aspect, the invention provides an amphiphilic nanoparticle containing a sulfonate hydrophilic unit, wherein the structure of the amphiphilic nanoparticle is as follows:
in the formula: r is 1 is-C 6 H 5 ；R 2 is-SO 3 - ，R 3 is-CH 2 CH 2 CH 2 -。
In a specific embodiment, R 1 And R 2 The molar ratio of (a) to (b) is 1:3 to 3: 1.
In another aspect, the present invention further provides a method for preparing an amphiphilic nanoparticle containing a sulfonate hydrophilic unit, including the following steps:
s1: taking ethanol as a solvent, adding a silane coupling agent I, a silane coupling agent II, a catalyst and deionized water, uniformly stirring, and heating to perform hydrolysis co-condensation reaction; the silane coupling agent I is phenyl trimethoxy silane or phenyl triethoxy silane, and the silane coupling agent II is mercaptopropyl trimethoxy silane or mercaptopropyl triethoxy silane;
in a specific embodiment, the molar ratio of the first silane coupling agent to the second silane coupling agent is 1:3 to 3: 1. The catalyst is tetramethylammonium hydroxide, and the addition amount of the tetramethylammonium hydroxide is 0.01-0.03 g/mL. The molar ratio of the deionized water to the two silane coupling agents is 3: 1. The reaction temperature for hydrolysis co-condensation reaction is 50-80 ℃, and the reaction time is 18-36 h.
S2: adding hydrogen peroxide into the reaction system of the step S1 to oxidize the mercapto group into a sulfonic group;
in a specific embodiment, the adding amount of the hydrogen peroxide is 2-4 g/mL, and the time for the hydrogen peroxide to participate in the reaction is greater than or equal to 12 h.
S3: adding sodium hydroxide into the reaction system of the step S2 to convert the sulfonic acid group into sodium sulfonate;
s4: and after the reaction is finished, filtering and drying to obtain white powder, namely the amphiphilic nano-particles containing the sulfonate hydrophilic units.
In the above examples, phenyltrimethyoxy silane and mercaptopropyltrimethyoxy silane were used as raw materials to prepare amphiphilic nanoparticles, wherein the mercapto group in the mercaptopropyltrimethyoxy silane was oxidized by hydrogen peroxide to generate a sulfonate group, thereby providing hydrophilicity to the nanoparticles; benzene rings in phenyltrimethyl (ethoxy) silicane are utilized to provide hydrophobicity for the nanoparticles; the hydrophilicity and hydrophobicity of the nano-particles can be effectively adjusted by adjusting the time of the hydrogen peroxide participating in the reaction and the charge ratio of the two coupling agents, the time of the hydrogen peroxide participating in the reaction in the embodiment is more than or equal to 12 hours so as to enable the amphiphilic nano-particles to reach a hydrophilic state, and other times of the hydrogen peroxide participating in the reaction can be adopted according to the requirements of the hydrophilicity and hydrophobicity when the invention is used. The reaction principle of the amphiphilic nanoparticles is as follows:
in the formula: r 4 is-OCH 3 or-OC 2 H 5 。
The amphiphilic nano particles can improve the foam stabilizing performance of the foam stabilizer, and can be firmly adsorbed on the surfaces of bubbles to form a densely arranged adsorption layer mainly through the hydrophobicity of benzene rings and the hydrophilicity of sulfonic acid groups of the amphiphilic nano particles, so that a foam liquid film is thickened, the mechanical strength is increased, the liquid drainage and gas diffusion speed is reduced, and the foam stability is enhanced. Under the condition that the structure of the product, i.e. the structure of the amphiphilic nanoparticles of the present invention, is definite, a person skilled in the art can select other raw materials, reaction conditions, etc. to generate the product through a compound generation mechanism, and the preparation method of the above embodiment is not a limitation of the present invention.
Example 1
Phenyltriethoxysilane (14.4g) was weighed out and dissolved in 180mL ethanolAdding 0.2mL of tetramethylammonium hydroxide and 3mL of deionized water, and stirring at 60 ℃ for reaction; after 2h, (3-mercaptopropyl) triethoxysilane (4.76g) is added into the reaction system, and the reaction is continued for 20 h; then, 20mL of hydrogen peroxide was added to the reaction system, and the reaction was carried out for 12 hours. After the reaction is finished, adjusting the pH value to be neutral by NaOH, filtering and drying the product to obtain white powder, namely R 1 :R 2 Amphiphilic nanoparticles at 3:1 (theoretical).
Example 2
Weighing phenyltriethoxysilane (9.65g) and dissolving in 180mL ethanol, adding 0.2mL tetramethylammonium hydroxide and 3mL deionized water, and stirring at 60 deg.C for reaction; after 2h, (3-mercaptopropyl) triethoxysilane (9.54g) is added into the reaction system, and the reaction is continued for 20 h; then 20mL of hydrogen peroxide was added to the reaction system and reacted for 12h, wherein contact angles were measured with samples taken at 0h, 3h, 5h and 12 h. After the reaction is finished, adjusting the pH value to be neutral by NaOH, filtering and drying the product to obtain white powder, namely R 1 :R 2 1:1 (theoretical) amphiphilic nanoparticles.
Example 3
Weighing phenyl triethoxysilane (4.8g) and dissolving in 180mL ethanol, adding 0.2mL tetramethyl ammonium hydroxide and 3mL deionized water, and stirring at 60 ℃ for reaction; after 2h, (3-mercaptopropyl) triethoxysilane (14.28g) is added into the reaction system, and the reaction is continued for 20 h; then, 20mL of hydrogen peroxide was added to the reaction system, and the reaction was carried out for 12 hours. After the reaction is finished, adjusting the pH value to be neutral by NaOH, filtering and drying the product to obtain white powder, namely R 1 :R 2 1:3 (theoretical) amphiphilic nanoparticles.
An infrared light experiment was performed on amphiphilic nanoparticles containing sulfonate hydrophilic units, wherein the infrared spectrum of example 2 is shown in fig. 1. From fig. 1, it can be seen that: 3450cm -1 Stretching vibration peak at hydroxyl, 2574cm -1 700cm at the peak of the thiol group for absorption of stretching vibration -1 、736cm -1 And 1430 and 1594cm -1 The characteristic peak in the range is attributed to oscillation of a benzene ring framework, and is 1000-1150 cm -1 The strong absorption band shown in the position belongs to the characteristic peak of Si-O-Si in the nanometer particle framework. 2574cm -1 In the form of mercapto groupsAnd (4) a characteristic peak which disappears after the hydrogen oxide oxidation. The characteristic peak of stretching and bending vibration peak of S ═ O in sulfonic group in the amphiphilic nano particle containing sulfonic acid radical hydrophilic unit is coincided with the characteristic peak area of Si-O, so that the characteristic peak is not obvious, but the hydrophilicity of the sulfonic group causes 3450cm -1 The vibration peak of hydroxyl groups is strengthened. The characteristic peaks show that the nanoparticles contain two characteristic units, namely phenyl and sulfonate, and the product structure is clear.
The contact angle of each sample obtained in example 2 was measured, and the results are shown in fig. 2, in which fig. 2(a) is the contact angle test result of the sample in which hydrogen peroxide was reacted for 0h, fig. 2(b) is the contact angle test result of the sample in which hydrogen peroxide was reacted for 3h, fig. 2(c) is the contact angle test result of the sample in which hydrogen peroxide was reacted for 5h, and fig. 2(d) is the contact angle test result of the sample in which hydrogen peroxide was reacted for 12 h. As can be seen from fig. 2, the contact angle of the nanoparticles decreases from 108.5 ° to 88 ° with the increase of the reaction time, and the nanoparticles are converted from weak hydrophobicity to weak hydrophilicity, and have amphiphilicity. The results show that: the hydrophilicity and hydrophobicity of the nano-particles can be regulated and controlled by regulating the time for hydrogen peroxide to participate in the reaction.
The foam stabilizing properties of the sulfonate-containing hydrophilic unit nanoparticles prepared in example 2 were tested: preparing the obtained nano particles into a dispersion liquid with a certain concentration, adding a certain amount of sodium dodecyl sulfate and sodium chloride, and performing ultrasonic dispersion for 30min to obtain a nano enhanced foam system with the concentration of the sodium dodecyl sulfate of 5000mg/L and the concentration of the sodium chloride of 10000 mg/L. The foam morphology was observed under a microscope at room temperature with a magnification of 40 and the foam stabilization results are shown in fig. 3, where fig. 3(a) is a test result of a foam system without amphiphilic nanoparticles of the present invention and fig. 3(b) is a test result of a nano-enhanced foam system with amphiphilic nanoparticles of the present invention added. As can be seen from fig. 3(a), the foam liquid film thickness gradually decreases with increasing liquid discharge time, the foam volume gradually increases, and the foam becomes unstable and collapses. As can be seen from fig. 3(b), the volume of the foam is reduced, the liquid film is thickened, and the foam is more stable after the amphiphilic nanoparticles of the present invention are added. The good amphipathy of the nano particles enables the nano particles to be firmly adsorbed on the surfaces of bubbles to form a densely arranged adsorption layer, so that a foam liquid film becomes thick, the mechanical strength is increased, the liquid drainage and gas diffusion speed is slowed, and the foam stability is enhanced.
The impact of different degrees of mineralization on the foam properties was evaluated by the waring blender method at 50 ℃ for the foam system made of the amphiphilic nanoparticles of example 2, and the results are shown in fig. 4. As can be seen from fig. 4, the volume of the foam system to which the amphiphilic nanoparticles of the present invention were added was not much different from the volume of the foam system to which the amphiphilic nanoparticles of the present invention were not added, and the tendency of the volume of the foam system to decrease was smaller than that of the foam system to which the amphiphilic nanoparticles of the present invention were not added as the degree of mineralization increased; the foam half-life period of the foam system added with the amphiphilic nano particles is obviously improved compared with that of the foam system not added with the amphiphilic nano particles, the foam half-life period reaches more than 60min under the condition of 10g/L mineralization degree, and is about 10min higher than that of the foam system not added with the amphiphilic nano particles under the condition of 50g/L mineralization degree. In addition, the nanoparticles obtained in examples 1 to 3 were used to stabilize the foam, and the volume of the foam was not much different from that of the SDS foam, but the half-life of the foam of the present invention was significantly improved, and the results are shown in FIG. 5. Therefore, the amphiphilic nano-particles containing the sulfonate hydrophilic unit can obviously improve the foam stabilizing performance.
In conclusion, the invention can utilize benzene ring to provide hydrophobic property for the nano-particles, utilize the sulfonate group to provide hydrophilicity for the nano-particles, and utilize the amphiphilic property of the nano-particles to improve the foam stabilizing property of the foam stabilizer, and has obvious progress compared with the prior art.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. An amphiphilic nanoparticle containing a sulfonate hydrophilic unit, wherein the structure of the amphiphilic nanoparticle is as follows:
in the formula: r 1 is-C 6 H 5 ；R 2 is-SO 3 - ，R 3 is-CH 2 CH 2 CH 2 -。
2. The amphiphilic sulfonate hydrophilic unit-containing nanoparticle of claim 1, wherein R is 1 And R 2 The molar ratio of (a) to (b) is 1:3 to 3: 1.
3. The method of preparing amphiphilic nanoparticles containing sulfonate hydrophilic units according to claim 1 or 2, comprising the steps of:
s1: taking ethanol as a solvent, adding a silane coupling agent I, a silane coupling agent II, a catalyst and deionized water, uniformly stirring, and heating to perform hydrolysis co-condensation reaction; the silane coupling agent I is phenyl trimethoxy silane or phenyl triethoxy silane, and the silane coupling agent II is mercaptopropyl trimethoxy silane or mercaptopropyl triethoxy silane;
s2: adding hydrogen peroxide into the reaction system of the step S1 to oxidize the mercapto group into a sulfonic group;
s3: adding sodium hydroxide into the reaction system of the step S2 to convert the sulfonic acid group into sodium sulfonate;
s4: and after the reaction is finished, filtering and drying to obtain white powder, namely the amphiphilic nano-particles containing the sulfonate hydrophilic units.
4. The method for preparing amphiphilic nanoparticles containing sulfonate hydrophilic units according to claim 3, wherein in step S1, the molar ratio of the first silane coupling agent to the second silane coupling agent is 1:3 to 3: 1.
5. The method for preparing amphiphilic nanoparticles containing sulfonate hydrophilic units according to claim 3, wherein in step S1, the catalyst is tetramethylammonium hydroxide, and the addition amount of the tetramethylammonium hydroxide is 0.01-0.03 g/mL.
6. The method for preparing amphiphilic nanoparticles containing sulfonate hydrophilic units as claimed in claim 3, wherein in step S1, the molar ratio of the deionized water to the two silane coupling agents is 3: 1.
7. The method for preparing amphiphilic nanoparticles containing sulfonate hydrophilic units as claimed in claim 3, wherein in step S1, the reaction temperature for the hydrolysis co-condensation reaction is 50-80 ℃ and the reaction time is 18-36 h.
8. The method for preparing amphiphilic nanoparticles containing sulfonate hydrophilic units as claimed in claim 3, wherein in step S2, the addition amount of hydrogen peroxide is 2-4 g/mL.
9. The method of claim 8, wherein the time for the hydrogen peroxide to participate in the reaction is greater than or equal to 12 hours in step S2.
10. The application of amphiphilic nanoparticles containing hydrophilic units of sulfonate in foam stabilizers is characterized in that the amphiphilic nanoparticles containing hydrophilic units of sulfonate are the amphiphilic nanoparticles containing hydrophilic units of sulfonate in claim 1 or 2 or the amphiphilic nanoparticles containing hydrophilic units of sulfonate prepared by the preparation method in any one of claims 3 to 9.
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