RU2390531C2 - Normal octadecyl ether of perfluoropolyoxa-proylene carboxylic acid as surfactant and detergent containing said compound - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: described is a normal octadecyl ether of perfluoropolyoxa-polypropylene carboxylic acid as a surfactant in a detergent for removing organic and inorganic contaminants from oil-loading equipment. Described also is a detergent for removing organic and inorganic contaminants from oil-loading equipment, where the detergent contains neonol, sodium silicate, sodium tripolyphosphate, a surfactant and water. The surfactant is a normal octadecyl ether of perfluoropolyoxa-polypropylene carboxylic acid with following content of components in wt %: neonol 3-5, sodium silicate 8-10, sodium tripolyphosphate 20-25, normal octadecyl ether of perfluoropolyoxa-polypropylene carboxylic 3-5, water - the rest.

EFFECT: design of a detergent for removing organic and inorganic contaminants from oil-loading equipment.

2 cl, 1 tbl

Description

The invention relates to the production of fluorine-containing 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.

Fluorine-containing surfactants (FS surfactants) are known, for example, “chromin”, “chromoxane” preparations, which are quite effective, but the method of obtaining them is multi-stage, fire- and explosive (Maksimov BN et al. Handbook. Industrial fluorine-organic products. 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 the interaction of 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 (Patent RF No. 20055718, publ. 1994.01.15).

Known FS 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).

The use of another class of compounds as a surfactant FS is not known to us.

In order to expand the assortment, it is proposed to use normal octadecyl ether of perfluoropolyoxapolypropylene propylene carboxylic acid of the general formula as a highly effective PS surfactant in the composition of detergents for cleaning oil and oil equipment from pollution of organic and inorganic nature.

The proposed fluorinated ester is prepared by known esterification in the reaction of equimolar amounts of normal octadecyl alcohol and perfluoropolyoxapolypropylene carbonic acid at a temperature of 50-60 ° C in the environment of HFC 113 (1,1,2-trifluorotripane) in the presence of catalytic amounts of chloroform. To this end, in a three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel, 20.3 g (0.075 mol) of n-octadecyl alcohol are placed in 100 ml of HFC 113, a catalytic amount of chloroform (0.45 g) is added dropwise with stirring 100.0 g (0.075 moles) of perfluoropolyoxapolypropylene carbonic acid.

The reaction mixture is heated and kept at 50-60 ° C for 6 hours, after which the resulting product is cooled to room temperature, dried with anhydrous sodium sulfate. After separating the desiccant and distilling off the solvent, 115.5 g (97.6%) of a yellowish amorphous substance are obtained.

Found,%: C 31.98, H 2.37, F 56.49. C ₄₂ H ₃₇ F ₄₇ O ₉ .

Calculated,%: C 31.96, H 2.36, F 56.56.

The structure of the obtained product is proved by analysis of its IR spectrum, the qualitative and quantitative composition is confirmed by elemental microanalysis. In the IR spectrum (KBr tablet) of the product, absorption bands were found that correspond to stretching vibrations of bonds (С-Н) in the region of 2900 cm ^-1 , bending vibrations of bonds (С-Н) in the region of -1470 cm ^-1 , stretching vibrations of the carbonyl group in the region of 1710 cm ^-1 and bond stretching vibrations (CF) in the region of 1100-1000 cm ^-1 . The absorption band corresponding to stretching vibrations of the hydroxo group in the region of 3650-3200 cm ^-1 is absent in the spectrum.

The proposed FS surfactant 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 anti-corrosion, anti-oxidative and anti-adhesive properties. The inventive compound was tested for the possibility of its use as a surfactant in the detergent solution for cleaning oil equipment from pollution of organic and inorganic nature. Numerous washing and cleaning agents are known for cleaning contaminants of various origins using surfactants (RF Patents No. 2135304, No. 2170630, No. 2166111, No. 2134719, No. 2195479, No. 2236443). As a surfactant, a nonionic surfactant is used, 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 systems. piping or equipment topics. To improve cleaning, an increase in the concentration of surfactants in the detergent composition is required, which leads to increased foaming and, as a result, complicates the technological processes.

The closest in composition to the proposed detergent is a tool containing, wt.%: Nonionic surfactant 2-5, sodium tripolyphosphate 15-25, sodium metasilicate 10-16, sodium sulfate 12-24, sulfur 1-3, mustard detergent 0, 5-2, soda ash to 100 (RF Patent No. 2096444, publ. 1997.11.20, prototype).

At a concentration of a 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 machines and equipment from contaminants of plant, mineral and animal origin, while at the same time achieve a disinfecting effect.

The disadvantage of the prototype detergent is the inability to reuse the detergent, especially during CIP washing and cleaning containers, such as railway tanks contaminated with oil or oil products.

In order to increase the washing action and technological properties of aqueous solutions (foaming ability) and the possibility of reuse of detergent when cleaning oil equipment, it is proposed as part of a detergent that includes well-known components: neonol, sodium silicate, sodium tripolyphosphate and surfactants, use normal octadecyl as a surfactant perfluoropolyoxapolypropylenecarboxylic acid ester (PS surfactant) with the following content of the listed components, wt.%: neonol 3-5, sodium silicate 8-10, tripoli sodium osfat 20-25, FS surfactant 3-5 Water - the rest.

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 8.5-9.0.

The washing ability of the proposed product with a new FS surfactant was tested when removing products of oil 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 a polluting 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 cleaning surfactant PS were tested for cleaning tanks contaminated with fuel oil with a volume of 0.5-1.0 m. 2.5-4.0 m of washing solution was applied for cleaning (an amount exceeding the amount of pollution by 3-5 times), heated to a temperature of 30-40 ° C. 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 with FS surfactant 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.

Detergent composition wt.% Volume of washing solution, ml Fuel oil volume, ml Temperature ° C Mixing time min Delamination time, min pH neonol 3 sodium silicate 10 sodium tripolyphosphate 25 120 30 (4: 1) thirty 5 12 9.0 FS surfactant 3 water rest neonol 5 sodium silicate 8 sodium tripolyphosphate twenty 120 60 (2: 1) 40 5 fifteen 8.5 FS surfactant 5 water rest neonol four sodium silicate 8 sodium tripolyphosphate 25 120 40 (3: 1) 40 5 fifteen 9.0 FS surfactant four water rest

Claims (2)

1. Normal octadecyl ether perfluoropolyoxapolypropylene carbonic acid as a surfactant in the detergent composition for cleaning oil equipment from pollution of organic and inorganic nature. 2. Detergent for cleaning oil-filling equipment from contaminants of organic and inorganic nature, including neonol, sodium silicate, sodium tripolyphosphate, surfactant and water, characterized in that it contains normal perfluoropolyoxapolypropylene polycarboxylic acid octadecyl ether in the following the content of the listed components, wt.%: neonol 3-5, sodium silicate 8-10, sodium tripolyphosphate 20-25, normal octadecyl ether perfluoropolyoxapolypropylene 3-5 rbonovoy acid, water - the rest.