CN114806530B - High-temperature acidification corrosion inhibitor and preparation method and application thereof - Google Patents
High-temperature acidification corrosion inhibitor and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high-temperature acidification corrosion inhibitor and a preparation method and application thereof. The invention provides a high-temperature acidification corrosion inhibitor, which comprises, by mass, 15-30% of a main agent, 5-15% of propenyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifier and 30-70% of a solvent; wherein the main agent is obtained by amidation reaction of benzoic acid and 1-amino-2-methylbutane. The acidizing corrosion inhibitor provided by the invention is not easy to decompose at high temperature, the temperature resistance of the acidizing corrosion inhibitor is effectively improved, and a good corrosion inhibition effect can be maintained at high temperature.
Description
Technical Field
The invention relates to a high-temperature acidification corrosion inhibitor, a preparation method and application thereof, and relates to the technical field of corrosion inhibitors.
Background
The research of the high-temperature acidizing corrosion inhibitor in China is started later until the middle and later stages of seventies are gradually developed, but the research and the application are improved rapidly, and after the middle eighties, various acidizing corrosion inhibitors are developed and produced successively, so that the production needs of partial oil fields are solved, for example, the Chinese patent with the application number of CN96104728.3 discloses an oil well acidizing corrosion inhibitor and a preparation method, and the main component of the acidizing corrosion inhibitor is a product obtained by quaternizing naphthenic acid imidazoline diamide polyoxyethylene ether and hydrochloric acid; the Chinese patent with the application number of CN02100697.0 discloses a steel corrosion inhibitor used in a high-temperature acidic medium and a preparation method thereof, wherein the main component is prepared by compounding a ketoaldehyde amine condensate, which is converted into a quaternary ammonium salt and then compounded with propynyl alcohol; the Chinese patent with application number of CN200510044927.6 discloses a novel high-temperature acidification corrosion inhibitor and a preparation method thereof, wherein the corrosion inhibitor is a homopolymer of N-allyl quinoline chloride, and the molecular weight is 2000-5000.
Because of the high underground temperature, the corrosion inhibition performance of the acidizing corrosion inhibitor in the environment with the temperature higher than 120 ℃ is not ideal, and in order to further improve the high-temperature corrosion inhibition performance of the acidizing corrosion inhibitor, 7801 type corrosion inhibitors developed by the university of Huazhong technology comprise Mannich base and propynyl alcohol generated by reaction of aniline, acetophenone and urotropine, and the corrosion rate in 28 percent HCl solution at 150 ℃ is less than 80 g/(m) 2 H); the Sichuan natural gas research institute develops a Sichuan 1-2 corrosion inhibitor which comprises Mannich base and propynyl alcohol generated by the reaction of aniline, cyclohexanone and formaldehyde, and the corrosion rate in 28 percent HCl solution at 150 ℃ is less than 80 g/(m) 2 H); however, the Mannich base is easy to decompose at high temperature and has high toxicity, which seriously affects the performance of the corrosion inhibitor; in order to solve the problem of easy decomposition of Mannich base at high temperature, related patents at abroad report a high temperature corrosion inhibitor which uses thiourea, formaldehyde and acetophenone to react, and then is compounded with antimony trichloride, wherein the corrosion rate is 0.005lb/ft at 300 DEG F (about 149℃) 2 (12.21g/(m 2 H), but antimony trichloride is very corrosive, which brings inconvenience to the production of the corrosion inhibitor. Therefore, how to provide a high-temperature acidification corrosion inhibitor with good corrosion inhibition effect at high temperature, safe production and low toxicityThe more attention is paid.
Disclosure of Invention
The invention provides a high-temperature acidizing corrosion inhibitor which can keep good corrosion inhibition performance at 160 ℃, and has the advantages of low component toxicity and high safety in the production process.
The invention also provides a preparation method of the high-temperature acidification corrosion inhibitor, and the high-temperature acidification corrosion inhibitor prepared by the preparation method has the advantages of good high-temperature corrosion inhibition performance, low toxicity and safe production process.
The invention provides a high-temperature acidification corrosion inhibitor, which comprises, by mass, 15-30% of a main agent, 5-15% of propenyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifier and 30-70% of a solvent;
wherein the main agent is obtained by amidation reaction of benzoic acid and 1-amino-2-methylbutane.
Further, the main agent is prepared by a preparation method comprising the following steps:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at 180-200 ℃, reacting for 2 hours until the 1-amino-2-methylbutane and water are not distilled out, adding 200g of 1-amino-2-methylbutane, reacting for 1 hour at 230 ℃ after the reaction is finished, washing, drying and recrystallizing the product to obtain the main agent.
Further, the aromatic aldehyde is cinnamaldehyde or benzaldehyde.
Further, the emulsifier is a diethanolamine cocoate condensate.
Further, the solvent is dimethylformamide or dimethyl sulfoxide.
The second aspect of the invention provides a method for preparing a high-temperature acidification corrosion inhibitor, which comprises the following steps:
step 1, carrying out an amide reaction on benzoic acid and 1-amino-2-methylbutane to obtain a main agent;
and step 2, mixing 15-30% of the main agent, 5-15% of propenyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifying agent and 30-70% of a solvent according to mass percentage to obtain the high-temperature acidification corrosion inhibitor.
Further, step 1 includes:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at 180-200 ℃, reacting for 2 hours until the 1-amino-2-methylbutane and water are not distilled out, adding 200g of 1-amino-2-methylbutane, reacting for 1 hour at 230 ℃ after the reaction is finished, washing, drying and recrystallizing the product to obtain the main agent.
Further, the washing comprises washing the product by sequentially using dilute hydrochloric acid, water, sodium hydroxide solution and water.
The invention provides a method for preventing oil pipes from corrosion in an acidizing and fracturing process, which comprises the step of adding any one of the high-temperature acidizing corrosion inhibitors into acidizing fluid.
Further, the mass of the high-temperature acidification corrosion inhibitor is 4% of the mass of the acidification liquid.
The implementation of the invention has at least the following advantages:
1. the high-temperature acidizing corrosion inhibitor provided by the invention is not easy to decompose at high temperature, the temperature resistance of the acidizing corrosion inhibitor is effectively improved, and a good corrosion inhibition effect can be maintained at high temperature.
2. The high-temperature acidification corrosion inhibitor provided by the invention can keep a slow release effect at 160 ℃.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing a high-temperature acidizing corrosion inhibitor according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a preparation method of a main agent according to an embodiment of the invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
At present, acidification is one of the main means for increasing the production of an oil and gas well, and is used for removing blocking substances in pores or cracks through an acidizing fluid, or improving the pores or cracks of crude oil in a stratum, and improving the stratum permeability, so that the recovery ratio of the oil and gas well is improved, the acidizing fluid has stronger corrosiveness to equipment pipelines such as metal pipelines, equipment and underground oil pipes, corrosion of the acidizing fluid to the equipment pipelines can be relieved to a certain extent by adding a corrosion inhibitor into the acidizing fluid, and meanwhile, the acidizing fluid also has to have corresponding temperature resistance due to higher underground temperature, so that the acidizing fluid can still maintain corresponding corrosion resistance in a high-temperature environment; the temperature of the high-temperature acidification corrosion inhibitor used at present is mostly 120-150 ℃, and the acidification corrosion inhibitor comprises toxic and highly corrosive substances such as Mannich base, antimony trichloride and the like, so that potential safety hazards are brought to the production of the acidification corrosion inhibitor. Based on the defects of the prior high-temperature acidification corrosion inhibitor, the invention is completed and is described in detail as follows:
the invention provides a high-temperature acidification corrosion inhibitor, which comprises, by mass, 15-30% of a main agent, 5-15% of propenyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifier and 30-70% of a solvent;
wherein the main agent is obtained by amidation reaction of benzoic acid and 1-amino-2-methylbutane.
The invention provides a high-temperature acidification corrosion inhibitor, which comprises a main agent and an auxiliary agent, wherein the main agent is prepared by amidation reaction of benzoic acid and 1-amino-2-methylbutane serving as raw materials, the reaction formula is shown as formula 1, and the main agent serving as a main component of the high-temperature acidification corrosion inhibitor can be effectively adsorbed on the inner wall of an oil pipe to form a protective film so as to prevent the inner wall of the oil pipe from being corroded by acidizing fluid; the auxiliary agent comprises propenyl amine, aromatic aldehyde, an emulsifier and a solvent, wherein the propenyl amine and the aromatic aldehyde are used as synergistic components in the corrosion inhibitor, so that the integrity of the protective film can be improved, and the corrosion inhibition performance of the corrosion inhibitor can be improved; the emulsifier has certain hydrophilicity, can improve the film forming effect of the acidizing corrosion inhibitor in the acidizing fluid, is beneficial to forming a protective film on the surface of the oil pipe, and prevents the acidizing fluid from corroding the oil pipe. The high-temperature acidizing corrosion inhibitor provided by the invention is not easy to decompose at high temperature, the temperature resistance of the acidizing corrosion inhibitor is effectively improved, and a good corrosion inhibition effect can be maintained at high temperature.
In one embodiment, in order to prevent the reaction of 1-amino-2-methylbutane and benzoic acid from being too violent and further improve the yield of the main agent, 1-amino-2-methylbutane may be reacted with benzoic acid in two steps, and in particular, the main agent is prepared by a preparation method comprising the following steps:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at 180-200 ℃, reacting for 2 hours until the 1-amino-2-methylbutane and water are not distilled out, adding 200g of 1-amino-2-methylbutane, reacting for 1 hour at 230 ℃ after the reaction is finished, washing, drying and recrystallizing the product to obtain the main agent.
First, according to the reaction formula shown in formula 1, the molar ratio of 1-amino-2-methylbutane to benzoic acid should be 1:1, but in order to ensure that benzoic acid is fully reacted, 1-amino-2-methylbutane should be in excess of benzoic acid, for example, 450g of 1-amino-2-methylbutane and 400g of benzoic acid are weighed and reacted as reaction raw materials; subsequently, the 1-amino-2-methylbutane is divided into a first fraction having a mass of 250g and a second fraction having a mass of 200g;
secondly, distilling the first part of 1-amino-2-methylbutane and benzoic acid at 180-220 ℃ to react for 2 hours until the 1-amino-2-methylbutane and water are not distilled out, adding the second part of 1-amino-2-methylbutane, and continuing to react after the temperature is increased;
wherein, because the temperature required by the reaction is higher, the temperature required by the reaction can be controlled by using an oil bath;
finally, after the reaction is finished, washing, drying and recrystallizing the reaction product to obtain the main agent;
specifically, the washing comprises washing the product sequentially by using dilute hydrochloric acid, water, sodium hydroxide solution and water, wherein the concentration of sodium hydroxide is 1mol/L, in a specific embodiment, the washing can be repeated twice by using the dilute hydrochloric acid, then the dilute hydrochloric acid is removed by using the water washing, then the washing is performed by using the sodium hydroxide solution, and finally the washing is performed by using the water;
the drying can be performed by using the conventional technical means in the field, and is used for drying and removing water, specifically, the drying can be performed in an oven, the drying temperature is 105 ℃, and the water is completely removed;
recrystallization is used for purification of the product, and in particular ethanol can be used as solvent, and the particular procedure is carried out according to conventional technical means in the art.
The main agent can be prepared by a person skilled in the art according to the content and the conventional technical means in the art, and the high-temperature acidizing corrosion inhibitor is prepared by matching the auxiliary agent according to the mass percent, wherein the auxiliary agent can be further selected in order to further improve the temperature resistance of the corrosion inhibitor, and the method comprises the following steps:
the aromatic aldehyde may be cinnamaldehyde or benzaldehyde.
The emulsifier is a cocoanut acid diethanolamine condensate, on one hand, the cocoanut acid diethanolamine condensate has higher hydrophilcity due to higher HLB value, and on the other hand, the cocoanut acid diethanolamine condensate can improve the dissolution stability of each component in a solvent, so that each component is not easy to decompose at high temperature, and the temperature resistance of the acidizing corrosion inhibitor is improved.
The solvent is dimethylformamide or dimethyl sulfoxide.
In conclusion, the high-temperature acidification corrosion inhibitor provided by the invention is not easy to decompose at high temperature, so that the temperature resistance of the acidification corrosion inhibitor is effectively improved, and a good slow release effect is maintained at high temperature; in addition, the acidizing corrosion inhibitor provided by the invention does not comprise substances with larger toxicity or stronger corrosiveness such as Mannich base, antimony trichloride and the like, so that the influence of toxic substances on the performance of the acidizing corrosion inhibitor is reduced, and the safety of the production process is improved.
The second aspect of the invention provides a method for preparing any one of the above high temperature acidification corrosion inhibitors, comprising the following steps:
step 1, carrying out an amide reaction on benzoic acid and 1-amino-2-methylbutane to obtain a main agent;
and step 2, mixing 15-30% of the main agent, 5-15% of propenyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifying agent and 30-70% of a solvent according to mass percentage to obtain the high-temperature acidification corrosion inhibitor.
The invention provides a preparation method of a high-temperature acidification corrosion inhibitor, and fig. 1 is a schematic flow chart of the preparation method of the high-temperature acidification corrosion inhibitor provided by an embodiment of the invention, as shown in fig. 1, and the preparation method comprises the following steps: step 1, carrying out an amide reaction on benzoic acid and 1-amino-2-methylbutane to obtain a main agent, and carrying out an amidation reaction on the benzoic acid and the 1-amino-2-methylbutane serving as raw materials to obtain the main agent, wherein the reaction formula is shown in a formula 1; and step 2, mixing 15-30% of main agent, 5-15% of propenyl amine, 5-15% of aromatic aldehyde, 5-10% of emulsifying agent and 30-70% of solvent according to mass percentage to obtain the high-temperature acidification corrosion inhibitor, wherein the aromatic aldehyde, the emulsifying agent and the solvent are selected as described above. The preparation method provided by the invention is simple to operate, has no generation of strong toxicity or corrosive substances in the reaction process, and has high safety in the preparation process.
In one embodiment, in order to further increase the yield of the main agent, the preparation method of the main agent comprises the following steps:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at 180-200 ℃, reacting for 2 hours until the 1-amino-2-methylbutane and water are not distilled out, adding 200g of 1-amino-2-methylbutane, reacting for 1 hour at 230 ℃ after the reaction is finished, washing, drying and recrystallizing the product to obtain the main agent.
Specifically, fig. 2 is a schematic flow chart of a preparation method of a main agent according to an embodiment of the present invention, and as shown in fig. 2, the preparation process of the main agent mainly includes the following steps: step 1-1, dividing 1-amino-2-methylbutane required for the reaction into a first part and a second part, wherein the total mass of benzoic acid is 400g, the total mass of 1-amino-2-methylbutane is 450g, the mass of the first part is 250g, and the mass of the second part is 200g; step 1-2, distilling a first part of 1-amino-2-methylbutane and benzoic acid at 180-200 ℃ to perform amidation reaction for 2 hours until the 1-amino-2-methylbutane and water are not distilled out; step 1-3, adding a second part of 1-amino-2-methylbutane to continuously react with benzoic acid, further increasing the reaction temperature to 230 ℃, and finishing the reaction for 1 h; and step 1-4, after the reaction is finished, washing, drying and recrystallizing the product to obtain the main agent.
Wherein, distillation can be carried out in an oil bath, and the specific operations of washing, drying and recrystallization are as described above.
In conclusion, the preparation method provided by the invention is simple to operate, has no generation of strong toxicity or corrosive substances in the reaction process, and has high safety in the preparation process.
The invention provides a method for preventing oil pipes from corrosion in an acidification process, which comprises the step of adding any one of the high-temperature acidification corrosion inhibitors into an acidification liquid.
In the specific use process, the high-temperature acidizing corrosion inhibitor provided by the invention can be added into acidizing fluid, and oil and gas wells are mined along with the acidizing fluid. The high-temperature acidification corrosion inhibitor provided by the invention has better temperature resistance, can still keep a slow release effect in a high-temperature environment, and can effectively protect an oil pipe.
According to the research of the inventor, when the mass of the high-temperature acidification corrosion inhibitor is 4% of the mass of the acidification liquor, an effective slow release effect can be achieved.
The following description is made in connection with the specific embodiments, and the starting materials used in the examples are all commercially available.
Example 1
The high-temperature acidification corrosion inhibitor provided by the embodiment comprises the following components:
30 parts by mass of a main agent;
10 parts by mass of propenyl amine;
5 parts by mass of cinnamaldehyde;
10 parts by mass of a diethanolamine cocoate condensate;
45 parts by mass of dimethylformamide.
The main agent is prepared by a preparation method comprising the following steps:
250g of 1-amino-2-methylbutane is added into a 1L round bottom flask, 400g of benzoic acid is added in the slow heating and stirring process, heating distillation is carried out in an oil bath, the temperature is maintained to be 180-200 ℃, 200g of 1-amino-2-methylbutane is added after the reaction for 2h until the 1-amino-2-methylbutane and water are not distilled out, the temperature is raised to 230 ℃, the heating and stirring reaction is carried out for 1h, after the reaction is finished, the reaction product is repeatedly washed for 2 times by dilute hydrochloric acid, 300g of water is added for washing and filtering again after the dilute hydrochloric acid solution is removed, then 1L of sodium hydroxide solution (with the concentration of 1 mol/L) is used for washing and filtering again for 1 hour, and then the main agent is obtained after the reaction is dried in an oven at 105 ℃ and recrystallized again by ethanol.
The preparation method of the corrosion inhibitor provided by the embodiment comprises the following steps:
the preparation method of the main agent in the step 1 is as described above.
And 2, uniformly mixing 30 parts by mass of the main agent prepared in the step 1 with 10 parts by mass of propenyl amine, 5 parts by mass of cinnamaldehyde, 10 parts by mass of cocoanut diethanol amine condensate and 45 parts by mass of dimethylformamide to obtain the acidizing corrosion inhibitor.
Example 2
The high-temperature acidification corrosion inhibitor provided by the embodiment comprises the following components:
20 parts by mass of a main agent;
10 parts by mass of propenyl amine;
5 parts by mass of benzaldehyde;
10 parts by mass of a diethanolamine cocoate condensate;
55 parts by mass of dimethylformamide.
The main agent is prepared by a preparation method comprising the following steps:
250g of 1-amino-2-methylbutane is added into a 1L round bottom flask, 400g of benzoic acid is added in the slow heating and stirring process, heating distillation is carried out in an oil bath, the temperature is maintained to be 180-200 ℃, 200g of 1-amino-2-methylbutane is added after the reaction for 2h until the 1-amino-2-methylbutane and water are not distilled out, the temperature is raised to 230 ℃, the heating and stirring reaction is carried out for 1h, after the reaction is finished, the reaction product is repeatedly washed for 2 times by dilute hydrochloric acid, 300g of water is added for washing and filtering again after the dilute hydrochloric acid solution is removed, then 1L of sodium hydroxide solution (with the concentration of 1 mol/L) is used for washing and filtering again for 1 hour, and then the main agent is obtained after the reaction is dried in an oven at 105 ℃ and recrystallized again by ethanol.
The preparation method of the corrosion inhibitor provided by the embodiment comprises the following steps:
the preparation method of the main agent in the step 1 is as described above.
And 2, uniformly mixing 20 parts by mass of the main agent prepared in the step 1 with 10 parts by mass of propenyl amine, 5 parts by mass of benzaldehyde, 10 parts by mass of cocoanut diethanol amine condensate and 55 parts by mass of dimethylformamide to obtain the acidizing corrosion inhibitor.
Example 3
The high-temperature acidification corrosion inhibitor provided by the embodiment comprises the following components:
15 parts by mass of a main agent;
10 parts by mass of propenyl amine;
10 parts by mass of cinnamaldehyde;
8 parts by mass of a diethanolamine cocoate condensate;
57 parts by mass of dimethyl sulfoxide.
The main agent is prepared by a preparation method comprising the following steps:
250g of 1-amino-2-methylbutane is added into a 1L round bottom flask, 400g of benzoic acid is added in the slow heating and stirring process, heating distillation is carried out in an oil bath, the temperature is maintained to be 180-200 ℃, 200g of 1-amino-2-methylbutane is added after the reaction for 2h until the 1-amino-2-methylbutane and water are not distilled out, the temperature is raised to 230 ℃, the heating and stirring reaction is carried out for 1h, after the reaction is finished, the reaction product is repeatedly washed for 2 times by dilute hydrochloric acid, 300g of water is added for washing and filtering again after the dilute hydrochloric acid solution is removed, then 1L of sodium hydroxide solution (with the concentration of 1 mol/L) is used for washing and filtering again for 1 hour, and then the main agent is obtained after the reaction is dried in an oven at 105 ℃ and recrystallized again by ethanol.
The preparation method of the corrosion inhibitor provided by the embodiment comprises the following steps:
step 1, the preparation method of the main agent is as described above;
and 2, uniformly mixing 15 parts by mass of the main agent prepared in the step 1 with 10 parts by mass of propenyl amine, 10 parts by mass of cinnamaldehyde, 8 parts by mass of cocoanut diethanol amine condensate and 57 parts by mass of dimethyl sulfoxide to obtain the acidizing corrosion inhibitor.
Example 4
The high-temperature acidification corrosion inhibitor provided by the embodiment comprises the following components:
30 parts by mass of a main agent;
10 parts by mass of propenyl amine;
10 parts by mass of benzaldehyde;
10 parts by mass of a diethanolamine cocoate condensate;
40 parts by mass of dimethyl sulfoxide.
The main agent is prepared by a preparation method comprising the following steps:
250g of 1-amino-2-methylbutane is added into a 1L round bottom flask, 400g of benzoic acid is added in the slow heating and stirring process, heating distillation is carried out in an oil bath, the temperature is maintained to be 180-200 ℃, 200g of 1-amino-2-methylbutane is added after the reaction for 2h until the 1-amino-2-methylbutane and water are not distilled out, the temperature is raised to 230 ℃, the heating and stirring reaction is carried out for 1h, after the reaction is finished, the reaction product is repeatedly washed for 2 times by dilute hydrochloric acid, 300g of water is added for washing and filtering again after the dilute hydrochloric acid solution is removed, then 1L of sodium hydroxide solution (with the concentration of 1 mol/L) is used for washing and filtering again for 1 hour, and then the main agent is obtained after the reaction is dried in an oven at 105 ℃ and recrystallized again by ethanol.
The preparation method of the corrosion inhibitor provided by the embodiment comprises the following steps:
step 1, the preparation method of the main agent is as described above;
and 2, uniformly mixing 30 parts by mass of the main agent prepared in the step 1 with 10 parts by mass of propenyl amine, 10 parts by mass of benzaldehyde, 10 parts by mass of cocoanut diethanol amine condensate and 40 parts by mass of dimethyl sulfoxide to obtain the acidizing corrosion inhibitor.
Example 5
The high-temperature acidification corrosion inhibitor provided by the embodiment comprises the following components:
30 parts by mass of a main agent;
5 parts by mass of propenyl amine;
10 parts by mass of cinnamaldehyde;
10 parts by mass of a diethanolamine cocoate condensate;
45 parts by mass of dimethylformamide.
The main agent is prepared by a preparation method comprising the following steps:
250g of 1-amino-2-methylbutane is added into a 1L round bottom flask, 400g of benzoic acid is added in the slow heating and stirring process, heating distillation is carried out in an oil bath, the temperature is maintained to be 180-200 ℃, 200g of 1-amino-2-methylbutane is added after the reaction for 2h until the 1-amino-2-methylbutane and water are not distilled out, the temperature is raised to 230 ℃, the heating and stirring reaction is carried out for 1h, after the reaction is finished, the reaction product is repeatedly washed for 2 times by dilute hydrochloric acid, 300g of water is added for washing and filtering again after the dilute hydrochloric acid solution is removed, then 1L of sodium hydroxide solution (with the concentration of 1 mol/L) is used for washing and filtering again for 1 hour, and then the main agent is obtained after the reaction is dried in an oven at 105 ℃ and recrystallized again by ethanol.
The preparation method of the corrosion inhibitor provided by the embodiment comprises the following steps:
step 1, the preparation method of the main agent is as described above;
and 2, uniformly mixing 30 parts by mass of the main agent prepared in the step 1 with 5 parts by mass of propenyl amine, 10 parts by mass of cinnamaldehyde, 10 parts by mass of cocoanut diethanol amine condensate and 45 parts by mass of dimethylformamide to obtain the acidizing corrosion inhibitor.
The invention further evaluates the slow release effect of the high-temperature acidification corrosion inhibitor provided by the embodiments 1-5, specifically, referring to a corrosion inhibitor performance test method and an evaluation index for SY5405-2019 acidification, corrosion test evaluation is carried out on CT80 steel under 20% hydrochloric acid solution, wherein 4% of the acidification corrosion inhibitor is added in the hydrochloric acid solution, the test temperature is 160 ℃, the test pressure is 16MPa, the stirring speed is 60r/min, the test time is 4h, and the test results are shown in Table 1:
TABLE 1 evaluation results of the sustained-release effect of the high-temperature acidizing corrosion inhibitors provided in examples 1 to 5
| Corrosion rate, g/(m) 2 ·h) | |
| Example 1 | 25.32 |
| Example 2 | 51.02 |
| Example 3 | 32.12 |
| Example 4 | 41.25 |
| Example 5 | 36.78 |
As can be seen from the data provided in Table 1, the corrosion rates of the high temperature acidizing corrosion inhibitors provided in examples 1 to 5 are all lower than 65 g/(m) at 160 ℃ 2 H) meets the evaluation index of SY5405-2019, so that the high-temperature acidification corrosion inhibitor provided by the invention can keep a slow release effect at 160 ℃.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The high-temperature acidification corrosion inhibitor is characterized by comprising, by mass, 15-30% of a main agent, 5-15% of propenyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifier and 30-70% of a solvent;
wherein the main agent is obtained by amidation reaction of benzoic acid and 1-amino-2-methylbutane.
2. The high temperature acidified corrosion inhibitor of claim 1 wherein said main agent is prepared by a process comprising:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at 180-200 ℃, reacting for 2 hours until the 1-amino-2-methylbutane and water are not distilled out, adding 200g of 1-amino-2-methylbutane, reacting for 1 hour at 230 ℃ after the reaction is finished, washing, drying and recrystallizing the product to obtain the main agent.
3. The high temperature acidizing corrosion inhibitor according to claim 1 or 2, wherein the aromatic aldehyde is cinnamaldehyde or benzaldehyde.
4. The high temperature acidizing corrosion inhibitor according to claim 1 or 2, wherein the emulsifier is a diethanolamine cocoate condensate.
5. The high temperature acidizing corrosion inhibitor according to claim 1 or 2, wherein the solvent is dimethylformamide or dimethylsulfoxide.
6. A method of preparing a high temperature acidizing corrosion inhibitor according to any one of claims 1 to 5, comprising the steps of:
step 1, carrying out an amide reaction on benzoic acid and 1-amino-2-methylbutane to obtain a main agent;
and step 2, mixing 15-30% of the main agent, 5-15% of propenyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifying agent and 30-70% of a solvent according to mass percentage to obtain the high-temperature acidification corrosion inhibitor.
7. The method of claim 6, wherein step 1 comprises:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at 180-200 ℃, reacting for 2 hours until the 1-amino-2-methylbutane and water are not distilled out, adding 200g of 1-amino-2-methylbutane, reacting for 1 hour at 230 ℃ after the reaction is finished, washing, drying and recrystallizing the product to obtain the main agent.
8. The method of claim 7, wherein the washing comprises washing the product with dilute hydrochloric acid, water, sodium hydroxide solution, and water in that order.
9. A method for corrosion protection of oil pipes in acidizing and fracturing processes, characterized in that a high temperature acidizing corrosion inhibitor according to any one of claims 1 to 5 is added to the acidizing fluid.
10. The method of claim 9, wherein the high temperature acidizing corrosion inhibitor is present in an amount of 4% by mass of the acidizing fluid.
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| CN102953067A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Decalcification Mannich base corrosion inhibitor, and preparation and application thereof |
| WO2014178738A1 (en) * | 2013-05-02 | 2014-11-06 | Instytut Nafty I Gazu - Panstwowy Instytut Badawczy | Water-soluble corrosion inhibitor for protection of lifting casings and natural gas pipelines as well as the method of its production. |
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| CN102953067A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Decalcification Mannich base corrosion inhibitor, and preparation and application thereof |
| WO2014178738A1 (en) * | 2013-05-02 | 2014-11-06 | Instytut Nafty I Gazu - Panstwowy Instytut Badawczy | Water-soluble corrosion inhibitor for protection of lifting casings and natural gas pipelines as well as the method of its production. |
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| 王欣 ; 曾璐明 ; 徐超 ; 呼文财 ; .N-烷基苯甲酰胺基双咪唑啉缓蚀剂的合成及性能研究.工业水处理.2020,(01),第87-90页. * |
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