CN113045499A - Asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic compound, and preparation and application thereof - Google Patents
Asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic compound, and preparation and application thereof Download PDFInfo
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- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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Abstract
The invention discloses an asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic compound, which has a structural formula shown as the following formula I:
wherein: r1、R2Each independently selected from CnH2n+1Or CnH2n‑1N is a positive integer from 12 to 18; m is 0, 1 or 2. The cationic compound can be used as a corrosion inhibitor for the exploitation of high-hydrogen-sulfide fields, has high slow release rate in the high-hydrogen-sulfide fields (the content of hydrogen sulfide can reach 1.5MPa or more), has no special pungent smell, low toxicity, good oil-soluble water dispersibility and film formationThe high-performance hydrogen sulfide corrosion-resistant agent has the advantage of strong capability, and has wide application prospect in corrosion resistance of equipment and pipelines in drilling, production and gathering of high-hydrogen sulfide fields. The invention also discloses a preparation method and application of the cationic compound.
Description
Technical Field
The invention relates to the field of oil and gas field exploitation. More particularly, relates to an asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic compound, and a preparation method and an application thereof.
Background
At present, natural gas reserves in China are quite rich, the quantity of gas fields which are already explored is more and more, particularly, the exploration of unconventional gas fields such as dense gas and shale gas has the advantages that with the rapid development of economy in China, the oil and gas requirements are larger and larger, but the oil reserves in China are relatively lacked, the oil yield in China is gradually reduced in recent years, the exploitation difficulty is continuously increased, the crude oil yield cannot meet the domestic energy requirements, and therefore the exploration and exploitation of the gas fields must be increased to meet the domestic energy requirements.
At present, the onshore exploration gas fields in China are mainly distributed in the plain of Chuannan and Songliao, the exploitation technology of the gas fields in Chuannan is mature, and the yield reaches a large scale. Because the gas is accompanied by a large amount of aggressive substances (such as H) during the drilling and production process of the gas field2S、CO2) Therefore, the corrosion to underground pipe columns of gas wells, ground pipelines and various process equipment causes huge economic loss and serious catastrophic accidents and environmental pollution. Particularly, natural gas produced in a plain gas field in China contains hydrogen sulfide corrosive gas with very high content, and the corrosion to drilling, production, gathering and transportation equipment is serious; in addition, due to the existence of gas in the process of gas field water injection exploitationAnd the two phases of the liquid and the liquid are simultaneously corroded, so the difficulty of corrosion prevention is very high, and therefore, the corrosion prevention measures suitable for metal corrosion in the high hydrogen sulfide environment of a gas field are very necessary.
At present, a plurality of methods for metal corrosion prevention are available, wherein the reasonable use of a chemical corrosion inhibitor is a convenient, economic and effective protection technology for preventing metals and alloys thereof from being corroded in environmental media. Imidazoline and its derivative are a new type, green corrosion inhibitor, it has excellent corrosion inhibition performance for carbon steel, alloy steel, copper, brass, aluminium alloy, etc. in the medium of high hydrogen sulfide, etc., and at the same time has the characteristics of no special pungent smell, good thermal stability and low toxicity.
Although documents and patents about the research of corrosion inhibitors of imidazoline and derivatives thereof are reported, the research of drilling and adopting the corrosion inhibitors under the specific conditions of high hydrogen sulfide gas fields, especially high hydrogen sulfide plain gas fields (the content reaches 1.5MPa) in China is less. The corrosion inhibitor for metal corrosion prevention under such environmental conditions does not only need to have the excellent properties of a liquid phase corrosion inhibitor, but also needs to have good gas phase corrosion inhibition performance, so that the corrosion inhibitor has new requirements on the chemical structure. Therefore, it is necessary to develop a corrosion inhibitor for gas field exploitation which can effectively inhibit high hydrogen sulfide corrosion in both gas phase and liquid phase.
Disclosure of Invention
The invention aims to provide an asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic compound which can be used as a corrosion inhibitor for high-hydrogen-sulfide field exploitation, has high slow release rate in the high-hydrogen-sulfide field (the content of hydrogen sulfide can reach 1.5MPa or above), has the advantages of no special pungent smell, low toxicity, good oil-soluble water dispersibility and strong film forming capability, and has wide application prospect in corrosion prevention of equipment and pipelines in drilling and production and gathering of high-hydrogen-sulfide fields.
The second purpose of the invention is to provide a preparation method of the asymmetric long-chain alkyl benzyl imidazoline polyvinyl long-chain alkylamide cationic compound.
The third purpose of the invention is to provide a corrosion inhibitor.
The fourth purpose of the invention is to provide the application of the corrosion inhibitor in the exploitation of the high hydrogen sulfide field.
In order to achieve the first purpose, the invention adopts the following technical scheme:
an asymmetric long-chain alkyl benzyl imidazoline polyvinyl long-chain alkylamide cationic compound, wherein the structural formula of the cationic compound is shown as the following formula I:
wherein:
R1、R2each independently selected from CnH2n+1Or CnH2n-1N is a positive integer from 12 to 18;
m is 0, 1 or 2.
Further, n is 17.
In order to achieve the second purpose, the invention adopts the following technical scheme:
the preparation method of the asymmetric long-chain alkyl benzyl imidazoline polyvinyl long-chain alkylamide cationic compound comprises the following steps:
1) taking long-carbon-chain fatty acid A and polyethylene polyamine as raw materials, and carrying out dehydration acylation and imidazole cyclization reactions to obtain a long-carbon-chain alkyl imidazoline intermediate;
2) and (3) carrying out acylation reaction on the long-carbon-chain alkyl imidazoline intermediate and a long-carbon-chain fatty acid B, and carrying out quaternization reaction on the obtained product and benzyl chloride to obtain the asymmetric long-chain alkyl benzyl imidazoline polyvinyl long-chain alkylamide cationic compound.
3. The method of claim 2, wherein the long carbon chain fatty acid A and the long carbon chain fatty acid B are each independently RCOOH, wherein R is selected from CnH2n+1Or CnH2n-1And n is a positive integer from 12 to 18.
Further, the long-carbon-chain fatty acids A and B are respectively and independently selected from one of stearic acid and oleic acid.
Further, in step 1), the ratio of long-chain fatty acid a: the molar ratio of the polyethylene polyamine is 1: 1-1: 1.2.
Further, the reaction in step 1) is carried out in the presence of a catalyst and a water-carrying agent.
Further, in the step 1), the catalyst is one or two selected from calcium oxide, magnesium oxide and aluminum oxide.
Further, in the step 1), the water-carrying agent is one or two of toluene and xylene.
In step 1), the addition amount of the catalyst is 0.1-1% of the total mass of the long-carbon-chain fatty acid A and the polyethylene polyamine, and the amount of the water-carrying agent is 20-30% of the total mass of the long-carbon-chain fatty acid A and the polyethylene polyamine.
Further, in the step 1), the conditions of the dehydration acylation and imidazole cyclization reaction are as follows: and heating to 120-160 ℃, reacting at constant temperature for 2-3 hours under continuous stirring, heating to 180-200 ℃, reacting at constant temperature for 2-3 hours, heating to 220-240 ℃, reacting at constant temperature until no liquid drop appears in the water separator, and stopping the reaction.
Further, the mole ratio of the long-carbon-chain fatty acid B in the step 2) to the polyethylene polyamine in the step 1) is 1: 0.8-1: 1.0; the molar ratio of the long-carbon-chain fatty acid A in the step 1) to the benzyl chloride in the step 2) is 1: 0.8-1: 0.9.
Further, in the step 2), the conditions of the acylation reaction are as follows: mixing the long-carbon-chain alkyl imidazoline intermediate with the long-carbon-chain fatty acid B at the temperature of 120-160 ℃, then heating to 180 ℃, and reacting for 2-3 hours at constant temperature.
Further, in the step 2), the quaternization reaction conditions are as follows: cooling the acylation reaction product to 80-90 ℃, adding benzyl chloride, heating to 90-110 ℃, carrying out heat preservation reaction for 1.5-2 hours, cooling to 70 ℃, and discharging.
Further, the polyethylene polyamine is selected from one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.
In order to achieve the third purpose, the invention adopts the following technical scheme:
the raw material of the corrosion inhibitor comprises the asymmetric long-chain alkyl benzyl imidazoline polyvinyl long-chain alkylamide cationic compound.
Further, the cationic compound can be used alone or in combination with an auxiliary agent to obtain the corrosion inhibitor.
When the cationic compound and the auxiliary agent are compounded for use, the auxiliary agent can be one or more of thiourea and OP-15, and the compounding method comprises the following steps: firstly, respectively weighing a certain amount of the cationic compound and OP-15 according to the proportion of each component in the formula, pouring the cationic compound and OP-15 into a mixing tank with stirring, then respectively weighing a certain amount of methanol and water according to the proportion of the formula, mixing, then weighing a certain amount of thiourea, putting the thiourea into a mixed solvent of the methanol and the water for full dissolution, finally heating the mixing tank to 50-60 ℃, adding the prepared thiourea methanol-water mixed solution into the mixing tank under the condition of continuous stirring, and continuously stirring for 0.5-1 hour after the addition is finished, thus obtaining the light yellow transparent compound liquid.
In order to achieve the fourth object, the invention adopts the following technical scheme:
the application of the corrosion inhibitor in the exploitation of high hydrogen sulfide fields.
Further, in the application, the corrosion inhibitor is dispersed in a solvent to form a solution, and the concentration of the corrosion inhibitor in the solution is 10 mg/L-50 mg/L. The solvent is preferably water or a mixed solvent of methanol and water. Wherein, when the solvent is a mixed solvent of methanol and water, the methanol and the water can be mixed in any proportion.
Furthermore, in the exploitation of a high hydrogen sulfide gas field, the concentration of the corrosion inhibitor is 10-30 ppm.
Furthermore, the mineralization degree of the high hydrogen sulfide gas field reaches 67800ppm and above.
In the high hydrogen sulfide field, hydrogen sulfide exists in a gaseous state, and the content of the hydrogen sulfide is as high as 1.5MPa and above. It is noted that the corrosion inhibitor is also suitable for gas fields with hydrogen sulfide content lower than 1.5 MPa.
Aiming at the corrosion inhibitor for metal corrosion protection under the condition of high hydrogen sulfide field exploitation environment, the invention selects long-chain alkyl carboxylic acid, polyethylene polyamine and benzyl raw materials to obtain long-chain alkyl benzyl imidazoline cations through a series of reactions. In order to further improve the oil-soluble water dispersibility and the film forming property of the corrosion inhibitor in a gas-liquid two-phase environment and enable the corrosion inhibitor to have more excellent film forming capability and corrosion inhibition performance under the high hydrogen sulfide environment condition, the invention designs and prepares the asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic corrosion inhibitor by adding the long-carbon-chain amide hydrophobic group on the basis of the long-chain alkyl benzyl imidazoline cationic structure, and the corrosion inhibitor with the structure is reported so far. The corrosion inhibitor molecule adopted by the high-hydrogen-sulfide field provided by the invention has the performance that both imidazoline cations and amide groups have imidazoline corrosion inhibitors and amide corrosion inhibitors, and the molecule contains a double-long carbon chain structure, so that the corrosion inhibitor has better film forming capability; in addition, by controlling the cationization degree, the corrosion inhibitor simultaneously contains asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cations and asymmetric long-chain alkyl imidazoline polyethylene long-chain alkylamide nonionic compounds, so that the corrosion inhibitor has better oil-soluble water dispersing capacity, and has excellent corrosion inhibition performance under the high hydrogen sulfide field environment by integrating the characteristics of various functional groups and functional molecules.
The invention has the following beneficial effects:
the cationic compound molecule contains long-chain alkyl imidazoline, benzyl and polyethylene polyamine multifunctional groups, the unique molecular structure determines that the cationic compound has excellent oil-soluble water dispersibility and green and environment-friendly characteristics, has a plurality of active sites which are coordinated and complexed with metal atoms and double long carbon chain alkyl groups, forms strong acting force with the metal surface, and is easy to form a firm and compact single-molecule adsorption film on the metal surface. When the cationic compound is used as the corrosion inhibitor for metal corrosion protection under the high hydrogen sulfide field exploitation environmental condition, the oil-soluble water dispersibility and the film forming performance in gas-liquid two phases of the corrosion inhibitor are improved, so that the corrosion inhibitor has more excellent film forming capability and corrosion inhibition performance under the high hydrogen sulfide environmental condition.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows FTIR (KBr pellet) spectra of the intermediate long chain alkyl imidazoline polyvinylamine nonionic prepared in example 1 of the present invention.
FIG. 2 shows the nonionic intermediate of long chain alkylimidazoline polyethyleneamines prepared in example 1 of the invention1HNMR(solution:D2O) spectrum.
FIG. 3 shows FTIR (KBr pellet) spectra of asymmetric long chain alkyl benzyl imidazoline vinyl long chain alkylamide cations in example 1 of the present invention.
FIG. 4 shows the asymmetric long-chain alkyl benzyl imidazoline vinyl long-chain alkylamide cation of example 1 of the present invention1HNMR(solution:D2O) spectrum.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
Preparation of asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic corrosion inhibitor
Preparation of long-chain alkyl imidazoline polyvinyl amine non-ion
Adding 1.0mol (282.5g) of oleic acid, 1.2mol (123.6g) of diethylenetriamine, 0.6g of alumina and 120g of dimethylbenzene into a 1000ml reactor three-port round-bottom flask provided with an electric stirrer, a temperature controller, a condensation pipe and a water separator, continuously stirring, heating to 160 ℃, reacting at constant temperature for 2 hours, then heating to 200 ℃, reacting at constant temperature for 3 hours, heating to 230 ℃, reacting at constant temperature until no liquid drops are generated in the water separator, cooling to 70 ℃, discharging, and obtaining the long-chain alkyl imidazoline vinylamine nonionic.
FT-IR and1H-NMR spectrum analysisAs shown in FIGS. 1 and 2
(II) preparation of asymmetric long-chain alkyl benzyl imidazoline long-chain alkyl polyvinyl amide cationic corrosion inhibitor
And (3) reducing the temperature of the reaction system in the step (I) to 120 ℃, adding 1.0mol (282.5g) of oleic acid into a reactor, heating to 180 ℃, reacting for 3 hours at a constant temperature, then reducing the temperature to 85 ℃, slowly dripping 0.8mol (101.2g) of benzyl chloride into the reactor by using a constant-pressure dripping funnel, heating to 100 ℃ after dripping is finished, reacting for 2 hours at a constant temperature, cooling to 70 ℃, and discharging to obtain the asymmetric long-chain alkyl benzyl imidazoline ethylene long-chain alkylamide cation.
FT-IR and1the H-NMR spectra are shown in FIGS. 3 and 4, respectively.
Example 2
Preparation of asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic corrosion inhibitor
Preparation of long-chain alkyl imidazoline polyvinyl amine non-ion
Adding 1.0mol (282.5g) of oleic acid, 1.2mol (175.2g) of triethylene tetramine, 0.7g of alumina and 120g of dimethylbenzene into a 1000ml reactor three-port round-bottom flask provided with an electric stirrer, a temperature controller, a condensation pipe and a water separator, continuously stirring, heating to 160 ℃, reacting at constant temperature for 2 hours, then heating to 200 ℃, reacting at constant temperature for 3 hours, heating to 240 ℃, reacting at constant temperature until no liquid drops are generated in the water separator, cooling to 70 ℃, and discharging to obtain the long-chain alkyl imidazoline-polyethylene polyamine nonionic.
(II) preparation of asymmetric long-chain alkyl benzyl imidazoline long-chain alkyl polyvinyl amide cationic corrosion inhibitor
And (3) reducing the temperature of the reaction system in the step (I) to 120 ℃, adding 1.0mol (282.5g) of oleic acid into a reactor, heating to 180 ℃, reacting at a constant temperature for 3 hours, then reducing the temperature to 85 ℃, slowly dripping 0.8mol (101.2g) of benzyl chloride into the reactor by using a constant-pressure dropping funnel, heating to 110 ℃ after dripping is finished, reacting at a constant temperature for 2 hours, cooling to 70 ℃, and discharging to obtain the asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cation.
Example 3
Preparation of asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic corrosion inhibitor
Preparation of long-chain alkyl imidazoline polyvinyl amine non-ion
Adding 1.0mol (284.5g) of stearic acid, 1.2mol (175.2g) of triethylene tetramine, 0.7g of alumina and 120g of dimethylbenzene into a 1000ml reactor three-port round-bottom flask provided with an electric stirrer, a temperature controller, a condensation pipe and a water separator, continuously stirring, heating to 160 ℃, reacting at constant temperature for 2 hours, then heating to 200 ℃, reacting at constant temperature for 3 hours, heating to 240 ℃, reacting at constant temperature until no liquid drops are generated in the water separator, cooling to 70 ℃, discharging, and obtaining the long-chain alkyl imidazoline-polyethylene polyamine nonionic.
(II) preparation of asymmetric long-chain alkyl benzyl imidazoline long-chain alkyl polyvinyl amide cationic corrosion inhibitor
And (3) reducing the temperature of the reaction system in the step (I) to 120 ℃, adding 1.0mol (284.5g) of oleic acid into a reactor, heating to 180 ℃, reacting at a constant temperature for 3 hours, then reducing the temperature to 85 ℃, slowly dripping 0.8mol (101.2g) of benzyl chloride into the reactor by using a constant-pressure dropping funnel, heating to 110 ℃ after dripping is finished, reacting at a constant temperature for 2 hours, cooling to 70 ℃, and discharging to obtain the asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cation.
Example 4
The cationic compound prepared in each example is used as a corrosion inhibitor in the exploitation of high hydrogen sulfide fields:
the data of the asymmetric long-chain alkyl benzyl imidazoline ethylene long-chain alkylamide cationic corrosion inhibitor subjected to corrosion inhibition rate measurement under the condition of simulating the gas reservoir environment of a plain gas field are shown in the following table 1.
The experimental operating method comprises the following steps: dynamic hanging piece weight loss method;
test equipment, namely a temperature-resistant, pressure-resistant and corrosion-resistant high-pressure kettle;
test solutions: 1.5L of standard simulation solution with the mineralization degree of 67800ppm, 20ppm of corrosion inhibitor concentration, 2 hours of pre-deoxidization, and 2g of reduced iron powder added into the solution before sealing the kettle;
experimental materials: l360MCS hanging piece, the gas phase hanging piece adopts a mixed solution pre-film of corrosion inhibitor and diesel oil in a ratio of 1:1 (the pre-film method refers to the technical requirement of corrosion inhibitor for Q/SH 10250876-2013 general optical gas field gathering and transportation system);
experiment pressure: 1.5MPa hydrogen sulfide, 15 minutes later the pressure was released to atmospheric pressure (simulated main body), experimental temperature: 40 ℃, experiment time: 168 hours, experimental state: the rotating speed is 300 revolutions per minute;
and (4) analyzing results: the average corrosion rate was measured, and the corrosion inhibition rate of the corrosion inhibitor of example 1 was measured under the same experimental conditions at different concentrations (the corrosion inhibition rate data measured by the weight loss method is shown in table 1 below).
The experimental results show that the corrosion rates of the corrosion inhibitor provided by the method are far lower than the national corrosion rate standard of 0.076mm/a, the corrosion inhibition rates in gas-liquid two phases are more than ninety percent, and the performance is excellent.
In addition, the present invention is also illustrated for comparison, wherein the cationic compound of comparative example 1 is
The cationic compound of comparative example 2 is
The above tests were carried out, and the test results are also shown in Table 1.
TABLE 1 Corrosion inhibitor dynamic inhibition Rate determination data
From the experimental results in table 1, it can be seen that, under the same conditions, the corrosion inhibitor provided by the invention has better corrosion inhibition effect than the corrosion inhibitors in comparative example 1 and comparative example 2, and particularly, the gas phase corrosion inhibition rate is remarkably improved.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. An asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic compound is characterized in that the structural formula of the cationic compound is shown as the following formula I:
wherein:
R1、R2each independently selected from CnH2n+1Or CnH2n-1N is a positive integer from 12 to 18;
m is 0, 1 or 2.
2. The method of preparing an asymmetric long chain alkyl benzyl imidazoline polyvinyl long chain alkylamide cationic compound as claimed in claim 1, comprising the steps of:
1) taking long-carbon-chain fatty acid A and polyethylene polyamine as raw materials, and carrying out dehydration acylation and imidazole cyclization reactions to obtain a long-carbon-chain alkyl imidazoline intermediate;
2) and (3) carrying out acylation reaction on the long-carbon-chain alkyl imidazoline intermediate and a long-carbon-chain fatty acid B, and carrying out quaternization reaction on the obtained product and benzyl chloride to obtain the asymmetric long-chain alkyl benzyl imidazoline polyvinyl long-chain alkylamide cationic compound.
3. The method of claim 2, wherein the long carbon chain fatty acid A and the long carbon chain fatty acid B are each independently RCOOH, wherein R is selected from CnH2n+1Or CnH2n-1N is a positive integer from 12 to 18;
preferably, the long carbon chain fatty acids a and B are each independently selected from one of stearic acid and oleic acid.
4. The method according to claim 2, wherein in step 1), the ratio of the long-chain fatty acid A: the molar ratio of the polyethylene polyamine is 1: 1-1: 1.2;
preferably, the reaction in step 1) is carried out in the presence of a catalyst and a water-carrying agent;
preferably, the catalyst is selected from one or two of calcium oxide, magnesium oxide and aluminum oxide;
preferably, the water-carrying agent is one or two of toluene and xylene;
preferably, the addition amount of the catalyst is 0.1-1% of the total mass of the long-carbon chain fatty acid A and the polyethylene polyamine, and the amount of the water-carrying agent is 20-30% of the total mass of the long-carbon chain fatty acid A and the polyethylene polyamine.
5. The preparation method according to claim 2, wherein in step 1), the conditions of the dehydration acylation and imidazole cyclization reaction are as follows: and heating to 120-160 ℃, reacting at constant temperature for 2-3 hours under continuous stirring, heating to 180-200 ℃, reacting at constant temperature for 2-3 hours, heating to 220-240 ℃, reacting at constant temperature until no liquid drop appears in the water separator, and stopping the reaction.
6. The method according to claim 2, wherein the molar ratio of the long-chain fatty acid B in the step 2) to the polyethylene polyamine in the step 1) is 1:0.8 to 1: 1.0; the molar ratio of the long-carbon-chain fatty acid A in the step 1) to the benzyl chloride in the step 2) is 1: 0.8-1: 0.9.
7. The process according to claim 2, wherein in the step 2), the conditions for the acylation reaction are: mixing the long-carbon-chain alkyl imidazoline intermediate with the long-carbon-chain fatty acid B at the temperature of 120-160 ℃, then heating to 180 ℃, and reacting for 2-3 hours at constant temperature;
preferably, in step 2), the quaternization conditions are: cooling the acylation reaction product to 80-90 ℃, adding benzyl chloride, heating to 90-110 ℃, carrying out heat preservation reaction for 1.5-2 hours, cooling to 70 ℃, and discharging.
8. A corrosion inhibitor characterized in that the raw material of the corrosion inhibitor comprises the asymmetric long-chain alkyl benzyl imidazoline polyvinyl long-chain alkylamide cationic compound as described in claim 1.
9. Use of the corrosion inhibitor according to claim 8 in the exploitation of high hydrogen sulfide fields.
10. The use according to claim 9, wherein the corrosion inhibitor is dispersed in a solvent to form a solution, and the concentration of the corrosion inhibitor in the solution is 10mg/L to 50 mg/L; preferably, the concentration of the corrosion inhibitor in the exploitation of the high hydrogen sulfide gas field is 10-30 ppm.
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| CN101921233A (en) * | 2010-08-10 | 2010-12-22 | 陕西科技大学 | Tree imidazoline quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN104232042A (en) * | 2014-08-15 | 2014-12-24 | 长江大学 | Polyphenyl polycyclic-imidazoline corrosion inhibitor |
| CN104233310A (en) * | 2014-07-25 | 2014-12-24 | 西安和泰化工有限公司 | Compound type imidazoline-quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN109678800A (en) * | 2019-02-21 | 2019-04-26 | 中国科学院理化技术研究所 | Benzyl imidazoline cationic compound, corrosion inhibiter and preparation method and application |
| CN109942493A (en) * | 2019-04-12 | 2019-06-28 | 中国科学院理化技术研究所 | Oil base sulfonyl amido benzyl imidazoline cationic compound, its preparation, comprising its corrosion inhibiter, corrosion inhibiter preparation and application |
| PL235363B1 (en) * | 2016-12-07 | 2020-06-29 | Inst Ciezkiej Syntezy Organicznej Blachownia | Method for obtaining modified montmorillonite |
-
2021
- 2021-03-16 CN CN202110279611.4A patent/CN113045499B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921233A (en) * | 2010-08-10 | 2010-12-22 | 陕西科技大学 | Tree imidazoline quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN104233310A (en) * | 2014-07-25 | 2014-12-24 | 西安和泰化工有限公司 | Compound type imidazoline-quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN104232042A (en) * | 2014-08-15 | 2014-12-24 | 长江大学 | Polyphenyl polycyclic-imidazoline corrosion inhibitor |
| PL235363B1 (en) * | 2016-12-07 | 2020-06-29 | Inst Ciezkiej Syntezy Organicznej Blachownia | Method for obtaining modified montmorillonite |
| CN109678800A (en) * | 2019-02-21 | 2019-04-26 | 中国科学院理化技术研究所 | Benzyl imidazoline cationic compound, corrosion inhibiter and preparation method and application |
| CN109942493A (en) * | 2019-04-12 | 2019-06-28 | 中国科学院理化技术研究所 | Oil base sulfonyl amido benzyl imidazoline cationic compound, its preparation, comprising its corrosion inhibiter, corrosion inhibiter preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| REGISTRY: "RN763041-47-0等", 《STN COLUMBUS》 * |
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