SU912048A3 - Method for tpanning skins - Google Patents

Description

The invention relates to leather industry and can be used in the process of tanning leather and fur skins. There is a known method of tanning leather by treating a pretreated gol with an aqueous solution containing chromium at 20-50 ° C and a pH of 1.5-4.2. To achieve the desired skin properties, tanning tanning should have a total chromium content of 1.5-4.5% Cr 0, calculated on the weight of the mole. You get a tanned semi-finished product containing 1.4-7% Cr2.0z, preferably 3.5-5%, calculated on the dry weight of U1. The disadvantage of this method is the significant consumption of tanning salts of chromium and the high content of chromium oxide in wastewater 3-8 g / l. The aim of the invention is to reduce the consumption of chrome tanning while maintaining the level of quality of the finished leather. This goal is achieved by. due to the fact that, according to the method of tanning leather by treating a mole with an aqueous solution of chrome tanning, the treatment of the mole is carried out in the presence of 1-3% by weight of the mole of the aluminosilicate of the general formula (Kat2 / nOX - Afi03- (sL02) i, where K, at - ion alkali metal and / or divalent cation, X 0.53-1.5 4., 83-14,8., or its mixture with Dicarboxylic acid, or with a mixture of dicarboxylic acids, or with water-soluble hydrolysable complex alkyl halofir Dicarboxylic acid when the ratio of aluminosilicate to the specified compound (40-98); (2-60). The aluminosilicates of the above formula were Insoluble in water may

contain bound water, have an O particle size of 1 micron-5 mm and the ability to bind calcium to 02.00 mg CaO / g dry weight.

Aluminosilicates are prepared by reacting water-soluble silicates with water-soluble aluminates. In this case, the starting components are used in the form of aqueous solutions, or one starting compound in solid form is reacted with another starting compound in the form of an aqueous solution. Aluminosilicates can also be obtained by reacting the solid starting components in the presence of water and, moreover, from A1 (OH), A12.0z or Si02 when reacting solutions of alkali metal silicate and aluminate. There is also a method for producing aluminosilicates from the melt of the starting components, but this method is not economical due to the high temperatures that are necessary for its implementation, and the need to convert the melt into fine products.

The introduction of polyvalent cations can be carried out using well-known methods of exchanging monovalent cations, for example sodium ions, into divalent and trivalent cations, such as calcium, magnesium, zinc or aluminum ions. In addition to these cations, natural aluminosilicates may also contain other cations in a small amount, for example, lithium, potassium, thallium, manganese, cobalt and nickel ions. Synthetic aluminosilicates may contain quaternary nitrogen compounds as additional cations, for example, ammonium ions

about .

A. hydromosilicates, obtained by precipitation or by another method and in a fine form, transferred into an aqueous suspension, are transferred from the amorphous to crystalline state by heating to 50-200 ° C. Amorphous or the alkali metal crystalline aluminosilicate contained in the aqueous suspension is separated by filtration and dried at a temperature of, for example, 50-800 C. Depending on the drying mode, the product contains bound water in greater or lesser quantity. Anhydrous products are obtained at 8-800C. But preferably getting water-containing products with

temperature drying conditions and optimal conditions are about 50-20СРС. The products obtained by this method contain 2-30% water, in

average 8-27% of the total weight.

The production of aluminosilicates with The rum of particles 1–12 µm contributes to the precipitation regime, and the aluminate and silicate solutions, which are simultaneously iodine to the reactor, are supplied with large shear forces, for example, due to intensive mixing. In order to obtain crystalline aluminosilicates, the crystallizing mass is slowly stirred, thereby eliminating production; large crystals.

In addition, such fine insoluble c. water

alkali metal aluminosilicates, which are obtained by precipitation or crystallization in the presence of soluble inorganic or organic dispersants. Such products can be obtained. - as follows. As soluble organic dispersants, surfactants are used, and compounds capable of binding.

complex with calcium. These dispersants can be added to the reaction mixture before or during precipitation, and the starting components can be added to them, for example as a solution, but they can be dissolved in the aluminate solution and / or the silicate solution. Particularly good results are achieved if the dispersant is dissolved in the silicate solution. The disperser is taken in a quantity of at least 0.05%, preferably based on the weight of the mixture to be precipitated. For crystallization, the precipitation product is heated to 50-200 ° C for 1 / 2-24 hours. Sodium lauryl ether sulfate, sodium polyacrylate, hydroxyethanediphosphonate, are used as dispersants.

The ability to bind calcium can be determined as follows.

pH 1 l of an aqueous solution containing 0.594 g CaCli (300 mg CaO / l

with stiffness .30), adjusted to 10 by the addition of dilute sodium hydroxide and mixed with 1 g of aluminum silicate, based on the anhydrous product. Then the suspension is stirred vigorously for 15 minutes. After filtration of the aluminum silicate, the residual stiffness X of the filtrate is determined. The ability to bind calcium in mg CaO / g of aluminosilicate is determined according to equation (30's) 10. Powdered aluminosilicates are converted to a stable dispersion by mixing with water or a solution containing a dispersant. Such a dispersion can be diluted with water without any difficulty. But aluminosilicates can also be added to the tanning solution in the form of granules, which can be filtered after the blowing process. The following alkaline silicates are used: 0.9, 04 S10, -4.3Hj ,, Degree of crystallization: fully crystalline product. Calcium Binding Ability: 170 mg CaO / g of active substance. The maximum particle size (determined by sedimentation analysis) is 3–6 μm. 0.3QNa20 1, OOA i03-U) SL02-AH20 (0) The shape of the crystals is cubic with rounded corners and edges ,. lower particle diameter 5.4 µm, calcium binding capacity: 172 mg CaO / g a1: active substance, 0, E6 NasO - 4 196 ftbO-AWjO (|) The shape of crystals is cubic with rounded corners and edges, the average particle diameter 5.4 µm, calcium binding capacity: 172 mg CaO / g of active substance. 0.9 NaiO-lAuiOs 5.1 5L02-5M20. The degree of crystallization: a completely crystalline product, the maximum particle size (determined by sedimentation analysis) is 3-6 microns, the ability to bind calcium: 110 m CaO / g of the active substance. O.OXUaiO-1AIL203-A / 2 & L02.-4, (v) Particles are made in the form of a ball with an average diameter of 3-6 microns, capable-. Calcium binding: 132 mg CaO / g of active substance at 60 C. Ijll NsiO 1 -1U SiOi b, 1 "jO (() Crystal structure: mixed type in ratios 1: 1, crystalline form: rounded crystallites, medium particle diameter 3.6 µm, calcium binding capacity: 105 mg CaO / g active substance at Q.S & N3 0 A feOs- HvSLbi S.HiO (o) Crystal structure: mixed type, the same as aluminosilicate 4J but with a ratio of 8: 2J, the average particle diameter is 7 µm, calcium binding capacity: 126.mg CaO / g of the active substance. 0.93 NazOtAliOa-3,60 102-bZMgO U (24.6% HjiO) Crystal structure: Bic crystallites, average particle diameter: 8 µm, calcium binding capacity: 105 mg CaO / g of the active substance. 0.28 No. 20 0.7030-Afcilb l.JSaiOz- MiO 6x) Crystalline form: type A, crystalline, average particle diameter 5.8 µm Calcium Binding Capacity: 20 mg CaO / g of active substance. O Ma20-0.7 MqO-At20 -2, eiSl02; 5.6 - "iO (). The average particle diameter is 10.5 µm, calcium binding capacity: 25 mg CaO / g of the active substance. 0.92 MagO- 0.1SHO - YES - -l. 6102- 6% 0 (XV). The average particle diameter is 36 µm, calcium binding capacity: 76 mg. CaO / g of the active substance. 0.6ma20-oMm oo, aaAe20zDo510g-4, a% ui) and 7% hexadecyltrimethylammonium chloride. The average particle diameter after using the MCM, calcium binding capacity: 84 mg CaO / g of the active substance ./-. .0.59 nazO-V46-2.03 I SlOj-A W O- Average particle diameter 50 µm, calcium binding capacity: 56 mg CaO / g of active substance. 4.05 NajiO - AQiOs-J.bSlOi (xTch) Average particle diameter of 12.3 μm, ability to bind calcium: About mg CaO / g of active substance, N32.0 MiOa - 2.H SiOi / () Average particle diameter 6.1 µm, Caldey Binding Capacity: 16 mg CaO / g of active substance. 0.06 MaiO 0.9 CaO AHzOi 1.92 8lOi (LO. Content of active substance 79%, calcium binding capacity: 15 mg CaO / g of active substance, average particle diameter 8 µm. 0.0) Mego - Ab-goa -.JS SiO () ii) Active Content 78%, Calcium Binding Capacity:, 15 mg CaO / g of active substance, average particle diameter 7 µm. 1,0 НЗгО 10 SLOi. 2 ° Average particle diameter 12 µm, calcium binding capacity: 25 mg CaO / g active substance. Amorphous aluminosilicate (XIX) brand zeolex 23A. Composition: 1.5 12.2 SiOj. Content of active substance is 82% capacity for Ca binding: 40 mg CaO / g of active substance, average particle diameter 5-15 microns. Amorphous aluminosilicate (XX) of the brand Zerolex 35 R. Composition: 1.5 "11.8 S i 0, Content of the active substance 82% Calcium binding capacity: 46 mg CaO / g of the active substance, average particle diameter 5-15 µm. Amorphous aluminosilicate (ХХ1) of the brand Silteg P 820. Composition: 1.1 N32.0 14.8 Si02 .. Content of active substance 80% Ca binding ability: 36 mg CaO / g of active substance, average particle diameter 5-15 microns . Natural zeolite (XXII). Composition: J .0.6 Na 0 -Al2.0fl, - 8.3 SiO. . Content of active substance is 86%. Binding ability: About mg CaO / g of active substance, average particle diameter 5-15 km. O, 0, d CaO 5102 No. 0 Active content 84%, Ca binding capacity: 10 mg CaO / g active substance, average particle diameter 5-15 µm. 0, & CaO OLM (0 A & 205 -2Si02 (WIV) Content of active substance 85%, ability to bind Ca: O mg CaO / g active substance, average particle diameter 5-15 microns. Example 1. Tanning Sheepskin Sheepskin. The skin, which passed through the stages of intensive washing, bleaching and picke removal, is tanned under the following conditions: water temperature is 30-35 ° C, bath module is 1:20, and the treatment solution contains, g / l: table salt 60, greases electrolyte resistant component 5, chromitane powder 4 containing chromitane tannin 4, aluminosilicate 7. Prodo The treatment time is 3.5 hours, then the skin is left to stand for 8-10 hours (pH of the solution is 4.0), and after the treatment, it is washed for 15 minutes and dried. Aluminosilicate 1 can be used equally well and aluminosilicates 1 , i, chi, and xxiv. When tanning is carried out in the presence of the indicated aluminosilicates, the consumption of chrome tanning is reduced by 1 / 3-1 / 2 compared to the consumption of the known, due to which the chromium content in the resulting wastewater is only 0.40 , 5 g / l. . The chromium content in the finished skin is 3.5%. Example 2. Tanning leather for the top of shoes from cattle hides. The glier, which has passed the stage of ashing, decalting, pickling pickling and pickling, is tanned. The consumption of the components of the processing of the following solution:% solution of the mass of the mole: salt 7, powdered chrome tanning substance (for example, l) 8, alumina TCiu 3. Water temperature 20-100 C. Treatment time 5 hours (pH 3 , 81 After finishing the treatment, the skin is subjected to a stale in the stack for 8-12 hours, followed by drying and finishing with known techniques. When tanning is carried out in the presence of the above aluminosilicates, the required amount of chrome tanning agent can be reduced by 25% from the usual one without deterioration leather. At the same time, the chromium content in wastewater is reduced from 8 to 0.60, 8 g / l. The chromium content in the skin is 3.75%. Example 3. Leather tanning for furnishing furniture from cattle hides. The desalting, pickling and spraying pickle stages are subjected to tanning at the expense of the components of the treatment solution (percent by weight a mole): sodium chloride 7, technical adipic acid 0.5, fatty substance obtained on the basis of sulfitized natural masses 2, emulsifier based on anionic surface-a of the chemical substance, ammonium salt (alkyl sulphate) 1, basic tannic chromium salt Chromozal B 6. Water temperature. 20-10 ° C. After 120 mph, 3% of aluminosilicate 1 is added, after which the treatment in the barrel is carried out for another 4 hours (pH of the medium is 3.0-3.2). The ratio of aluminosilicate to adipic acid is 86:14 instead of aluminosilicate 1, it is also possible to apply aluminosilicates with the same success (the content of chromium in wastewater is reduced to 0.3-0.5 g / l (according to a known method, 7.82 g / l). After finishing in a known manner. get soft skin with a uniform degree of tanning. The chromium content in the skin is 4.0%., Example 4: Cocoa tanning: clothing (haberdashery) and skins of horned cattle. Pelt, past the stages of ash, dezolizovanie, piklevani and pickle removal, subjected to tanning. The consumption of the components of the solution (percent of the mass of the mole): a mixture of technical aliphatic dicarboxylic acids 0.8, an emulsifier based on anionic surfactant substances, uni salt salt of G j-Cjg alkyl sulfate 0.3, main chrome tannic substance Chromozal B b (basicity: 75% chromium oxide) Water temperature 20-100 ° C. After 120 min, add 3% aluminosilicate V2, after which skin is once again treated for 90 m with slow heating to 35-40 0 (pH of 3.8-4.0). At the same time, the ratio of aluminoscate to the mixture of technical aliphatic dicarboxylic acids is 79:21. Instead of aluminosilicate W, aluminosilicates I-VI and VIII-XXIV can be used with equal success. The final pH of the medium is 4.1-4.3. At the same time, the chromium content in wastewater is up to 0.20, 5 g / l (according to a known method, 7.8 g / l). After finishing the known images, soft skin with a uniform degree of tanning is obtained. The content of xpotvs in the skin is 4.3%. Example 5: Tanning leather for finishing furniture from cattle hides. , Gollier, past the stage of ash, desalting, pickled and pickled, subjected to tanning. Consumption of the components of the solution (percentage of the mass of the mole): sodium salt of methyl polyester of technical glutaric acid 0.9, electrolyte resistant component, chlorophenylsulfonate 2.0, main chrome tanning agent Chromozal B 1.5, Water temperature 22- 100 C. After 3 hours, 2.6% aluminosilicate Viv is added, after which the treatment is continued for another 4 hours (pH 4.0-4.2). Instead of aluminosilicate VJU, aluminosilicates I-VII and IX-XX1V can be used with equal success. At the same time, the chromium content in wastewater is reduced. After separation by known methods, soft furniture leather with a good neck is obtained, the chromium content of which is 4.2% chromium oxide. Example-. 6. Tanning of leather for the upper of shoes made from raw materials of cattle. Golya, which has passed through the stages of ash, desalting, pickling and shzhel beats & l, is subjected to duplicate under the following conditions: the sodium salt of the complex methyl hemi-ester of adipnic acid I, I, 5% of the main chromium lubic substance Hromvzal BUS. Water temperature is 22-100C. After 4 hours, 1.5% aluminosilicate JOI is added. after which the treatment is continued for another 3 hours. The skin is left to stand in the solution for 8-12 hours with occasional stirring (pH of the medium 4.0). The ratio of the aluminosilicate to the complex methyl half-ester of adipic acid is 60:40. Instead of aluminosilicate X1, al-silicates l-XI and XIII-XXIV can be used with equal success. At the same time, the chromium content in wastewater is reduced to 0.2-0.5 g / l. After finishing the famous techniques of mi. get the top skin of normal quality, the chromium content in which corresponds to 4.1%. Example 7. Double skin for finishing furniture from cattle hides. The glier, which has passed through the stage of ash, desalting, pickling, and picke removal, is tanned. Consumption of the components of the composition (percent by weight of the mole): glutaric acid 0.6, oleaginous substance based on sulfitated natural mass 2, emulsifier based on anionic surfactant, for example, ammonium salt a kilosulfate 1, the main chrome tanning substance Chromozal B 6. The water temperature is 20-100 ° C. After 120 minutes, it is added. 3% of aluminosilicate W, after which the treatment is continued for another 4 hours (pH of 4.1-4.2). The ratio of aluminosilicate to glutaric acid is 83.3: 16.7 Instead of aluminosilicate §, aluminosilicates 1-X and XII-XXIV can be used with equal success. At the same time, the chromium content in the standing waters is reduced to 0.2-0.5 g / l (according to a known method, 7-8 g. After finishing, soft furniture leather with a uniform degree of tanning, in which the chromium content corresponds to 4 , 2% chromium oxide. Example 8. The exfoliate, which passed through the stages of ash, desalting, pickling and removing the pickles, is subjected to tanning. The consumption of the components of the solution (percentage of the mass of the mole), the sodium salt of the complex of isopropyl glutaric acid half-ether 0.9, oily resistant oily substance electrolyte, for example, chloroparaffinsulfonate, 1.5% basic chromic. double substance Chromozal B 1.5 .812 Water temperature 22-100 6. After J h, 2.6% aluminosilicate W is added, after which the treatment is continued for another 4 h (pH 4.0–4.2) The ratio of aluminosilicate to the complex isopropyl half-ester of glutaric acid is 74.3: 25.7. Aluminosilicates 1-III and V-XXIV can also be used instead of aluminosilicate I. The chromium content in wastewater is reduced to 0.2-0.5 g / l of chromium oxide (by a known method, 7.8 g / l). After finishing with well-known techniques, soft furniture leather with a good neck is obtained, the chromium content of which corresponds to 4.1% chromium oxide, in terms of 0% of the skin's water content. Example 9. Example 6 is repeated, with the difference that instead of the sodium salt of the adipic acid methyl half ester, 1.0% by weight of a mole is used: a) the sodium salt of the methyl ester maleic acid; b) sodium salt of the complex of isopropyl half ester of succinic acid J c) sodium salt of the complex methyl half ester of glutamic acid, d) sodium salt of the complex butyl half ester of adipic acid. The chromium content in the wastewater is 0.4 g / l, and the chromium content in the skin is 4.1% (in the form of chromium trioxide). Example 10. Example 6 is repeated, with the difference that tanning is carried out with a solution containing, (b% by weight a mole) J table salt 8.0, phthalic acid 1.4, the main chromium tannic substance is chromatane HA ON 1.5. The water temperature is 22-100 ° C. After the expiration, 1.5% of aluminum silicate W is added (the ratio of aluminum silicate to phthalic acid is 31.7-48.3), after which the treatment is continued further in. 360 minutes at a slow temperature up to 40 ° {1 ° C / 20 minutes, pH 4.1–4.2), The chromium content in the wastewater is 0.35 g / l, and the chromium content in the skin 4.2% (as chromium trioxide). EXAMPLE 7 Example 7 is repeated, with the difference that tanning is carried out with a solution containing (percent by weight mole), sodium chloride 8.0, sodium salt of a) phthalic acid butyl half-ester, b) amyl half-ester of maleic acid; or c) a complex of amyl half-esters of aspartic acid 1.0, the main chromium tannic substance Chromosal B 1.6,. The water temperature is 25-100 ° C. But after 120 minutes .1.6% of aluminosilicate IX (the ratio of aluminosilicate to the specified half-ester a and b 61.5: 38.5) is added. Processing is continued for another 360 minutes with a slow rise in temperature to (. min., pH of 3.8-4.0. The content of chromium in the wastewater is 0.4 g / l, and the chrome content in the skin is 4.0% (in chromium trioxide), Example 12. Repeat Example 11 with the difference that instead of the nitrite salt of the half-esters a and b, 0.8% of fumaric acid is used (pH of the medium 4.1-4.2, the ratio of silica-alumina to fumaric acid is 66.6: 33.4). The content of chromium in the wastewater is the same as in Example 11. Example 13. Example 2 is repeated with the difference that tanning is carried out with a solution containing (percent by weight a mole): sodium chloride 7.0, sodium salt complex methyl half-ester of maleic acid 2.1, chloroparaffinsulfonate 0.5, chromium-containing substance chromitan 1.5, aluminosilicate VIII (ratio of aluminosilicate to the complex hemi-ester 40:60) 1.4. The temperature of water is 20-100 C, pH of 3.9-4.0. The content of chromium in this water is 0.5 g / l, and the content of chromium trioxide in the same 3.9%. Example 14. Example 2 is repeated with the difference that tanning is carried out with a solution containing (percent by weight a mole): sodium chloride 7.0, sodium salt of the complex 814 methyl half-ester of glutamic acid 0.03, chromiferous tannin 1.5 , aluminosilicate-V AND (the ratio of aluminosilicate to the specified complex methyl ester 98: 2) 1.35. pH of 3.8-4.0, water temperature, treatment time 6h .; At the same time, the chromium content in wastewater is g / l, and the chromium treoxide content in the skin is 4, 1%, in terms of 0%. zhani skin. The table summarizes the data on the strength and tensile strength and tensile strength of the leathers treated in Examples 1-14. With this, in order to reduce the consumption of chrome tanning while maintaining the level of quality of the skin, the treatment is done in the presence of 1-3% by weight of the alumina silicate of the general formula (Kati / O) ASgOb (SIO.,), where t is the ion alkali metal and / or divalent cation, P 1-3,, 53-1.5, 83-14,8, or its mixture with a dicarboxylic acid, or with a mixture of dicarboxylic acids, or with a water-soluble hydrolyzable complex alkyl dimer ester acids with a ratio of aluminosilicate to the specified compound (40-98) :( 2-60) “Priority on the basis of: 16.07.77 when the Kat is an alkali ion metal, X 0, .7 itz 1.83-b; 05/20/78 with an alkali metal Kat-ion and / or a bivalent ion, 53-0.7, (6-14.8, or with a mixture of dicarboxylic acids, or with a hydrolyzable alkyl polyester of a dicarboxylic acid, soluble in water. Sources of information, taken into account in the examination 1. Stather F. Gerbereichemie und Gerbereitechnologle, 4th ed., Berlin, Akademle, 1967,

Claims (1)

Claim A method for tanning leathers by treating pre-treated goblet with an aqueous solution of chrome tanning agent, characterized in that, in order to reduce the consumption of chrome tanning agent while maintaining the quality level of the skin, the goblet treatment is carried out in the presence of 1-3% by weight of a5 goblet of aluminosilicate of the general formula (Kat2y _n O) ₄ , where is an alkali metal ion and / or 10 divalent cation, P = 1-3, x = 0.53-1.5, q = 1.83-14.8, or a mixture thereof with dicarboxylic acid, or with a mixture of dicarboxylic acids, or with a water-soluble hydrolyzable dicarboxylic alkyl half-ester acid with a ratio of aluminosilicate to the indicated mu compound (40-98) :( 2-60). Priority according to signs: 07.16.77 with Kat-ion of an alkali metal, x = 0, .7 and 4 = 1.83-6; 25 05/20/78 at Kat-ion of an alkali metal and / or divalent ion, x = 0.53-0.7, 4 = 6-14.8, or with a mixture of dicarboxylic acids, or with a water-soluble hydrolyzable dicarboxylic alkyl polyester oh kis l o you.