CN111499527B - Preparation method and application of high-temperature-resistant acidizing corrosion inhibitor of crosslinked acid system - Google Patents
Preparation method and application of high-temperature-resistant acidizing corrosion inhibitor of crosslinked acid system Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a high-temperature resistant acidizing corrosion inhibitor of a cross-linked acid system. The preparation method comprises the following steps: respectively adding an aldehyde monomer, a ketone monomer and an amine monomer into a reactor, dispersing with absolute ethyl alcohol, and reacting at 60-100 ℃ to obtain a Mannich base; after the system is cooled, the halogenated alkane is added, and the reaction is continued at the temperature of 60-100 ℃ to obtain the Mannich base quaternary ammonium salt corrosion inhibitor. The obtained Mannich base quaternary ammonium salt corrosion inhibitor can be directly used without purification. The acidizing corrosion inhibitor has better temperature resistance and compatibility, is used at a high temperature of 180 ℃, and is suitable for each process of acidizing construction of an oil field.
Description
Technical Field
The invention relates to a preparation method and application of a high-temperature-resistant acidizing corrosion inhibitor of a crosslinked acid system, and belongs to the technical field of oilfield corrosion prevention in the process of oil and gas resource reservoir transformation.
Background
In the development process of petroleum and natural gas resources, particularly when an oil-gas field enters the later development stage, the exploitation cost is increased, the yield is gradually reduced year by year, the development difficulty is increased more and more, and the economic benefit is reduced more and more. The acidification technique is a very effective production-increasing measure, and in order to enlarge oil flow channel and reduce oil flow resistance, a mechanical method is commonly used to inject acid liquor with a certain concentration (about 20%) into the stratum so as to dissolve the blocking substances in the stratum near the bottom of the well and some components in the stratum rock, thus achieving the purpose of increasing production. During the acidizing process, hydrochloric acid or earth acid is mainly used for corrosion of carbonate formations or silicate formations. Surface pitting, hydrogen embrittlement and weight loss corrosion of oil and gas well tubing and downhole metal equipment due to acid injection may sometimes result in downhole corrosionSudden rupture accidents of the pipe cause huge economic loss. Fe simultaneously corroded by acid 3+ Entering the formation can cause permanent damage to the formation. Therefore, it becomes critical to add corrosion inhibitors to sour liquors to prevent corrosion of metals.
Most of the acidification corrosion inhibitors are polar or ionic compounds, mainly including Mannich bases, propiolic alcohol, fatty amines and derivatives thereof, quaternary ammonium salts, amide carboxylic acid type, rosin derivative corrosion inhibitors, pyridine corrosion inhibitors and the like. The Mannich base type acidizing corrosion inhibitor has good effect, stable structure, strong acid solubility and good temperature and acid resistance, is typical of a novel acidizing corrosion inhibitor, and is particularly used in various fields of oil and gas field exploitation in a cross-linked acid system. Mannich reaction to prepare Mannich base (formula I) the general reaction formula is as follows:
in the formula, R 1 ＇、R 2 ＇、R 3 ＇、R 4 The functional group may be an alkyl group, an aromatic group, a hydrogen radical, or the like.
As the development of oil and gas wells is in the middle and later stages, the well depth is continuously increased, and the bottom temperature is increased, so that higher performance requirements are provided for the corrosion inhibitor used in the acidification operation of the oil and gas wells. Most of the existing acidizing corrosion inhibitors on the market can only be suitable for low-medium temperature acidizing operation below 150 ℃, and when the formation temperature exceeds 160 ℃ or even higher, the common corrosion inhibitors are decomposed at high temperature or are separated out and have serious coking, adsorption weakening and the like with an injection system, so that the corrosion inhibition effect is poor. And although the corrosion inhibitors are used for inhibiting corrosion of hydrochloric acid and the like, the corrosion inhibitors have good corrosion inhibition effect, but are not suitable for a cross-linking acid system for acid fracturing, so that the cross-linking and temperature resistance of cross-linking acid are influenced.
Chinese patent document CN109810040A discloses a preparation method and application of a Mannich base quaternary ammonium salt high-temperature resistant acidizing corrosion inhibitor, and the prepared acidizing corrosion inhibitor has an obvious inhibiting effect on acid corrosion of carbon steel of an oil and gas well. But it is only suitable for use at a temperature of 90 c. CN110982508A discloses a preparation method of a Mannich base acidizing corrosion inhibitor, which keeps good corrosion inhibition performance and dissolution dispersibility in a medium-high temperature environment at 100 ℃. But the temperature resistance is only improved to 140 ℃, and a large amount of emulsifying cosolvent is required to be added in the process of preparing the corrosion inhibitor. The temperature resistance of the corrosion inhibitor prepared by CN110105943A is improved to 180 ℃, but propiolic alcohol is added in the process of preparing the corrosion inhibitor, so that certain harm is caused to the environment.
Disclosure of Invention
Aiming at the problems in the prior art, the preparation method of the high-temperature resistant acidizing corrosion inhibitor of the cross-linked acid system is provided.
The technical task of the invention is as follows: the corrosion inhibitor has the advantages of simple formula, mild synthesis conditions and capability of meeting the harsh requirements of acidizing operation at high temperature (more than 160 ℃) of an oil-gas well, is particularly suitable for a cross-linked acid system for acid fracturing and does not influence the cross-linked acid performance.
The invention also provides application of the high-temperature resistant acidizing corrosion inhibitor.
The Mannich base quaternary ammonium salt acidizing corrosion inhibitor prepared by the invention has stable property, simple synthesis condition and good compatibility with acid liquor, can be used at a high temperature of 180 ℃ or above, can be uniformly dispersed in a cross-linked acid system, and shows excellent corrosion inhibition performance under the condition of not influencing the cross-linked acid performance.
Summary of the invention: the invention takes Mannich (Mannich) reaction as the basis, and performs quaternization reaction on the Mannich base corrosion inhibitor on the basis of the prepared Mannich base corrosion inhibitor, thereby preparing the Mannich base quaternary ammonium salt high-temperature acidification corrosion inhibitor. The long-chain aliphatic hydrocarbon chain segment is introduced into the corrosion inhibitor, so that the temperature resistance of the acidizing corrosion inhibitor is enhanced, the effect of an emulsifier can be realized after quaternization, the dispersibility of the corrosion inhibitor in strong acid is improved, and the corrosion inhibition effect of the corrosion inhibitor is improved. The corrosion inhibitor is used in different acid solutions at a high temperature of 180 ℃, is particularly suitable for a cross-linked acid system, and can enable the corrosion rate of the N80 steel sheet to reach the first grade of the performance index of the corrosion inhibitor for acidification (SY/T5405-1996).
Detailed description of the invention:
the technical scheme of the invention is as follows:
a preparation method of a high-temperature resistant acidizing corrosion inhibitor of a cross-linked acid system comprises the following steps:
(1) Mannich reaction
Respectively adding an aldehyde monomer, a ketone monomer and an amine monomer into a reactor, dispersing by using a proper amount of absolute ethyl alcohol, adjusting the pH value to 2-6 by using hydrochloric acid, and stirring and reacting for 2-8 h in a water bath at 60-100 ℃ to obtain a Mannich base;
the ketone monomer is acetophenone or cyclohexanone;
the aldehyde monomer is formaldehyde, acetaldehyde, propionaldehyde, n-hexanal, phenylacetaldehyde, 1-hydroxy-2-naphthaldehyde or 9-anthracenal;
the amine monomer is methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine or diethylenetriamine;
(2) Quaternization reaction
After the system is cooled, adding halogenated alkane according to the mol ratio of the Mannich base to the halogenated alkane of 1-2, and continuously reacting for 2-6 h in water bath at 60-100 ℃ to obtain the Mannich base quaternary ammonium salt corrosion inhibitor.
The halogenated alkane is chlorododecane, bromododecane, chlorotetradecane, bromotetradecane, chlorohexadecane, bromohexadecane, chlorooctadecane or bromooctadecane.
According to the invention, the aldehyde monomer is preferably phenylacetaldehyde, 1-hydroxy-2-naphthaldehyde or 9-anthracenal. The amine monomer is dimethylamine. The halogenated alkane is one of chlorododecane, chlorotetradecane, bromohexadecane and bromooctadecane.
Preferably, according to the present invention, the molar ratio of the monomers in step (1) is ketone: aldehyde: amine = (1-2): 1-2); further preferably, the monomer molar ratio is ketone: aldehyde: amine =1, 1.2.
Preferably, according to the present invention, the reaction conditions in step (1) include one or more of:
a. the pH value is adjusted to be 4;
b. the reaction temperature is 90 ℃; the reaction time is 6h;
c. the molar ratio of the monomers is ketone: aldehyde: amine is 1.
d. The dispersion is carried out by using a proper amount of absolute ethyl alcohol, and the addition amount of the absolute ethyl alcohol is as follows: the mass-to-volume ratio of the total mass of the aldehyde, ketone and amine monomers to the anhydrous mass of ethanol is (30-85) g:100mL.
Preferably, according to the present invention, the molar ratio of the amine in step (1) to the haloalkane in step (2) is 1.0 to 1.2.
Preferably, according to the present invention, in the step (2), the system is cooled to a temperature of not higher than 60 ℃.
According to the invention, in the step (2), the reaction temperature is 90 ℃ and the reaction time is 4h.
The reactor is a reaction vessel with a condensing pipe, electromagnetic stirring and a starting material adding port.
The target product prepared by the invention is a novel Mannich base quaternary ammonium salt corrosion inhibitor which is a red brown transparent liquid.
The high-temperature acidizing corrosion inhibitor prepared by the invention has a structure shown in a formula II or a formula III:
in the formulae II and III, R 1 Is phenyl, naphthyl or anthryl, R 2 Is C12-C18 alkyl, and X is Cl or Br atom.
The reaction process using acetophenone as an example is shown in scheme 1:
wherein R is 1 Is phenyl, naphthyl or anthryl, R 2 Is C12-C18 alkyl, and X is Cl or Br atom.
The Mannich base quaternary ammonium salt prepared by the application of the high-temperature resistant acidizing corrosion inhibitor is used as the corrosion inhibitor and can be directly used without purification. The addition amount of the Mannich base quaternary ammonium salt high-temperature acidification corrosion inhibitor in acid liquor is 3-4.5wt.%, based on the mass of the acid liquor; preferably the addition is 4wt.%.
The application of the high-temperature resistant acidizing corrosion inhibitor prepared by the invention can lead the corrosion inhibitor to be capable of being used at a high temperature of 180 ℃; the method is applicable to acid liquids of different systems, and particularly has good compatibility with an acid fracturing crosslinking acid system of an oil field.
The invention has the technical characteristics and excellent effects that:
the invention provides a preparation method of a novel Mannich base quaternary ammonium salt high-temperature resistant acidizing corrosion inhibitor, which is based on the quaternization reaction of Mannich base and is synthesized by two steps, and the obtained acidizing corrosion inhibitor has better temperature resistance and compatibility than the conventional acidizing corrosion inhibitor, is suitable for each process of acidizing construction of an oil field, and is especially suitable for an acid fracturing crosslinking acid system of the oil field. The corrosion inhibitor has the excellent corrosion inhibition effect of the Mannich base corrosion inhibitor and the strong adsorbability of the quaternary ammonium salt corrosion inhibitor, and the introduction of the aromatic ring and the long-chain alkane chain segment further enhances the temperature resistance and the blocking effect of the corrosion inhibitor on an action interface.
1. The raw materials used in the invention have been industrialized, the raw materials are easy to obtain, the reaction process is simple, and the preparation can be completed under general chemical conditions.
2. The preparation method has mild conditions, the two-step reaction conditions are the same, the reaction is easy to control, and the process is safe.
3. The Mannich quaternary ammonium salt corrosion inhibitor prepared by the invention has stable property and can be stably stored for a long time at normal temperature and normal pressure.
4. The corrosion inhibitor prepared by the invention has simple use method and can be directly used without purification.
5. The high-temperature-resistant corrosion inhibitor prepared by the invention has good compatibility with different strong acid systems, particularly good compatibility with an oil field acid fracturing crosslinking acid system, and does not influence the performance of the crosslinking acid.
6. The corrosion inhibitor prepared by the invention can resist high temperature, and can enable the corrosion rate of N80 steel sheets to reach the first grade in the performance index (SY/T5405-1996) of the corrosion inhibitor for acidification when used in different acid liquor at the high temperature of 180 ℃.
Detailed Description
The invention is further described by referring to specific examples and an evaluation method of a corrosion inhibitor performance index (SY/T5405-1996) for oilfield acidification, wherein the corrosion inhibition performance of different examples is measured, but the protection scope of the invention is not limited to the specific examples, and the raw materials in the examples are all conventional commercial products. The raw materials used in the examples are all commercially available products.
In the corrosion inhibition performance test under different acid solutions in the following examples, the composition of the crosslinking acid system I is 20% HCl +1.0% thickening agent +1.0% crosslinking agent + balance water, and the composition of the crosslinking acid system II is 12% HCl +3% HF +1.0% thickening agent +1.0% crosslinking agent + balance water. The thickening agent is an acrylamide thickening agent, and the crosslinking agent is an organic zirconium crosslinking agent, which are all known products.
In the examples and experiments, "%" is used in percentage by mass unless otherwise specified.
Example 1
0.12mol of acetophenone (14.4 g), 0.12mol of benzaldehyde (12.7 g) and 0.1mol of diethylamine (7.3 g) are respectively added into a 250mL three-neck flask with a serpentine condenser and electromagnetic stirring, 100mL of absolute ethanol is used for dispersing, the pH value is slowly adjusted to 4 by hydrochloric acid, and the Mannich base is obtained by stirring and reacting for 6h in a water bath at 90 ℃. And after the system is cooled to 60 ℃, 0.12mol of chlorododecane (24.5 g) is added, and the reaction is continued for 4h at the temperature of 90 ℃ in a water bath to obtain the reddish brown transparent Mannich base quaternary ammonium salt corrosion inhibitor, which has the structure shown in the formula IV.
The corrosion inhibitor prepared in example 1 was formulated into different acid liquor systems at a use level of 4.0wt.% (the same applies below), and the obtained acid liquor was free of precipitation and delamination. The corrosion rate of the corrosion inhibitor was measured on N80 steel sheets at 180 ℃ at a 4.0wt.% use concentration, and the results are shown in table 1.
Table 1 example 1 corrosion inhibition performance under different acid solutions
Example 2
The same as in example 1, except that: mixing a ketone: aldehyde: the ratio of amines was changed from 1.2.
The corrosion inhibitor prepared in example 2 was formulated into different acid liquor systems, and the obtained acid liquor was free of precipitation and delamination. The corrosion rate of the N80 steel sheet at 180 ℃ at the corrosion inhibitor use concentration of 4.0wt.% was measured, and the results are shown in table 2.
Table 2 example 2 corrosion inhibition performance under different acid solutions
Example 3
The same as in example 1, except that: the amount of haloalkane used was changed from 1.2 to 1, and 0.1mol (20.4 g) of chlorododecane was used, to give a corrosion inhibitor of the same structure.
The corrosion inhibitor prepared in example 3 was formulated into different acid systems and the resulting acid was free of precipitation and delamination. The corrosion rate of the N80 steel sheet at 180 ℃ at the use concentration of 4.0wt.% corrosion inhibitor was measured, and the results are shown in table 1.
Table 3 example 3 corrosion inhibition performance in different acid liquors
Example 4
The procedure was followed as described in example 1, except that 0.12mol of bromooctadecane (39.8 g) was used as the haloalkane, and the Mannich base quaternary ammonium salt corrosion inhibitor obtained had the structure of formula V.
The corrosion inhibitor prepared in example 4 was formulated into different acid systems and the resulting acid was free of precipitation and delamination. The corrosion rate of the N80 steel sheet at 180 ℃ at the use concentration of 4.0wt.% corrosion inhibitor was measured, and the results are shown in table 4.
Table 4 example 4 corrosion inhibition performance under different acid solutions
Example 5
As in example 1, except that: the Mannich base quaternary ammonium salt corrosion inhibitor obtained by replacing 0.12mol of benzaldehyde with 0.12mol of 1-hydroxy-2 naphthaldehyde (20.6 g) has a structure shown in a formula VI.
The corrosion inhibitor prepared in example 5 was formulated into different acid systems and the resulting acid was free of precipitation and delamination. The corrosion rate of the N80 steel sheet at 180 ℃ at the use concentration of 4.0wt.% corrosion inhibitor was measured, and the results are shown in table 5.
Table 5 example 5 corrosion inhibition performance under different acid solutions
Example 6
As in example 1, except that: the used aldehyde is replaced by 0.12mol of 9-anthracene aldehyde (24.7 g), and the obtained Mannich base quaternary ammonium salt corrosion inhibitor has a structure shown in a formula VII.
The corrosion inhibitor prepared in example 6 was formulated into different acid systems and the resulting acid was free of precipitation and delamination. The corrosion rate of the N80 steel sheet at 180 ℃ at the corrosion inhibitor use concentration of 4.0wt.% was measured, and the results are shown in table 6.
Table 6 example 6 corrosion inhibition performance in different acid liquors
Example 7
As in example 1, except that: the ketone is replaced by 0.24mol of cyclohexanone (23.5 g), the aldehyde is 0.24mol of benzaldehyde (25.4 g), the amine is 0.1mol of diethylenetriamine (10.3 g), and the obtained Mannich base quaternary ammonium salt corrosion inhibitor has the structure shown in the formula VIII.
The corrosion inhibitor prepared in example 7 was formulated into different acid systems and the resulting acid was free of precipitation and delamination. The corrosion rate of the N80 steel sheet at 180 ℃ at the corrosion inhibitor use concentration of 4.0wt.% was measured, and the results are shown in table 7.
Table 7 example 7 corrosion inhibition performance in different acid liquors
Example 8
As described in example 7, except that: the used halogenated alkane is 0.12mol of bromo-octadecane (39.8 g), and the obtained Mannich base quaternary ammonium salt corrosion inhibitor has a structure shown as formula IX.
The corrosion inhibitor prepared in example 8 was formulated into different acid systems and the resulting acid was free of precipitation and delamination. The corrosion rate of the N80 steel sheet at 180 ℃ at the corrosion inhibitor use concentration of 4.0wt.% was measured, and the results are shown in table 8.
Table 8 example 8 corrosion inhibition performance in different acid liquors
Example 9
The procedure was followed as described in example 6, except that 0.12mol of bromooctadecane (39.8 g) was used as the haloalkane, and the Mannich base quaternary ammonium salt corrosion inhibitor obtained had the formula X.
The corrosion inhibitor prepared in example 9 was formulated into different acid systems and the resulting acid was free of precipitation and delamination. The corrosion rate of the N80 steel sheet at 180 ℃ at the use concentration of 4.0wt.% corrosion inhibitor was measured, and the results are shown in table 9.
Table 9 example 9 corrosion inhibition performance under different acid solutions
Example 10
The procedure was followed as described in example 7, except that the aldehyde used was substituted for 0.24mol of 9-anthracenal (49.4 g), and the resulting Mannich base quat corrosion inhibitor has the formula XI.
The corrosion inhibitor prepared in example 10 was formulated into different acid liquor systems, and the resulting acid liquor was free of precipitation and delamination. The corrosion rate of the N80 steel sheet at 180 ℃ at the corrosion inhibitor use concentration of 4.0wt.% was measured, and the results are shown in table 10.
TABLE 10 example 10 Corrosion inhibition Performance under different acid solutions
Comparative experiment:
comparative example 1, patent document CN110982508A describes a mannich base acidification corrosion inhibitor prepared in example 3, and the properties are shown in table 3 of the description.
Comparative example 2, patent document CN110105943A describes a high temperature acidification corrosion inhibitor prepared in example 2.
Comparative example 3, novel high temperature resistant acidizing corrosion inhibitor XAI-180, see Li Hui, lubin, tangzu soldiers, blue flow-rate source, dajunqing research and development of novel high temperature resistant acidizing corrosion inhibitor XAI-180 and Performance evaluation [ J ] the Natural gas industry, 2019,39 (09): 89-95.
Comparative example 4, a novel high-temperature acidizing corrosion inhibitor, see Shushao, lihongjun, xuqingxiang, matianli, linan, preparation and Performance evaluation of a novel high-temperature acidizing corrosion inhibitor [ J ]. Surface technique, 2017,46 (10): 229-233).
Comparative example 5, a ultra-high temperature acidizing corrosion inhibitor, see wuwenggang, research and application of ultra-high temperature acidizing corrosion inhibitor [ C ]. China petroleum institute gas professional committee, petroleum institute of sichuan province, the collection of national gas academy proceedings of the national gas academy of the year 2016, china petroleum institute gas professional committee, petroleum institute of sichuan province 2016, gas professional committee of china petroleum institute, 2016 2896-2900.
Comparative example 6, patent document CN 108359438A description of the high temperature acidification corrosion inhibitor prepared in example 2.
The corrosion inhibiting properties of inventive example 10 were compared with other prior art high temperature acidizing corrosion inhibitors and the comparison of the properties of the various corrosion inhibitors is summarized in table 11.
TABLE 11 comparison of the Performance of different acidified corrosion inhibitors
From the corrosion rates of the steel sheets in the examples in combination with their structures, it can be seen that in the different examples, the higher the charge density of the aldehyde monomer added in the preparation conditions (examples 1, 5, 6) and the longer the carbon chain used for quaternization (examples 1, 4, examples 7, 8), the better the corrosion inhibition performance of the corrosion inhibitors obtained. In the acidification corrosion inhibitor, the main function of the Mannich base part is to carry out complexation or adsorption with the metal surface, and the higher the charge density of the used aldehyde monomer is, the stronger the binding capacity of the product and the metal surface is, thus better corrosion inhibition effect can be realized; the main function of the alkane chain segment of the quaternary ammonium salt part is to isolate the acid liquor from the metal surface, so that the longer the carbon chain of the quaternary ammonium salt part is, the stronger the barrier effect of the corrosion inhibitor on the metal surface is, and the better corrosion inhibition effect can be achieved. In the same embodiment, the corrosion rate of the crosslinking acid system added with the crosslinking agent and the thickening agent is higher than that of the conventional acid system because the viscosity of the system is increased after the acid liquor is crosslinked, and the diffusion and the migration of the corrosion inhibitor in the system are hindered to change the adsorption balance of the corrosion inhibitor on the surface of the steel sheet, so the corrosion rate is increased to a certain extent.
According to the Mannich base quaternary ammonium salt acidizing corrosion inhibitor synthesized by the invention, the optimal reaction temperature of the Mannich reaction is 90 ℃, and the reaction time is 6h; the optimal reaction temperature for the quaternization reaction is 90 ℃, and the reaction time is 4h. In the range that the corrosion inhibition performance of the synthesized product reaches the first-level index, in the selected Mannich reaction, the ratio of ketone: aldehyde: the amine is optimal at 1.2; in the quaternization reaction chosen, the amine: the halogenated alkanes are most preferred in 1. In the synthetic embodiment, the dispersion can be effectively carried out in a conventional acid system and a crosslinking acid system, and the construction first-level standard can be achieved. The brominated quaternary ammonium salt corrosion inhibitor with the anthracene structure and the octadecyl has the optimal performance. Wherein example 9 is a mono mannich base quaternary ammonium salt compound and example 10 is a bis mannich base quaternary ammonium salt compound.
Compared with other groups of corrosion rates in proportion, the corrosion inhibitor prepared by the invention has better temperature resistance under the condition that the corrosion inhibition effect reaches a first-level index (comparative examples 1 and 4). Under the same temperature resistant condition, the corrosion inhibition effect of the corrosion inhibitor prepared by the invention is far higher than that of most high-temperature acidification corrosion inhibitors (comparative examples 3, 5 and 6), and is closer to that of comparative example 2, but the propiolic alcohol added in the comparative example 2 has larger harm to the environment, and the system is not applied in a cross-linked acid system.
Claims (9)
1. A preparation method of a high-temperature resistant acidizing corrosion inhibitor of a cross-linked acid system comprises the following steps:
(1) Mannich reaction
Respectively adding an aldehyde monomer, a ketone monomer and an amine monomer into a reactor, dispersing by using a proper amount of absolute ethyl alcohol, adjusting the pH value to 2-6 by using hydrochloric acid, and stirring and reacting for 2-8 h in a water bath at 60-100 ℃ to obtain a Mannich base;
the ketone monomer is acetophenone or cyclohexanone;
the aldehyde monomer is benzaldehyde, 1-hydroxy-2-naphthaldehyde or 9-anthracenal;
the amine monomer is methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine or diethylenetriamine;
the molar ratio of the monomers is ketone: aldehyde: amine = (1-2): 1-2);
(2) Quaternization reaction
After the system is cooled, adding halogenated alkane according to the mol ratio of the Mannich base to the halogenated alkane of 1-2, and continuously reacting for 2-6 h in a water bath at 60-100 ℃ to obtain the Mannich base quaternary ammonium salt corrosion inhibitor;
the halogenated alkane is chlorododecane, bromododecane, chlorotetradecane, bromotetradecane, chlorohexadecane, bromohexadecane, chlorooctadecane or bromooctadecane.
2. The method for preparing the high temperature resistant acidizing corrosion inhibitor of the crosslinked acid system according to the claim 1, wherein the molar ratio of the monomers is ketone: aldehyde: 1, 1.2.
3. The method for preparing a high temperature resistant acidizing corrosion inhibitor of a crosslinked acid system as claimed in claim 1 wherein the reaction conditions in step (1) include one or more of the following:
a. the pH value is adjusted to be 4;
b. the reaction temperature is 90 ℃; the reaction time is 6h;
c. the molar ratio of the monomers is ketone: aldehyde: amine is 1;
d. dispersing with a proper amount of absolute ethyl alcohol, wherein the addition amount of the absolute ethyl alcohol is as follows: the volume ratio of the total mass of the aldehyde, ketone and amine monomers to the absolute ethyl alcohol is (30-85) g:100mL.
4. The method of claim 1, wherein in step (2), the system is cooled to a temperature of not more than 60 ℃.
5. The method for preparing the high temperature resistant acidizing corrosion inhibitor of the crosslinked acid system according to the claim 1, wherein the reaction temperature in the step (2) is 90 ℃ and the reaction time is 4h.
6. The high temperature acidification resistant corrosion inhibitor of the cross-linked acid system prepared by the preparation method of any one of claims 1 to 5, having one of the structures shown in the following structural formula:
7. use of a high temperature resistant acidification corrosion inhibitor of a cross-linked acid system prepared by the process of any one of claims 1 to 5, wherein the obtained Mannich base quaternary ammonium salt corrosion inhibitor is used directly without purification.
8. The use of the high temperature resistant acidizing corrosion inhibitor of the crosslinked acid system of claim 7 wherein the high temperature resistant acidizing corrosion inhibitor is added to the acid liquor in an amount of from 3 to 4.5wt.%, based on the mass of the acid liquor.
9. Use of a high temperature resistant acidification corrosion inhibitor for a cross-linked acid system as claimed in claim 7 wherein said corrosion inhibitor is used at a high temperature of 180 ℃ for a cross-linked acid system.
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