EP3110978B1 - Procédé de tannage de peaux d'animaux et cuir tanné ainsi obtenu - Google Patents

Procédé de tannage de peaux d'animaux et cuir tanné ainsi obtenu Download PDF

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Publication number
EP3110978B1
EP3110978B1 EP15720592.3A EP15720592A EP3110978B1 EP 3110978 B1 EP3110978 B1 EP 3110978B1 EP 15720592 A EP15720592 A EP 15720592A EP 3110978 B1 EP3110978 B1 EP 3110978B1
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Prior art keywords
pressure
tanning
minutes
animal hides
pressure vessel
Prior art date
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EP15720592.3A
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German (de)
English (en)
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EP3110978A1 (fr
Inventor
Manfred Renner
Eckhard Weidner
Helmut Geihsler
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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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
    • C14C3/30—Chemical tanning using physical means combined with chemical means

Definitions

  • the application relates to a method of tanning animal skins.
  • the method can be used for any type of tanning (mineral, vegetable or synthetic tanning) and it is suitable for all types of tanning hides (in particular, cattle, goat, sheep, buffalo, ostrich, crocodile, pig, snake, etc.).
  • the conventional production of leather according to the prior art is divided into the work in the so-called water workshop (because all steps in aqueous solution, the so-called fleet done), the actual tanning and subsequent dressing of the leather.
  • the water workshop is subdivided into the steps of weeding, dehairing, liming, pickling and pimpling, whereby a washing process can take place after liming and pickling.
  • the raw material is freed from dirt and preserving salt and gets back to its original water content.
  • the switch is performed at a pH between 7 and 10. In the process, water-soluble proteins are dissolved out.
  • the depilation is done by the addition of lime and sulfur compounds.
  • the hair is dissolved and destroyed the heavily water and fatty epidermis.
  • non-collagenous proteins are dissolved by hydrolysis and washed out.
  • the pH during liming can be up to 13. Due to the high alkalinity the skin shows a strong swelling.
  • the rawhide is called nakedness.
  • the nakedness is characterized by a water content of 60 to 80%, i. 10 kg of nakedness contain 6 - 8 kg of water.
  • the dry matter of the nakedness consists to 98% of collagen.
  • the skin components and limescale removed during depilation are removed from the skin.
  • Different acids can be used.
  • the deliming is carried out with ammonium salts.
  • Deliming with organic acids or carbon dioxide and other chemicals that lower the pH in aqueous solution can also be used.
  • the aqueous solution (liquor) used for the treatment must have a pH of less than 3.5, usually even less than 3, so that the tanning process does not start immediately after the addition of the tanning agents, resulting in uneven and locally too strong tanning (so-called tanning ) would lead.
  • This acidification of the aqueous solution is called pimples and usually achieved by the addition of sulfuric and formic acid. The pimples time is about 3 to 14 h and the pH can drop to 2.5.
  • salt is added to the pimple bath.
  • the salinity of a solution is characterized by the Baume value.
  • the resulting Baume value is set to 5 to 9.
  • the amount of salt needed to achieve the desired Baume value depends on the water content of the pelts, and especially on the amount of peat used in pimpling.
  • the electrolyte concentration in the free liquor caused by the addition of salt leads to a reduction in the osmotic swelling of the skin cells, since the relative difference in the electrolyte concentration between the skin and the surrounding liquor is reduced.
  • non-swelling acids can be used instead of sulfuric acid.
  • aromatic sulfonic acids that have a tanning effect. This tanning effect strengthens the collagen structure and thereby prevents the accumulation of additional water, which is ultimately responsible for the swelling of the skin cells.
  • the Skin soaked after pimpling, soaked in aqueous solution, is called pimpling skin.
  • the central step following pimpling is tanning.
  • the tanning takes 12 to 48 hours.
  • the so-called liquor ratio ratio of the Gerbriesmasse to the mass of Pickelblête
  • the tanning is typically done in rolling barrels.
  • various alkalis such as sodium bicarbonate or magnesium oxide can be used.
  • the pH is raised to values between 3.6 and 4 to start and drain the tanning process.
  • the bondable groups of the collagens crosslink with the tannins.
  • the residual tanning solution represents wastewater to be disposed of.
  • tanning alone accounts for 160-200 million t of wastewater per year.
  • the amount of salt used, which is completely contained in the wastewater, can be estimated at approx. 500,000 t per year. This, unless wastewater treatment techniques are used, causes great environmental impact.
  • An optional wastewater treatment usually requires several stages. First, the clarification of the wastewater either by means of decanters for solids separation and by means of subsequent biological clarification or by a purely biological clarification. In both cases the costs are high. Decanters are used by tanneries to reduce the load on the wastewater. Special fees for subsequent clarification - depending on the legal situation - still have to be paid. In addition, if chromium-containing tanning agents have been used for tanning, the chromium sludge must be disposed of as special waste. A purely biological clarification is expensive and therefore rarely performed today.
  • the tanning acid contained in the leather is first neutralized. It follows, depending on the desired leather type, certain retanning or dressing steps. These are known in the art and are therefore not explained in detail.
  • the present invention has for its object to provide a further improved tanning process and in particular to provide a tanning process in which the use of chemicals can be further reduced, the duration of the process can be reduced and / or reduced by the entire tanning process environmental impact is reduced.
  • the method according to the invention is based on the finding that by treating the wet animal skins by means of compressed carbon dioxide, the steps of deliming, subsequent pickling and pimpling which have been carried out in excess liquid can be replaced by the pressure treatment according to the invention by means of carbon dioxide, ie a pressure treatment by means of Carbon dioxide can be made after the hair removal step and can go directly into the taking place under carbon dioxide pressure Gerbön if before the pressure treatment step of the dewatering step is performed.
  • the inventive method leads to tanned leather, which is at least equal in quality to conventionally tanned leather. At the same time, the environmental impact is significantly lower due to the significantly reduced amount of wastewater. In addition, the inventive method is time-saving.
  • the success of the method according to the invention is due to the fact that carbon dioxide under pressure in conjunction with the only low liquid content of the wet animal skins after the dewatering step, the decarburization, pickling and pickling can take and that in the subsequent tanning step by means of compressed carbon dioxide on the one hand sufficiently lowered the pH to prevent tanning at least to a great extent during the time required to disperse the tanning agent (s) in the hides and, secondly, that the acid swelling described in the prior art can be avoided by using no aqueous acid. but a gaseous inorganic acid anhydride is added under pressure.
  • the pressure treatment step occurs without the presence of free liquid in the pressure vessel, i. it is only the liquid that is in the wet hides.
  • the presence of a small amount of free liquid during the pressure treatment step does not harm, it only increases the amount of sewage to be disposed of later.
  • the skinning of the skins becomes conventional in liquid at a pH in the range of about 6 to carried out about 9.5 and only then passed to the pressure treatment by means of carbon dioxide, wherein before the pressure treatment of the dewatering step.
  • the decarburizing and the pickling are carried out conventionally in liquid and it is then transferred to the pressure treatment by means of carbon dioxide, wherein before the pressure treatment of the dewatering step.
  • the method according to the present invention further allows to perform the steps of whitening (pickling) and tanning without the use of salt or salt substitutes.
  • the reduction (to stop the tanning reaction) and increase (to start and carry out the tanning reaction) of the pH value during the pickling and tanning step can be achieved solely by means of the compression and decompression of the carbon dioxide introduced into the pressure vessel.
  • a reduction in the pH to at least pH 3.5 to pH 3 is achieved by the choice of the carbon dioxide pressure.
  • the bleaching (pimpling) which takes place during the pressure treatment with carbon dioxide is carried out in particular over a period of at least 2 minutes to 3 hours (longer times are possible, but not required), as a rule for 15 to 120 minutes.
  • the animal skin Before the oxygenation, the animal skin usually has a pH of pH 4.5 to pH 9.5, depending on whether the pressure treatment step according to the invention takes place only after pickling, after deliming or even after depilation.
  • the lowering of the pH of the skins to be tan is caused by the dissolution of carbon dioxide in the liquid contained in the skins.
  • the pH of the skins can thus be lowered without the addition of chemicals.
  • the pH of water drops below pH 3.5 (much higher pressure does not lead to a much lower pH).
  • the pH value can thus be controlled by pressure.
  • An optimum is a pH adjustment before the picking step in a range between pH 8 to pH 9.
  • Skins with a pH value up to 12 have been tanned with the method according to the invention.
  • the Gerbmmkeit is in the Container introduced and also in this the pH decreases.
  • the pH achieved at the end of the tanning process is about pH 3.6 - 4 for a standard wtblue or up to above pH 5, if tanning is to be performed in one step and at the same time subtasks of retanning are to be adopted.
  • the tanning solution can be introduced under CO 2 pressure or in the pressureless autoclave. Variants are possible in which the pH of the skin is selected to be higher, for example, and the pH of the tanning solution is lower, resulting in a combination of pH 4 or pH 5.
  • both processes involve a reduction in the fluid content of the skin, for example by mechanical squeezing as in the WO 2010/121804 A1 to which reference is generally made in this respect and also with respect to the tanning step in general.
  • the liquor ratio is about 0.1: 1 to 0.7: 1, preferably 0.25 to 0.65.
  • the skins to be tanned are placed in the autoclave, charged with the tanning solution in the pressure-free state and then carbon dioxide pressure is built up.
  • the introduction of the tanning solution should not exceed a period of 30 minutes.
  • the pressure build-up should also not exceed a period of 30 minutes. Otherwise, a so-called “tanning” occurs, i. a chemical reaction taking place on the surface which prevents further diffusion of chromium ions into the fibrillar structure of the skin and thus does not lead to gerber success.
  • a pressure increase to 15 bar, ideally to between 15 and 30 bar causes the necessary first, sufficient lowering of the pH of the skin. Due to the subsequent pressure reduction and the concomitant release of carbon dioxide from water and skin, the pH rises again and the tanning reaction can proceed as desired.
  • the pH of the tanned leather (wet blues) is achieved.
  • the pH can be adjusted between pH 3.5 and pH 5.5.
  • the skins to be tanned are also charged in the autoclave, but the interior of the autoclave is pressurized before tanning solution is introduced into the autoclave to realize the pressure-induced pimples before adding the tanning solution.
  • the minimum CO 2 pickling duration is 2 minutes, optimally 15 to 120 minutes; Also a duration of 3 to 10 minutes can be advantageous in certain cases.
  • the tanning solution is then introduced into the pressurized autoclave, ie after the desired CO 2 -pick-up time. Deadbat is so safely excluded.
  • salt or a salt substitute is added to the pimpling and tanning step to counteract acid swelling of the skin to balance or balance the electrolyte concentration between the skin and the free liquor.
  • the salinity is measured in degrees Baume and should usually be at Baume 6.
  • the water that causes the unwanted swelling diffuses into the skins from the high excess liquid present in conventional pimple / tannery by conventional procedures.
  • so-called non-swelling acids as auxiliary syntenes as salt substitutes, these substance classes are almost completely unrelated to the overall tannery market due to the higher costs.
  • no salt was used in wash baths or tanning liquors.
  • a tanning solution (liquor) was metered into the pressurized vessel whose mass corresponded to 30% by weight of the weighed wet puddles (thus, the liquid mass which had previously been wilted was re-added).
  • the tanning agent used was a conventional chrome tanning agent and the amount of tanning agent was 4.5 kg.
  • the pressure hold time was another 2.5 hours, ie the total pressure treatment time was 4.5 hours.
  • the pH in the wetblue increased to 4.9. This basification is done without the addition of other chemicals.
  • a chromium oxide content 4.4% by weight based on the dry skin substance and a Kochgare (shrinkage temperature) of over 100 ° C in a water bath were achieved. These are default values for wetblue.
  • Embodiment 2 Same procedure as Embodiment 1, but the deliming was carried out with ammonium sulfate.
  • the skins had a pH of 9.1 before the pressure treatment. After the pressure reduction, the pH in the wet blue was 5.
  • a chromium oxide content of 4.6% by weight, based on the dry skin substance, and a cooking product of more than 100 ° C. in the water bath were achieved.
  • Example 2 Same procedure as Example 1, but the tanning material mass was reduced to 2.7 kg. After the pressure reduction, the pH in the wet blue was 5.2. A chromium oxide content of 3.1 percent by weight based on the dry skin substance and a cooking product of over 100 ° C in a water bath were achieved.
  • Embodiment 3 Same procedure as Embodiment 3, but only 20 percent by weight of the liquid was decoked and tanned accordingly with 20 percent by weight liquor. After the pressure reduction, the pH in the wet blue was 5. Ein Chromium oxide content of 3% by weight based on the dry skin substance and a cooking product of over 100 ° C in a water bath were achieved.
  • the tanning agent used was a conventional chrome tanning agent and the amount of tanning agent was 4 kg.
  • the pressure hold time was 2.5 hours, ie the total pressure treatment time was 195 minutes.
  • the subsequent one-hour pressure reduction to ambient pressure the pH has risen to pH 4.3 in wetblue. This basification is done without the addition of other chemicals.
  • a chromium content of 4 percent by weight of chromium oxide and a Kochgare of about 100 ° C in a water bath were achieved.
  • Embodiment 9 Same procedure as Embodiment 9, but the tanning was carried out at 50 bar. Result as Embodiment 9.
  • Embodiment 9 Same procedure as Embodiment 9, but the tanning was carried out at 100 bar and the pressure relaxation time was 2 hours. Result as Embodiment 9.
  • Embodiment 9 Same procedure as Embodiment 9, but only 20 weight percent were wilted off and tanned accordingly with 20 weight percent liquor. Result as Embodiment 9.
  • Embodiment 9 Same procedure as Embodiment 9, but only 10 weight percent were wilted and tanned with 10 weight percent liquor accordingly. Result as Embodiment 9.

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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)

Claims (10)

  1. Procédé de tannage de peaux d'animaux, comprenant les étapes consistant à :
    - tremper les peaux d'animaux dans un liquide à un pH dans une plage d'environ 7 à environ 10,
    - débourrer les peaux d'animaux dans un liquide à un pH jusqu'à 13,
    - égoutter les peaux trempées de 5 à 40 % en poids
    - traiter les peaux d'animaux humides dans une cuve sous pression à une pression de 5 à 60 bar pendant un temps de traitement sous pression de 60 à 360 minutes, la pression étant établie par un apport de gaz carbonique,
    - introduire une solution de tannage dans la cuve sous pression, la masse de la solution de tannage correspondant de préférence au moins substantiellement à la masse dont les peaux d'animaux trempées ont été égouttées à l'étape d'égouttage,
    - abaisser de manière au moins substantiellement continue la pression régnant dans la cuve sous pression jusqu'à une pression ambiante pendant une période de détente de pression de 15 à 90 minutes.
  2. Procédé selon la revendication 1, caractérisé en ce que l'introduction de la solution de tannage dans la cuve sous pression est effectuée avant l'établissement de la pression par l'apport de gaz carbonique.
  3. Procédé selon la revendication 1, caractérisé en ce que l'introduction de la solution de tannage dans la cuve sous pression est effectuée pendant le temps de traitement sous pression.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le traitement des peaux d'animaux humides dans la cuve sous pression est effectué à une pression de 15 à 50 bar, de préférence de 15 à 40 bar et de plus grande préférence de 15 à 30 bar.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le temps de traitement sous pression dure de 100 à 300 minutes, de préférence de 120 à 250 minutes et de plus grande préférence de 160 à 220 minutes.
  6. Procédé selon la revendication 5, caractérisé en ce que la part du temps de traitement sous pression utilisée pour l'acidification dure de 15 à 120 minutes, de préférence de 15 à 120 minutes et de plus grande préférence de 15 à 60 minutes.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la période de détente de pression dure de 15 à 60 minutes, de préférence de 15 à 45 minutes et de plus grande préférence de 30 à 45 minutes.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'un enlèvement de chaux conventionnel des peaux d'animaux dans un liquide à un pH dans une plage d'environ 6 à environ 9,5 est effectué avant l'étape d'égouttage.
  9. Procédé selon la revendication 8, caractérisé en ce qu'après l'enlèvement de la chaux et avant l'étape d'égouttage, un confitage conventionnel des peaux d'animaux dans un liquide est effectué.
  10. Cuir tanné, obtenu par l'exécution du procédé selon l'une quelconque des revendications précédentes.
EP15720592.3A 2014-02-25 2015-02-25 Procédé de tannage de peaux d'animaux et cuir tanné ainsi obtenu Active EP3110978B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014102460 2014-02-25
PCT/DE2015/200102 WO2015127935A1 (fr) 2014-02-25 2015-02-25 Procédé de tannage de peaux d'animaux et cuir tanné produit à partir de celles-ci

Publications (2)

Publication Number Publication Date
EP3110978A1 EP3110978A1 (fr) 2017-01-04
EP3110978B1 true EP3110978B1 (fr) 2018-02-14

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EP15720592.3A Active EP3110978B1 (fr) 2014-02-25 2015-02-25 Procédé de tannage de peaux d'animaux et cuir tanné ainsi obtenu

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EP (1) EP3110978B1 (fr)
DE (1) DE112015000953A5 (fr)
DK (1) DK3110978T3 (fr)
ES (1) ES2662614T3 (fr)
WO (1) WO2015127935A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016004237A1 (de) * 2016-04-08 2017-10-12 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Gerbvorrichtung mit drehbar gelagertem Druckbehälter

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2800389B1 (fr) * 1999-10-29 2002-04-12 Commissariat Energie Atomique Procede de tannage de peaux ou de materiaux contenant du collagene, avec un fluide dense sous pression
CN1281766C (zh) * 2005-03-07 2006-10-25 四川大学 以二氧化碳超临界流体为介质的制革方法
DE102009018232B8 (de) 2009-04-21 2011-11-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Gerbung von Tierhäuten

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Publication number Publication date
ES2662614T3 (es) 2018-04-09
DE112015000953A5 (de) 2016-11-17
DK3110978T3 (en) 2018-05-28
EP3110978A1 (fr) 2017-01-04
WO2015127935A1 (fr) 2015-09-03

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