CN114806530A - High-temperature acidizing corrosion inhibitor and preparation method and application thereof - Google Patents
High-temperature acidizing corrosion inhibitor and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high-temperature acidizing corrosion inhibitor and a preparation method and application thereof. The invention provides a high-temperature acidification corrosion inhibitor, which comprises 15-30% of a main agent, 5-15% of allyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifier and 30-70% of a solvent by mass percent; 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 kept at high temperature.
Description
Technical Field
The invention relates to a high-temperature acidizing corrosion inhibitor, a preparation method and application thereof, relating to the technical field of corrosion inhibitors.
Background
The research of the high-temperature acidizing corrosion inhibitor in China starts late, and does not develop gradually until the middle and later seventies, but the research and the application are improved quickly, after the middle eighty, a plurality of acidizing corrosion inhibitors are developed and produced in sequence, and the production needs of part of oil fields are solved, for example, Chinese patent with application number CN96104728.3 discloses an oil well acidizing corrosion inhibitor and a preparation method, wherein the main component is a product obtained by quaternizing naphthenic acid imidazoline diamide polyoxyethylene ether and hydrochloric acid; chinese patent with application number CN02100697.0 discloses a steel corrosion inhibitor used in high-temperature acidic medium and a preparation method thereof, the main component is prepared by ketone-aldehyde-amine condensate, which is converted into quaternary ammonium salt and then compounded with propiolic alcohol; the Chinese patent with the 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 chloroquinoline and has the molecular weight of 2000-5000-.
As the underground temperature is higher, the corrosion inhibition performance of the acidizing corrosion inhibitor in the environment with the temperature higher than 120 ℃ is not ideal, in order to further improve the high-temperature corrosion inhibition performance of the acidizing corrosion inhibitor, 7801 type corrosion inhibitor developed by Huazhong university of science and technology comprises Mannich base and propiolic alcohol which are generated by the reaction of aniline, acetophenone and urotropine, and the corrosion inhibitor accounts for 28 percent at the temperature of 150 DEG CThe corrosion rate in HCl solution is less than 80 g/(m) 2 H); the Sichuan natural gas research institute developed Sichuan natural gas type 1-2 corrosion inhibitor comprises Mannich base and propiolic alcohol which are generated by the reaction of aniline, cyclohexanone and formaldehyde, and the corrosion rate is less than 80 g/(m) in 28% HCl solution at 150 DEG C 2 H); however, Mannich bases are easily decomposed at high temperature and have high toxicity, so that the performance of the corrosion inhibitor is seriously influenced; in order to solve the problem that the Mannich base is easy to decompose at high temperature, a related patent reports a high-temperature corrosion inhibitor abroad, which uses thiourea, formaldehyde and acetophenone for reaction, and is compounded with antimony trichloride, and 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, more and more attention is paid to how to provide a high-temperature acidification corrosion inhibitor which has good corrosion inhibition effect at high temperature, is safe to produce and has low toxicity.
Disclosure of Invention
The invention provides a high-temperature acidification corrosion inhibitor which can keep good corrosion inhibition performance at 160 ℃, and has the advantages of low component toxicity and higher safety in the production process.
The invention also provides a preparation method of the high-temperature acidizing corrosion inhibitor, and the high-temperature acidizing 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 15-30% of a main agent, 5-15% of allyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifier and 30-70% of a solvent by mass percent;
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 of:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at the temperature of 180 ℃ and 200 ℃, reacting for 2h until the 1-amino-2-methylbutane and water are not evaporated, then adding 200g of 1-amino-2-methylbutane, raising the temperature to 230 ℃ for reacting for 1h, and washing, drying and recrystallizing the product after the reaction is finished to obtain the main agent.
Further, the aromatic aldehyde is cinnamaldehyde or benzaldehyde.
Further, the emulsifier is a cocodiethanolamine cocoate condensate.
Further, the solvent is dimethylformamide or dimethyl sulfoxide.
The second aspect of the invention provides a preparation method of a high-temperature acidizing corrosion inhibitor, which comprises the following steps:
step 1, performing an amide reaction on benzoic acid and 1-amino-2-methylbutane to obtain a main agent;
and 2, mixing 15-30% of the main agent, 5-15% of allylamine, 5-15% of aromatic aldehyde, 5-10% of emulsifier and 30-70% of solvent according to mass percentage to obtain the high-temperature acidizing corrosion inhibitor.
Further, step 1 comprises:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at the temperature of 180 ℃ and 200 ℃, reacting for 2h until the 1-amino-2-methylbutane and water are not evaporated, then adding 200g of 1-amino-2-methylbutane, raising the temperature to 230 ℃ for reacting for 1h, and washing, drying and recrystallizing the product after the reaction is finished to obtain the main agent.
Further, the washing comprises washing the product by using dilute hydrochloric acid, water, a sodium hydroxide solution and water in sequence.
The third aspect of the invention provides a method for preventing oil pipe corrosion in the process of acidizing and fracturing, wherein any one of the high-temperature acidizing corrosion inhibitors is added into acidizing fluid.
Further, the mass of the high-temperature acidizing corrosion inhibitor is 4% of the mass of the acidizing fluid.
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 kept 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 in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing a high-temperature acidizing corrosion inhibitor according to an embodiment of the invention;
fig. 2 is a schematic flow chart of a preparation method of the main agent according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
At present, acidification is one of the main means for increasing the yield of oil and gas wells, and is used for removing blocking substances in pores or cracks or improving the pores or cracks of crude oil in a stratum and improving the permeability of the stratum, so that the recovery ratio of the oil and gas wells is improved, the acidizing fluid has strong corrosivity to equipment pipelines such as metal pipelines, equipment, underground oil pipes and the like, 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, due to high underground temperature, the acidizing fluid also has corresponding temperature resistance, so that the acidizing fluid still can maintain corresponding corrosion inhibition performance 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, and also brings potential safety hazards to the production of the acidification corrosion inhibitor. The invention is completed based on the defects of the prior high-temperature acidizing corrosion inhibitor, and the detailed description is as follows:
the invention provides a high-temperature acidification corrosion inhibitor, which comprises 15-30% of a main agent, 5-15% of allyl amine, 5-15% of aromatic aldehyde, 5-10% of an emulsifier and 30-70% of a solvent by mass percent;
wherein the main agent is obtained by amidation reaction of benzoic acid and 1-amino-2-methylbutane.
The invention provides a high-temperature acidizing corrosion inhibitor, which comprises a main agent and an auxiliary agent, wherein the main agent is obtained by taking benzoic acid and 1-amino-2-methylbutane as raw materials to carry out amidation reaction, the reaction formula is shown as formula 1, the main agent is used as the main component of the high-temperature acidizing corrosion inhibitor, and the main agent can be effectively adsorbed on the inner wall of an oil pipe to form a protective film so as to prevent acidizing fluid from corroding the inner wall of the oil pipe; the auxiliary agent comprises allyl amine, aromatic aldehyde, an emulsifier and a solvent, and the allyl 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 acidizing fluid, is beneficial to forming a protective film on the surface of an 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 kept at high temperature.
In one embodiment, in order to prevent the 1-amino-2-methylbutane and the benzoic acid from reacting too vigorously and further improve the yield of the base compound, the 1-amino-2-methylbutane may be reacted with the benzoic acid in two separate steps, and specifically, the base compound is prepared by a preparation method comprising the following steps:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at the temperature of 180 ℃ and 200 ℃, reacting for 2h until the 1-amino-2-methylbutane and water are not evaporated, then adding 200g of 1-amino-2-methylbutane, raising the temperature to 230 ℃ for reacting for 1h, and washing, drying and recrystallizing the product after the reaction is finished 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 the benzoic acid is fully reacted, the 1-amino-2-methylbutane is excessive in amount relative to the benzoic acid, for example, 450g of 1-amino-2-methylbutane and 400g of benzoic acid are weighed as reaction raw materials and reacted; subsequently, the 1-amino-2-methylbutane was divided into a first fraction and a second fraction, wherein the mass of the first fraction was 250g and the mass of the second fraction was 200 g;
secondly, distilling the first part of 1-amino-2-methylbutane and benzoic acid at 220 ℃ for 2 hours until the 1-amino-2-methylbutane and water are not distilled out, adding the second part of 1-amino-2-methylbutane, raising the temperature and continuing to react;
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 with dilute hydrochloric acid, water, a sodium hydroxide solution and water in sequence, wherein the concentration of sodium hydroxide is 1mol/L, in a specific embodiment, the diluted hydrochloric acid can be used for washing twice, then the diluted hydrochloric acid is cleaned by using water, then the sodium hydroxide solution is used for washing, and finally the water is used for washing;
the drying can be carried out by using the conventional technical means in the field and is used for drying and removing water, specifically, the drying can be carried out in an oven, the drying temperature is 105 ℃, and the moisture is completely removed;
recrystallization is used for the purification of the product, in particular ethanol can be used as a solvent, and the particular operation is carried out according to the conventional technical means in the field.
The technical personnel in the field can prepare the main agent according to the above content by combining with the conventional technical means in the field, and obtain the high-temperature acidizing corrosion inhibitor by matching the auxiliary agent according to the above mass percentage, wherein the auxiliary agent can be further selected in order to further improve the temperature resistance of the corrosion inhibitor, wherein:
the aromatic aldehyde may be cinnamaldehyde or benzaldehyde.
The emulsifier is a coconut diethanol amine condensate, on one hand, the coconut diethanol amine condensate has higher hydrophily due to higher HLB value, and on the other hand, the coconut diethanol amine 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 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 slow release effect is kept at high temperature; in addition, the acidizing corrosion inhibitor provided by the invention does not contain substances with higher toxicity or stronger corrosivity, 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 preparation method of any one of the high-temperature acidizing corrosion inhibitors, which comprises the following steps:
step 1, performing an amide reaction on benzoic acid and 1-amino-2-methylbutane to obtain a main agent;
and 2, mixing 15-30% of the main agent, 5-15% of allylamine, 5-15% of aromatic aldehyde, 5-10% of emulsifier and 30-70% of solvent according to mass percentage to obtain the high-temperature acidizing corrosion inhibitor.
The invention provides a preparation method of a high-temperature acidizing corrosion inhibitor, and figure 1 is a flow schematic diagram of the preparation method of the high-temperature acidizing corrosion inhibitor provided by one embodiment of the invention, as shown in figure 1, the preparation method comprises the following steps: step 1, performing an amide reaction on benzoic acid and 1-amino-2-methylbutane to obtain a main agent, and performing an amidation reaction on the benzoic acid and 1-amino-2-methylbutane to obtain the main agent, wherein the reaction formula is shown as formula 1; and 2, mixing 15-30% of the main agent, 5-15% of allylamine, 5-15% of aromatic aldehyde, 5-10% of emulsifier and 30-70% of solvent according to the mass percentage to obtain the high-temperature acidizing corrosion inhibitor, wherein the aromatic aldehyde, the emulsifier and the solvent are selected as described above. The preparation method provided by the invention is simple to operate, and has the advantages of strong non-toxicity or corrosive substances in the reaction process and high safety in the preparation process.
In one embodiment, to further improve the yield of the base compound, the preparation method of the base compound comprises the following steps:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at the temperature of 180 ℃ and 200 ℃, reacting for 2h until the 1-amino-2-methylbutane and water are not evaporated, then adding 200g of 1-amino-2-methylbutane, raising the temperature to 230 ℃ for reacting for 1h, and washing, drying and recrystallizing the product after the reaction is finished 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, a preparation process of the main agent mainly includes the following steps: step 1-1, dividing 1-amino-2-methylbutane required by 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 200 g; step 1-2, distilling a first part of 1-amino-2-methylbutane and benzoic acid at the temperature of 180-200 ℃ to perform amidation reaction for 2 hours until no more 1-amino-2-methylbutane and water are distilled out; step 1-3, adding a second part of 1-amino-2-methylbutane to continue reacting with benzoic acid, further increasing the reaction temperature to 230 ℃, and finishing the reaction for 1 hour; and 1-4, after the reaction is finished, washing, drying and recrystallizing the product to obtain the main agent.
Wherein, the 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, no toxic or strong corrosive substances are generated in the reaction process, and the safety of the preparation process is high.
In a third aspect, the invention provides a method for preventing corrosion of an oil pipe in an acidification process, wherein any one of the high-temperature acidification corrosion inhibitors is added 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 an oil and gas well is exploited along with the acidizing fluid. The high-temperature acidizing corrosion inhibitor provided by the invention has good temperature resistance, can still maintain a slow release effect in a high-temperature environment, and effectively protects an oil pipe.
The research of the inventor of the application finds that when the mass of the high-temperature acidification corrosion inhibitor is 4% of that of the acidification liquid, the effective slow release effect can be achieved.
The following description is given with reference to specific embodiments, and the raw materials used in the examples are all commercially available.
Example 1
The high temperature acidizing corrosion inhibitor provided by the embodiment comprises:
30 parts by mass of a main agent;
10 parts by mass of a propylenylamine;
5 parts by mass of cinnamaldehyde;
10 parts by mass of a coconut diethanol amine condensate;
45 parts by mass of dimethylformamide.
The main agent is prepared by a preparation method comprising the following steps:
adding 250g of 1-amino-2-methylbutane into a 1L round-bottom flask, adding 400g of benzoic acid during slow heating and stirring, heating and distilling in an oil bath, maintaining the temperature at 180 ℃ and 200 ℃, reacting for 2h until 1-amino-2-methylbutane and water are not steamed, then adding 200g of 1-amino-2-methylbutane, heating to 230 ℃, heating and stirring for reacting for 1h, after the reaction is finished, repeatedly washing the reaction product for 2 times by using dilute hydrochloric acid, removing the dilute hydrochloric acid solution, then adding 300g of water for secondary washing, then washing and filtering by using 1L of sodium hydroxide solution (the concentration is 1mol/L), further washing and filtering by using 2L of water for 1h, drying in a 105 ℃ oven, and recrystallizing by using ethanol to obtain the main agent.
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 acrylamide, 5 parts by mass of cinnamaldehyde, 10 parts by mass of coconut diethanol amine condensate and 45 parts by mass of dimethylformamide to obtain the acidizing corrosion inhibitor.
Example 2
The high temperature acidizing corrosion inhibitor provided by the embodiment comprises:
20 parts by mass of a main agent;
10 parts by mass of a propylenylamine;
5 parts by mass of benzaldehyde;
10 parts by mass of a coconut diethanol amine condensate;
55 parts by mass of dimethylformamide.
The main agent is prepared by a preparation method comprising the following steps:
adding 250g of 1-amino-2-methylbutane into a 1L round-bottom flask, adding 400g of benzoic acid during slow heating and stirring, heating and distilling in an oil bath, maintaining the temperature at 180 ℃ and 200 ℃, reacting for 2h until 1-amino-2-methylbutane and water are not steamed, then adding 200g of 1-amino-2-methylbutane, heating to 230 ℃, heating and stirring for reacting for 1h, after the reaction is finished, repeatedly washing the reaction product for 2 times by using dilute hydrochloric acid, removing the dilute hydrochloric acid solution, then adding 300g of water for secondary washing, then washing and filtering by using 1L of sodium hydroxide solution (the concentration is 1mol/L), further washing and filtering by using 2L of water for 1h, drying in a 105 ℃ oven, and recrystallizing by using ethanol to obtain the main agent.
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 20 parts by mass of the main agent prepared in the step 1 with 10 parts by mass of allyl amine, 5 parts by mass of benzaldehyde, 10 parts by mass of coconut diethanol amine condensate and 55 parts by mass of dimethylformamide to obtain the acidizing corrosion inhibitor.
Example 3
The high temperature acidizing corrosion inhibitor provided by the embodiment comprises:
15 parts by mass of a main agent;
10 parts by mass of a propylenylamine;
10 parts by mass of cinnamaldehyde;
8 parts by mass of a coconut diethanol amine condensate;
57 parts by mass of dimethyl sulfoxide.
The main agent is prepared by a preparation method comprising the following steps:
adding 250g of 1-amino-2-methylbutane into a 1L round-bottom flask, adding 400g of benzoic acid during slow heating and stirring, heating and distilling in an oil bath, maintaining the temperature at 180 ℃ and 200 ℃, reacting for 2h until 1-amino-2-methylbutane and water are not steamed, then adding 200g of 1-amino-2-methylbutane, heating to 230 ℃, heating and stirring for reacting for 1h, after the reaction is finished, repeatedly washing the reaction product for 2 times by using dilute hydrochloric acid, removing the dilute hydrochloric acid solution, then adding 300g of water for secondary washing, then washing and filtering by using 1L of sodium hydroxide solution (the concentration is 1mol/L), further washing and filtering by using 2L of water for 1h, drying in a 105 ℃ oven, and recrystallizing by using ethanol to obtain the main agent.
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 allyl amine, 10 parts by mass of cinnamaldehyde, 8 parts by mass of coconut diethanol amine condensate and 57 parts by mass of dimethyl sulfoxide to obtain the acidizing corrosion inhibitor.
Example 4
The high temperature acidizing corrosion inhibitor provided by the embodiment comprises:
30 parts by mass of a main agent;
10 parts by mass of a propylenylamine;
10 parts by mass of benzaldehyde;
10 parts by mass of a coconut diethanol amine condensate;
40 parts by mass of dimethyl sulfoxide.
The main agent is prepared by a preparation method comprising the following steps:
adding 250g of 1-amino-2-methylbutane into a 1L round-bottom flask, adding 400g of benzoic acid during slow heating and stirring, heating and distilling in an oil bath, maintaining the temperature at 180 ℃ and 200 ℃, reacting for 2h until 1-amino-2-methylbutane and water are not steamed, then adding 200g of 1-amino-2-methylbutane, heating to 230 ℃, heating and stirring for reacting for 1h, after the reaction is finished, repeatedly washing the reaction product for 2 times by using dilute hydrochloric acid, removing the dilute hydrochloric acid solution, then adding 300g of water for secondary washing, then washing and filtering by using 1L of sodium hydroxide solution (the concentration is 1mol/L), further washing and filtering by using 2L of water for 1h, drying in a 105 ℃ oven, and recrystallizing by using ethanol to obtain the main agent.
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 allyl amine, 10 parts by mass of benzaldehyde, 10 parts by mass of coconut diethanol amine condensate and 40 parts by mass of dimethyl sulfoxide to obtain the acidizing corrosion inhibitor.
Example 5
The high temperature acidizing corrosion inhibitor provided by the embodiment comprises:
30 parts by mass of a main agent;
5 parts by mass of a propylenylamine;
10 parts by mass of cinnamaldehyde;
10 parts by mass of a coconut diethanol amine condensate;
45 parts by mass of dimethylformamide.
The main agent is prepared by a preparation method comprising the following steps:
adding 250g of 1-amino-2-methylbutane into a 1L round-bottom flask, adding 400g of benzoic acid during slow heating and stirring, heating and distilling in an oil bath, maintaining the temperature at 180 ℃ and 200 ℃, reacting for 2h until 1-amino-2-methylbutane and water are not steamed, then adding 200g of 1-amino-2-methylbutane, heating to 230 ℃, heating and stirring for reacting for 1h, after the reaction is finished, repeatedly washing the reaction product for 2 times by using dilute hydrochloric acid, removing the dilute hydrochloric acid solution, then adding 300g of water for secondary washing, then washing and filtering by using 1L of sodium hydroxide solution (the concentration is 1mol/L), further washing and filtering by using 2L of water for 1h, drying in a 105 ℃ oven, and recrystallizing by using ethanol to obtain the main agent.
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 coconut 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 acidizing corrosion inhibitor provided by the embodiment 1-5, and concretely, by referring to a performance test method and an evaluation index of the corrosion inhibitor for SY5405-2019 acidizing, corrosion test evaluation is carried out on CT80 steel in a 20% hydrochloric acid solution, wherein 4% of the acidizing corrosion inhibitor is added in hydrochloric acid dissolution, 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 sustained-release effect of high-temperature acidizing corrosion inhibitor 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 by examples 1 to 5 are all less 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 used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The high-temperature acidification corrosion inhibitor is characterized by comprising 15-30% of a main agent, 5-15% of allylamine, 5-15% of aromatic aldehyde, 5-10% of an emulsifier and 30-70% of a solvent by mass percent;
wherein the main agent is obtained by amidation reaction of benzoic acid and 1-amino-2-methylbutane.
2. The high-temperature acidizing corrosion inhibitor according to claim 1, wherein said host agent is prepared by a preparation method comprising the following steps:
distilling 250g of 1-amino-2-methylbutane and 400g of benzoic acid at the temperature of 180 ℃ and 200 ℃, reacting for 2h until the 1-amino-2-methylbutane and water are not evaporated, then adding 200g of 1-amino-2-methylbutane, raising the temperature to 230 ℃ for reacting for 1h, and washing, drying and recrystallizing the product after the reaction is finished to obtain the main agent.
3. A high temperature acidizing corrosion inhibitor according to claim 1 or 2 wherein said aromatic aldehyde is cinnamaldehyde or benzaldehyde.
4. A high temperature acidizing corrosion inhibitor according to claim 1 or 2 characterized in that said emulsifier is a cocodiethanolamine condensate.
5. A high temperature acidizing corrosion inhibitor according to claim 1 or 2 wherein said solvent is dimethylformamide or dimethylsulfoxide.
6. A method for preparing a high temperature acidizing corrosion inhibitor according to any one of the claims 1 to 5, characterized in that it comprises the following steps:
step 1, performing an amide reaction on benzoic acid and 1-amino-2-methylbutane to obtain a main agent;
and 2, mixing 15-30% of the main agent, 5-15% of allylamine, 5-15% of aromatic aldehyde, 5-10% of emulsifier and 30-70% of solvent according to mass percentage to obtain the high-temperature acidizing 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 the temperature of 180 ℃ and 200 ℃, reacting for 2h until the 1-amino-2-methylbutane and water are not evaporated, then adding 200g of 1-amino-2-methylbutane, raising the temperature to 230 ℃ for reacting for 1h, and washing, drying and recrystallizing the product after the reaction is finished 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 this order.
9. A method for preventing corrosion of oil pipes in an acidizing and fracturing process, which is characterized in that the high-temperature acidizing corrosion inhibitor according to any one of the claims 1 to 5 is added into acidizing fluid.
10. The method of claim 9, wherein the high temperature acidizing corrosion inhibitor is present in an amount of 4% by weight of the acidizing fluid.
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| US20120142563A1 (en) * | 2010-12-01 | 2012-06-07 | Halliburton Energy Services, Inc. | Corrosion Inhibitor Compositions Comprising Reaction Products of Aldehydes and Amides and Related Methods |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120142563A1 (en) * | 2010-12-01 | 2012-06-07 | Halliburton Energy Services, Inc. | Corrosion Inhibitor Compositions Comprising Reaction Products of Aldehydes and Amides and Related Methods |
| 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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