UA117583C2 - Water-soluble corrosion inhibitor for protection of lifting casings and natural gas pipelines as well as the method of its production - Google Patents

Abstract

The water-soluble corrosion inhibitor for protection of lifting casings and natural gas pipelines contains: - component a) obtained through neutralization from 0.1 to 50 % by weight, of the new mixture of modified imidazoline derivatives, which constitutes a mixture of substances of general formulas (1) and (2), wherein R1: C12-C22 wherein R2:C2-C12 with the possible addition of a product of general formula (1’) wherein R3: C12-C24 with an aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 carbon atoms per molecule, - component b) that is oxyethylenated fatty amines containing from 2 to 20 ethoxyl groups per molecule-component c) that is an alkalizing agent-optional component d) that is an aliphatic polyol-component e) that is an aliphatic alcohol containing from 1 to 6 carbon atoms per molecule, optionally with the addition of water-component f) that is an anti-foaming agent.

Description

TECHNICAL FIELD

The subject of the invention is a water-soluble corrosion inhibitor for the protection of operational pipes and natural gas transportation pipelines, and a method of its production.

TECHNICAL LEVEL

The phenomenon of corrosion is a serious problem in the production of natural gas and is the result of chemical or electrochemical reactions of metallic elements with the environment.

There is more than one type of corrosion in gas mines. Drilling fluids are, most often, aqueous solutions of salt that act as an electrolyte. Formation water present in natural gas production also contains inorganic salts such as chlorides (sodium, potassium, magnesium), sulfates (sodium, potassium, magnesium) and carbonates. In water systems containing salts, electrochemical corrosion occurs easily. This is due to the action of galvanic elements formed between the passivated surface of the metal and the surface that does not have such a layer.

The effect of electrochemical corrosion is mainly a corrosion ulcer on the surfaces of operational pipes and pipelines, as well as on operational equipment. The greatest damages on the surface of the pipes occur in salt solutions with a concentration of 7 - 13 95.

Significant corrosion damage is caused by the presence of carbon dioxide in the formation being drilled. A characteristic feature of corrosion caused by the presence of carbon dioxide in the extracted gas is the presence of smooth edges of the mine shaft. Corrosion associated with the presence of carbon dioxide in oil and gas production wells is often called "neutral". Carbon dioxide, dissolving in water, forms carbonic acid Не2СОз, which reacts with iron to form iron carbonate ГеСоз; hydrogen gas No is also formed. Carbon dioxide, dissolving in water, additionally reduces the pH reaction of water, which, in turn, increases the rate of corrosion.

Corrosion associated with the presence of hydrogen sulfide, which is also called "acid", is no less dangerous. Hydrogen sulfide causes more aggressive corrosion than carbon dioxide. Like carbon dioxide, hydrogen sulfide dissolves in water, lowering the pH. As a result of the reaction of hydrogen sulfide with iron, iron sulfide Rez and hydrogen He are formed. Iron sulfide forms a shell on the surface of metals and in the first phase slows down "acidic" corrosion, but even a small damage to this shell causes intense corrosion. "Acid" corrosion leads to formation

From ulcers, which are often accompanied by cracks in metal coatings, which arise in connection with the formation of hydrogen. Part of the hydrogen penetrates into the steel and becomes the cause of bubbling, cracks and the so-called hydrogen embrittlement.

Corrosion processes in gas mines are intensified by sulfate-reducing bacteria of the genus

Beziyomirgio YuOesiiigisap5. These bacteria are most active below the surface of the sediment formed as a result of sediment deposition.

The rate of corrosion caused by carbon dioxide and hydrogen sulfide increases with the oxygen content in the system. Oxygen enters drilling fluids as they pass through well and reservoir maintenance equipment. The rate of corrosion also depends on temperature; the higher it is, the greater the corrosion rate, which reaches a maximum at a temperature of about 7026. In mines not protected by corrosion inhibitors, it can be even several mm/year.

As a result of long-term contact of natural gas with formation water in formation conditions, gas saturation with water vapor occurs. The amount of steam in the gas depends on the temperature, pressure and salt content of the water. The amount of water vapor in the gas increases during the operation of the field, and the older it is, the higher the amount of water vapor in the gas. In gas pipelines, as a result of a decrease in pressure, water is released, the presence of which accelerates corrosion.

As a result of corrosion processes, there is a decrease in the thickness of the walls of operational pipes and pipelines, deep ulcers appear, which can lead to leakage of pipes and a strong decrease in their strength properties.

In order to prevent corrosion, corrosion inhibitors are used in gas mines, which reduce the corrosive effect of extracted natural gas on steel parts of operational equipment and pipelines. As corrosion inhibitors, chemically diverse liquid corrosion inhibitors are used: most often, quaternary ammonium salts, imidazoline derivatives, fatty acid salts, and gas phase protection inhibitors, usually amines. To be effective, the corrosion inhibitor used must dissolve in water in order to neutralize the corrosive effect of water-soluble salts and acid gases.

A water-soluble corrosion inhibitor for the protection of production pipes and pipelines for the transportation of natural gas provides anti-corrosion protection against such agents as: hydrogen sulfide and carbon dioxide, which are contained in the produced gas, chlorides, which are present in formation waters and drilling fluids, as well as oxygen, which is contained in the water. because water-soluble corrosion inhibitors are presented in patent descriptions 05 3629104 and 05 3758493,

containing a carboxylic acid salt of an imidazoline derivative obtained by condensation of dimerized fatty acids with diethylenetriamine.

Patent 05 5759485 describes a method of obtaining a corrosion inhibitor by neutralizing tricarboxylic acids Cg", and then adding imidazoline or amidoamine.

UMO patent application 2003/054251 describes the positive anticorrosive properties of oxyethylated fatty alkylamines, in particular, oxyethylated alkylpyramines.

Patent descriptions RI 61535 and RI 85729 describe a method of obtaining imidazoline inhibitors by the condensation reaction of diethylenetriamine with fatty acids or naphthenic acids.

Patent descriptions PI 135655 and PI 175452 describe a method of obtaining an inhibitor of increased activity as a result of the condensation of diethylenetriamine with fatty acids modified with the use of urotropin introduced in the final phase of the condensation reaction.

According to patent RI 182943, the water-soluble corrosion inhibitor contains a salt of an imidazoline derivative, which is a condensation product of fatty acids with diethylenetriamine and urotropin or formaldehyde and low molecular weight carboxylic acids.

Patent application 05 2004/0087448 recommends the use as a corrosion inhibitor of the condensation product of Steve's unsaturated fatty acid dimers containing 1 and 2 double bonds and diethylenetriamine.

Patent 05 6695897 describes a method of obtaining amidoamine as a condensation product of M-ethylethylenediamine and a fatty acid. The reaction product, after solubilization with acetic acid, can act as a water-soluble corrosion inhibitor.

Patent description OB 7057050 describes a method of obtaining a water-soluble corrosion inhibitor. The product of the reaction is M-propyl-2-heptadecinyl imidazoline. The resulting product is solubilized to a water-soluble form when using acrylic acid.

In patent application MO 2006/078723, a method of obtaining a microemulsion containing imidazoline and amidoamine derivatives obtained with the participation of oleic acid is described. The microemulsion also contains oxyethylated nonylphenols and acetic acid.

The patent literature describes the condensation of diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms in the molecule, while maintaining the molar ratio of diethylenetriamine to fatty acids in the amount of 1: 0.5 - 1.0. Examples of such condensation are known, in particular, from American patent descriptions 05 2267965, 005 2355837 and Polish patent description RI. 61535.

Patent description 05 5322630 presents an imidazoline corrosion inhibitor, which is a reaction product of unsaturated monocarboxylic acids with fatty amines, amino-amides or fatty imidazole-amines.

Patent description KO 2394941 describes a mixture of modified imidazoline derivatives with aldimines or Schiff bases. According to this patent, imidazoline derivatives are the reaction product of polyamines with oletic acid or monocarboxylic acids. Imidazoline derivatives are further cyanethylated with nitrile acrylic acid or undergo oxyalkylation.

A water-soluble corrosion inhibitor obtained by neutralizing tricarboxylic acid with amine-ethyl-ethanol-amine, and then with an imidazoline derivative, amidoamine or their mixture, is presented in patent description 05 5759485.

Patent description ZB 2340505 presents a method of obtaining imidazoline derivatives in the process of condensation of tall oil fatty acids with amine-ethyl-ethanol-amine. The inhibitor is characterized by good anti-corrosion properties, and also, forming a complex with mercaptans, removes the smell of sulfur compounds.

Patent 05 5723061 and application 05 2007/0152191 describe compositions that include salts formed as a result of the reaction of dicarboxylic acids Сно-Си2 with polyamines.

Corrosion inhibitors, which include bis-amides, are described in US patents. Bisamide, as a product of the reaction of polyamines with dimers of fatty acids, is described in patent О5 4614600, and the product of the reaction of polyamines with dicarboxylic acids is described in patent 05 4344861.

Patent application UUO 2003/054251 discloses the anticorrosive properties of oxyethylated fatty alkylamines, in particular, oxyethylated alkylpyramines.

Patent application 05 2009/181678 recommends the use as a corrosion inhibitor of the condensation product of dimers of unsaturated fatty acids (containing 1 and 2 double bonds) and diethylenetriamine.

Patent application О5 2007/0261842 describes the process of corrosion inhibition of oil/gas transportation pipelines - by using as a corrosion inhibitor at least one amine with a boiling point of 105-1302С or at least one amine selected from mono-, bodi - and trialkylpyridine, 3-methoxypropylamine (MORA), ethyldiisopropylamine (EPIRA); the inhibitor composition may also contain at least one imidazoline or its derivative and/or phosphoric esters of ilabo thioacids.

Many available corrosion inhibitors for the protection of utility pipes and natural gas pipelines are not effective enough and require high dosage levels to provide corrosion protection. It is accepted that the level of protection against corrosion at a dosage of 100 mg of corrosion inhibitor per 1 kg of corrosive working substance should be higher than 8095, according to the AZTM MACE 10182 standard.

Most of the proposed corrosion inhibitors intended for use in natural gas wells are based on quaternary ammonium salts. Compounds of this type are completely soluble in water, so they are often used by manufacturers. The best corrosion inhibitors are those that dissolve very well in water while leaving a layer of corrosion inhibitor on the metal surface. The corrosion inhibitor must protect the pipeline/installation for at least 24 hours against an emergency shutdown of the dosing pump. The disadvantage of corrosion inhibitors based on quaternary ammonium salts is that they have much lower anti-corrosion properties than inhibitors with imidazoline derivatives, since they do not protect against pitting corrosion to the required extent.

Many corrosion inhibitors available for the protection of wells and natural gas pipelines are insufficiently effective and require high dosage levels to provide corrosion protection. Many of them, after mixing with reservoir water, form a non-homogeneous liquid, releasing deposits and leading to precipitation of a part of the inhibitor. This leads to insufficient corrosion protection and can be the cause of dangerous pitting corrosion.

An additional disadvantage of available inhibitors is their tendency to form an emulsion with reservoir waters; others have a high tendency to foam, and the presence of foam leads to obstacles in the operation of devices serving gas mines.

The purpose of the invention was to create a water-soluble corrosion inhibitor for the protection of service pipes and natural gas pipelines, which would provide much better anti-corrosion properties than previously used corrosion inhibitors.

ESSENCE OF THE INVENTION

This invention relates to a water-soluble corrosion inhibitor for the protection of operational pipes and pipelines for the transportation of natural gas and a method of its production.

One aspect of the invention is to provide a water-soluble corrosion inhibitor for the protection of service pipes and natural gas pipelines.

It was found that the composition containing: - component a) in the amount from 0.15 to 75 wt. 95, preferably from 1.5 to 35 wt. 95 obtained as a result of neutralization from 0.1 to 50 wt. 95, preferably from 1 to 30 wt. 95, a new mixture of modified imidazoline derivatives, which is a condensation product of diethylenetriamine with fatty acids containing from 12 to 22 carbon atoms in the molecule and aliphatic dicarboxylic acids containing from 2 to 12 carbon atoms in the molecule, which is a mixture of compounds with the general formula (1) | (2), g: study

MM.

B, where Ki: C2-C22 (1)

I-m M- I si and she

MB tyu i

I and r and n / and ; ts MN. where EC": C2-St12 (2),

with the possible addition of 0.05 to 20 wt. 95 known condensation product of diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms in the molecule, created by a known method at a temperature from 18092C to 2802C, preferably from 2209C to 2602C, with the general formula (1) g

M Ve yours

Kz de Kz: Cg2-C23z (1) with aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 carbon atoms in the molecule, used in an amount from 0.05 to 25 wt. 95, while maintaining the mass ratio of the mixture of compounds with the general formulas (1), (2), and possibly (1), to monocarboxylic acid 1: 0.15 - 0.70, with obtaining the final product, which is a mixture of compounds with the general formulas (5), (b) and possibly (5) i

M M and More VaSOO:

MN

KI de Ki: C12-C22 (5)

You: H, C:1-Sv, aromatic radical (SeNb) ra p

Zh Zh Y

НЗМ МН de ЕК»: C2-St12 (6)

You: H, C:-Sv, aromatic radical (SeNb) and

M M and More VaSOO:

MN

Kz de Kz: Сг»-Сгз (5)

You: H, С:1-Св, aromatic radical (СеНб) - component B), which are fatty amines containing from 14 to 22 carbon atoms in the molecule and oxyethylated with from 2 to 20, preferably from 3 to 15 ethoxyl groups in a molecule, in an amount from 0.01 to 10 wt. 90; - component c), as an alkaline agent, which is at least one low-boiling amine selected from: C-methoxypropylamine, 2-aminoethanol (monoethanolamine), diethylamine or their mixture in an amount from 0.06 to 25 wt. 95, preferably from 1 to 20 wt. 905; - possible component 4), which are aliphatic polyols in the amount from 0.04 to 50 wt. 95; - component is), which are aliphatic alcohols containing from 1 to 6 carbon atoms in the molecule, in an amount from 15 to 99.7 wt. 95 with the possible addition of water, and - its component), which is an antifoam agent in the amount of 0.01 to 2 wt. 95.

The next aspect of the invention is to create a method of obtaining a water-soluble corrosion inhibitor for the protection of operational pipes and natural gas transportation pipelines, which includes the following steps:

And obtaining component a) is carried out at room temperature, in a reaction medium containing component e), that is, aliphatic alcohols containing from 1 to 6 carbon atoms in the molecule, in an amount from 15 to 99.7 wt. 95, 3 by the possible addition of water, neutralization of a new mixture of modified imidazoline derivatives, which is a condensation product of diethylenetriamine with fatty acids containing from 12 to 22 carbon atoms in the molecule and aliphatic dicarboxylic acids containing from 2 to 12 carbon atoms in the molecule, which is a mixture of compounds with general formulas (1) and (2), g y - 5 x

Kk, where Ki: C12-C22 (1) em We

S A Ky she How: and K-Ya and - she

She has

Te ME de Co: Se-St12 (2) used in amounts from 0.1 to 50 wt. 95, preferably from 1 to 30 wt. 95, with the possible addition of 0.05 to 20 wt. 95 known condensation product of diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms in a molecule obtained by a known method at a temperature of 18090 - 2802С, preferably 22096 - 2609С, with the general formula (1),

M. Shy

Ki Kz de Kz: Cg2-C23z (1) aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 carbon atoms in the molecule, used in an amount from 0.05 to 25 wt. 95, while maintaining the mass ratio of the mixture of compounds with the general formulas (1), (2), and in some cases (1, to monocarboxylic acid 1: 0.15 - 0.70, with obtaining the final product, which is a mixture of compounds with the general formulas (5), (b), and in some cases (5), i

M M xx More SUN

MN

KI de Ki: C12-C22 (5)

You: H, C:-Sv, aromatic radical (SeNb) 2

her

Zh Zh I

NzM MN de B2: C2-Sch2 (6)

You: H, C:-Sv, aromatic radical (SeNb) and

M M xx More VaSOO:

MN

Kz de Kz: Cg2-C23z (5)

You: H, C:-Sv, aromatic radical (SeNb)

II) introduction into component a) in the amount from 0.15 to 75 wt. 95, preferably from 1.5 to 35 wt. 95, and the mentioned component is) further components of the inhibitor: component b), that is, fatty amines containing from 14 to 22 carbon atoms and oxyethylated with from 2 to 20, preferably from 3 to 15 ethoxyl groups in the molecule, in an amount from 0, 01 to 10 wt. 95; component c), that is, an alkaline agent in an amount from 0.06 to 25, preferably from 1 to 20 wt. for; and optionally component 4), that is, aliphatic polyols in an amount from 0.04 to 50 wt.

Fo, and at the end, the Her component), i.e., an antifoam agent in the amount of 0.01 to 2 wt. 905.

DESCRIPTION OF PREFERRED OPTIONS OF THE INVENTION

It unexpectedly turned out that the use of a new mixture of modified imidazoline derivatives with higher anti-corrosion properties and the possible addition of a known product

From the condensation of diethylenetriamine with fatty acids, neutralized aliphatic and/or aromatic monocarboxylic acid to the salt state, as well as a surface-active substance from the group of oxyethylated, hydrogenated talc amines with a dual function: corrosion inhibitor and dispersant, in combination with a volatile amine, an antifoam agent and , possibly with aliphatic polyols dissolved in an alcoholic solvent with the possible addition of water, led to a corrosion inhibitor with increased anticorrosion properties compared to corrosion inhibitors containing conventional imidazoline derivatives.

The invention uses a new mixture of modified imidazoline derivatives with general formulas (1) and (2),

Kk where Ki: C12-C22 (1) ; her

М в и -7 Ше і і і і і шча ME de ЕК»: C2-St12 (2), which can be obtained as follows: condensation of diethylenetriamine with fatty acids containing 12-22 carbon atoms in the molecule and aliphatic dicarboxylic acids is made, containing 2-12 carbon atoms in the molecule, while maintaining the molar ratio of diethylenetriamine to fatty acids and aliphatic dicarboxylic acids of 1:0.5-0.99:0.01-0.5, at a temperature of at least 1409С, preferably 1509С, with obtaining mixtures of amino amides with general formulas (3) and (4), (6)

КК МН МН» de Ki: C12-C22 (3) o (6; rachu l XX reran cha

М МН in МН МНо de ЕК»: C2-St12 (4) with an acid value of "10 mg KOH/g, and then the temperature rises above 1802, preferably to 2202С and a condensation reaction is carried out to obtain a mixture of compounds with general formulas (1) and (2)

Yi Ya

/ u

Ka de Ki: C12-C22 (1) you In her in ; and | her and

HOW

M V i i i - ska ! ! and. now MN where Co: C2-C12 (2) with an acid number of "1 mg KOH/g.

The mentioned new mixture of modified imidazoline derivatives creates a very strong corrosion protection layer on the metal surface. The use of volatile amine as an inhibitor complements its anti-corrosion effect in the gas phase.

Many corrosion inhibitors available for the protection of wells and natural gas pipelines contain dispersants that are nonylphenol derivatives. Phenolic groups are particularly harmful to the natural environment - due to their very low ability to biodegrade. The use in the composition of the corrosion inhibitor according to the invention of a surfactant from the group of oxyethylated, hydrogenated tallow amines with a high degree of biological decomposition had a positive effect on the biocompatibility of the corrosion inhibitor according to the invention.

There may be many variants of the invention, depending on the differentiation and method of connecting its components. Useful modifications of the invention relating to components a), g), 9), c) and C are presented below.

Corrosion inhibitor, according to the invention, as component a) contains a product obtained as a result of neutralization with acetic acid and/or benzoic acid of the following imidazoline derivatives: i) a mixture of modified imidazoline derivatives, which is a condensation product of diethylenetriamine with fatty acids containing from 12 to 22 carbon atoms in the molecule, and aliphatic dicarboxylic acids containing from 6 to 10 carbon atoms in the molecule, which is carried out while maintaining the molar ratio of diethylenetriamine to fatty acid and alliratic dicarboxylic acids 1:0.5-0.99:0.01- 0.5, at a temperature of at least 1409C, preferably 1502C, to obtain a mixture of amino amides with general formulas (3) and (4), (6)

ХХ рн чу

КК МН МН» de Ki: C12-C22 (3)

Co., Ltd. (9) (9)

МН Ж re МН pay et vo se a it r, where Kg: Sv-Schio (4) with an acid number of "10 mg KOH/g, and then, after raising the temperature above 18092С, preferably to 2209С, a condensation reaction is carried out to obtain a mixture compounds with general formulas (1) and (2)

Yi Ya

/ у и ки де Ки: С12-С22 (1)

Bl; E an i I sh i g Yi i

M g h i : ; i pt sa

She and and. now MN where B": Sv-Sto (g) with an acid value of "1 mg KOH/g, and) with the possible addition of a known condensation product of diethylenetriamine with fatty acids.

According to the invention, the corrosion inhibitor as component e) contains methanol, isopropanol, ethanol or their mixtures.

According to the invention, the corrosion inhibitor as component 4) contains ethyl glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol or their mixtures.

According to the invention, the corrosion inhibitor as component c) contains 3-methoxypropylamine, 2-aminoethanol (monoethanolamine), diethylamine, or their mixtures.

According to the invention, the corrosion inhibitor as a component of it) contains a siloxane derivative, usefully branched siloxane polymers.

The percentage composition of the corrosion inhibitor, according to the invention, is given in mass percent, calculated in relation to the total mass of the inhibitor.

In the best embodiment of the invention, which relates to the method of obtaining a water-soluble corrosion inhibitor for the protection of operational pipes and natural gas transportation pipelines, the following imidazoline derivatives are subjected to neutralization with glacial acetic acid: i) a mixture of modified imidazoline derivatives, which is a condensation product of diethylenetriamine with fatty acids, containing from 12 to 22 carbon atoms in the molecule, and aliphatic dicarboxylic acids containing from 6 to 10 carbon atoms in the molecule, which is carried out while maintaining the molar ratio of diethylenetriamine to fatty acids and aliphatic dicarboxylic acids of 1:0.5-0.99 :0.01-0.5, at a temperature of at least 1409С, preferably 1509С, with obtaining a mixture of amino amides with general formulas (3) and (4), (6)

KE MN MN" where Ki: C12-C22 (3) 6) 6)

MN X re shoraa pal ae Mn MN; where Kg: Sv-Sto (4) with an acid value of "10 mg KOH/g,

and then, after the temperature rises above 1809С, preferably up to 2209С, a condensation reaction occurs to obtain a mixture of compounds with general formulas (1) and (2) only / y.

Mt! Hom

Hey de Key: C12-C22 what (1)

WITH

7 annia th In / in what and / and

MU M de Kg: Sv-Sto (2) with an acid value of "1 mg KOH/g, and) with the possible addition of a known condensation product of diethylenetriamine with fatty acids.

The percentage composition of the components used to obtain the corrosion inhibitor by the method according to the invention was indicated in mass percentages calculated in relation to the total mass of the inhibitor.

The corrosion inhibitor obtained on the basis of a mixture of modified imidazoline derivatives is characterized by better anticorrosive and hydrophilic properties compared to inhibitors containing known imidazoline derivatives.

The inhibitor, which is the subject of the invention, with the invention forms homogeneous liquids with formation waters that contain up to 3095 salts and, even at a temperature of 802C, no precipitation of the inhibitor is observed from them. The exceptional compatibility of the inhibitor, which is the subject of the invention, with formation waters of varying degrees of salinity leads to an increase in its anti-corrosion properties - both in the aqueous and in the gas phase.

If high transparency of the inhibitor that is the subject of the invention is required during long-term storage in winter conditions, at a temperature below -309C, a useful introduction into the inhibitor composition of a known imidazoline derivative, a small addition of which leads to the fact that, at very low temperatures, the inhibitor according to with the invention becomes completely transparent.

If high transparency of the inhibitor is required, according to the invention, during long-term storage in winter conditions, at a temperature below -402C, aliphatic polyols, preferably ethyl glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol, or their mixtures in the amount of 0.5 up to 50 wt. 95, and optionally aliphatic alcohols containing from 1 to b carbon atoms in the molecule, except for methanol, isopropanol and ethanol.

Obtained by the method according to the invention, the corrosion inhibitor creates a strong protective layer on the metal surface, protects against corrosion in the gas phase, preventing corrosion even in very aggressive environments containing carbon dioxide, hydrogen sulfide, and chlorides. Corrosion inhibitor, according to the invention, is resistant to high temperatures that occur in the formation, is not prone to separation from formation waters and sedimentation. Corrosion inhibitor is effective at low dosage continuously, from 10 to 80 mg/kg of natural gas and reservoir water. High anti-corrosion efficiency allows to protect operational equipment not only from uniform corrosion, but, above all, from pitting corrosion. It also protects metal surfaces from corrosion in case of a temporary breakdown of the dosing system. An additional advantage of the inhibitor according to the invention is the lack of tendency to foam in the water-inhibitor system.

Corrosion inhibitor according to the invention (in one of the many modifications of production) contains benzoic acid, which has a bactericidal effect.

In practice, the water-soluble corrosion inhibitor for the protection of operational pipes and natural gas pipelines, according to the invention, is added to the gas-water mixture continuously. As a rule, the corrosion inhibitor according to the invention is added to the liquid in an amount from about 0.01 to 5000 ppt, preferably from 1 to 500 ppt, most preferably from 10 to 100 ppt.

The following examples illustrate the invention without limiting its scope.

Examples 1 to 5 relate to obtaining a new mixture of modified imidazoline derivatives, and examples 6 to 11 relate to obtaining a corrosion inhibitor according to the invention.

Example 1.

103.16 kg (1 mol) of diethylenetriamine, 141.23 kg (0.5 mol) of distilled olein, in which the main component is oleic acid SivNzaO2 and 45.02 kg (0.5 mol) of oxalic acid, are introduced into the reactor. The content is heated with constant stirring with a mechanical stirrer and additionally nitrogen bubbling is used to remove the water formed during the reaction. After reaching a temperature of 1502C, it is kept for 3 hours to obtain an acid number of 3.51 mg KOH/Hg, after which it is heated further until a temperature of 22096 is reached.

The reaction was carried out for 4 hours, while maintaining the temperature at a constant level of 2209C, with simultaneous bubbling with nitrogen in order to remove water from the reaction. 226 kg of product with an acid value of 0.25 mg KOH/g was obtained.

Example 2.

103.16 kg (1 mol) of diethylenetriamine, 279.64 kg (0.99 mol) of oleic acid and 1.88 kg (0.01 mol) of azelaic acid are introduced into the reactor. The content was heated with constant stirring with a mechanical stirrer and nitrogen bubbling was additionally used to remove the water formed during the reaction. After reaching a temperature of 1502C, it is maintained continuously

For hours (acid number 4.32 mg KOH/Hg), after which it was heated further until reaching a temperature of 22020. The reaction was carried out for 5 hours, while maintaining the temperature at a constant level of 2202C, with simultaneous bubbling with nitrogen in order to remove water from the reaction. 317 kg of product (mixtures of modified imidazoline derivatives) with an acid number of 0.38 mg KOH/g were obtained.

Example 3.

103.16 kg (1 mol) of diethylenetriamine, 264.10 kg (0.95 mol) of tall oil fatty acids and 10.11 kg (0.05 mol) of sebacic acid are introduced into the reactor. The content was heated with constant stirring with a mechanical stirrer and nitrogen bubbling was additionally used to remove the water formed during the reaction. After reaching a temperature of 1509C, it is maintained for 3 hours (acid number 5.1 mg KOH/Hg), after which it is further heated until a temperature of 2202C is reached. The reaction was carried out for 5 hours, while maintaining the temperature at a constant level of 2209C, with simultaneous nitrogen bubbling - in order to remove water from the reaction. 308 kg of product (mixture of modified imidazoline derivatives) 3 with an acid number of 0.7 mg KOH/g was obtained.

Example 4.

103.16 kg (1 mol) of diethylenetriamine, 268.34 kg (0.95 mol) of distilled olein, in which the main component is oleic acid SivNzaOg and 5.90 kg (0.05 mol) of succinic acid, are introduced into the reactor. The content was heated with constant stirring with a mechanical stirrer and nitrogen bubbling was additionally used to remove the water formed during the reaction. After reaching a temperature of 1502C, it is maintained for 3 hours (acid number 3.94 mg KOH/g), after which it is heated further - until a temperature of 2102C is reached. The reaction was carried out for 5 hours, while maintaining the temperature at a constant level of 2109C, with simultaneous bubbling with nitrogen - in order to remove water from the reaction. 312 kg of product (mixtures of modified imidazoline derivatives) with an acid number of 0.24 mg KOH/g were obtained.

Example 5.

103.16 kg (1 mol) of diethylenetriamine, 268.34 kg (0.95 mol) of distilled olein, in which the main component is oleic acid SivNzaOg, and 7.67 kg (0.05 mol) of adipic acid are introduced into the reactor. The contents were heated with constant stirring with a mechanical stirrer, while a vacuum of 100 mm Hg was carried out at the same time. in order to remove water from the reaction. After reaching a temperature of 1502C, it is maintained for 3 hours (acid number 4.72 mg

KONU/g), after which it is heated further - until reaching a temperature of 22020. The reaction was carried out for 5 hours, while maintaining the temperature at a constant level of 2202С, with the simultaneous application of a vacuum of 100 mm Hg. in order to remove water from the reaction. 299 kg of product (mixtures of modified imidazoline derivatives) with an acid number of 0.33 mg KOH/g were obtained.

Example 6.

440.9 kg (44.0995 by mass) of methyl alcohol, 400 kg (4095 by mass) of isopropyl alcohol, and then 66 kg (6.695 by mass) of the condensation product of diethylenetriamine with distilled olein and sebacic acid, with an acid number of 0, are introduced into the mixer. .7 mg KOH/g obtained by the method according to example 3, but in the condensation process, instead of tall oil fatty acids, distilled olein was used in the amount of 0.95 mol per 1 mol of diethylenetriamine and 0.05 mol of sebacic acid. After complete dissolution, 33 kg (3.395 by weight) of glacial acetic acid was introduced. After the complete reaction, at room temperature, to a neutral pH, 10 kg (195 by weight) of oxyethylated hydrogenated tallow amine, containing 5 ethoxyl groups in the molecule, and 20 kg (295 by weight) of glycerol were introduced. After complete dissolution, 30 kg (395 by mass) of 3-methoxypropylamine and 0.1 kg (0.0195 by mass) of a siloxane derivative under the trade name were introduced

Boat VAP NR 732, company Myplipd. After complete dissolution at room temperature, a corrosion inhibitor was obtained in the amount of 1000 kg (10095 by weight), which is a light, low-viscosity liquid with a pour point below -609C and a kinematic viscosity of 2.7 mm/s at a temperature of 2026.

Example 7.

405.0 kg (40.595 by mass) of methyl alcohol, 302 kg (30.290 by mass) of isopropyl alcohol, and then 150 kg (1595 by mass) of the condensation product of diethylenetriamine with fatty acids of tall oil and azelaic acid, with an acid value of 0, are introduced into the mixer. .4 mg of KOH/g, obtained by the method according to example 2, but in the condensation process, instead of oleic acid, tall oil fatty acids were used - in the amount of 0.99 mol per 1 mol of diethylenetriamine and 0.01 mol of azelaic acid. After complete dissolution, 90 kg (9956 by weight) of benzoic acid was introduced. After complete reaction, at room temperature, to a neutral pH, 7 kg (0.795 by mass) of oxyethylated hydrogenated tallow amine, containing 6 ethoxyl groups in the molecule, and 5 kg (0.595 by mass) of ethyl glycol were introduced. After complete dissolution, 40 kg (495 by mass) of Z-methoxypropylamine was introduced, and then 1 kg (0.195 by mass) of a siloxane derivative under the trade name Boat Vap НР732, manufactured by Maplipod. After complete dissolution at room temperature, a corrosion inhibitor was obtained in the amount of 1000 kg (10095 by weight), which is a light, low-viscosity liquid with a pour point of -602C and a kinematic viscosity of 7.6 mm/s at a temperature of 2096.

Example 8.

79 kg (7.995 by mass) of water, 150 kg (1595 by mass) of isopropanol, 100 kg (1095 by mass) of ethanol and 200 kg (2095 by mass) of the condensation product of diethylenetriamine, tall oil fatty acids and adipic acid are introduced into the mixer, with with an acid value of 0.3 mg KOH/g obtained by the method according to example 5, but in the condensation process, instead of distilled olein, tall oil fatty acids were used in the amount of 0.95 mol per 1 mol of diethylenetriamine and 0.05 mol of adipic acid. After complete dissolution, 110 kg (1195 by weight) of glacial acetic acid was introduced.

After the complete reaction, at room temperature, to neutral pH, 100 kg (1095 by weight) of oxyethylated hydrogenated talc amine, containing 5 ethoxyl groups in the molecule, was introduced. After complete dissolution, 50 kg (595 by weight) of 3-methoxypropylamine, 100 kg (1095 by weight) of monoethanolamine, 100 kg (1095 by weight) of diethylamine, 10 kg (195 by weight) of dipropylene glycol monomethyl ether, and then 1 kg ( 0.195 by mass) of a siloxane derivative under the trade name Boat Vap NR 732, Mypoipodo company. After complete dissolution at room temperature, a corrosion inhibitor was obtained in the amount of 1000 kg (10095 by weight), which is a light liquid with a pour point of -302C and a kinematic viscosity of 37 mm/s at a temperature of 2096.

Example 9.

770 kg (7795 by mass) of methyl alcohol, 80 kg (895 by mass) of the condensation product of diethylenetriamine, distilled olein, in which the main component is oleic acid SiviNzaO", and succinic acid with an acid number of 0.25 mg KOH/g are introduced into the mixer , obtained by the method according to example 4, and 20 kg (295 by weight) of the known condensation product of diethylenetriamine and oleic acid. After complete dissolution, 40 kg (4 wt. 95) of glacial acetic acid was introduced. After complete reaction, at room temperature, to neutral pH, 10 kg (195 by weight) of oxyethylated hydrogenated thallium amine containing 5 ethoxyl groups in the molecule was introduced, and, after lowering to room temperature, 40 kg (495 by weight) of 3- of methoxypropylamine and 30 kg (395 by weight) of diethylamine, and then 10 kg (195 by weight) of a siloxane derivative under the trade name Boat Vap HP 732, Mypoipd company. After complete dissolution at room temperature, a corrosion inhibitor was obtained in the amount of 1000 kg (10095 by weight), which is a light liquid of low viscosity with a pour point below -602C, a kinematic viscosity of 4.5 mm2/s at a temperature of 209C and a high transparency during storage at a temperature of -409C for 1 year.

Example 10.

177.9 kg (17.7995 by mass) of isopropyl alcohol are introduced into the mixer, and then 500 kg (509595 by mass) of the condensation product of diethylenetriamine with oleic acid (the trade name is distilled olein, in which the main component is oleic acid SiVH3Og) and oxalic acid, with an acid value of 0.25 mg KOH/g, obtained by the method according to example 1. After complete dissolution, 250 kg (25,906 by weight) of glacial acetic acid was introduced. After the complete reaction, at room temperature, to neutral pH, 0.1 kg (0.0195 by mass) of oxyethylated hydrogenated thallium amine, containing 5 ethoxyl groups in the molecule, and 50 kg (595 by mass) of diethylene glycol butyl ether were introduced. Next, 1 kg (0.195 by mass) of monoethanolamine and 1 kg (0.195 by mass) of diethylamine were introduced, and then 20 kg (295 by mass) of a siloxane derivative under the trade name Goat Vap НР7З2, from the MapleGipd company. After complete dissolution at room temperature, a corrosion inhibitor was obtained in the amount of 1000 kg (10095 by mass), which is a light liquid with a pour point of -459C, a kinematic viscosity of 57 mm/s at a temperature of 2096.

Example 11.

596.72 kg (59.6729 by mass) of methyl alcohol, 400 kg (40.95 by mass) of isopropyl alcohol, and then 1.32 kg (0.132905 by mass) of the condensation product of diethylenetriamine with distilled olein (oleic acid) are introduced into the mixer. C:ivNzaO" is the main component of distilled olein) and sebacic acid, with an acid value of 0.7 mg KOH/g, obtained by the method according to example 3, but in the condensation process, instead of tall oil fatty acids, distilled olein was used in the amount of 0.95 mol for 1 mol of diethylenetriamine and for 0.05 mol of sebacic acid. After complete dissolution, 0.66 kg (0.06695 by weight) of glacial acetic acid was introduced. After complete reaction, at room temperature, to neutral pH, 0.2 kg (0.0295 by weight) of oxyethylated hydrogenated thallium amine containing 5 ethoxyl groups in the molecule and 0.4 kg (0.0495 by weight) of propylene glycol were introduced. After complete dissolution, 0.6 kg (0.0695 by mass) of 3-methoxypropylamine and 0.1 kg (0.0195 by mass) of a siloxane derivative under the trade name Boat Vap НР7З2 of the Miaploipd company were introduced. After complete dissolution at room temperature, a corrosion inhibitor was obtained in the amount of 1000 kg (10095 by weight), which is a light, low-viscosity liquid with a pour point below -602C and a kinematic viscosity of 1.2 mm/s at a temperature of 2096.

Some gas wells are equipped with pumps of such design performance and design that allows dosing of corrosion inhibitors with very low kinematic and dynamic viscosity in a wide temperature range; therefore, with a low content of active ingredients. The required inhibitor dosage can be 1000, 2000 or 3000 mg/kg per water-gas system (continuously). Corrosion inhibitor according to example 11 is intended for such dispensers

From the pumps.

Example 12 is comparative.

440.9 kg (44.0995 by mass) of methyl alcohol, 400 kg (4095 by mass) of isopropyl alcohol, and then 6b kg (6.695 by mass) of the known condensation product of diethylenetriamine with distilled olein according to formula (1") are introduced into the mixer. with an acid number of 1.1 mg

KONU"UG. After complete dissolution, 33 kg (3.390 by mass) of glacial acetic acid was introduced. After complete reaction, at room temperature, to neutral pH, the product with formula (5) was obtained.

Next, 10 kg (195 by weight) of oxyethylated hydrogenated tallow amine containing 5 ethoxyl groups in the molecule and 20 kg (295 by weight) of glycerol were introduced. After complete dissolution, 30 kg (395 by mass) of 3-methoxypropylamine and 0.1 kg (0.0195 by mass) of a siloxane derivative under the trade name Boat Vap НР732 of the Maplipod company were introduced. After complete dissolution at room temperature, 1000 kg (100.095 by weight) of corrosion inhibitor was obtained, which is a light, low-viscosity liquid with a pour point below -602C and a kinematic viscosity of 2.9 mm/s at a temperature of 2096.

Example 13.

Studies of the anti-corrosion properties of the water-soluble corrosion inhibitor for the protection of boreholes and natural gas pipelines according to the present invention were carried out according to the Umpeyi test! Tev5i, in accordance with the ATM MACE standard 1 0 182 "Method of studying the stability of the protective layer formed by pipe corrosion inhibitors in boreholes". This is a traditional weight loss test method used to evaluate the effectiveness of an inhibitor by simulating a continuous flow of a corrosive working environment.

A. Preparation of corrosion water: prepared corrosion water in the composition: 9.6295 Mass and 0.30590

Sasi" and 0.18695 MgSi" 6H2O and 89.8995 distilled water. The water is bubbled with nitrogen for 30 minutes, and then, for about 10 minutes, with carbon dioxide - until the pH of the corrosive water is between 4.4 and 4.8.

B. Preparation of paraffin oil (a mixture of isoparaffinic hydrocarbons): the oil is homogenized at a temperature of 629C, and then poured into test bottles.

S. Preparation of metal samples: metal tiles of the type "zapa Viaziei Mpa egeei! The 0.13 x 12.7 x 76 mm sputum cells were washed with acetone, wiped with a dry cloth, weighed, and stored in a desiccator.

Corrosive water in the amount of 90 ml and paraffin oil in the amount of 10 ml were introduced into the bottles with a capacity of 200 ml, from which the air was removed in advance. Next, the inhibitor according to the invention, according to examples 6, 7, 8, 9, 10, was introduced in the amount of 30, 50 and 80 mg/kg, and the inhibitor according to the invention, according to example 11, in the amount of 1500, 2500 mg/kg to the corrosive working body. The metal tiles described in paragraph C) are inserted into the bottles prepared in this way. Carbon dioxide was repeatedly dosed into the bottles for about 30 seconds and the bottles were hermetically closed. The bottles were placed in a thermostat at a temperature of 65.59C in a rotation chamber that rotated at a speed of 15 revolutions/minute. The test was conducted for 72 hours. After the study, metal samples were removed from the bottles, washed with isopropyl alcohol, treated with 1095 hydrochloric acid solution for 10-15 seconds. The metal samples were further washed with water, acetone, and alcohol, and then weighed to the nearest 0.1 mg. The weight reduction of the metal sample was estimated; the possible presence of ulcerative corrosion was additionally assessed.

The percentage of corrosion protection was calculated from the decrease in the weight of the metal sample in the presence of the UZhippib inhibitor) and without the UMM(O) inhibitor.

Percentage of protection, 90 R x UMO) - M(ippiVIM (0) x 10095

The results of studies of anticorrosive properties of corrosion inhibitors according to example 6, 7, 8, 10 and 11, containing a neutralized new mixture of imidazoline derivatives according to the invention, according to formulas (5) and (6), and the results of studies of anticorrosive properties of corrosion inhibitors according to of example 9, containing a neutralized mixture of modified imidazoline derivatives according to the invention, according to formula (5), (6) and (5), was compared with the corrosion inhibitor obtained in example 12, containing instead of a neutralized mixture of modified imidazoline derivatives according to formula (5) and (6) the neutralized known product, obtained by a known method - as a result of the condensation reaction of diethylenetriamine with oleic acid according to formula (5), is presented in the table below.

Table

Water-soluble corrosion inhibitor, according to the invention, that the neutralized known contains in examples 6,7,8,10,11 a neutralized mixture of the product obtained by the known modified imidazoline derivatives, according to the formula (5), (6) and in the method as a result of the reaction of example 9 a neutralized mixture of modified condensation derivatives of diethylenetriamine with imidazoline according to the invention according to formula (5), (6) and (5) with oleic acid according to formula (5) 1 Zpidnozprilladom.i// | 6|71|81|9|70|71| sh-:КЙЖМ 1 corrosive working body (mg/kg 11178077 172|191196|182|97|-|. .....ЮюЮюЮю.5 g sh 77777171717.7юЮЮKB7550..yu.yur r 180192198186198|-| Yush (6 69 sh sh 7777717171717IYUKB780..yu.yurur r 194196198195198|-| Yush 85 zh 15001111 -1-1-1-1-11111111111111111111 11112500 1 -1-1-1-1-181 11111111

From INDUSTRIAL APPLICATION

The above examples have shown that the water-soluble corrosion inhibitor for the protection of operational pipes and pipelines for natural gas transportation, as well as the method of its production, according to the invention, create opportunities for their industrial application.

Claims (14)

FORMULA OF THE INVENTION 1. A water-soluble corrosion inhibitor for the protection of operational pipes and pipelines for the transportation of natural gas, containing imidazoline derivatives, oxyethylated fatty amines, low-boiling amines and alcohol solvents, which is distinguished by the fact that it includes: component a) in an amount from 0.15 to 75 mass . 95, obtained as a result of neutralization from 0.1 to mass. 95 of a new mixture of modified imidazoline derivatives, which is a mixture of compounds with general formulas (1) and (2): M « M and M, vk 0) where EI: С11-Сай, ЧЖА во and МН ня with (2) where Кг: С2-Сто (2), which is a condensation product of diethylenetriamine with fatty acids containing from 12 up to 22 carbon atoms in the molecule and aliphatic dicarboxylic acids containing from 4 to 12 carbon atoms in the molecule, which is carried out while maintaining the molar ratio of diethylenetriamine and fatty acid and aliphatic dicarboxylic acid 1:0.80-0.99:0.01- 0.10 at a temperature of at least 140 "C, with the formation of a mixture of amino amides with the general formula (3) and (4): (c) laundry in. MH Mn, (3) where EI: C11-Cai, (in ) (c) МН р р МН МНОвВУ мной ит, и де ЕК»: С2-Си2, with an acid value of «10 mg KOH/g, and then, after raising the temperature above 180 «С, a condensation reaction is carried out to obtain a mixture of compounds with general formulas (1) and (2): М « М and М, вк 0) where Ки: С11-Сай, ваш МН 200 М 2 (2) where КК»: С2-Счо, with an acid value of "1 mg KOH/, with an aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 atoms of jug in the molecule, used in an amount from 0.05 to 25 wt. 95, while maintaining the mass ratio of the mixture of compounds with the general formulas (1), (2) and monocarboxylic acid 1:0.15-0.70, with obtaining the final product, which is a mixture of the compounds with the general formulas (5), (6) : th M M Z Still V, Soo- MN, K.; (5) where Ki: С11-Сай, Бе: Н, С:-Св, aromatic radical (SeНб) 2 а У А во and 2 В, сСО0: nm МН, ; (6) where Bo: С2-Счо, Бе: Н, С:-Св, aromatic radical (SenHb), component B), which are fatty amines containing from 14 to 22 carbon atoms in the molecule and oxyethylated with from 2 to 20 ethoxyl groups, in the amount from 0.01 to 10 wt. 95; component c) as an alkaline agent, which is at least one low-boiling amine selected from: 3-methoxypropylamine, 2-aminoethanol (monoethanolamine), diethylamine or their mixture, in an amount from 0.06 to 25 wt. 95; component e), which are aliphatic alcohols containing from 1 to 6 carbon atoms in the molecule in an amount from 15 to 99.7 wt. 95, with the possible addition of water; component Her), which is an antifoam agent, which are siloxane derivatives in the amount from 0.01 to 2 wt. 95. 2. Corrosion inhibitor according to claim 1, which differs in that it includes an additional component 4), which is aliphatic polyols in an amount from 0.04 to 50 wt. 95. 3. Corrosion inhibitor according to any of claims 1-2, which is characterized by the fact that as component a) it contains the product of neutralization with acetic and/or benzoic acid of the following imidazoline derivatives: and a new mixture of modified imidazoline derivatives, which is a condensation product of diethylenetriamine with fatty acids containing from 12 to 22 carbon atoms in the molecule, and aliphatic dicarboxylic acids containing from 6 to 10 carbon atoms in the molecule. 4. Corrosion inhibitor according to any of claims 1-3, which is characterized by the fact that component e) contains methanol, isopropanol, ethanol or their mixtures with the possible addition of water. 5. Corrosion inhibitor according to claim 1, which is characterized by the fact that component 4) contains ethyl glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol or their mixtures. b. Corrosion inhibitor according to any of claims 1-3, which is characterized by the fact that siloxane derivatives are branched siloxane polymers. 7. Corrosion inhibitor according to any of claims 1-3, which is characterized by the fact that as component a) it contains the product of neutralization of a new mixture of modified imidazoline derivatives and the product of condensation of diethylenetriamine with fatty acids in an amount from 0.05 to 20 wt. 95, containing from 23 to 24 carbon atoms in the molecule, obtained at a temperature of 180-280 "С with the general formula (1: з ши Ма мн, Кк ' З (1) where Кз: С11-Сгз, while maintaining the mass ratio of the mixture of compounds with the general formulas (1), (3) and (13th monocarboxylic acid 1:0.15-0.70, obtaining the final product, which is a mixture of compounds with the general formulas (5), (b) and (5: th M M Z Still V, Soo- MN, K.; (5) where Ky: Si1-C», Be: H, C:-Sv, aromatic radical (SenNb), 2 ve Ж A vo and 2 B,СООНУ МН»; (6) where Bo: С2-Счо, Бе: Н, С:-Св, aromatic radical (SenNb), и М М х Шче Б, Соо- МН Кз (5) where Кз: Сг2-Согз, Бе Н, С :i-Sv, aromatic radical (SeNb). 8. Corrosion inhibitor according to any of claims 1-3, 7, which is characterized by the fact that it contains component a) in an amount from 1.5 to 35 wt. 95. 9. The method of obtaining a water-soluble corrosion inhibitor for the protection of operational pipes and pipelines for the transportation of natural gas, which includes neutralization with an imidazoline derivative and the addition of further components of the inhibitor, which is distinguished by the fact that it includes the following stages: I) obtaining component a), i.e., carrying out neutralization in reaction medium containing component e), such as aliphatic alcohols containing from 1 to b carbon atoms in the molecule in an amount from 15 to 99.7 wt. 96, with the possible addition of water, neutralization at room temperature of a new mixture of modified imidazoline derivatives, which is a mixture of compounds with the general formula (1) and (2): and nya MN 7 7, (2) where": Se-So, which is the product of the condensation of diethylenetriamine with fatty acids containing from 12 to 22 carbon atoms in the molecule and aliphatic dicarboxylic acids containing from 4 to 12 carbon atoms in the molecule, which is carried out while maintaining the molar ratio of diethylenetriamine and fatty acids and aliphatic dicarboxylic acid 1 :0.80-0.99:0.01-0.10, at a temperature of at least 140 "C, with the preparation of a mixture of amino amides with the general formulas (3) and (4): (c) laundry in MN Mn, (3) where EI: С11-Сай, (c) (c) МН р р МН н МН ни ЗИМОВИ мно ин, and where К2: Se-Sto, with an acid value of "10 mg KOH/g, and when the temperature rises above 180"C, preferably up to 220"C, the condensation reaction is carried out further until a mixture of compounds with the general formulas (1) and (2) is obtained: 2 (2) where КК»: С2-Счо, with an acid number of "1 mg KOH/, used in an amount from 0.1 to 50 wt. 95, with an aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 atoms of carbon in the molecule, you used in amounts from 0.05 to 25 wt. 95, while maintaining the mass ratio of the mixture of compounds with the general formulas (1), (2) and monocarboxylic acid 1:0.15-0.70, with obtaining the final product, which is a mixture of the compounds with the general formulas (5), (6) : i M M x Still in, soo: MN, K. de Ki: C11-Sgch, (5) Be: H, C:-Sv, aromatic radical (SenNb), and U A Kk; at 2 p.SOO:- NU MN" ; (6) where КК»: C2-Scho, Ba: H, C:-Sv, aromatic radical (SenNb); I) introduction into component a) in the amount from 0.15 to 75 wt. 95, and the mentioned component e) of further inhibitor components: component B), such as oxyethylated fatty amines containing from 14 to 22 carbon atoms, and from 2 to 20, ethoxyl groups in an amount from 0.01 to 10 wt. 95; component c), such as an alkaline agent, in an amount from 0.06 to 25, and at the end, component Her), which is an antifoam agent, which are siloxane derivatives, in an amount from 0.01 to 2 wt. 9. 10. The method according to claim 9, which is characterized by the fact that the component Her), which are siloxane derivatives, contains branched siloxane polymers. 11. The method according to claim 9, which differs in that at stage II) after component c), an additional component a) is introduced, such as aliphatic polyols, in an amount from 0.04 to 50 wt. 95. 12. The method according to claim 9, which differs in that at stage I) neutralization of a new mixture of modified imidazoline derivatives, which is a condensation product of diethylenetriamine with fatty acids containing from 12 to 22 carbon atoms in the molecule and aliphatic dicarboxylic acids, is carried out with glacial acetic acid , containing from b to 10 carbon atoms in the molecule. 13. The method according to any of claims 9 or 12, which is characterized by the fact that at stage I) neutralization of a new mixture of modified imidazoline derivatives is carried out in an amount from 1 to 30 wt. 95 and the condensation product of diethylenetriamine with fatty acids in an amount from 0.05 to 20 wt. 95, containing from 23 to 24 carbon atoms in the molecule, obtained at a temperature of 180-280 C with the general formula (1): zx SHY Ma mn, k Z ; where Kz: Сг2-Сгз, (1) while maintaining the mass ratio of the mixture of compounds with the general formulas (1), (2) and (1) and monocarboxylic acid 1:0.15-0.70, with obtaining the final product, which is by a mixture of compounds with general formulas (5), (b) and (5: i M M x Also v,soo: МН Kk Zo ; (5) where Ki: C11-Cai, Be: H, C:-Sv, aromatic radical (SenNb), a U A Kk, u 2 K,СО00: НУ МН» ; (6) where КК»: С2-Счо, Бе: Н, С:-Св, aromatic radical (SenNb), и М М х Шче к,СОО: МН, Кз ,; (5) where Kz: Cg2-Cgz, Be H, C:i-Cv, aromatic radical (SeNb). 14. The method according to any one of claims 9, 12 or 13, which is characterized by the fact that component a), obtained by neutralization of a new mixture of modified imidazoline derivatives, is taken in an amount from 1 to 30 wt. 95.