RU2547823C1 - Derivatives of 2-hydroxy-3-phenylethinylthio(seleno)-1,4-quinones as surface-active substances and detergent containing thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: claimed are derivatives of 2-hydroxy-3-phenylethinylthio(seleno)-1,4-quinones as surface-active substances in a composition of a detergent for the purification of oil-carrying equipment from pollutions of an organic and inorganic origin. Also claimed is the detergent for the purification of oil-carrying equipment from pollutions of an organic and inorganic origin, which includes sodium silicate, sodium carbonate, a humectant OP-10, a surface-active substance and water, as the surface-active substance it contains listed components with the following content, wt %: sodium silicate - 0.70, sodium carbonate - 3.5-3.75, humectant OP-10- 0.23-0.25, derivative of 2-hydroxy-3-phenylethinylthio(seleno)-1,4-quinones - 0.23-0.25, water - the remaining part.

EFFECT: complete purification of purified surfaces with the minimal detergent consumption and reduction of time for its processing.

2 cl, 1 tbl

Description

The invention relates to the production of surfactants and may find application in the composition of detergents for cleaning from pollution of the organic and inorganic nature of oil equipment of any shape and size.

When cleaning hydrocarbon contaminants with a detergent solution, an unstable emulsion is formed, which decomposes into the aqueous and organic phases. The organic phase is disposed of, and the aqueous detergent solution is reused, which ensures complete cleaning. Numerous washing and cleaning agents are known for cleaning contaminants of various origins using surfactants (RU Patents Nos. 2135304, 2170630, 2166111, 2134719, 2195479, 2236443).

A nonionic surfactant is used as a surfactant, which contains ethoxy groups, ethoxylated monononylphenol, containing 12 moles of oxirane and containing 9 moles of oxirane, neonol, alkylbenzyldimethylammonium chloride (Katapav), fatty acids, etc. (Degtyarev G.P. Use of detergents (Fundamentals of theory and practice.) - M .: Kolos, 1981). However, detergents with known surfactants, having a good cleaning effect on a certain group of contaminants, for example, oils, were less effective when used in cleaning in closed piping systems or equipment. To improve cleaning, an increase in the concentration of surfactants in the detergent composition is required, which leads to increased pricing and, as a result, complicates the technological processes.

Known detergent for cleaning metal and other surfaces from technological lubricants and microparticles of metal, oils, greases, bitumen, preservation compounds, traces of cutting fluid and other contaminants. Detergent for cleaning surfaces from contaminants includes a nonionic surfactant based on propylene trimers with a boiling point above 230 ° C at a pressure of 760 mm Hg. and with a concentration of hydrogen ions of pH in a water-alcohol emulsion with a concentration of 10 g / dm ^{3 of} at least 6.0-8.0, characterized by the absence of a flash before boiling, and the petroleum solvent of the paraffin fraction C7-C18, in the following ratio of components, mass. %: Nonionic surfactants - 0.02-0.5, oil solvent of the paraffin fraction - the rest. As a nonionic surfactant, the detergent contains neonol 9- (4-12) or neonol 9-6, and as a petroleum solvent - wide liquid petroleum paraffin. Also in the detergent add 0.3-7.0 wt.% Anionic surfactants, consisting of a mixture of sodium salts of alkyl sulfonic acids. The detergent provides a high degree of purification due to the use of the indicated surfactants in paraffin solvents, which have demulsifying properties and stabilizing abilities and allow the detergent to be reused (RU Patent No. 2439205).

Known detergent containing, wt.%: Nonionic surfactant 2-5, sodium tripolyphosphate 15-25, sodium metasilicate 10-16, sodium sulfate 12-24, sulfur 1-3, washing mustard 0.5-2, soda ash to 100 (RU Patent No. 2096444).

When the concentration of the solution of the specified detergent 0.2-0.8 g / l with a processing time of 5-15 minutes, it is possible to clean the surface of the machinery and equipment from contaminants of plant, mineral and animal origin, at the same time achieve a disinfecting effect.

The disadvantage of the detergent is the inability to reuse it, especially when cleaning and cleaning tanks without interruption, for example, railway tanks contaminated with oil or oil products.

A known composition of powdered synthetic detergent (CMC). The tool contains the following components in wt.%: Anionic surfactant - sodium alkylbenzenesulfonate 10-16; nonionic surfactant - ethoxylated fatty alcohols or ethoxylated alkyl phenol 2-5; sodium tripolyphosphate 15-25; organophosphonate compound - sodium salt of 1-hydroxyethylidenephosphonic acid or diethylenetriaminopentaxis- (methylenephosphonate) sodium 0.2-0.6; polycarboxylate 0.5-1.5; carboxymethyl cellulose 0.3-0.6; modified polyalkylene glycol 0.2-0.6; optical brightener 0.05-0.3; soda ash 3-6; water glass 3.5-6.0; enzyme 0.4-0.7; antifoam 0.05-1.5; perfume 0.15-0.3; sodium sulfate and water to 100.

The specified detergent composition CMC has a high efficiency detergent with a whitening effect, removing all types of contaminants, but its use is limited only to use for cleaning soft tissues with imparting extra softness and the absence of irritating effects on the skin of the hands during hand washing (RU Patent No. 2354685) .

The most effective are known fluorine-containing surfactants (FS surfactants), for example, the preparations “chromin”, “chromoxane”, however, the method of obtaining them is multi-stage, fire and explosive (Maksimov B.N. et al. Handbook. Industrial fluorine-organic products. M: Chemistry, 1990. P.394-396).

Fluorine-containing β-ketosulfonic acids or their salts are known as surfactants for processes occurring in aqueous media obtained by reacting methyl polyfluoroalkyl ketone with sulfuric anhydride in an equimolar ratio at a temperature of 20-50 ° C, followed by isolation of the target product in free form or in the form of a salt (RU Patent No. 20055718).

Known surfactants have the ability at a concentration of 0.1 wt.% To reduce the surface tension of water to 14-15 mN / m, which allows to increase the efficiency of their use at a low concentration (up to 5 mg / l).

Known as a highly effective surfactant in the composition of detergents for cleaning oil equipment from pollution of organic and inorganic nature, normal octadecyl ether perfluoropolyoxapolypropylene carbonic acid of the general formula

The well-known fluorinated ester (PS surfactant) is obtained by esterification with the interaction of equimolar amounts of normal octadecyl alcohol and perfluoropolyoxypolypropylene carbonic acid at a temperature of 50-60 ° C in the environment of HFC 113 (1,1,2-trifluoropropane) in the presence of catalytic amounts of chloroform (RU Patent No. RU 2390531 - prototype).

FS surfactant according to the prototype has high chemical and thermal stability and the ability to reduce the surface tension of water to 14-15 mN / m at low concentrations of FS surfactant. In addition, it has anticorrosive, antioxidant and anti-adhesive properties in the detergent solution for cleaning oil equipment from pollution of organic and inorganic nature. Detergent FS surfactant consists of the following components, wt%: neonol 3-5, sodium silicate 8-10, sodium tripolyphosphate 20-25, normal octadecyl ether perfluoropolyoxapolypropylene carboxylic acid 3-5, water - the rest.

With the aim of increasing the range of surfactants, expanding the temperature regimes used in the washing process, enhancing the washing action and technological properties of aqueous solutions (foaming ability) and the possibility of reuse of detergent when cleaning oil equipment, it was proposed as part of a detergent containing well-known components: sodium silicate, Surfactants and water, as surfactants use derivatives of 2-hydroxy-3-phenylethynylthio (seleno) -1,4-quinones and additionally sodium carbonate and wetting agent OP-10 (G PT 8433-81) with the following component washing, wt.%:

derivatives of 2-hydroxy-3-phenylethynylthio (selenium) -

1,4-quinones - 0.23-0.25

sodium silicate - 0.70-0.75

sodium carbonate - 3.5-3.75

wetting agent OP-10 - 0.23-0.25

water is the rest.

As derivatives of 2-hydroxy-3-phenylethynylthio (seleno) -1,4-quinones are proposed:

2,3-dihydro-2-hydroxy-3-phenylethynylthio (seleno) -1,4-benzoquinones (surfactant-1)

3-hydro-2-methyl-2-hydroxy-3-phenylethynylthio (seleno) -1,4-benzoquinones (surfactant-2)

2,3-dihydro-2-hydroxy-3-phenylethynylthio (seleno) -1,4-naphthoquinones (surfactant-3)

The structural formulas of the proposed surfactants are given below (on a separate sheet).

These substances were synthesized by the interaction of the corresponding quinone oxides (n-benzoquinone, toluquinone and n-naphthoquinone) with acetylene thiolates and selenolates in an inert medium. Moreover, the opening of the α-oxide ring with α, β-unsaturated thiolates and selenolates, acting as nucleophilic reagents, was carried out by us for the first time. The structure of the obtained products is proved by the analysis of their IR and PMR spectra. The qualitative and quantitative composition was confirmed by elemental microanalysis (Zachinyaev Y.V. Reactions of α, β-unsaturated thiolates and selenolates with N-aryl-C-chlorohydrazones and derivatives of 1,4-quinones. Abstract of diss. ... Candidate of Chemical Sciences. 02.00.03, L .: LTI named after Lensoviet. - 1988. - 19 p .; Zachinyaev Y.V., Bobrov A.I., Antsiferova N.E., Lysenko NL Interaction of quinone oxides with some nucleophilic reagents - Dep. 07/02/1987, No. 837-xp 87, 8 pp. Bibliographer .: 3 names - ONIITEKHIM, Cherkasy).

A detergent is prepared by mixing the components without their chemical interaction and subsequent dissolution of the mixture in water.

An aqueous solution at a temperature of 20-40 ° C has a pH of 9.0-9.5.

In appearance, the proposed detergents are a powder or gel of white or yellowish color with a smell characteristic of the raw materials used. The density of a 5% solution, g / cm ³ - 1.03-1.05.

Mass fraction of insoluble precipitate,% - 0.1-0.2. The washing ability at a temperature of 30-70 ° C is not less than 98-99%.

The washing abilities of the proposed product with new surfactants were tested when removing products of petroleum origin from containers at first in laboratory conditions. In a flat-bottomed heat-resistant flask mounted on an electric stove, with a magnetic stirrer and adjustable heating, a pre-measured amount of washing solution is placed.

The washing solution is heated to a temperature of 40-50 ° C, stirring is turned on, after which a pre-measured amount of contaminating product (fuel oil) is placed in the flask. Stirring is continued for 15-30 minutes. After mixing, the resulting emulsion is discharged into a separatory funnel for delamination. The end of delamination is fixed in time. The degree of purity of the flask is visually determined after it is treated with a washing solution. The comparison of the quality of the washing solutions is carried out by temperature, mixing time, mixing speed and volume ratio of the used impurities and the washing solution.

The compositions of the proposed detergent were tested for cleaning tanks contaminated with fuel oil, a volume of 0.5-1.0 m ³ . 2.5-4.0 m ^{3 of} washing solution (amount exceeding the amount of contamination by 3-5 times), heated to a temperature of 30-40 ° C, was supplied for cleaning. The duration of the cleaning cycle was 12-15 minutes. The separated washing solution with a residual hydrocarbon concentration not exceeding 0.25 mg / L was reused to clean another tank with residual fuel oil. The isolated fuel oil without additional processing was used for its intended purpose.

The results confirming the industrial applicability of the new detergent are shown in the Table.

The use of a solution of the proposed detergent in an amount exceeding the volume of hydrocarbon contaminants by 2-4 times, provides complete cleaning of the surfaces to be cleaned with a minimum consumption of detergent and reduces its processing time.

(1-2) 2,3-dihydro-2-hydroxy-3-phenylethynylthio (seleno) -1,4-benzoquinones

(3-4) 3-hydro-2-methyl-2-hydroxy-3-phenylethynylthio (seleno) -1,4-benzoquinones

(5-6) 2,3-dihydro-2-hydroxy-3-phenylethynylthio (seleno) -1,4-naphthoquinones

EVERYWHERE Z = -S-, -Se-

Claims (2)

1. Derivatives of 2-hydroxy-3-phenylethynylthio (seleno) -1,4-quinones as surfactants in the detergent composition for cleaning oil-loading equipment from pollution of organic and inorganic nature. 2. Detergent for cleaning oil-filling equipment from pollution of organic and inorganic nature, including sodium silicate, a surfactant and water, characterized in that as a surfactant it contains derivatives of 2-hydroxy-3-phenylethinylthio (selenium) - 1,4-quinones and optionally sodium carbonate and wetting agent OP-10 with the following content of the listed components, wt.%:
derivatives of 2-hydroxy-3-phenylethynylthio (selenium) 1,4-quinones 0.23-0.25 sodium silicate 0.70-0.75 sodium carbonate 3,5-3,75 wetting agent OP-10 0.23-0.25 water rest