RU2479614C1 - Bactericidal composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: bactericidal composition contains the following, wt %: a quaternary ammonium chloride salt in commodity form 10-65, at least one amino alcohol from mono-, di-, triethanolamine, methyldiethanolamine, dimethylethanolamine, diethylethanolamine 1-15, aldehyde in commodity form - formalin and/or paraformaldehyde - the balance. The invention is developed in subclaims.

EFFECT: high efficiency and low setting point.

2 cl, 3 tbl, 9 ex

Description

The invention relates to bactericidal compositions used, in particular, in the oil and gas industry to inhibit the growth of sulfate-reducing bacteria (BSC) in oilfield environments and in a water-flooding oil reservoir, and to protect equipment from hydrogen sulfide corrosion.

It is known to use quaternary ammonium compounds as a biocidal reagent for suppressing the growth of SVB in a water-filled oil reservoir and inhibiting corrosion of chlorinated derivatives of organic amines and chloride salts of the quaternary ammonium compounds (Auth. USSR No. 652315, 815985, 1100879, 1102235, 1107540, 1356403, 1422577, 1536770 1570999, RU 2122108, etc.).

The disadvantages of the known reagents are their relatively low biocidal activity and high specific consumption, as well as the high cost and low technology for use in commercial conditions in the winter.

It is also known the use of formaldehyde in the form of an aqueous solution - formalin to inhibit the growth of SVB and inhibit corrosion (Rakhmankulov D.G. et al. Chemical reagents in oil production and transportation. Reference book. M: Chemistry. 1987. P.85). The specified bactericidal composition (formalin) is an affordable and relatively cheap product. However, it is not effective enough and requires high dosages - up to 2 kg / m ³ (Ibragimov GZ and other Chemical reagents for oil production. M: Nedra. 1986. P.129). In addition, the use of formalin in commercial conditions poses technological difficulties due to the polymerization of formaldehyde and precipitation of polyformaldehyde during transportation and storage in the cold season. Polymerization of formaldehyde with the formation of solid products in a water-flooded oil reservoir leads to a decrease in rock permeability, a decrease in injectivity of injection wells and plugging of the reservoir (exploitation of deposits and preparation of oil with a high content of hydrogen sulfide. OI Ser. Oilfield business. M .: VNIIOENG. 1984. Issue 16. P.74).

Known bactericidal composition containing the commercial form of the alkyl derivatives of hexamethylene tetramine chloride (LET-11 bactericide) and additionally bottoms production of synthetic glycerol (Polyglycerins) 30-70% wt. (RU 2078914).

Also known is a biocidal composition for suppressing the growth of SVB in oil fields, containing the product of the interaction of hexamethylenetetramine with a light fraction of unsaturated chlorohydrocarbons - glycerol production wastes (LET-11B bactericide) and additionally formaldehyde in the form of its aqueous solution (formalin) in the ratio LET-11B bactericide: formalin 1: 9-9: 1 (RU 2180323).

These biocidal formulations are not effective enough and require high dosages (200-300 mg / l). In addition, they do not provide effective corrosion protection.

Closest to the proposed invention is a bactericidal composition comprising formaldehyde in marketable form - formalin or paraformaldehyde and spent absorption solution formed during gas desulfurization with an aqueous solution of a mixture of monoethanolamine and formalin, in the following ratio, wt.%: Commodity form of formaldehyde - 15- 65. spent absorption solution - 35-85 (RU 2192542).

The specified composition has a higher biocidal activity and protective anticorrosive effect in comparison with formalin. However, to ensure complete suppression of the growth of SVB and effective protection against corrosion, relatively high dosages of the composition are required - at least 100-200 mg / l. In addition, the component of the specified composition - the spent absorption solution is not currently industrially produced due to the lack of gas desulfurization plants in the country using mixtures of amines and formalin as a neutralizer, which prevents the use of the specified composition on an industrial scale. The specified composition also does not have the required adaptability for use in the winter cold season due to the insufficient low pour point (minus 12-18 ° C).

The basis of the present invention is the creation of a bactericidal composition based on formaldehyde, which is highly effective in combating the growth of SVB and hydrogen sulfide corrosion at low specific costs, as well as manufacturability (low pour point) and availability for wide industrial use.

The invention also solves the problem of expanding the range of effective bactericides, which is important in connection with the rapid adaptation of microorganisms to them.

The problem is solved in that the bactericidal composition comprising formaldehyde in commercial form — formalin and / or paraformaldehyde — additionally contains a quaternary ammonium chloride salt in commercial form and at least one amino alcohol from the group mono-, di-, triethanolamine, methyldiethanolamine, dimethylethanolamine, diethylethanolamine in the following ratio of components, wt.%:

Commercial Quaternary Ammonium Chloride Salt 10-65 Amino alcohol (s) above (e) 1-15 Formalin and / or Paraformaldehyde Rest

In an advantageous embodiment, the proposed bactericidal composition as formaldehyde in commercial form contains formalin and additionally contains urotropin (hexamethylenetetramine) and, optionally, a bactericidal preparation of bacteriostatic action, preferably of the brand Bacticide, a nonionic surfactant (nonionic surfactant). mainly hydroxyethylated alkyl phenols or alcohols, alkali metal hydroxide in the following ratio, wt.%:

Commercial Quaternary Ammonium Chloride Salt 10-50 Amino alcohol (s) 1-15 Urotropin 2-22 Bactid 0-12 Oxyethylated alkyl phenols or alcohols 0-10 Alkali metal hydroxide 0-1 Formalin Rest

As a quaternary ammonium chloride salt (HOUR) in the commodity form, the proposed reagent mainly contains a cationic substance of the brand KATAPAV C.50. KATAPAV S.80 or KATAPAV S.35 according to TU 2482-003-04706205-2004. representing an alcoholic solution of alkylbenzyldimethylammonium chlorides, or ALKAPAV S.50 according to TU 2482-004-04706205-2005, representing an alcoholic solution of alkyltrimethylammonium chlorides, or SEPTAPAV X.70 according to TU 2482-021-04706205-2005, representing an alcoholic solution of dimethyl dimethyl chloride or AB Catamine according to TU 9392-003-48482528-99 or KATAPAV 12.50 according to TU 2482-008-04706205-2004, or KSINAL according to TU 9392-001-76639615-06. representing about 50% aqueous solution of alkylbenzyldimethylammonium chlorides or mixtures thereof. The indicated HOUR solutions are intended to be used as raw materials (active base) in the production of detergents and disinfectants, textile auxiliary substances, household chemical goods, antiseptic preparations for preserving wood, processing leather, fur, etc.

As a nonionic surfactant, the proposed reagent mainly contains ethoxylated mono- and / or dialkylphenols, preferably of the brand Neonol AF 9-12 or AF 9-10 according to TU 2483-077-05766801-98 or OP-7, OP-10 according to GOST 8433, or ethoxylated alcohols, for example, Sintanol ALM-10 brand according to TU 6-14-864-98. These nonionic surfactants are used as an oil-displacing additive for water during flooding of oil reservoirs and feedstock for the production of corrosion inhibitors (RU 2168561, RU 2405861, etc.).

The bactericidal preparation of bacteriostatic action of the Bactic brand, manufactured according to TU 2484-010-05744685-96, is a liquid product with a density of 1.1-1.2 g / cm ³ based on an ethanolamine trimer of the formula C ₉ H ₂₁ N ₃ O ₃ and is intended use as a long-acting bacteriostatic to protect against microbial damage to organic products, their solutions and emulsions.

As an inorganic base (alkaline agent), the proposed reagent may contain hydroxides and / or carbonates of alkali metals, mainly sodium hydroxide (sodium hydroxide according to GOST 2263 or GOST 11078) or potassium (GOST 9285).

As a commodity form of formaldehyde, the proposed reagent contains methanol formalin according to TU 2417-138-05766801-2009 or technical formalin FM of the state standard specification 1625, produced by the domestic industry on a large-scale scale. Paraformaldehyde (paraform) technical (TU 6-05-930-78 or TU 6-09-141-03-89) can also be used as a commercial form of formaldehyde. However, paraformaldehyde is an expensive product, therefore, from an economic point of view, the use of formalin is preferable. Urotropin used for the manufacture of the proposed reagent is available on a large-scale scale in accordance with GOST 1381.

Thus, from the point of view of the availability of raw materials, the inventive bactericidal composition is industrially applicable.

The proposed bactericidal composition under normal conditions is a light yellow to brown mobile liquid with a density of 0.95-1.11 g / cm ³ , with a pH of 8 to 12 and a pour point below minus 40 ° C, readily soluble in fresh and mineralized (formation) water.

The feasibility of using formalin as a biocidal reagent in a mixture with QAS and amino alcohol is due to the appearance of a synergistic effect of suppressing the growth of SVB. It was found that the addition of QAS to formalin leads to a sharp increase in bactericidal activity against SVB. In this case, a synergistic effect is observed in a wide range of ratios of the components of the mixture, and the greatest effect is when the concentration of the commercial form of HOUR in the reagent is from 10 to 70%. In addition, the addition of HOURs in amounts up to 50-70% also leads to an increase in biocidal activity with respect to hydrocarbon-oxidizing bacteria. It was also found that the additional introduction of the amino alcohol in the reagent in the optimal amounts found makes it possible to obtain a biocidal composition with a low pour point and high storage stability. The additional introduction of urotropine into the reagent leads to an increase in its protective anticorrosive effect in hydrogen sulfide-containing environments, and also eliminates the precipitation of polyformaldehyde during storage of the reagent in winter cold. The additional introduction of a bactericidal preparation of bacteriostatic action, for example, Bacticide brand, allows one to obtain a biocidal composition with an extended period of bactericidal action, suitable for protection against microbial damage to drilling fluids on an organic basis.

Thus, this technical solution allows to obtain a substantially new, more effective and technologically advanced bactericidal composition with a low pour point and high stability during long-term storage, suitable for all-weather use in field conditions, moreover, as a complex reagent, a bactericide and a corrosion inhibitor.

An analysis of the known technical solutions selected in the search process showed that in science and technology in this area there is no object similar in terms of the claimed combination of features and the presence of properties, which allows us to conclude that its criteria are “novelty” and “inventive step”.

The invention is illustrated by the following specific, but not limiting examples of obtaining the proposed bactericidal composition and testing it for effectiveness.

Example 1. Obtaining a bactericidal composition. 70 g of formalin are charged into a reaction flask equipped with a stirrer, thermometer and reflux condenser and 12 g of triethanolamine (TEA) and 18 g of quaternary ammonium salt (HOUR) are introduced in stirring in the KATAPAV C.50 brand name according to TU 2482-003-04706205 2004. The mixture is further stirred at room temperature for 5-10 minutes until a homogeneous product is obtained and used as a bactericide.

Examples 2-4. Samples of bactericidal compositions No. 2-4 receive analogously to example 1, using other HOUR, amino alcohols and changing the ratio of components.

Example 5. In the reactor of example 1 load 58 g of formalin, 7 g of tea, 15 g of urotropine and stirred at room temperature until complete dissolution of urotropin. Then, 20 g HOUR in the marketable form of KATAPAV C.80 brand is added to the resulting solution and stirred at room temperature until a homogeneous product is obtained.

Example 6. In the reactor of example 1, 56 g of formalin, 4 g of TEA, 14 g of urotropin, 8 g of bactericidal preparation of bacteriostatic action of the Bactic brand are loaded and the resulting mixture is stirred until complete dissolution of urotropin. Then add 18 g HOUR in the marketable form of Catamine AB and mix at room temperature until a homogeneous product is obtained.

Example 7. In the reactor of Example 1, 57 g of formalin are charged and 4 g of TEA, 6 g of bactericidal preparation of the Baccid brand, 18.5 g of urotropin, 14 g of HOUR of the KATAPAV brand of S. 50 and 0.5 g of nonionic surfactants - Sintanol ALM- ethoxylated alcohols are introduced with stirring 10. The resulting mixture is stirred until complete dissolution of urotropin and obtain a homogeneous product.

Example 8. In the reactor of example 1, 35 g of formalin is charged and 0.2 g of sodium hydroxide, 8 g of a mixture of mono-, di- and triethanolamine (MEA, DEA, TEA) are added with stirring, and then 4.8 g of paraformaldehyde (paraform) and 2 g of urotropin. The resulting mixture is stirred at a temperature of 40-50 ° C until complete dissolution of paraform and urotropin. Then add 49 g HOUR brand KATAPAV C.50, 1 g nonionic surfactants - ethoxylated monoalkylphenol brand Neonol AF 9-12 and mix until a homogeneous product.

Example 9. In the reactor of example 1, 50 g of formalin is loaded and 0.1 g of potassium hydroxide, 2 g of methyldiethanolamine (MDEA), 10 g of the bactericidal preparation Bactid, 2 g of paraformaldehyde and 10 g of urotropin are introduced with stirring. The resulting mixture is stirred at a temperature of 40-50 ° C until the paraform is completely dissolved. Then add 25 g HOUR brand KATAPAV C.50, 0.9 g of ethoxylated mono-and dialkylphenols brand OP-10 and mix until a homogeneous product.

Example 10. In the reactor of Example 1, 65 g of an HOUR of KATAPAV C.35 brand are charged and 15 g of MEA are added with stirring, then 20 g of paraformaldehyde are added in portions. The resulting mixture is stirred at a temperature of 30-40 ° C until the paraform is completely dissolved and a homogeneous product is obtained.

Example 11. In the reactor of example 1, 65 g of HOUR of KATAPAV C.35 brand is charged and 15 g of DEA are added with stirring, then 20 g of paraformaldehyde are added in portions. The resulting mixture is stirred at a temperature of 40-50 ° C until the paraform is completely dissolved and a homogeneous product is obtained.

The component composition of the bactericidal reagents obtained according to examples 1-11 is shown in table 1. Here are the test results of the reagents and known reagents according to the prototype and analogue for pour point according to standard methods (GOST 20287).

The proposed bactericidal compositions are tested for the effectiveness of suppressing the growth of SVB according to the well-known method “Assessing the infestation of oilfield media and the bactericidal action of reagents relative to sulfate reducing agents. Laboratory, bench and pilot tests ”RD 03-00147275-067-2001. Ufa DOOO "BashNIPIneft" LLC "ANK Bashneft". 2001. The quantitative composition of SVB is determined by the method of limiting 10-fold dilutions using Postgate culture medium (OST 39-151-83).

The active accumulative culture of SVB is isolated from the commercial fluid of the Gremikhinsky oil field (Udmurt Republic). After diluting the SSC, the sample is reseeded 3 more times in fresh culture medium. For the tests, a culture culture system of 4–5 days old is used, giving blackening in 24 hours at a dosage of 1 cm ³ in a nutrient medium. Into a series of labeled glass penicillin vials with a deoxygenated formation water model, a 1 cm ^{3 of an} accumulative culture culture product is injected with a sterile syringe and the studied biocidal reagent is dosed in an amount that provides the required concentration in mg / L. The vials are mixed and incubated for 24 hours at 20-22 ° C, after which 1 cm ^{3 of the} treated biocidal reagent is introduced into the Postgate culture medium and thermostated at 32-35 ° C. For each concentration of biocidal reagent, 3 parallel tests are performed. As a control, use similar samples without the addition of a biocidal reagent and with the addition of a prototype reagent. Thermostatically controlled vials at 32-35 ° C are observed for 15 days, noting the appearance of a black color. The effectiveness of the bactericidal action of the reagent is evaluated by the appearance or absence of hydrogen sulfide. The presence of hydrogen sulfide is determined by the formation of a black precipitate of iron sulfides. Effective are those reagents that provide complete (100%) inhibition of the growth of SSC at low dosages. In this case, the nutrient medium containing iron sulfate remains transparent or only slightly colored. Table 2 presents comparative test results with the prototype.

The proposed bactericidal composition (samples No. 1, 5, 6 and 9) is tested for the effectiveness of its protective action against corrosion in accordance with the "Methodology for assessing the corrosiveness of oilfield environments and the protective effect of corrosion inhibitors using corrosion meters" RD 39-3-611-81 . Ufa VNIISPTneft. 1982. The protective effect of the reagent is determined in the inhibited (with the addition of the test reagent) standard and hydrogen sulfide-containing solution according to GOST 9.506-87. As an aggressive environment, a reservoir water model with a density of 1.12 g / cm ³ and a hydrogen sulfide concentration of 100 mg / l is used. Table 3 presents comparative results of the corrosion test with the prototype.

From the data presented in tables 1 and 2, it can be seen that the proposed bactericidal composition, in comparison with the known one, has a higher effect of suppressing the growth of SVB (100% suppression at concentrations of 25-50 mg / l) and a low pour point (below minus 40 ° С ), therefore, is suitable for all-weather storage and field use. The data in table 3 show that the proposed bactericidal composition has a higher effect of inhibiting hydrogen sulfide corrosion and, therefore, can be used as a bactericidal corrosion inhibitor. In addition, the proposed reagent will expand the range of currently used bactericides, which is necessary to exclude the adaptation of microorganisms to them.

Table 1 room Component composition, wt.% Temperature sample HOUR in commodity form Amino alcohol Formalin Paraform Urotropin Bactid Nonionic surfactants Hydroxide solidification, ° C one KATAPAV S.80 - 18 TEA - 12 70 - - - - - Below minus 40 2 KATAPAV S.50 - 65 IEA - 5 thirty - - - - - Below minus 40 3 SEPTAPAV XC.70 - 25 DMEA-15 60 - - - - - Below minus 40 four ALKAPAV S.50 - 25 DEEA-15 60 - - - - - Below minus 40 5 KATAPAV S.80 - 20 TEA - 7 58 - fifteen - - - Below minus 40 6 Catamine AB - 18 TEA - 4 56 - fourteen 8 - - Below minus 40 7 KATAPAV 50 - 14 TEA - 4 57 18.5 6 Syntanol ALM-10 - 0.5 Below minus 40 8 KATAPAV S.50 - 49 IEA - 6 35 4.8 2 - Neonol AF9-12 - 1.0 NaOH - 0.2 Below minus 40 DEA - 1 TEA - 1 9 KATAPAV S.50 - 25 MDEA-2 fifty 2 10 10 OP-10-0.9 KOH - 0.1 Below minus 40 10 KATAPAV S.35 - 65 IEA - 15 - twenty - - - - Below minus 40 eleven KATAPAV S.35 - 65 DEA - 15 - twenty - - - - Below minus 40 12 Prototype Minus 18 13 Formalin Minus 28 fourteen Catamine AB Minus 1

table 2 Sample Number Bactericidal effect against SVB at a dosage of reagent, mg / l 200 one hundred fifty 25 one complete suppression complete suppression complete suppression incomplete suppression 2 also also also complete suppression 3 also also also also four also also also also 5 also also also also 6 also also also also 7 also also also also 8 also also also also 9 also also also also 10 also also also also eleven also also also incomplete suppression 12 (prototype) also also incomplete suppression incomplete suppression 13 (formalin) also also incomplete suppression incomplete suppression 14 (Catamine AB) also also incomplete suppression incomplete suppression

Table 3 Sample Number Reagent concentration, mg / l The degree of protection against corrosion,% one fifty 83 5 fifty 94 6 fifty 97 9 fifty 93 12 (prototype) fifty 57 13 (formalin) fifty 48 14 (Catamine AB) fifty 82

Claims (2)

1. A bactericidal composition comprising formaldehyde in commercial form — formalin and / or paraformaldehyde, characterized in that it further comprises a quaternary ammonium chloride salt in commercial form and at least one amino alcohol from the group of mono-, di-, triethanolamine, methyldiethanolamine , dimethylethanolamine, diethylethanolamine in the following ratio of components, wt.%:
Commercial Quaternary Ammonium Chloride Salt 10-65 Amino alcohol (s) 1-15 Formalin and / or Paraformaldehyde Rest 2. The bactericidal composition according to claim 1, characterized in that it additionally contains urotropin and, optionally, a bactericidal preparation of bacteriostatic action, preferably of the brand Bacticide, a nonionic surfactant, mainly ethoxylated alkyl phenols or alcohols, alkali metal hydroxide in the following ratio of components, wt.%:
Commercial Quaternary Ammonium Salt 10-50 Amino alcohol (s) 1-15 Urotropin 2-22 Bactid 0-12 Oxyethylated alkyl phenols or alcohols 0-10 Alkali metal hydroxide 0-1 Formalin Rest