The method of obtaining emulsifier for oiling compositions

 

(57) Abstract:

The method is concerned with the obtaining of emulsifier for the fatliquoring of leather. The mixture of fish oil with vegetable oils or meblowymi esters of fatty acids of these oils sulfurous at 30-35oC concentrated sulfuric acid at ratios, respectively, from 9: 1 to 1:1. Unreacted sulfuric acid washed with 10% sodium hydroxide solution in the presence of 3 wt.% sodium chloride. Sulfones defend and drained acidic water. The resulting neutralized sulfonic ethers 20% solution of sodium hydroxide to a pH of 7-7,5. The method allows to improve the quality of fattening compositions and conditions for the fatliquoring of leather due to more uniform distribution of fat on the thickness of the skin, improves viviremos fat from feeding tubs, reduces loss of fattening material and facilitates maintenance of the sewage treatment problem. 1 C.p. f-crystals, 1 table.

The invention relates to the production of fattening materials used in the leather industry.

One of the main components of fattening compositions for the skin is the emulsifier. Because when greasing oiling composition is used in the form of an aqueous emulsion, the role of the emulsifier is ware is islandsthe use the products of sulfonation or sulfotyrosine fish oil.

Known /1/ a method of producing emulsifiers sulphurization fish oils concentrated sulfuric acid at a temperature no higher than 30-35oC followed by the separation of the excess water and neutralization with alkali received sulfonic ethers. The disadvantage of this method is the relatively low degree of sulfonation and emulsifying ability of the obtained product. In the process of sulfonation due to the rapidly increasing viscosity of sulfatase there are serious problems of heat and mass transfer, resulting in increased processing time, the development of parallel running of adverse reactions redox nature of the formation of by-products and even gas emissions - sulphur dioxide.

Closest to the proposed method is /2/ emulsifier for the fatliquoring of leather, by which the sulfonation of fish oil carried out with concentrated sulfuric acid in the amount of 23-25% by weight of the original fat in the presence of 7-8 wt.% urea, washing is carried out in the presence of aluminum sulfate in the amount of 2-3 wt.%, after settling and separation of acidic and sulfate water sulfonic ethers neutralized solutions of sodium hydroxide.

This method allows to improve the EU's long, in the final product are accumulated impurities due to the parallel running of adverse reactions, etc.

The purpose of the invention is to simplify the process of obtaining emulsifier, increasing hardware performance and depth of sulfonation, while also improving the quality of the finished product.

This goal is achieved by the fact that sulfurous concentrated sulfuric acid fish oil mixed with vegetable oils or methyl esters of fatty acids of these oils at a ratio of from 9:1 to 1:1.

Achieved positive effect consists in the following. When the sulfonation of the proposed mixtures observed increase in viscosity of the reaction medium is substantially lower than in the known methods, which allows to increase the rate of feed of sulfuric acid while keeping the temperature optimum for the sulfonation fat range is not higher than the 33oC due to a significantly better conditions of heat and mass transfer. In General, reduces the duration of sulfonation, reduced yield by-products that reduce typically the emulsifying ability of the finished emulsifier.

When washing the reaction mass from an excess of sulfuric acid improves sucks and reduced it on the nogo SO3and high emulsifying ability.

Application received emulsifiers improves the quality of fattening compositions and conditions for the fatliquoring of leather due to more uniform distribution of fat on the thickness of the skin, improves viviremos fat from feeding tubs, decrease feeding material and facilitated technological problems of wastewater treatment, which generally solves the complex problems of the process of fatliquoring leather /3/.

Getting emulsifier for the fatliquoring of leather, the proposed method is as follows.

The mixture of fish oil with vegetable oil in a ratio of from 9:1 to 1:1 sulfurous concentrated (above 96%) sulfuric acid under efficient stirring. The feed rate of sulfuric acid is adjusted so that the temperature of the reaction medium does not exceed 33oC, because it is known that the higher the temperature of sulfonation fats dramatically reduce the depth of sulfonation ready emulsifier and increase the content of by-products, reducing its consumer properties.

After the filing of the total volume of sulfuric acid, usually 20 wt.% from mass sulfiram mixture, the reaction mass is maintained with stirring for another 0.5 hour. Then prontopass fat sodium chloride and serves a 10% solution of sodium hydroxide in the amount of 100% by weight of fat. The feed rate of the solution is regulated so that the temperature of the reaction medium does not exceed 65oC. After the filing of the total volume of sodium hydroxide solution, if necessary, adjusted pH environment of the reaction mass to pH3 . Give the reaction mass to stand for 2-3 hours. Drain the washing water. The resulting neutralized sulfonic ethers 20% sodium hydroxide solution to pH 7-7,5 with efficient stirring.

Below are examples of the implementation of this method in the laboratory. Used the following oils: fish oil GOST 1304-76, rapeseed oil GOST 8988-77, mustard oil GOST 8807-74, soybean oil GOST 7825-76, sunflower oil GOST 1129-73. Determination of the concentration of sulfonated products of sodium sulfate and linked SO3was performed by standard methods /1/. To assess emulsifying ability used method ZNIIK, to prepare a 5% emulsion of sulphonated products in water (temperature 60oC, stirring was carried out in a glass beaker with a stick for 30 seconds). The stability of the emulsion was determined visually in the cylinder to 100 ml and characterized by a time prior to the separation of the emulsion.

Example 1. 140 g of a mixture of fish oil and gorc the coy for feeding sulfuric acid (98%). With stirring, serving 28 g of sulfuric acid for 1 hour with a speed that the temperature of the reaction medium does not exceed 33oC, usually 25-30oC. the Observed increase of viscosity is small. After submitting all of the acid reaction medium under stirring incubated for another 0.5 hour. Make 4 g of sodium chloride and poured with stirring to 140 g of a 10% aqueous sodium hydroxide solution, and with the speed that the temperature of the reaction mixture did not rise above 65oC. If necessary, adjust the pH of the medium up to 3. Disable mixing and defend the reaction mass 2-3 hours, which is divided into two layers - the bottom water layer and the upper sulfonic ethers. Separate the lower aqueous layer remaining in the flask the neutralized sulfonic ethers 20% sodium hydroxide solution to pH 7-7,5.

The finished product - a fluid transparent brown viscous mass with the content of linked SO3- 4,2%, sodium sulfate and 2.7%, gives stable for more than 24 hours 5% water microemulsion. Cooked on the resulting emulsifier oiling compositions have high technical and qualitative indicators.

Example 2. 140 g of a mixture of fish oil and methyl esters of fatty acids of sunflower oil at a mass ratio of mesheanii gradually serving 28 g of sulfuric acid (98%) for 1 hour at the temperature of the reaction mass to 25-30oC. the Observed increase of viscosity is negligible. The reaction mass is maintained with stirring for another 0.5 hour. Make 4 g of sodium chloride and poured with stirring to 140 g of a 10% aqueous solution of sodium hydroxide at a temperature not exceeding 65oC. If necessary, adjust the pH of the medium up to 3.

Disable mixing and defend the reaction mass of 1-1,5 hours. The aqueous layer was separated. The layer of neutralized sulfonic ethers 20% solution to pH 7-7,5.

The finished product - a fluid transparent brown viscous liquid with the contents of the linked SO33.9 per cent, of sodium sulfate and 2.0%, gives stable for more than 24 hours 5% water microemulsion.

The results of retrieval described in terms of emulsifiers on mixtures of fish oil with other vegetable oils and other ratios given in the table.

The data given in the table and examples 1, 2, show the advantages of the proposed method in comparison with analog (example 10) and the prototype (example 11). The content of linked SO3significantly lower than the claimed method, based emulsions are characterized by a relatively low resistance.

The ratio of fish oil to various plant substances (linked SO3- from 3.6 to 4.0 wt.%), the low content of sodium sulfate (not more than 3 wt.%) and having a high stability of the formed emulsion.

When you reduce the amount of vegetable oils (example 9) are obtained products with relatively low sulfur content-related and as a consequence emulsion based on them not to be stable.

An excess amount of vegetable oils above the claimed ratio of 1: 1 is impractical for economic and technological reasons. When exceeding this ratio is obtained a product with a high content of emulsifier, but when greasing leads to loss of skin elasticity.

Thus, examples of fully confirm the essence of the invention.

The inventive method is tested in pilot scale and laid the basis for the design of industrial production.

Ispolzovaniya literature

1. The Gilbert E. E. Sulfonation of organic compounds.- Chemistry. M., 1969.

2. Auth. St. USSR 1227624,1986.

3. Levenko P. I. Greasing and properties of the skin.- Light industry. M., 1970.

1. The method of obtaining an emulsifier for the fatliquoring of leather, including sulfonation is ω sodium get sulfonic ethers, characterized in that sulphurous mixture of fish oil with vegetable oils or with methyl esters of fatty acids of these oils.

2. The method according to p. 1, characterized in that the quality of vegetable oil use mustard, rapeseed, soybean and sunflower oil at a ratio of fish oil is from 1 : 9 to 1 : 1.

 

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