EP0007555B1 - Verwendung wasserunlöslicher Aluminiumsilikate bei der Lederherstellung - Google Patents

Verwendung wasserunlöslicher Aluminiumsilikate bei der Lederherstellung Download PDF

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Publication number
EP0007555B1
EP0007555B1 EP79102490A EP79102490A EP0007555B1 EP 0007555 B1 EP0007555 B1 EP 0007555B1 EP 79102490 A EP79102490 A EP 79102490A EP 79102490 A EP79102490 A EP 79102490A EP 0007555 B1 EP0007555 B1 EP 0007555B1
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EP
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Prior art keywords
cao
water
aluminium silicates
active substance
carboxylic acids
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Expired
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EP79102490A
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German (de)
English (en)
French (fr)
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EP0007555A1 (de
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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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
    • 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 (Kat 2 / n O) X. A) , 03 . (SiO 2 ) y, 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 connection with carboxylic acids containing ester and / or urethane and / or amide groups in leather production .
  • auxiliaries that heavily pollute the wastewater of the factories.
  • 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.
  • FR-A-2354383 claims a process for tanning hides and / or leather, using a tanning agent and at least one carboxylic acid which has an ester and / or urethane and / or amide function.
  • the aim of the invention is to improve the known tanning processes, in particular the use of chemicals and the wastewater load in leather production are to be reduced.
  • 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 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 for tanning becomes more flexible and safer.
  • the ester and / or urethane and / or amide Group-containing carboxylic acids can be used together with the aluminum silicates in the chrome tanning of leather.
  • the carboxylic acids mentioned can already be added in the strongly acidic pimple, that is, before the actual tanning begins, since this achieves a high chromium content in the leather with a particularly uniform distribution.
  • Suitable ester or urethane and / or amide group-containing carboxylic acids to be used according to the invention are those which have molecular weights of about 170-30000, preferably 310-10000 and have at least 2 carboxyl groups per molecule.
  • 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 carboxy-containing products are accordingly by reacting compounds containing hydroxyl and / or amino groups 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.
  • 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, polybutylene glycol, amino ethanol, 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 dimethyl malonate with in each case 1 mol of diethylene glycol or dipropylene glycol or 1,6-hexanediol or 1,12-octadecanediol or hexamethylenediamine, or 5 mol of adipic acid or terephthalic anhydride with 3 moles of trimethylolpropane, etc.
  • the polyesters can also continue, for example be reacted with glutaric acid or ammonia. Further examples of suitable compounds can be found in DE-A-2626430, pages 12-17.
  • 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 carbon acids with 2-8 C atoms in the chain, such as 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, for example with mono- or polyhydric alcohols with 1-6 C atoms, such as methanol, ethanol, n- and isopropanol, butanols, amyl alcohols, ethylene, propylene-butylene glycols, glycerol, Trimethylolpropane, pentaerythritol, sorbitol.
  • monoesters of di- or trivalent acids are preferred, since they hydrolyze relatively quickly in the acidic medium, for example pickle or tanning liquor.
  • 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 0.7-1.5
  • y is a number from 0.8-6, preferably 1.3-4 whose particle size is 0.1 to 25 u, preferably 1-12 u 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.
  • Alkali aluminum silicates of this type 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.
  • 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.
  • Al (CH) 3 , Al 2 0 3 or SiO z can also be reacted with alkali silicate or.
  • substances of this type also form from the melt, but because of the high melting temperatures required and the need to convert the melt into finely divided products, this process appears to be less interesting economically.
  • 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 amorphous or crystalline alkali aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and at temperatures e.g. Dry 50-800 ° C. Depending on the drying conditions, 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 ⁇ , 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. 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 2ln 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, especially if the deviation only relates to relates 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, for example presented as a solution or dissolved in the aluminate and / or silicate solution. Particularly good effects are achieved when the dispersant is dissolved in the silicate solution.
  • 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. For aging or crystallization, the precipitate is heated to temperatures of 50-200 ° C. for 1 / 2-24 hours. From the multitude of usable dispersants e.g. Sodium lauryl ether sulfate, sodium polyacrylate, hydroxyethane phosphonate 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 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 100-200.degree. C., preferably 130-160.degree. C., with vigorous stirring for at least 1 ⁇ 2 hour.
  • the crystalline product is isolated in a simple manner by separating 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 form spherical particles, possibly hollow spheres of approximately 1 to 4 p. Store the diameter together.
  • Alkali aluminum silicates which can be produced 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 cat is an alkaline cation, in particular a sodium cation.
  • 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 mainly consist of the clay mineral kaolinite with the approximate composition AI203 2 Si02. 2 H 2 0, which has a layer structure.
  • 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 2000 to 10000 ppm. Fe significantly higher than the values from 20 to 100 ppm. Fe in the case of the alkali aluminum silicates produced 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 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 sili kat J, which has several names in the literature, e.g. B.
  • molecular sieve 13 X or zeolite NaX (cf. O. Grubner, P. Jiru and M. Rälek, "Molecular Sieves", Berlin 1968, pp. 32, 85-89) when considering the approach to hydrothermal treatment preferably does not stir, possibly introduces low shear energies, and remains at a temperature preferably 10-20 ° C below the boiling temperature (approx. 103 ° C).
  • 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”, 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 be adjusted if necessary 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 CaO / 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.
  • 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 is 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 ⁇ 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 abovementioned formula, Kat has 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, with a particle size of 0.1 ⁇ 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 1 to 50 g / 1, preferably 15-30 g / l, of aluminum silicate, based on the anhydrous product, are used in the tanning liquor.
  • 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 auxiliary substances e.g. anionic, cationic or nonionic surfactants, chromium salts etc. are used.
  • dicarboxylic acids such as adipic acid or glutaric acid or their monomethyl esters, are additionally used in amounts of 1 to 20 g / l of liquor.
  • 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 3000 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 suctioned off from the crystal slurry and rinsed 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. Washed up to a pH of approx. 10 Beautiful or neutralized and then dry 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 2-6 6 ⁇ .
  • the maximum particle size was 3-6 ⁇ .
  • 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 (paddle mixer from Lödige) for 20 minutes. With further mixing, the granulate formation was brought about within a further 8 minutes by the gradual addition of 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 100 ° 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 binding capacity of the product was 110 mg 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 treated in accordance with the above manufacturing instructions.
  • aluminosilicate L 50 kg were slurried in a 300 l stirred tank with 180 l water and adjusted to a pH of 6 using 25% hydrochloric acid. The suspension was stirred moderately vigorously 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. The granules were formed within a further 8 minutes with stirring by gradually adding 13.5 l of water adjusted to a pH of 6. The granulate was dried at 150 ° C. for 60 minutes and solidified by heating to 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 above-mentioned 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, the particle size is 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 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.
  • Natural zeolite (Clinoptilolite) as it is extracted in large quantities from the open pit in the western United States.
  • the percentages relate to the weight of the pimple and to the weight of the pelvis 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 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 liquor is 0.55 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 broth is 0.2 to 0.3 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 Verwendung wasserunlöslicher Aluminiumsilikate bei der Lederherstellung Expired EP0007555B1 (de)

Applications Claiming Priority (2)

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

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EP0007555A1 EP0007555A1 (de) 1980-02-06
EP0007555B1 true EP0007555B1 (de) 1981-12-30

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US (1) US4264319A (enrdf_load_stackoverflow)
EP (1) EP0007555B1 (enrdf_load_stackoverflow)
JP (1) JPS5516096A (enrdf_load_stackoverflow)
BR (1) BR7904607A (enrdf_load_stackoverflow)
DE (1) DE2831846A1 (enrdf_load_stackoverflow)

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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
EP0235431B1 (en) * 1985-08-23 1994-06-22 Hagiwara Research Corporation Amorphous aluminosilicate & process for producing the same
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
FR2754274B1 (fr) * 1996-10-03 1999-12-31 Beaud Challes Solap Sa Procede de tannage de peaux
GB0017212D0 (en) * 2000-07-14 2000-08-30 Pittards Plc An improved process for manufacturing leather
PL2574682T3 (pl) 2011-09-30 2014-03-31 Kemira Oyj Przyjazna dla środowiska kompozycja, odpowiednia do garbowania skóry, zawierająca zeolit
ES2646285T3 (es) 2015-02-19 2017-12-13 Taminco Finland Oy Un método de curtido al cromo respetuoso con el medio ambiente
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

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US2395472A (en) * 1942-02-25 1946-02-26 Du Pont Tanning compositions and their manufacture
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
AR208085A1 (es) * 1974-05-18 1976-11-30 Bayer Ag Procedimiento de curtido al cromo
US4049379A (en) * 1974-05-30 1977-09-20 Basf Aktiengesellschaft Complex basic zirconium salts and aluminum salts
DE2626430C2 (de) * 1976-06-12 1982-06-03 Bayer Ag, 5090 Leverkusen Verfahren zum Gerben von Leder und Gerbmischung
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

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EP0007555A1 (de) 1980-02-06
US4264319A (en) 1981-04-28
DE2831846A1 (de) 1980-02-07
JPS5516096A (en) 1980-02-04
JPS6234800B2 (enrdf_load_stackoverflow) 1987-07-29
BR7904607A (pt) 1980-03-25

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