RU2298555C1 - Oxyethylated alkyl- (or phenol)methyl- or ethyl phosphites of n-methyl- or ethylalkylammonium as corrosion inhibitors possessing bactericidal activity with respect to sulfate-reducing microorganisms - Google Patents

Abstract

FIELD: chemistry of organophosphorus compounds.

SUBSTANCE: invention relates to nitrogen- and phosphorus-containing compounds. Invention describes oxyethylated alkyl- (or phenol)methyl- or ethyl phosphites of N-methyl- or ethylalkylammonium of the general formula:

, wherein R means i-C₉H₁₉-C₆H₄-(OCH₂CH₂)_n (wherein n = 4, 6, 10, 12), C_8-10H_17-37-(OCH₂CH₂)₆; R₁ means CH(CH₃)-C_nH_2n+1 (wherein n = 8-18), C_8-18H_17-37; R₂ means hydrogen atom (H), -CH₃, -C₂H₅ as a corrosion inhibitor and bactericidal agent with respect to sulfate-reducing microorganisms and as a reagent for prevention of hydrogen sulfide formation in petroleum bed and for replacing the oil. Also, invention describes a corrosion inhibitor, i. e. bactericidal agent in mineralized aqueous and aqueous-oil media comprising a base and a solvent wherein inhibitor comprises oxyethylated alkyl- (or phenol)methyl- or ethyl phosphites of N-methyl- or ethylalkylammonium by claim 1 as an active base and taken in the following ratio, wt.-%: oxyethylated alkyl- (or phenyl)methyl- or ethyl phosphites of N-methyl- or ethylalkylammonium, 20-80, and solvent, the balance. The present invention is based on the development of effective corrosion inhibitor soluble in mineralized waters and possessing the bactericidal effect with respect to sulfate-reducing microorganisms that can be used as a reagent for prevention of formation of hydrogen sulfide in oil bed and as additive to water for replacing oil from the bed. Proposed compounds can be used as agents for protection of oil field equipment against hydrogen sulfide and microbiological corrosion, in output systems, transport and storage of oil, in flooded oil beds and in secondary methods in oil output.

EFFECT: valuable technical properties of compounds.

2 cl, 6 tbl, 7 ex

Description

The invention relates to the chemistry of organophosphorus compounds, in particular to nitrogen and phosphorus-containing compounds that can be used as means of protecting oilfield equipment from hydrogen sulfide and microbiological corrosion, in production systems, transportation, oil storage, in flooded oil reservoirs and in secondary production methods oil.

A known corrosion inhibitor is a bactericide, which is a compound based on hydrogen chloride and islamine alkyl amines called ANP-2 to prevent the formation of hydrogen sulfide in a water-flooded formation of the general formula:

,

,

(ed. certificate of the USSR No. 652315, Cl. E21B 43/00, 1979).

The ANP-2 corrosion inhibitor has a number of disadvantages that limit its use: it has a low degree of corrosion protection (100 mg / l) and the suppression of SVB (300 mg / l).

The closest in chemical nature and the achieved inhibitory and bactericidal effect are known alkylammonium salts of phosphorus acids, which are obtained by the traditional method of interaction of a phosphorus-containing compound and an amine, for example, N-methyldodecylammonium O-methylphosphite of the formula:

which is obtained by reacting dimethylphosphorous acid and dodecylamine. (Oil industry No. 2, 1991, p.29-31. R.F. Tishankina, I.M.Shermergorn and others)

However, the known corrosion inhibitor-bactericide is not effective enough due to its poor dispersibility in mineralized waters, it has a high pour point.

The basis of the present invention is the creation of an effective, water-soluble corrosion inhibitor with a bactericidal action against sulfate-reducing bacteria, which can be used as a reagent to prevent the formation of hydrogen sulfide in the oil reservoir, and also as an additive to water to displace oil from layer.

The problem is solved by the synthesis of hydroxyethylated alkyl- (or phenol) methyl or ethylphosphites N-methyl or ethylalkylammonium of the general formula:

Where:

R = i-C ₉ H ₁₉ -C ₆ H ₄ - (OCH ₂ CH ₂ ) _n (n = 4, 6, 10; 12), C _8-10 H _17-37 (OCH ₂ CH ₂ ) ₆ ;

as a corrosion inhibitor and bactericide against sulfate-reducing bacteria and as a reagent for preventing the formation of hydrogen sulfide in the oil reservoir and for displacing oil and a corrosion-bactericide inhibitor in mineralized aqueous and oil-water environments, including methyl or ethyl phosphites N-methyl or ethylalkylammonium in the following ratio wt.%:

Oxyethylated alkyl (or phenol) methyl or ethyl phosphites N-methyl or ethylalkylammonium 20-80 Solvent Rest

Hydroxyethylated alkyl (or phenol) methyl or ethylphosphites N-methyl or ethylalkylammonium is obtained by reacting aminoparaffins with hydroxyethylated alkyl (or phenol) methyl or ethylphosphites while stirring the reaction mixture at a temperature of 70-110 ° C.

Hydroxyethylated alkyl- (or phenol) methyl or ethylphosphites are hydroxyethylated isononylphenol methyl or ethylphosphites or methyl or ethylphosphites of ethoxylated fatty alcohols, which are prepared in a known manner (E.E. Nifantiev, Chemistry of Organophosphorus Compounds, ed. Moscow University, 1971, p. 71 ; Usp. Chemistry. 1978, 47, No. 9, p. 1565) of the interaction by mixing hydroxyethylated alkyl phenol or hydroxyethylated fatty alcohol with dialkylphosphite while heating the reaction mixture to a temperature of 100-150 ° C with removal of methanol ( reaction product) by purging with an inert gas.

The following are used as ethoxylated alkyl phenol: monoalkyl phenols based on propylene trimers — ethoxylated neonols AF 9-4, AF 9-6, AF 9-10, AF 9-12 with C ₉ alkyl and the number of hydroxyethyl groups equal to 4, 6, 10, 12 according to TU 2483-077-05766801-98, or polyethylene distillate-based ethylene alkyl phenols - OP-4, 7, 10 with C ₈ -C ₁₀ alkyl and the number of hydroxyethyl groups equal to 4, 7, 10 according to GOST 8433-81, respectively. (Surfactants, Handbook, edited by A.A. Abramzon and G.M. Gayev, L., Chemistry, 1979, p.305) (Technical conditions 38.507-63-171-91).

As ethoxylated fatty alcohol use ethoxylated fatty alcohols fr. C ₈ , C ₁₀ with the number of hydroxyethyl groups equal to 6, the so-called oxanol KD-6-; or syntanol DT-7 - ethoxylated fatty alcohol fr. C ₁₀ -C ₁₃ with the number of hydroxyethyl groups equal to 7; or syntanol DS-10- ethoxylated fatty alcohol fr. C ₁₀ -C ₁₈ with the number of hydroxyethyl groups equal to 8-10. (Surfactants, Handbook, edited by A.A. Abramzon and G.M. Gaevoy, L .: Chemistry, 1979, pp. 302-303).

As dialkyl phosphite take diethyl phosphite or dimethyl phosphite according to TU 6-36-5763445-6-88.

Examples of the preparation of hydroxyethylated alkyl (or phenol) methyl or ethyl phosphites.

Example 1

One mole of dimethylphosphorous acid is introduced to one mole of the ethoxylated isononylphenol AF 9-12, and the reaction mixture is stirred at a temperature of 100-150 ° C for 3 hours while stirring the reaction mixture. The process is carried out with distillation of methanol by blowing inert gas.

Examples 2-7 are conducted in a similar way, changing the source and the ratio of the mass fractions of the source (in grams) depending on their molecular weight.

The data are summarized in table 1.

где n= от 8 до 18;As aminoparaffins take amines of the formula

where n = from 8 to 18;

or amines of normal structure with the general formula H ₂ NR with the number of carbon atoms in the radical R from C ₈ to C ₁₈ .

Obtaining the claimed hydroxyethylated alkyl- (or phenol) methyl or ethylphosphites N-methyl or ethylalkylammonium:

Example 1

To the ethoxylated isononylphenolmethylphosphite of formula A (example 1, table 1), where n = 12

water and an alkylamine of the formula are introduced

Phosphite, water and alkylamine are successively mixed in a molar ratio of 1: 1.5: 1. Within 2 hours, the process is carried out at a temperature of 80 ° C. The yield of the substance is determined by the amine number in mg HCl / g (with an amine number equal to zero, the yield is 100%). When a constant amine value is reached, synthesis is stopped. The product yield is 99.3%. The resulting product is a homogeneous viscous liquid with a pour point of + 5 ° C.

Example 2

To the ethoxylated isononylphenolmethylphosphite of formula A, where n = 10, water and an alkylamine of the formula are added

Phosphite, water and alkylamine are successively mixed in a molar ratio of 1: 1.5: 1. The process is carried out at a temperature of 80 ° C for 2 hours. The yield of the substance is determined by the amine number in mg HCl / g (with an amine number equal to zero, the yield is 100%). When a constant amine value is reached, synthesis is stopped. The product yield is 99.5%. The resulting product is a homogeneous viscous liquid with a pour point of 0 ÷ + 5 ° C.

Example 3

To the ethoxylated isononylphenolmethylphosphite of the formula A, where n = 6, an alkylamine of the formula is introduced in a 1: 1 molar ratio

The interaction process is carried out for 5 hours at a temperature of 80 ° C. The yield of the basic substance is controlled by the amine number in mg HCl / g. When a constant amine value is reached, synthesis is stopped. The product yield is 96%. The resulting product is a homogeneous viscous liquid with a pour point of minus 1-3 ° C.

Example 4

To the ethoxylated isononylphenolmethylphosphite of formula A, where n = 4, an alkylamine of the formula C ₁₂ H ₂₅ NH ₂ is introduced in a 1: 1 molar ratio. The process of interaction with the control of the amine number is carried out for 4-6 hours at a temperature of 95 ° C. The yield is 97%. The resulting product is a homogeneous liquid with a pour point of minus 10 ° C.

Example 5

To one mole of the ethoxylated octyl methylphosphite of formula B:

water and alkylamine C ₁₂ H ₂₅ NH ₂ are sequentially introduced in a molar ratio of 1: 1.5: 1. The interaction process is carried out with stirring the mixture for 1 hour at a temperature of 80 ° C. The process is monitored by the amine number in mg HCl / g. When a constant amine value is reached, synthesis is stopped. The yield is 100%. The resulting product is a homogeneous viscous liquid with a pour point of minus 1 ° C.

Example 6

To one mole of ethoxylated decylmethylphosphite of the formula C:

administered in a 1: 1 molar ratio alkylamine of the formula

The interaction process is carried out for 3 hours at a temperature of 80 ° C. The yield of the substance is controlled by the amine number in mg HCl / g. When a constant amine value is reached at 80 ° C, the temperature of the reaction mixture is raised to 100 ° C. Synthesis is continued at this temperature for one hour. The product yield is 99%. The resulting product is a homogeneous liquid with a pour point of minus 10-13 ° C.

Example 7

To one mole of ethoxylated isononyl phenol ethyl phosphite of formula D:

alkylamine C ₁₄ H ₂₉ NH ₂ is introduced in an amount of one mole. The interaction process is carried out with stirring the mixture for 2 hours at a temperature of 80 ° C. When a constant amine number is reached at this temperature, the temperature of the reaction mixture is raised to 100 ° C. Synthesis is continued at this temperature for two hours. The product yield is 99%. The resulting product is a homogeneous liquid with a pour point of minus 4 ° C.

The data in examples 1-7 are summarized in table 2.

The IR spectra of the obtained products contain bands of stretching vibrations of the P = O group at 1225-1230 cm ^-1 , a shift of this band to lower frequencies (1) indicates the presence of P-O ^- bonds in the molecules (2). Chem. _p σ31 shifts them lie in the + 1- + 4 ppm Displacement chem. A shift to weak fields is characteristic of amine compounds with phosphorus acids (3).

1. Thomas L.C., Chittenden R.A. Spectrochim. Acta. - 1964. - V.20. - P.467.

2. Bellamy L. Spectra of complex molecules. M., 1963.

3. Topics in Phosphorus Chemistry. - 1967, 5. - P.489.

Data on the physicochemical properties of the compounds are given in table.3.

The proposed product is tested as a corrosion inhibitor in mineralized aqueous and oil-water environments containing hydrogen sulfide and carbon dioxide. Assessment of the protective properties of the obtained compounds is performed according to GOST 9.50687. As an aggressive environment using a model of produced water with a density of 1.12 g / DM ³ . The content of hydrogen sulfide in the experiments is 100 mg / l, dissolved carbon dioxide - 1000 mg / l. The degree of reduction of hydrogen corrosion in a medium of 5% NaCl + 0.5% CH ₃ COOH was determined at a hydrogen sulfide concentration of 200 mg / L (NACE standard). The exposure time of the metal plates was 336 hours. In all corrosion tests, steel 3 was used as metal samples.

In a water-oil medium, the protective properties of the obtained products are evaluated at a ratio of oil / saline water of 1: 4. The inhibitor is injected onto the surface of the oil. The inhibition effect (in%) is determined according to GOST 9.50687 in the aqueous phase of the oil-water mixture, which contains 100 mg / l of dissolved hydrogen sulfide.

The bactericidal activity of the compounds is carried out in accordance with the methodological recommendations RD 39-3-973-83, 1984, "Methodology for controlling the microbiological contamination of oilfield waters and evaluating the bactericidal effect of reagents." The studies are carried out using an accumulative culture of sulfate-reducing bacteria (SBB), isolated from oilfield water deposits in Western Siberia. Effective are those concentrations of compounds that provide 100% suppression of SVB, i.e. the nutrient medium with SVB into which the inhibitor was introduced remains transparent for 15 days, while the medium without the inhibitor blackens.

The test results of the protective and bactericidal efficacy are given in table.2.

The data in Table 2 allow us to conclude that, in terms of their effectiveness, corrosion protection (90-99% at a concentration of 2.0-3.0 mg / l) in aqueous and water-oil media containing hydrogen sulfide or carbon dioxide, and 100% - the bactericidal action against SVB at a concentration of 10-20 mg / l, the proposed O-hydroxyethylated alkyl (phenol) methyl- or ethylphosphites of N-methyl- or ethylalkylammonium are highly effective reagents. They are superior in their anticorrosive efficiency to O-methylphosphite N-methyldodecylammonium, whose anticorrosive activity is 78-81% at a concentration of 3 mg / L. The bactericidal efficacy of the proposed compounds No. 4,6,7 also exceeds the effectiveness of O-methylphosphite N-methylodecylammonium, 100% bactericidal effect of which is achieved at 10 mg / L.

The advantage of using the proposed compounds is their solubility in water, high efficiency as corrosion inhibitors in aqueous and in oil-water environments containing dissolved hydrogen sulfide and carbon dioxide, high bactericidal activity against SVB, and the availability of a raw material base for their production.

The resulting compounds are dissolved in organic solvents. Aliphatic alcohols, for example, are taken as organic solvents: methanol (MS), ethanol (ES), butanol (BS), isopropanol (IPA); aromatic solvent: nefras AR 120/200, nefras 150/330 or a mixture thereof.

Corrosion inhibitors-bactericides in a solvent are tested similarly to the methods described above. The data are summarized in table 4.

From the data given in table 4, it can be seen that the claimed compounds in solutions provide high efficiency as corrosion inhibitors in aqueous and oil-water environments containing dissolved hydrogen sulfide and carbon dioxide, as well as high bactericidal activity against SVB.

The claimed compounds and their solutions in these solvents are tested as reagents to prevent the formation of hydrogen sulfide in a water-filled oil reservoir and as an additive to water during water flooding of a reservoir for oil displacement.

As a prototype for comparing the effectiveness of the reagent to prevent the formation of hydrogen sulfide in a water-flooded oil reservoir, a bactericide was taken according to ed. testimonial. USSR No. 652315, Cl. ЕВВ 43/00, 1979. The test data are presented in table.5.

The use of hydroxyethylated alkyl or (phenol) methyl- or ethyl phosphites N-methyl or ethylalkylammonium prevents the formation of hydrogen sulfide in the oil reservoir and its penetration into the production of wells.

As an additive to water for displacing oil from a formation, the claimed compounds are tested on a model of an oil formation representing a tube filled with crushed rock. To create the oil saturation of the model, oil was used from fields in Western Siberia and OAO Tatneft. Before the introduction of the test reagent, the porous medium after water displacement with water had a water cut of 100%. Data on the increase in oil displacement when using this technology are given in table.6.

Table 6 No. p / p Example No. The concentration of the compound in water, mg / l The increase in the coefficient of displacement,% from table 2 from table 4 one four 400 9.0 (oil of Western Siberia) 2 6 400 8.5 (oil of OAO Tatneft) 3 3 700 11.0 (oil of Western Siberia) four four 900 15.3 (oil of OAO Tatneft)

From the data given in table.6 it is seen that the use of the claimed compounds and their solutions as additives to water for oil displacement leads to an increase in the effect of oil displacement.

The proposed hydroxyethylated alkyl or (phenol) methyl or ethyl phosphites of N-methyl (or ethyl) alkyl ammonium expand the range of chemicals that can be used in the oil and gas industry as bactericidal inhibitors. Reagents have an oil-displacing property and the ability to prevent the formation of hydrogen sulfide in the reservoir.

Claims (2)

1. Ethoxylated alkyl (or phenol) methyl or ethylphosphites N-methyl or ethylalkylammonium of the General formula

Where R = I-C ₉ H ₁₉ -C ₆ H ₄ - (OCH ₂ CH ₂ ) _n (n = 4, 6, 10, 12), C _8-12 H _17-37 (OCH ₂ CH ₂ ) ₆ ;

as a corrosion inhibitor and bactericide against sulfate-reducing bacteria and as a reagent to prevent the formation of hydrogen sulfide in the oil reservoir and to displace oil. 2. A corrosion inhibitor is a bactericide in mineralized aqueous and water-oil media, including an active base and a solvent, characterized in that it contains, as an active base, the ethoxylated alkyl (or phenol) methyl or ethylphosphites N-methyl or ethylalkylammonium according to claim 1 with the following ratio, wt.%: Oxyethylated alkyl (or phenol) methyl or ethylphosphites N-methyl or ethylalkylammonium 20-80 Solvent Rest