2, 4, 6-tri (aminoethanesulfonic acid)-1, 3, 5-triazine as well as preparation method and application thereof

Abstract

The invention discloses 2, 4, 6-tri (aminoethanesulfonic acid)-1, 3, 5-triazine as well as a preparation method and application thereof, and relates to the technical field of corrosion inhibitor synthesis. The preparation method comprises the following steps: (1) dissolving an aminoethanesulfonic acid solid with alkali in a polar solvent to obtain a solution I; (2) dissolving cyanuric chloride with an acetone solution to obtain a solution II; and (3) dropwise adding the solution I obtained in the step (1) into the solution II obtained in the step (2), reacting under an ice bath condition, regulating the pH value by adopting an acid-binding agent, and sequentially carrying out suction filtration, washing and drying after the reaction is finished, so as to obtain the 2, 4, 6-tri (aminoethanesulfonic acid)-1, 3, 5-triazine. According to the invention, a polysulfamic acid hydrophilic chain is introduced to a triazine ring, so that the triazine ring has excellent surface activity, reduced surface tension and directional adsorption capacity, and can effectively inhibit acidification corrosion and prolong the service life of equipment.

Description

Technical Field

[0001] The present invention relates to the technical field of corrosion inhibitor synthesis, and particularly relates to a 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine, a preparation method thereof, and an application thereof. Background Art

[0002] Acidification is a measure for enhanced oil recovery in the process of oil and gas field development. During the acidification construction process, the injection of acid solution will cause corrosion of the tubing and downhole metal equipment in oil and gas wells. In severe cases, it may lead to sudden rupture accidents of downhole tubing, posing serious safety hazards. To prevent the corrosion of equipment such as tubing and casing by acid solution, adding corrosion inhibitors to the acid solution is an essential, commonly used, and effective anti-corrosion measure. Most traditional corrosion inhibitors are based on inorganic salts or organic compounds, which inhibit corrosion by adsorbing on the metal surface to form a protective layer. However, these corrosion inhibitors often have some problems in practical applications, such as poor environmental protection, high toxicity, low corrosion inhibition efficiency, etc. Especially under extreme conditions such as high acidity, high temperature, or high pressure, the corrosion inhibition effect of traditional corrosion inhibitors is often unsatisfactory. In recent years, with the improvement of environmental awareness and the progress of science and technology, people have begun to pay attention to more environmentally friendly and efficient corrosion inhibitors. Among them, corrosion inhibitors based on organic heterocyclic compounds have attracted much attention due to their unique molecular structure and excellent corrosion inhibition performance. Such corrosion inhibitors usually contain multiple active groups, such as amino groups, hydroxyl groups, sulfonic acid groups, etc., which can form strong chemical bonds with the metal surface, thereby significantly improving the corrosion inhibition effect. However, although organic heterocyclic corrosion inhibitors show good corrosion inhibition performance under laboratory conditions, they still face some challenges in practical applications.

[0003] Therefore, the present invention proposes a novel corrosion inhibitor based on organic heterocyclic compounds, aiming to solve the problems existing in the existing corrosion inhibitors and provide a more environmentally friendly, efficient, and stable corrosion inhibition solution. Summary of the Invention

[0004] In order to solve the above technical problems, the object of the present invention is to provide a 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine, a preparation method thereof, and an application thereof. By introducing a multi-amino sulfonic acid hydrophilic chain on the triazine ring, it has excellent surface activity, can reduce the surface tension, has the ability of directional adsorption, can effectively inhibit acidification corrosion, and prolong the service life of equipment.

[0005] The technical solution for the present invention to solve the above technical problems is as follows: providing a preparation method of 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine, comprising the following steps: (1) Dissolve solid aminoethanesulfonic acid with an alkali in a polar solvent to obtain Solution 1; (2) Dissolve cyanuric chloride with an acetone solution to obtain Solution 2; (3) Add one drop of the solution obtained in step (1) to solution two obtained in step (2), react under ice bath conditions, and simultaneously adjust the pH value using an acid-binding agent. After the reaction is completed, perform suction filtration, washing, and drying in sequence to obtain 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine.

[0006] Furthermore, in step (1), the polar solvent is water and the base is sodium hydroxide.

[0007] Furthermore, in steps (1) and (2), the molar ratio of the base, aminoethanesulfonic acid, cyanuric chloride, and acetone solution is 2 - 6:3:0.5 - 1:5 - 8.

[0008] Furthermore, in step (3), perform an ice-salt bath at a temperature of -5 to 0 °C and adjust the pH value to 7.5 - 8.5.

[0009] Furthermore, in step (3), perform an ice-salt bath at a temperature of -5 to 0 °C and adjust the pH value to 7.5 - 8.5.

[0010] Furthermore, the concentrations of the sodium hydroxide solution, sodium carbonate solution, and sodium bicarbonate solution are all 10 wt%.

[0011] Furthermore, in step (3), monitor the reaction end point using a developing agent; the developing agent is composed of acetone, toluene, and water in a volume ratio of 6:1:0.5.

[0012] Furthermore, in step (3), wash with acetone 2 - 3 times to remove unreacted cyanuric chloride, and perform vacuum drying at a temperature of 60 - 80 °C for 12 - 24 h.

[0013] The present invention also provides 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine prepared by the preparation method of the above-mentioned 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine.

[0014] Furthermore, the structural formula of 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine is: .

[0015] The present invention also provides the application of the above-mentioned 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine as a corrosion inhibitor in inhibiting metal corrosion in an acidic environment.

[0016] Furthermore, the metal is carbon steel.

[0017] The present invention has the following beneficial effects: 1. The 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine of the present invention combines the synergistic effects of nitrogen atom-containing hydrophilic chains and triazine rings, improving the corrosion inhibition performance. The rigid structure of the triazine ring helps the molecule form a dense protective layer on the metal surface, while the introduction of multiple amino and sulfonic acid groups provides active sites for interaction with the metal surface. The hydrophilic aminoethanesulfonic acid groups not only improve solubility, but also the chain structure enables the molecule to better penetrate into the tiny gaps on the metal surface, thereby enhancing the corrosion inhibition effect. At the same time, the nitrogen and oxygen atoms in the base chain also have certain nucleophilicity and electrophilicity, which can interact with the electron cloud on the metal surface, thus slowing down the corrosion rate of the metal.

[0018] 2. The 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine of the present invention is non-toxic as a corrosion inhibitor, has good corrosion inhibition effect, and low cost; when widely used for the corrosion inhibition of carbon steel in strongly acidic media, it can effectively inhibit the corrosion of carbon steel. Compared with traditional corrosion inhibitors, it has better corrosion inhibition effect, less dosage, and simpler synthesis process, conforms to the world environmental protection trend, can replace traditional corrosion inhibitors such as organic phosphorus and nitrite, and reduce the impact on the environment.

[0019] 3. The corrosion inhibitor not only has excellent corrosion inhibition performance, can effectively inhibit the corrosion of carbon steel in strongly acidic media, has good compatibility with acid solutions, can meet the corrosion inhibition requirements under harsh conditions such as acidification construction of oil and gas wells, but also has good biocompatibility and environmental friendliness, and is expected to be widely used in many fields such as metal processing, oil exploitation, and chemical production. Detailed implementation mode

[0020] The principles and characteristics of the present invention are described below. The examples given are only used to explain the present invention and are not intended to limit the scope of the present invention. For those not specified in the examples, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0021] Example 1 A 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine, and its preparation method includes the following steps: (1) Disperse aminoethanesulfonic acid (62.58 g, 0.50 mol) and sodium hydroxide (20.00 g, 0.50 mol) in 200 mL of water, and stir at 60 °C until dissolved to obtain Solution 1; (2) In a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, stir and dissolve cyanuric chloride (31.50 g, 0.17 mol) with acetone solution (48.40 g, 0.83 mol) to obtain Solution 2; (3) Using a constant-pressure dropping funnel, add the solution obtained in step (1) drop by drop to solution two obtained in step (2) at a rate of 1 - 2 drops per second. React in an ice-salt bath at 0 °C, and simultaneously adjust the pH value to 8 using sodium hydroxide solution (10 wt%). Monitor the reaction endpoint with the developing agent (acetone, toluene, and water with a volume ratio of 6:1:0.5). After the reaction is completed, perform suction filtration, wash three times with acetone to remove unreacted cyanuric chloride, and vacuum dry at 60 °C for 12 h to obtain 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine.

[0022] Example 2 A 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine, and its preparation method includes the following steps: (1) Disperse aminoethanesulfonic acid (62.58 g, 0.50 mol) and sodium hydroxide (13.33 g, 0.33 mol) in 150 mL of water, and stir until dissolved at 60 °C to obtain solution one; (2) In a three-necked flask equipped with a stirrer, thermometer, and constant-pressure dropping funnel, dissolve cyanuric chloride (31.50 g, 0.17 mol) with acetone solution (58.08 g, 1.00 mol) by stirring to obtain solution two; (3) Using a constant-pressure dropping funnel, add the solution obtained in step (1) drop by drop to solution two obtained in step (2) at a rate of 1 - 2 drops per second. React in an ice-salt bath at 0 °C, and simultaneously adjust the pH value to 8 using sodium carbonate solution (10 wt%). Monitor the reaction endpoint with the developing agent (acetone, toluene, and water with a volume ratio of 6:1:0.5). After the reaction is completed, perform suction filtration, wash three times with acetone to remove unreacted cyanuric chloride, and vacuum dry at 70 °C for 12 h to obtain 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine.

[0023] Example 3 A 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine, and its preparation method includes the following steps: (1) Disperse aminoethanesulfonic acid (62.58 g, 0.50 mol) and sodium hydroxide (40.00 g, 1.00 mol) in 200 mL of water, and stir until dissolved at 60 °C to obtain solution one; (2) In a three-necked flask equipped with a stirrer, thermometer, and constant-pressure dropping funnel, dissolve cyanuric chloride (15.75 g, 0.08 mol) with acetone solution (48.40 g, 0.83 mol) by stirring to obtain solution two; (3) Using a constant-pressure dropping funnel, add the solution obtained in step (1) drop by drop to solution two obtained in step (2) at a rate of 1 - 2 drops per second. React in an ice-salt bath at 0 °C, and simultaneously adjust the pH value to 8 using a sodium bicarbonate solution (10 wt%). Monitor the reaction endpoint with a developing agent (acetone, toluene, and water in a volume ratio of 6:1:0.5). After the reaction is completed, perform suction filtration, wash three times with acetone to remove unreacted cyanuric chloride, and dry in vacuo at 80 °C for 24 h to obtain 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine.

[0024] Example 4 A 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine, and its preparation method comprises the following steps: (1) Disperse aminoethanesulfonic acid (62.58 g, 0.50 mol) and sodium hydroxide (16.00 g, 0.40 mol) in 150 mL of water, and stir until dissolved at 50 °C to obtain solution one; (2) In a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel, stir and dissolve cyanuric chloride (31.50 g, 0.17 mol) with an acetone solution (58.08 g, 1.00 mol) to obtain solution two; (3) Using a constant-pressure dropping funnel, add the solution obtained in step (1) drop by drop to solution two obtained in step (2) at a rate of 1 - 2 drops per second. React in an ice-salt bath at 0 °C, and simultaneously adjust the pH value to 8 using a sodium carbonate solution (10 wt%). Monitor the reaction endpoint with a developing agent (acetone, toluene, and water in a volume ratio of 6:1:0.5). After the reaction is completed, perform suction filtration, wash three times with acetone to remove unreacted cyanuric chloride, and dry in vacuo at 60 °C for 24 h to obtain 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine.

[0025] Test Example Test the dissolution and dispersibility of the 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine obtained in Test Examples 1 - 4 as a corrosion inhibitor after being placed in a 15% HCl solution for 7 d. The experimental results are shown in Table 1.

[0026] Table 1 Water Solubility Test Results

[0027] The static coupon method was used to determine the slow-release performance of 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine obtained in Examples 1-4 as a corrosion inhibitor. The specific process was as follows: In a 15% HCl solution, the products obtained in Examples 1-4 were added respectively, and the corrosion rates of N80 steel sheets under different corrosion inhibitors were tested. The experimental time was 4 h, the test temperature was 60 °C, and the addition amount of the corrosion inhibitor was 0.5%. The experimental results are shown in Table 2.

[0028] Table 2 Statistical table of slow-release rate

[0029] As can be seen from Table 1 and Table 2, 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine of the present invention has excellent corrosion inhibition effect on N80 steel and good dissolution and dispersion properties. The corrosion inhibitor can form a dense protective film on the metal surface, thereby isolating the metal from the corrosive medium and slowing down the corrosion rate.

[0030] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine, characterized in that: The following steps are involved: (1) Dissolve aminoethanesulfonic acid solid in a polar solvent with a base to obtain solution 1; (2) Dissolve cyanuric chloride in acetone solution to obtain solution 2; (3) adding the solution 1 obtained in step (1) dropwise to the solution 2 obtained in step (2), reacting in an ice bath, and adjusting the pH value with an acid binding agent. After the reaction is completed, filtering, washing and drying are performed in sequence to obtain 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine.

2. The method for preparing 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine according to claim 1, characterized in that: In step (1), the polar solvent is water and the base is sodium hydroxide.

3. The method for preparing 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine according to claim 1, characterized in that: In step (1) and step (2), the molar ratio of the alkali, aminoethanesulfonic acid, cyanuric chloride and acetone solution is 2-6:3:0.5-1:5-8.

4. The method for preparing 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine according to claim 1, characterized in that: In step (3), the pH value is adjusted to 7.5-8.5 in an ice-salt bath at a temperature of -5-0°C.

5. The method for preparing 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine according to claim 1, characterized in that: In step (3), the acid binding agent is one of sodium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution.

6. The method for preparing 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine according to claim 5, characterized in that: The concentrations of the sodium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution were all 10 wt%.

7. The method for preparing 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine according to claim 1, characterized in that: In step (3), the reaction endpoint is monitored by a developing agent; the developing agent is composed of acetone, toluene and water in a volume ratio of 6:1:0.

5.

8. The method for preparing 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine according to claim 1, characterized in that: In step (3), the unreacted cyanuric chloride is removed by washing with acetone for 2 to 3 times, and then vacuum dried at 60 to 80°C for 12 to 24 hours.

9. 2,4,6-Tris(aminoethanesulfonic acid)-1,3,5-triazine obtained by the preparation method of 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine according to any one of claims 1 to 8.

10. Use of the 2,4,6-tris(aminoethanesulfonic acid)-1,3,5-triazine according to claim 9 as a corrosion inhibitor in inhibiting metal corrosion in an acidic environment.

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