CN108671850B - Fluorine-silicon surfactant containing single perfluorooctyl and oil-based foam oil displacement agent - Google Patents
Fluorine-silicon surfactant containing single perfluorooctyl and oil-based foam oil displacement agent Download PDFInfo
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Abstract
The specification provides a fluorosilicone surfactant containing single perfluorooctyl and an oil-based foam oil displacement agent. The fluorine-silicon surfactant containing the single perfluorooctyl has the following structure: a perfluorooctyl group, two short-chain alkyls and polyethoxy with a specific polymerization degree are connected on a silicon atom; the other end of the polyethoxy group is linked to stearic acid via an ester group. Tests show that the fluorosilicone surfactant with the structure is excellent in foam stabilizing performance, and is particularly used in emulsion taking oil as a continuous phase. Meanwhile, the surfactant also has good foaming performance. Therefore, the fluorine-silicon surfactant can be used for preparing a foam oil displacement agent (the foaming amount can reach more than 300 percent, and the foam half-life period is more than 72 hours) which has good foaming and foam stabilizing characteristics at the same time.
Description
Technical Field
The specification relates to a fluorosilicone surfactant containing single perfluorooctyl and an oil-based foam oil displacement agent.
background
The foam fluid has been applied to oil field development for over 40 years at home and abroad, and the foam fluid is applied to various aspects of oil and gas field development such as conventional oil displacement, profile control, steam foam flooding, steam foam huff and puff, circulating steam foam flooding, water drainage and gas production of water-containing gas wells, sand washing and well flushing, well drilling, profile control, water plugging, acidification, cement well cementation, fracturing and the like, and has a positive effect.
A large number of practices show that foam flooding is an important means for protecting oil layers, preventing oil layer pollution and improving oil and gas yield. With the increasing acceptance of foam technology, foam flooding means and foam flooding agent are one of the main pumping technologies for tertiary oil recovery.
In oil fields in China, a large number of low-permeability water-sensitive oil fields exist, the oil field stratum is mostly narrow in passage and extremely low in permeability, and oil reservoirs are difficult to move in the stratum; and stratum constitution is mostly water sensitive stratum such as montmorillonite, meets water inflation, blocks narrow passageway originally, leads to oil recovery work to go on. Therefore, conventional water flooding or water-based foam flooding cannot be adopted for the oil layer.
Oil-based foam flooding is an effective means to solve the above problems. Foam displacement agents with oil (usually diesel or mineral oil) as the continuous phase are called oil-based foam displacement agents. Compared with water-based foam oil displacement agents, the oil-based foam oil displacement agent has the main characteristics of high temperature resistance, strong inhibition, salt resistance and pollution resistance, good lubricity, capability of effectively avoiding the problem that stratum expansion such as montmorillonite caused by water flooding blocks a channel and lightening the damage to an oil-gas layer.
However, the oil phase has a very low surface energy compared with water, and is difficult to form foam and not stable, so that conventional foaming agents used in water-based oil displacement agents completely fail to meet the requirements for forming suitable oil-based foams. For this reason, technicians are required to develop suitable oil displacing agents for oil-based foam systems. At present, the existing oil-based foam oil displacement agent mainly comprises oil, water, a foaming agent, a foam stabilizer, an emulsifier and the like; the system is an emulsion foam system with similar oil property, which is formed by taking water as a disperse phase and oil as a continuous medium and adding materials such as an emulsifier, a foaming agent, a foam stabilizer and the like, and is also called as an inverse emulsion foam oil displacement agent, wherein the volume ratio of oil to water is (50-80): (50-20) or so. For oil-based foam oil displacement agents, the foaming amount (foamability) and the foam half-life (foam stability) are two most important indexes, and technicians are always searching for a scheme for improving the foaming amount and the foam half-life of the oil displacement agent (generally, the foaming amount is more than 300%, the half-life is more than 1h, and the application value is certain, and preferably more than 10h), wherein the improvement of the foam half-life is the most outstanding problem. For example, the formulations developed by Tianyun et al are: 1.5 percent of AE-a and AE-b compounded foaming agent and 0.5 percent of modified ethylene propylene type Polymer (PHB) are added into 100ml of diesel oil; the test results showed that the foaming volume reached 500ml (corresponding to 500%) and the half-life was 353 s. The formula developed by the talking people and the like is as follows: 0.1 percent of foaming agent DRI-YF-1 and 2 percent of foam stabilizer DRI-YW-1 are added into 100ml of diesel oil to be the main components of the oil-based foam drilling fluid; the test results show that the foaming volume reaches 500ml and the half-life period is 630 s.
Disclosure of Invention
The purpose of the specification is to provide a fluorosilicone surfactant with excellent foam stabilizing performance, and an oil-based foam oil displacement agent.
In order to achieve the above object, the present specification provides a fluorosilicone surfactant containing a monoperfluorooctyl group, wherein the fluorosilicone surfactant has a structural formula as follows:
wherein R is1selected from methyl or ethyl; r2Selected from methyl or ethyl; n is 6 to 22.
The fluorosilicone surfactant has very outstanding foam stabilizing performance, especially in an oil-based foam system.
in the above fluorosilicone surfactant, preferably, n is 10 to 18.
In the above fluorosilicone surfactant, preferably, R1and R2And is simultaneously methyl; or, R1And R2And is also ethyl.
The specification also provides a preparation method of the fluorosilicone surfactant, wherein the method comprises the following steps:
Reacting perfluorooctane with dialkyl chlorosilane to obtain a product A; reacting the product A with ethylene oxide to obtain a product B; and reacting the product B with stearic acid to obtain the fluorosilicone surfactant.
In the above production method, the amount of the dialkylchlorosilane to be used is preferably 1 to 1.5 times the amount of the perfluorooctane based on the molar amount of the perfluorooctane.
In the above production method, it is preferable that the amount of ethylene oxide is 10 to 20 times the amount of perfluorooctane based on the molar amount of perfluorooctane.
In the above production method, the amount of stearic acid is preferably 1 to 1.2 times the amount of perfluorooctane based on the molar amount of perfluorooctane.
In the above production method, preferably, in the step of producing the product A, the reaction temperature is 50 to 70 ℃ and the reaction time is 0.5 to 4 hours.
In the above preparation method, preferably, in the step of preparing the product B, the reaction temperature is 150 ℃ and 170 ℃, and the reaction time is 0.5-4 h.
In the above production method, preferably, in the step of reacting the product B with stearic acid, the reaction temperature is 80 to 120 ℃ and the reaction time is 0.5 to 4 hours.
in the above production method, preferably, in the step of producing the product B, a ring-opening polymerization reaction and a substitution reaction are included, and the ring-opening polymerization reaction may be an acidic environment or a basic environment. Further preferably, the pH of the acidic environment is 1-3. More preferably, the acid used in the acidic environment is concentrated sulfuric acid.
In the above preparation method, preferably, after the reaction in the corresponding step is finished, the product a and/or the product B is not separated from the reaction system after the reaction in the corresponding step is finished, and the material is continuously fed into the reaction system for the subsequent reaction.
The specification provides an oil-based foam oil displacement agent, wherein the oil-based foam oil displacement agent contains at least one fluorosilicone surfactant containing single perfluorooctyl as shown in the following structural formula:
Wherein R is1Selected from methyl or ethyl; r2selected from methyl or ethyl; n is 6 to 22.
The oil-based foam oil-displacing agent shows a very excellent foam half-life. Tests show that the foam half-life of the oil-based foam oil displacement agent is still greatly over 1h at the conventional addition amount even if other auxiliary agents are not used.
In the above oil-based foam oil-displacing agent, preferably, n is 10 to 18.
In the above oil-based foam oil-displacing agent, preferably, R1and R2And is simultaneously methyl; or, R1And R2And is also ethyl.
In the oil-based foam oil-displacing agent, preferably, the fluorosilicone surfactant is contained in the oil-based foam oil-displacing agent in an amount of 0.1 to 10% by weight. More preferably 1 to 3%.
The specification also provides an application of the oil-based foam oil displacement agent in mineral oil exploitation; preferably in the production of mineral oil from low permeability, water sensitive oil fields.
Drawings
FIG. 1 is an IR spectrum of dimethyl-perfluorooctyl silicon-polyethoxy-stearate prepared in Experimental example 1 of this specification;
FIG. 2 is a graph showing the results of testing the foaming properties of an oil-based foam flooding system in test example 1 of the present specification;
FIG. 3 is a graph showing the results of foam stability tests of an oil-based foam flooding system in test example 1 of the present specification;
FIG. 4 is a microscopic morphology of an oil-based foam flooding system in test example 1 of this specification.
Detailed Description
In order to clearly understand the technical features, purposes and advantages of the present specification, the following detailed description will be given of the technical solutions of the present specification, but the present specification is not to be construed as limiting the implementable scope of the present specification.
The embodiment of the specification provides a fluorine-silicon surfactant containing single perfluorooctyl, and the structural formula of the surfactant is as follows:
Wherein R is1Selected from methyl or ethyl; r2Selected from methyl or ethyl; n is 6 to 22.
In the structure, n represents the average value of the number of the ethoxy repeating units, and the value range is 6-22. Because the ethoxy part is formed by ring-opening polymerization of ethylene oxide, the polymerization number (i.e. the number of ethoxy groups) has a certain distribution range (i.e. n value range), and the distribution range can be changed into integer or decimal according to the reaction conditions and the mixture ratio of reactants. Specific values can be determined in a manner conventional in the art.
The fluorosilicone surfactant with the structure belongs to a multipolymer.
The fluorine-silicon surfactant has a special structure: a perfluorooctyl group, two short-chain alkyls and polyethoxy with a specific polymerization degree are connected on a silicon atom; the other end of the polyethoxy group is linked to stearic acid via an ester group. Tests show that the fluorosilicone surfactant with the structure is excellent in foam stabilizing performance, and is particularly used in emulsion taking oil as a continuous phase. In a specific test, 2% of fluorosilicone surfactant is added into an emulsion taking oil as a continuous phase, and the foam system can still keep the foam amount more than 80% after 72 hours. It can be seen that the foam half-life is actually longer than 72 h. While conventional foam stabilizers, when used in oil-based foam systems, tend to have foam half-lives of only a few minutes, which is nearly as long as 1 hour. Therefore, the fluorosilicone surfactant provided by the embodiment has very outstanding foam stabilizing performance. In addition, a foaming experiment shows that (in a foam system with the water content of 20-50%), the foaming multiplying power of the fluorosilicone surfactant provided by the embodiment can reach more than 300% under the condition of conventional addition. Therefore, the fluorosilicone surfactant has excellent foaming performance and foam stabilizing performance, and particularly has excellent foam stabilizing performance. Therefore, the fluorosilicone surfactant can not only greatly improve the half-life period of the oil-based foam oil-displacing agent, but also solve the problem that the performance of a foaming agent and a foam stabilizer in the conventional oil-based foam oil-displacing agent is often mutually limited. Can provide a new solution for the main obstacle in the development of the oil-based foam oil displacement agent.
Based on the above properties, the fluorosilicone surfactant provided by the present embodiment can be used alone as a foaming agent component in combination with other reagents, and can also be used alone as a foam stabilizer component in combination with other reagents; or the components are used as a foaming agent component and a foam stabilizer component at the same time and are matched with other reagents for use; or as an emulsifier.
In addition, further tests show that the oil-based foam system prepared by using the fluorosilicone surfactant provided by the embodiment can obtain a foam size significantly smaller than that of the conventional scheme. Micrographs show that the foam size in this system is mainly concentrated on the micron scale (mostly around 10-15 microns). In conventional foam systems, the foam size is typically on the order of a sub-millimeter (i.e., 100 microns or more). The characteristic enables an oil-based foam system prepared by the fluorine-silicon surfactant to realize good migration in a low-permeability oil field with small gaps, and the oil-based foam system is suitable for the low-permeability oil field and is difficult to realize by a common foaming agent.
Also, the smaller the foam size, the less easily broken, which is one of the reasons why the fluorosilicone surfactant has excellent foam stabilizing properties. For example, when the foam is subjected to microscopic testing, the foam can maintain the original foam morphology for a longer time under the compression of a cover glass, which indicates that the small-sized foam has good stability and foam strength. This is another advantage of the fluorosilicone surfactant provided by this embodiment. Since the oil-based foam formed in the prior art is basically in a quasi-millimeter size which can be distinguished by naked eyes, the foam strength is not high, and therefore, when the oil-based foam is observed by a microscope, the whole foam is broken due to the squeezing action of a cover glass, and cannot be observed and photographed by the microscope. In addition, oil-based foams are electrically non-conductive and difficult to observe with an endoscope, so the reports of micrographs of oil-based foams are rare. However, this reflects precisely the general state of the art in which oil-based foams have poor strength and stability.
Further, in the process of preparing the oil-based foam system by using the fluorosilicone surfactant provided by the embodiment, the fluorosilicone surfactant also has the characteristic of easy foaming. When the foaming agent of the common oil-based foam is foamed by a mechanical method, the stirring rotating speed of the foaming agent needs to reach 3000r/min, namely the foaming needs to be implemented under the condition of high shear rate, which has very high requirements on equipment and can not be implemented by most equipment, while the fluorosilicone surfactant serving as a foaming component can realize good foaming generally at 800-.
In the fluorosilicone surfactant provided in the present embodiment, n is preferably 10 to 18. This embodiment has more pronounced foamability and foam stability than the other options.
In the fluorosilicone surfactant provided in the present embodiment, R1And R2May be simultaneously methyl; or, R1And R2May be simultaneously ethyl. The two schemes do not differ much in performance, but in view of economy, R1And R2Meanwhile, the scheme of the methyl group has more practical value.
The embodiment provides a preparation method of a fluorosilicone surfactant containing single perfluorooctyl, and the fluorosilicone surfactant has the following structural formula:
wherein R is1Selected from methyl or ethyl; r2selected from methyl or ethyl; n is 6 to 22; the preparation method comprises the following steps:
Reacting perfluorooctane with dialkyl chlorosilane to obtain a product A; reacting the product A with ethylene oxide to obtain a product B; and reacting the product B with stearic acid to obtain the fluorosilicone surfactant.
In the preparation method provided by the above embodiment, the product a is a compound in which one chlorine in the dialkylchlorosilane is substituted by a perfluorooctyl group; the product B is a compound obtained by substituting the other chlorine in the dialkylchlorosilane by polyethoxy. And the product B and stearic acid are subjected to esterification reaction, and the esterification of the terminal hydroxyl of the polyethoxy and the stearic acid can be carried out, so that the fluorosilicone surfactant is obtained.
In the preparation method provided in the present embodiment, a solvent that is conventional in the art may be used. However, in the preferred embodiment, as the main reaction raw materials including perfluorooctane, dialkylchlorosilane and ethylene oxide are all liquid, the solvent is not added basically.
In the preparation method provided by the embodiment, protective gas (nitrogen and the like) can be introduced in the reaction process, so that the reaction has better yield. In addition, the stirring can be carried out in a conventional manner, and no special requirements are imposed on the stirring speed.
In the preparation method provided by the present embodiment, the raw material ratio in preparing the product a may be set according to a conventional method. Because the dialkylchlorosilane is monosubstituted, the amount (molar amount) of perfluorooctane is generally less than that of the dialkylchlorosilane. In a preferred embodiment, the amount of the dialkylchlorosilane is 1 to 1.5 times the amount of the perfluorooctane based on the molar amount of the perfluorooctane. The reaction conditions for this step may also be set as usual. In a preferred embodiment, the reaction temperature may be 50 to 70 ℃; the reaction time may be from 0.5 to 4 hours. In most cases, this step is completed in 1-2 h. In addition, the substitution reaction is easy to carry out, and better effect can be obtained without using a catalyst. Of course, the reaction is not limited to the use of catalysts and other auxiliary reagents.
In the preparation method provided in this embodiment, when preparing the product B, an appropriate ratio can be set according to the n value of the target compound (this step determines that the product is a series of mixtures having ethoxy chains of different lengths, in this case, n is an average value of all molecules). In a preferred embodiment, ethylene oxide is used in an amount of 10 to 20 times the molar amount of perfluorooctane, based on the molar amount of perfluorooctane. This step involves the ring opening of ethylene oxide, polymerization, and substitution of one of the remaining chloro groups in the dialkylchlorosilane by an ethoxy group. The ring opening of the ethylene oxide can be acid environment ring opening or alkaline environment ring opening. In a preferred embodiment, the ring is opened using an acidic environment. The acidic environment can be realized by using conventional inorganic strong acid, such as concentrated sulfuric acid. The dosage of the strong acid is based on the pH value of 1-3. The reaction conditions for this step may be set as usual. In a preferred embodiment, the reaction temperature may be 150-170 ℃; the reaction time may be from 0.5 to 4 hours. In most cases, this step is completed in 1-2 h. The reaction is not limited to the use of other auxiliary reagents.
In the production method provided by this embodiment, in the step of subjecting the product B to esterification reaction with stearic acid, the terminal hydroxyl group of the polyethoxy group is mainly esterified with stearic acid, thereby obtaining a fluorosilicone surfactant. The reaction conditions and the amounts of the reactants may be set as usual. In a preferred embodiment, the reaction temperature is 80-120 ℃ and the reaction time is 0.5-4 h. In a preferred embodiment, stearic acid is used in an amount of 1 to 1.2 times the molar amount of perfluorooctane. No special catalyst is needed in the reaction of the step. Of course, the reaction is not limited to the use of catalysts and other auxiliary reagents. After the esterification reaction is finished, adding acid or alkali for neutralization to obtain the fluorine-silicon surfactant. The neutralizing agent may be an agent commonly used in the art. In a preferred embodiment, in order to neutralize the acidic environment, the selected alkalizing agents are sodium hydroxide and potassium hydroxide.
In the preparation method provided by the embodiment, a one-pot method can be adopted for preparation, that is, after the reaction of the corresponding step is finished, the product a and/or the product B are/is not separated from the reaction system, and the material is continuously fed into the reaction system for subsequent reaction. In a preferred embodiment, the method comprises the steps of: (1) reacting perfluorooctane with dialkyl chlorosilane at 50-70 ℃ for 1-2 h; (2) after the reaction product is acidified by strong acid and heated to 150-170 ℃, ethylene oxide is added for continuous reaction for 1-2 h; (3) adding stearic acid into the reaction product, and reacting for 1.5-2 h; (4) adjusted to neutral with sodium hydroxide.
In the preparation method provided in the present embodiment, the fluorosilicone surfactant prepared in the last step is generally used without being separated from the reaction solution. However, if necessary, it can be isolated by: after the reaction liquid containing the fluorine-silicon surfactant is adjusted to be neutral, n-hexane is added to precipitate inorganic salt (no new precipitate is generated), the inorganic salt is filtered and removed, unreacted raw materials and solvent are removed by reduced pressure distillation at 70 ℃, and then the pH value is adjusted again to obtain a final product. Of course, complete separation of such fluorosilicone surfactants (for a single molecule) with different n values is not necessary, and is difficult to achieve with existing separation techniques.
Other suitable methods for preparing the fluorosilicone surfactants described above may also be used by those skilled in the art. However, in comparison, the preparation method provided by the specification is short in flow, has low requirements on reaction environment, does not use expensive catalysts, and can realize one-pot operation; therefore, the method has obvious industrial advantages.
The embodiment provides an oil-based foam oil displacement agent, wherein the oil-based foam oil displacement agent comprises at least one fluorosilicone surfactant containing single perfluorooctyl as shown in the following structural formula:
Wherein R is1Selected from methyl or ethyl; r2selected from methyl or ethyl; n is 6 to 22.
In the present embodiment, the fluorosilicone surfactant has particularly excellent foam stabilizing performance in an emulsion foam system in which water is used as a dispersed phase and oil is used as a continuous phase. In specific tests, the foam system can still maintain the foam amount after 72h more than 80% even if other auxiliary agents (conventional foaming agents, foam stabilizers and the like) are not used at all at conventional addition amounts, which is far more than the conventional target of 1h half-life.
In addition, foaming experiments show that the foaming multiplying power can reach more than 300% in a foam system with the water content of 20-50% under the condition of not using other auxiliary agents at all.
Therefore, the oil-based foam oil displacement agent has good foaming amount and half-life period at the same time, and particularly the half-life period can reach more than 72 h. This means that the method not only can solve the problem in the art that the half-life of the oil-based foam oil-displacing agent is too short, but also is a solution in which both the foaming amount and the half-life are excellent. In the art, the foaming amount and half-life are generally considered to be difficult to combine, for example, in the two prior arts listed in the background section, both of which achieve a higher foaming amount but have too short a half-life. In the art, there are also attempts to balance the amount of foaming and the half-life, but the result is often that both are difficult to meet simultaneously. For example, in one U.S. patent, the oil-based foam drilling fluid solution described therein is: 1 percent of foaming agent DC-1250 and 1 percent of foam stabilizer SV-150 are added into 100ml of crude oil; tests have shown that the half-life is 4min, but the foam height is also only 180ml (corresponding to a foaming amount of 180%).
The existing oil-based foam oil displacement agent is usually a compound of multiple components, and the most basic is a foaming agent and a foam stabilizer (an emulsifier is also used in most cases). The foaming agent mainly plays a foaming role, and the foam stabilizer mainly delays the breaking of foam. With such conventional oil-based foam systems, there is often a conflict in performance of the separate blowing and foam stabilizers, which is a major problem that results in the difficulty in combining the foaming amount and half-life of the system. In the scheme provided by the embodiment, the fluorine-silicon surfactant with a special structure has two performances in the same compound, so that the problem is solved. May be the specific structure of the fluorine-silicon surfactant, and has the function of harmonizing the foaming function and the foam stabilizing function.
Based on the characteristic that the oil-based foam oil displacement agent provided by the embodiment has good foaming amount and half-life, the unique advantages of the oil-based foam oil displacement agent in practical application can be further expected. In the conventional oil-based foam oil displacement agent, the foaming agent and the foam stabilizer have large differences in chemical structures, functional groups and polarities, and serious chromatographic separation occurs during migration in a stratum, so that components are respectively positioned at different positions in the stratum (or the content of the components in each layer is greatly changed), the synergistic effect of the components is weakened or even lost, and the oil-based foam agent cannot achieve the expected oil displacement effect. And the oil-based foam oil-displacing agent provided by the embodiment integrates the foaming performance and the foam stabilizing performance into a whole by the fluorosilicone surfactant, and the exertion of the function of the oil-based foam oil-displacing agent is not influenced by the chromatographic separation of the stratum, so that the scheme has special advantages in the application level compared with the conventional oil-based oil-displacing agent. However, the oil-based foam oil displacement agent provided by the embodiment does not exclude the combination of the fluorosilicone surfactant and other conventional auxiliary agents. Under the compounding scheme, the fluorosilicone surfactant can still play the roles of foaming and foam stabilization, so that the influence of the chromatographic separation effect on the overall effect of the oil displacement agent can be reduced to a great extent.
In the oil-based foam oil-displacing agent provided by the present embodiment, n is 10 to 18. This embodiment has a more pronounced foaming amount and half-life than the other options.
In the oil-based foam oil-displacing agent provided by the present embodiment, R1And R2And is simultaneously methyl; or, R1And R2and is also ethyl. The two schemes do not differ much in performance, but in view of economy, R1And R2meanwhile, the scheme of the methyl group has more practical value.
In the oil-based foam oil-displacing agent provided by the present embodiment, the content of the fluorosilicone surfactant in the oil-based foam oil-displacing agent may be a conventional amount added in the art. In a preferred embodiment, the content of the fluorine-silicon surfactant in the oil-based foam oil-displacing agent is 0.1-10% by weight. In another embodiment, the content of the fluorosilicone surfactant in the oil-based foam oil displacement agent is 1-3% by weight.
In the above oil-based foam oil-displacing agent, preferably, the oil-based foam oil-displacing agent has a wax content of less than 2.5%.
The embodiment of the specification also provides application of the oil-based foam oil displacement agent in mineral oil exploitation; preferably in the production of mineral oil from low permeability, water sensitive oil fields.
Examples of the invention
The following experimental examples may provide reference for those having ordinary skill in the art to practice the present invention or verify the effects. These examples do not limit the scope of the claims.
Experimental example 1
Placing 40g of perfluorooctane and 12g of dimethylchlorosilane in a reactor, introducing nitrogen for protection, stirring for 1.5h at the temperature of 60 ℃, adding concentrated sulfuric acid (to enable the pH to reach about 2) into the system, heating to 150 ℃, slowly adding 60g of ethylene oxide, continuing to react for 1.5h, cooling to about 100 ℃, adding 28g of stearic acid for reaction for 1.5h, adding sodium hydroxide to adjust the pH value to 7, and obtaining the liquid containing the fluorosilicone surfactant (dimethyl-perfluorooctyl silicon-polyethoxy-stearate).
The number average n of the polyethoxy repeat units in this example was found to be 16.6 by test and calculation.
Infrared characterization
because the n value in the prepared dimethyl-single perfluorooctyl silicon-polyethoxy-stearate is in a data range and the molecular weight is not a single result, a very complex fragment structure can be formed in a mass spectrum and cannot be analyzed, so that the mass spectrum identification is not suitable; nuclear magnetism also has similar problems. For this purpose, the experiment was still characterized by infrared characterization, a standard manner customary in the art.
Before infrared characterization of the dimethyl-monoperfluorooctylsine-polyethoxy-stearate of experimental example 1 above, the dimethyl-monoperfluorooctylsine-polyethoxy-stearate was isolated from the reaction solution in the following manner: after salifying the fluorosilicone surfactant (adding sodium hydroxide to adjust the pH value to 7), adding n-hexane to precipitate inorganic salt (adding until no new precipitate is generated), filtering to remove the inorganic salt, distilling at 70 ℃ under reduced pressure to remove unreacted raw materials and solvents, and then adjusting the pH value again to obtain the final product, namely dimethyl-perfluorooctylsiloxane-polyethoxy-stearate. The obtained IR spectrum is shown in FIG. 1.
The resolution of the ir spectrum (fig. 1) is as follows:
At 2870cm-1About 1395cm, there is C-H stretching vibration-1And 1365cm-1Bending vibration with methyl group, and 1365cm-1The intensity of the peak is greater, thus demonstrating that dimethylchlorosilane has modified perfluorooctane. At 2921cm-1，2848cm-1antisymmetric stretching vibration of the methylene group at 1560cm-1The carboxylic acid salt ion has an antisymmetric stretching vibration absorption peak, thereby proving that stearic acid is modified. Therefore, the infrared spectrogram can prove that the product synthesized by the experimental example is dimethyl-perfluorooctyl silicon-polyethoxy-stearate.
Experimental example 2
placing 40g of perfluorooctane and 9.4g of dimethylchlorosilane in a reactor, introducing nitrogen for protection, stirring for 1.5h at 60 ℃, adding concentrated sulfuric acid (to ensure that the pH value reaches about 2), heating to 150 ℃, slowly adding 40g of ethylene oxide, continuing to react for 1.5h, cooling to about 100 ℃, adding 25g of stearic acid for reaction for 1.5h, adding sodium hydroxide for regulating the pH value to 7, and obtaining the liquid containing dimethyl-perfluorooctyl silicon-polyethoxy-stearate.
Through testing and calculation, the average value n of the number of the polyethoxy repeating units in the embodiment is 12.5.
Experimental example 3
Placing 40g of perfluorooctane and 9.4g of dimethylchlorosilane in a reactor, introducing nitrogen for protection, stirring for 1.5h at 60 ℃, adding concentrated sulfuric acid (to ensure that the pH value reaches about 2), heating to 150 ℃, slowly adding 55g of ethylene oxide, continuing to react for 1.5h, cooling to about 100 ℃, adding 26g of stearic acid for reaction for 1.5h, adding sodium hydroxide for regulating the pH value to 7, and obtaining the liquid containing dimethyl-perfluorooctyl silicon-polyethoxy-stearate.
through testing and calculation, the average value n of the number of the polyethoxy repeating units in the embodiment is 15.3.
Experimental example 4
Placing 40g of perfluorooctane and 14g of dimethylchlorosilane in a reactor, introducing nitrogen for protection, stirring for 1.5h at 60 ℃, adding concentrated sulfuric acid (to ensure that the pH value reaches about 2) into the system, heating to 150 ℃, slowly adding 80g of ethylene oxide, continuing to react for 1.5h, cooling to about 100 ℃, adding 39g of stearic acid for reaction for 1.5h, adding sodium hydroxide for regulating the pH value to 7, and obtaining the liquid containing dimethyl-mono-perfluorooctyl silicon-polyethoxy-stearate.
through testing and calculation, the average value n of the number of the polyethoxy repeating units in the embodiment is 18.0.
Experimental example 5
Placing 40g of perfluorooctane and 11g of dimethylchlorosilane in a reactor, introducing nitrogen for protection, stirring for 1.5h at 60 ℃, adding concentrated sulfuric acid (to ensure that the pH value reaches about 2) into the system, heating to 150 ℃, slowly adding 62g of ethylene oxide, continuing to react for 1.5h, cooling to about 100 ℃, adding 28g of stearic acid for reaction for 1.5h, adding sodium hydroxide for regulating the pH value to 7, and obtaining the liquid containing dimethyl-perfluorooctylsilicon-polyethoxy-stearate.
The number average n of the polyethoxy repeat units in this example was found to be 16.7 by test and calculation.
Experimental example 6
Placing 40g of perfluorooctane and 12g of dimethylchlorosilane in a reactor, introducing nitrogen for protection, stirring for 1.5h at the temperature of 60 ℃, adding concentrated sulfuric acid (to enable the pH to reach about 2), heating to 150 ℃, slowly adding 70g of ethylene oxide, continuing to react for 1.5h, cooling to about 100 ℃, adding 26g of stearic acid for reaction for 1.5h, adding sodium hydroxide to adjust the pH value to 7, and obtaining the liquid containing dimethyl-perfluorooctyl silicon-polyethoxy-stearate.
Through testing and calculation, the average value n of the number of the polyethoxy repeating units in the embodiment is 17.3.
Test example 1
The oil-based foam oil displacement system prepared from the dimethyl-monoperfluorooctylsine-polyethoxy-stearate prepared in the experimental example 1 comprises the following specific steps:
The fluorosilicone surfactant was added to a white oil foam system (low wax system) of varying water content for foaming and foam stability testing.
The foaming performance was tested as follows:
(1) Compounding white oil and water according to different proportions, wherein the specific proportions are as follows: oil/water (95/5; 90/10; 85/15; 80/20; 75/25; 70/30; 65/35; 60/40; 55/45; 50/50) to obtain solutions of 10 different oil-water ratios.
(2) 50mL of the above solution was taken, and 1g of dimethyl-monoperfluorooctylsine-polyethoxy-stearate obtained in Experimental example 1 was added to the above solution system.
(3) The emulsification and the foaming are simultaneously realized by mechanical stirring, the stirring speed is 1000r/min, and the stirring time is 5 min.
(4) And slowly pouring the obtained foam system into a measuring cylinder, and measuring the foam height to obtain a foaming rate result.
All the tests are carried out at least three times of parallel experiments, and the test results are the average values of 3 effective test results. The results are plotted as a histogram of water content and expansion ratio, as shown in FIG. 2.
As can be seen from fig. 2, when the water content is greater than (equal to or greater than) 20%, the expansion ratio requirement of 300% required for the oil-based foam can be achieved.
The foam stabilizing performance was tested as follows:
The foam stability of the foam system whose foaming performance was tested, and the test results are shown in FIG. 3. As can be seen in fig. 3: after 72h, the foam retention rate of the oil-based system with different water contents still reaches more than 85%, namely the foam half-life period is more than 72h (which is far higher than the requirement of 1 h). The foam stabilizing performance of the foam stabilizer meets the oil displacement requirement.
Fig. 4 is a microscopic image of the above-described foam system at 100 times magnification (foam system with a water content of 30%), and it can be seen that:
1. The average size of the foam in the oil-based foam system is about 10-15 microns (micron level), and the size is much smaller than that of the foam formed by a common foaming agent (most of common foams are in quasi-millimeter level, namely, the size is far larger than more than 100 microns), so that compared with the foam formed by the common foaming agent, the foam system can realize good migration in a low-permeability oil field with small gaps, is suitable for the low-permeability oil field, and is difficult to realize by the common foam system;
2. The foam can still keep the original foam appearance under the extrusion of the cover glass, which shows that the foam has good stability and foam strength and is beneficial to oil displacement of oil fields.
Claims (18)
1. a fluorine-silicon surfactant containing single perfluorooctyl is characterized in that the fluorine-silicon surfactant has the following structural formula:
Wherein R is1Selected from methyl or ethyl; r2Selected from methyl or ethyl; n is 6 to 22;
The preparation method of the fluorosilicone surfactant comprises the following steps:
Reacting perfluorooctane with dialkyl chlorosilane to obtain a product A;
reacting the product A with ethylene oxide to obtain a product B;
And reacting the product B with stearic acid to obtain the fluorosilicone surfactant.
2. The fluorosilicone surfactant of claim 1, wherein n in the above structural formula is 10 to 18.
3. The fluorosilicone surfactant of claim 1, wherein R is1And R2And is simultaneously methyl; or, R1And R2and is also ethyl.
4. a method for preparing a fluorosilicone surfactant according to any one of claims 1 to 3, comprising the steps of:
Reacting perfluorooctane with dialkyl chlorosilane to obtain a product A;
Reacting the product A with ethylene oxide to obtain a product B;
And reacting the product B with stearic acid to obtain the fluorosilicone surfactant.
5. The method for producing a fluorosilicone surfactant according to claim 4, wherein the amount of the dialkylchlorosilane is 1 to 1.5 times the amount of the perfluorooctane based on the molar amount of the perfluorooctane.
6. The method according to claim 4, wherein the amount of ethylene oxide is 10 to 20 times that of perfluorooctane.
7. the method according to claim 4, wherein the amount of stearic acid is 1 to 1.2 times that of perfluorooctane.
8. the process according to claim 4, wherein the reaction temperature in the step of preparing the product A is 50 to 70 ℃ and the reaction time is 0.5 to 4 hours.
9. The method as claimed in claim 4, wherein the reaction temperature is 150 ℃ to 170 ℃ and the reaction time is 0.5 to 4 hours in the step of preparing the product B.
10. The process according to claim 4, wherein the esterification of the product B with stearic acid is carried out at a temperature of 80 to 120 ℃ for a period of 0.5 to 4 hours.
11. The production method according to claim 4, wherein the product A and/or the product B are not separated from the reaction system after the reaction in the corresponding step is completed, and the reaction system is continuously fed for a subsequent reaction.
12. The oil-based foam oil displacement agent is characterized by comprising at least one fluorosilicone surfactant containing single perfluorooctyl as shown in the following structural formula:
Wherein R is1selected from methyl or ethyl; r2Selected from methyl or ethyl; n is 6 to 22;
The preparation method of the fluorosilicone surfactant comprises the following steps:
Reacting perfluorooctane with dialkyl chlorosilane to obtain a product A;
reacting the product A with ethylene oxide to obtain a product B;
And reacting the product B with stearic acid to obtain the fluorosilicone surfactant.
13. the oil-based foam oil-displacing agent according to claim 12, wherein n in the above structural formula is 10 to 18.
14. The oil-based foam oil-displacing agent according to claim 12, wherein R is1And R2And is simultaneously methyl; or, R1And R2And is also ethyl.
15. the oil-based foam oil-displacing agent according to claim 12, wherein the content of the fluorosilicone surfactant in the oil-based foam oil-displacing agent is 0.1 to 10% by weight.
16. The oil-based foam oil-displacing agent according to claim 15, wherein the content of the fluorosilicone surfactant in the oil-based foam oil-displacing agent is 1 to 3% by weight.
17. Use of the oil-based foam oil-displacing agent as claimed in any one of claims 12 to 16 for the production of mineral oil.
18. The use of claim 17, wherein the oil-based foam oil displacement agent is used in the production of mineral oil in a hypotonic, water-sensitive oil field.
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| CN114075429A (en) * | 2020-08-20 | 2022-02-22 | 东营麦克卓尔石油化工有限公司 | Gas-to-oil foam drilling fluid and preparation method and application thereof |
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| EP0394963A1 (en) * | 1989-04-25 | 1990-10-31 | Shin-Etsu Chemical Co., Ltd. | Fluorine-containing surfactant and process for producing the same |
| US6815040B2 (en) * | 2000-10-27 | 2004-11-09 | 3M Innovative Properites Company | Optical elements comprising a polyfluoropolyether surface treatment |
| CN101343358A (en) * | 2008-08-20 | 2009-01-14 | 南京德美世创化工有限公司 | End capping polyether prepared with end hydroxyl radical polyether and preparation thereof |
| CN101653708A (en) * | 2008-08-18 | 2010-02-24 | 中国中化集团公司 | Disilane surfactant, preparation thereof and use thereof |
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| EP0394963A1 (en) * | 1989-04-25 | 1990-10-31 | Shin-Etsu Chemical Co., Ltd. | Fluorine-containing surfactant and process for producing the same |
| US6815040B2 (en) * | 2000-10-27 | 2004-11-09 | 3M Innovative Properites Company | Optical elements comprising a polyfluoropolyether surface treatment |
| CN101653708A (en) * | 2008-08-18 | 2010-02-24 | 中国中化集团公司 | Disilane surfactant, preparation thereof and use thereof |
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