EP0005546B1 - Verwendung wasserunlöslicher Aluminiumsilikate bei der Chromgerbung von Leder - Google Patents

Verwendung wasserunlöslicher Aluminiumsilikate bei der Chromgerbung von Leder Download PDF

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Publication number
EP0005546B1
EP0005546B1 EP79101513A EP79101513A EP0005546B1 EP 0005546 B1 EP0005546 B1 EP 0005546B1 EP 79101513 A EP79101513 A EP 79101513A EP 79101513 A EP79101513 A EP 79101513A EP 0005546 B1 EP0005546 B1 EP 0005546B1
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EP
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Prior art keywords
water
aluminium silicates
dicarboxylic
partial esters
tricarboxylic acids
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EP79101513A
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German (de)
English (en)
French (fr)
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EP0005546A2 (de
EP0005546A3 (en
Inventor
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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Publication of EP0005546A3 publication Critical patent/EP0005546A3/xx
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Classifications

    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • 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
    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • 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

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 1-3, x a number from 0.5-1.8, y a number from 0.8-50, preferably 1, 3-20 mean, with a particle size of 0.1 ⁇ to 5 mm, which have a calcium binding capacity of 0-200 mg CaO / g of anhydrous active substance, in conjunction with di- and / or tricarboxylic acids and / or their water-soluble hydrolyzable partial esters the chrome inheritance of leather.
  • auxiliaries such as solvents and degreasing agents, tensides, electrolytes, phosphates, neutralizing agents, etc. used.
  • solid tanning agent compositions which contain precipitated aluminum silicates as the sole tanning agent. They are used in the acidic medium together with organic hydrogen-binding donor compounds such as ethers, amides, alcohols, ketones and phosphoric acid esters.
  • organic hydrogen-binding donor compounds such as ethers, amides, alcohols, ketones and phosphoric acid esters.
  • a masking agent u. a. Salts of di- and tricarboxylic acids such as citrates, oxalates, adipates can also be used.
  • an application in the chrome tanning of leather is not considered.
  • a process is known from FR-A-2 271 290 in which di- or tricarboxylic acids are used in chrome tanning, but not in connection with aluminum silicates.
  • 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 di- and / or tricarboxylic acids and / or their water-soluble hydrolyzable partial esters, which enable a considerable reduction in the auxiliaries commonly used, in particular chromium tanning agents, and, as a result of their ecological safety, to substantially improve the wastewater situation to lead.
  • 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 aluminum silicates are expediently added to the chrome tanning solution at the end of the tanning process.
  • 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 pH values 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. It is therefore not necessary to use additional blunting agents.
  • the tanning liquor shows improved stability when dulling and the tanning of the skins is increased. Overall, the process control in tanning becomes more flexible and safer.
  • the di- and / or tricarboxylic acids or their hydrolyzable partial esters can be used together with the aluminum silicates in the chrome tanning of leather.
  • the acids or the partial esters can advantageously be added in the strongly acidic pimple, ie before the actual tanning begins, since this achieves a high chromium content in the leather with a particularly uniform distribution.
  • Suitable di- or tricarboxylic acids according to the invention are aliphatic and / or aromatic carboxylic acids with 2-8 C atoms, such as Succinic acid, glutaric acid, adipic acid, meleinic acid, fumaric acid, aspartic acid, glutamic acid, phthalic acid, terephthalic acid, citric acid.
  • the hydrolyzable partial esters of these carboxylic acids with mono- or polyhydric alcohols having 1-6 C atoms can also be used in the same way.
  • Such alcohols are e.g. B. methanol, ethanol, n- and iso-propanols, butanols, amyl alcohols, ethylene, propylene, butylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol.
  • the monoesters of the di- or trivalent 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.
  • the same importance is to be attached to the products which correspond to those mentioned in the meaning of cat, x, y and the calcium binding capacity and differ only by a particle size of more than 25 ⁇ m 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 ' Al 2 0 3 or Si0 2 by reaction with alkali silicate or aluminate solutions.
  • the alkali aluminum silicates produced 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.
  • the product contains more or less bound water.
  • Anhydrous products are obtained at 800 ° C.
  • the water-containing products are preferred, especially those 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 ⁇ m, 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, e.g. the suspension is stirred intensively.
  • 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. Nevertheless, undesired agglomeration of crystal particles can occur during drying, so that it may be advisable to use these secondary particles in a suitable manner, e.g. to remove by air sighting.
  • Alkaline aluminum silicates obtained in the coarser state, which have been ground to the desired grain size, can also be used. For this, e.g. Mills and / or air classifiers or their combinations.
  • Preferred products are, for example, 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 aluminum aluminum silicates with rounded corners and edges, it is advantageous to start from an approach whose molar composition is preferably in the range lies, wibei Kat 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 to 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 specified above, products with rounded corners and edges are still obtained, in particular if the deviation relates only to one of the four concentration parameters specified above.
  • Suitable water-soluble organic dispersants are surfactants, non-enviable aromatic sulfonic acids and compounds with complexing ability for Celclum.
  • the dispersants mentioned can be introduced into the reaction mixture in any manner before or during the precipitation, they can e.g. presented as a solution or dissolved in the aluminate and / or Sillkat solution. Particularly good effects are achieved when the dispersing agent is dissolved in the Sillkat solution.
  • the amount of dispersant should be at least 0.05% by weight, preferably 0.1-5% by weight, based on the total amount of precipitation. For aging or crystallization, the precipitate is heated to temperatures of 50-200 ° C. for 1 / 2-24 hours. From the variety of useful dispersants such. As sodium lauryl ether sulfate, sodium polyaarylate, hydroxyethiphosphonate 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 the.
  • a further variant of the finely divided, water-insoluble alkali aluminum 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 10D-200 ° C., preferably to 130-160 ° C., with vigorous stirring for at least 1/2 hour.
  • the crystalline product is isolated in a simple manner by separating the liquid phase. It may be advisable to wash the products with water before further processing and to dry them at temperatures of 20-200 ° C. The products dried in this way still contain bound water. If you manufacture the products in the catfish described, you get very fine crystallites, which assemble into spherical particles, possibly hollow spheres with a diameter of approx. 1 to 4 ⁇
  • alkali aluminum silicates which can be prepared from calcined (destructurized) kaolin by hydrothermal treatment with aqueous alkali metal hydroxide.
  • the formula comes to the products to, where cat is an alkaline cation, in particular a sodium cation.
  • the production of the alkali aluminum sulfates from calcined kaolin leads directly to a very finely divided product without any particular technical effort.
  • the hydrothermal treatment of the Keollns 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 Si0 2 . 2 H 2 0, which has a layer structure.
  • 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 exposure of sodium hydroxide to destructured kaolin creates 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 ⁇ m and are usually composed 100% of particles smaller than 10 ⁇ m.
  • 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.
  • 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 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", New York 1974, p. 72 ).
  • 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 without difficulty in addition to the finely divided form with particle sizes of 0.1-25 ⁇ m and 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 di- and / or tricarboxylic acids and / or their water-soluble hydrolyzed partial esters 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 0.7-1.5, n a number from 1-3, y a number from 0.8-6, preferably 1.3- 4 mean, with a particle size of 0.1 microns to 5 mm and a calcium binding capacity of 20-200 mg CaO / g of anhydrous active substance.
  • Kat is an alkali metal ion and / or a divalent and / or trivalent cation
  • Kat consists of at least 20 mol% of alkali metal ions, preferably sodium ions, x a number from 0.7-1.5,
  • 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.
  • 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 above-mentioned formula Kat, an alkali metal ion and / or a divalent and / or a trivalent cation, x is a number from 0.5 to 1.8, y is a number from 0, 8-6, preferably 1.3-4, mean with a particle size of 0.1 .mu.m to 5 mm and a calcium binding capacity of 0 to ⁇ 20 mg CaO / g of anhydrous active substance.
  • Aluminum silicates can also be used for the use according to the invention in leather production, 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, y a number> 6 to 50, preferably> 6 to 20 mean, with a particle size of 0.1 microns to 5 mm and a calcium binding capacity of 0-200 mg CaO / g of anhydrous active substance.
  • 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 10 to 50 g / l aluminum silicate, based on the anhydrous product, is used in the tanning liquor.
  • the di- and tricarboxylic acids or their water-soluble hydrolyzable partial esters are used in the tanning liquor in an amount of 1 to 20 g / l.
  • Adipic acid and glutaric acid or their partial esters are preferred.
  • the acid can also be added 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 non-ionic surfactants, chromium salts etc. are used in the tanning liquor as well as in the pimple.
  • the concentration of the 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-ray amorphous sodium aluminum silicate formed as the primary precipitation product under an exothermic reaction.
  • 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 sucked 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 contents were determined by heating the pre-dried products at 800 ° C for one hour. The up to the pH of. About 10 washed or neutralized and then dried sodium aluminum silicates were then ground in a ball mill. The grain size distribution was determined using a sedimentation balance.
  • the maximum particle size was found to be 3-6 p.m.
  • 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% KCI 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 crystallization process was complete.
  • 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 of bentonite and 20.1 kg of water, which had been adjusted to a pH of 6 with 25% hydrochloric acid, and in a 100 kg "Lödige" mixer (paddle 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.
  • the calcium binding 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 ⁇ m to 5 mm can be produced if alkali aluminum silicates of types B-J of the main patent are treated in accordance with the above manufacturing instructions.
  • aluminosilicate L 50 kg were slurried in a 300 l stirred tank 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 0 obtained in this way was 1 to 2 mm.
  • the production of the aluminum silicates in which in the aforementioned formula Kat an alkali metal ion and / or a divalent and / or trivalent cation, x is a number from 0.5-1.8, the particle size 0.1 ⁇ m to 5 mm and once y is a number from 0.8 to 6 and the calcium binding capacity is 0 to ⁇ 20 mg CaO / 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 information 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% Si0 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.
  • the percentages relate to the weight of the pimple and to the weight of the skin when tanning.
  • the aluminum silicate H can be replaced by the above-mentioned aluminum silicates A-G and J-Z with an equally good or approximately equally good effect.
  • the final pH of the liquor is 4.1-4.3.
  • the residual chromium content of the liquor is 0.2-0.9 g / l chromium oxide.
  • the residual chromium content in a conventional tanning process is between 7 and 11 g / l chromium oxide.
  • the final pH of the liquor is 4.0-4.2.
  • the residual chromium content of the liquor is 0.2-0.8 g / I chromium oxide compared to a residual chromium content of 7-11 g / I chromium oxide in conventional tanning processes.
  • a soft, non-slip furniture leather of good quality is obtained with a chromium content corresponding to 4.2% chromium oxide, based on 0% water content of the leather.
  • the residual chromium content of the liquor is 0.2-0.7 g / I chromium oxide compared to a residual chromium content of 7-11 g / I chromium oxide in conventional tanning processes.
  • the residual chromium content of the liquor is 0.2-0.8 g / I chromium oxide compared to a residual chromium content of 7-11 g / I chromium oxide with conventional chrome tanning.
  • the final pH of the liquor is 4.0-4.2.
  • the residual chromium content of the liquor is 0.2-0.7 g / I chromium oxide compared to a residual chromium content of 7-11 g / I chromium oxide in conventional tanning processes.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
EP79101513A 1978-05-20 1979-05-17 Verwendung wasserunlöslicher Aluminiumsilikate bei der Chromgerbung von Leder Expired EP0005546B1 (de)

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Application Number Priority Date Filing Date Title
DE19782822072 DE2822072A1 (de) 1978-05-20 1978-05-20 Verwendung wasserunloeslicher aluminiumsilikate bei der lederherstellung
DE2822072 1978-05-20

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EP0005546A2 EP0005546A2 (de) 1979-11-28
EP0005546A3 EP0005546A3 (en) 1979-12-12
EP0005546B1 true EP0005546B1 (de) 1982-06-23

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US (1) US4221564A (enrdf_load_stackoverflow)
EP (1) EP0005546B1 (enrdf_load_stackoverflow)
JP (1) JPS54154501A (enrdf_load_stackoverflow)
KR (1) KR840002218B1 (enrdf_load_stackoverflow)
BR (1) BR7903084A (enrdf_load_stackoverflow)
CA (1) CA1121109A (enrdf_load_stackoverflow)
DE (1) DE2822072A1 (enrdf_load_stackoverflow)
ES (1) ES480706A1 (enrdf_load_stackoverflow)
HU (1) HU180777B (enrdf_load_stackoverflow)
MX (1) MX158184A (enrdf_load_stackoverflow)
NZ (1) NZ190493A (enrdf_load_stackoverflow)
PL (1) PL115247B1 (enrdf_load_stackoverflow)
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US5306435A (en) * 1991-07-11 1994-04-26 Nihon Junyaku Co., Ltd. Treating agent composition for leather, for fibrous materials
FR2754274B1 (fr) * 1996-10-03 1999-12-31 Beaud Challes Solap Sa Procede de tannage de peaux
GB201306607D0 (en) 2013-04-11 2013-05-29 Xeros Ltd Method for treating an animal substrate
GB201417487D0 (en) 2014-10-03 2014-11-19 Xeros Ltd Method for treating an animal substrate
GB201418007D0 (en) 2014-10-10 2014-11-26 Xeros Ltd Animal skin substrate Treatment apparatus and method
GB201418006D0 (en) 2014-10-10 2014-11-26 Xeros Ltd Animal skin substrate treatment apparatus and method
PT3059327T (pt) * 2015-02-19 2017-11-16 Taminco Finland Oy Método de curtimento com crómio ambientalmente amigo
NL2024455B1 (en) * 2019-12-13 2021-02-18 Smit Tanning B V Zeolite composition suitable for tanning leather

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DE2424300C3 (de) * 1974-05-18 1984-11-08 Bayer Ag, 5090 Leverkusen Verfahren zum Chromgerben und Gerbmischung dafür
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DE2424301C3 (de) * 1974-05-18 1981-05-27 Bayer Ag, 5090 Leverkusen Verfahren zum Chromgerben und Gerbmischung dafür
DE2535283A1 (de) * 1974-10-09 1976-04-22 Degussa Bleichend bzw. oxydierend wirkende wasserunloesliche silikate mit kationenaustauschvermoegen
DE2626429C3 (de) * 1976-06-12 1981-06-19 Bayer Ag, 5090 Leverkusen Verfahren zum Chromgerben von Häuten oder Nachgerben von Leder in Gegenwart von Carbonsäuren als Komplexbildner
DE2626430C2 (de) * 1976-06-12 1982-06-03 Bayer Ag, 5090 Leverkusen Verfahren zum Gerben von Leder und Gerbmischung
DE2635357A1 (de) * 1976-08-06 1978-02-09 Degussa Verfahren zur herstellung eisenarmer zeolithischer aluminiumsilikate

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TR20107A (tr) 1980-08-06
EP0005546A2 (de) 1979-11-28
NZ190493A (en) 1982-03-16
CA1121109A (en) 1982-04-06
KR830000722A (ko) 1983-04-18
YU115179A (en) 1983-10-31
YU42096B (en) 1988-04-30
MX158184A (es) 1989-01-16
EP0005546A3 (en) 1979-12-12
JPS54154501A (en) 1979-12-05
PL215664A1 (enrdf_load_stackoverflow) 1980-02-25
ES480706A1 (es) 1979-12-01
HU180777B (en) 1983-04-29
BR7903084A (pt) 1979-12-04
US4221564A (en) 1980-09-09
JPS6219800B2 (enrdf_load_stackoverflow) 1987-05-01
PL115247B1 (en) 1981-03-31
DE2822072A1 (de) 1979-11-29
KR840002218B1 (ko) 1984-12-03

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