CN110845372A - Multiolefin hook type surfactant gel fracturing fluid and preparation and gel breaking methods thereof - Google Patents
Multiolefin hook type surfactant gel fracturing fluid and preparation and gel breaking methods thereof Download PDFInfo
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Abstract
The invention discloses a multiolefin hook-type surfactant gel fracturing fluid and a preparation method and gel breaking method thereof, wherein the preparation method comprises the following steps: (1) adding linolenic acid, N, N-dimethyl-1, 3-propanediamine and p-toluenesulfonic acid into a flask, heating to 130-150 ℃, reacting for 8-10 hours, and carrying out vacuum pumping under reduced pressure to obtain an intermediate. (2) And (3) adding the intermediate obtained in the step one and 3-chloro-2-hydroxypropanesulfonic acid sodium into a flask containing a mixed solvent of water and ethanol, wherein the reaction temperature is 60-80 ℃, and the reaction time is 6-8 hours, so as to obtain a crude product. (3) Vacuum drying the crude product, dissolving with ethanol, and adding petroleum ether into the ethanol betaine solution. After stirring, the petroleum ether phase was removed and the ethanol was removed using a rotary evaporator to obtain the product. (4) The product is formulated into a fracturing fluid. The multiolefin hook-type surfactant gel fracturing fluid solves the problem of incomplete self-gel breaking of the stratum of the clean fracturing fluid when meeting oil, and the gel breaking theory is novel.
Description
Technical Field
The invention relates to fracturing fluid preparation and gel breaking technology, in particular to multiolefin hook-type surfactant gel fracturing fluid and a preparation and gel breaking method thereof.
Background
The viscoelastic surfactant fracturing fluid is a clean fracturing fluid taking a viscoelastic surfactant as a main agent. The viscoelastic surfactant fracturing fluid system has the characteristics of no residue after gel breaking, good sand carrying property, good fluid loss control performance and the like, but with increasing attention to environmental protection problems and increasing drilling depth, enrichment of the viscoelastic surfactant fracturing fluid system is in the forefront. For the gel breaking technology of clean fracturing fluid, researchers think that the clean fracturing fluid system does not need to add a gel breaker, and the stratum can be automatically broken when meeting oil, but in practical application, the proportion of the fracturing fluid contacting the crude oil of the stratum is limited, and part of the clean fracturing fluid system can not break gel, so that the development of the novel fracturing fluid gel breaking technology aiming at the clean fracturing fluid has important significance for improving the economic benefit of oil field development, maintaining the stable yield of the oil field and increasing the yield.
Disclosure of Invention
In order to solve the problem that part of clean fracturing systems can not break gel due to limited proportion of the fracturing fluid contacting formation crude oil when the fracturing fluid is used for clean fracturing in the prior art, the invention aims to provide the multiolefin hook-type surfactant gel fracturing fluid and the preparation and gel breaking methods thereof. The long fatty chain of the clean fracturing fluid contains unsaturated double bonds, has a certain angle naturally, is similar to a hook shape, and is more easy to gather and intertwine with each other in the solution to form spherical micelles at a certain concentration, so that vermiform micelles are formed, the viscosity of the solution is increased, and the sand carrying capacity is improved. When the gel is broken in the later period, the unsaturated double bonds in the long fatty chain are subjected to addition reaction, so that the hydrophobic groups are changed into strong hydrophilic groups, the surfactant is subjected to hydrophobic and hydrophilic conversion, the capacity among molecules is lost, and the worm-shaped micelles and the spherical micelles are broken. The invention solves the problem of incomplete self-gel breaking of the clean fracturing fluid stratum when meeting oil.
The technical scheme adopted by the invention is as follows:
a multiolefin hook-type surfactant gel fracturing fluid, wherein the structural formula of the multiolefin hook-type surfactant gel in the fracturing fluid is as follows:
a preparation method of multiolefin hook-type surfactant gel fracturing fluid comprises the following steps:
1) mixing linolenic acid, N-dimethyl-1, 3-propanediamine and a catalyst, heating to 130-150 ℃ under the protection of nitrogen, reacting for 8-10 hours, and carrying out vacuum pumping under reduced pressure to obtain an intermediate;
2) adding sulfonate and a solvent into the intermediate, and reacting at the temperature of 60-80 ℃ for 6-8 hours under the protection of nitrogen to obtain a crude product;
3) vacuum drying the crude product, dissolving with ethanol, adding petroleum ether, stirring, removing petroleum ether phase, and removing ethanol to obtain product;
4) the product is formulated into a fracturing fluid.
As a further improvement of the invention, in the step 1), the molar ratio of the linolenic acid to the N, N-dimethyl-1, 3-propanediamine is 1 (1-1.1).
As a further improvement of the invention, in the step 1), the catalyst is sodium p-toluenesulfonate, and the addition amount is 0.5 wt%.
As a further improvement of the invention, in step 2), the sulfonate is sodium 3-chloro-2-hydroxypropanesulfonate; the molar ratio of the intermediate to the 3-chloro-2-hydroxypropanesulfonic acid sodium salt is 1 (1-1.1); in the mixed solution, the mass percentage of the intermediate and the 3-chloro-2-hydroxypropanesulfonic acid sodium salt is 25-45 wt%.
As a further improvement of the invention, in the step 2), the solvent is a mixed solution of water and ethanol, and the mass ratio of the water to the ethanol is 10 (1-3).
As a further improvement of the method, in the step 3), the mass of the crude product in the ethanol accounts for 20-40 wt%; the mass ratio of the ethanol solution of the crude product to the petroleum ether is 70-90 wt%.
The gel breaking method of the multiolefin hook-type surfactant gel fracturing fluid comprises the following steps:
adding NaHSO into fracturing fluid3And simulating the formation environment, and completing gel breaking when the gel is changed into an aqueous solution.
Optionally, the concentration of the fracturing fluid is 5-10 wt%; NaHSO3The addition amount of (B) is 3-6 wt% of the mass of the fracturing fluid.
Alternatively, the simulated formation temperature is 80 ℃ and the pH is 5.
The invention has the following advantages:
the long fatty chain of the clean fracturing fluid contains unsaturated double bonds, has a certain angle naturally, is similar to a hook shape, and is more easy to gather and intertwine with each other in the solution to form spherical micelles at a certain concentration, so that vermiform micelles are formed, the viscosity of the solution is increased, and the sand carrying capacity is improved. When the gel is broken in the later period, the unsaturated double bonds in the long fatty chain are subjected to addition reaction, so that the hydrophobic groups are changed into strong hydrophilic groups, the surfactant is subjected to hydrophobic and hydrophilic conversion, the capacity among molecules is lost, and the worm-shaped micelles and the spherical micelles are broken. The invention solves the problem of incomplete self-gel breaking of the clean fracturing fluid stratum when meeting oil.
When the multiolefin hook-type surfactant gel fracturing fluid is prepared, a natural product, namely, linolenic acid, which is a vegetable oil ester hydrolysate, is used as a basic raw material, carboxyl is modified into amide, and meanwhile, unsaturated groups are provided in a donor system, so that the multiolefin hook-type surfactant gel is prepared, and the used basic raw material and formula are environment-friendly. The long fatty chain is natural and has a certain angle, the shape is similar to a hook shape, and the long fatty chain is easy to continuously aggregate and intertwine with each other in a solution at a certain concentration to form a spherical micelle, further form a wormlike micelle, increase the viscosity of the solution and improve the sand carrying capacity. When the gel is broken in the later period, the unsaturated double bonds in the long fatty chain are subjected to addition reaction, so that the hydrophobic groups are changed into strong hydrophilic groups, the surfactant is subjected to hydrophobic and hydrophilic conversion, the capacity among molecules is lost, and the worm-shaped micelles and the spherical micelles are broken. The invention solves the problem of incomplete self-gel breaking of the clean fracturing fluid stratum when meeting oil, and the gel breaking theory is novel.
When the clean fracturing fluid breaks gel at the later stage, unsaturated double bonds in long fatty chains are subjected to addition reaction, so that hydrophobic groups are changed into strong hydrophilic groups, the surfactant is subjected to hydrophobic and hydrophilic conversion, the capacity among molecules is lost, and worm-shaped micelles and spherical micelles are broken. The invention solves the problem of incomplete self-gel breaking of the clean fracturing fluid stratum when meeting oil.
Description of the drawings:
FIG. 1 is a simulation diagram of a multiolefin hook-type surfactant gel fracturing fluid long fatty chain entanglement;
FIG. 2 shows nuclear magnetic hydrogen spectrum of a multiolefin hook-type surfactant gel fracturing fluid obtained in example 4;
FIG. 3 shows nuclear magnetic hydrogen spectrum of fracturing fluid gel breaking liquid of multiolefin hook type surfactant gel obtained in example 4;
FIG. 4 is a photograph of a multiolefin hook type surfactant gel fracturing fluid gel broken for performance testing in example 4;
FIG. 5 SEM images of a multiolefin hook type surfactant gel liquid (a) and a gel breaker liquid (b) in example 4.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to multiolefin hook-type surfactant gel fracturing fluid, which has the following structural formula:
the principle is as follows: when the multiolefin hook-type surfactant gel fracturing fluid is prepared, a natural product, namely, linolenic acid, which is a vegetable oil ester hydrolysate, is used as a basic raw material, carboxyl is modified into amide, and meanwhile, an unsaturated group is provided in a donor system. The long fatty chain is natural and has a certain angle, the shape is similar to a hook shape, and the long fatty chain is easy to continuously aggregate and intertwine with each other in a solution at a certain concentration to form a spherical micelle, further form a wormlike micelle, increase the viscosity of the solution and improve the sand carrying capacity. And during later gel breaking, performing addition reaction on unsaturated double bonds in the long fatty chain to change hydrophobic groups into strong hydrophilic groups, so that the surfactant is subjected to hydrophobic and hydrophilic conversion, the capacity among molecules is lost, the worm-shaped micelles and the spherical micelles are disintegrated, and gel breaking is completed. The principle is realized by the following reaction:
the synthesis and gel breaking mechanism is as follows:
specifically, the preparation and gel breaking method of the multiolefin hook-type surfactant gel fracturing fluid comprises the following steps:
(1) adding linolenic acid, N, N-dimethyl-1, 3-propanediamine and p-toluenesulfonic acid into a flask, wherein the molar ratio of the linolenic acid to the N, N-dimethyl-1, 3-propanediamine is 1 (1-1.1). The addition amount of the sodium p-toluenesulfonate is 0.5 wt%. And under the protection of nitrogen, heating to 130-150 ℃, reacting for 8-10 hours, and carrying out vacuum pumping under reduced pressure to obtain an intermediate.
(2) And (2) adding the intermediate obtained in the step one and 3-chloro-2-hydroxypropanesulfonic acid sodium into a flask containing a mixed solvent of water and ethanol, wherein the molar ratio of the intermediate to the 3-chloro-2-hydroxypropanesulfonic acid sodium is 1 (1-1.1), the mass ratio of water to ethanol is 10 (1-3), the mass ratio of the intermediate to the 3-chloro-2-hydroxypropanesulfonic acid sodium is 25-45 wt%, reacting at the temperature of 60-80 ℃ under the protection of nitrogen, and reacting for 6-8 hours to obtain a crude product.
(3) And (3) drying the crude product in vacuum, dissolving the crude product in ethanol (removing inorganic salts), wherein the mass of the crude product in the ethanol accounts for 20-40 wt%, and adding petroleum ether into the ethanol crude product solution, wherein the mass of the ethanol solution of the crude product and the petroleum ether accounts for 70-90 wt%. After stirring, the petroleum ether phase (containing unreacted tertiary amine) was removed and the ethanol was removed using a rotary evaporator to give the product.
(4) And preparing the product into fracturing fluid, wherein the concentration of the fracturing fluid is 5-10 wt%.
(5) Adding NaHSO into fracturing fluid3NaHSO at a simulated formation temperature of 80 ℃, pH 53The addition amount of the gel is 3-6 wt% of the fracturing fluid, the gel is changed into an aqueous solution, and gel breaking is completed.
The invention is further illustrated by the following specific examples and figures:
example 1
Adding a mixture of linolenic acid and N, N-dimethyl-1, 3-propanediamine with the molar ratio of 1:1.05 and 0.5 wt% of sodium p-toluenesulfonate into a flask, reacting for 8 hours at 130 ℃ under the protection of nitrogen, and carrying out vacuum pumping under reduced pressure to obtain an intermediate. Taking the intermediate and 3-chloro-2-hydroxypropanesulfonic acid sodium salt with the molar ratio of 1:1.05, adding a mixed solvent of water and ethanol with the mass ratio of 10:2, wherein the reaction concentration is 40 wt%, and reacting for 8 hours at 60 ℃ under the protection of nitrogen to obtain a crude product. And (3) drying the crude product in vacuum, preparing 40 wt% ethanol solution of the crude product, removing inorganic salt, and adding petroleum ether into the ethanol crude product solution, wherein the mass ratio of the ethanol solution of the crude product to the petroleum ether is 80 wt%. After stirring, the petroleum ether phase (containing unreacted tertiary amine) was removed and the ethanol was removed using a rotary evaporator to give the product. The product was formulated into a fracturing fluid at a concentration of 5 wt% and NaHSO was then added to the fracturing fluid3(the mass ratio of the fracturing fluid is 3 wt%), and the gel is changed into an aqueous solution at the simulated formation temperature of 80 ℃ and the pH value of 5, so that gel breaking is finished.
Viscosity of fracturing fluid: 59.20 mPas, viscosity of the gel breaking solution is 2.01 mPas (test conditions: temperature 80 ℃ C., pH 5).
Example 2
Adding a mixture of linolenic acid and N, N-dimethyl-1, 3-propanediamine in a molar ratio of 1:1.1, wherein the mixture is 0.5 wt% of sodium p-toluenesulfonate into a flask, reacting for 8 hours at 150 ℃ under the protection of nitrogen, and carrying out vacuum pumping under reduced pressure to obtain an intermediate. Taking the intermediate and 3-chloro-2-hydroxypropanesulfonic acid sodium salt with the molar ratio of 1:1.05, adding a mixed solvent of water and ethanol with the mass ratio of 10:2, wherein the reaction concentration is 40 wt%, and reacting for 8 hours at 60 ℃ under the protection of nitrogen to obtain a crude product. And (3) drying the crude product in vacuum, preparing 40 wt% ethanol solution of the crude product, removing inorganic salt, and adding petroleum ether into the ethanol crude product solution, wherein the mass ratio of the ethanol solution of the crude product to the petroleum ether is 80 wt%. After stirring, the petroleum ether phase (containing unreacted tertiary amine) was removed and the ethanol was removed using a rotary evaporator to give the product. The product was formulated into a fracturing fluid at a concentration of 6 wt%, and NaHSO was then added to the fracturing fluid3(the mass ratio of the fracturing fluid is 4 wt%), and the gel is changed into an aqueous solution at the simulated formation temperature of 80 ℃ and the pH value of 5, so that gel breaking is finished.
Viscosity of fracturing fluid: 70.52 mPas, viscosity of gel breaking solution 1.93 mPas (test conditions: temperature 80 ℃ C., pH 5).
Example 3
Adding a mixture of linolenic acid and N, N-dimethyl-1, 3-propanediamine with the molar ratio of 1:1.05 and 0.5 wt% of sodium p-toluenesulfonate into a flask, reacting for 8 hours at 130 ℃ under the protection of nitrogen, and carrying out vacuum pumping under reduced pressure to obtain an intermediate. Taking the intermediate and 3-chloro-2-hydroxypropanesulfonic acid sodium salt with the molar ratio of 1:1.05, adding a mixed solvent of water and ethanol with the mass ratio of 10:2, wherein the reaction concentration is 40 wt%, and reacting for 8 hours at 60 ℃ under the protection of nitrogen to obtain a crude product. And (3) drying the crude product in vacuum, preparing 40 wt% ethanol solution of the crude product, removing inorganic salt, and adding petroleum ether into the ethanol crude product solution, wherein the mass ratio of the ethanol solution of the crude product to the petroleum ether is 80 wt%. After stirring, the petroleum ether phase (containing unreacted tertiary amine) was removed and the ethanol was removed using a rotary evaporator to give the product. The product was formulated into a fracturing fluid at a concentration of 7 wt% and NaHSO was then added to the fracturing fluid3(the mass ratio of the fracturing fluid is 5 wt%), the gel is changed into aqueous solution at the simulated formation temperature of 80 ℃ and the pH value of 5,and (5) breaking the gel.
Viscosity of fracturing fluid: 76.91 mPas, viscosity of the gel breaker solution 1.29 mPas (test conditions: temperature 80 ℃ C., pH 5).
Example 4
Adding a mixture of linolenic acid and N, N-dimethyl-1, 3-propanediamine in a molar ratio of 1:1.1, wherein the mixture is 0.5 wt% of sodium p-toluenesulfonate into a flask, reacting for 8 hours at 140 ℃ under the protection of nitrogen, and carrying out vacuum pumping under reduced pressure to obtain an intermediate. Taking the intermediate and 3-chloro-2-hydroxypropanesulfonic acid sodium salt with the molar ratio of 1:1.05, adding a mixed solvent of water and ethanol with the mass ratio of 10:2, wherein the reaction concentration is 40 wt%, and reacting for 8 hours at 60 ℃ under the protection of nitrogen to obtain a crude product. And (3) drying the crude product in vacuum, preparing 40 wt% ethanol solution of the crude product, removing inorganic salt, and adding petroleum ether into the ethanol crude product solution, wherein the mass ratio of the ethanol solution of the crude product to the petroleum ether is 80 wt%. After stirring, the petroleum ether phase (containing unreacted tertiary amine) was removed and the ethanol was removed using a rotary evaporator to give the product. The product was formulated into a fracturing fluid at a concentration of 8 wt% and NaHSO was then added to the fracturing fluid3(the mass ratio of the fracturing fluid is 6 wt%), and the gel is changed into an aqueous solution at the simulated formation temperature of 80 ℃ and the pH value of 5, so that gel breaking is finished.
Viscosity of fracturing fluid: 89.33 mPas, viscosity of the gel breaking solution 2.79 mPas (test conditions: temperature 80 ℃ C., pH 5).
Example 5
Adding a mixture of linolenic acid and N, N-dimethyl-1, 3-propanediamine with the molar ratio of 1:1.05 and 0.5 wt% of sodium p-toluenesulfonate into a flask, reacting for 8 hours at 130 ℃ under the protection of nitrogen, and carrying out vacuum pumping under reduced pressure to obtain an intermediate. Taking the intermediate and 3-chloro-2-hydroxypropanesulfonic acid sodium salt with the molar ratio of 1:1.1, adding a mixed solvent of water and ethanol with the mass ratio of 10:2, wherein the reaction concentration is 40 wt%, and reacting for 8 hours at 60 ℃ under the protection of nitrogen to obtain a crude product. And (3) drying the crude product in vacuum, preparing 40 wt% ethanol solution of the crude product, removing inorganic salt, and adding petroleum ether into the ethanol crude product solution, wherein the mass ratio of the ethanol solution of the crude product to the petroleum ether is 70 wt%. After stirring, the petroleum ether phase (containing unreacted tertiary amine) was removed and the ethanol was removed using a rotary evaporator to give the product. The product was formulated to a concentration of 10 wt% fracturing fluid, followed by the addition of NaHSO to the fracturing fluid3(the mass ratio of the fracturing fluid is 6 wt%), and the gel is changed into an aqueous solution at the simulated formation temperature of 80 ℃ and the pH value of 5, so that gel breaking is finished.
Viscosity of fracturing fluid: 90.27 mPas, viscosity of the gel breaking solution 3.32 mPas (test conditions: temperature 80 ℃ C., pH 5).
Example 6
(1) Linolenic acid, N, N-dimethyl-1, 3-propanediamine and p-toluenesulfonic acid are added into a flask, wherein the molar ratio of the linolenic acid to the N, N-dimethyl-1, 3-propanediamine is 1:1. The addition amount of the sodium p-toluenesulfonate is 0.5 wt%. And under the protection of nitrogen, heating to 130 ℃, reacting for 8 hours, and carrying out vacuum pumping under reduced pressure to obtain an intermediate.
(2) And (2) adding the intermediate obtained in the step one and 3-chloro-2-hydroxypropanesulfonic acid sodium into a flask containing a mixed solvent of water and ethanol, wherein the molar ratio of the intermediate to the 3-chloro-2-hydroxypropanesulfonic acid sodium is 1:1, the mass ratio of water to ethanol is 10:1, the mass ratio of the intermediate to the 3-chloro-2-hydroxypropanesulfonic acid sodium is 25 wt%, reacting at the temperature of 60 ℃ for 6 hours under the protection of nitrogen to obtain a crude product.
(3) Vacuum drying the crude product, dissolving with ethanol (removing inorganic salt), wherein the mass of the crude product in ethanol is 20 wt%, and adding petroleum ether into the ethanol crude product solution, wherein the mass of the ethanol solution and the petroleum ether of the crude product is 70 wt%. After stirring, the petroleum ether phase (containing unreacted tertiary amine) was removed and the ethanol was removed using a rotary evaporator to give the product.
(4) The product is prepared into a fracturing fluid, and the concentration of the fracturing fluid is 5 wt%.
(5) Adding NaHSO into fracturing fluid3NaHSO at a simulated formation temperature of 80 ℃, pH 53The addition amount of the gel is 3 wt% of the mass of the fracturing fluid, the gel becomes an aqueous solution, and the gel breaking is completed.
Example 7
(1) Linolenic acid, N, N-dimethyl-1, 3-propanediamine and p-toluenesulfonic acid are added into a flask, wherein the molar ratio of the linolenic acid to the N, N-dimethyl-1, 3-propanediamine is 1: 1.1. The addition amount of the sodium p-toluenesulfonate is 0.5 wt%. And under the protection of nitrogen, heating to 150 ℃, reacting for 10 hours, and carrying out vacuum pumping under reduced pressure to obtain an intermediate.
(2) And (2) adding the intermediate obtained in the step one and 3-chloro-2-hydroxypropanesulfonic acid sodium into a flask containing a mixed solvent of water and ethanol, wherein the molar ratio of the intermediate to the 3-chloro-2-hydroxypropanesulfonic acid sodium is 1:1.1, the mass ratio of water to ethanol is 10:3, the mass ratio of the intermediate to the 3-chloro-2-hydroxypropanesulfonic acid sodium is 45 wt%, reacting at the temperature of 80 ℃ under the protection of nitrogen, and reacting for 8 hours to obtain a crude product.
(3) Vacuum drying the crude product, dissolving with ethanol (removing inorganic salt), adding petroleum ether into the ethanol crude product solution, wherein the mass of the crude product in ethanol is 40 wt%, and the mass of the ethanol solution and the petroleum ether in the crude product is 90 wt%. After stirring, the petroleum ether phase (containing unreacted tertiary amine) was removed and the ethanol was removed using a rotary evaporator to give the product.
(4) The product is prepared into a fracturing fluid, and the concentration of the fracturing fluid is 10 wt%.
(5) Adding NaHSO into fracturing fluid3NaHSO at a simulated formation temperature of 80 ℃, pH 53The addition amount of the gel is 6 wt% of the mass of the fracturing fluid, the gel becomes an aqueous solution, and the gel breaking is completed.
In order to illustrate the winding manner of the long fatty chain of the multiolefin hook-type surfactant gel fracturing fluid, a simulation diagram of the winding manner of the fatty chain is given, and is shown in fig. 1.
In order to characterize the structural characteristics of a multiolefin hook-type surfactant gel fracturing fluid, the surfactant fracturing fluid and the gel breaker fluid synthesized in example 4 were subjected to nuclear magnetic hydrogen spectroscopy, and the results are shown in fig. 2.
FIG. 2 shows nuclear magnetic hydrogen spectrum of a multiolefin hook-type surfactant gel fracturing fluid obtained in example 4.
1H NMR(300MHz，DMSO)：δ7.70(s，H)，5.49～5.35(m，6H)，4.77(s，H)，4.2(t，H)，3.5～3.04(m，14H)，2.8(t，2H)，2.39(t，2H)，2.16～2.13(t，4H)，1.99(t，2H)，1.53(t，2H)，1.33～1.26(t，8H)，0.9(s，3H)ppm。
FIG. 2 shows nuclear magnetic hydrogen spectrum of gel breaking liquid of multiolefin hook type surfactant gel fracturing fluid obtained in example 4.
1H NMR(300MHz，DMSO)：δ7.70(s，H)，4.77(s，H)，4.2(t，H)，3.5～3.04(m，14H)，2.8(t，2H)，2.13(t，2H)，1.99(t，2H)，1.83～1.77(m，8H)，1.53(t，2H)，1.3～1.25(m，15H)，0.89(t，3H)ppm。
As can be seen from FIG. 2, the present invention successfully prepared a multiolefin hook-type surfactant gel fracturing fluid having a target structure. By comparing fig. 2 and fig. 3, the fracturing fluid is transformed by hydrophobic and hydrophilic, and gel breaking is completed.
Figure 4 is a photograph of a performance test conducted on a multiolefin hook-type surfactant gel fracturing fluid of example 4. The sand-carrying gel breaking experiment shows that: the multiolefin hook-type surfactant gel fracturing fluid has strong sand-carrying capacity and thorough gel breaking.
FIG. 5 is a photograph of SEM test of a gel (a) and a breaker liquid (b) of a multiolefin hook type surfactant of example 4, as is apparent from the figure: the wormlike micelles of the multiolefin hook-type surfactant gel (a) are intertwined with each other, and the structure is inferred to have good sand carrying capacity; after gel breaking, (b) the worm-like micelle is disintegrated, and the gel breaking technology is proved to be capable of completely breaking the gel.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. The multiolefin hook-type surfactant gel fracturing fluid is characterized in that the structural formula of multiolefin hook-type surfactant gel in the fracturing fluid is as follows:
2. a preparation method of multiolefin hook-type surfactant gel fracturing fluid is characterized by comprising the following steps:
1) mixing linolenic acid, N-dimethyl-1, 3-propanediamine and a catalyst, heating to 130-150 ℃ under the protection of nitrogen, reacting for 8-10 hours, and carrying out vacuum pumping under reduced pressure to obtain an intermediate;
2) adding sulfonate and a solvent into the intermediate, and reacting at the temperature of 60-80 ℃ for 6-8 hours under the protection of nitrogen to obtain a crude product;
3) vacuum drying the crude product, dissolving with ethanol, adding petroleum ether, stirring, removing petroleum ether phase, and removing ethanol to obtain product;
4) the product is formulated into a fracturing fluid.
3. The method for preparing the multiolefin hook-type surfactant gel fracturing fluid according to claim 1, wherein in the step 1), the molar ratio of the linolenic acid to the N, N-dimethyl-1, 3-propanediamine is 1 (1-1.1).
4. The method for preparing multiolefin hook-type surfactant gel fracturing fluid according to claim 3, wherein in the step 1), the catalyst is sodium p-toluenesulfonate, and the addition amount is 0.5 wt%.
5. The method for preparing multiolefin hook-type surfactant gel fracturing fluid according to claim 2, wherein in the step 2), the sulfonate is sodium 3-chloro-2-hydroxypropanesulfonate; the molar ratio of the intermediate to the 3-chloro-2-hydroxypropanesulfonic acid sodium salt is 1 (1-1.1); in the mixed solution, the mass percentage of the intermediate and the 3-chloro-2-hydroxypropanesulfonic acid sodium salt is 25-45 wt%.
6. The preparation method of the multiolefin hook-type surfactant gel fracturing fluid according to claim 2, wherein in the step 2), the solvent is a mixed solution of water and ethanol, and the mass ratio of the water to the ethanol is 10 (1-3).
7. The preparation method of the multiolefin hook-type surfactant gel fracturing fluid according to claim 2, wherein in the step 3), the mass of the crude product in ethanol accounts for 20-40 wt%; the mass ratio of the ethanol solution of the crude product to the petroleum ether is 70-90 wt%.
8. The method of breaking gel of multiolefin hook-type surfactant gel fracturing fluid of claim 1, comprising the steps of:
adding NaHSO into fracturing fluid3And simulating the formation environment, and completing gel breaking when the gel is changed into an aqueous solution.
9. The gel breaking method of the multiolefin hook-type surfactant gel fracturing fluid according to claim 8, wherein the concentration of the fracturing fluid is 5-10 wt%; NaHSO3The addition amount of (B) is 3-6 wt% of the mass of the fracturing fluid.
10. The method of breaking gel of multiolefin hook-type surfactant gel fracturing fluid of claim 8, wherein the simulated formation temperature is 80 ℃ and the pH is 5.
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