The tribochemical method of obtaining the metal-containing soaps - component feeding mixtures

 

(57) Abstract:

Usage: the invention relates to soap and leather production and the receipt of metal Soaps. Essence: in the way tribochemical get used as components of feeding mixtures of Soaps of metals 1-8 groups of the periodic system and carboxylic acids C7and above by reacting the metal-containing reagents with acid or mixture of acids in a bead mill at 20-60oC for 10-40 min in the presence of 1-2 wt. % water, 0.05 to 0.4 % of tribochemical catalyst, an oil component and a solvent at a molar ratio of the metal-containing reagent : acid from 1 : m to 1 : (mn), where m is the number of metal atoms in the original metal-containing reagent, and n is the valence of the metal content in the reagent, first prepare a solution of acid and tribochemical catalyst in the liquid phase system: a solvent, an oil component, liquid components kislotosoderzhashchih compositions, the water in which after reaching the set temperature of the injected metal-containing reagent (oxide, hydroxide, carbonate of the metal). As tribochemical catalyst used nitrogen-containing compounds, the best of which are alausa use fish oil and sunflower oil, ester and unsaponifiable constituents of tall oil and acid oils, resinous components of the waste FLC, industrial oil, while the solvent is represented paraffin and aromatic hydrocarbons, their technical mixtures and oil. 5 C.p. f-crystals, 4 PL.

The invention relates to leather production, namely the production of fattening materials and emulsifiers for the leather industry.

Soap metals and carboxylic acids are widely used in practice, fatliquoring of leather. Sodium and potassium Soaps of fatty acids fraction C15-C20possess emulsifying properties and because of this are used as emulsifiers in the preparation of fattening mixes /1-3/. Aluminum and chrome soap fatty acid fraction C15-C20give the skin a hydrophobic properties /3/. Soaps of naphthenic acids have the ability to fill the skin, and increase their strength and organoleptic characteristics /3/. Soap heavy metals are used as catalysts for oxidation and sookielee fat to get mulgirigala compositions for the fatliquoring of leather /8/ prototype.

A method of obtaining washed by interaction metalloorganic the Xia, they can receive only a limited range of Soaps (sodium, potassium, aluminum). The process itself is difficult, as it requires prior ORGANOMETALLIC compounds, bulky in technical use, fire, unsafe because of the high toxicity of ORGANOMETALLIC compounds requires high temperatures.

A method of obtaining washed by saponification of natural fats and oils in an aqueous solution of caustic alkali /4/. The disadvantage of this method is that it is suitable only for sodium and potassium Soaps and cannot be used to produce Soaps of alkaline earth and other heavy metals.

A method of obtaining washed by double exchange reaction by precipitation from an aqueous solution of sodium soap water-soluble salt of the corresponding metal /3-5/. This method is unchanged widely used for the waterproofing of leather, for which the skin first, it is greased composition containing sodium or ammonium soap, and then the skin is treated with an aqueous solution of alum or aluminum sulfate chromium /3,4/.

The disadvantages of this method are: 1. education in the process of getting washed water-soluble sodium sulphate (Kali is ranenie environment. On the other hand, water-soluble sulfates are easily adsorbed by the skin and significantly reduce the effect of hydrophobization /6/; 2. the variability of the chemical composition and properties respectively obtained by this method Soaps /4/.

A method of obtaining manganese Soaps by direct oxidative interaction of oxides (hydroxides) manganese rosin acids in the environment of sunflower oil at a temperature of 120-160oC and mechanical stirring until a homogeneous viscous mass, not giving a solid phase when diluted with white spirit /7/.

The disadvantage of this method is a fairly large temperature (120-160oC) and duration (>2 h) process, as a result, low productivity, it is hard to bind to compounds of manganese and rosin acids, as well as unfavorable conditions for fine grinding of the solid phase metal-containing reagent.

The aim of the invention is to increase the productivity of the method of obtaining metallic Soaps, lowering the temperature of the holding and the replacement of thermal energy to mechanical.

This objective is achieved in that the interaction of oxides, hydroxides and carbonates of metals with carboxylic cyclotides reagent during the process is conducted in tribochemical variant in a bead mill at temperatures of 20-60oC for 10-40 min in the presence of 1-2 wt. water, 0.05 to 0.4 wt. tribochemical catalyst, an oil component and a solvent at a molar ratio of the metal-containing reagent acid in the initial download (1:m) (1:nm), where m is the number of atoms of this metal in the metal-containing reagent, and n is the valence state of the metal, in this first prepare a solution of acid and tribochemical catalyst in the liquid phase (solvent, an oil component, liquid components kislotosoderzhashchih compositions), in which after reaching the set temperature of the injected metal-containing reagent.

As the metal-containing reagent is used oxides, hydroxides and carbonates of metals 1-8 groups of the periodic system.

As the acid, use C7and higher carboxylic acids, both individually and as containing these acids compositions and waste.

As tribochemical catalysts used nitrogen-containing compounds, the best of which are the nitrates of ammonium and alkali metals, secondary and tertiary amines and amides of acids.

As the oil component used fish oil and sunflower oil, esters and unsaponifiable constituents tall is the determinant using paraffin and aromatic hydrocarbons, their technical mixture and oil.

Characteristics of the raw materials used.

Technical fish oil 1-3 grades according to GOST 1304-76 "Fats of fish and marine mammals technical: fish oil substandard with HT 75 mg KOH/g; oil UNDER THE 113-03-476-82 "Oil (a mixture of high-boiling oxidation products of cyclohexane, dehydrogenation of cyclohexanol, polycondensation cyclohexanone)"; waste FLC THAT 38-1071231-89 "bottoms products production FLC"; pine rosin GOST 19113-84; tall oil substandard with HT 135 mg KOH/g; acid oils waste autookislenia sunflower oil with HT 114 mg KOH/g; acid stearic technical GOST 6484-65; oleic acid technical GOST 7580-55; oxide (dioxide) manganese: artificial pasta on THE 6-14-831-72; pyrolusite technical on THE 6-10-1808-81; oxide of cobalt (3+) GOST 4467-79; lead litharge GOST 9199-77; zinc oxide THE technical 48-7-17-82; zinc white GOST 202-84; oxide of chromium (3+) MSTU 6-09-6259-69; red iron oxide GOST 8135-74; chalk natural enriched GOST 12085-88; ochre OST 6-10-430-80; manganese oxide (4+) reactive GOST 4470-79; lead oxide reactive GOST 9199-77; zinc oxide GOST 10262-73; calcium oxide GOST 8677-66; calcium hydroxide GOST 9262-66; titanium oxide MSTU 6-09-1211-64; barium hydroxide Ba(OH)28H2O GOST 4107-69; oxide Noah frequency.

Heptane MSTU 6-09-2937-66; white spirit GOST 3134-78; petroleum products fuels (class F), including kerosene GOST 28577.2-90; ISO 8217-87; xylenes oil (GOST 9410-78) and coal (GOST 9949-77); solvent oil GOST 10214-78; solvent coal GOST 1928-79; oil industrial General purpose GOST 20799-88.

Obtaining a metal-containing component feeding mixtures of the claimed method consists in the following.

A mixture of carboxylic acid, fat or oil, hydrocarbon or other solvent, water and tribochemical catalyst in the desired weight ratio of load in a bead mill with a mass of glass beads in relation to loading in the ratio 1:2, and then produce a mechanical stirring system and heated until a homogeneous acid solution, then enter the solid metal-containing reagent and lead his fine grinding and tribochemical interaction with acids, controlling the completeness of the conversion by sampling the reaction mixture and then reviewing them on the dry residue and the acid number and the calculation of the degree of conversion of the reactant in the gap at the time of sampling.

The finished product overload in a container and use as components of the LM the bead 50 of the mass of the initial load. Boot sequence: ball mill, vertical type, enter 200 kg substandard fish oil with HT 75 mg KOH/g, 2.5 kg of water, 0.25 kg of triethylamine and 32.5 kg of kerosene. Include mixing, which are 10 minutes the temperature of the 20oC. turn Off the stirring and quickly insert 14,75 kg technical pyrolusite (the molar ratio of the metal-containing reagent acid 1:2). Resume bead mill at a specified temperature and control the process method of sampling over time and analyzed for their content of acid and metal salts with subsequent calculation of the appropriate degree of conversion of the reactant in the lack. For this process after 10 min, the degree of conversion of 90 through 40, respectively, 96 and 100 98 Therefore, for the duration of the process can take 40 minutes Obtained finely dispersed suspension of manganese salt is filtered through a metal mesh to separate the glass beads and collected in a container for storage and later use.

Examples 2-36. Laboratory bead mill vertical type heated using a liquid bath, freely movable along the longitudinal axis of the mill. Loading weight 250, the Ratio of the Avila 34,1 of the total mass of the initial reaction mixture. Download water 1.2 pyridine as tribochemical catalyst of 0.1 sunflower oil 0.5 as the hydrocarbon solvent used white spirit. Stearic acid and all liquid components of the system was stirred for 45 min and was heated to 55oC. During this time, all of stearic acid went into solution. After the specified time has introduced a metal-containing reagent, was resumed bead mill and implement specified in example 1, the monitoring process. The amount of metal-containing reactant molar ratio and stearic acid and the change in the degree of conversion with time is shown in table.1. Examples of the use of these suspensions salts discussed below.

As can be seen from the table.1 (and it presents metal compounds all groups of the periodic system of elements), the process is almost insensitive to the nature of the metal not only in qualitative but also in quantitative terms. Insensitive he and the purity of the metal-containing reagent.

The sensitivity of the process to the nature of the carboxylic acid, as well as to the purity cyclododecane raw materials is characterized by the data of examples 37-65.

Examples 37-65. Labogena described in the examples 2-37. Content loading water 1.5 pyridine 0,16 fish oil 1 or industrial oils 5 (example 51). As the hydrocarbon solvent used heptane (example 39, 59), xylenes (examples 37, 46-48, 57), solvent (examples 43, 44, 52, 55, 61), oil (example 54), in other cases kerosene. The temperature of the process: 20oC (examples 39, 42, 43, 51, 53, 54, 59, 62, 63), 40oC (examples 44, 45, 55, 56, 64, 65) and 60oC (examples 37, 38, 40, 41, 46-50, 52, 57, 58, 60, 61). The duration of mixing before entering the metal-containing reagent was 60 min (examples 37, 38, 40, 41, 44, 46-50, 52, 55, 57, 58, 60, 61, 64), in other cases, 30 minutes the nature of the acid used, its amount, the molar ratio of the metal-containing reagent acid, the nature of the metal-containing reagent and the distribution of degrees of transformation in time is presented in table.2.

As can be seen from the table.2, the nature of the acids in high-speed characteristics of the considered process is not playing not only defining, but in General any significant role. The same applies to the purity of the used acid. In contrast to the above, the nature of tribochemical catalyst plays a much greater and can say that the decisive role in the management of the considered process that you is agrusti and beads, the sequence of loading operations and monitoring process similar to that described in examples 37 - 65. The water content in the download 2 fish oil as the oil component 0,5 waste FLC as cyclododecane composition and additional oil component 45 lead litharge as metal-containing reagent 6.6 ratio of the metal-containing reagent acid 1:2. Hydrocarbon solvent white spirit. The temperature of the 47oC, the duration of mixing and exit at this temperature (up to input lead litharge) 50 minutes Nature tribochemical catalyst, its amount, and changing the degree of conversion of the reactant in time are given in table. 3.

As can be seen from example 81, in the absence of tribochemical catalyst process is just beginning, but quickly braked when technologically unacceptable degrees of transformation, which indicates the need for a tribochemical catalyst. Role played by many nitrogen-containing compounds (inorganic and organic). Here are seen the following pattern:

the least effective catalyst is ammonia;

go to ammonium salts, and salts of nitrous and nitric acids soprovozh have the last catalytic properties;

in a series of primary, secondary and tertiary amines is increased catalytic properties;

amines acids are more effective catalysts than with primary amines.

The positive effect from the use of this invention, consider the example of making a composition for the fatliquoring of leather the method according to the patent /8/.

1. Getting fatten cited method is carried out by liquid phase air oxidation of a mixture of fat with oil in the presence of a catalyst: a mixture of copper, chromium and barium chloride salts of fatty acids. The specified catalyst was prepared by the method of metabolic decomposition and tribochemical interaction of oxides of copper, chromium and barium with acids of tall oil and kerosene as solvent. Technological sequence of operations the preparation of the catalyst in a known manner in comparison with declare shown in table. 4.

As follows from the table. 4, when using the proposed method the number of operations upon receipt of the catalyst was reduced from seven to two, and the duration of the process 220 min to 30 min (i.e., more than 7 times). The efficiency obtained by the claimed method of the catalyst is not inferior efficiency katalizatoram full use of their thickening ability in the preparation of fattening compositions. The tests showed that the introduction of the composition for fatliquoring 5 oleate of aluminum allows you to completely eliminate this undesirable phenomenon of stratification oiling composition during prolonged storage. To enter tribochemical the oleate of aluminum in the composition for fatliquoring is extremely simple. For this purpose it is necessary to carry out the tribochemical reaction of obtaining aluminum soap directly in the presence of one of the components of the oiling composition components: fish oil, industrial oil, oil, etc. short duration of the process and the simplicity of its hardware design is practically not complicate the process of obtaining oiling.

At the same time to solve the same task in a known manner, you must create a plot, equipped autoclave to obtain the sodium Soaps of fatty acids, the capacity to prepare an aqueous solution of aluminum salt, a reactor for carrying out the interaction of the above mentioned compounds, a filter system, a system for cleaning aluminum soap from water-soluble salts of sodium, drying to remove free moisture, the apparatus for dispensing aluminum soap and mixing indicates the final result.

Finally, a simple way to enter into the composition for the fatliquoring of leather soap heavy metals can not only improve the physical properties of fattening compositions, but also to obtain compositions that improve the quality giovanny their skins. Test oiling composition initially containing in its composition 5 oleate of aluminum, in comparison with the composition without it showed that the samples of the oiling composition containing aluminum soap, allow to obtain much softer and filled the skin than control samples oiling.

Sources of information

1. The leather industries /Ed. by Sergeeva. Meters Light industry, 1978 - 463 S.

2. A new drug for the emulsion fatliquoring leather /Century A. Gubanov, A. A. Pikulski, E. E. Bykovskaya, N. And. Palenikova etc. /Leather and footwear industry, 1977, No. 5, S. 27-30.

3. New in greasing leather /P. I., Levenko, B. S. of Kochetkov, N. P. Babich. M Food industry, 1982, 136 S.

4. Technology greases /Iswc Y. L., Kiev: Naukova Dumka, 1986, 248 S.

5. Excipients for polymeric materials. The Handbook. M. Chemistry, 1966, 176 S.

6. The Bayer A., Tanning, dyeing and finishing of leather. Section dyes. 5090 Leverkusen. 1980 CH compositions for the fatliquoring of leather. Will believe. the decision on the application N 92-012644/12/0 58488 from 24.03.94, RU, patent, 2039087, CL C 14 C 9/02, 1995 (prototype).

1. A method of obtaining a metal-containing Soaps-component feeding mixtures by direct interaction of the metal-containing reagent with carboxylic acids in the presence of an oil component and solvent conditions for fine grinding of the solid phase of the system during the process, characterized in that the interaction of metal-containing reagent with acid lead in tribochemical variant in a bead mill at 20 60oC for 10 to 40 min in the presence of 1 to 2 wt. water, 0.05 to 0.4 wt. tribochemical catalyst, an oil component and a solvent at a molar ratio of the metal-containing reagent acid 1: m m n, where m is the number of metal atoms in this reagent, n valent metal content in the reagent, in this first prepare a solution of the acid tribochemical catalyst in the liquid phase system: a solvent, an oil component, liquid components kislotosoderzhashchih compositions, water, in which after reaching the set temperature of the injected metal-containing reagent.

2. The method according to p. 1, characterized in that the metal-containing reagent is used oxides, hydroxides and carbolit use WITH7and higher carboxylic acids, both individually and in the form containing these acids compositions and waste.

4. The method according to p. 1, characterized in that as a tribochemical catalysts used nitrogen-containing compounds, the best of which are the nitrates of ammonium and alkali metals, secondary I tertiary amines and amides of acids.

5. The method according to p. l, characterized in that the oil component used fish oil and sunflower oil, esters and unsaponifiable constituents of tall oil and acid oils, resinous components of the waste FLC, industrial oils.

6. The method according to p. 1, characterized in that the solvent used paraffin and aromatic hydrocarbons, their technical mixture and oil.

 

Same patents:

The invention relates to methods for feeding means for the leather and fur industry.

The invention relates to the leather industry and can be used for the fatliquoring of leather

The invention relates to the leather industry and can be used for the fatliquoring of leather

The invention relates to the use of N,N-disubstituted-aminopropionic acids as emulsifiers, wetting, surface-active substances in drugs for treatment and for imparting water-repellent properties of the leathers and furs

The invention relates to a method of determining the quality of the skin

FIELD: soap manufacture.

SUBSTANCE: soap lump composition comprises the following components, wt.-%: soap, 59-84; non-soap non-triglyceride substances, 0-10; water, 10-18, and triglyceride oil or triglyceride oils, 6-13. The fluidity limit value of soap lump exceeds about 90 and foam volume is at least 65% of a base. Triglyceride oil or triglyceride oils are added at final step after crystallization. Invention provides preparing soap containing relatively the large amount of triglyceride oils that provide the necessary fluidity limit value and integrity of soap lump and retain desirable consumer properties, namely, foam formation.

EFFECT: improved and valuable properties of soap.

4 cl, 4 tbl, 13 ex

FIELD: method for production of disinfecting agent and detergent for items made of black fabric.

SUBSTANCE: claimed method is carried out in apparatus with vibration fluidized bed and includes blending of non-ionic surfactant, anionic surfactant, sodium silicate aqueous solution, sodium carboxymethyl cellulose, sodium tripolyphosphate, enzymes, antifoaming additive, flavoring, wherein primarily nozzle sprayed liquid raw materials and then dry components are introduced into apparatus, and process is carried out at certain temperature.

EFFECT: fabric disinfections without losses of its characteristics and color intensity; prolonged storage time without activity losses.

1 tbl, 1 dwg, 6 ex

Toilet soap // 2514922

FIELD: chemistry.

SUBSTANCE: invention relates to the soap industry and specifically to samples of soap with high biological activity, and can be used as toilet soap with improved consumer properties. Described is a toilet soap, having a soap base and a natural additive, characterised by that the natural additive used is silt-argillaceous deposits from lake Bolshoi Tambukan in amount of 0.5-35%, wherein the soap meets the following characteristics: qualitative number (mass of fatty acids per nominal mass of 100 g), not less than 78; weight ratio of soda products with respect to N2O, %, not more than 0.20; setting point of fatty acids, extracted from the soap (titre), °C, 35-41; weight ratio of sodium chloride, %, not more than 0.7; initial foam volume, cm3, not less than 320.

EFFECT: improved consumer properties of the soap.

2 cl

FIELD: cosmetology.

SUBSTANCE: cosmetic soap comprises soap base, flavouring and mud from sulphur springs of the village of Sernovodsk (Sunzhensky district, Chechen Republic). All the components are taken in certain proportions. After entering all the components, the mass is kept in a water bath at a temperature of 45-55°C for 15-20 minutes, moulded by filling in forms, and then cooled to room temperature and kept in moulds for three days. The component which has a major cosmetic effect is used as mud from sulphur springs of the village of Sernovodsk (Sunzhensky district, Chechen Republic).

EFFECT: improvement of cosmetic properties.

Solid toilet soap // 2575014

FIELD: cosmetology.

SUBSTANCE: solid toilet soap is described, consisting of soap chips, lanolin, additionally comprising zinc oxide, a perfume and an abrasive component, at that the perfume is used as an essential oil, and the abrasive component is used as milled Macley amicrocarpa with the following component ratio, wt %: soap chips 86.9-96.1, lanolin 2.0, abrasive component 1.0-10.0, perfume 0.5-0.7, zinc oxide 0.4.

EFFECT: increase in abrasive properties and ensuring long-term antibacterial effect of solid toilet soap, improvement of its detergent capacity.

3 cl, 3 tbl

Soap bar // 2585620

FIELD: hygiene.

SUBSTANCE: invention relates to soap bars. Described is soap bar, which does not contain surfactants, including soap, from 0.1 to 2.5 wt% of free fatty acids, from 3 to 7 wt% of coarse talc and from 0.1 to 5 wt% of glycerine, wherein coarse-crystalline talc has index D90 ≥ 40 mqm and soap contains less than 0.5 wt% of anionic, nonionic, amphoteric and zwitterion surface-active substances, and also described is method of skin cleaning and use of soap bar.

EFFECT: technical result is reduction of skin dryness and providing after soap applying of increased perception of aroma.

13 cl, 2 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.

2 dwg

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

Up!