The method of obtaining titanium tanning agent for leather

 

(57) Abstract:

The invention relates to the production of mineral tanning material of titanium containing materials, in particular chlorine solution of titanyl sulphate. The invention solves the problem of reducing the volume of wastewater and losses titanium with mother liquor, stabilization of the quality of tanning agent on basicity. The method of obtaining titanium tanning agent for leather includes preparation of the starting solution of titanyl sulphate, which further added ammonium chloride in the amount of 8 - 36 g/l as compounds containing ammonium chloride, use the mother liquor after filtration of the tanning agent, which dilute the original solution to the concentration of the titanium 80 - 120 g/l, the ratio of the volume of the starting solution for the liquor must be at least 2 : 1. The method also includes mixing and cooling of the solution, salting out sulphatoethyl ammonium sulfate ammonium subsequent crystallization, filtration of the resulting suspension and sludge treatment. 1 C. p. F.-ly, 2 tab.

The invention relates to the production of mineral tanning material of titanium containing materials, in particular from a solution of titanyl sulphate.

Currently, tanneries Russia along the x tannins most widely titanium tanning agent, derived from a variety of such materials in different ways.

The known method [1] obtain titanium tanning agent for leather by treating such materials with a mixture of sulfuric acid and ammonium sulfate to obtain SPECA, followed by leaching with water for translation of titanium in the solution from which vymalivayut double sulfate salt of Titania and ammonium ammonium sulfate and sulfuric acid, washed her solution containing 350 g/l of sulfuric acid and 20 g/l of ammonium sulfate, and the solution-preservative containing ammonium sulfate in the amount of 300-400 g/. The disadvantage of this method is the presence of a significant amount of industrial waste waters, increased consumption of sulfuric acid, the impossibility of re-use to obtain valuable tanning material components contained in the waste waters, which leads to reduction of technical and economic indicators of the process.

The known method [2] obtain zirconium, titanium and titanzincoated of tannins by evaporation of sulfate rastrow zirconium or titanium or both of these elements in the presence of additives sodium sulphate or ammonium or both of these compounds, as well as in the presence of additives of chromium compounds or aluminumaluminium, chrome and MeIVzirconium, titanium) is not less than 0.25.

The disadvantage of this method is that the process of evaporation of sulfate solutions require expenditure of significant amounts of electricity, and this method is distinguished by the instability of the quality of tanning agent on basicity.

The closest technical solution chosen by the authors for the prototype is the way [3] obtain titanium tanning agent for leather comprising preparing a starting solution of titanyl sulphate, his stirring and cooling, salting out sulphatoethyl ammonium sulfate ammonium subsequent crystallization, filtration of the resulting suspension and sludge treatment.

The disadvantage of this method is a significant amount of wastewater, increased loss of titanium with mother liquor, the instability of the quality of tanning agent on the basicity and the impossibility of re-use to obtain valuable tanning material components contained in the waste waters, which leads to reduction of technical and economic indicators of the process.

The invention is aimed at reducing the volume of wastewater and losses titanium with mother liquor, to stabilize the quality of the tanning agent in basicity.

Specified for the La skins (prototype), comprising preparing a starting solution of titanyl sulphate, his stirring and cooling, salting out sulphatoethyl ammonium, ammonium sulfate, subsequent crystallization, filtration of the resulting suspension and sludge treatment by the present method in the original solution is further added ammonium chloride in the amount of 8-36 g/l as compounds containing ammonium chloride, use the mother liquor after filtration of the tanning agent, which dilute the original solution to the concentration of the titanium 80-120 g/l, the ratio of the volume of the starting solution for the liquor must be at least 2:1.

Comparative analysis of the proposed technical solution with the prototype shows that the inventive method differs from the known fact that in the original solution is further added ammonium chloride in the amount of 8-36 g/L.

As compounds containing ammonium chloride, use the mother liquor after filtration of the tanning agent, which dilute the original solution to the concentration of the titanium 80-120 g, and the ratio of the volume of source solution for the liquor must be at least 2:1.

In the analysis of patent and scientific and technical sources not identified technical solutions, obradivog about the novelty of this technical solution, and according to its patentability criteria of "novelty."

Comparison of proposed method with other technical solutions in this field of technology shows that it is known the use of mother solutions after evaporation as a raw material for titanium tanning agent. However, the use of additives ammonium chloride or untreated uterine solutions containing ammonium chloride, to obtain an initial solution of titanyl sulphate unknown. The claimed technical solution is not obvious from the prior art and meets the patentability criteria of "inventive step".

The mother liquor after filtration of a suspension of titanium tanning agent containing ammonium chloride, also contains, g/l: titanium 2-5; sulfate ion 200-400; ammonium ion 40-100; chlorine-ion up to 60.

Introduction to the original solution of titanyl sulphate supplementation of ammonium chloride in the amount of 8-36 g/l stock solution when the ratio of the volume of source solution for the liquor is not less than 2:1 allows you to:

to reduce the loss of titanium with mother liquor by increasing the concentration of vicariates (ammonium chloride) in solution;

reduce the amount of industrial waste waters upon receipt of the tanning agent for the repayment of part of the wastewater into the operation of cooking the outcome of the number of ammonium chloride, acting as a buffer.

Uterine solutions can be reused in the manufacture of tanning agent.

For experimental verification of the proposed method has undertaken the following activities. The prototype titanium tanning agent obtained by dissolving titanyl sulphate in 300 ml of water to a concentration of 650 g/l and stirring until complete dissolution within 1 h the resulting solution of titanyl sulphate was cooled with constant stirring to a temperature of not more than 28aboutC. To the cooled solution was injected into the ammonium sulfate in the amount of 1 kg/1 kg of titanyl sulphate. After the filing of ammonium sulfate in the solution, the suspension was stirred for 15 min (the time of crystallization) with the help of a mixer. Filtering suspensions of titanium tanning agent was carried out in a Buechner funnel on the filter paper under vacuum. The obtained product was dried at room temperature to a moisture content of 10%

By the present method titanium tanning agent obtained by dissolving titanyl sulphate in 300 ml of water to a concentration of 650 g/ and stirred until complete dissolution within 1 h Then the original solution was injected additive is ammonium chloride. The amount of ammonium chloride was: 5, 8, 22, 36, 40 g/l

On druh volume of the original solution and the mother liquor: 1:1; 2:1; 3:1; 4:1.

The resulting solution of titanyl sulphate was cooled with constant stirring to a temperature of not more than 28aboutC. To the cooled solution was injected into the ammonium sulfate in the amount of 1 kg/1 kg of titanyl sulphate. After the filing of ammonium sulfate in the solution, the suspension was stirred for 15 min (the time of crystallization) with the help of a mixer. Filtering suspensions of titanium tanning agent was carried out in a Buechner funnel on the filter paper under vacuum. The obtained product was dried at room temperature to a moisture content of 10%

Additionally was given the experience of multiple use of the cells for the preparation of the starting solution. In the experience of 11 for the preparation of the starting solution used mother liquor after tenfold use in a closed system.

During execution of this work was estimated volume of wastewater, the titanium content in the mother liquor, and also assessed the quality obtained by different variants of the tanning material for compliance with requirements of THE 95.290-79. the results are shown in table. 1 and 2.

The analysis results are given in table.1 and 2 shows that the inventive method differs from the prototype a lower content of ti is 5 l/kg of tanning agent on the prototype), more consistent quality of tanning agent on the basicity (44,3-45,1% instead of 42-47% on prototype) throughout the claimed range of the content of ammonium chloride or the ratio of the starting solution and the mother liquor.

The optimal parameters of the proposed method are:

the content of ammonium chloride 8-36 g/l (experiments 3-5);

the ratio of the volume of source solution for the liquor is not less than 2:1 (experiments 7-9).

A reduction in the content of ammonium chloride in the solution is less than 8 g/l (experiment 2) does not have a significant impact on the reduction of titanium in the mother liquor and the stabilization of the quality of tanning agent on basicity.

The excess content of the ammonium chloride in solution more than 36 g/l (6) leads to the precipitation of sulphatoethyl ammonium in the preparation of the solution, as a result, if the salting out formed small crystals and worse filterability of the suspension.

The decrease in the ratio of the volume of the starting solution for the liquor less than 2:1 (experiment 10) leads to an increase in the proportion of cells in the prepared solution, the increase in the content of ammonium chloride above the permissible limit, resulting in the precipitation of sulphatoethyl ammonium in the preparation of the solution, and the formation of melquist titanium tanning agent, obtained by the claimed method with optimal parameters, shows that the tanning agent is no different in properties from the tanning agent obtained by the prototype, and meets the requirements of THE 95.290-79. Reuse of the mother liquor does not lead to deterioration of the quality of the tanning agent.

This method tested in production conditions at the release parties titanium tanning agent with a positive result.

1. The METHOD of OBTAINING TITANIUM tanning agent FOR LEATHER comprising preparing a starting solution of titanyl sulphate with stirring, cooling, salting out sulphatoethyl ammonium sulfate ammonium subsequent crystallization, filtration of the resulting suspension and drying the precipitate, characterized in that in the original solution is further added ammonium chloride in the amount of 8 - 36 g/L.

2. The method according to p. 1, characterized in that the ammonium chloride used in the form of the mother liquor after filtration of the suspension, which was diluted original solution to the concentration of the titanium 80 - 120 g/l when the ratio of the volume of the source and uterine fluids at least 2 : 1.

 

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FIELD: coal-chemical products.

SUBSTANCE: weathered vitrinite brown coals from Baga-Nursk coal field having ash level 36-48% and moisture 20% are ground to granule size 0.5-0.9 mm. Resulting powder us sulfurized for 6-8 h with 98% sulfuric acid at 60-80°С and coal-to-acid weight ratio from 1:3 to 2:3. Sulfurized coal is neutralized and treated with 10-15% sodium hydroxide aqueous solution at weight ratio of alkali solution to initial coal (10-15):1 to form water-soluble sodium sulfohumate, after which water-soluble residual coal is separated by centrifugation. Centrifugate is mixed with 10-15% aqueous hydrochloric acid at volume ratio (10-15):6 to form precipitate, which is allowed to settle into compact form during 40-60 min. After decantation of liquid phase, solid residue is partially dried at 40-60°С until pasty mass is obtained.

EFFECT: increased content of tanning substances in humate-containing compounds and enabled utilization of oxidized brown coal in open-cut production of brown coals.

4 tbl, 5 ex

FIELD: coal-chemical products.

SUBSTANCE: weathered vitrinite brown coals from Baga-Nursk coal field having ash level 36-48% and moisture 20% are ground to granule size 0.5-0.9 mm. Resulting powder us sulfurized for 6-8 h with 98% sulfuric acid at 60-80°С and coal-to-acid weight ratio from 1:3 to 2:3. Sulfurized coal is neutralized and treated with 10-15% sodium hydroxide aqueous solution at weight ratio of alkali solution to initial coal (10-15):1 to form water-soluble sodium sulfohumate, after which water-soluble residual coal is separated by centrifugation. Centrifugate is mixed with 10-15% aqueous hydrochloric acid at volume ratio (10-15):6 to form precipitate, which is allowed to settle into compact form during 40-60 min. After decantation of liquid phase, solid residue is partially dried at 40-60°С until pasty mass is obtained.

EFFECT: increased content of tanning substances in humate-containing compounds and enabled utilization of oxidized brown coal in open-cut production of brown coals.

4 tbl, 5 ex

FIELD: tannery industry, in particular method for syntan (synthetic tanning material) production.

SUBSTANCE: claimed method includes diphenolepropane sulgation and condensation with formaldehyde followed by acidifying with sulfuric acid. Formed product is dispersed in lignosulfates containing 0.5-1.5 % of aluminum sulfate as calculated to aluminum oxide.

EFFECT: syntans with stable content of tanned materials: environmentally friendly and economical process.

1 ex

FIELD: tannery industry, in particular method for syntan (synthetic tanning material) production.

SUBSTANCE: claimed method includes diphenolepropane sulgation and condensation with formaldehyde followed by acidifying with sulfuric acid. Formed product is dispersed in lignosulfates containing 0.5-1.5 % of aluminum sulfate as calculated to aluminum oxide.

EFFECT: syntans with stable content of tanned materials: environmentally friendly and economical process.

1 ex

FIELD: tannery industry, in particular method for syntan (synthetic tanning material) production.

SUBSTANCE: claimed method includes diphenolepropane sulgation and condensation with formaldehyde followed by acidifying with sulfuric acid. Formed product is dispersed in lignosulfates containing 0.5-1.5 % of aluminum sulfate as calculated to aluminum oxide.

EFFECT: syntans with stable content of tanned materials: environmentally friendly and economical process.

1 ex

FIELD: light industry.

SUBSTANCE: invention relates to a method for treatment of fur hides before oxidative whitening of hair cover. Additional tanning and pickling are carried out separately at pH value 6.5-7.0. The preparation based on low-molecular alcohol polyacetals - "Dubitel M" is used as a tanning agent. Tanning agent is added for two steps wherein at the second step tanning agent is added in twice dose as compared at the first step. Additional tanning is carried out in the required ratio of components of an aqueous composition comprising sodium chloride, surface-active substance, preparation based on low-molecular alcohol polyacetals. Pickling is carried out with smearing on hair cover in the consumption 2-4 ml per 1 dm2 with the composition comprising iron sulfate, citric acid, surface-active substance and gelatin as a protecting additive. After pickling lying is carried out for 12-16 h. Method provides improved the quality of whitened fur hides.

EFFECT: improved method for treatment.

2 cl, 2 tbl

FIELD: light industry.

SUBSTANCE: invention relates to a method for treatment of fur hides before oxidative whitening of hair cover. Additional tanning and pickling are carried out separately at pH value 6.5-7.0. The preparation based on low-molecular alcohol polyacetals - "Dubitel M" is used as a tanning agent. Tanning agent is added for two steps wherein at the second step tanning agent is added in twice dose as compared at the first step. Additional tanning is carried out in the required ratio of components of an aqueous composition comprising sodium chloride, surface-active substance, preparation based on low-molecular alcohol polyacetals. Pickling is carried out with smearing on hair cover in the consumption 2-4 ml per 1 dm2 with the composition comprising iron sulfate, citric acid, surface-active substance and gelatin as a protecting additive. After pickling lying is carried out for 12-16 h. Method provides improved the quality of whitened fur hides.

EFFECT: improved method for treatment.

2 cl, 2 tbl

FIELD: light industry.

SUBSTANCE: invention relates to a method for treatment of fur hides before oxidative whitening of hair cover. Additional tanning and pickling are carried out separately at pH value 6.5-7.0. The preparation based on low-molecular alcohol polyacetals - "Dubitel M" is used as a tanning agent. Tanning agent is added for two steps wherein at the second step tanning agent is added in twice dose as compared at the first step. Additional tanning is carried out in the required ratio of components of an aqueous composition comprising sodium chloride, surface-active substance, preparation based on low-molecular alcohol polyacetals. Pickling is carried out with smearing on hair cover in the consumption 2-4 ml per 1 dm2 with the composition comprising iron sulfate, citric acid, surface-active substance and gelatin as a protecting additive. After pickling lying is carried out for 12-16 h. Method provides improved the quality of whitened fur hides.

EFFECT: improved method for treatment.

2 cl, 2 tbl

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