CN109020956A - A kind of more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter and its preparation method and application - Google Patents

Abstract

The invention discloses a polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor and its preparation method and application. The preparation method of the anti-oxidative corrosion inhibitor comprises the following steps: dissolving cyanuric chloride in an organic solvent to obtain For solution A, add organic amine into organic solvent to obtain solution B, add solution B to solution A at 0-5°C, stir for 2-3 hours, then raise the temperature to 30-45°C for 4-6 hours, and then heat up React at 70-80°C for 8-12h; cool to room temperature, filter, wash, and dry to obtain. The corrosion inhibitor has good corrosion inhibition performance at high temperature. When the corrosion inhibitor is used as an anti-oxygen corrosion inhibitor for gas injection wells, it has good solubility in high-salinity formation water, and it is resistant to oxygen corrosion of carbon steel in gas injection wells. have obvious inhibitory effect.

Description

A kind of polyheterocyclic cyanuric chloride antioxidation corrosion inhibitor and its preparation method and application

technical field

The invention relates to the technical field of corrosion inhibitor materials, in particular to a polyheterocyclic cyanuric chloride anti-oxidation corrosion inhibitor and its preparation method and application.

Background technique

Gas flooding is widely used in oilfield enhanced oil recovery. The nitrogen flooding technology adopted in the process of gas injection flooding in my country's oilfields, due to cost and construction reasons, the injected nitrogen often contains a certain amount of oxygen, and the injected formation water is mostly high-salinity formation water, and conventional corrosion inhibitors have poor solubility. , poor compatibility, slow adsorption and film formation in formation water. At present, there are few types of corrosion inhibitors for oxygen corrosion in neutral medium of gas injection wells. Although oxidized corrosion inhibitors can inhibit the corrosion of carbon steel in neutral medium, their dosage is high and the cost is high, especially when the dosage is lower than the critical concentration However, it will accelerate local pitting corrosion; although the precipitation type corrosion inhibitor can effectively form a precipitation film on the cathode area of the carbon steel surface, the erosion effect during the gas injection process leads to poor film formation stability and accelerated corrosion; organic adsorption corrosion inhibitors are mostly There are situations such as poor compatibility and poor solubility with high-salinity formation water. Conventional imidazoline corrosion inhibitors are mostly used in _CO2 corrosion protection, Mannich base corrosion inhibitors are mostly used in acidification, and fatty amines and Schiff bases are water-soluble Therefore, developing an anti-oxidant corrosion inhibitor for gas injection wells with excellent performance has become a new development direction in the field of corrosion inhibitor research.

Contents of the invention

Aiming at the above-mentioned deficiencies in the prior art, the present invention provides a polyheterocyclic cyanuric chloride anti-oxidation corrosion inhibitor and its preparation method and application. The preparation method is simple and feasible, and the prepared corrosion inhibitor is resistant to oxygen and high temperature And non-toxic.

In order to achieve the above object, the technical solution adopted by the present invention to solve the technical problems is:

A preparation method of polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor, comprises the following steps:

Dissolve cyanuric chloride in an organic solvent to obtain solution A; add organic amine to the organic solvent to obtain solution B; slowly add solution B to solution A at 0-5°C, and stir for 2-3 hours , and then heated up to 30-45°C for 4-6h, then heated up to 70-80°C for 8-12h; cooled to room temperature, filtered, washed, and dried to obtain; wherein, the organic amine is a tertiary nitrogen heterocyclic amine compound.

Further, the organic solvent is acetone, ethanol or ethyl acetate.

Further, the molar ratio of cyanuric chloride and organic amine is 1:2-4.

Further, the molar ratio of cyanuric chloride and organic amine is 1:3.

Further, the organic amine is pyridine or quinoline.

Further, solution B was slowly added dropwise to solution A at 0°C, stirred for 2 hours, then heated to 45°C for 4 hours, and then heated to 80°C for 8 hours.

Further, the dropping rate of solution B is 15-20mL/min.

The application of the polyheterocyclic cyanuric chloride anti-oxygen corrosion inhibitor prepared by the above method in inhibiting the corrosion of carbon steel in gas injection wells of oil fields.

The multi-heterocyclic cyanuric chloride anti-oxidant corrosion inhibitor and its preparation method and application provided by the present invention have the following beneficial effects:

The preparation method of the present invention is simple, and in preparation process, cyanuric chloride reacts with pyridine, quinoline etc., has a plurality of heterocycles in the product of generation, and the large π bond on the heterocycles and metal (oilfield produced water reinjection process) The empty orbitals on the tubes used in the pipe) form a coordination bond, which is tightly adsorbed on the metal surface to form a stable adsorption film; at the same time, the heterocycle also contains multiple nitrogen atoms, and the nitrogen atom has a lone pair of electrons, which can interact with the iron atom. The empty orbitals form hybrid orbitals, and the two form strong adsorption, which further strengthens the stability of the adsorption film and delays the corrosion of its pipes.

Corrosion inhibitors in high-salinity brines in oil fields have been less studied and their effects are poor. Anti-oxidation corrosion has always been a difficult problem. There is no good solution for high-temperature corrosion. The agent is non-toxic and tasteless. It is an environmentally friendly corrosion inhibitor. It has a good anti-oxidation corrosion effect and also has good corrosion inhibition performance at high temperatures. When using this corrosion inhibitor as an anti-oxygen corrosion inhibitor for gas injection wells , has good solubility in high-salinity formation water, and has obvious inhibitory effect on the oxygen corrosion of carbon steel in gas injection wells. It can play a role in protecting pipes in the process of oilfield produced water reinjection and promote the return of oilfield produced water. Notes are widely used.

Description of drawings

Fig. 1 is the infrared spectrum of the polyheterocyclic cyanuric chloride anti-oxygen corrosion inhibitor that the present invention makes.

Fig. 2 is the mass spectrogram of the polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor prepared in the present invention.

Detailed ways

Example 1

A preparation method of polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor, comprises the following steps:

(1) Add 3.08g of cyanuric chloride to a 250mL three-necked flask, and simultaneously add 30mL of acetone as a solvent, and mix well;

(2) Dissolve 4g of pyridine in 50mL of acetone, and slowly add it dropwise to the result of step (1) at a rate of 15mL/min in an ice-water bath, continue the reaction for 2h after the dropwise addition, and then raise the temperature to 30°C Continue to react for 4 hours, then raise the temperature to 70°C for 8 hours under reflux, cool to room temperature and filter to obtain the precipitate, wash the precipitate with 50 mL of absolute ethanol for 3 times, and dry at 50°C for 6 hours to obtain a white solid product, namely polyheterocyclic trimeric chloride Cyanide antioxidant corrosion inhibitor.

The above reaction formula is as follows:

The obtained product was detected by infrared spectrum, and the results of its infrared spectrum are shown in Figure 1. It can be seen from Figure 1 that 1547cm ^-1 is the vibration of the C=N bond of the triazine ring, 1633cm ^-1 and 1547cm ^-1 are the vibrations of the aromatic heterocycle, and 1486cm ^-1 , 1401cm ^-1 and 828cm ^-1 are the vibrations of the triazine ring The characteristic vibration, 1392cm ^-1 is the CN bond vibration of the quaternary ammonium salt, indicating that the quaternization reaction is proceeding.

The resulting product was subjected to mass spectrometry analysis, and the mass spectrogram results are shown in Figure 2. It can be seen from Figure 2 that the m/z peak is 315.1358, which is consistent with the molecular weight of the cationic part of the corrosion inhibitor molecule. After adding chloride ions, the molecular weight is consistent with the molecular weight of the target product, indicating that the product is consistent with the expected product.

Example 2

A preparation method of polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor, comprises the following steps:

(1) Add 3.08g of cyanuric chloride to a 250mL three-necked flask, and simultaneously add 30mL of ethyl acetate as a solvent, and mix well;

(2) Dissolve 6.5g of quinoline in 50mL of acetone, slowly add it dropwise to the resultant of step (1) at a rate of 15mL/min under ice-water bath conditions, continue to react for 2h after the dropwise addition, and then heat up to Continue the reaction at 45°C for 4h, then raise the temperature to 80°C for 8h under reflux, cool to room temperature and filter to obtain the precipitate, wash the precipitate with 50mL of absolute ethanol for 3 times, and dry at 50°C for 6h to obtain a white solid product, polyheterocyclic three Polycyanogen chloride anti-oxidant corrosion inhibitor.

The above reaction formula is as follows:

Example 3

A preparation method of polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor, comprises the following steps:

(1) Add 3.08g of cyanuric chloride to a 250mL three-necked flask, and simultaneously add 30mL of ethyl acetate as a solvent, and mix well;

(2) Dissolve 4.4g of quinoline in 50mL of acetone, slowly add it dropwise to the resultant of step (1) at a speed of 17mL/min under ice-water bath conditions, continue to react for 3h after the dropwise addition, and then heat up to Continue to react at 30°C for 6h, then raise the temperature to 80°C for reflux reaction for 12h, cool to room temperature and filter to obtain a precipitate, wash the precipitate with 50mL of absolute ethanol three times, and dry at 50°C for 6h to obtain a white solid product, polyheterocyclic three Polycyanogen chloride anti-oxidant corrosion inhibitor.

Example 4

A preparation method of polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor, comprises the following steps:

(1) Add 3.08g of cyanuric chloride to a 250mL three-necked flask, and simultaneously add 30mL of ethyl acetate as a solvent, and mix well;

(2) Dissolve 8.6g of quinoline in 50mL of acetone, slowly add it dropwise to the resultant of step (1) at a rate of 18mL/min at 5°C, continue the reaction for 2h after the dropwise addition, and then heat up to Continue the reaction at 40°C for 5h, then raise the temperature to 75°C for reflux reaction for 10h, cool to room temperature and filter to obtain a precipitate, wash the precipitate with 50mL of absolute ethanol three times, and dry at 50°C for 6h to obtain a white solid product, polyheterocyclic three Polycyanogen chloride anti-oxidant corrosion inhibitor.

Example 5

A preparation method of polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor, comprises the following steps:

(1) Add 3.08g of cyanuric chloride to a 250mL three-necked flask, and simultaneously add 30mL of acetone as a solvent, and mix well;

(2) Dissolve 3g of pyridine in 50mL of acetone, and slowly add it dropwise to the result of step (1) at a rate of 20mL/min in an ice-water bath, continue the reaction for 3h after the dropwise addition, and then raise the temperature to 45°C Continue to react for 4 hours, then heat up to 80°C for reflux reaction for 12 hours, cool to room temperature and filter to obtain the precipitate, wash the precipitate with 50 mL of absolute ethanol for 3 times, and dry at 50°C for 6 hours to obtain a white solid product, polyheterocyclic trimeric chloride Cyanide antioxidant corrosion inhibitor.

Comparative example 1

A preparation method of polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor, comprises the following steps:

(1) Add 3.08g of cyanuric chloride to a 250mL three-necked flask, and simultaneously add 30mL of acetone as a solvent, and mix well;

(2) Dissolve 4g of pyridine in 50mL of acetone, add it directly to the result of step (1) in an ice-water bath, then raise the temperature to 70°C for 12h, cool to room temperature and filter to obtain a precipitate, and use 50mL of anhydrous The precipitate was washed with ethanol for 3 times, and dried at 50° C. for 6 h to obtain a white solid product, namely polyheterocyclic cyanuric chloride antioxidant corrosion inhibitor.

Comparative example 2

A preparation method of polyheterocyclic cyanuric chloride anti-oxidant corrosion inhibitor, comprises the following steps:

(1) Add 3.08g of cyanuric chloride to a 250mL three-necked flask, and simultaneously add 30mL of ethyl acetate as a solvent, and mix well;

(2) Dissolve 6.5g of quinoline in 50mL of acetone, add it directly to the result of step (1) in an ice-water bath, then raise the temperature to 80°C for 12h, cool to room temperature and filter to obtain a precipitate, use 50mL The precipitate was washed three times with absolute ethanol, and dried at 50° C. for 6 h to obtain a white solid product, namely polyheterocyclic cyanuric chloride antioxidant corrosion inhibitor.

Water Solubility Determination of Test Example 1 Corrosion Inhibitor

Measure the water-solubility of the corrosion inhibitors that embodiment 1-5 and comparative example 1-2 make, concrete process is: take by weighing each corrosion inhibitor 0.1g respectively, be dissolved in corrosion inhibitor 200mL simulated produced water respectively (Northwest area oil field The produced water is the standard preparation simulated produced water), stirred, and observed its dissolution. The results are shown in Table 1.

The water solubility result of table 1 corrosion inhibitor of the present invention

Water Soluble Appearance Example 1 soluble colorless transparent liquid Example 2 soluble colorless transparent liquid Example 3 soluble colorless transparent liquid Example 4 soluble colorless transparent liquid Example 5 soluble colorless transparent liquid

It can be seen from Table 1 that the corrosion inhibitor prepared by the present invention has excellent water solubility.

Corrosion inhibition performance measurement of test example 2 corrosion inhibitor

The simulated produced water was prepared based on the produced water of oilfields in Northwest China as the corrosion medium (the total salinity is 220000mg/L, the Ca2 ⁺ concentration is 12000mg/L, the Mg2 ⁺ concentration is 1200mg/L), 1% oxygen Under the condition of content, adopt P110 carbon steel, at 120 ℃, measure the corrosion inhibition performance of corrosion inhibitor prepared by the present invention and commercially available similar product JHJ and MNX by 72h corrosion coupon test at 120 DEG C, the consumption of corrosion inhibitor is 500ppm, its The results are shown in Table 2.

Table 2 The corrosion inhibition performance measurement result of corrosion inhibitor of the present invention and commercially available corrosion inhibitor

It can be seen from Table 2 that, with high salinity formation water as the corrosion medium, under the conditions of 120°C and 1% oxygen content, an equivalent amount of the corrosion inhibitor of the present invention and the corrosion inhibitor prepared in Comparative Examples 1-2 are The corrosion inhibitors of similar products sold, the corrosion inhibitors of the present invention, the corrosion inhibitors of comparative examples 1-2 and the commercially available corrosion inhibitors of similar products all have corrosion inhibitory effect, but the corrosion inhibitors of the present invention The corrosion inhibition rate is significantly better than the commercially available corrosion inhibitors and the corrosion inhibitors prepared in Comparative Examples 1-2, indicating that only the corrosion inhibitors prepared by the method of the present invention have the best corrosion inhibition efficiency.

Corrosion inhibition performance measurement of test example 3 corrosion inhibitor

The simulated produced water was prepared based on the produced water of oilfields in Northwest China as the corrosion medium (the total salinity is 220000mg/L, the Ca2 ⁺ concentration is 12000mg/L, the Mg2 ⁺ concentration is 1200mg/L), 1% oxygen content, adopt P110S carbon steel, at 120 ℃, measure the corrosion inhibition performance of the corrosion inhibitor prepared by the present invention and commercially available similar products JHJ and MNX by 72h corrosion coupon test, the corrosion inhibitor consumption is 500ppm, its result sees table 3.

Table 3 Corrosion inhibition performance determination of corrosion inhibitor of the present invention and commercially available corrosion inhibitor

As can be seen from Table 3, with high salinity formation water as the corrosion medium, under the conditions of 120°C and 1% oxygen content, an equivalent amount of the corrosion inhibitor of the present invention and the corrosion inhibitor prepared in Comparative Examples 1-2 are The corrosion inhibitors of similar products sold, the corrosion inhibitors of the present invention, the corrosion inhibitors of comparative examples 1-2 and the commercially available corrosion inhibitors of similar products all have corrosion inhibitory effect, but the corrosion inhibitors of the present invention The corrosion inhibition rate is significantly better than the commercially available corrosion inhibitors and the corrosion inhibitors prepared in Comparative Examples 1-2, indicating that only the corrosion inhibitors prepared by the method of the present invention have the best corrosion inhibition efficiency.

In summary, the preparation process of the present invention is simple and feasible. In the synthesis process, organic solvents are used to dissolve cyanuric chloride and organic amines, which avoids the hydrolysis of cyanuric chloride and organic amines, so that the prepared corrosion inhibitor product has high purity , the corrosion inhibitor is ionic, has good water solubility in high-salinity formation water, and has obvious inhibitory effect on the corrosion of carbon steel in gas injection wells at 120°C and 1% oxygen content. After washing, the surface is smooth without obvious pitting corrosion, which shows that the corrosion inhibitor prepared by the present invention has the characteristics of oxygen resistance and high temperature resistance.

Claims (9)

1. a kind of preparation method of more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter, which comprises the following steps:

Cyanuric Chloride is dissolved in organic solvent, solution A is obtained；Organic amine is added in organic solvent, solution B is obtained；In 0-5 DEG C of item Solution B is slowly dropped in solution A under part, is stirred to react 2-3h, then heats to 30-45 DEG C of reaction 4-6h, then be warming up to 70-80 DEG C of reaction 8-12h；It after being cooled to room temperature, is filtered, washed, dries, be made；Wherein, organic amine is tertiary carbon heterocyclic amine Close object.

2. the preparation method of more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter according to claim 1, which is characterized in that You Jirong Agent is acetone, ethyl alcohol or ethyl acetate.

3. the preparation method of more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter according to claim 1, which is characterized in that three polychlorostyrene The molar ratio of cyanogen and organic amine is 1:2-4.

4. the preparation method of more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter according to claim 3, which is characterized in that three polychlorostyrene The molar ratio of cyanogen and organic amine is 1:3.

5. the preparation method of more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter described according to claim 1 or 3 or 4, which is characterized in that Organic amine is pyridine or quinoline.

6. the preparation method of more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter according to claim 1, which is characterized in that at 0 DEG C Under the conditions of solution B is slowly dropped in solution A, be stirred to react 2h, then heat to 45 DEG C of reaction 4h, then be warming up to 80 DEG C it is anti- Answer 8h.

7. the preparation method of more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter according to claim 1 or 6, which is characterized in that molten The rate of addition of liquid B is 15-20mL/min.

8. the more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter being prepared using the described in any item methods of claim 1-7.

9. more heterocycle Cyanuric Chloride antioxygen corrosion inhibiter according to claim 8 are in inhibiting oilfield gas injection well corrosion of carbon steel Using.