CN109731526B - Fluorine-containing surfactant compound, preparation method and application thereof - Google Patents
Fluorine-containing surfactant compound, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a fluorine-containing surfactant compound, a preparation method and application thereof. The fluorosurfactant has the structure shown in formula I. The preparation method comprises the following steps: (1) reacting a perfluorooctanoyl chloride compound with n-heptylamine to obtain a compound shown in a formula II, (2) reacting the compound shown in the formula II with a chloroheptanoic acid compound to obtain a compound shown in a formula III, and (3) reacting the compound shown in the formula III with alkali to obtain the fluorine-containing surfactant shown in the formula I. The fluorine-containing surfactant has good hydrophobic and oleophobic characteristics, can obviously convert the liquid wettability of a reservoir into gas wettability so as to keep the surface of a crack clean, reduce the adsorption of a shaft working fluid on the surface of the reservoir, and can obviously improve the fluidity of the fluid particularly in narrow gaps and croup of a hypotonic reservoir, thereby achieving the purpose of increasing the yield.
Description
Technical Field
The invention relates to a fluorine-containing surfactant for changing the surface wettability of a shale reservoir, a preparation method and application thereof, belonging to the technical field of petrochemical industry for improving the recovery ratio of shale gas.
Technical Field
Surfactants are substances that significantly reduce the surface tension of a solvent at very low concentrations. The molecular structure of the compound has the common characteristic that the molecules of the compound are composed of two parts, namely a non-polar hydrophobic group and a polar hydrophilic group. The molecular fragments or groups with the structure and the property which are opposite are positioned at two ends of the same molecule and are connected by chemical bonds to form an asymmetric and polar structure. Therefore, the substances are not hydrophilic or lipophilic but not the overall hydrophilic or lipophilic characteristics. So that the detergent can play a series of roles of emulsification, dispersion, solubilization, washing and the like.
The fluorocarbon surfactant is used as the most important special surfactant, and fluorine (F) elements are introduced into the molecules of the fluorocarbon surfactant, so that the fluorocarbon surfactant has more, more and more unique and more excellent performances than the common surfactant, the use value of the fluorocarbon surfactant is greatly improved, and the fluorocarbon surfactant is highly valued and widely applied in various industries. Structurally, the hydrogen atoms in conventional hydrocarbon surfactants are partially or completely replaced by fluorine atoms, which are the most electronegative of all elements, and the van der waals atomic radius is the smallest except hydrogen, with the lowest atomic polarizability. Therefore, the single bond formed by fluorine atoms has larger energy than that formed by carbon atoms and other atoms, and the bond length is shorter, so that the structure is more stable than a hydrocarbon structure, the hydrophobic effect of the fluorocarbon chain is far stronger than that of the hydrocarbon chain, and the interaction force among the fluorocarbon chains is weak. The special structure endows the oil-soluble organic silicon oil with high surface activity, high heat-resistant stability, high chemical stability and excellent hydrophobic and oleophobic properties, has incomparable effects of other surfactants, can be applied to special application fields which cannot be met by other surfactants, and has wide market prospect. However, most of the fluorocarbon surfactants which can be applied to the market in the process of oil and gas field development to change the wettability of the reservoir are high polymer type (such as CN101449026), the fluorocarbon surfactants of the type have large relative molecular mass, are easy to block porous media of the reservoir, reduce the permeability of the reservoir, are particularly serious for low permeability reservoirs, and the high polymer is difficult to biodegrade, thus causing environmental pollution to the stratum.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel micromolecule fluorine-containing surfactant capable of being applied to change the surface wettability of a shale reservoir, and the surfactant has the advantages of high polymer fluorocarbon surfactant, small molecular weight, difficult blockage of porous media, strong biodegradability and the like.
The invention also provides a preparation method and application of the fluorine-containing surfactant.
The technical scheme of the invention is as follows:
a fluorosurfactant having the structure of formula I:
wherein M is K, Na or Li.
The above-mentioned fluorosurfactants have a triple-chain hydrophobic or oleophobic structure. Has good hydrophobic and oleophobic characteristics.
According to the present invention, a method for preparing a fluorosurfactant compound comprises the steps of:
(1) in the presence of a catalyst, in an absolute ethyl alcohol solvent, reacting a perfluorooctanoyl chloride compound with n-heptylamine to prepare a compound shown in a formula II,
(2) reacting a compound of formula II with a chloroheptanoic acid compound in an acetone solvent in the presence of a catalyst to obtain a compound of formula III,
(3) reacting a compound of formula III with a base in an acetone solvent in the presence of a base to produce a fluorosurfactant compound of formula I:
wherein M is K, Na or Li.
According to the present invention, it is preferable that the reaction raw materials and reagents used in the above steps (1) to (4) are analytically pure and have the above purity. The reactions described in steps (1) to (4) are carried out in glass reaction vessels, respectively.
According to the present invention, preferably, the catalyst of step (1) is selected from pyridine or dimethylformamide;
according to the present invention, preferably, the catalyst in step (2) is selected from pyridine or dimethylformamide.
According to the present invention, it is preferred that the reaction of step (1) comprises one or more of the following conditions:
a1, the amount ratio of perfluorooctanoyl chloride to catalyst material is 9-15:1, more preferably 10-12: 1;
a2, wherein the mass ratio of the perfluorooctanoyl chloride to the n-heptylamine is 1: 2;
a3, carrying out the reaction under the condition of stirring, wherein the reaction temperature is 65-75 ℃; preferably, the reaction time is 2 to 3 hours;
a4, after the reaction is finished, carrying out suction filtration, then carrying out rotary evaporation to remove the solvent, and drying to obtain the compound product of the formula II.
According to the present invention, it is preferred that the reaction of step (2) comprises one or more of the following conditions:
b1 the ratio of the amount of formula II to catalyst material is 9-15:1, more preferably 10-12: 1;
b2, the mass ratio of the compound of the formula II to the chloroheptanoic acid compound is 1: 1-2; more preferably, the ratio of the compound of the formula II to the chloroheptanoic acid is 1: 1.2-1.6.
b3, carrying out the reaction under the stirring condition, wherein the reaction temperature is 50-55 ℃, and the pH value of the reaction system is 8; preferably, the reaction time is 8 to 10 hours;
b4, performing suction filtration after the reaction is finished, then performing rotary evaporation to remove the solvent, and drying to obtain a compound product of the formula III;
according to the present invention, it is preferred that the reaction of step (3) comprises one or more of the following conditions:
c 1: the mass ratio of the compound shown in the formula III to the alkali is 1: 2-1.6;
c 2: the alkali is added in the form of 30-60% aqueous solution by mass;
c 3: the alkali is sodium hydroxide, potassium hydroxide or lithium hydroxide;
c 4: the reaction is carried out under the condition of stirring, and the reaction temperature is 25-30 ℃; preferably, the reaction time is 3 to 4 hours;
c 5: and (3) after the reaction is finished, removing the solvent by rotary evaporation, adding alcohol, and filtering to remove chloride to obtain a finished product of the compound shown in the formula I.
In the above-mentioned process for preparing the compound of formula I according to the present invention, all solvents are used in dissolved amounts, unless otherwise specifically limited.
The reaction route of the invention is as follows:
the application of the fluorine-containing surfactant compound is used for changing the surface wettability of a shale reservoir to improve the shale gas recovery rate.
The application of the fluorine-containing surfactant compound of the invention comprises the following steps:
the fluorine-containing surfactant compound shown in the formula I and deionized water are prepared into a solution, and the solution and the shaft working fluid are pressed into a well together, so that the reservoir is reversed from liquid wettability to gas wettability, and the adsorption of the shaft working fluid on the surface of the formation is reduced. The fluorosurfactant compound and deionized water are formulated into a solution that requires sealed storage if not immediately used. Further preferably, the fluorosurfactant compound of the present invention is used in a solution with a mass fraction of 0.07-1.2% prepared by adding deionized water.
The invention has the following excellent effects:
1. the fluorine-containing surfactant compound provided by the invention has a triple-chain hydrophobic or oleophobic structure and good hydrophobic and oleophobic characteristics, can remarkably reverse the liquid wettability of a reservoir stratum into gas wettability (see fig. 2-14), so as to keep the fracture surface clean, reduce the adsorption of a shaft working fluid on the surface of the stratum, and particularly can obviously improve the fluidity of the fluid in narrow gaps and hole roars of a low-permeability reservoir stratum, thereby achieving the purpose of increasing the yield. The conventional fluorocarbon surfactant only has a hydrophobic or oleophobic single-chain structure, and cannot achieve the purpose of the invention.
2. The fluorine-containing surfactant compound provided by the invention is easy to prepare, the yield is over 86 percent, the highest yield can be close to 90 percent, the fluorine-containing surfactant compound can be prepared into an aqueous solution with water in any proportion, the surface of a reservoir can be changed from liquid wettability to gas wettability, the application effect is good, and the fluorine-containing surfactant compound is beneficial to field popularization.
3. The preparation method of the fluorine-containing surfactant is simple to operate, mild in reaction conditions, few in by-products and easy to control, and the key point is that water cannot exist in the first-step reaction.
Drawings
Fig. 1 shows the spreading state and the contact angle size θ of the water phase on the surface of the core which is not treated by the fluorosurfactant, where θ is 35 °;
fig. 2 spreading state and contact angle size θ of the aqueous phase on the surface of the core after treatment with the fluorosurfactant solution described in this example 1, θ being 101 °;
fig. 3 spreading state and contact angle size θ, 125 for the aqueous phase on the surface of the core after treatment with the fluorosurfactant solution described in this example 2;
fig. 4 spreading state and contact angle size θ, 128 ° -of the aqueous phase on the core surface after treatment with the fluorosurfactant solution described in this example 3;
fig. 5 spreading state and contact angle size θ, 133 ° of the aqueous phase on the surface of the core after treatment with the fluorosurfactant solution described in this example 4;
fig. 6 shows the spreading state and contact angle size θ of the water phase on the surface of the core after treatment with the fluorosurfactant solution described in this example 5, θ being 134 °;
fig. 7 spreading state and contact angle size θ, 133 ° of the aqueous phase on the surface of the core after treatment with the fluorosurfactant solution described in this example 6;
fig. 8 shows the spreading state and contact angle size θ, θ is 0, of an oil phase on a shale surface that has not been treated with a gas-moisture reversal agent;
fig. 9 spreading state and contact angle size θ, 73 ° -of the oil phase on the core surface after treatment with the fluorosurfactant solution described in this example 1;
fig. 10 spreading state and contact angle size θ, 95 ° -of the oil phase on the core surface after treatment with the fluorosurfactant solution described in this example 2;
fig. 11 spreading state and contact angle size θ, which is 108 °, of the oil phase on the core surface after treatment with the fluorosurfactant solution described in this example 3;
fig. 12 spreading state and contact angle size θ, 115 ° -of the oil phase on the core surface after treatment with the fluorosurfactant solution described in this example 4;
fig. 13 spreading state and contact angle size θ, 121 ° -of the oil phase on the core surface after treatment with the fluorosurfactant solution described in this example 5;
fig. 14 spreading state and contact angle size θ, 120 ° -of the oil phase on the core surface after treatment with the fluorosurfactant solution described in this example 6;
wherein the water phase is deionized water, the oil phase is n-hexadecane, and the fluorine-containing surfactant solution is prepared in situ.
FIG. 15 is an IR spectrum of a fluorocarbon surfactant compound prepared as in example 1; the abscissa is the wavelength (nm) and the ordinate is the% transmittance.
Detailed Description
The present invention will be described in more detail with reference to examples, which are not intended to limit the scope of the present invention, but are commercially available. In the examples, "%" is a mass percentage unless otherwise specified.
Example 1
A fluorosurfactant compound is prepared by the steps of:
(1) 138g (1.2mol) of n-heptylamine and 4.8g (0.06mol) of pyridine are taken to be put in a round-bottom flask with magnetons, absolute ethyl alcohol is taken as a solvent, 259g (0.6mol) of perfluorooctanoyl chloride is slowly dripped by a constant-pressure dropping funnel under ice bath, after the dripping is finished, the temperature is raised to 75 ℃ after 2 hours of reaction, the reaction is carried out for 8 hours under oil bath, and the compound shown in the formula II is obtained after suction filtration, desolventization and drying.
(2) 153g (0.3mol) of the compound of the formula II prepared in the step (1) is put into a round-bottom flask with magnetons, an appropriate amount of acetone is used as a solvent, the temperature is raised to 55 ℃, after the compound is dissolved, 49.2g (0.3mol) of chloroheptanoic acid is slowly dripped into the mixture by using a constant-pressure dripping funnel, after the dripping is finished, the reaction is carried out for 8 hours under the condition of oil dissolution, and the compound of the formula III is obtained by standing, filtering, concentrating, crystallizing and drying.
(3) 63.7g (0.1mol) of the compound of formula III prepared in step (2) was put into a glass reaction kettle, and 9g (0.12mol) of 50% aqueous sodium hydroxide solution was slowly added into the kettle using acetone as a solvent under stirring using a constant pressure dropping funnel, after 2 hours of reaction, the solvent and water were removed by rotary evaporation, concentrated, crystallized, and dried to obtain a compound of formula I (66.5 g). The yield was 86.2%.
The structure characterization infrared spectrum is shown in FIG. 15.
And (3) performance measurement:
the fluorosurfactant prepared in this example was added with deionized water to make a 0.5% solution, the pretreated core was soaked in the 0.5% fluorosurfactant solution and aged for 48 hours, dried at 90 ℃ and left at room temperature for 8 hours, and the contact angle between the water phase and the oil phase on the core surface was measured using a JC2000D contact angle measuring instrument, the contact angle between the water phase and the oil phase being 101 ° (as shown in fig. 2) and the contact angle between the oil phase and the oil phase being 73 ° (as shown in fig. 9). The water phase used was deionized water and the oil phase was n-hexadecane (the same applies below).
Example 2
Fluorosurfactants were prepared as described in example 1, except that: and adding deionized water into the prepared fluorine-containing surfactant to prepare a 0.7% solution, soaking the core for 48 hours by using the solution, drying the solution, standing the solution at normal temperature for 8 hours, and measuring the contact angle of the treated water phase and the oil phase on the surface of the core, wherein the contact angle of the water phase is 125 degrees (shown in figure 3), and the contact angle of the oil phase is 95 degrees (shown in figure 10).
Example 3
Fluorosurfactants were prepared as described in example 1, except that: and adding deionized water into the prepared fluorine-containing surfactant to prepare a 1.0% solution, soaking the core for 48 hours by using the solution, drying the core, standing the core for 8 hours at normal temperature, and measuring the contact angle of the treated water phase and the oil phase on the surface of the core, wherein the contact angle of the water phase is 128 degrees (shown in figure 4), and the contact angle of the oil phase is 108 degrees (shown in figure 11).
Example 4
Fluorosurfactants were prepared as described in example 1 except that in step (2), the amount ratio of compound of formula II to chloroheptanoic acid species was 1: 1.2. The final product of the fluorine-containing surfactant is prepared through the step (3). The yield was 86.8%.
And (3) performance measurement:
the fluorosurfactant prepared in this example was added with deionized water to make a 0.7% solution, the pretreated core was soaked in the above 0.7% fluorosurfactant solution and aged for 48 hours, dried at 90 ℃ and left at room temperature for 8 hours, and the contact angle of the treated water phase and oil phase on the core surface was measured, the water phase contact angle was 133 ° (as shown in fig. 5) and the oil phase contact angle was 115 °, as shown in fig. 12.
Example 5
Fluorosurfactants were prepared as described in example 1 except that in step (2), the amount ratio of compound of formula II to chloroheptanoic acid species was 1: 1.4. The final product of the fluorine-containing surfactant is prepared through the step (3). The yield was 88.6%.
And (3) performance measurement:
the fluorosurfactant prepared in this example was added with deionized water to make a 0.7% solution, the pretreated core was soaked in the 0.7% fluorosurfactant solution and aged for 48 hours, dried at 90 ℃ and left at room temperature for 8 hours, and the contact angle between the treated water phase and the oil phase on the core surface was measured, the water phase contact angle was 134 ° (as shown in fig. 6) and the oil phase contact angle was 121 ° (as shown in fig. 13).
Example 6
Fluorosurfactants were prepared as described in example 1 except that in step (2), the amount ratio of compound of formula II to chloroheptanoic acid species was 1: 1.6. The final product of the fluorine-containing surfactant is prepared through the step (3). The yield was 89.2%.
And (3) performance measurement:
the fluorosurfactant prepared in this example was added with deionized water to make a 0.7% solution, the pretreated core was soaked in the 0.7% fluorosurfactant solution and aged for 48 hours, dried at 90 ℃ and left at room temperature for 8 hours, and the contact angle between the treated water phase and the oil phase on the core surface was measured, the water phase contact angle was 133 ° (as shown in fig. 7) and the oil phase contact angle was 120 ° (as shown in fig. 14).
In the above examples, the fluorosurfactant solution of example 1 has a small concentration, limited hydrophobic and oleophobic abilities, and the air wetting effect is achieved in examples 2-3 with high concentrations, the stronger the wetting reversal performance is with the increase of the fluorosurfactant solution concentration, and when the concentration exceeds 0.7%, the performance change is not large, and considering the cost problem, the concentration of 0.7% is preferably used in the application; the quantitative ratio of the compound of formula II to the chloroheptanoic acid species was examined in examples 4 to 6, and as the reactant chloroheptanoic acid is more excessive, the intermediate compound of formula II reacts more sufficiently, and when the quantitative ratio thereof exceeds 1:1.4, the yield thereof does not change much.
Claims (12)
1. A fluorosurfactant compound having the structure of formula I:
wherein M is K, Na or Li.
2. A method of making a fluorosurfactant compound comprising the steps of:
(1) in the presence of a catalyst, in an absolute ethyl alcohol solvent, reacting a perfluorooctanoyl chloride compound with n-heptylamine to prepare a compound shown in a formula II,
(2) reacting a compound of formula II with a chloroheptanoic acid compound in an acetone solvent in the presence of a catalyst to obtain a compound of formula III,
(3) reacting a compound of formula III with a base in an acetone solvent in the presence of a base to produce a fluorosurfactant of a compound of formula I:
wherein M is K, Na or Li.
3. The method of claim 2, wherein the catalyst of step (1) is selected from pyridine or dimethylformamide; the catalyst in the step (2) is selected from pyridine or dimethylformamide.
4. The method of claim 2, wherein the reacting of step (1) comprises one or more of the following conditions:
a1, the weight ratio of the perfluorooctanoyl chloride to the catalyst substance is 9-15: 1;
a2, wherein the mass ratio of the perfluorooctanoyl chloride to the n-heptylamine is 1: 2;
a3, carrying out the reaction under the condition of stirring, wherein the reaction temperature is 65-75 ℃, and the reaction time is 2-3 hours;
a4, after the reaction is finished, carrying out suction filtration, then carrying out rotary evaporation to remove the solvent, and drying to obtain the compound product of the formula II.
5. The method of claim 2, wherein the amount ratio of perfluorooctanoyl chloride to catalyst material in step (1) is 10-12: 1.
6. The method of claim 2, wherein the reacting of step (2) comprises one or more of the following conditions:
b1, the quantity ratio of the formula II to the catalyst substance is 9-15: 1;
b2, the mass ratio of the compound of the formula II to the chloroheptanoic acid compound is 1: 1-2;
b3, carrying out the reaction under the stirring condition, wherein the reaction temperature is 50-55 ℃, and the pH value of the reaction system is 8; the reaction time is 8-10 hours;
b4, after the reaction is finished, carrying out suction filtration, then carrying out rotary evaporation to remove the solvent, and drying to obtain the compound product of the formula III.
7. The process of claim 2, wherein in step (2), the amount ratio of formula II to catalyst material is 10-12: 1.
8. The method for preparing a fluorosurfactant compound according to claim 2 wherein in step (2) the mass ratio of the compound of formula II to chloroheptanoic acid is 1: 1.2-1.6.
9. The method of claim 2, wherein the reacting of step (3) comprises one or more of the following conditions:
c 1: the mass ratio of the compound shown in the formula III to the alkali is 1: 2-1.6;
c 2: the alkali is added in the form of 30-60% aqueous solution by mass;
c 3: the alkali is sodium hydroxide, potassium hydroxide or lithium hydroxide;
c 4: the reaction is carried out under the condition of stirring, the reaction temperature is 25-30 ℃, and the reaction time is 3-4 hours;
c 5: and (3) after the reaction is finished, removing the solvent by rotary evaporation, adding alcohol, and filtering to remove chloride to obtain a finished product of the compound shown in the formula I.
10. Use of the fluorosurfactant compound of claim 1 to modify shale reservoir surface wettability for enhanced shale gas recovery.
11. Use of a fluorosurfactant compound according to claim 10 by:
the fluorosurfactant compound of formula I of claim 1 in solution with deionized water and pumped into the well with the wellbore servicing fluid to reverse the reservoir from liquid to gas wet and reduce the adsorption of the wellbore servicing fluid to the surface of the formation.
12. The use of the fluorosurfactant compound of claim 10 wherein the fluorosurfactant compound of formula I of claim 1 is used in a solution with a mass fraction of 0.07-1.2% with deionized water.
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