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WO2014178737A1 - Inhibiteur de corrosion destiné à la protection d'un équipement d'extraction de pétrole brut, de conduites pour pétrole brut et de réservoirs pour pétrole brut et procédé pour sa fabrication - Google Patents

Inhibiteur de corrosion destiné à la protection d'un équipement d'extraction de pétrole brut, de conduites pour pétrole brut et de réservoirs pour pétrole brut et procédé pour sa fabrication Download PDF

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Publication number
WO2014178737A1
WO2014178737A1 PCT/PL2014/000047 PL2014000047W WO2014178737A1 WO 2014178737 A1 WO2014178737 A1 WO 2014178737A1 PL 2014000047 W PL2014000047 W PL 2014000047W WO 2014178737 A1 WO2014178737 A1 WO 2014178737A1
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weight
mixture
per molecule
optionally
carbon atoms
Prior art date
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PCT/PL2014/000047
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English (en)
Inventor
Barbara GAŹDZIK
Michał PAJDA
Wojciech MAZELA
Leszek ZIEMIAŃSKI
Iwona SKRĘT
Stefan PTAK
Ewa ZEGARMISTRZ
Mieczysław SOCHA
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INSTYTUT NAFTY I GAZU - PANSTWOWY INSTYTUT BADAWCZY
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INSTYTUT NAFTY I GAZU - PANSTWOWY INSTYTUT BADAWCZY
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Priority claimed from PL403749A external-priority patent/PL230807B1/pl
Priority claimed from PL403752A external-priority patent/PL226809B1/pl
Application filed by INSTYTUT NAFTY I GAZU - PANSTWOWY INSTYTUT BADAWCZY filed Critical INSTYTUT NAFTY I GAZU - PANSTWOWY INSTYTUT BADAWCZY
Priority to RU2015150552A priority Critical patent/RU2641148C2/ru
Priority to UAA201511858A priority patent/UA117131C2/uk
Priority to EP14729473.0A priority patent/EP2992065A1/fr
Publication of WO2014178737A1 publication Critical patent/WO2014178737A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

  • Corrosion inhibitor for protection of crude oil extraction equipment, crude oil pipelines, and crude oil tanks as well as the method of its production
  • the invention relates to a corrosion inhibitor for protection of crude oil extraction equipment, crude oil pipelines, and crude oil tanks as well as to the method of its production.
  • Corrosion inhibitors for protection of crude oil extraction equipment, pipelines, and tanks provide corrosion protection against factors such as: hydrogen sulfide and carbon dioxide found in crude oil and natural gas as well as oxygen and chlorides contained in formation water and drilling fluids.
  • Drilling fluids are usually aqueous saline solutions that behave as an electrolyte. Extracted crude oil and the produced water accompanying it also contain inorganic salts such as chlorides (sodium, potassium, magnesium), sulfates (sodium, potassium, magnesium), and carbonates. Electrochemical corrosion occurs readily in aqueous systems containing salts. It is caused by the action of galvanic cells forming between the passivated metal surface and a surface that does not possess such a layer. The effect of electrochemical corrosion is mainly pitting corrosion on the surfaces of lifting casings and operational equipment. The most damage to pipe and casing surfaces occurs in saline solutions with concentrations of 7 - 13 %.
  • the rate of corrosion induced by carbon dioxide and hydrogen sulfide increases as the oxygen content in the system increases. Oxygen penetrates into drilling fluids when they pass through machinery servicing wells and tanks. The rate of corrosion is also dependent on temperature; the greater it is, the greater the corrosion rate, which reaches its maximum at a temperature of approx. 70°C. In wells that are not protected with corrosion inhibitors, it may reach from 1 to several mm/year.
  • the effects of corrosion processes are: reduction of the thickness of lifting casing walls and pipeline walls, deep pitting that may lead to leaks, and severe reduction of their strength properties.
  • corrosion inhibitors In order to prevent corrosion in oil wells, corrosion inhibitors reducing the corrosive action of extracted crude oil and gas on steel parts of extraction equipment, pipelines, and tanks are used. Corrosion inhibitors of varying chemical nature, most often imidazoline derivatives, are used as corrosion inhibitors. In order for a corrosion inhibitor to be effective, it should dissolve not only in crude oil but, above all, in water. Salts of imidazoline derivatives are usually used for this purpose.
  • Patent descriptions US 3629104 and US 3758493 present water-soluble corrosion inhibitors containing a carboxylic acid of an imidazoline derivative produced by condensation of dimerized fatty acids with diethylenetriamine.
  • US Patent 5759485 describes the method of producing the corrosion inhibitor by neutralization of C 2 2-tricarboxylic acids and subsequent addition of imidazoline or amidoamine.
  • Patent application WO 2003/054251 contains a description of the good anti- corrosion properties of ethoxylated fatty alkyl amines, particularly ethoxylated alkyl ether amines.
  • Patent descriptions PL 61535 and PL 85729 disclose that imidazoline inhibitors are produced in a condensation reaction of diethylenetriamine with fatty acids or naphthenic acids.
  • Patent descriptions PL 135655 and PL 175452 present production of an inhibitor with increased activity which is a result of condensation of diethylenetriamine with fatty acids and is then modified using hexamethylenetriamine introduced during the final phase of the condensation reaction.
  • the water-soluble corrosion inhibitor contains a salt of an imidazoline derivative that constitutes the product of condensation of fatty acids with diethylenetriamine and urotropine or formaldehyde as well as low molecular carboxylic acids.
  • Patent application US 2004/0087448 discloses the use of the product of condensation of C 18 unsaturated fatty acid dimmers, containing 1 or 2 double bonds, and diethylenetriamine as a corrosion inhibitor.
  • US Patent 6695897 contains a description of a method of producing amidoamine by condensation of N-ethylethylenediamine and fatty acid.
  • the product of the reaction after solubilization with acetic acid may perform the role of a water-soluble corrosion inhibitor.
  • US patent 7057050 presents a method for producing a water-soluble corrosion inhibitor.
  • the product of the reaction is N-propyl-2-heptadecenyl imidazoline.
  • the obtained product is solubilized to a water-soluble state using acrylic acid.
  • Patent application WO 2006/078723 contains a description of a method of producing micro-emulsions containing imidazoline derivatives and amidoamines produced in the presence of oleic acid.
  • the micro-emulsion also contains ethoxylated nonylphenols and acetic acid.
  • Patent description US 5322630 discloses an imidazoline corrosion inhibitor that is the product of the reaction of unsaturated monocarboxylic acids with fatty amines, aminoamides, or fatty imidazol-amines.
  • Patent description RU 2394941 describes a mixture of imidazoline derivatives modified with aldimines or Schiff bases.
  • the imidazoline derivative is the product of the reaction of polyamines with oleic acid or monocarboxylic acids. The imidazoline derivative is then cyanoethylated with nitriles, acrylic acid, or subjected to oxyalkylation.
  • N-ethoxylated imidazoline derivative with unsaturated and saturated fatty acid chains substituted in position 2 is cited as a corrosion inhibitor in American patent description US 5785895.
  • Patent description GB 2340505 presents a method for producing imidazoline derivatives by the process of condensation of tall oil fatty acids with aminoethylethanolamine.
  • the thus obtained inhibitor is characterized by good anti- corrosion properties, and by forming complexes with mercaptans, it also reduces the characteristic odour of sulfur compounds.
  • Patent literature contains descriptions of condensation of diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms per molecule, with a molar ratio of diethylenetriamine to fatty acids equal to 1 :0.5 - 1.0. Examples of such condensation are known from, among others, American patent descriptions US 2267965, US 2355837, and Polish patent description PL 61535.
  • Corrosion inhibitors containing bis-amides are described in American patents US 4614600 and US 4344861.
  • US patent 4614600 describes a bis-amide as a product of the reaction of polyamines with fatty acid dimers
  • patent US 4344861 described the product of the reaction of polyamines with dicarboxylic acids.
  • the purpose of the invention is to develop a corrosion inhibitor for protection of crude oil extraction equipment, pipelines, and tanks that would provide much better anti-corrosion properties than currently utilized corrosion inhibitors.
  • This invention concerns corrosion inhibitor for protection of crude oil extraction equipment, crude oil pipelines, and crude oil tanks as well as the method of its production.
  • One aspect the invention is to provide a corrosion inhibitor for protection of crude oil extraction equipment, crude oil pipelines, and crude oil tanks, which contains: - component a) in the amount from 0.1 5 to 85 % by weight, preferably from 1.55 to 51% by weight, produced by the following processes:
  • R 2 C 2 -C 12 (2), which is the product of condensation of diethylenetriamine with fatty acids containing from 12 to 22 carbon atoms per molecule and aliphatic dicarboxylic acids containing from 2 to 12 carbon atoms per molecule,
  • R 3 C 12 -C 24 with an aliphatic and/or an aromatic monocarboxylic acid containing from 1 to 7 carbon atoms per molecule, used in an amount from 0.025 to 25 % by weight, in which neutralization the mass ratio of the mixture of compounds of general formulae (1), (2), and optionally ( ⁇ ) to monocarboxylic acid is 1: 0.15 - 0.70 with obtaining of an intermediate product that is a mixture of compounds of general formulae (5), (6), and optionally (5') as well as a mixture of non-neutralized compounds of general formulae (1), (2), and optionally (1') wherein Rj: C 12 -C 22 (5)
  • R4 H, C ! -C 6 , aromatic radical (C 6 H 6 )
  • R4 H, C ! -C 6 , aromatic radical (C 6 H )
  • R4 H, C]-C 6 , aromatic radical (C 6 H 6 ) and B) - further neutralization of the obtained intermediate product, which is a mixture of the compounds of general formulae (5), (6), and optionally (5') as well as a mixture of non-neutralized compounds of general formulae (1), (2), and optionally ( ⁇ ), with fatty acids containing from 12 to 22 carbon atoms per molecule, used in an amount from 0.03 to 10 % by weight, and/or fatty acid polymers containing from 18 to 54 carbon atoms per molecule, used in an amount from 0.03 to 10 % by weight, in which neutralization the mass ratio of the total mass of the mixture of compounds of general formulae (1), (2), and optionally ( ), to fatty acids and/or polymers is 1 : 0.02 - 0.5, with obtaining of a product containing a mixture of compounds of general formulae (7), (8), and optionally (7'),
  • R 5 C 12 -C 22 and/or C 18 -C 54
  • R 5 C 12 -C 22 and/or C ]8 -C 54
  • - component b that is oxyethylenated fatty amines containing from 14 to 22 carbon atoms per molecule and from 2 to 22, preferably from 5 to 15, ethoxyl groups per molecule, in an amount from 0.01 to 20 % by weight;
  • component c that is aliphatic polyols in an amount from 0.1 to 50 % by weight
  • component d that is aliphatic alcohols containing from 1 to 6 carbon atoms per molecule, optionally with the addition of water, in an amount from 15.0 to 99.6 % by weight,
  • Another aspect of the present invention is to provide the method of production of corrosion inhibitor for protection of crude oil extraction equipment, crude oil pipelines, and crude oil tanks, which contains the following stages:
  • component a) in a reaction medium containing component d), that is aliphatic alcohols containing from 1 to 6 carbon atoms per molecule, optionally with the addition of water, in an amount from 15 to 99.6 % by weight which comprises the following processes: A) - neutralization of the new mixture of modified imidazoline derivatives, of general formulae (1) and (2), which is the product of condensation of diethylenetriamine with fatty acids containing from 12 to 22 carbon atoms per molecule and aliphatic dicarboxylic acids containing from 2 to 12 carbon atoms per molecule,
  • R 2 C2-Q2 (2) used in an amount from 0.1 to 50 % by weight, preferably from 1 to 30 % by weight, with the optional addition of 0.05 to 20 % by weight of the known product of condensation of diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms per molecule, produced by a known method at a temperature of 180-280°C, preferably 220-260°C, of general formula ( ⁇ ),
  • R 3 C 12 -C 24 with an aliphatic and/or an aromatic monocarboxylic acid containing from 1 to 7 carbon atoms per molecule, used in an amount from 0.025 to 25 % by weight, where the mass ratio of the mixture of compounds of general formulae (1), (2), and optionally ( ⁇ ) to monocarboxylic acid is 1 : 0.15 - 0.70, with obtaining of an intermediate product, that is a mixture of compounds of general formulae (5), (6), and optionally (5') as well as a mixture of non-neutralized compounds of general formulae (1), (2), and optionally ( ⁇ )
  • R4 H, CrC 6 , aromatic radical (C 6 H 6 )
  • R 4 H, Q-C 6 , aromatic radical (C H 6 );
  • R 5 C 12 -C 22 and/or C
  • R 5 C 12 -C 22 and/or C 18 -C 54
  • component a) introduction to component a), in an amount from 0.155 to 85 % by weight, preferably from 1.55 to 51 % by weight, and to the mentioned component d), of further inhibitor components:
  • component b) that is oxyethylenated fatty amines containing from 14 to 22 carbon atoms per molecule and from 2 to 22, preferably from 5 to 15, ethoxyl groups per molecule, in an amount from 0.01 to 20 % by weight
  • component c) that is aliphatic polyols in an amount from 0.1 to 50 % by weight
  • component e that is an anti-foaming agent in an amount from 0.01 to 2 % by weight.
  • condensation of diethylenetriamine is performed with fatty acids containing 12-22 carbon atoms per molecule and aliphatic dicarboxylic acids containing 2-12 carbon atoms per molecule, where the molar ratio of diethylenetriamine to fatty acids and to aliphatic dicarboxylic acids is 1:0,5-0,99: 0.01- 0.5, at a temperature of at least 140°C, preferably 150°C, with the formation of an aminoamide mixture of general formulae (3) and (4),
  • R 2 C 2 -C 12 ( 4) with acid number ⁇ 10 mg KOH/g, and next, the temperature is raised to above 180 °C, preferably to 220 °C, and the condensation reaction is performed further until a mixture of compounds of general formulae (1) and (2) is obtained
  • R 2 C 2 -C 12 (2) with acid number ⁇ 1 mg KOH/g.
  • the corrosion inhibitor contains as component a) a product formed by neutralization with acetic acid and/or benzoic acid of the following imidazoline derivatives :
  • modified imidazoline derivatives which is condensation product of diethylenetriamine with fatty acids containing 12-22 carbon atoms per molecule and aliphatic dicarboxylic acids containing 6-10 carbon atoms per molecule, where the molar ratio of diethylenetriamine to fatty acids and to aliphatic dicarboxylic acids is 1 : 0,5-0,99: 0.01-0.5, at a temperature of at least 140°C, preferably 150°C, with the formation of an aminoamide mixture of general formulae (3) and (4),
  • R 2 C 6 -C 10 ( 4) with acid number ⁇ 10 mg KOH/g, and next, the temperature of the reaction is raised to above 180 °C, preferably to 220 °C, and the condensation reaction is performed further until a mixture of compounds of general formulae (1) and (2) are obtained
  • the main component is oleic acid C 18 H 34 0 2 and or fatty acid polymers containing dimers as their main component, with acid number from 190 to 197 mg KOH/g.
  • the corrosion inhibitor contains, as component a), a product formed by neutralization of the new mixture of modified imidazoline derivatives, with the optional addition of the known product of condensation of diethylenetriamine with fatty acids produced by a known method, using first glacial acetic acid, and after that, neutralization of the resultant intermediate product with fatty acids in which the main ingredient is oleic acid C 18 H 34 0 2 and/or fatty acid polymers containing fatty acid dimers as their main component.
  • the corrosion inhibitor contains methanol, isopropanol, ethanol, optionally added water or their mixtures as component d).
  • the corrosion inhibitor contains aliphatic polyols, preferably ethylene glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol, or their mixtures as component c).
  • the corrosion inhibitor contains a siloxane derivative, most preferably branched siloxane polymers as component e).
  • composition of the corrosion inhibitor according to the invention has been given in percentages by weight calculated in reference to the total mass of the inhibitor.
  • neutralization with acetic acid and/or benzoic acid of the following imidazoline derivatives is carried out in a process A): i) the new mixture of modified imidazoline derivatives, which is condensation product of diethylenetriamine with fatty acids containing 12-22 carbon atoms per molecule and aliphatic dicarboxylic acids containing 2-12 carbon atoms per molecule, where the molar ratio of diethylenetriamine to fatty acids and to aliphatic dicarboxylic acids is 1 : 0,5-0,99: 0.01-0.5, at a temperature of at least 140°C, preferably 150°C, with the formation of an aminoamide mixture of general formulae (3) and (4),
  • R 2 C -C 10 (2) with acid number ⁇ 1 mg KOH/g ii) optionally added the known product of condensation of diethylenetriamine with fatty acids produced by a known method, and then neutralization is carried out in a process B), of the resultant intermediate product, with fatty acids with acid number from 180 to 210 mg KOH/g, saponification number from 180 to 210 mg KOH/g and iodine number from 80 to 130 g J 2 /100 g, in which the main component is oleic acid C 18 H 34 0 2 and/or fatty acid polymers containing dimers as their main component, with acid number from 190 to 197 mg KOH/g.
  • neutralization of the new mixture of modified imidazoline derivatives with the optional addition of the known product of condensation of diethylenetriamine with fatty acids is performed using glacial acetic acid, and after that, the obtained intermediate product is neutralized with fatty acids, in which the main component is oleic acid C 18 H 34 0 2 , and/or fatty acid polymers containing dimers as their main component.
  • aliphatic polyols preferably ethylene glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol, or their mixtures, can be applied as solubilizers in an amount from 0.1 to 50 % by weight, and possibly alcohols other than methanol, isopropanol, and ethanol.
  • the corrosion inhibitor produced using the base of the mixture of modified imidazoline derivatives is characterized by better anti-corrosion and hydrophilic properties as compared to inhibitors containing known imidazoline derivatives.
  • the best corrosion inhibitors used in oil and gas wells are those that are very well soluble in water while leaving a persisting film of the corrosion inhibitor on metal surfaces.
  • a corrosion inhibitor should provide protection for a pipeline/installation for at least 24 h from an emergency stop of the dosing pump.
  • the inhibitor according to this invention forms homogenous fluids with formation water containing up to 30 % salt, and even at a temperature of 80°C, no precipitation of the inhibitor from these fluids is observed.
  • the exceptional compatibility of the inhibitor that is the subject of this invention with formation water of varying salinity increases its anti-corrosion properties in the entire oil-gas-water or oil-water system.
  • the formation water accompanying the crude oil is characterized by low mineralization level, which favors foaming of the inhibitor in the water. Foaming is also fostered by a large amount of formation water relative to the extracted crude oil.
  • an anti-foaming agent preferably a siloxane derivative
  • the corrosion inhibitor according to this invention is characterized by high anti- corrosion properties under conditions of crude oil extraction at low inhibitor doses in crude oil production installations.
  • the corrosion inhibitor produced using the method according to the invention is a clear liquid with low viscosity. It is easily soluble in formation water and exhibits high stability under operating conditions, even up to very high temperatures above 80°C. It protects metal surfaces against corrosion well, even in the case of a periodical failure of the dosing system.
  • One of the numerous versions of the corrosion inhibitor according to this invention contains benzoic acid, which may act as a bactericide.
  • crude oil pipelines and crude oil tanks is added to the crude oil or crude oil - water or crude oil-water-gas, preferably it is added to the fluid: crude oil or crude oil - water or crude oil-water-gas continuously.
  • Corrosion inhibitor according to the invention in general, is added to the fluid in amount from about 0,01 to 5000 ppm, preferably from about 1 to 500 ppm, the most preferably from about 10 to 30 ppm.
  • the examples given below illustrate the invention while not limiting its scope.
  • the following components were introduced into a reactor: 103.16 kg (1 mole) diethylenetriamine, 141.23 kg (0.5 mole) distilled olein, in which the main component is oleic acid C 18 H 3 40 2 , and 45.02 kg (0.5 mole) oxalic acid.
  • the content was heated while being mixed constantly with a mechanical stirrer and nitrogen barbotage was additionally applied in order to remove the water forming during the reaction. After a temperature of 150°C was achieved, it was maintained for 3 hours until an acid number of 3.51 mg KOH/g was obtained, and after that, further heating was applied until the temperature of 220°C was achieved.
  • reaction was performed for 4 hours while the temperature was maintained constant at 220°C and while nitrogen barbotage was applied for the purpose of removing water from the reaction. 226 kg of product -mixture of modified imidazoline derivatives - with acid number 0.25 mg KOH/g were obtained.
  • the following components were introduced into a reactor: 103.16 kg (1 mole) diethylenetriamine, 264.10 kg (0.95 mole) tall oil fatty acids, and 10.11 kg (0.05 mole) sebacic acid.
  • the content was heated while being mixed constantly with a mechanical stirrer, and nitrogen barbotage was additionally applied in order to remove the water forming during the reaction. After a temperature of 150°C was achieved, it was maintained for 3 hours (acid number 5.1 mg KOH/g was obtained), and after that, further heating was applied until the temperature of 220°C was achieved.
  • the reaction was performed for 5 hours while the temperature was maintained constant at 220°C and while nitrogen barbotage was applied for the purpose of removing water from the reaction. 308 kg of product (mixture of modified imidazoline derivatives) with acid number 0.7 mg KOH/g were obtained.
  • the following components were introduced into a reactor: 103.16 kg (1 mole) diethylenetriamine, 268.34 kg (0.95 mole) distilled olein, in which the main component is oleic acid C 18 H 34 02, and 5.90 kg (0.05 mole) succinic acid.
  • the content was heated while being mixed constantly with a mechanical stirrer, and nitrogen barbotage was additionally applied in order to remove the water forming during the reaction. After a temperature of 150°C was achieved, it was maintained for 3 hours (acid number 3.94 mg KOH/g was obtained), and after that, further heating was applied until the temperature of 210°C was achieved.
  • the following components were introduced into a reactor: 103.16 kg (1 mole) diethylenetriamine, 268.34 kg (0.95 mole) distilled olein, in which the main component is oleic acid C 18 H 3 402, and 7.67 kg (0.05 mole) adipic acid.
  • the content was heated while being mixed continuously with a mechanical stirrer, and at the same time, a 100 mm Hg vacuum was applied in order to remove water from the reaction. After a temperature of 150°C was achieved, it was maintained for 3 hours (acid number 4.72 mg KOH/g was obtained), and after that, further heating was applied until the temperature of 220°C was achieved.
  • reaction was performed for 5 hours while the temperature was maintained constant at 220°C and while a 100 mmHg vacuum was applied for the purpose of removing water from the reaction. 299 kg of product (mixture of modified imidazoline derivatives) with acid number 0.33 mg KOH/g were obtained.
  • the following components were introduced into a reactor: 425 kg (42.5 % by weight) of isopropyl alcohol, 10 kg (1 % by weight) of ethanol, 100 kg (10 % by weight) of water, and then 100 kg (10 % by weight) of the product of condensation of diethylenetriamine with distilled olein, in which the main component is oleic acid C 18 H3 4 0 2 and with adipic acid, produced according to example 5, with acid number 0.33 mg KOH/g.
  • the following components were introduced into a reactor: 335 kg (33.5 % by weight) of methyl alcohol, 143 kg (14.3 % by weight) of isopropyl alcohol, and then 300 kg (30 % by weight) of the product of condensation of diethylenetriamine with distilled olein, in which the main component is oleic acid C 18 H340 2 and with succinic acid, produced according to example 4, with acid number 0.24 mg KOH/g.
  • the following components were introduced into a reactor: 335 kg (33.5 % by weight) of methyl alcohol, 143 kg (14.3 % by weight) of isopropyl alcohol, and then 180 kg (18 % by weight) of the product of condensation of diethylenetriamine with distilled olein, in which the main component is oleic acid C 18 H 34 0 2 and oxalic acid, produced according to example 1, with acid number 0.25 mg KOH/g, as well as 20 kg (2 % by weight) of the known product of condensation of diethylenetriamine with tall oil acids, with water content below 2% by weight and pH of a 5 % by volume alcohol water solution equal to 11.2. After complete dissolution, 45 kg (4.5 % by weight) of glacial acetic acid were introduced.
  • the following components were introduced into a reactor: 994.25 kg (99.425 % by weight) of isopropyl alcohol, 0.1 kg (0.01 % by weight) of ethanol, 1 kg (0.1 % by weight) of water, and then 1 kg (0.1 % by weight) of the product of condensation of diethylenetriamine with distilled olein, in which the main component is oleic acid C 18 H 34 0 2 and with adipic acid, produced according to example 5, with acid number 0.33 mg KOH/g.
  • a corrosion inhibitor with low kinematic and dynamic viscosity over a wide temperature range is required, and thus, a low content of active components is also required.
  • Required inhibitor dosages may be 1000, 2000, or 3000 mg/kg.
  • the corrosion inhibitor according to example 6 is destined for such dosing pumps.
  • Tests of the anti-corrosion properties of the corrosion inhibitor for protection of crude oil extraction equipment, pipelines, and tanks according to this invention were performed according to the Wheel Test in accordance with standard ASTM NACE 1 D 182 "Wheel test method used for evaluation of film-persistent corrosion inhibitors for Oilfield applications". This is a conventional method of testing mass decrement, used to evaluate the effectiveness of an inhibitor through simulation of continuous flow of a corrosive medium.
  • corrosive water was prepared according to the following composition: 9.62 % by weight NaCl and 0.305 % by weight CaCl 2 and 0.186 % by weight MgCl 2 -6H 2 0 and 89.89 % by weight distilled water. The water was subjected to nitrogen barbotage for 30 minutes, and then to carbon dioxide barbotage for approx. 10 minutes until the achievement of corrosive water pH within the range of 4.4 to 4.8.
  • the inhibitor according to the invention was introduced in the amount of 10, 20, and 30 ppm by weight, and in the case of the inhibitor according to example 11, in the amount of 1000, 2000, and 3000 ppm by weight, into the corrosive medium.
  • the metal plates described in point C) were introduced into the thus prepared bottles. Carbon dioxide was once again dosed into the bottles over a time of approx. 30 s, and bottles were hermetically closed. The bottles were placed in a thermostat at a temperature of 65.5°C, in a rotating apparatus that rotated with a speed of 15 rotations/minute.
  • the test was performed for a period of 72 hours. After the test, metal samples were removed from bottles, rinsed with isopropyl alcohol, and subjected to the action of a 10% hydrochloric acid solution for a period of 10 - 15 seconds. Metal samples were then rinsed with water, acetone, and alcohol, after which they were weighed with an accuracy to 0.1 mg. The mass decrement of metal samples was assessed, and the possible presence of pitting corrosion was also assessed. The percentage of protection against corrosion was calculated from the mass decrement of the metal sample in the presence of the inhibitor W(inhib) and without the inhibitor W(0).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un inhibiteur de corrosion destiné à la protection d'un équipement d'extraction de pétrole brut, de conduites pour pétrole brut et de réservoirs pour pétrole brut, qui contient : • - un composant a) produit à la suite de la réalisation des procédés suivants : • A) - neutralisation partielle du nouveau mélange de dérivés modifiés d'imidazoline, de formules générales (1) et (2), où R2- C2-C12 avec l'addition possible de composé (Γ), où R3 : C12-C24 • avec un acide monocarboxylique aliphatique et/ou aromatique contenant de 1 à 7 atomes de carbone par molécule • et B) - une neutralisation partielle supplémentaire du produit intermédiaire obtenu, avec des acides gras contenant de 12 à 22 atomes de carbone par molécule, et/ou des polymères d'acide gras contenant de 18 à 54 atomes de carbone par molécule • - un composant b), à savoir des amines grasses rendues oxyéthyléniques contenant de 14 à 22 atomes de carbone par molécule et de 2 à 22, de préférence de 5 à 15, groupes éthoxyle par molécule • - un composant d), à savoir des alcools aliphatiques contenant de 1 à 6 atomes de carbone par molécule, éventuellement avec l'addition d'eau.
PCT/PL2014/000047 2013-05-02 2014-05-05 Inhibiteur de corrosion destiné à la protection d'un équipement d'extraction de pétrole brut, de conduites pour pétrole brut et de réservoirs pour pétrole brut et procédé pour sa fabrication Ceased WO2014178737A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
RU2015150552A RU2641148C2 (ru) 2013-05-02 2014-05-05 Ингибитор коррозии для защиты оборудования для добычи сырой нефти, трубопроводов и резервуаров для сырой нефти, а также способ его получения
UAA201511858A UA117131C2 (uk) 2013-05-02 2014-05-05 Інгібітор корозії для захисту видобувного устаткування, трубопроводів для транспортування нафти і резервуарів з нафтою, а також спосіб його виготовлення
EP14729473.0A EP2992065A1 (fr) 2013-05-02 2014-05-05 Inhibiteur de corrosion destiné à la protection d'un équipement d'extraction de pétrole brut, de conduites pour pétrole brut et de réservoirs pour pétrole brut et procédé pour sa fabrication

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PLP.403749 2013-05-02
PLP.403752 2013-05-02
PL403749A PL230807B1 (pl) 2013-05-02 2013-05-02 Kompozycja zmodyfikowanych pochodnych imidazoliny i sposób jej wytwarzania
PL403752A PL226809B1 (pl) 2013-05-02 2013-05-02 Inhibitor korozji doochrony urzadzen wydobywczych, rurociagów transportujacych rope naftowa izbiorników zropa naftowa isposób jego wytwarzania

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WO2014178737A1 true WO2014178737A1 (fr) 2014-11-06

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EP (1) EP2992065A1 (fr)
RU (1) RU2641148C2 (fr)
UA (1) UA117131C2 (fr)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017140836A1 (fr) 2016-02-18 2017-08-24 Versalis S.P.A. Inhibiteur de corrosion comportant des structures oligomères complexes dérivées d'huiles végétales
WO2020046967A1 (fr) * 2018-08-28 2020-03-05 Kao Corporation Compositions d'inhibiteur de corrosion destinées au domaine du pétrole et du gaz
US12385143B2 (en) 2021-08-05 2025-08-12 Ecolab Usa Inc. Corrosion inhibitor for mitigating alkaline carbonate stress corrosion cracking

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2723123C1 (ru) * 2019-05-07 2020-06-08 Общество с ограниченной ответственностью «ИФОТОП» Применение амидов, являющихся продуктами конденсации анизидина или его производных с нафтеновой кислотой в качестве ингибитора коррозии и водородного охрупчивания

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US2646399A (en) * 1950-12-28 1953-07-21 Cities Service Res & Dev Co Method of inhibiting corrosion of metals
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US4344861A (en) 1980-01-15 1982-08-17 Uop Inc. Bis-amides as corrosion inhibitors
PL135655B2 (en) 1983-10-18 1985-11-30 Politechnika Lodzka Method of and system for linearization of characteristics of frequency-to-voltage converter
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US7057050B2 (en) 2003-04-11 2006-06-06 Nalco Energy Services L.P. Imidazoline corrosion inhibitors
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US20070152191A1 (en) 2005-12-29 2007-07-05 Trahan David O Corrosion inhibitors
RU2394941C1 (ru) 2008-12-29 2010-07-20 Общество с ограниченной ответственностью "Промышленно-торговая компания ТАНТАНА" Способ получения ингибиторов коррозии

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017140836A1 (fr) 2016-02-18 2017-08-24 Versalis S.P.A. Inhibiteur de corrosion comportant des structures oligomères complexes dérivées d'huiles végétales
WO2020046967A1 (fr) * 2018-08-28 2020-03-05 Kao Corporation Compositions d'inhibiteur de corrosion destinées au domaine du pétrole et du gaz
CN112771207A (zh) * 2018-08-28 2021-05-07 花王株式会社 油气田腐蚀抑制剂组合物
US12043794B2 (en) 2018-08-28 2024-07-23 Kao Corporation Oil and gas field corrosion inhibitor compositions
US12385143B2 (en) 2021-08-05 2025-08-12 Ecolab Usa Inc. Corrosion inhibitor for mitigating alkaline carbonate stress corrosion cracking

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EP2992065A1 (fr) 2016-03-09
UA117131C2 (uk) 2018-06-25
RU2015150552A (ru) 2017-06-07
RU2641148C2 (ru) 2018-01-16

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