CN116333706B - Corrosion inhibitor system for acidification with temperature resistance of 180 ℃ and preparation method and application thereof - Google Patents

Corrosion inhibitor system for acidification with temperature resistance of 180 ℃ and preparation method and application thereof Download PDF

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CN116333706B
CN116333706B CN202111584388.0A CN202111584388A CN116333706B CN 116333706 B CN116333706 B CN 116333706B CN 202111584388 A CN202111584388 A CN 202111584388A CN 116333706 B CN116333706 B CN 116333706B
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corrosion
corrosion inhibitor
corrosion inhibition
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inhibition
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CN116333706A (en
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许可
刘博祥
卢拥军
方波
李阳
石阳
邱晓惠
翁定为
段贵府
高航
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Petrochina Co Ltd
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54Compositions for in situ inhibition of corrosion in boreholes or wells
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
    • C09K8/72Eroding chemicals, e.g. acids
    • C09K8/74Eroding chemicals, e.g. acids combined with additives added for specific purposes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32Anticorrosion additives

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Abstract

The invention discloses a corrosion inhibitor system for acidification with temperature resistance of 180 ℃ and a preparation method and application thereof. The corrosion inhibitor system comprises: 10-20wt% of corrosion inhibition A, 10-20wt% of corrosion inhibition B, 3-8wt% of corrosion inhibition C, 5-20wt% of corrosion inhibition synergist, 3-10wt% of surfactant and the balance solvent; the corrosion inhibitor A comprises p-dimethylaminobenzaldehyde, acetone, diethylamine, n-butanol and hydrochloric acid according to the mass ratio of (10-15): (25-30): (30-40): (10-20): (1-5) carrying out reaction to obtain the catalyst; the corrosion inhibition B agent comprises 8-hydroxyquinoline, chloromethyl naphthalene and N, N-dimethylformamide according to the mass ratio of (25-40): (25-40): (30-50) carrying out reaction to obtain the catalyst; the corrosion inhibitor C is 2, 6-diaminopurine, 2-amino-6-mercaptopurine or 2, 6-dimercaptopurine.

Description

Corrosion inhibitor system for acidification with temperature resistance of 180 ℃ and preparation method and application thereof
Technical Field
The invention relates to the technical field of oil and gas field development, in particular to a corrosion inhibitor system for acidification with temperature resistance of 180 ℃, and a preparation method and application thereof.
Background
The corrosion inhibitor for modifying and acidizing the oil and gas reservoir plays an important role in acidizing fluid of the oil and gas well, and can effectively reduce the corrosion rate of pipeline equipment. With the large-scale development of shallow petroleum oil and gas resources, the oil and gas exploration development is developed to depth, the proportion of ultra-deep wells is increased year by year, and the stratum temperature faced by fracturing transformation is also higher and higher. Therefore, there is a need to develop corrosion inhibitor systems for high temperature acidizing resistance in the reconstruction of high temperature deep well reservoirs
Patent application CN108359438A discloses a quinoline quaternary ammonium salt type corrosion inhibitor suitable for 160-180 ℃, the corrosion rate of the corrosion inhibitor is 43.91 g/(m 2. H) under the condition of 20% hydrochloric acid at 180 ℃, the performance is slightly low, and meanwhile, the synthesis process of the quinoline quaternary ammonium salt corrosion inhibitor is too complex, so that the industrial production is not facilitated.
Patent application CN107987822A reports a synthesis process and an application method of a high-temperature-resistant corrosion inhibitor, wherein the synthesis process of the corrosion inhibitor is simple, but the highest temperature resistance is only 140 ℃, the temperature resistance is poor, and the acidification transformation requirement of a high-temperature stratum oil and gas reservoir cannot be met.
Disclosure of Invention
The invention aims to provide a corrosion inhibitor system for acidification with temperature resistance of 180 ℃ and a preparation method and application thereof, so as to solve the problem of serious corrosion of N80 carbon steel in acid liquor of 20% hydrochloric acid at 180 ℃ and achieve corrosion inhibition performance meeting the requirements.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention provides a corrosion inhibitor system for acidification at a temperature of 180 ℃, which comprises the following components in percentage by mass:
The corrosion inhibition A agent is 10 to 20 weight percent
The corrosion inhibition B agent is 10 to 20 weight percent
The corrosion inhibition C agent is 3 to 8 weight percent
The corrosion inhibition synergist is 5 to 20 weight percent
Surfactant (3 wt% -10 wt%)
And the balance of solvent.
The corrosion inhibitor A comprises p-dimethylaminobenzaldehyde, acetone, diethylamine, n-butanol and hydrochloric acid according to the mass ratio of (10-15): (25-30): (30-40): (10-20): (1-5) carrying out reaction to obtain the catalyst; wherein n-butanol is solvent, hydrochloric acid provides hydrogen ion, and concentrated hydrochloric acid with concentration of 37.5wt% is used as hydrochloric acid. The product is 4-diethylamino-4- (4-dimethylaminophenyl) -butan-2-one, and the specific reaction process is as follows:
The corrosion inhibition B agent comprises 8-hydroxyquinoline, chloromethyl naphthalene and N, N-dimethylformamide according to the mass ratio of (25-40): (25-40): (30-50) carrying out reaction to obtain the catalyst; wherein, N-dimethylformamide is taken as a solvent, and the generated product is 8-hydroxyquinoline-chloromethyl naphthalene quaternary ammonium salt, and the specific reaction process is as follows:
the corrosion inhibitor C is 2, 6-diaminopurine, 2-amino-6-mercaptopurine or 2, 6-dimercaptopurine, and has the following structural formula:
The corrosion inhibitor system comprises a corrosion inhibitor A, a corrosion inhibitor B and a corrosion inhibitor C. The corrosion inhibition A belongs to a Mannich base corrosion inhibitor, and mainly has the effects of passivating the metal surface, forming a film on the surface and preventing metal cations on the electrode surface from diffusing into the solution. The corrosion inhibitor B belongs to quinoline corrosion inhibitors and mainly plays a role in resisting high temperature. The corrosion inhibition C belongs to purine corrosion inhibitors, is a heterocyclic compound, can provide lone pair electrons, and contains a plane conjugated system capable of providing pi electrons. The three corrosion inhibitors play the role of a mixed corrosion inhibitor, increase the polarization of the anode and the cathode, and do not obviously change the self-corrosion potential of the metal.
According to the corrosion inhibitor system of the present invention, preferably, the corrosion inhibition enhancer is selected from one or a combination of two or more of iodide, formic acid derivative, magnesium salt, urea, alkynol and urotropine. More preferably, the iodide includes, but is not limited to, potassium iodide, cuprous iodide, and the like. The formic acid derivatives include, but are not limited to, formic acid, benzoic acid, 2-naphthoic acid, and the like. The magnesium salts include, but are not limited to, magnesium chloride, magnesium nitrate, and the like. Such alkynols include, but are not limited to, propargyl alcohol, 3-methyl-1-pentyn-3-ol, ethyl 2-hydroxy-3-butynoate, and the like.
According to the corrosion inhibitor system of the present invention, preferably, the surfactant is selected from one or a combination of two or more of polyoxyethylene esters, alkylphenol ethoxylates, and fatty alcohol ethoxylates. More preferably, the polyoxyethylene esters include tween 20, tween 21, tween 40, tween 60, tween 61, tween 80, tween 81, tween 85, atlas G-2129, atlas G-2159 and Atlas G-2079; the alkylphenol ethoxylates comprise OP-4, OP-7, OP-10, OP-15, TX-9, TX-10 and TX-15; the fatty alcohol-polyoxyethylene ether comprises AEO-7, AEO-9 and peregal O-20.
The corrosion inhibitor system according to the present invention, preferably, the solvent is selected from one or a combination of two or more of isopropanol, ethylene glycol, N-butanol, methanol, ethanol, N-Dimethylformamide (DMF), heavy aromatic hydrocarbon solvents and tetralin.
In another aspect, the present invention provides a method for preparing the above corrosion inhibitor system for acidification with 180 ℃ temperature resistance, which comprises: and stirring and mixing the corrosion inhibitor A, the corrosion inhibitor B, the corrosion inhibitor C, the corrosion inhibition synergist, the surfactant and the solvent to obtain the corrosion inhibitor system.
According to the preparation method of the invention, preferably, the corrosion inhibition A agent is prepared by the following steps: and mixing the p-dimethylaminobenzaldehyde, acetone, diethylamine, n-butanol and hydrochloric acid, heating for reaction, and obtaining the corrosion inhibition A agent after the reaction is finished. More preferably, the heating temperature is 80-110 ℃, and the reaction time is 3-12h.
According to the preparation method of the invention, preferably, the corrosion inhibition B agent is prepared by the following steps: and mixing the 8-hydroxyquinoline, chloromethyl naphthalene and N, N-dimethylformamide, heating for reaction, and obtaining the corrosion inhibition B agent after the reaction is finished. More preferably, the heating temperature is 80-110 ℃, and the reaction time is 5-8h.
In one aspect, the invention provides an application of the corrosion inhibitor system for acidification at 180 ℃ in oil-gas reservoir acidification reconstruction at 180 ℃ or below.
The corrosion inhibitor system can effectively solve the problem of serious corrosion of N80 carbon steel in acid liquor of 20% hydrochloric acid at 180 ℃, and has corrosion inhibition performance meeting the requirements.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, etc., including ranges for each) can generally be approximations that vary (+) or (-) as appropriate in 0.1 or 1.0 increments. All numerical designations are to be understood as preceded by the term "about".
Example 1
The embodiment prepares a corrosion inhibitor system for acidification with the temperature resistance of 180 ℃ and comprises the following steps:
Corrosion inhibition A:
Adding 10g of p-dimethylaminobenzaldehyde, 25g of acetone, 30g of diethylamine, 10g of n-butanol and 1g of 37.5wt% hydrochloric acid into a flask, placing into an oil bath pot, heating and refluxing, and reacting at the temperature of 80 ℃ for 3 hours to obtain the corrosion inhibition A agent after the reaction is finished.
Corrosion inhibition B agent:
Adding 25g of 8-hydroxyquinoline, 25g of chloromethyl naphthalene and 50g of N, N-dimethylformamide into a flask, placing the flask in an oil bath, reacting at 80 ℃ for 5 hours, and obtaining the corrosion inhibition B agent after the reaction is finished.
Corrosion inhibition C: 2, 6-diaminopurine.
Corrosion inhibitor system:
And (3) stirring and mixing 10g of corrosion inhibitor A, 10g of corrosion inhibitor B, 3g of corrosion inhibitor C, 5g of potassium iodide, 3g of Tween 80 surfactant and 69g of methanol.
Example 2
The embodiment prepares a corrosion inhibitor system for acidification with the temperature resistance of 180 ℃ and comprises the following steps:
Corrosion inhibition A:
adding 12g of p-dimethylaminobenzaldehyde, 28g of acetone, 35g of diethylamine, 15g of n-butanol and 3g of 37.5wt% hydrochloric acid into a flask, placing into an oil bath, heating and refluxing, reacting at 100 ℃ for 4h, and obtaining the corrosion inhibition A agent after the reaction is finished.
Corrosion inhibition B agent:
25g of 8-hydroxyquinoline, 25g of chloromethylnaphthalene and 50g of N, N-dimethylformamide are added into a flask, and the mixture is placed in an oil bath at a reaction temperature of 100 ℃ for 6 hours. And after the reaction is finished, the corrosion inhibition B agent is obtained.
Corrosion inhibition C: 2, 6-diaminopurine.
Corrosion inhibitor system:
and (3) stirring and mixing 10g of corrosion inhibitor A, 10g of corrosion inhibitor B, 3g of corrosion inhibitor C, 5g of cuprous iodide, 3g of Tween 80 surfactant and 69g of ethanol.
Example 3
The embodiment prepares a corrosion inhibitor system for acidification with the temperature resistance of 180 ℃ and comprises the following steps:
Corrosion inhibition A:
Adding 12g of p-dimethylaminobenzaldehyde, 28g of acetone, 35g of diethylamine, 15g of n-butanol and 3g of 37.5wt% hydrochloric acid into a flask, placing into an oil bath, heating and refluxing, and reacting at 100 ℃ for 4 hours. And after the reaction is finished, the corrosion inhibition A agent is obtained.
Corrosion inhibition B agent:
35g of 8-hydroxyquinoline, 35g of chloromethylnaphthalene and 30g of N, N-dimethylformamide are added into a flask, and the mixture is placed in an oil bath at a reaction temperature of 110 ℃ for 8 hours. And after the reaction is finished, the corrosion inhibition B agent is obtained.
Corrosion inhibition C: 2-amino-6-mercaptopurine.
Corrosion inhibitor system:
And (3) stirring and mixing 20g of a corrosion inhibitor A, 20g of a corrosion inhibitor B, 8g of a corrosion inhibitor C, 5g of urotropine, 3g of peregal O-20 surfactant and 44g of isopropanol.
Example 4
The embodiment prepares a corrosion inhibitor system for acidification with the temperature resistance of 180 ℃ and comprises the following steps:
Corrosion inhibition A:
Adding 12g of p-dimethylaminobenzaldehyde, 28g of acetone, 28g of diethylamine, 12g of n-butanol and 2g of 37.5wt% hydrochloric acid into a flask, placing into an oil bath pot, heating and refluxing, and reacting at 110 ℃ for 12 hours. And after the reaction is finished, the corrosion inhibition A agent is obtained.
Corrosion inhibition B agent:
35g of 8-hydroxyquinoline, 35g of chloromethylnaphthalene and 30g of N, N-dimethylformamide are added into a flask, and the mixture is placed in an oil bath at a reaction temperature of 110 ℃ for 8 hours. And after the reaction is finished, the corrosion inhibition B agent is obtained.
Corrosion inhibition C: 2-amino-6-mercaptopurine.
Corrosion inhibitor system:
18g of corrosion inhibitor A, 18g of corrosion inhibitor B, 8g of corrosion inhibitor C, 5g of urea, 5g of OP-10 surfactant and 46g of glycol are stirred and mixed.
Example 5
The embodiment prepares a corrosion inhibitor system for acidification with the temperature resistance of 180 ℃ and comprises the following steps:
Corrosion inhibition A:
Adding 12g of p-dimethylaminobenzaldehyde, 28g of acetone, 28g of diethylamine, 12g of n-butanol and 2g of 37.5wt% hydrochloric acid into a flask, placing into an oil bath pot, heating and refluxing, and reacting at 110 ℃ for 12 hours. And after the reaction is finished, the corrosion inhibition A agent is obtained.
Corrosion inhibition B agent:
35g of 8-hydroxyquinoline, 35g of chloromethylnaphthalene and 30g of N, N-dimethylformamide are added into a flask, and the mixture is placed in an oil bath at a reaction temperature of 110 ℃ for 8 hours. And after the reaction is finished, the corrosion inhibition B agent is obtained.
Corrosion inhibition C: 2, 6-dithiopurine.
Corrosion inhibitor system:
And (3) stirring and mixing 18g of corrosion inhibitor A, 18g of corrosion inhibitor B, 8g of corrosion inhibitor C, 10g of potassium iodide, 8g of OP-10 surfactant and 38g of DMF.
Example 6
The embodiment prepares a corrosion inhibitor system for acidification with the temperature resistance of 180 ℃ and comprises the following steps:
Corrosion inhibition A:
15g of p-dimethylaminobenzaldehyde, 30g of acetone, 30g of diethylamine, 15g of n-butanol and 3g of 37.5wt% hydrochloric acid are added into a flask, and the flask is placed in an oil bath kettle, heated and refluxed, and the reaction temperature is 110 ℃ and the reaction time is 12 hours. And after the reaction is finished, the corrosion inhibition A agent is obtained.
Corrosion inhibition B agent:
40g of 8-hydroxyquinoline, 40g of chloromethylnaphthalene and 20g of N, N-dimethylformamide are added into a flask, and the flask is placed in an oil bath at a reaction temperature of 110 ℃ for 8 hours. And after the reaction is finished, the corrosion inhibition B agent is obtained.
Corrosion inhibition C: 2, 6-dimercaptopurine.
Corrosion inhibitor system:
And (3) stirring and mixing 20g of corrosion inhibitor A, 20g of corrosion inhibitor B, 8g of corrosion inhibitor C, 20g of propynyl alcohol, 10g of OP-10 surfactant and 22g of tetralin.
Comparative example 7
The comparative example prepares a corrosion inhibitor system for acidification with temperature resistance of 180 ℃ and comprises the following processes:
Corrosion inhibition A:
15g of p-dimethylaminobenzaldehyde, 30g of acetone, 30g of diethylamine, 15g of n-butanol and 3g of 37.5wt% hydrochloric acid are added into a flask, and the flask is placed in an oil bath kettle, heated and refluxed, and the reaction temperature is 110 ℃ and the reaction time is 12 hours. And after the reaction is finished, the corrosion inhibition A agent is obtained.
Corrosion inhibition B agent:
40g of 8-hydroxyquinoline, 40g of chloromethylnaphthalene and 20g of N, N-dimethylformamide are added into a flask, and the flask is placed in an oil bath at a reaction temperature of 110 ℃ for 8 hours. And after the reaction is finished, the corrosion inhibition B agent is obtained.
Corrosion inhibitor system:
And (3) stirring and mixing 20g of corrosion inhibitor A, 20g of corrosion inhibitor B, 20g of propynyl alcohol, 10g of OP-10 surfactant and 30g of tetralin.
Comparative example 8
The comparative example prepares a corrosion inhibitor system for acidification with temperature resistance of 180 ℃ and comprises the following processes:
Corrosion inhibition A:
15g of p-dimethylaminobenzaldehyde, 30g of acetone, 30g of diethylamine, 15g of n-butanol and 3g of 37.5wt% hydrochloric acid are added into a flask, and the flask is placed in an oil bath kettle, heated and refluxed, and the reaction temperature is 110 ℃ and the reaction time is 12 hours. And after the reaction is finished, the corrosion inhibition A agent is obtained.
Corrosion inhibition C: 2, 6-dimercaptopurine.
Corrosion inhibitor system:
And (3) stirring and mixing 20g of corrosion inhibitor A, 8g of corrosion inhibitor C, 20g of propynyl alcohol, 10g of OP-10 surfactant and 42g of tetralin.
Comparative example 9
The comparative example prepares more than one corrosion inhibitor system for acidification with temperature resistance of 180 ℃ and comprises the following processes:
Corrosion inhibition B agent:
40g of 8-hydroxyquinoline, 40g of chloromethylnaphthalene and 20g of N, N-dimethylformamide are added into a flask, and the flask is placed in an oil bath at a reaction temperature of 110 ℃ for 8 hours. And after the reaction is finished, the corrosion inhibition B agent is obtained.
Corrosion inhibition C: 2, 6-dimercaptopurine.
Corrosion inhibitor system:
And (3) stirring and mixing 20g of corrosion inhibitor B, 8g of corrosion inhibitor C, 20g of propynyl alcohol, 10g of OP-10 surfactant and 42g of tetralin.
Performance test:
The testing method comprises the following steps: according to the oil and gas industry standard SY/T5405-2019, namely the performance test method and the evaluation index of the corrosion inhibitor for acidification, the hanging piece weight loss method is adopted to measure the corrosion rate of the N80 steel sheet in acid liquor with a certain concentration. The specific test results are shown in table 1 below.
Table 1 dynamic Corrosion Rate test Table (180 ℃ C., 20% hydrochloric acid, corrosion inhibitor 5% by mass in the corrosion System)
As can be seen from Table 1, the three corrosion inhibitors A, B, C have better compounding effect than the combination of two by two; the greater the concentration of the corrosion inhibitor A, B, C, the smaller the corrosion rate and the better the effect.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (3)

1. The corrosion inhibitor system for acidification with the temperature resistance of 180 ℃ is characterized by comprising the following components in percentage by mass:
the corrosion inhibition A agent is 18 to 20 weight percent
The corrosion inhibition B agent is in the concentration of 18-20wt%
The corrosion inhibition agent is in weight percent of
The corrosion inhibition synergist is 5 to 20 weight percent
Surfactant (5 wt% -10 wt%)
The balance of solvent;
The corrosion inhibitor A comprises p-dimethylaminobenzaldehyde, acetone, diethylamine, n-butanol and hydrochloric acid according to the mass ratio of (10-15): (25-30): (30-40): (10-20): (1-5) carrying out reaction to obtain the catalyst; the corrosion inhibitor A is prepared through the following steps: mixing the p-dimethylaminobenzaldehyde, acetone, diethylamine, n-butanol and hydrochloric acid, heating to react at 80-110 ℃ for 3-12 h hours to obtain the corrosion inhibition A agent after the reaction;
The corrosion inhibition B agent comprises 8-hydroxyquinoline, chloromethyl naphthalene and N, N-dimethylformamide according to the mass ratio of (25-40): (25-40): (30-50) carrying out reaction to obtain the catalyst; the corrosion inhibition B agent is prepared through the following steps: mixing the 8-hydroxyquinoline, chloromethyl naphthalene and N, N-dimethylformamide, heating to react at 80-110 ℃ for 5-8 h hours, and obtaining the corrosion inhibition B agent after the reaction is finished;
The corrosion inhibitor C is 2, 6-diaminopurine, 2-amino-6-mercaptopurine or 2, 6-dimercaptopurine;
The corrosion inhibition synergist is one or a combination of more than two of urea, potassium iodide and propargyl alcohol;
The surfactant is selected from OP-10 surfactant;
The solvent is selected from one or more of isopropanol, ethylene glycol, N-butanol, methanol, ethanol, N-dimethylformamide, heavy aromatic hydrocarbon solvent and tetrahydronaphthalene.
2. A method of preparing the 180 ℃ acidification corrosion inhibitor system according to claim 1, comprising: and stirring and mixing the corrosion inhibitor A, the corrosion inhibitor B, the corrosion inhibitor C, the corrosion inhibition synergist, the surfactant and the solvent to obtain the corrosion inhibitor system.
3. The corrosion inhibitor system for acidification at 180 ℃ resistant temperature as set forth in claim 1, which is applied to the transformation of oil-gas reservoir acidification at 180 ℃ or below.
CN202111584388.0A 2021-12-22 2021-12-22 Corrosion inhibitor system for acidification with temperature resistance of 180 ℃ and preparation method and application thereof Active CN116333706B (en)

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