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.
SUBSTANCE: invention relates to composition of pigment containing a pigment consisted of product of modified carbon, which contains carbon product having at least one bound organic group where it contains at least one ion group, one ionisable group or its mixture; and composition of dispersing agent containing anionic surface active agent, which does not solve in water at the ambient temperature with concentration more than 2% and remains solved in these conditions for more than a day; and polymer containing at least one salt of carbonic acid. The composition of dispersing agent contains anionic surface active agent and polymer containing at least one salt group of carbonic acid.
EFFECT: provision of high colour characteristics.
12 cl, 2 tbl
SUBSTANCE: invention relates to a method of producing a composition for reducing cohesion forces by dissolving in a base liquid containing water in which the following components are dispersed in given volume percent concentration: sodium chloride 1-3%, magnesium ions 1-2%, calcium ions 1-2%, potassium ions 1-2%, sulphate 1-2%, carbon 0.5-1%, nitrate 1-2%, and phosphate 1-2%, sodium chloride and sodium alkyl ether sulphate. The volume ratio of the amount of the base liquid to the amount of sodium chloride and sodium alkyl ether sulphate ranges from 1:1:1.5 to 1:1:5. Said method involves: obtaining the base liquid of the composition; heating the base liquid to temperature of 50°C-100°C; dissolving sodium chloride in said base liquid by high-speed dispersion; dissolving sodium alkyl ether sulphate in said base liquid by high-speed dispersion; and spontaneous cooling of the obtained composition.
EFFECT: method enables to obtain a composition which enables cheap and efficient neutralisation of space charges arising on particles.
6 cl, 2 ex, 1 tbl
FIELD: tannery or furry production.
SUBSTANCE: the invention is pertaining to the field of tannery or furry production and may be used for a piece by piece treatment of a tanning, furry semi-finished product with emulsions of "water in oil" type. The device for impregnation of sheets contains a mounted on the frame bath with a working compound, in which a corrugated roller is dipped, and also a feeding and auxiliary conveyers and a smoothing roller, a supporting means with a resilient counterbody, an actuator, a tool for removal of a finished semi-product, a device for creation of a hydrodynamic wedge and a pinch roller for engagement of the ribbed roller with the feeding conveyor. The problem of the presented invention is - development of the device simple in its servicing with a high reliability allowing to realize the process of impregnation more efficiently with a possibility of its installation in an automatic production line.
EFFECT: the invention presents a device simple in its servicing, having a high reliability, more efficient realization of the process of impregnation, a possibility of its usage in an automatic production line.
FIELD: chemical technology.
SUBSTANCE: invention relates to greasing and emulsifying substances used in fur, leather and other branches of industry. Invention describes a method for deep sulfonation of oxidized vegetable oils, fats and their mixtures, and oxidized mixtures with the nominal viscosity value in the range 33-75 by viscosimeter VZ-4 at 20°C in their treatment with sodium sulfite. The process is carried out in system consisting of oxidized component or mixture of oxidized components, sodium sulfite, water and soap additives, carboxylic acid, phenol and copper (II) salt as a catalyst in bead mill of vertical type at temperature of environment up to practically complete ceasing or quantitative consumption of sodium sulfite and charge of the latter is calculated by the following formula: mNA2SO3 = 0.006 x mOX x (I.N.)OX wherein mOX and (I.N.)OX mean mass and iodine number of oxidized component or mixture of oxidized components, respectively. The mass ratio of oxidized component and water varies in the range from 1:4 to 1:2.5. Dosing additives with respect to oxidized component are following: soap, 2%; carboxylic acid, 4%; phenol, 2.5%. Oxidized flax, sunflower, soybean and cotton oils, oxidized fish oil and mixtures of vegetable oils with fish oil or pig fat are subjected for sulfonation reaction with air in regimen of intensive bubble bubbling at 105 ± 5°. Soaps in indicated system are represented by sodium stearate and sodium oleate and by reaction mixtures of practically quantitative alkaline hydrolysis of fats and vegetable oils also. Benzoic, oxalic, malonic and citric acids are used as acid, and sulfate, acetate and other water-soluble salts of copper (II) are sued as a catalyst dosed in the amount (2-7.5) x 10-4 mole/kg of the parent charge. The sulfonation reaction degree is 33-40%.
EFFECT: improved preparing method.
5 cl, 1 tbl, 16 ex
FIELD: tanning industry.
SUBSTANCE: process is conducted in vertical mill to which soot, induline, kerosene and diesel fuel are introduced. Then components are mixed and slow heating the apparatus and its content is started after which mixing is switched off and slow heating of mill content is continued. Upon expiration of said time, acids or their compositions, white spirit and fatty additive are introduced and chemical mass-exchange process is performed at spontaneously fixed temperature due to thermal effects of this process and natural cooling at the beginning and at the end, as well as due to forced cooling at intermediate stage characterized by high rates of temperature at maximum of 140-150°C. At the moment when forced cooling is discontinued, 0.5-1.5 h before discontinuation of mixing and beginning of withdrawal at temperature of 80-115°C, 43-52-% solution of aluminum salts and C10-C20 of carboxylic acids is introduced into product being prepared.
EFFECT: facilitated procedure; increased amount of product.
1 tbl, 15 ex
FIELD: leather industry.
SUBSTANCE: preparation of composition is conducted on vertical-type bead mill. Induline, kerosene, and diesel fuel are consecutively charged into mill before stirring mechanism is energized, after which apparatus and contents thereof are slowly heated. Stirring is then stopped for 1 h while slow heating of mill contents is continued. When specified time expires, carboxylic acid or acid mixture, white spirit, fat additive, and aluminum oxide or hydroxide are added. Mechanic stirring is then switched on and contents of the bead mill are ground and the process is carried out at spontaneously fixed temperature caused by heat effects of the processes and natural cooling. When temperature is lowered to 85-120°C, desired product is discharged.
EFFECT: simplified process and increased product discharge degree.
1 tbl, 19 ex
FIELD: process engineering.
SUBSTANCE: oil, fat or polymer is applied on leather in amount of less that 20%, preferably, less than 15%, particularly preferably less than 10%, per leather weight. Then leather is treated by compressed air. Carbon dioxide is used as compressed air, treatment if carried out at pressure below 70 bar and temperature below 25°C. Leather is processed by compressed air unless leather weight is at least 1% smaller than its weight prior to applying oil, fat or polymer.
EFFECT: improved leather structure due to increased non-blocking property of molecules.
SUBSTANCE: method involves chrome tanning and post-tanning a semi-finished product through chrome tanning in the presence of a product of reaction of 3-aminopropyltriethoxysilane and glycidylmethacrylate in molar ratio of 1:2 and consumption of the chrome tanning agent and reaction product of 3-4% and 2-3% of the weight of the semi-finished product respectively. Neutralisation and hydrophobisation with a polymer tanning agent are then carried out for 30-40 minutes with consumption of the tanning agent equal to 8-10% of the weight of the semi-finished product. After that dyeing is carried out in the presence of a synthetic tanning agent in amount of 3-4% of the weight of the semi-finished product. Post-tanning is carried out with a plant-material tanning agent and the semi-finished product is also treated for 20-30 minutes with a product of reacting hexamethylenediamine with phosphoric acid and urea in the presence of glycerin in molar ratio of 1:3:3:0.5 respectively, in amount of 3-4% of the weight of the semi-finished product and for 20-30 minutes with organic acid in amount of 0.5-1.0% of the weight of the semi-finished product. Further, the semi-finished product undergoes greasing and re-treated for 40-50 minutes with a product of reacting hexamethylenediamine with phosphoric acid and urea in the presence of glycerin in molar ratio of 1:3:3:0.5 and consumption of 7-8% of the weight of the semi-finished product, volume ratio of 0.8-1.0 and temperature of 20-22°C. Hydrophobisation with a polymer tanning agent, dyeing in the presence of a synthetic tanning agent, post-tanning with a plant-material tanning agent, further treatment with a product of reacting hexamethylenediamine with phoshoric acid and urea in the presence of glycerin in the said molar ratio and with organic acid is carried out in one bath. Separation and drying are carried out after all operations.
EFFECT: higher water-, fungus- and heat-resistance of leather under high moisture and temperature conditions, and wide range of special types of leather.
2 cl, 3 tbl, 5 ex
SUBSTANCE: method involves tanning a semi-finished product with a chrome tanning agent, neutralisation, washing, dyeing and tanning with organic tanning agents twice. The first tanning is carried out with a polymeric tanning agent, while the second is carried out with a mixture of synthetic and vegetable tanning agents. Hydrophobicising greasing, treatment with an organic acid and re-tanning with a chrome tanning agent are then carried out. Additional washing is carried out before neutralisation. Dyeing is carried out after the second tanning. Neutralisation, tanning twice and dyeing are carried out at water-to-goods ratio of 0.5-0.7. Hydrophobicising greasing is carried out in the presence of a 20% solution of the product of reacting amino alcohol with fatty acids of vegetable oils of the C12-C22 fraction and boric acid in molar ratio of 2:1:1 in mineral oil in amount of 0.5-1.5% of the weight of the semi-finished product.
EFFECT: good hygienic properties of hydrophobic leather and prolonged fungus resistance of the leather in high humidity and temperature conditions.
2 tbl, 5 ex
FIELD: leather industry.
SUBSTANCE: invention relates to leather industry in production of leather of various assortment, in particular, to methods of drumming leather in presence of fungicide, and can be used in skin processing for improving operational properties. Method of drumming leather is implemented with drumming composition in presence of an effective antifungal inhibitor, the latter is represented by 6.0 % solution of N1-chloro-methylbenzimidazole fungicide. Fungicide is dissolved in ethyl alcohol taken in the amount of 0.2-0.5 % of squeezed leather weight at the drumming composition consumption of 20-22 % of the squeezed leather weight in terms of 100 % fat. Drumming time is 1.5-2.5 hours at the temperature of 70-80 °C.
EFFECT: proposed method of drumming leather provides effective antifungal inhibition at high quality of finished skin.
1 cl, 2 tbl, 3 ex