Method of preparing corrosion inhibitor-bactericide for hydrogen sulfide-containing and acidic media

FIELD: corrosion protection.

SUBSTANCE: invention, in particular, relates to protection of oil-field equipment to suppress vitality of microorganisms and to inhibit corrosion in hydrogen sulfide-containing and acidic media, in oil production, transportation, and storage systems as well as in flooded formations. Task is solved by that, in a method of preparing corrosion inhibitor-bactericide, alkyl-substituted pyridines are brought into reaction alkyl bromides at elevated temperature, said alkyl-substituted pyridines being picolines or picoline fractions at molar ratio of picolines or picoline fractions to C₁₀-C₁₆-alkyl bromides 1.05:1. Picolines or picoline fractions are introduced into three-step reaction each time by 0.35 mole with time interval 40-50 min, while overall reaction proceeds for 2-5 h at 120-140°C. If necessary, reaction product is mixed with solvent to form 20-70% reagent solution.

EFFECT: simplified preparation technology and imparted hydrogen sulfide bacteria growth suppression.

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The invention relates to a method for protection of oilfield equipment to suppress microorganisms and inhibiting corrosion in hydrogen sulfide, mineralized water and acidic environments, and can be used in the oil industry in the systems of production, transportation and storage of oil and savedname oil reservoirs, including secondary oil production.

A method of obtaining a corrosion inhibitor is a Quaternary pyridinium salts interaction alkyl substituted pyridines with alkylhalogenide when heated to 90°C for 2 hours (application Germany No. 2813126 class. C 23 F 11/10, publ. 12.10.1978 year).

However, the known corrosion inhibitors are not effective in hydrogen sulfide-containing oilfield environments.

A method of obtaining corrosion inhibitor-bactericide by the interaction of celibrated with 2-methyl-5-ethylpyridine in a stream of nitrogen at a temperature of 150-160°C for 6 hours followed by purification of the resulting product is ethyl ether. The output 76% together with the hydrobromide, which is a side product of the reaction (U.S. Pat. U.S. No. 2909525, class of 260-240, 1959).

However, the known method is not enough economical as cleaning stage requires the construction of additional facilities, vzryvopozharoopasnyh performed, has come izkuyu yield of the target product, requires create an inert environment, and without the selection of the target product has a low effect of inhibition.

Closest to the present invention is a method of producing a corrosion inhibitor-bactericide - N-alkyl-2-methyl-5-ethylenedibromide, where the alkyl, C₈-C₂₀. The process is carried out at a temperature of 110°C for 1 hour, the reaction products purified additionally by ethyl acetate. The yield of the target product is 85% together with hydrogen bromide (Japan patent No. 37-7237, CL 07 In 213/20 publ. 05.07.1962). The disadvantages of this method are: low-tech, the need for purification stages ethyl acetate, the fire this stage, the duration of the process.

Education byproduct hydrobromide 2-methyl-5-ethylpyridine adversely affect the antibacterial and corrosion performance of alkylpyridinium, therefore, when carrying out the process on an industrial scale should the process proceed under conditions that would minimize the formation of by-product, and also to eliminate the purification step and to obtain a highly efficient product.

The problem to which this invention is directed, is to create a new method of obtaining a highly effective corrosion inhibitor-bactericide in hydrogen sulfide and acidic environments, technological, not trebouxiophyceae equipment for purification of the inhibitor.

The problem is solved so that, in the method of producing corrosion inhibitor-bactericide in hydrogen sulfide and acidic environments by reacting alkyl substituted pyridines were synthesized with at elevated temperatures as alkyl substituted pyridines take pikolines (PC), or picolinate fraction (PF) at a molar ratio of pikolines or picolinafen fractions: were synthesized equal to 1.05:1, respectively, and the pikolines or picolinate fraction is introduced into the reaction in three stages 0.35 mole with an interval in time is 40-50 minutes, and the process is conducted at a temperature of 120-140°C for 2-5 hours, the resulting product is if necessary, mixed with a solvent to obtain a reagent containing the product in the amount of 20-70 wt. %.

As the solvent used, for example, aliphatic alcohols methyl (MS), or ethyl (ES), or propyl (PS), or isopropanol (IPA), or butyl (BS), or isobutyl (CHD), or a mixture of aliphatic and aromatic solvents, for example: oil solvent (nefras, THE 10214-78); or a heavy oil solvent (nefras T, TU 38.101809-90); or a heavy oil solvent (nefras ARTICLE, THE 38.1011049-98); or middle distillate process (SDT, TU 38.401-58-196-97); or diethylethanamine fraction of the production of cumene (DABF, THE 38.102144-90), or ethylbenzol is raccio production of cumene in the alkylation of benzene by propylene (ABF, THE 6-01-10-37-78); or butylbenzene fraction of the production of cumene (BBF, THE 38.10297-78) with a ratio of aliphatic and aromatic 1-0,25-4, respectively.

The were synthesized charge saturated, primary, normal structure containing carbon atoms in the alkyl radical of 10 to 16. The pikolines take according to THE 6-09-3037-88 (alpha-picoline), THE 6-09-4478-87 (Beta-picoline), THE 14-7-35-90 (Beta picolina fraction).

The claimed method of receiving is carried out in an industrial reactor equipped with a stirrer and a jacket for cooling water or steam; download allylbromide and picoline or Pikalyovo fraction, mixed and heated to a temperature of 120-140°C for 2-5 hours, and picoline or Pikalyovo fraction is introduced into the reaction in three stages at a 1/3 of the calculated amount of the reagent with interval time-40-50 minutes

Examples of the method of obtaining the inhibitor.

Example 1. In the reactor load 250 kg (1 mol) of dodecylamine and one third of the calculated amount of pikolines 42,5 kg (0,35 mol). The reaction mass is stirred and heated to 130°C. When the temperature rises above this value in the jacket cooling water is supplied. After 40 min, poured the pikolines in the amount of 42.5 mg (0,35 mol) and continue mixing. After 40 minutes add the remaining number pikolines 42,5 kg (0,35 mol). Pace is the atur process constant in the range of 120-130° and the process is continued for 5 hours. The resulting product is a low-melting crystalline material light brown color.

Examples 2-10. Carried out in the same manner as example 1, replacing the original components and their number.

The data in examples 1-10 are summarized in table 1.

Obtained in examples 1-10 products to give them the technology, without reducing effect, is dissolved in a solvent (table 2).

The resulting interaction products have antibacterial and anti-corrosion activity. Antibacterial efficiency determined according to EP 03-00147275-067-2001 "Assessment of contamination oilfield environments and bactericidal action of reagents relative to sulfate-reducing bacteria".

The model produced water free from oxygen, infect sulfatoxymelatonin bacteria (SRB)isolated from oilfield produced water from different fields, and is treated with a reagent in the form of a 0.5%aqueous solution at certain dosages. Samples incubated 24 h at 20-22°C, after which to detect activity of cells in SSC is part of the treated samples contribute to the nutrient medium, placed in a thermostat and incubated for 15 days at 35°C. the Efficiency of the reagent appreciate the amount of released hydrogen sulfide relative to control experiments without the addition is of eagent.

Protective effect determine the gravimetric method of circulating cells in inhibited (with the addition of reagent) standard hydrogen sulfide-containing solution according to OST 39-099-79. "Corrosion inhibitors. Method of assessing the effectiveness of the protective action of corrosion inhibitors in oil-field wastewater".

As an aggressive environment using the model produced water with a density of 1.12 g/DM³when hydrogen sulfide concentration of 100 mg/DM³. Test duration 6 hours. Data examples and the results are given in tables 1,2.

Presented in tables 1,2 data shows that the obtained products have interaction in comparison with the product obtained by the method prototype, higher properties of inhibiting corrosion. At the dosage of 15 mg/DM³the products obtained by the present method, have the effect of 91-98%, while the product according to the method-prototype - 84%; and are also highly effective reagents suppression SSC (100% at the dosage of 12.5 mg/DM³). The claimed method of producing corrosion inhibitor-bactericide does not require purification stages as you get the product of the interaction of (100% output).

The test reagent, obtained by the claimed method for determining the rate of corrosion of the metal is performed on the samples from station 3 according to the requirements of the standards THAT 2458-017-12966038-2002. In the cylinder device for determining corrosion rate is poured 150 cm³inhibited hydrochloric or sulfuric acid and place the rod with three plates so that the plates are completely immersed in the solution. Cylinder with plates placed in a thermostat or a water bath with a temperature of (20±2)°C. After 30 hours, the plates are removed from the solution, washed with water, alcohol, dried and weighed. Then calculate the corrosion rate of the samples and the degree of protection of the metal inhibitor. Hydrochloric acid take 23%concentration; sulfuric acid - 60%concentration.

The results of the test reagent, obtained by the claimed method, the effect of inhibition in acidic environments are presented in tables 3 and 4.

Presented in tables 3,4 data shows that the corrosion rate in 23%hydrochloric acid at a concentration of inhibitor 10 kg/t decreased more than 10 times, and in 60%sulfuric acid is more than 16 times. Protective effect in acid environments is about 90%.

The method of producing corrosion inhibitor-bactericide in hydrogen sulfide and acidic environments by reacting alkyl substituted pyridines were synthesized with at elevated temperature, from which causesa fact, as alkyl substituted pyridines take pikolines or picolinate faction at a molar ratio of pikolines or picolinafen fractions: C₁₀-C₁₆the were synthesized equal to 1.05:1, respectively, and the pikolines or picolinate fraction is introduced into the reaction in three stages 0.35 mole with an interval of time equal to 40-50 minutes, and the process is conducted at a temperature of 120-140°C for 2-5 h, the resulting product is, if necessary, is mixed with a solvent to obtain a reagent containing the product in the amount of 20-70 wt.%.