RU2464359C2 - Corrosion inhibitor-bactericide - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: inhibitor contains a product of reacting primary aliphatic amines of general formula RNH₂, where R-N- is an alkyl with 10-16 carbon atoms, with dimethyl phosphite or a mixture of primary and secondary aliphatic amines of general formula RNH₂, where R-N- is an alkyl with 8-30 carbon atoms, in ratio 50-98:2-50, respectively, with industrial dimethyl phosphite, taken in molar ratio 1.0-1.2:0.8-1.0, respectively, wherein the inhibitor additionally contains a product of reacting alkyl-substituted pyridines with alkyl bromides with 10-18 carbon atoms and a nonionic surfactant, with the following ratio of components in wt %: product of reacting primary aliphatic amines with dimethyl phosphite or a mixture of primary and secondary aliphatic amines with industrial dimethyl phosphite 60-70, product of reacting alkyl-substituted pyridines with alkyl bromides 20-25, nonionic surfactant - the balance.

EFFECT: corrosion inhibitor-bactericide is cheap, stable during use and storage, and ensures complete inhibition of sulphate-reducing bacteria.

3 cl, 2 tbl

Description

The invention relates to means for protecting equipment from hydrogen sulfide and carbon dioxide corrosion in mineralized aqueous and oil-water environments and can be used in the oil industry.

A known corrosion inhibitor is a bactericide of hydrogen sulfide corrosion, which is a 0-alkylphosphite N-alkylammonium (RF Patent No. 1434718, BI No. 28.11.86, C07F 9/142).

The specified inhibitor has a high pour point, which complicates its use in the winter.

A known corrosion inhibitor is a bactericide in mineralized hydrogen sulfide-containing aqueous media, including the reaction product of aliphatic amines of the general formula RNH ₂ , where RN-alkyl is C ₈ -C ₁₈ , technical dimethyl phosphite and water taken in a molar ratio of 1: (0.8-1.2 ) :( 0.8-1.2), and a hydrocarbon solvent (RF Patent No. 2038421, C23F 11/00, BI No. 18, 1995).

The disadvantage of the inhibitor is the complexity of the technology for producing the product. Due to the use of water, the process is difficult to control; it can proceed in several directions. This results in a product with reduced potency and viability.

Known corrosion inhibitor-bactericide - N-alkyl -2 methyl-5-ethylpyridinium bromide with alkyl C ₈ -C ₂₀ (Japan Patent No. 37-7237, CL C07D 213/20, publ. 05.07.1962).

However, the known inhibitor is a bactericide expensive, low-tech in use due to the increased pour point and not effective enough.

The closest in technical essence and the achieved effect is known to be a corrosion inhibitor-bactericide in hydrogen sulfide-containing media, containing the product of the interaction of a mixture of primary and secondary aliphatic amines at a ratio of 50-98: 2-50, respectively, with technical dimethylphosphite taken in a molar ratio of 1.0-1 , 2: 0.8-1.0, respectively. The corrosion inhibitor-bactericide additionally contains a hydrocarbon solvent (RF Patent No. 2128729, C23F 11/167, BI No. 10, 04/10/99).

The specified inhibitor is not effective enough in carbon dioxide oil-water environments.

The objective of the invention is to provide an effective corrosion inhibitor-bactericide in mineralized hydrogen sulfide-containing aqueous and oil-water media containing hydrogen sulfide and carbon dioxide.

The problem posed by the invention is solved so that the corrosion inhibitor is a bactericide, including the reaction product of primary aliphatic amines of the general formula RNH ₂ , where RN is alkyl with the number of carbon atoms C ₁₀ -C ₁₆ , with dimethylphosphite (PV ₁ ) or the reaction product of a mixture of primary and secondary aliphatic amines of the general formula RNH ₂ , where RN-alkyl with the number of carbon atoms C ₈ -C ₃₀ at a ratio of 50-98: 2-50, respectively, with technical dimethylphosphite (PV ₂ ), taken in a molar ratio of 1.0-1.2 : 0.8-1.0, respectively, additionally contains the product the interaction of alkyl substituted pyridines with alkyl bromides with the number of carbon atoms C ₁₀ -C ₁₈ (PV ₃ ) and a nonionic surfactant in the following ratio of components, wt.%:

reaction product of primary aliphatic amines or mixtures of primary and secondary aliphatic amines with technical dimethylphosphite 60-70 reaction product of alkyl substituted pyridines with carbon bromides 20-25 nonionic surfactant rest

In an embodiment, the corrosion inhibitor-bactericide as the product of the interaction of alkyl substituted pyridines with alkyl bromides contains the products of the interaction of 2-methyl-5-ethyl-pyridine, or picoline, or picoline fraction, or 2-methyl-5-vinyl-pyridine with alkyl bromides with the number of carbon atoms in the alkyl C ₁₀ -C ₁₈ .

In a preferred embodiment, the corrosion inhibitor-bactericide further comprises a hydrocarbon solvent in the following ratio of components, wt.%:

Corrosion inhibitor-bactericide according to claim 1 or according to claim 2 20-50 Hydrocarbon solvent rest

As nonionic surfactants use, for example, neonol brand AF9 / 12 or AF9 / 6 according to TU 2483-077-05766801-98.

As a hydrocarbon solvent, the inhibitor may contain, for example, aromatic and aliphatic solvents or mixtures thereof, for example,

- methyl alcohol (MS)

- isobutyl alcohol (IHD)

- isopropyl alcohol (IPA)

- butyl alcohol (BS)

- orthoxylene according to TU 38.101254-72 with amendment 1-9

- oil solvent according to TU 38.1011049-98

- butylbenzene fraction (BBF) according to TU 38.10297-78

- diethylbenzene fraction (DEBP) according to TU 38.102144-90

- ethylbenzene fraction (EBF) according to TU 6-01-10-37-78

- Nefras according to TU 10214-78.

The product of the interaction of primary aliphatic amines of the general formula RNH ₂ , where RN is alkyl with the number of carbon atoms C ₁₀ -C ₁₆ , with dimethylphosphite (PV ₁ ) is obtained in a known manner by reacting primary aliphatic amines with dimethylphosphite (RF Patent 1434718, C07F 9/142, publ. 11/28/86, example No. 12). 3.61 g of cetylamine and 1.65 g of dimethylphosphite are taken, heated to 85 ° C. A viscous clear mass is obtained. Yield 92%.

The reaction product of a mixture of primary and secondary aliphatic amines of the general formula RNH ₂ , where RN is alkyl with the number of carbon atoms C ₈ -C ₃₀ with technical dimethylphosphite (PV ₂ ) is obtained in a known manner (RF Patent No. 2128729, C23F 11/167, publ. 10.04 .99, example No. 1). 108 g of technical dimethyl phosphite are taken and 200 g of a C ₁₀ -C ₁₆ amine containing 180 g of primary and 20 g of secondary amine are added with stirring. The process temperature is 70 ° C for 2 hours. A homogeneous viscous mass of light brown color is obtained. Yield 99%.

The product of the interaction of picolina or picolina fraction with alkyl bromides with the number of carbon atoms C ₁₀ -C ₁₆ (PV _3-1 ) is obtained in a known manner (RF Patent No. 2261293, C23F 11/14, publ. September 27, 2005, example No. 1). The interaction is 1.0 mole of alkyl bromide and 1.03 mole of picolines. Picolins are added in several stages. Initially, 0.35 mol (42.5 kg) of picolins are added to 250 g of dodecyl bromide, stirred and heated to 130 ° C, after another 40 minutes, 0.35 mol is added, mixed, after 40 minutes the remaining 0.35 mol is introduced (42, 5 kg) picolines. The process is carried out with stirring for 5 hours at a temperature not exceeding 130 ° C. A fusible, crystalline substance of a light brown color is obtained.

The product of the interaction of 2-methyl-5-ethyl-pyridine with alkyl bromides with the number of carbon atoms in the alkyl C ₁₀ -C ₁₆ (PV _3-2 ) is obtained in a known manner (RF Patent No. 2243291, C23F 11/14, publ. 27.12.2004, example 1). Dodecyl bromide and methyl ethyl pyridine (MEP) are taken at a molar ratio of 1.05: 1, respectively, with MEP being administered in three stages of 0.35 mol with an interval of 40-50 minutes in time at a process temperature of 120-140 ° C. A brown fusible crystalline material is obtained.

The reaction products of 2-methyl-5-vinyl-pyridine with alkyl bromides (PV _3-3 ) are obtained in a known manner by the interaction of 2-methyl-5-vinyl-pyridine with alkyl bromides in their molar ratio of 1.05: 1, respectively. Take 133 kg of 2-methyl-5-vinyl-pyridine according to TU 38.103490-80 as amended. 1-5 and 250 kg of normal alkyl bromides with a carbon atom content of 10 to 16 in the alkyl radical. The process is carried out under the conditions described above for the reaction products of PV _3-1 and PV _3-2 . The resulting product is a low-melting crystalline, dark brown color.

An inhibitor is prepared by mixing the components.

To prove the compliance of the claimed inhibitor with the criterion of "industrial applicability", we present the specific compositions of the claimed corrosion inhibitor-bactericide: examples No. 1-11 - without solvent, and No. 12-28 - with solvent (table 1).

The resulting inhibitor without solvent is a homogeneous viscous-mobile mass, with a solvent - a homogeneous, mobile fluid with a pour point of not higher than minus 30-40 ° C.

The resulting compositions are evaluated as corrosion inhibitors, determining their protective effect, and antibacterial activity (table 2).

The protective effect in mineralized hydrogen sulfide-containing aqueous media is determined in accordance with OST 39-099-79 “Corrosion inhibitors. A method for evaluating the effectiveness of the protective effect of corrosion inhibitors in oilfield wastewater. " The determination is carried out by the gravimetric method in the circulation cells in an inhibited standard model of produced water containing 100 mg / l of hydrogen sulfide.

The effectiveness of the inhibitor in oil-water environments is carried out in accordance with RD 39-3-519-81 by the electrochemical method. Initially, a water-oil emulsion is prepared. To do this, in each of the two tanks, equipped with a stirrer, pour oil and a model of mineralized water in a ratio of 1: 4. The calculated amount of inhibitor is poured into one of the containers. The contents of the containers are mixed at a speed of 500 rpm. The finished emulsion is poured into a separatory funnel and, after separation of the emulsion, the aqueous phase is deaerated. Deoxygenated water is transferred into two cells in which the water is saturated with carbon dioxide and additionally hydrogen sulfide. Further in these cells the corrosion rate is measured. The effectiveness of the protective effect of the inhibitor is evaluated by the difference in the readings of the corrosion rate in inhibited and non-inhibited environments.

Antibacterial effectiveness is determined according to RD 03-00147275-067-2001 "Assessment of infection of oilfield environments and bactericidal action of reagents with respect to sulfate-reducing bacteria."

Analysis of the data presented in tables 1 and 2 shows that the proposed corrosion inhibitor-bactericide is a more effective inhibitor in mineralized aqueous and oil-water environments containing hydrogen sulfide and carbon dioxide. The reagent exhibits bactericidal properties, is stable during use and storage, and is also more economical to use compared to the prototype.

Claims (3)

1. A corrosion inhibitor is a bactericide to protect equipment from hydrogen sulfide and carbon dioxide corrosion in mineralized aqueous and oil-water environments, including the reaction product of primary aliphatic amines of the general formula RNH ₂ , where RN is alkyl with the number of carbon atoms C ₁₀ -C ₁₆ with dimethyl phosphite or mixtures of primary and secondary aliphatic amines of the general formula RNH ₂ , where RN is alkyl with the number of carbon atoms C ₈ -C ₃₀ , at a ratio of 50-98: 2-50, respectively, with technical dimethylphosphite, taken in a molar ratio of 1.0- 1.2: 0.8-1.0 respectively However, characterized in that it further comprises a reaction product of alkyl substituted pyridines with alkyl bromides with a number of carbon atoms of C ₁₀ -C ₁₈ and a nonionic surfactant in the following ratio, wt.%:
reaction product of primary aliphatic amines with dimethyl phosphite or a mixture of primary and secondary aliphatic amines with technical dimethyl phosphite 60-70 reaction product of alkyl substituted pyridines with alkyl bromides 20-25 nonionic surfactant rest 2. The corrosion inhibitor-bactericide according to claim 1, characterized in that, as the product of the interaction of alkyl substituted pyridines with alkyl bromides, it contains the product of the interaction of 2-methyl-5-ethyl-pyridine with alkyl bromides, or the product of the interaction of picoline or picoline fraction with alkyl bromides, or the product of the interaction of 2-methyl-5-vinyl-pyridine with alkyl bromides. 3. The corrosion inhibitor is a bactericide according to claim 1 or 2, characterized in that it further comprises a hydrocarbon solvent in the following ratio of components, wt.%:
corrosion inhibitor-bactericide 20-50 hydrocarbon solvent rest