EP0007555A1 - Application d'aluminosilicates insolubles dans l'eau à la fabrication du cuir - Google Patents

Application d'aluminosilicates insolubles dans l'eau à la fabrication du cuir Download PDF

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Publication number
EP0007555A1
EP0007555A1 EP79102490A EP79102490A EP0007555A1 EP 0007555 A1 EP0007555 A1 EP 0007555A1 EP 79102490 A EP79102490 A EP 79102490A EP 79102490 A EP79102490 A EP 79102490A EP 0007555 A1 EP0007555 A1 EP 0007555A1
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Prior art keywords
water
aluminum silicates
carboxylic acids
urethane
ester
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EP79102490A
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German (de)
English (en)
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EP0007555B1 (fr
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Jürgen Dr. Plapper
Klaus Dr. Schumann
Emanuel Arndt
Emil Ruscheinsky
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning

Definitions

  • the invention relates to the use of water-insoluble, preferably water-containing aluminum silicates of the general formula in the cat an alkali metal ion and / or a divalent and / or a trivalent cation, n a number from 1 to 3, x a number from 0.5 to 1.8, y a number from 0.8 to 50, preferably 1, 3 to 20 mean, with a particle size of 0.1 .mu.m to 5 mm, which have a calcium binding capacity of 0-200 mg CaO / g of anhydrous active substance, in conjunction with carboxylic acids containing ester and / or urethane and / or amide groups in leather production
  • tanning fur skins and leather In addition to degreasing and pre-tanning pimples, this is particularly the case when tanning fur skins and leather.
  • other auxiliaries such as solvents and degreasing agents, tensides, electrolytes, phosphates, neutralizing agents, etc. are used in the processes of leather production.
  • the aim of the invention is to reduce the use of chemicals and the wastewater load in leather production.
  • certain aluminum silicates are used in combination with carboxylic acids containing ester and / or urethane and / or amide groups, which allow a considerable reduction in the auxiliaries commonly used, in particular chromium tanning agents, and, as a result of their ecological safety, lead to a substantial improvement in the wastewater situation .
  • chrome tanning is based on the formation of an azide complex and the agglomeration of the basic chromium salts with the carboxyl groups of the collagen.
  • the penetration and distribution of the combination tanning agents in the skin is increased, the disadvantages of the usual silicon tanning agents being avoided, since the aluminum silicates in the acidic medium present in the tanning process have a pH value of around 3-4.5 to form aluminum salts and polymeric silicas dissolve finest distribution.
  • the aluminum silicates are self-dulling due to their own acid consumption.
  • additional dulling agents can therefore be used to be dispensed with.
  • the tanning liquor shows improved stability when dulling and the tanning of the skins is increased. All in all, process control in tanning becomes more flexible and safer.
  • the carboxylic acids containing ester and / or urethane and / or amide groups can be used together with the aluminum silicates in the chrome tanning of leather.
  • the carboxylic acids mentioned can advantageously already be added in the strongly acidic pimple, that is to say before the actual tanning begins, since this achieves a high chromium content in the leather with a particularly uniform distribution.
  • the products to be used for the process according to the invention can be prepared by processes known per se (cf., for example, BE Müller, Houben-Weyl, "Methods of Organic Chemistry", Vol. XIV / 2, 1963, p. 16 ff).
  • the csrbcxyily-containing products are accordingly by reaction of hydroxyl and / or amino group-containing compounds in a molar ratio receive.
  • the molecular weight of the resulting products is generally more than 170 and less than 100,000; the substances contain at least 2 COOH groups.
  • Halogenated polycarboxylic acids preferably dicarboxylic acids such as e.g. Adipine, glutaric, oxalic; Malonic, maleic, terephthalic acid, phthalic acid, isophthalic acid, succinic acid, fumaric acid, aspartic acid, glutamic acid.
  • dicarboxylic acids such as e.g. Adipine, glutaric, oxalic; Malonic, maleic, terephthalic acid, phthalic acid, isophthalic acid, succinic acid, fumaric acid, aspartic acid, glutamic acid.
  • alcohols such as alkanols, alkenols, alkynols, diols, polyols, amino alcohols, ether alcohols.
  • Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, dibutylene glycol, polybutyleil glycol, aminoathanol, N-alkyl-diethanolamine, stearyl alcohol, oleyl alcohol, e.g. Related to sorbitol.
  • Compounds containing amido or urethane groups are also suitable for the process according to the invention.
  • Compounds as used for the production of polyester amides such as diaminoethane, aminoethanol, diaminopropane, diaminohexane, diaminocyclohexane, diaminodicyclohexylmethane.
  • Suitable carboxylic acids containing ester, urethane or amide groups are obtained, for example, by reacting in each case 2 mol of adipic acid or terephthalic anhydride or malic acid dimethyl ester with in each case 1 mol of diethylene glycol or dipropylene glycol or 1,6-hexanediol or 1, 12-octadecanediol or hexatnethylenediamine, or of 5 mol of adipiric acid or tcrephthalic anhydride with 3 moles of trimethylolpropane, etc.
  • the polyesters can continue, for. B. with clutaric acid or ammonia. Further examples of suitable compounds can be found in DE-OS 26 26 43 0 , pages 12-17.
  • the carboxylic acids containing ester, urethane or amide groups can be used with particular advantage together with di- and / or tricarboxylic acids and / or their water-soluble hydrolyzable partial esters in chrome tanning.
  • Examples of such compounds are aliphatic and / or aromatic carboxylic acids with 2-8 C atoms in the chain, such as. B. succinic acid; Glutaric acid, adipic acid, maleic acid, fumaric acid, aspartic acid, glutamic acid, phthalic acid, terephthalic acid, citric acid.
  • These acids can also be used in the form of their hydrolyzable partial esters, e.g. B.
  • mono- or polyhydric alcohols with 1-6 carbon atoms such as methanol, ethanol, n- and isopropanol, butanols, amyl alcohols, ethylene, Prcpylen- butylene glycols, glycerin, trimethylolpropane, pentaerythritol, sorbitol.
  • monoesters of diacids or trihydric acids are preferred, since these are in an acid medium, e.g. B. pimple or tanning liquor, hydrolyze relatively quickly.
  • the aluminum silicates to be used according to the invention are amorphous, crystalline, synthetic and natural ' products which meet the conditions mentioned above.
  • an alkali metal ion, preferably sodium ion, x is a number from 0.7 to 1.5
  • y is a number from 0.8 to 6, preferably 1.3 to 4 whose particle size is 0.1 to 25 ⁇ , preferably 1 - 12 ⁇ and which have a calcium binding capacity of 20-200 mg CaO / g of anhydrous active substance.
  • the same importance should be attached to the products which correspond to the mentioned ones in the meaning of cat, x, y and the calcium binding capacity and differ only by a particle size of more than 25 ⁇ to 5 mm.
  • Such alkali aluminum silicates can be prepared synthetically in a simple manner, for. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water.
  • aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution.
  • the desired aluminum silicates are also obtained by mixing the two components present in the solid state in the presence of water.
  • Alkali aluminum silicates can also be prepared from Al (OH) 3 , A1 2 0 3 or SiO 2 by reaction with alkali silicate or aluminate solutions. Finally, such substances also form from the melt, but this process appears because of the high melting temperatures required and the need to fine-tune the melt having to transfer distributed products is economically less interesting.
  • the alkali aluminum silicates prepared by precipitation or converted into aqueous suspension in a finely divided state by other processes can be converted from the amorphous to the aged or to the crystalline state by heating to temperatures of 50-200 ° C.
  • the present in aqueous suspension, amorphous or crystalline alkali aluminum silicate can be separated by filtration from the remaining aqueous solution and at temperatures of, for. B. Dry 50 - 800 ° C. Depending on the drying conditions, the product contains more or less bound water. Anhydrous products are obtained at 800 ° C. However, the water-containing products are preferred, in particular those such as are obtained when drying at 50-400 ° C., in particular 50-200 ° C. Suitable products can be based on their total weight e.g. Have water contents of approx. 2 - 30%, mostly approx. 8 - 27%.
  • Precipitation conditions can already contribute to the formation of the desired small particle sizes of 1 - 12 ⁇ , whereby the mixed aluminate and silicate solutions - which can also be fed into the reaction vessel at the same time - are exposed to strong shear forces, for example by stirring the suspension intensively. If crystallized alkali aluminum silicates are produced - these are preferably used according to the invention - the formation of large, possibly penetrating crystals is prevented by slowly stirring the crystallizing mass.
  • Preferred products are e.g. B, synthetically produced crystalline alkali aluminum silicates of the composition in the cat represents an alkaline cation, preferably a sodium cation. It is advantageous if the alkali aluminum silicate crystallites have rounded corners and edges. If you want to produce the alkali aluminum silicates with rounded corners and edges, it is advantageous to start from an approach whose molar composition is preferably in the range is, where cat 2 / n has the meaning given above and in particular means the sodium ion. This approach is brought to crystallization in the usual way. This is advantageously done by heating the batch to 70-120 ° C., preferably 80-95 ° C., with stirring, for at least 1/2 hour.
  • the crystalline product is isolated in a simple manner by separating the liquid phase. If necessary, it is advisable to wash and dry the products with water before further processing. Even when working with An approach, the composition of which differs little from that given above, still gives products with rounded corners and edges, especially if the deviation relates only to one of the four concentration parameters given above.
  • water-soluble alkali aluminum silicates which have been precipitated and aged or crystallized in the presence of water-soluble inorganic or organic dispersants. Products of this type are accessible in a technically simpler manner.
  • Suitable water-soluble organic dispersants are surfactants, non-surfactant-like aromatic sulfonic acids and compounds with complex formation capacity for calcium.
  • the dispersants mentioned can be introduced into the reaction mixture in any manner before or during the precipitation.
  • the amount of the dispersant should be at least 0.05% by weight, preferably 0.1-5% by weight, based on the total amount of precipitation.
  • the precipitation product is heated to temperatures of 50-200 ° C. for 1/2 to 24 hours.
  • useful dispersants such as sodium lauryl ether sulfate, sodium polyacrylate, hydroxy relihandiphosphonat and others to name a few.
  • a particular variant of the crystal structure of the alkali aluminum silicates to be used according to the invention is represented by compounds of the general formula
  • a further variant of the finely divided, water-insoluble alkali aluminum silicates to be used according to the invention are compounds of the formula
  • the manufacture of such products is based on an approach whose molar composition is preferably in the range lies. This approach is brought to crystallization in the usual way. This is advantageously done by heating the batch to 100-200 ° C., preferably 130-160 ° C. for at least 1/2 hour with vigorous stirring.
  • the crystalline product is isolated in a simple manner by separating off the liquid phase. If necessary, we recommend washing the products with water before further processing and drying them at temperatures of 20 - 200 ° C. The products dried in this way still contain bound water. If the products are produced in the manner described, very fine crystallites are obtained which assemble into spherical particles, possibly hollow spheres of approximately 1 to 4 ⁇ m in diameter.
  • Alkali aluminum silicates which can be prepared from calcined (destructured) kaolin by hydrothermal treatment with aqueous alkali hydroxide are also suitable for the use according to the invention.
  • the formula comes to the products to, where Kat is an alkaline application, especially a Sodium cation means.
  • the production of the alkali aluminum silicates from calcined kaolin leads directly to a very finely divided product without any special technical effort.
  • the hydrothermal treatment of the kaolin previously calcined at 500 to 800 ° C. with aqueous alkali hydroxide is carried out at 50 to 100 ° C. The crystallization reaction taking place is generally complete after 0.5-3 hours.
  • slurried kaolins consist mainly of the clay mineral kaolinite with the approximate composition Al 2 O 3 , 2 SiO 2 . 2 H 2 0, which is a layered structure. having.
  • the kaolin In order to obtain the alkali aluminum silicates to be used according to the invention by hydrothermal treatment with alkali metal hydroxide, the kaolin must first be destroyed, which is most conveniently carried out by heating the kaolin to temperatures of 500 to 800 ° C. for two to four hours.
  • the x-ray-amorphous water-free metakaolin is formed from the kaolin.
  • the kaolin can also be destroyed by mechanical treatment (grinding) or by acid treatment.
  • the kaolins that can be used as starting material are light powders of great purity; however, their iron content is around 2,000 to 10,000 ppm. Fe significantly higher than the values from 20 to 100 ppm. Fe in the case of the alkali aluminum silicates prepared by precipitation from alkali silicate and alkali aluminate solutions. This higher iron content in the alkali aluminum silicates made from kaolin is not a disadvantage, since the iron in the form of iron oxide is firmly built into the alkali aluminum silicate lattice and is not dissolved out.
  • the hydrothermal action of sodium hydroxide on destructured kaolin produces a sodium aluminum silicate with a cubic, faujasite-like structure.
  • Alkali aluminum silicates which can be used according to the invention can also be prepared from calcined (destructured) kaolin by hydrothermal treatment with aqueous alkali metal hydroxide with the addition of silicon dioxide or a compound which provides silicon dioxide.
  • the generally obtained mixture of alkali aluminum silicates of different crystal structure consists of very finely divided crystal particles which have a diameter of less than 20 ⁇ and are usually composed 100% of particles smaller than 10 ⁇ .
  • this conversion of the destructured kaolin is preferably carried out using sodium hydroxide solution and water glass. This creates a sodium aluminum silicate J, which has several names in the literature, e.g. B. is referred to as molecular sieve 13 X or zeolite NaX (see. 0.
  • the sodium aluminum silicate J has a cubic crystal structure similar to the naturally occurring faujasite.
  • the conversion reaction can be influenced in particular by stirring the batch, by elevated temperature (boiling heat at atmospheric pressure or in an autoclave) and higher amounts of silicate, ie by a molar batch ratio Si0 2 : Na 2 0 of at least 1, in particular 1.0-1.45 be that in addition to or instead of sodium aluminum silicate J, the sodium aluminum silicate F is formed.
  • the sodium aluminum silicate F is referred to in the literature as "zeolite P" or "type B” (cf. DW Breck, "Zeolite Molecular Sieves",
  • the sodium aluminum silicate F has a structure similar to the naturally occurring zeolites Gismondin and Garronit and is in the form of crystallites that appear to be spherical on the outside. In general, the production conditions for sodium aluminum silicate F and for mixtures of J and F are less critical than those for a pure crystal type A.
  • the types of various alkali aluminum silicates described above can be produced not only in the finely divided form with particle sizes of 0.1-25 ⁇ m without difficulty, but also in coarser form with particle sizes of more than 25 ⁇ m to 5 mm. This can either be done by omitting the measures that prevent crystal growth or agglomerate formation or by subsequently converting finely divided products into a granular form in a known manner.
  • the desired particle size can then optionally be adjusted by grinding and air separation.
  • Also suitable for the use according to the invention in leather production in combination with carboxylic acids containing ester and / or urethane and / or amide groups are aluminum silicates in which, in the aforementioned formula, Kat is an alkali metal ion and / or a divalent and / or trivalent cation , where Kat consists of at least 20 mol% of alkali metal ions, preferably sodium ions, x a number from 0.7 to 1.5, n a number from 1 to 3, y a number from 0.8 to 6, preferably 1.3 - 4 mean, with a particle size of 0.1 ⁇ to 5 mm and a calcium binding capacity of 20-200 mg Ca0 / g of anhydrous active substance.
  • corresponding aluminum silicates are obtained by ion exchange from alkali aluminum silicates with polyvalent cations, e.g. Calcium, magnesium, zinc or aluminum ions obtained in a known manner.
  • aluminum silicates in which the alkali cations are partially replaced by polyvalent cations, in particular calcium, magnesium or zinc ions, can be given by the following formulas:
  • the products contain about 8-27% by weight of water. They can be used in crystalline and amorphous form.
  • Further aluminum silicates suitable for the use according to the invention are those in which, in the abovementioned formula Kat, an alkali metal ion and / or a divalent and / or a trivalent cation, x is a number from 0; 5-1.8, y is a number from 0, 8-6, preferably 1.3-4, mean with a particle size of 0.1 ⁇ to 5 mm and a calcium binding capacity of 0 to ⁇ 20 mg CaO / g of anhydrous active substance.
  • the aluminum silicates in this group include amorphous, crystalline, synthetic and natural products. They can be prepared synthetically in a simple manner, for example by reaction of water-soluble silicates with water-soluble aluminates in the presence of water, as has already been described in principle in the above preparation processes.
  • the following aluminum silicates can be mentioned as examples of such products:
  • Aluminum silicates can also be used for the use according to the invention in leather production, in which, in the aforementioned formula, Kat is an alkali metal ion and / or a divalent and / or trivalent cation, x is a number from 0.5 to 1.8, y is a number> 6 to 50, preferably> 6 to 20, with a particle size of 0.1 ⁇ to 5 mm and a calcium binding capacity of 0-200 mg Ca0 / g of anhydrous active substance.
  • Kat is an alkali metal ion and / or a divalent and / or trivalent cation
  • x is a number from 0.5 to 1.8
  • y is a number> 6 to 50, preferably> 6 to 20, with a particle size of 0.1 ⁇ to 5 mm and a calcium binding capacity of 0-200 mg Ca0 / g of anhydrous active substance.
  • Such aluminum silicates can be amorphous or crystalline and of synthetic or natural origin. They can be prepared synthetically in a simple manner, for example by reacting water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution. Polyvalent cations can be introduced by processes known from the literature by exchanging monovalent cations, for example sodium ions, for divalent and trivalent cations such as calcium, magnesium, zinc or aluminum ions. In addition to the cations mentioned, the natural aluminum silicates can also contain other cations in a fluctuating, usually small amount.
  • Quaternary nitrogen compounds such as, for example, ammonium ions, can also be present in varying amounts as cations in synthetic aluminum silicates.
  • the extent to which the aluminum silicates are loaded with the cations mentioned largely depends on the size of the selectivity coefficients.
  • those aluminum silicates of the stated general composition are advantageously used in which, in the general formula, Kat represents an alkali metal ion, preferably a sodium ion.
  • An essential criterion for the usability according to the invention of all of the above-mentioned aluminum silicates is their at least partial acid solubility in the pH range from 2.5 to 5, preferably 3.5 to 4.5.
  • the products that meet this requirement are at least partially dissolved by a solution of 2.5 ml of concentrated formic acid in 100 ml of water. This acid solubility test is carried out in the following way:
  • a suspension of 2 g of aluminum silicate (based on anhydrous active substance) in 100 ml of distilled water is slowly mixed with 2 ml of concentrated formic acid over a period of 8 to 30 minutes at a temperature of 22 ° C.
  • the pH of the suspension must be above 2.5, between 2.5 and 5.5, preferably between 3.5 and 4.5. If these pH values are reached during the titration, then an aluminum silicate is present which is suitable for the use according to the invention with regard to its acid-binding capacity.
  • Products in which a pH value outside this range is found by this method either have an acid binding capacity which is too low or an alkalinity which is too high and cannot be used in the sense of the invention.
  • more alkaline aluminum silicates can also be used.
  • the tanning of fur skins and leather is carried out in the usual way. Pimples and tanning can be combined in a known manner.
  • the leather can then be greased.
  • chrome tanning about 1 to 50 g / l, preferably 15-30 g / l, of aluminum silicate, based on the anhydrous product, are used in the tanning liquor.
  • the ester and / or urethane and / or amide group-containing carboxylic acids are used in the tanning liquor in an amount of 1 to 20 g / l.
  • the addition can also take place in the pimple, the amount is then also about 1 to 20 g / l of liquor.
  • the usual active ingredients and auxiliaries e.g. anionic, cationic or nonionic surfactants, chromium salts etc. are used.
  • dicarboxylic acids such as adipic acid or glutaric acid or their monomethyl ester, are additionally used in amounts of 1 to 20 g / l of liquor.
  • the concentration of chromium salts in the tanning liquor can be reduced by 25-50% compared to the normal tanning processes.
  • the silicate solution was added to the aluminate solution with vigorous stirring in a 15 liter container. Was stirred with a stirrer with a dispersing disc at 3,000 revolutions / min. Both solutions were at room temperature.
  • An X-amorphous sodium aluminum silicate was formed as an initial precipitation product under an exothermic reaction. After stirring for 10 minutes, the suspension of the precipitate was transferred to a crystallization container, where it remained for 6 hours at 90 ° C. with stirring (250 revolutions / min.) For the purpose of crystallization. After the lye had been suctioned off from the crystal slurry and washed with deionized water until the wash water running off had a pH of approximately 10, the filter residue was dried.
  • the water levels were increased by one hour
  • the maximum particle size was found to be 3 - 6 ⁇ .
  • the sodium aluminum silicate C was first produced. After sucking off the mother liquor and washing the crystal mass with demineralized water up to pH 10, the filter residue was slurried in 6.1 l of a 25% KCl solution. The suspension was briefly heated to 80-90 ° C; it was then cooled and filtered off and washed again.
  • Alkali lye was placed in a stirred vessel and the calcined kaolin stirred in at temperatures between 20 and 100.degree.
  • the suspension was brought to the crystallization temperature of 70 to 100 ° C. with stirring and kept at this temperature until the end of the crystallization process.
  • the mother liquor was then filtered off with suction and the residue was washed with water until the wash water running off had a pH of 9 to 11.
  • the filter cake was dried and then crushed to a fine powder, or it was ground to remove the agglomerates formed during drying. This grinding process was omitted if the filter residue was further processed wet or if the drying was carried out using a spray dryer or a current dryer.
  • the hydrothermal treatment of the calcined kaolin can also be carried out according to a continuous procedure.
  • This thus dried aluminosilicate was mixed with 10 kg bentonite and 20.1 kg water, which had been adjusted to pH 6 with 25% hydrochloric acid, and in a 100 kg "Lödige" mixer (blade mixer from Lödige) Homogenized for 20 minutes. With further mixing, the granulate formation was brought about within a further 8 minutes by gradually adding 13.5 kg of further water, likewise adjusted to a pH of 6.
  • the granules were dried in a drying cabinet at 150 ° C. for 60 minutes and solidified by subsequent heating (15 minutes at 780 ° C.).
  • the calcium binding capacity of the product was 120 mg CaO / g active substance.
  • the grain size was 0.08 to 2 mm.
  • an Eirich turbo mixer plate / turbo mixer from Eirich
  • the required homogenization and granulation times were shorter. If one proceeded as described above for the production of the sodium aluminum silicate A in the form of granules, the homogenization and the formation of the granules was completed after a total of 5 minutes (instead of after 28 minutes with the paddle mixer). After drying for 15 minutes at 140 ° C. and calcining for 5 minutes at 800 ° C. in a forced air muffle furnace, granules were obtained which had good exchangeability, good hot water resistance and grain strength.
  • the calcium retention capacity of the product was 110 g CaO / g active substance.
  • the grain size was 0.08 to 2 mm.
  • alkali aluminum silicates with particle sizes of more than 25 ⁇ to 5 mm can be produced if alkali aluminum silicates of types B - J of the main patent are used. treated according to the above manufacturing instructions.
  • aluminosilicate L 50 kg were slurried in a 300 l stirred container with 180 l of water and adjusted to a pH of 6 with 25% hydrochloric acid. The suspension was moderately stirred for 40 minutes. The aluminosilicate was then filtered off, washed out several times with water and dried at 105 ° C. for 10 hours. The dried aluminosilicate was mixed with 10 kg of bentonite and 20 l of water, which had been adjusted to a pH of 6 with 25% hydrochloric acid, and homogenized in a 100 kg paddle mixer for 20 minutes. With stirring, the granulate formation was brought about within a further 8 minutes by gradually adding 13.5 l of water adjusted to a pH of 6. The granules were dried at 150 ° C. for 60 minutes and solidified by heating at 780 ° C. for 15 minutes. The grain size distribution of the aluminosilicate D obtained in this way was 1 to 2 mm.
  • the preparation of the aluminum silicates in which in the aforementioned formula Kat an alkali metal ion and / or a divalent and / or trivalent cation, x a number from 0.5 to 1.8 bc practitioner, the particle size 0.1 ⁇ to 5 mm and once y is a number from 0.8 to 6 and the calcium binding capacity is 0 to ⁇ 20 mg Ca0 / g and on the other hand y is a number from> 6 to 50 and the calcium binding capacity is 0 to 200 mg CaO / g of anhydrous active substance, can in principle be the same Be done as indicated in the manufacturing processes described above. In addition, some of the products are naturally occurring aluminum silicates.
  • the product obtained which is a synthetic crystalline zeolite (analcite), had the following characteristics:
  • the preparation was carried out analogously to the data for aluminum silicate R, with 6.91 kg of aluminate (18.0% Na 2 O, 11.2% Al 2 O 3 , 70.8% H 2 0) and 3.09 kg for the precipitation Silicate (8.0% Na 2 O, 26.9% SiO 2 , 65.1% H 2 O) were used. Crystallization of the precipitate was carried out at 100 ° C for 4 hours. After washing, the filter cake was dried at 100 ° C. for 24 hours and then crushed to a fine powder.
  • the product obtained, a field spatoid hydrosodalite had the following characteristics:
  • This aluminum silicate is a synthetic zeolite (mordenite), in which y has a value> 6 according to the aforementioned formula.
  • the production of such aluminum silicates is described in more detail in the monograph by Donald W. Breck, Zeolite, Molecular Sieves, published by John Wiley & Sons, NY.
  • the synthetic mordenite is produced from the reaction components sodium aluminate and silica at temperatures between 265 - 295 ° C for 2 - 3 days and provides a product with the following composition:
  • Natural zeolite (Clinoptilolite), as it is extracted in large quantities in the open-cast mine in the western United States.
  • Further examples of natural aluminum silicates which can be used according to the invention and in which y has a value> 6 according to the abovementioned formula are the following commercial products from The Anaconda Comp., Denver, USA:
  • the nakedness are with let run at 20 ° C in the barrel for 10 minutes. Then add and another runtime of 2 hours. The pelts are then left to stand in the bath overnight (pH 3.8 in pelvic cross-section). After a further run time of 30 minutes, an addition of and another runtime of 30 minutes. After that added and let run for 90 minutes. Then add after which another 4 hours in the barrel is treated.
  • the aluminum silicate A can with equally good or approximately equally good effect, the aluminum silicates B, D, J, K, M, P.
  • the final pH of the liquor is 4.1 - 4.2.
  • the residual chromium content of the liquor is 0.3 to 0.9 g / l chromium oxide. If tanning is carried out using conventional chrome tanning processes, the residual chromium content is 7 - 11 g / l chromium oxide.
  • the percentages relate to the weight of the pimple and to the weight of the skin when tanning.
  • Aluminum silicate H can be replaced by aluminum silicate C, F, L, U, W with an equally good or approximately equally good effect.
  • the final pH value of the liquor is 4.1.
  • the residual chromium content of the broth is 0.33 g / l chromium oxide.
  • the residual chromium content in a conventional tanning process is between 7 and 11 g / l chromium oxide.
  • the residual chromium content of the fleet is 0.55 g / l chromium oxide compared to a pest chromium content of 7-11 g / l chromium oxide in conventional tanning processes.
  • the residual chromium content of the broth is 0.2 to 93 g / l chromium oxide compared to a residual chromium content of 6 - 10 g / l chromium oxide with conventional chrome tanning.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Detergent Compositions (AREA)
EP79102490A 1978-07-20 1979-07-17 Application d'aluminosilicates insolubles dans l'eau à la fabrication du cuir Expired EP0007555B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2831846 1978-07-20
DE19782831846 DE2831846A1 (de) 1978-07-20 1978-07-20 Verwendung wasserunloeslicher aluminiumsilikate bei der lederherstellung

Publications (2)

Publication Number Publication Date
EP0007555A1 true EP0007555A1 (fr) 1980-02-06
EP0007555B1 EP0007555B1 (fr) 1981-12-30

Family

ID=6044854

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79102490A Expired EP0007555B1 (fr) 1978-07-20 1979-07-17 Application d'aluminosilicates insolubles dans l'eau à la fabrication du cuir

Country Status (5)

Country Link
US (1) US4264319A (fr)
EP (1) EP0007555B1 (fr)
JP (1) JPS5516096A (fr)
BR (1) BR7904607A (fr)
DE (1) DE2831846A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998014620A1 (fr) * 1996-10-03 1998-04-09 Beaud-Challes-Solap Sa Procede de tannage de peaux

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4502859A (en) * 1983-04-11 1985-03-05 Rockmont Industries, Inc. Hide tanning composition and method of preparing same
GB8409266D0 (en) * 1984-04-10 1984-05-23 Alcan Int Ltd Tanning of leather using aluminium compounds
DE3689932T2 (de) * 1985-08-23 1994-11-24 Hagiwara Research Corp Amorfes Alumosilikat und Verfahren zu dessen Herstellung.
JPS6323960A (ja) * 1986-07-16 1988-02-01 Zenji Hagiwara 非晶質アルミノ珪酸塩粒子を含有する高分子体及びその製造方法
US5306435A (en) * 1991-07-11 1994-04-26 Nihon Junyaku Co., Ltd. Treating agent composition for leather, for fibrous materials
GB0017212D0 (en) * 2000-07-14 2000-08-30 Pittards Plc An improved process for manufacturing leather
PT2574682E (pt) 2011-09-30 2014-01-21 Kemira Oyj Composição amiga do meio ambiente, adequada para curtimenta de couro, compreendendo zeólito
PL3059327T3 (pl) 2015-02-19 2018-03-30 Taminco Finland Oy Przyjazny dla środowiska sposób garbowania chromowego
CN114214471B (zh) * 2021-12-08 2024-04-02 兴业皮革科技股份有限公司 一种提升紧实性皮革均匀度的湿整理方法
CN114854908B (zh) * 2022-04-24 2024-01-19 陕西科技大学 以水滑石为催化剂制备的多糖基纳米复合无铬鞣剂及方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2395472A (en) * 1942-02-25 1946-02-26 Du Pont Tanning compositions and their manufacture
FR2271290A1 (fr) * 1974-05-18 1975-12-12 Bayer Ag
FR2354383A1 (fr) * 1976-06-12 1978-01-06 Bayer Ag Procede de tannage avec un acide carboxylique portant une fonction ester et/ou urethanne et/ou amide

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GB568180A (en) * 1943-04-03 1945-03-22 Ici Ltd Improvements in or relating to tanning compositions and processes for tanning
DE1945006A1 (de) * 1969-09-05 1971-03-11 Basf Ag Komplexe Aluminium- und Aluminium-Chrom-Salze
GB1353024A (en) * 1970-07-24 1974-05-15 Nat Res Dev Tanning
US4049379A (en) * 1974-05-30 1977-09-20 Basf Aktiengesellschaft Complex basic zirconium salts and aluminum salts
DE2822072A1 (de) * 1978-05-20 1979-11-29 Henkel Kgaa Verwendung wasserunloeslicher aluminiumsilikate bei der lederherstellung
JPS5460615A (en) * 1977-10-21 1979-05-16 Fuji Heavy Ind Ltd Exhaust gas purifier for internal combustion engine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2395472A (en) * 1942-02-25 1946-02-26 Du Pont Tanning compositions and their manufacture
FR2271290A1 (fr) * 1974-05-18 1975-12-12 Bayer Ag
FR2354383A1 (fr) * 1976-06-12 1978-01-06 Bayer Ag Procede de tannage avec un acide carboxylique portant une fonction ester et/ou urethanne et/ou amide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 69, 1968 Nr. 20430t, Seite 1935 Columbus, Ohio, U.S.A; & SU-A-215 393 (S. Kuraitis, 03-04-1968). *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998014620A1 (fr) * 1996-10-03 1998-04-09 Beaud-Challes-Solap Sa Procede de tannage de peaux
FR2754274A1 (fr) * 1996-10-03 1998-04-10 Beaud Challes Solap Sa Procede de tannage de peaux

Also Published As

Publication number Publication date
BR7904607A (pt) 1980-03-25
DE2831846A1 (de) 1980-02-07
JPS5516096A (en) 1980-02-04
US4264319A (en) 1981-04-28
JPS6234800B2 (fr) 1987-07-29
EP0007555B1 (fr) 1981-12-30

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