CN114181691A - Acid-pressing gelling acid and application thereof - Google Patents
Acid-pressing gelling acid and application thereof Download PDFInfo
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- CN114181691A CN114181691A CN202010960491.XA CN202010960491A CN114181691A CN 114181691 A CN114181691 A CN 114181691A CN 202010960491 A CN202010960491 A CN 202010960491A CN 114181691 A CN114181691 A CN 114181691A
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Abstract
The invention provides an acid-pressing gelling acid and application thereof. The acid-pressing gelling acid comprises the following raw materials in parts by mass: 100 parts of hydrochloric acid with the mass concentration of 20%, 4-6 parts of corrosion inhibitor, 0.5-1.5 parts of iron ion stabilizer, 0.5-1.5 parts of cleanup additive, 0.5-1.5 parts of clay stabilizer and 0.4-0.9 part of gelling agent, wherein the corrosion inhibitor is obtained by reacting organic primary amine and unsaturated aldehyde at 0-35 ℃. The invention also provides application of the acid fracturing gelled acid in acid fracturing modification of a deep carbonate reservoir at 180-200 ℃. The acid-pressing gelling acid provided by the invention can keep homogeneous phase within the range of 20-200 ℃, and at the temperature of 180 ℃ and 200 ℃ for 170s‑1Has a viscosity of 25 mPas or more under a shear condition and a corrosion rate of less than 40g/m at 180-2And h, the method can be used for acid fracturing modification of a high-temperature carbonate reservoir.
Description
Technical Field
The invention relates to the technical field of acid fracturing modification, in particular to acid fracturing gelled acid and application thereof.
Background
Acid fracturing modification is an important storage and production increasing means in oil and gas field exploration and development, wherein gelling acid fracturing is the most common acid fracturing process due to the fact that the preparation process is simple and the cost is low. The exploration and development of carbonate rock oil and gas in the world tend to be deep, the reservoir temperature is high and can reach 180-220 ℃, and a plurality of adverse effects are brought. The method mainly reflects the serious acid liquor corrosion and large operation risk under the high-temperature condition; the acid rock reaction rate is high under the high-temperature condition, and the acid liquor is completely consumed in the near-well bore area, so that deep penetration cannot be realized; the length of a shaft of the deep well is large, the friction of the shaft is large, high construction pressure and discharge capacity are needed, and the operation risk is large; the compatibility of each component in the gelled acid is poor, and a heterogeneous system is easily formed before/after the acid rock reaction. Due to these problems, a gelled acid system resistant to temperatures as high as 180-.
CN103820100A provides a thickening acid for acid fracturing of high-temperature fracture-cavity carbonate rock reservoir. The thickening acid is prepared from commercially available hydrochloric acid, an emulsion type thickening agent, an ascorbic acid type iron ion stabilizer and a quaternary ammonium salt type surfactant. The gelled acid is suitable for carbonate reservoir transformation at 130 ℃.
CN102433111A provides an acid liquid for acid fracturing and a preparation method thereof, which is prepared by hydrochloric acid (or hydrofluoric acid or earth acid) and polyacrylamide type thickening agent, zirconium oxychloride, aldehyde crosslinking agent and phenol crosslinking agent. The acid gel is crosslinked at 150 deg.C and 170S-1The viscosity of the oil is 12 mPas under the speed condition, and the oil can basically meet the requirement of 150 ℃ reservoir acid fracturing. No gelled acid system suitable for use in 180-.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide an acid-pressing gelling acid and its use. The gelled acid can be kept homogeneous at the temperature of 20-200 ℃, and at the temperature of 180-200 ℃ for 170s-1Has a viscosity of 25 mPas or more and a corrosion rate of less than 40g/m at 180-2h, can be suitable for the deep carbonate reservoir with the reservoir temperature of 180-And (5) acid fracturing modification.
In order to achieve the purpose, the invention provides an acid fracturing gelling acid, wherein the acid fracturing gelling acid comprises the following raw materials in parts by mass: 100 parts of hydrochloric acid with the mass concentration of 20%, 4-6 parts of corrosion inhibitor, 0.5-1.5 parts of iron ion stabilizer, 0.5-1.5 parts of cleanup additive, 0.5-1.5 parts of clay stabilizer and 0.4-0.9 part of gelling agent; wherein, the corrosion inhibitor is obtained by the reaction of organic primary amine and unsaturated aldehyde at 0-35 ℃.
According to the specific embodiment of the invention, the corrosion inhibitor, the iron ion stabilizer, the cleanup additive, the clay stabilizer and the gelling agent have good compatibility, do not precipitate after mixing, and can form a uniform gelled acid system with certain fluidity.
In the acid fracturing gelling acid, preferably, the acid fracturing gelling acid comprises the following raw materials in parts by mass: 100 parts of hydrochloric acid with the mass concentration of 20%, 4-5 parts of corrosion inhibitor, 0.5-1.5 parts of iron ion stabilizer, 0.5-1.5 parts of cleanup additive, 0.5-1.5 parts of clay stabilizer and 0.4-0.8 part of gelling agent.
According to the specific embodiment of the invention, the mass concentration of the hydrochloric acid can be controlled to be 5-20%, the dosage of the hydrochloric acid can be correspondingly adjusted along with the concentration, and the mass of the solute in the used hydrochloric acid is ensured to be the same as that of 100 parts of the solute in the hydrochloric acid with the mass concentration of 20%.
According to a specific embodiment of the present invention, the organic primary amine and the unsaturated aldehyde are subjected to a prepolymerization reaction at 0-35 ℃ to obtain the corrosion inhibitor, which is usually an oligomer with a weight average molecular weight of 5000-10000. The corrosion inhibitor is generally soluble in polar solvents, such as polar organic solvents, polar inorganic solvents.
According to a specific embodiment of the invention, in the raw material of the corrosion inhibitor, the organic primary amine has a primary amine group, and both H atoms on the N atom in the primary amine can be substituted during the reaction process, so that the N atom forms a chemical bond with other atoms (such as C, N, O and the like). The organic primary amine preferably includes one or a combination of two or more of dodecylamine, octadecylamine, aniline, and p-methoxyaniline.
According to a particular embodiment of the invention, in the starting materials of the corrosion inhibitor, the unsaturated aldehydes are generally bifunctional, including, for example, unsaturated hydrocarbon groups and aldehyde groups. The unsaturated aldehyde preferably includes one or a combination of two or more of acrolein, crotonaldehyde, and cinnamaldehyde.
According to a specific embodiment of the present invention, the mass ratio of the organic primary amine to the unsaturated aldehyde in the raw material of the corrosion inhibitor may be controlled to (1:6) to (8: 3).
According to a specific embodiment of the present invention, the corrosion inhibitor is prepared by a method generally comprising: mixing organic primary amine, unsaturated aldehyde, a catalyst and a drying agent at 0-35 ℃ for reaction to obtain the corrosion inhibitor. In some embodiments, the reaction time may be controlled to be 2 to 12 hours.
According to an embodiment of the present invention, in the above-mentioned method for preparing the corrosion inhibitor, the catalyst may include one or a combination of two or more of formic acid, acetic acid and benzoic acid. The desiccant may comprise one or a combination of two or more of 4A molecular sieve, anhydrous calcium chloride and anhydrous sodium carbonate. The reaction may be carried out in an organic solvent including one or a combination of two or more of acetonitrile, tetrahydrofuran, and dioxane. The mass ratio of the organic primary amine to the catalyst can be controlled to be (10:1) - (200: 1); the mass ratio of the organic primary amine to the drying agent can be controlled to be (1:10) - (8: 5); the mass ratio of the organic solvent to the organic primary amine can be controlled to be (15:8) - (30: 1).
According to an embodiment of the present invention, the method for preparing the corrosion inhibitor may further comprise an operation of post-treating the product after the reaction, preferably, the post-treatment comprises removing a drying agent in the reaction system.
According to the specific embodiment of the present invention, the preparation method of the corrosion inhibitor adopts a mode of reaction while stirring, and preferably, the stirring speed is 50-200 rpm.
According to a particular embodiment of the invention, the corrosion inhibitor is further polymerizable as an oligomer at a temperature above 80 ℃ to give a polymer.
In the embodiment of the invention, when the temperature is raised to be more than 80 ℃, the oligomer in the corrosion inhibitor can undergo further cross polymerization to form a polymer (high polymer) capable of adhering to the metal surface, and the adsorption principle of the corrosion inhibitor is different from that of the existing corrosion inhibitor containing Schiff base and Mannich base. The weight average molecular weight of the polymer (high polymer) is generally more than 500000, the pendulum hardness is more than 50, the contact between metal and a corrosive environment can be blocked, and the function of inhibiting corrosion can be realized in a high-temperature environment of more than 80 ℃.
FIG. 1 is a schematic representation of the principle of prepolymerization and further cross-polymerization. The single arrows in FIG. 1 indicate the prepolymerization, pointing to the product which can be described by means of finite letters or symbols, while the parallel double arrows indicate that prepolymerization and further cross-polymerization take place. In particular embodiments, the reaction pathways of prepolymerization and further cross-polymerization are difficult to win, and thus the product structures listed in FIG. 1 are only partial products, not full products.
According to a specific embodiment of the present invention, the iron ion stabilizer may be a high temperature resistant iron ion stabilizer, and may include an aqueous glutathione solution having a concentration of 0.001 to 0.01 mol/L. In a specific embodiment, the dosage of the glutathione solution can be adjusted according to the concentration of the solution, and the mass of a solute in the used glutathione solution is ensured to be the same as that of 0.5-1.5 parts of the glutathione aqueous solution with the concentration of 0.001-0.01 mol/L.
According to a specific embodiment of the present invention, the discharge assistant may be a high temperature resistant discharge assistant and may include an aqueous solution of 1, 16-bis (triethylammonium) difluoride in a concentration of 0.001 to 0.01 mmol/L. In a specific embodiment, the amount of the 1, 16-bis (triethylammonium) difluoride solution can be adjusted according to the concentration of the solution, and the mass of the solute in the 1, 16-bis (triethylammonium) difluoride solution used can be ensured to be the same as that of 0.5-1.5 parts of an aqueous 1, 16-bis (triethylammonium) difluoride solution with a concentration of 0.001-0.01 mmol/L.
According to a specific embodiment of the present invention, the clay stabilizer may be a high temperature resistant clay stabilizer, and may include an aqueous pentaerythritol solution having a concentration of 0.001 to 0.01 mmol/L. In a specific embodiment, the amount of the pentaerythritol solution can be adjusted according to the concentration of the solution, so as to ensure that the mass of the solute in the pentaerythritol solution is the same as that of 0.4-0.9 part of pentaerythritol aqueous solution with the concentration of 0.001-0.01 mmol/L.
According to a particular embodiment of the invention, the gelling agent may be a refractory gelling agent, generally comprising a copolymer of methacryloyloxyethyl trimethyl ammonium chloride and N-benzylbutenamide, the molar ratio of methacryloyloxyethyl trimethyl ammonium chloride to N-benzylbutenamide in the copolymer being (3:7) to (7:3), the copolymer being generally solid.
According to a specific embodiment of the present invention, the above raw materials of the acid-pressure gelling acid may include, in parts by mass: 100 parts by mass of 20% hydrochloric acid, 4 to 6 parts (preferably 4 to 5 parts) of a corrosion inhibitor, 0.5 to 1.5 parts of an aqueous glutathione solution having a concentration of 0.001 to 0.01mol/L, 0.5 to 1.5 parts of an aqueous 1, 16-bis (triethylammonium) difluoride solution having a concentration of 0.001 to 0.01mmol/L, 0.5 to 1.5 parts of an aqueous pentaerythritol solution having a concentration of 0.001 to 0.01mmol/L, 0.4 to 0.9 parts (preferably 0.4 to 0.8 part) of a copolymer of methacryloyloxyethyltrimethylammonium chloride and N-benzylbutenamide, the molar ratio of methacryloyloxyethyltrimethylammonium chloride to N-benzylbutenamide in the copolymer being preferably (3:7) to (7: 3).
According to a specific embodiment of the present invention, the method for preparing the acid-press gelling acid may comprise: and adding the corrosion inhibitor, the iron ion stabilizer, the cleanup additive, the clay stabilizer and the gelling agent into hydrochloric acid, and stirring to obtain the acid fracturing gelled acid.
The invention further provides application of the acid fracturing gelled acid in acid fracturing modification of a deep carbonate reservoir at 180-200 ℃. Namely, the acid fracturing gelling acid solution can be used as a high temperature resistant (180-. In some embodiments, the acid-pressure gelling acid has a viscosity of 180 ℃ at 200 ℃ for 170s-1Can be maintained at 25 mPas or more under the shearing conditions of (3).
The invention has the beneficial effects that:
the invention providesThe compatibility of each component in the supplied acid fracturing gelled acid is good, and the homogeneous phase can be kept in the atmosphere of 20-200 ℃; at the temperature of 180 ℃ and 170s-1The viscosity of the acid-press gelling acid can be maintained at 25 mPas or more under the shearing condition of (1); the corrosion rate in the range of 180 ℃ and 200 ℃ is less than 40g/m2h; the acid rock reaction rate of the acid fracturing gelled acid is less than half of that of hydrochloric acid with the same concentration; the resistance reduction rate of the acid-pressing gelling acid at room temperature is more than 70 percent. The acid fracturing gelled acid provided by the invention is suitable for acid fracturing modification of a deep carbonate reservoir with the reservoir temperature of 180-200 ℃.
Drawings
FIG. 1 is a schematic diagram of the prepolymerization and further cross-polymerization in the present invention.
FIG. 2 is a photograph showing a corrosion inhibition experiment of the corrosion inhibitor prepared in example 1 on the surface of N80 steel sheet.
FIG. 3 shows the results of the shear stability test of the acid-pressed gelling acid prepared in example 4.
Fig. 4 is a photograph of the acid-press gelling acid prepared in example 4 after shear stability testing.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Except for special emphasis, the following examples and comparative examples used the following components of the high temperature resistant iron ion stabilizer, the high temperature resistant cleanup additive, the high temperature resistant clay stabilizer, and the high temperature resistant gelling agent as follows:
the high-temperature resistant iron ion stabilizer is composed of glutathione aqueous solution with the concentration of 0.005 mol/L;
the high-temperature resistant cleanup additive comprises a 1, 16-bis (triethylammonium) difluoride aqueous solution with the concentration of 0.006 mmol/L;
the high-temperature resistant clay stabilizer is pentaerythritol aqueous solution with the concentration of 0.004 mmol/L;
the high temperature resistant gel is TP8098 type cationic polymer product of Beijing Tuopan North science and technology development Limited company, and the product meets SY/T5762-1995 standard. The product comprises the components of a copolymer of methacryloyloxyethyl trimethyl ammonium chloride and N-benzyl butene amide in a mass ratio of 6: 4.
Example 1
This example provides an acid-pressed gelling acid prepared by the following method:
1. adding acetonitrile 30ml into a round-bottom flask, adding acetic acid 100mg and anhydrous calcium chloride 10g, adding cinnamyl aldehyde 5.3g and octadecylamine 3.8g, stirring at room temperature for 4h at 100rmp, and filtering the reacted solution to remove insoluble anhydrous calcium chloride solid to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomer of unsaturated aldehyde and organic primary amine.
2. Sequentially adding 4g of corrosion inhibitor, 0.7g of high-temperature-resistant iron ion stabilizer, 0.7g of high-temperature-resistant cleanup additive, 0.7g of high-temperature-resistant clay stabilizer and 0.6g of high-temperature-resistant gelling agent into 92mL of hydrochloric acid with the mass concentration of 20%, and uniformly stirring to obtain the acid-fracturing gelled acid.
Example 2
This example provides an acid-pressed gelling acid prepared by the following method:
1. adding 50ml of acetonitrile into a round-bottom flask, adding 200mg of benzoic acid and 25g of 4A molecular sieve, adding 10g of acrolein and 6g of aniline, stirring at room temperature for 6 hours at 100rmp, and filtering the reacted solution to remove the insoluble 4A molecular sieve to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomers of unsaturated aldehyde and organic primary amine.
2. Adding 7g of corrosion inhibitor, 1.3g of high-temperature-resistant iron ion stabilizer, 1.3g of high-temperature-resistant cleanup additive, 1.3g of high-temperature-resistant clay stabilizer and 1.1g of high-temperature-resistant gelling agent into 125mL of hydrochloric acid with the mass concentration of 20% in sequence, and uniformly stirring to obtain the acid-fracturing gelled acid.
And (3) extracting a clear and transparent solution from the corrosion inhibitor solution obtained in the step (1) for molecular weight test, and extracting another clear and transparent solution for curing at 200 ℃ to obtain a high polymer for polymer molecular weight test and pendulum hardness test.
Example 3
This example provides an acid-pressed gelling acid prepared by the following method:
1. adding 30ml of dioxane into a round-bottom flask, adding 100mg of benzoic acid and 10g of anhydrous sodium carbonate, adding 5g of cinnamyl aldehyde and 4g of dodecylamine, stirring at room temperature for 4 hours at 100rmp, and filtering the reacted solution to remove insoluble sodium carbonate solid to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomers of unsaturated aldehyde and organic primary amine.
2. Sequentially adding 6g of corrosion inhibitor, 0.7g of high-temperature resistant iron ion stabilizer, 0.7g of high-temperature resistant cleanup additive, 0.7g of high-temperature resistant clay stabilizer and 0.6g of high-temperature resistant gelling agent into 125mL of hydrochloric acid with the mass concentration of 20%, and uniformly stirring to obtain the acid-fracturing gelled acid.
And (3) extracting a clear and transparent solution from the corrosion inhibitor solution obtained in the step (1) for molecular weight test, and extracting another clear and transparent solution for curing at 200 ℃ to obtain a high polymer for polymer molecular weight test and pendulum hardness test.
Example 4
This example provides an acid-pressed gelling acid prepared by the following method:
1. adding 30ml of tetrahydrofuran into a round-bottom flask, adding 100mg of benzoic acid and 10g of anhydrous sodium carbonate, adding 5g of cinnamyl aldehyde and 10g of aniline, stirring and reacting at room temperature for 4 hours at 100rmp, and filtering the solution after reaction to remove insoluble sodium carbonate solid to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomers of unsaturated aldehyde and organic primary amine.
2. Adding 7.2g of corrosion inhibitor, 0.7g of high-temperature resistant iron ion stabilizer, 0.7g of high-temperature resistant cleanup additive, 0.7g of high-temperature resistant clay stabilizer and 0.6g of high-temperature resistant gelling agent into 125mL of hydrochloric acid with the mass concentration of 20% in sequence, and uniformly stirring to obtain the acid-fracturing gelled acid.
And (3) extracting a clear and transparent solution from the corrosion inhibitor solution obtained in the step (1) for molecular weight test, and extracting another clear and transparent solution for curing at 200 ℃ to obtain a high polymer for polymer molecular weight test and pendulum hardness test.
Example 5
This example provides an acid-pressed gelling acid prepared by the following method:
1. adding 50ml of acetonitrile into a round-bottom flask, adding 200mg of benzoic acid and 25g of 4A molecular sieve, adding 10g of acrolein and 6g of aniline, stirring at room temperature for 6 hours at 100rmp, and filtering the reacted solution to remove the insoluble 4A molecular sieve to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomers of unsaturated aldehyde and organic primary amine.
2. Adding 7.1g of corrosion inhibitor, 1.8g of high-temperature-resistant iron ion stabilizer, 1.8g of high-temperature-resistant cleanup additive, 0.7g of high-temperature-resistant clay stabilizer and 1.1g of high-temperature-resistant gelling agent into 125mL of hydrochloric acid with the mass concentration of 20% in sequence, and uniformly stirring to obtain the acid-fracturing gelled acid.
And (3) extracting a clear and transparent solution from the corrosion inhibitor solution obtained in the step (1) for molecular weight test, and extracting another clear and transparent solution for curing at 200 ℃ to obtain a high polymer for polymer molecular weight test and pendulum hardness test.
Example 6
This example provides an acid-pressed gelling acid prepared by the following method:
1. adding 50ml of acetonitrile into a round-bottom flask, adding 200mg of benzoic acid and 25g of 4A molecular sieve, adding 10g of acrolein and 6g of aniline, stirring at room temperature for 6 hours at 100rmp, and filtering the reacted solution to remove the insoluble 4A molecular sieve to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomers of unsaturated aldehyde and organic primary amine.
2. Adding 7g of corrosion inhibitor, 1.3g of high-temperature-resistant iron ion stabilizer, 1.3g of high-temperature-resistant cleanup additive, 1.3g of high-temperature-resistant clay stabilizer and 1.0g of high-temperature-resistant gelling agent into 130mL of hydrochloric acid with the mass concentration of 20% in sequence, and uniformly stirring to obtain the acid-fracturing gelled acid.
And (3) extracting a clear and transparent solution from the corrosion inhibitor solution obtained in the step (1) for molecular weight test, and extracting another clear and transparent solution for curing at 200 ℃ to obtain a high polymer for polymer molecular weight test and pendulum hardness test.
Comparative example 1
The present comparative example provides an acid-pressed gelling acid prepared by the following method:
1. a round-bottomed flask was charged with 30ml of tetrahydrofuran, 100mg of benzoic acid and 10g of anhydrous sodium carbonate were added, 5g of cinnamaldehyde and 0.8g of aniline were further added, the reaction was stirred at 100rmp for 4 hours at room temperature, and the solution after the reaction was filtered to remove insoluble sodium carbonate solids, to obtain a corrosion inhibitor.
2. Adding 7.2g of corrosion inhibitor, 0.7g of high-temperature resistant iron ion stabilizer, 0.7g of high-temperature resistant cleanup additive, 0.7g of high-temperature resistant clay stabilizer and 0.6g of high-temperature resistant gelling agent into 125mL of hydrochloric acid with the mass concentration of 20% in sequence, and uniformly stirring to obtain the acid-fracturing gelled acid.
And (3) extracting a clear and transparent solution from the corrosion inhibitor solution obtained in the step (1) for molecular weight test, and extracting another clear and transparent solution for curing at 200 ℃ to obtain a high polymer for polymer molecular weight test and pendulum hardness test.
Comparative example 2
The comparative example provides an acid fracturing gelling acid solution prepared by the following method:
1. adding 50ml of acetonitrile into a round-bottom flask, adding 200mg of benzoic acid and 25g of 4A molecular sieve, adding 10g of acrolein and 6g of aniline, stirring at room temperature for 6 hours at 100rmp, and filtering the reacted solution to remove the insoluble 4A molecular sieve to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomers of unsaturated aldehyde and organic primary amine.
2. Adding 7g of corrosion inhibitor, 1.3g of iron ion stabilizer (ascorbic acid as a component), 1.3g of cleanup additive, 1.3g of clay stabilizer and 1.1g of gelling agent into 125mL of hydrochloric acid with the mass concentration of 20% in sequence, and stirring uniformly to obtain the acid fracturing gelling acid solution.
The component of the iron ion stabilizer in the comparative example is ascorbic acid, and unlike the components of the high temperature resistant iron ion stabilizers in examples 1-6, the corrosion rate of gelled acid prepared with it is up to 255.5g/m2·h。
Comparative example 3
The comparative example provides an acid fracturing gelling acid solution prepared by the following method:
1. adding 50ml of acetonitrile into a round-bottom flask, adding 200mg of benzoic acid and 25g of 4A molecular sieve, adding 10g of acrolein and 6g of aniline, stirring at room temperature for 6 hours at 100rmp, and filtering the reacted solution to remove the insoluble 4A molecular sieve to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomers of unsaturated aldehyde and organic primary amine.
2. Adding 7g of corrosion inhibitor, 1.3g of iron ion stabilizer, 1.3g of cleanup additive (the component is sodium dodecyl benzene sulfonate), 1.3g of clay stabilizer and 1.1g of gelling agent into 125mL of hydrochloric acid with the mass concentration of 20% in sequence, and stirring uniformly to obtain the acid fracturing gelling acid solution.
The effective component of the cleanup additive in the comparative example is sodium dodecyl benzene sulfonate, and the corrosion rate of gelled acid prepared by the cleanup additive is 296.1g/m which is different from the components of the high-temperature resistant cleanup additives in examples 1-62·h。
Comparative example 4
The comparative example provides an acid fracturing gelling acid solution prepared by the following method:
1. adding 50ml of acetonitrile into a round-bottom flask, adding 200mg of benzoic acid and 25g of 4A molecular sieve, adding 10g of acrolein and 6g of aniline, stirring at room temperature for 6 hours at 100rmp, and filtering the reacted solution to remove the insoluble 4A molecular sieve to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomers of unsaturated aldehyde and organic primary amine.
2. Adding 7g of corrosion inhibitor, 1.3g of iron ion stabilizer, 1.3g of cleanup additive, 1.3g of clay stabilizer (the component is diethanolamine) and 1.1g of gelling agent into 125mL of hydrochloric acid with the mass concentration of 20% in sequence, and stirring uniformly to obtain the acid-pressing gelling acid solution.
The composition of the clay stabilizer in this comparative example was diethanolamine, and unlike the high temperature resistant clay stabilizers of examples 1-6, the corrosion rate of gelled acid formulated therewith was as high as 356.8g/m2·h。
Comparative example 5
The comparative example provides an acid fracturing gelling acid solution prepared by the following method:
1. adding 50ml of acetonitrile into a round-bottom flask, adding 200mg of benzoic acid and 25g of 4A molecular sieve, adding 10g of acrolein and 6g of aniline, stirring at room temperature for 6 hours at 100rmp, and filtering the reacted solution to remove the insoluble 4A molecular sieve to obtain the corrosion inhibitor, wherein the corrosion inhibitor contains oligomers of unsaturated aldehyde and organic primary amine.
2. Adding 7g of corrosion inhibitor, 1.3g of iron ion stabilizer, 1.3g of cleanup additive, 1.3g of clay stabilizer and 1.1g of gelling agent (the component is polyacrylamide) into 125mL of hydrochloric acid with the mass concentration of 20% in sequence, and stirring uniformly to obtain the acid-pressing gelling acid solution.
The component of the gel in the comparative example is polyacrylamide, and unlike the components of the high temperature resistant gels in examples 1-6, the corrosion rate of the gelled acid prepared by the gel is as high as 1796.5g/m2·h。
Test example 1
In this test example, the acid-fracturing gelled acid liquids prepared in examples 1 to 6 and comparative example 1 were subjected to the following test procedures and evaluation indexes for corrosion inhibitor performance for acidification in SYT5405-1996, section 4: the high-temperature high-pressure dynamic corrosion rate and corrosion inhibition rate measuring method and evaluation indexes are used for testing corrosion inhibition performance, and the testing temperature is 180 ℃ or 200 ℃. Meanwhile, the weight average molecular weights of the corrosion inhibitors (oligomers) and the polymers formed by curing the corrosion inhibitors prepared in examples 1 to 6 and comparative example 1 were measured by gel permeation chromatography, and the reference standard for the measurement is SH/T1759-2007 determination of the molecular weight distribution of the solution polymer by gel permeation chromatography.
TABLE 1
As can be seen from Table 1, the corrosion rates of the N80 steel sheets of acid-pressed gelled acid prepared in examples 1-6 were < 40g/m under the conditions of 200 ℃ and 20% hydrochloric acid2H. Proves that the acid liquor gelled acid provided by the invention has good corrosion inhibitionAnd (4) performance.
The dosage of the organic primary amine adopted in the preparation method of the comparative example 1 is less than that of the organic primary amine in the preparation method of the corrosion inhibitor provided by the invention, and oligomers cannot be effectively formed to further form high polymers to play a corrosion inhibition role. The corrosion rate tested by applying the corrosion inhibitor prepared in the comparative example 1 to the N80 steel sheet is much higher than the corrosion rate of the N80 steel sheet tested in the examples 1-6, which proves that the corrosion inhibitor contained in the acid-pressing gelled acid can effectively protect metals from corrosion.
Comparative examples 2-5 changed the composition of the iron ion stabilizer, the cleanup additive, the clay stabilizer, and the gelling agent, respectively, compared to the composition used to prepare the acid fracturing gelling acids of examples 1-6, and the acid fracturing gelling acids prepared in comparative examples 2-5 had significantly higher corrosion efficiencies when tested on N80 steel sheets than when tested under the same conditions for the acid fracturing gelling acids of examples 1-6. The results show that the prepared acid fracturing gel acid can fully exert the corrosion prevention protection capability of the corrosion inhibitor on metal due to the fact that the compatibility of each component in the acid fracturing gel acid raw material provided by the invention is good.
FIG. 2 is a photograph showing a corrosion inhibition experiment of the corrosion inhibitor prepared in example 1 on the surface of N80 steel sheet. The picture a in fig. 2 is a photograph of a N80 steel sheet after a corrosion inhibition experiment, the picture b in fig. 2 is a photograph of the steel sheet and a surface protective film (black shining part in the picture b), and the picture c in fig. 2 is a photograph of the N80 steel sheet after the surface protective film is completely abraded. FIG. 2 shows that the corrosion inhibitor prepared in example 1 can form a protective film on the surface of N80 steel sheet, thereby effectively protecting the steel sheet from corrosion.
Test example 2
The test example refers to the first part of NB/T14003.1-2015 shale gas fracturing fluid: the acid-fracturing gelled acid prepared in example 4 is tested by standard slickwater performance indexes and evaluation methods, and the drag reduction rate of the acid-fracturing gelled acid relative to clear water is 71.2%.
Test example 3
The test example performs a 180 ℃ acid rock reaction kinetics test on the acid pressing gelled acid prepared in the example 4, and the test process refers to' zhangzhiyong, jiang lingzhi, beam punching and the like; study of gelled acid reaction kinetics[J]Drilling and completion fluids 2005,22(5):28-30 ", the same test was performed with 20% by mass hydrochloric acid as a reference sample. The acid rock reaction rate of hydrochloric acid having a measured mass concentration of 20% was 5.98X 10-4mol/cm2H, acid rock reaction rate of acid-pressed gelled acid prepared in example 4 was 2.66X 10-4mol/cm2H, is 44.5% of the acid rock reaction rate of 20% hydrochloric acid by mass.
Test example 4
This test example performed shear stability testing on gelled acid prepared in example 4, with reference to the method in subsection 6.6 of the standard "SY/T5107-2005 aqueous fracturing fluid Performance evaluation method", and FIG. 3 shows the shear stability test results of gelled acid prepared in example 4. As shown in FIG. 3, at 200 deg.C for 170s-1And continuously shearing the gelled acid sample for 2h, wherein the viscosity of the gelled acid is kept above 25 mPas. FIG. 4 is a photograph of the gelled acid prepared in example 4 after shear stability testing, and as can be seen from FIG. 4, the gelled acid after testing was visually free of precipitate, residue, and delamination and exhibited a homogeneous system. The above results demonstrate that the gelled acids provided by the present invention have good shear stability.
Test example 5
In the test example, the gelled acid prepared in comparative example 5 is subjected to a shear stability test, and the test process is carried out by referring to a method in 6.6 sections in SY/T5107-2005 water-based fracturing fluid performance evaluation method, at 200 ℃ for 170s-1And continuously shearing the gelled acid sample for 2h, wherein the viscosity of the gelled acid is lower than 5 mPas. Comparing the test result of the comparative example with that of test example 4, it can be seen that the components of the raw material of the acid fracturing gelled acid provided by the invention have good compatibility, and the prepared acid fracturing gelled acid shows higher viscosity and uniformity.
Claims (15)
1. The acid fracturing gelling acid comprises the following raw materials in parts by mass:
100 parts of hydrochloric acid with the mass concentration of 20%, 4-6 parts of corrosion inhibitor, 0.5-1.5 parts of iron ion stabilizer, 0.5-1.5 parts of cleanup additive, 0.5-1.5 parts of clay stabilizer and 0.4-0.9 part of gelling agent;
wherein, the corrosion inhibitor is obtained by the reaction of organic primary amine and unsaturated aldehyde at 0-35 ℃.
2. The acid fracturing gelling acid of claim 1, wherein the acid fracturing gelling acid comprises the following raw materials in parts by mass: 100 parts of hydrochloric acid with the mass concentration of 20%, 4-5 parts of corrosion inhibitor, 0.5-1.5 parts of iron ion stabilizer, 0.5-1.5 parts of cleanup additive, 0.5-1.5 parts of clay stabilizer and 0.4-0.8 part of gelling agent.
3. The acid-fracturing gelling acid as claimed in claim 1 or 2, wherein the weight average molecular weight of the corrosion inhibitor is 5000-10000.
4. Acid-fracturing gelling acid according to any of claims 1 to 3, wherein the corrosion inhibitor is soluble in a polar solvent.
5. The acid fracturing gelling acid of any of claims 1-4, wherein said primary organic amine comprises one or a combination of two or more of dodecylamine, octadecylamine, aniline, and p-methoxyaniline;
the unsaturated aldehyde comprises one or more of acrolein, crotonaldehyde and cinnamaldehyde.
6. The acid gelling acid according to any one of claims 1 to 5, wherein the mass ratio of said organic primary amine to said unsaturated aldehyde is (1:6) - (8: 3).
7. The acid gelling acid according to any one of claims 1-6, wherein said corrosion inhibitor is prepared by a method comprising: mixing organic primary amine, unsaturated aldehyde, a catalyst and a drying agent at 0-35 ℃ for reaction to obtain the corrosion inhibitor;
preferably, the reaction time is 2-12 h.
8. The acid fracturing gelling acid of claim 7, wherein said catalyst comprises one or a combination of two or more of formic acid, acetic acid, and benzoic acid;
the drying agent comprises one or the combination of more than two of 4A molecular sieve, anhydrous calcium chloride and anhydrous sodium carbonate;
the reaction is carried out in an organic solvent, and the organic solvent comprises one or the combination of more than two of acetonitrile, tetrahydrofuran and dioxane.
9. The acid fracturing gelling acid of claim 7 or 8, wherein the mass ratio of said primary organic amine to said catalyst is (10:1) - (200: 1);
the mass ratio of the organic primary amine to the drying agent is (1:10) - (8: 5);
the mass ratio of the organic solvent to the organic primary amine is (15:8) - (30: 1).
10. Acid-pressed gelling acid according to any of claims 1-9, wherein the corrosion inhibitor is further polymerizable at above 80 ℃ to give a polymer;
preferably, the weight average molecular weight of the polymer is greater than 500000;
preferably, the pendulum hardness of the polymer is > 50.
11. The acid fracturing gelling acid of claim 1 or 2, wherein said iron ion stabilizer comprises an aqueous solution of glutathione at a concentration of 0.001-0.01 mol/L.
12. Acid fracturing gelling acid according to claim 1 or 2, wherein said cleanup additive comprises an aqueous solution of 1, 16-bis (triethylammonium) difluoride in a concentration of 0.001-0.01 mmol/L.
13. The acid fracturing gelling acid of claim 1 or 2, wherein said clay stabilizer comprises an aqueous pentaerythritol solution at a concentration of 0.001-0.01 mmol/L.
14. Acid fracturing gelling acid according to claim 1 or 2, wherein said gelling agent comprises a copolymer of methacryloyloxyethyl trimethyl ammonium chloride and N-benzyl butene amide, preferably in a molar ratio of methacryloyloxyethyl trimethyl ammonium chloride to N-benzyl butene amide from the copolymer of (3:7) to (7: 3).
15. Use of an acid fracturing gelling acid as claimed in any of claims 1 to 14 in acid fracturing modification of deep carbonate reservoirs at 180 ℃ and 200 ℃.
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| CN115873585A (en) * | 2022-11-30 | 2023-03-31 | 中石化石油工程技术服务有限公司 | Integrated acid liquid system for hot dry rock fracturing and application thereof |
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