CN115612473B - A kind of high temperature resistant acidification corrosion inhibitor and its preparation method and application, corrosion inhibition acidification fracturing fluid - Google Patents

Abstract

The invention belongs to the technical field of oil well auxiliary agents, and provides a high-temperature-resistant acidizing corrosion inhibitor, a preparation method and application thereof, and a corrosion-inhibiting acidizing fracturing fluid. The high-temperature resistant acidizing corrosion inhibitor provided by the invention takes the quinoline benzyl chloride substances with the structures shown in the formula I and the formula II as main agents, and nitrogen atoms in the quinoline benzyl chloride substances form multi-point adsorption on the surface of the metal pipeline, so that the film forming capability of the high-temperature resistant acidizing corrosion inhibitor on the surface of the metal pipeline is enhanced, the desorption speed of the high Wen Shinai high-temperature acidizing corrosion inhibitor from the surface of the metal pipeline is reduced, and the high-temperature resistant acidizing corrosion inhibitor can play a good role in corrosion inhibition in a high-temperature environment.

Description

A kind of high temperature resistant acidification corrosion inhibitor and its preparation method and application, corrosion inhibition acidification pressure cracking fluid

technical field

The invention relates to the technical field of oil well additives, in particular to a high temperature resistant acidification corrosion inhibitor, a preparation method and application thereof, and a corrosion inhibition acidification fracturing fluid.

Background technique

In the development process of oil and natural gas, acid fracturing technology is often used to achieve the purpose of increasing production. Oil well acid fracturing is one of the important measures to increase production and injection in various oilfields in my country. During operation, the acid fracturing fluid (general concentration is 15% HCl, 20% HCl, 7.5% HCl+1.5% HF, 12% HCl+3% HF and other media with various auxiliary materials) are injected into the formation by common mechanical methods to dissolve the clogging substances in the formation near the bottom of the well and some components in the formation rock, expand the oil flow channel, and reduce the oil flow resistance to achieve purpose of increasing production.

However, during the construction process, the injection of acidified fracturing fluid will cause surface pitting, hydrogen embrittlement and even brittle fracture of oil and gas well tubing and downhole equipment, and sometimes may lead to sudden rupture of downhole tubing, resulting in serious economic losses. At the same time, metallic iron ions that react with the acid in the acidified fracturing fluid may also cause permanent damage to the formation. In order to prevent acid fracturing fluid from corroding oil and gas well tubing and downhole equipment, adding acid corrosion inhibitors to acid fracturing fluid is a necessary anti-corrosion measure. With the increasing demand for oil and gas resources in the world economy and the continuous improvement of drilling and oil production technology, a large number of deep wells, ultra-deep wells (>7000m) and ultra-deep wells (15000m) have been put into development, and more and more high-temperature wells have begun to appear. This has higher and higher requirements for acidification corrosion inhibitors.

At present, a wide variety of acidification corrosion inhibitor products have been developed at home and abroad, but the generally applicable temperature is 140°C and below, and the high temperature resistance is poor.

Contents of the invention

In view of this, the object of the present invention is to provide a high temperature resistant acidification corrosion inhibitor, its preparation method and application, and corrosion inhibition acidification fracturing fluid. The high temperature resistant acidification corrosion inhibitor provided by the invention is resistant to high temperature.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides a high-temperature resistant acidification corrosion inhibitor, which includes quinoline chloride benzyl substances, acetylenic alcohols, metal iodides and solvents;

The mass ratio of quinoline benzyl chloride, acetylenic alcohol, metal iodide and solvent is 0.5-1.5:0.5-4.5:0.5-4.0:3.0-5.0;

The quinoline benzyl chloride substances include quinoline benzyl chloride compounds or quinoline benzyl chloride exchange products;

The quinoline benzyl chloride compound has a structure shown in formula I:

The quinoline benzyl chloride exchange product has a structure shown in formula II:

Preferably, the alkynyl alcohol includes one or more of propynyl alcohol, 1,4-butynediol and 2-propyn-1-ol methanesulfonate.

Preferably, the metal iodide includes one or more of cuprous iodide, potassium iodide and sodium iodide.

Preferably, the solvent is an alcoholic solvent.

Preferably, the alcoholic solvent includes n-butanol and/or ethanol.

The present invention also provides a preparation method of the high temperature resistant acidification corrosion inhibitor described in the technical solution, comprising the following steps:

The quinoline chloride benzyl substance, acetylenic alcohol, metal iodide and solvent are mixed to obtain the high temperature resistant acidification corrosion inhibitor.

Preferably, the mixing is carried out under ultrasonic conditions, the temperature of the ultrasonic is room temperature, the output power density is 0.3-0.6 W/cm ² , and the time is 10-30 min.

The present invention also provides the application of the high-temperature resistant acidification corrosion inhibitor described in the above technical solution in corrosion inhibition and acidification fracturing fluid.

The present invention also provides a corrosion-inhibiting acidizing fracturing fluid, including the high-temperature-resistant acidizing corrosion inhibitor described in the above technical solution and an acidic medium;

The mass percent content of quinoline benzyl chloride in the high temperature resistant acidification corrosion inhibitor in the corrosion inhibition acidification fracturing fluid is 0.5%-1.5%.

Preferably, the acidic medium is an acid solution with a mass concentration of hydrochloric acid of 12% and a mass concentration of hydrofluoric acid of 3%.

The invention provides a high temperature resistant acidification corrosion inhibitor, comprising quinoline chloride benzyl substances, acetylenic alcohol, metal iodide and solvent; The mass ratio is 0.5～1.5:0.5～4.5:0.5～4.0:3.0～5.0; the quinoline benzyl chloride compounds include quinoline benzyl chloride compounds or quinoline benzyl chloride exchange products; the quinoline chloride benzyl chloride The benzyl compound has the structure shown in formula I, and the quinoline benzyl chloride exchange product has the structure shown in formula II. The high-temperature acidification corrosion inhibitor provided by the invention uses quinoline chloride benzyl as the main agent, and the nitrogen atoms in the quinoline chloride benzyl substance form multi-point adsorption on the surface of the metal pipeline, which enhances the high temperature resistance to acidification corrosion inhibition The film-forming ability of the agent on the surface of the metal pipe reduces the desorption speed of the high temperature resistant acidification corrosion inhibitor from the surface of the metal pipe at high temperature, so it can play a good corrosion inhibition effect in the high temperature environment. In particular, the high-temperature acidification corrosion inhibitor based on the quinoline benzyl chloride exchange product shown in formula II uses multiple nitrogen atoms in the quinoline benzyl chloride exchange product to form more points on the surface of the metal pipe. Adsorption makes the high temperature resistant acidification corrosion inhibitor more resistant to high temperature. The data in the examples show that the high-temperature acidification corrosion inhibitor with quinoline benzyl chloride compound as the main agent can withstand 160°C, and the high-temperature acidification corrosion inhibitor with quinoline benzyl chloride exchange product as the main agent can withstand 200°C .

The present invention also provides a preparation method of the high temperature resistant acidification corrosion inhibitor described in the above technical scheme, comprising the following steps: mixing quinoline benzyl chloride, acetylenic alcohol, metal iodide and a solvent to obtain the high temperature resistant acidification corrosion inhibitor Corrosion inhibitor. The preparation method provided by the invention has easy-to-obtain raw materials and simple operation.

The present invention also provides the application of the high-temperature resistant acidification corrosion inhibitor described in the above technical solution in corrosion inhibition and acidification fracturing fluid. Because the high temperature resistant acidification corrosion inhibitor provided by the invention has excellent high temperature resistance and corrosion inhibition, it can be better applied to corrosion inhibition acidification fracturing fluid.

The present invention also provides a corrosion-inhibiting and acidizing fracturing fluid, including the high-temperature resistant acidifying corrosion inhibitor described in the above technical scheme and acidic medium; The mass percent content in the etching and acidizing fracturing fluid is 0.5% to 1.5%. The corrosion inhibiting and acidizing fracturing fluid provided by the invention has excellent corrosion inhibition and high temperature resistance.

Detailed ways

The invention provides a high-temperature resistant acidification corrosion inhibitor, which includes quinoline chloride benzyl substances, acetylenic alcohols, metal iodides and solvents;

The mass ratio of quinoline benzyl chloride, acetylenic alcohol, metal iodide and solvent is 0.5-1.5:0.5-4.5:0.5-4.0:3.0-5.0;

The quinoline benzyl chloride substances include quinoline benzyl chloride compounds or quinoline benzyl chloride exchange products;

The quinoline benzyl chloride compound has a structure shown in formula I, and the quinoline benzyl chloride exchange product has a structure shown in formula II.

In the present invention, unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.

The high-temperature acidification corrosion inhibitor provided by the invention includes quinoline benzyl chloride substances. In the present invention, the quinoline benzyl chloride-based substances include the quinoline benzyl chloride compound with the structure shown in formula I or the quinoline benzyl chloride exchange product with the structure shown in formula II.

In the present invention, the preparation method of described quinoline benzyl chloride compound preferably comprises the following steps:

Benzyl chloride and quinoline are dissolved, and the first reaction is carried out to obtain the quinoline benzyl chloride compound.

In the present invention, the molar ratio of benzyl chloride to quinoline is preferably 1:1. In the present invention, the dissolved reagent preferably includes acetonitrile. In the present invention, the first reaction is preferably carried out under the condition of heating to reflux. In the present invention, the time for the first reaction is preferably 24 hours. After the first reaction, the present invention preferably further includes cooling to room temperature and performing suction filtration to obtain the quinoline benzyl chloride compound.

In the present invention, benzyl chloride and quinoline are the flow process of preparing quinoline benzyl chloride compound as raw materials as shown in the following formula:

In the present invention, the preparation method of described quinoline chloride benzyl exchange product preferably comprises the following steps:

Mixing benzotriazole and sodium hydroxide for a second reaction to obtain an intermediate product;

The intermediate product and the quinoline benzyl chloride compound are mixed for ion exchange reaction to obtain the quinoline benzyl chloride exchange product.

The invention mixes the benzotriazole and sodium hydroxide to carry out the second reaction to obtain the intermediate product. In the present invention, the molar ratio of benzotriazole to sodium hydroxide is preferably 1:1. In the present invention, the sodium hydroxide is used in the form of an aqueous sodium hydroxide solution, and the mass concentration of the aqueous sodium hydroxide solution is preferably 30% to 50%, more preferably 40%. In the present invention, the temperature of the second reaction is preferably 60-80° C., and the time is preferably 12 hours. After the second reaction, the present invention preferably uses the obtained second reaction feed liquid directly as an intermediate product for subsequent reactions.

After the intermediate product is obtained, the present invention mixes the intermediate product with the quinoline benzyl chloride compound to carry out an ion exchange reaction to obtain the quinoline benzyl chloride exchange product. In the present invention, the molar ratio of the benzotriazole to the quinoline benzyl chloride compound is preferably 1:1. In the present invention, the temperature of the ion exchange reaction is preferably 60-80° C., and the time is preferably 24 hours. After the ion exchange reaction, the present invention preferably further includes extracting the obtained ion exchange reaction feed liquid, and sequentially drying and distilling the obtained organic phase to obtain the quinoline benzyl chloride exchange product. In the present invention, the extraction agent used in the extraction is preferably dichloroethane; the number of times of the extraction is preferably 3 times. In the present invention, the drying method is preferably desiccant drying; the desiccant is preferably anhydrous sodium sulfate. The present invention does not specifically limit the parameters of the distillation, as long as the solvent in the organic phase can be completely removed.

In the present invention, the flow process of preparing said quinoline benzyl chloride exchange product is shown in the following formula:

In the present invention, the nitrogen atoms in the quinoline chloride benzylic substances can form multi-point adsorption on the surface of the metal pipe, which enhances the film-forming ability of the high-temperature resistant acidification corrosion inhibitor on the surface of the metal pipe, and reduces the corrosion resistance at high temperature. The desorption speed of the high-temperature acidification corrosion inhibitor from the surface of the metal pipe can exert a good corrosion inhibition effect in a high-temperature environment.

The high temperature acidification corrosion inhibitor provided by the invention includes acetylenic alcohol. In the present invention, the alkynyl alcohol preferably includes one or more of propynyl alcohol, 1,4-butynediol and methanesulfonic acid-2-propyn-1-ol, more preferably propynyl alcohol. In the present invention, the alkynyl alcohol, as a synergist, mainly utilizes π electrons to be adsorbed in the gaps between quinoline benzyl chlorides to form a complete and dense adsorption film, which has a good corrosion inhibition effect.

The high-temperature acidification corrosion inhibitor provided by the invention includes metal iodides. In the present invention, the metal iodide preferably includes one or more of cuprous iodide, potassium iodide and sodium iodide, more preferably cuprous iodide. In the present invention, there is characteristic adsorption between the metal iodide and the easily corroded active metal in the pipeline in the application environment, and can coordinate with the active metal, thereby enhancing the interaction between the high temperature resistant acidification corrosion inhibitor and the surface of the pipeline. The adsorption force can promote the formation of a complete and dense adsorption film of quinoline benzyl chloride, which has a good corrosion inhibition effect.

The high temperature acidification corrosion inhibitor provided by the invention includes a solvent. In the present invention, the solvent is preferably an alcoholic solvent; the alcoholic solvent preferably includes n-butanol and/or ethanol.

The mass ratio of quinoline benzyl chloride, acetylenic alcohol, metal iodide and solvent in the high temperature resistant acidification corrosion inhibitor provided by the present invention is 0.5～1.5:0.5～4.5:0.5～4.0:3.0～5.0, specifically preferably 0.5: 4.5: 1.0: 3.0, 0.5: 4.5: 0.5: 3.0, 0.5: 4.0: 1.0: 3.0, 1.0: 3.0: 0.5: 3.0, 0.5: 0.5: 4.0: 3.0, 1.5: 1.5: 1.0: 3.0, 1.0: 1.0:2:3.0, 1.0:1.0:1.0:3.0, 0.5:0.5:2.0:3.0, 0.5:0.5:1.0:3.0, 1.0:1.0:0.5:3.0 or 0.5:0.5:0.5:3.0.

The present invention also provides a preparation method of the high temperature resistant acidification corrosion inhibitor described in the technical solution, comprising the following steps:

The quinoline chloride benzyl substance, acetylenic alcohol, metal iodide and solvent are mixed to obtain the high temperature resistant acidification corrosion inhibitor.

In the present invention, the mixing is preferably performed under ultrasonic conditions. In the present invention, the temperature of the ultrasound is preferably room temperature. In the present invention, the output power density of the ultrasound is preferably 0.3-0.6 W/cm ² , and the time is preferably 10-30 min.

The present invention also provides the application of the high-temperature resistant acidification corrosion inhibitor described in the above technical solution in corrosion inhibition and acidification fracturing fluid.

The present invention also provides a corrosion-inhibiting acidizing fracturing fluid, which comprises the high-temperature-resistant acidizing corrosion inhibitor described in the above technical solution and an acidic medium. In the present invention, the mass percent content of quinoline benzyl chloride in the high temperature resistant acidification corrosion inhibitor in the corrosion inhibition acidification fracturing fluid is 0.5%-1.5%, preferably 1%.

In the present invention, the acidic medium is preferably an acid solution with a mass concentration of hydrochloric acid of 12% and a mass concentration of hydrofluoric acid of 3%.

The high-temperature resistant acidification corrosion inhibitor provided by the present invention, its preparation method and application, and the corrosion-inhibited acidification fracturing fluid will be described in detail below in conjunction with the examples, but they should not be understood as limiting the protection scope of the present invention.

Example 1

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain quinoline benzyl chloride compound. Weigh 0.1mol of benzotriazole and add it to 7mL NaOH aqueous solution (mass concentration: 40%), and react at 70°C for 12h to obtain an aqueous solution of sodium benzotriazole; add 0.1mol of quinoline benzyl chloride to Into the aqueous solution of sodium benzotriazole, carry out ion exchange reaction at 70°C for 24 hours, extract 3 times with dichloromethane, dry the organic phase with anhydrous sodium sulfate overnight, filter off the desiccant, and distill off the solvent to obtain the main Quinoline Chloride Benzyl Exchanger.

High temperature acidification corrosion inhibitor:

Weigh the main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol according to the mass ratio of 0.5:4.5:1.0:3.0, and add them to a 3mL centrifuge tube in turn, in an ultrasonic cleaner at 25°C, output power density At 0.5W/cm ² , mix for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 2

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain quinoline benzyl chloride compound. Weigh 0.1mol of benzotriazole and add it to 7mL NaOH aqueous solution (mass concentration: 40%), and react at 70°C for 12h to obtain an aqueous solution of sodium benzotriazole; add 0.1mol of quinoline benzyl chloride to Put it into benzotriazole sodium aqueous solution, carry out ion exchange reaction at 70°C for 24 hours, extract with dichloromethane for 3 times, dry the organic phase with anhydrous sodium sulfate overnight, filter off the desiccant, and distill off the solvent to obtain the main ingredient Quinoline Chloride Benzyl Exchanger.

High temperature acidification corrosion inhibitor:

Weigh the main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol according to the mass ratio of 0.5:4.5:0.5:3.0, and add them to a 3mL centrifuge tube in turn, in an ultrasonic cleaner at 25°C, output power density At 0.5W/cm ² , mix for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 3

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain quinoline benzyl chloride compound. Weigh 0.1mol of benzotriazole and add it to 7mL NaOH aqueous solution (mass concentration: 40%), and react at 70°C for 12h to obtain an aqueous solution of sodium benzotriazole; add 0.1mol of quinoline benzyl chloride to Put it into benzotriazole sodium aqueous solution, carry out ion exchange reaction at 70°C for 24 hours, extract with dichloromethane for 3 times, dry the organic phase with anhydrous sodium sulfate overnight, filter off the desiccant, and distill off the solvent to obtain the main ingredient Quinoline Chloride Benzyl Exchanger.

High temperature acidification corrosion inhibitor:

Weigh the main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol according to the mass ratio of 0.5:4.0:1.0:3.0, and add them to a 3mL centrifuge tube in turn, in an ultrasonic cleaner at 25°C, output power density At 0.5W/cm ² , mix for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 4

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain quinoline benzyl chloride compound. Weigh 0.1mol of benzotriazole and add it to 7mL NaOH aqueous solution (mass concentration: 40%), and react at 70°C for 12h to obtain an aqueous solution of sodium benzotriazole; add 0.1mol of quinoline benzyl chloride to Put into benzotriazole sodium aqueous solution, carry out ion exchange reaction at 70°C for 24 hours, extract with dichloromethane three times, dry the organic phase with anhydrous sodium sulfate overnight, filter off the desiccant, distill off the solvent to obtain the main ingredient Quinoline Chloride Benzyl Exchanger.

High temperature acidification corrosion inhibitor:

Weigh the main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol according to the mass ratio of 1.0:3.0:0.5:3.0, and add them to a 3mL centrifuge tube in turn, in an ultrasonic cleaner at 25°C, output power density At 0.5W/cm ² , mix for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 5

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain quinoline benzyl chloride compound. Weigh 0.1mol of benzotriazole and add it to 7mL NaOH aqueous solution (mass concentration: 40%), and react at 70°C for 12h to obtain an aqueous solution of sodium benzotriazole; add 0.1mol of quinoline benzyl chloride to In aqueous solution of sodium benzotriazole, conduct ion exchange reaction at 70°C for 24 hours, extract with dichloromethane for 3 times, dry the organic phase with anhydrous sodium sulfate overnight, filter off the desiccant, and distill off the solvent to obtain the main ingredient Quinoline Chloride Benzyl Exchanger.

High temperature acidification corrosion inhibitor:

Weigh the main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol according to the mass ratio of 0.5:0.5:4.0:3.0, and add them to a 3mL centrifuge tube in turn, in an ultrasonic cleaner at 25°C, output power density At 0.5W/cm ² , mix for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

performance evaluation

The retest rate experiment was carried out on the high temperature resistant acidification corrosion inhibitors prepared in Examples 1-5.

The dynamic experiment was carried out in accordance with the industry standard SY/T 5405-1996 "Performance Test Methods and Evaluation Indexes of Corrosion Inhibitors for Acidification". Polish the steel sheet with metallographic sandpaper, degrease and degrease with distilled water, absolute ethanol, and acetone in sequence, blot with filter paper and dry in an oven for 2 hours. Weigh its mass accurately with an analytical balance. The steel sheet is suspended vertically in the high temperature and high pressure dynamic corrosion tester and immersed in the experimental medium. After the experiment, the coupons were taken out, washed with distilled water, absolute ethanol, and acetone to remove oil, dried for 2 hours, and then weighed. The evaluation test conditions are: working temperature: 200°C, test pressure: 16.0MPa, stirring speed: 60r/min, and reaction time: 4h. The acidic medium used is: 12% concentrated hydrochloric acid + 3% hydrofluoric acid; the steel used is N80; based on the total mass of the main agent, propargyl alcohol and cuprous iodide, the addition of high temperature resistant acidification corrosion inhibitor in the acidic medium The amount is 4.0-6.0%.

The calculation of corrosion rate is as follows:

Among them, V _i --- monolithic corrosion rate, g/(m ² ·h);

Δm _i ------ corrosion mass of test piece, g;

Δ _i ------ surface area of test piece, mm ² ;

Δt------reaction time, h.

The corrosion inhibition properties of the high temperature acidification corrosion inhibitors obtained in Examples 1 to 5 are shown in Table 1.

Corrosion inhibition performance of the high temperature acidification corrosion inhibitor obtained in Table 1 Examples 1 to 5

Example 6

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain the main agent quinoline benzyl chloride compound.

High temperature acidification corrosion inhibitor:

The main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol were weighed according to the mass ratio of 1.5:1.5:1.0:3.0, and added to a 3mL centrifuge tube in sequence, and placed in an ultrasonic cleaner at 25°C with an output power density of 0.5W/cm ² , mixed for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 7

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain the main agent quinoline benzyl chloride compound.

High temperature acidification corrosion inhibitor:

The main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol were weighed according to the mass ratio of 1.0:1.0:2:3.0, and added to a 3mL centrifuge tube in sequence, and placed in an ultrasonic cleaner at 25°C with an output power density of 0.5W/cm ² , mixed for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 8

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain the main agent quinoline benzyl chloride compound.

High temperature acidification corrosion inhibitor:

The main ingredient, propargyl alcohol, cuprous iodide and absolute ethanol were weighed according to the mass ratio of 1.0:1.0:1.0:3.0, and added to a 3mL centrifuge tube in sequence, and placed in an ultrasonic cleaner at 25°C with an output power density of 0.5W/cm ² , mixed for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 9

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain the main agent quinoline benzyl chloride compound.

High temperature acidification corrosion inhibitor:

The main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol were weighed according to the mass ratio of 0.5:0.5:2.0:3.0, and added to a 3mL centrifuge tube in sequence, and placed in an ultrasonic cleaner at 25°C with an output power density of 0.5W/cm ² , mixed for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 10

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain the main agent quinoline benzyl chloride compound.

High temperature acidification corrosion inhibitor:

The main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol were weighed according to the mass ratio of 0.5:0.5:1.0:3.0, and added to a 3mL centrifuge tube in sequence, and placed in an ultrasonic cleaner at 25°C with an output power density of 0.5W/cm ² , mixed for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 11

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain the main agent quinoline benzyl chloride compound.

High temperature acidification corrosion inhibitor:

The main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol were weighed according to the mass ratio of 1.0:1.0:0.5:3.0, and added to a 3mL centrifuge tube in sequence, and placed in an ultrasonic cleaner at 25°C with an output power density of 0.5W/cm ² , mixed for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

Example 12

Put 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round bottom flask, add 150mL of acetonitrile as a solvent, heat and reflux for 24h, cool to room temperature, and wait for the precipitation of quinoline benzyl chloride quaternary ammonium salt, pump Filter to obtain the main agent quinoline benzyl chloride compound.

High temperature acidification corrosion inhibitor:

The main ingredient, propargyl alcohol, cuprous iodide, and absolute ethanol were weighed according to the mass ratio of 0.5:0.5:0.5:3.0, and added to a 3mL centrifuge tube in sequence, and placed in an ultrasonic cleaner at 25°C with an output power density of 0.5W/cm ² , mixed for 30 minutes to obtain a high temperature resistant acidification corrosion inhibitor.

performance evaluation

The retest rate experiment was carried out on the high temperature acidification corrosion inhibitors prepared in Examples 6-12.

The test method is consistent with the test method of the high-temperature acidification-resistant corrosion inhibitor obtained in Examples 1-5, the difference is only: the working temperature is: 160 ° C, based on the total mass of the main agent, propargyl alcohol and cuprous iodide, the high-temperature acidification-resistant The addition amount of the corrosion inhibitor in the acidic medium is 1.5-4.0%.

The results are shown in Table 2.

Corrosion inhibition performance of high temperature acidification corrosion inhibitor obtained in Table 2 Examples 6-12

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. A high-temperature resistant acidification corrosion inhibitor is characterized in that, comprising quinoline chloride benzyl substances, acetylenic alcohols, metal iodides and solvents; The mass ratio of quinoline benzyl chloride, acetylenic alcohol, metal iodide and solvent is 0.5-1.5:0.5-4.5:0.5-4.0:3.0-5.0; The quinoline benzyl chloride substance is a quinoline benzyl chloride exchange product; The quinoline benzyl chloride exchange product has a structure shown in formula II:

2. The high-temperature resistant acidification corrosion inhibitor according to claim 1, characterized in that, the alkynyl alcohol comprises propynyl alcohol, 1,4-butynediol and methanesulfonic acid-2-propyn-1-alcohol one or more of . 3. The high temperature resistant acidification corrosion inhibitor according to claim 1, characterized in that the metal iodide comprises one or more of cuprous iodide, potassium iodide and sodium iodide. 4. The high temperature resistant acidification corrosion inhibitor according to claim 1, characterized in that the solvent is an alcoholic solvent. 5. The high temperature resistant acidification corrosion inhibitor according to claim 4, characterized in that the alcohol solvent comprises n-butanol and/or ethanol. 6. The preparation method of the high temperature resistant acidification corrosion inhibitor according to any one of claims 1 to 5, characterized in that it comprises the following steps: The quinoline chloride benzyl substance, acetylenic alcohol, metal iodide and solvent are mixed to obtain the high temperature resistant acidification corrosion inhibitor. 7. The preparation method according to claim 6, characterized in that the mixing is carried out under the condition of ultrasound, the temperature of the ultrasound is room temperature, the output power density is 0.3-0.6 W/cm ² , and the time is 10- 30min. 8. The application of the high-temperature resistant acidification corrosion inhibitor according to any one of claims 1 to 5 in corrosion inhibition and acidification fracturing fluid. 9. A corrosion inhibiting acidizing fracturing fluid, characterized in that it comprises the high temperature resistant acidizing corrosion inhibitor and acidic medium according to any one of claims 1 to 5; The mass percent content of the quinoline chloride benzyls in the corrosion inhibiting acidizing fracturing fluid is 0.5% to 1.5%. 10. The corrosion-inhibiting and acidizing fracturing fluid according to claim 9, wherein the acidic medium is an acid solution with a mass concentration of hydrochloric acid of 12% and a mass concentration of hydrofluoric acid of 3%.