RU2316615C1 - Method of production of the corrosion inhibitors used for the oilfield mineralized and hydrogen sulfide-containing mediums - Google Patents

Abstract

FIELD: oil-producing industry; natural gas industry; methods for protection against corrosion of the gas-field and oil-field equipment operating in the hydrogen sulfide containing highly mineralized aqueous mediums.

SUBSTANCE: the invention is pertaining to the method of production the corrosion inhibitors and may be used for protection against corrosion of the gas-field and oil-field equipment operating in the hydrogen sulfide containing highly mineralized aqueous mediums. The method of production of the corrosion inhibitors for the oilfield, mineralized and hydrogen sulfide containing mediums consists that the active base is produced by interaction of the polyethylenepolyamines with the oleinic acid or with the oxidate of 2-ethylhexene aldehyde with the acid number of 155-165 mgKOH at the temperature of 120-180°C within 4-6 hours, then at the temperature of 180-230°C within 3 hours and holding at the temperature of 230-250°C within 1-2 hours with simultaneous distillation of the water and the easily boiling ingredients. Then the reaction mixture is cooled and stirred with the available dissolvents and dispensers at the temperature of 20-60°C within 1-2 hours. The method allows to reduce considerably the net cost of the produced articles due to usage of the cheap and available dissolvents and the minimal quantity of the qualitative active basis, and also to ensure the high protective properties of the produced corrosion inhibitors.

EFFECT: the invention ensures the considerable reduction of the net cost of the produced corrosion inhibitors with the high their protective properties.

12 ex, 1 tbl

Description

The invention relates to the field of protection of gas and oilfield equipment and pipelines operating in hydrogen sulfide-containing highly mineralized aqueous media against corrosion and hydrogen disturbance, as well as oil and gas transportation.

A known method of producing corrosion inhibitors by the interaction of α-branched monocarboxylic acids fraction C ₁₀ -C ₂₀ with polyethylene polyamines and 1,4-di (2-aminoethyl) piperazine. The process is carried out at a temperature of 250-280 ° C for 2-6 hours with a molar ratio of acid: polyethylene polyamines: 1,2-di (2 aminoethyl) piperazine equal to 1: 0.7-0.9: 0.2-0.5 , then when evacuating 1-30 mm of water. reaction water and excess polyethylene polyamines are distilled off over 2-4 hours, the reactor is cooled to 160-180 ° C and α, α-branched monocarboxylic acids or tallow oil fatty acids are loaded with stirring in a molar ratio of condensation product: acid equal to 1: 1, stirred for 2-4 hours, cooled to 40-60 ° C and introduced with stirring 2-8% (wt.) of the surfactant of nonionic type, 1-25% (wt.) C ₁ -C ₄ saturated monohydric alcohol , 32-73% (wt.) Composite aromatic solvent. [RF patent 2239671, publ. November 10, 2004, Bull. No. 31].

A known method of obtaining a corrosion inhibitor based on the condensation product of polypropylene polyamines with higher isomeric monocarboxylic acids or synthetic fatty acids, followed by cyanethylation, hydroxyalkylation, alkylation and the manufacture of the inhibitor by adding a solvent to a certain part of the active base. Polypropylene polyamines or their technical mixture are used as amines, and higher isomeric α-branched monocarboxylic acids with C ₆ -C ₂₈ carbon atoms or synthetic fatty acids with C ₁₀ -C ₂₈ carbon atoms are used as monocarboxylic acids [RF Patent 2267562, publ. 01/10/2006, Bull. No. 1].

A disadvantage of the known methods for producing corrosion inhibitors is the use of α-branched monocarboxylic acids - the lack of their production.

The closest in technical essence and the achieved results is a method of obtaining a corrosion inhibitor by the interaction of polyethylene polyamines, polyethylene propylene polyamines and polypropylene polyamines with dichloroethane or 1,2-dichloropropane with isomeric α-branched monocarboxylic acids with carbon atoms C ₅ -C ₂₈ at 250-280 ° C followed by the reaction of obtaining imdazolines with haloalkyls acrylonitrile and alkylene oxides at 40-80 ° C [RF Patent 2135483, publ. 08/27/1999

The disadvantage of this method of obtaining a corrosion inhibitor is the multi-stage technology, the absence of α-branched monocarboxylic acids, the relatively low protective effect.

The objective of the invention is to develop a method for producing corrosion inhibitors, expanding the raw material base and assortment of corrosion inhibitors, using affordable and cheap raw materials and materials, simplifying the technology for its production, improving performance indicators.

The technical result when using the invention is expressed in obtaining an active base of a corrosion inhibitor from polyethylene polyamine and oleic acid or an oxidation product of 2-ethylhexene aldehyde under milder conditions, using a relatively smaller amount of active base and a cheap solvent.

The above result of obtaining corrosion inhibitors is achieved by the fact that PEPA interacts with oleic acid or the oxidation product of 2-ethylhexene aldehyde with an acid number of 155-165 mgKOH with a molar ratio of the starting reagents equal to 1-1.1: 1.0, at a temperature of 120-180 ° C for 4 hours, then at a temperature of 180-230 ° C for 3 hours and at 230-250 ° C for 2 hours with simultaneous distillation of water and low-boiling components.

After which the reaction mixture is cooled, mixed with a solvent - bottoms of butyl alcohols (BACS) and toluene, neonol (surfactant) at a temperature of 25-60 ° C for 1.5-2.0 hours.

The active base (AO), COBS, toluene, neonol are taken in the following proportions, wt.%:

AO fifteen COBS 65-70 Toluene 11-16 Neonol 3-4

Polyethylene polyamines (PEPA) are a mixture of individual amines - diethylene triamine (DETA), triethylenetetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEG), etc. general formula H ₂ N (CH ₂ ) ₂ NH (CH ₂ CH ₂ NH) _n H, where n = 0,1,2,3,4 ... or more.

PEPA consists mainly of DETA (n is 1), TETA (n is 2), TEPA (n is 3), PEGA (n is 4), etc. PEPA are produced at Sterlitamaksky OJSC "Caustic" TU2413-214-00203312-2002. The authors of the proposed method identified by rectification fractions containing mainly DETA (light PEPA), containing mainly TETA (medium PEPA), containing mainly TEPA, PEGA, etc. (heavy PEPA). The average molecular weight of the light fraction is 130 g / mol, the middle fraction is 170 g / mol, the heavy fraction is 200 g / mol.

The method is illustrated by the following examples.

Example 1. a) In a reactor equipped with a mechanical stirrer, thermometer, reflux condenser, 85 g (0.5 mol) of medium fractions of polyethylene polyamines (PEPA) (M. weight 170 g / mol) and 141 g (0.5 mol) are loaded oleic acid, the temperature of the reaction mixture is raised to 140-150 ° C with the simultaneous distillation of water and boiling impurities under a stream of nitrogen, stirred at this temperature for 4 hours and another 3 hours at 180-230 ° C. The reaction mixture was maintained at 230-240 ° C for one hour. As a result, derivatives of 2-alkylimidazoline (imidazoline) with an acid number of 8-12 mg KOH / g (active base of the corrosion inhibitor) are predominantly formed.

b) preparation of a corrosion inhibitor formulation.

Take 15 g of the active base, 65 g of COBBS, 16 g of toluene and 4 g of neonol and stirred at 25-60 ° C for 1.5-2 hours and then determine the protective properties. The test results are shown in the table.

Example 2. Under the conditions of example 1, 65 g (0.5 mol) of light fractions of PEPA (M. weight 130 g / mol) and 141 g (0.5 mol) of oleic acid are charged to the reactor, heated to a temperature of 140 ° C and stirred at a temperature of 140-150 ° C for 4 hours, then another 3 hours at 180-230 ° C with simultaneous distillation of water and impurities (light impurities of amines) under a stream of nitrogen, after which the contents of the reactor were kept at 240 ° C for 1 hour . As a result, derivatives of 2-alkylimidazoline (imidazoline) with an acid number of 8-12 mg KOH / g (active base of the corrosion inhibitor) are predominantly formed.

b) in the conditions of paragraph 1 of paragraph. b) a mixture of 15 g of the active base, 70 g of COBBS, 11 g of toluene and 4 g of neonol is stirred at 20-40 ° C for 1.5 hours. Protective properties are given in the table.

Example 3. Under the conditions of example 1, 88 g (0.55 mol) of PEPA (M. weight 160 g / mol) and 169.4 g (0.5 mol) of the oxidation product of 2-ethylhexene aldehyde with an acid number of 165 mgKOH are charged into the reactor / g (average molecular weight 338.4), stirred at a temperature of 120-130 ° C under a stream of nitrogen for 3 hours with simultaneous distillation of water and boiling components, then at a temperature of 140-230 ° C for 3 hours and kept at 230-245 ° C for 1.5 hours. The calculated amount of water corresponding to the formation of imidazolines and amidoamines is isolated.

b) the preparation of the commodity form (formulation) of the corrosion inhibitor. A mixture of 15 g of the active base, 66 g of COBBS, 16 g of toluene and 3 g of neonol is stirred at 25-50 ° C for 2 hours and then the protective properties are determined, which are shown in the table.

Example 4. Under the conditions of example 1, 100 g (0.5 mol) of heavy PEPA fractions (M. weight 200 g / mol) and 169.4 g (0.5 mol) of the acid product of 2-ethylhexene aldehyde with an acid number are loaded into the reactor 155 mgKOH / g (average molecular weight 362), stirred at a temperature of 160-180 ° C for 3 hours, at a temperature of 190-230 ° C for 3 hours and kept at 245-250 ° C for 1.5 hours.

b) to prepare a commodity form, take a mixture of 15 g of the active base, 65 g of COBBS, 16 g of toluene and 4 g of neonol, which is stirred at 30-60 ° C for 1.5-2 hours, then the protective properties are determined, which are given in table.

Example 5. A mixture of 14 g of an active base based on PEPA and oleic acid, 80 g of COBS, 4 g of toluene and 2 g of neonol is stirred at 25-40 ° C for 1 hour and the protective properties are determined. The results are shown in the table.

Example 6. A mixture of 20 g of an active base based on PEPA and oleic acid, 50 g of COBS, 25 g of toluene and 5 g of neonol is stirred at 25-30 ° C for 0.5 hours. The experimental results are shown in the table.

Examples 1-4, provided that the claimed process parameters are maintained, confirm the high protective properties of the obtained corrosion inhibitors.

Examples 5-6 indicate that a deviation from the claimed process parameters leads to a decrease in the protective properties of corrosion inhibitors. To a small extent, the protective properties increase with an increase in the amount of active base within 20% (example 6), p. 11-12 of the table.

Corrosion inhibitor test results for protective efficacy. No. p / p The composition of the corrosion inhibitor, wt.% Dosage, mg / l Protective action,% one 15% active base (AO) according to example 1, 65% COBS, 16% toluene, 4% neonol thirty 98.8 2 15% active base (AO) according to example 1, 70% COBS, 11% toluene, 4% neonol fifty 99,4 3 15% active base (AO) according to example 2, 70% COBS, 11% toluene, 4% neonol thirty 98.2 four 15% active base (AO) according to example 2, 65% COBS, 16% toluene, 4% neonol fifty 99,2 5 15% active base (AO) according to example 3, 66% COBS, 16% toluene, 3% neonol thirty 99.0 6 15% active base (AO) according to example 3, 70% COBS, 12% toluene, 3% neonol fifty 99.5 7 15% active base (AO) according to example 4, 65% COBS, 16% toluene, 4% neonol thirty 98.6 8 15% active base (AO) according to example 4, 70% COBS, 12% toluene, 3% neonol fifty 99.3 9 14% active base (AO) according to example 5, 80% COBS, 4% toluene, 2% neonol thirty 84.0 10 14% active base (AO) according to example 5, 80% COBS, 4% toluene, 2% neonol fifty 89.2 eleven 20% active base (AO) according to example 6, 50% COBS, 25% toluene, 5% neonol thirty 90.6 12 15% active base (AO) according to example 6, 55% COBS, 25% toluene, 5% neonol fifty 92.4

Claims (1)

A method of producing corrosion inhibitors for oilfield, mineralized and hydrogen sulfide-containing environments using the interaction of individual amines or their technical mixture with higher isomeric monocarboxylic acids as the active product base, followed by mixing with a solvent and dispersant, characterized in that the active base is obtained by the interaction of polyethylene polyamines with oleic acid or an oxidation product of 2-ethylhexene aldehyde with an acid number of 155-165 mg KOH / g in molar ratio and initial reagents equal to 1.0-1.1: 1, at a temperature of 120-180 ° C for 3-4 hours, then at a temperature of 180-230 ° C for 3 hours and at 230-250 ° C for 1-2 hours, by mixing with the bottom residue of the production of butyl alcohols, toluene and neonol at a temperature of 25-60 ° C for 1.5-2.0 hours in the following ratio of starting components, wt.%: Active foundation fifteen VAT residue production of butyl alcohols 65-70 Toluene 11-16 Neonol 3-4