EP4180541B1 - Procédé de préparation d'un produit tanné - Google Patents
Procédé de préparation d'un produit tanné Download PDFInfo
- Publication number
- EP4180541B1 EP4180541B1 EP22207624.2A EP22207624A EP4180541B1 EP 4180541 B1 EP4180541 B1 EP 4180541B1 EP 22207624 A EP22207624 A EP 22207624A EP 4180541 B1 EP4180541 B1 EP 4180541B1
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- EP
- European Patent Office
- Prior art keywords
- hide
- drum
- executed
- product
- comprised
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 52
- 229920001864 tannin Polymers 0.000 claims description 52
- 239000001648 tannin Substances 0.000 claims description 52
- 235000018553 tannin Nutrition 0.000 claims description 52
- 238000011282 treatment Methods 0.000 claims description 49
- 238000005554 pickling Methods 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 7
- 240000007817 Olea europaea Species 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000005238 degreasing Methods 0.000 description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000000654 additive Substances 0.000 description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 235000019253 formic acid Nutrition 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000004280 Sodium formate Substances 0.000 description 6
- 239000004310 lactic acid Substances 0.000 description 6
- 235000014655 lactic acid Nutrition 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 6
- 235000019254 sodium formate Nutrition 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000002879 macerating effect Effects 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000009264 composting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 231100000209 biodegradability test Toxicity 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 229960002836 biphenylol Drugs 0.000 description 2
- 239000002361 compost Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 235000011468 Albizia julibrissin Nutrition 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000005852 Mimosa quadrivalvis Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 235000017343 Quebracho blanco Nutrition 0.000 description 1
- 241000065615 Schinopsis balansae Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010868 animal carcass Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000035617 depilation Effects 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- -1 for example hides Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 206010033675 panniculitis Diseases 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 210000004304 subcutaneous tissue Anatomy 0.000 description 1
- 230000003655 tactile properties Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
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
- C14C1/06—Facilitating unhairing, e.g. by painting, by liming
-
- 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
- C14C3/08—Chemical tanning by organic agents
- C14C3/10—Vegetable 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
- C14C3/28—Multi-step processes
Definitions
- the present invention regards a method for obtaining a tanned product according to the preamble of the independent claim 1.
- the present method for obtaining a tanned product is intended to be advantageously employed in tanneries, in the field of production of tanned products, such as for example hides, leather or other finished products deriving from a raw hide.
- the method for obtaining tanned products is advantageously employable for producing a semifinished tanned product, therefore intended to sustain subsequent transformations in order to obtain a tanned product which is for example employable as a semifinished product for the clothing industry and fashion industry in general, or also for the furniture/interior design industry.
- the method, object of the present invention advantageously allows obtaining a biodegradable tanned product, hence susceptible of being autonomously degraded over time following the disposal thereof.
- the invention is therefore inserted in the industrial field of production of tanned products, or more generally in the field of production of semifinished products for the clothing industry and fashion in general, or also for the furniture/interior design industry.
- the methods for obtaining a tanned product usually provide for a pretanning step, which comprises a calcination operation, executed in a drum, in order to depilate the raw hide, a subsequent decalcination operation, executed in a drum in order to remove the lime residues of the calcination operation from the depilated raw hide and a subsequent pickling operation, executed in a drum, in order to obtain a complete lime-removal of the hide and thus obtain a hide ready to be tanned.
- a pretanning step which comprises a calcination operation, executed in a drum, in order to depilate the raw hide, a subsequent decalcination operation, executed in a drum in order to remove the lime residues of the calcination operation from the depilated raw hide and a subsequent pickling operation, executed in a drum, in order to obtain a complete lime-removal of the hide and thus obtain a hide ready to be tanned.
- the aforesaid methods also provide for a tanning step, usually chrome tanning, in which the pretanned hide is treated in a drum, by means of trivalent chromium salts or compounds, in order to obtain a tanned hide.
- a tanning step usually chrome tanning
- chrome tanning in which the pretanned hide is treated in a drum, by means of trivalent chromium salts or compounds, in order to obtain a tanned hide.
- the tanning step is followed by a subsequent retanning step, which has the object of substantially entirely stopping the degradation processes of the hide, in fact rendering it a stabilized hide that is suitable to be employed as semifinished product in the various fields in which hides are used.
- the tanned hide by means of chrome tanning is capable of being stored for a long time, usually even 9 months, before sustaining a retanning working.
- the main drawback lies in the fact that such tanning is polluting and potentially dangerous for the environment, due to the heavy metals employed which are inevitably released into the environment following tanning.
- a further drawback lies in the fact that the chrome tanning is unable to ensure a completely natural aspect for the tanned hide and moreover the latter, if chrome-tanned, has an altered odor, of chemical type, which confers a not very nice appearance to the tanned hide for the final user.
- a first drawback lies in the fact that the aforesaid method comprising a step of vegetable tanning and retanning resulted unsuitable for being industrialized and employed large scale on a high number of hides, and has only found use for small productions of hides. This is due to the fact that such hides have a considerable degradation caused by the lack of stabilization of the hide, due to the lack of chrome.
- a further drawback lies in the fact that the tanned hides obtained with the aforesaid method have revealed themselves to be not very nice to the touch, and in particular they have proven themselves to be provided with poor softness, lacking the properties necessary for their commercialization, in particular in the field of fashion and of clothing in general.
- a further drawback lies in the fact that the tanned hides obtained with the aforesaid method have proven hard to dye and generally complicated to be worked in the subsequent finishing steps aimed to confer to the hide the aesthetic characteristics necessary for its use, in particular in the fashion and clothing field.
- a further drawback lies in the fact that the tanned hides obtained with the aforesaid method have demonstrated that they are not completely biodegradable, and therefore not classifiable as biodegradable product.
- Also known from the document EP 2110446 A1 is a tanning method which provides for employing vegetable tannins, such as in particular 10% Quebracho ATO, 5% Mimosa and 5% Chestnut, and for employing, in a final retanning step, tannins deriving from an apple extract.
- vegetable tannins such as in particular 10% Quebracho ATO, 5% Mimosa and 5% Chestnut
- the document WO 2018025210 A1 describes the use, in a process of tanning the hides, of olive mill wastewater as tanning product, in a quantity greater than 50%.
- the document EP 2862944 A1 describes a method of known type for the treatment of the sheep hide, which comprises a tanning step, during which a product based on vegetable tannins is employed for a duration of 2-3 days.
- the problem underlying the present invention is therefore that of overcoming the drawbacks manifested by the methods in order to obtain a tanned product of known type, by providing a method for obtaining a tanned product, which allows obtaining a tanned product that is stabilized and substantially lacking degradations.
- a further object of the present invention is to provide a method for obtaining a tanned product, which allows obtaining a biodegradable tanned product.
- a further object of the present invention is to provide a method for obtaining a tanned product, which allows obtaining a tanned product provided with high tactile properties and in particular is provided with a high softness.
- a further object of the present invention is to provide a method for obtaining a tanned product, which allows obtaining a tanned product provided with high mechanical properties.
- a further object of the present invention is to provide a method for obtaining a tanned product, which allows obtaining a tanned product which is easily workable in the subsequent finishing operations and which is in particular easily dyeable.
- a further object of the present invention is to provide a method for obtaining a tanned product, which allows reducing the environmental impact of one's working operations.
- reference number 1 overall indicates a method for obtaining a tanned product, according to the present invention.
- a tanned product which can be for example a tanned product made of hide or a tanned product made of leather, which is advantageously intended to sustain subsequent working operations so as to obtain a product made of semifinished hide or leather employable in variable commodity fields, such as for example in the field of clothing or of fashion in general.
- the method for obtaining a tanned product comprises at least one step for arranging raw hide.
- the aforesaid step for arranging the raw hide provides for placing at least one raw hide within a container, usually made of wood, known in the technical jargon with the term drum and which can be actuated in rotation in order to allow the treatment of the raw hide contained at its interior.
- the drum employed for the aforesaid method is configured for containing, at its interior, about five hundred raw hides.
- the raw hide is a hide which has not been previously subjected to salt treatments, which are usually aimed to increase the preservation times of the raw hide but have negatively affected the biodegradability results of the raw hide. Therefore, for the purpose of optimally preserving the raw hide notwithstanding the absence of a salt treatment, the raw hides are transported to the destination site by means of refrigerated vehicles, so as to sufficiently slow the degradation process before the treatment of the raw hides.
- the method also comprises at least one pretanning step, in which the raw hide is worked so as to obtain a pretanned hide, and such pretanning step comprises at least one calcination operation, executed in a drum, in order to depilate the raw hide.
- the pretanning step also comprises a subsequent decalcination operation, executed in a drum, in order to remove at least lime residues from the depilated raw hide.
- the aforesaid decalcination operation comprises a first decalcination operation, in which the raw hide is placed within the drum together with a first solution comprising water, preferably in a quantity comprised between 80% and 120% with respect to the weight of the raw hide in the drum and still more preferably in a quantity substantially equal to the weight of the raw hide.
- the first solution of the first decalcination operation also comprises metabisulfite, which is added in the drum in a quantity comprised between 0.1% and 1% with respect to the weight of the raw hide in the drum.
- the aforesaid first decalcination operation is executed at a temperature comprised between 20°C and 30°C, preferably for a time comprised between 20 and 60 minutes.
- the drum is advantageously drained in order to remove the first solution.
- the duration times of the single operations will be indicated, or the times of the entire steps of the method, object of the present invention, which will be intended as the time for which the drum is actuated in rotation with the hides and with the different components added within the drum.
- the decalcination step comprises a second decalcination operation, preferably following the first decalcination operation, in which the raw hide is treated by means of a second solution.
- the second solution comprises water, ammonium sulfate and lactic acid.
- the second solution comprises a quantity of water comprised between 10% and 30% with respect to the weight of the raw hide, preferably moreover the quantity of ammonium sulfate is comprised between 0.2% and 1% with respect to the weight of the raw hide and preferably the quantity of lactic acid is comprised between 0.5% and 1.5% with respect to the weight of the raw hide.
- the aforesaid second decalcination operation is executed at a temperature comprised between 20°C and 30°C, preferably for a time comprised between 30 and 120 minutes.
- the admixing is executed of further lactic acid, preferably in a quantity close to 0.3% with respect to the weight of the raw hide.
- the aforesaid admixing of lactic acid is executed at about 30 minutes from the end of the second decalcination operation.
- the pretanning step also comprises a subsequent pickling operation, executed in a drum, in order to obtain the pretanned hide, ready to be subsequently tanned.
- At least one washing operation is executed, which provides for introducing within the drum water, preferably an ambient temperature and preferably in a quantity close to 100% by weight with respect to the weight of the raw hide, and during such washing operation the drum is actuated for at least 5 minutes, and preferably for a time less than 20 minutes.
- the water of the washing operation is subsequently drained from the drum.
- the pickling operation provides for a first pickling operation, in which formic acid is added into the drum, preferably at a temperature comprised between 20°C and 30°C, and such first pickling operation is executed for a duration comprised between 15 and 45 minutes.
- the formic acid is added in a quantity comprised between 0.5 and 1.5 % with respect to the weight of the raw hide in the drum.
- the pickling operation provides for a second pickling operation, in which sulfuric acid is added in the drum, preferably at a temperature comprised between 20°C and 30°C, and such second pickling operation is executed for a duration comprised between 150 and 270 minutes.
- the sulfuric acid is added without having executed any operation of removal of the formic acid, and of possible other additives, previously inserted in the pickling operation.
- the sulfuric acid is added in a quantity comprised between 0.2 and 1.6% with respect to the weight of the raw hide in the drum.
- the aforesaid quantity of sulfuric acid is added in two doses introduced in two different moments of the second pickling operation and in particular at the start of the second pickling operation and after a first time interval comprised between 20 and 60 minutes.
- the two doses of sulfuric acid are substantially equal to each other such to equally divide the total introduced quantity of sulfuric acid.
- the drum is drained of the solutions introduced during the different operations of the pretanning step.
- the set of operations executed in the pretanning step are usually known in the technical j argon of the field with the expression "beamhouse operations" and group together the set of operations adapted to prepare the raw hide to receive the subsequent tanning treatments.
- the pretanning step comprises at least one soaking operation, executed in a drum and preferably preceding the calcination.
- the aforesaid soaking operation is advantageously adapted to restore to the raw hide the water that it had lost in the preservation process, and to clean the raw hide, eliminating the dirt and in particular the blood.
- the pretanning step comprises at least one stripping operation, which is a mechanical operation executed preferably before the calcination and with which the residue subcutaneous tissues of the connection tissues of the raw hide are eliminated at the animal carcass.
- the pretanning step comprises at least one maceration operation, which is an enzymatic operation preferably executed after the decalcination in order to complete the latter operation, eliminating residues of other non-useful interfibrillar substances and at the same time loosening the fibrous structure of the hide.
- Such maceration operation also advantageously allows obtaining a softer and more flexible pretanned hide.
- a macerating solution is inserted in the drum, preferably at a temperature comprised between 20°C and 35°C, and such macerating solution is maintained within the drum for a time comprised between 20 and 60 minutes.
- the aforesaid macerating solution comprises a first degreasing component, in particular the product known in the market with the name "Eusapon OC" provided by the company BASF SE, and a second macerating component, in particular the product known in the market with the name "Oropon On 2" provided by the company TFL.
- the method also provides for at least one tanning step, in which the pretanned hide is treated in a drum and such tanning step comprises a first tannin treatment, executed by a temperature comprised between 15 and 30°C.
- the first tannin treatment is executed with at least one first tanning product comprising tannins, in particular synthetic tannins.
- the first tanning product is added in a percentage comprised between 5 and 15% with respect to the weight of the raw hide in the drum.
- the first tannin treatment provides for employing, as first tanning product, the product known in the market with the name "SUSTAN PRE” provided by the company “GSC Group Spa”, preferably added in a quantity of about 10% with respect to the total weight of the raw hide in the drum.
- the first tanning product is admixed with a degreasing product, in particular the product known in the market with the name "G-SOFT O” provided by the company "GSC Group Spa”, in a quantity advantageously comprised between 0.5 and 1.5% with respect to the weight of the pretanned hide in the drum.
- the first tannin treatment of the tanning step is executed for a time interval comprised between 60 and 120 minutes and still more preferably for about 90 minutes.
- the tanning step also comprises a second tannin treatment, executed by a temperature comprised between 20 and 35°C, with at least one second tanning product, so as to obtain a tanned hide.
- the second tanning product is added in a percentage comprised between 2 and 10% with respect to the weight of the raw hide in the drum.
- the aforesaid second tanning product comprises tannins deriving from olive mill wastewater, preferably from a condensate of olive mill wastewater.
- the olive mill wastewater are aqueous substances deriving from olive oil working processes.
- the second tanning product comprises the product known in the market with the name "SUSTAN FP” and the product known in the market with the name “AMINEX PF” both provided by the company "GSC Group Spa”.
- the second treatment of said tanning step is executed for a time interval comprised between 150 and 330 minutes and still more preferably for about 240 minutes.
- the first tannin treatment is executed before the second tannin treatment.
- such tannin treatments can be executed in reverse order.
- the method also provides for at least one retanning step, in which the tanned hide is treated by means of at least one first retanning product, comprising tannins.
- the retanning step is executed within 168 hours from the start of the pretanning step and preferably within 72 hours from the start of the same pretanning step.
- a pressing and a subsequent shaving operation are executed, which are aimed to remove the excess liquids that are present from the hide, before the subsequent retanning step.
- the retanning step comprises at least one third tannin treatment, in which the first retanning product is employed, which comprises advantageously synthetic tannins, in a quantity comprised between 10% and 16% with respect to the weight of the hide in the drum.
- the retanning step comprises at least one fourth tannin treatment, in which a second retanning product comprising synthetic tannins is employed, in a quantity comprised between 7% and 13% with respect to the weight of the hide in the drum.
- a second retanning product comprising synthetic tannins
- two first retanning products are employed, comprising synthetic tannins, preferably different from each other.
- the third tannin treatment provides for employing, as first retanning products, the product known in the market with the name "G-TAN RB” and the product “G-TAN PQ, both provided by the company "GSC Group Spa”, preferably both added in a quantity close to 7% with respect to the total weight of the hides in the drum.
- two second retanning products are employed, comprising synthetic tannins, preferably different from each other.
- the fourth tannin treatment provides for employing, as second retanning products, the product known in the market with the name "G-TAN RB” and the product “G-TAN SL POLV.”, both provided by the company "GSC Group Spa”, preferably both added in a quantity close to 5% with respect to the total weight of the hides in the drum.
- the third tannin treatment is executed for a duration comprised between 10 and 50 minutes and still more preferably for about 30 minutes.
- the fourth tannin treatment is executed for a duration comprised between 30 and 150 minutes and still more preferably for about 90 minutes.
- a resin-based additive is added into the drum, in particular the product known in the market with the name "G-PLAST FM” provided by the company “GSC Group Spa” and still more preferably in a quantity comprised between 2 and 10% with respect to the weight of the hide in the drum.
- the third tannin treatment and/or the fourth thermal treatment are executed at a temperature comprised between 20°C and 45°C.
- the tanning step also provides a stabilization operation, preceding the first tannin treatment, which provides for the addition in the drum of a saline solution of water and salt, preferably at a temperature of about 20°C.
- the aforesaid solution comprises water, preferably in a quantity comprised between 50 and 70% with respect to the weight of the raw hide in the drum, and salt, preferably in a quantity comprised between 2 and 10% with respect to the weight of the raw hide in the drum.
- the aforesaid saline solution is provided with a density, measured in Baumé, which is comprised between 6 and 9 Bé.
- the tanning step provides for a treatment aimed to increase the tanning power of the second tannin treatment, which is attained between the first and the second tannin treatment, preferably by means of addition of sodium formate within the drum.
- the aforesaid treatment with sodium formate is executed for a time interval comprised between 30 and 90 minutes and preferably the sodium formate is added into two separate doses and in particular, in accordance with the preferred embodiment, the second dose of sodium formate is added after a time from the first dose comprised between 15 and 45 minutes.
- the entire tanning step is executed for a time interval comprised between 300 and 500 minutes and preferably the entire tanning step is executed without ever draining the drum of the various products and additives added during the tanning step and therefore the various products and additives are added on each other.
- the retanning step provides for a soaking operation, preceding the third tannin treatment, which provides for the addition in the drum of a soaking solution of water and of a soaking additive, adapted to increase the absorption of water by the hide, and in particular the product known in the market with the name "NEOFAT AM/C" provided by the company "GSC Group Spa", preferably at a temperature of about 30°C.
- the aforesaid soaking solution comprises water, preferably in a quantity comprised between 200 and 300% with respect to the weight of the raw hide in the drum, and the aforesaid soaking additive is preferably added in a quantity comprised between 0.5 and 3% with respect to the weight of the raw hide in the drum.
- the aforesaid soaking operation is executed for a time interval comprised between 30 and 90 minutes and preferably subsequently such soaking solution is drained from the drum.
- the retanning step provides for a first degreasing operation, executed between the soaking operation and the third tannin treatment, which provides for the addition of a degreasing solution of water and of at least one degreasing additive in the drum, preferably two degreasing additives and in particular the products known in the market with the name "G-SOFT STH 73" and "G-SOFT CLP" both provided by the company "GSC Group Spa".
- the aforesaid degreasing operation is advantageously attained at a temperature of about 30°C, preferably for a time interval comprised between 10 and 30 minutes.
- the aforesaid degreasing solution comprises water, preferably in a quantity comprised between 50 and 110% with respect to the weight of the raw hide in the drum, and the degreasing additives are preferably added in a quantity comprised between 1 and 3% with respect to the weight of the raw hide in the drum.
- the retanning step also provides for the addition, preferably executed between the degreasing operation and the third tannin treatment, of at least one resin, and preferably two resins, in particular "G-PLAST CSS” and "G-PLAST J 8".
- the aforesaid addition of resins is advantageously attained at two different moments, at a time interval preferably comprised between 10 and 40 minutes from each other.
- the first resin is added in a quantity comprised between 3 and 9% with respect to the weight of the raw hide in the drum, while the second resin is added in a quantity comprised between 2 and 6% with respect to the weight of the raw hide in the drum.
- the retanning step provides for a second degreasing operation, executed between the third tannin treatment and the fourth tannin treatment, which preferably has the same dosage described above for the first degreasing operation.
- the second degreasing operation is executed for a time interval comprised between 5 and 15 minutes.
- the retanning step provides for a third degreasing operation, executed after the fourth tannin treatment, which is preferably executed at a temperature comprised between 30°C and 60°C.
- the third degreasing operation is executed by means of the same degreasing additives employed in the first and in the second degreasing operation, but preferably employed in a greater quantity and in particular in a quantity comprised between 4% and 12% (the two degreasing additives summed together).
- the aforesaid third degreasing operation is advantageously attained for a time interval comprised between 30 and 90 minutes.
- formic acid is added within the drum, preferably in a quantity of about 1.5% with respect to the total weight of the hides within the drum, so as to improve the action of the abovementioned degreasing additives.
- the formic acid is also added before the third degreasing operation, preferably in a quantity of about 1.5% with respect to the total weight of the hides within the drum.
- the entire retanning step is executed for a time interval comprised between 250 and 450 minutes and preferably the third and the fourth tannin treatment of the retanning step are executed without ever draining the drum of the various retanning products and additives added during the retanning step.
- the hides are discharged from the drum within a tank, preferably made of steel or plastic material, and within such tank the tanned hides are rewashed, preferably with water, in order to then be extended in order to drain the excess water deriving from the aforesaid washing.
- the hides undergo an operation of pressing and softening, which is a mechanical operation in which, by means of a machinery provided with rotating cylinders, the hides are subjected to a pressing force preferably variable between 7 and 25 tons.
- a drying step is attained, in which the excess liquids are moved from the hides.
- the drying step comprises a vacuum drying operation, still more preferably at a temperature comprised between 30°C and 50°C.
- the drying step is executed for a duration comprised between 250 and 600 seconds.
- drying step also comprises a drying operation.
- the tanned hides thus obtained can be subsequently subjected to operations of finishing and/or dyeing aimed to confer to the hide the desired final appearance as a function of their use.
- the treated hide by means of the method, object of the present invention is biodegradable.
- biodegradable it will be intended hereinbelow a hide capable of being converted in CO 2 and H 2 O by means of the action of microorganisms and in which in particular the level of biodegradation is greater than 90% in a time of less than six months.
- Step of the method Product added in a drum Quantity of product added in a drum Time Interval Temperature Operation at end of time interval [% with respect to the weight of the hide in a drum] [min] [°C]
- the compound used as inoculation advantageously derives from a composting plant that treats the organic fraction of solid urban waste.
- the age of the compost in question is about 3 months.
- the material, once it reached the laboratory, was sieved between 0.5 and 1 cm, in a manner such to eliminate possible rough materials and subsequently expanded clay was added with the function of inert structuring material, so as to improve the pores of the compost and hence ensure optimal aerobic conditions for the entire duration of the test.
- the hide specimen was instead ground and reduced to a grain size of about 1 mm.
- the aforesaid test was executed for a duration of 51 days, in accordance with the aforesaid norm in fact the test can be stopped when a percentage biodegradability value is reached Dt > 90%.
- the percentage biodegradability represents the quantity of CO 2 developed by the specimen, removed from the value of the blank (C of the inoculation compound), in relation to the maximum theoretical CO 2 that can be developed by the specimen based on the content of organic carbon (TOC).
- CTOT is the proportion of the total organic carbon (TOC) present in MTOT in grams per gram
- 44 and 12 are respectively the molecular weight of the carbon dioxide and the atomic weight of the carbon.
- (CO 2 )T is the cumulative quantity of carbon dioxide developed by each composting reactor containing the specimen being tested, in grams per reactor
- (CO 2 )B is the cumulative quantity of carbon dioxide developed by each composting reaching containing the blank in grams per reactor
- ThCO 2 is the theoretical quantity of carbon dioxide that can be produced by the specimen being tested, in grams per reactor.
- the invention thus conceived therefore attains the pre-established objects.
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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)
- Procédé de préparation d'un produit tanné, caractérisé en ce qu'il comprend:- au moins une phase de préparation de la peau brute;- au moins une phase de pré-tannage, dans laquelle ladite peau brute est travaillée jusqu'à obtenir une peau pré-tannée, ladite phase de pré-tannage comprenant au moins:• une opération de calcination, réalisée en tonneau, pour épiler ladite peau brute;• une opération suivante de décalcination, réalisée en tonneau, pour éliminer de ladite peau brute épilée tout résidu de chaux, et• une opération suivante de picklage, réalisée en tonneau, pour obtenir ladite peau pré-tannée;- au moins une phase de tannage, dans laquelle ladite peau pré-tannée est traitée en tonneau, ladite phase de tannage comprenant:• un premier traitement tannique, réalisé à une température comprise entre 15 et 30 °C, avec au moins un premier produit tannant comprenant des tannins;• un second traitement tannique, réalisé à une température comprise entre 20 et 35 °C, avec au moins un second produit tannant, comprenant des tannins dérivant d'eaux de végétation des olives, afin d'obtenir une peau tannée;- au moins une phase de retannage, dans laquelle ladite peau tannée est traitée par au moins un premier produit retannant, comprenant des tannins;ladite phase de retannage étant réalisée dans les 168 heures à compter du début de ladite phase de pré-tannage.
- Méthode selon la revendication 1, caractérisée en ce que ladite phase de retannage est réalisée dans les 72 heures à compter du début de ladite phase de pré-tannage.
- Méthode selon la revendication 1 ou 2, caractérisée en ce que ledit premier produit tannant est utilisé en tonneau, à un pourcentage compris entre 5 et 15 % par rapport au poids de ladite peau brute dans ledit tonneau.
- Méthode selon l'une quelconque des revendications précédentes, caractérisée en ce que ledit second produit tannant est utilisé en tonneau, à un pourcentage compris entre 2 et 10 % par rapport au poids de ladite peau brute dans ledit tonneau.
- Méthode selon l'une quelconque des revendications précédentes, caractérisée en ce que le premier traitement de ladite phase de tannage est réalisé pendant un laps de temps compris entre 60 et 120 minutes.
- Méthode selon l'une quelconque des revendications précédentes, caractérisée en ce que le second traitement de ladite phase de tannage est réalisé pendant un laps de temps compris entre 150 et 330 minutes.
- Méthode selon l'une quelconque des revendications précédentes, caractérisée en ce que ladite phase de retannage comprend:- au moins un troisième traitement tannique, utilisant un premier produit retannant comprenant des tannins synthétiques, dans une quantité comprise entre 10% et 16% par rapport au poids de la peau dans ledit tonneau, et- au moins un quatrième traitement tannique, utilisant un second produit retannant comprenant des tannins synthétiques, dans une quantité comprise entre 7% et 13% par rapport au poids de la peau dans ledit tonneau.
- Méthode selon la revendication 7, caractérisée en ce que ledit troisième traitement tannique est réalisé pendant une durée comprise entre 10 et 50 minutes.
- Méthode selon la revendication 7 ou 8, caractérisée en ce que ledit quatrième traitement tannique est réalisé pendant une durée comprise entre 30 et 150 minutes.
- Méthode selon l'une quelconque des revendications 7 à 9 ci-dessus, caractérisée en ce que ledit troisième traitement tannique et/ou ledit quatrième traitement tannique sont réalisés à une température comprise entre 20 et 45 °C.
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ES2453945T3 (es) | 2008-04-18 | 2014-04-09 | C & J Clark International Limited | Curtido de cueros y pieles |
ES2625320T3 (es) | 2013-10-16 | 2017-07-19 | Balenciaga | Proceso ecológico de curtido y teñido y producto obtenido |
IT201600081688A1 (it) | 2016-08-03 | 2018-02-03 | Tannow S R L | Impiego di acque di vegetazione olearia nell'industria conciaria |
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