EP3094754B1 - Composition pour le tannage de chrome des peaux sans eau et sans picklage - Google Patents
Composition pour le tannage de chrome des peaux sans eau et sans picklage Download PDFInfo
- Publication number
- EP3094754B1 EP3094754B1 EP14786723.8A EP14786723A EP3094754B1 EP 3094754 B1 EP3094754 B1 EP 3094754B1 EP 14786723 A EP14786723 A EP 14786723A EP 3094754 B1 EP3094754 B1 EP 3094754B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- skins
- hides
- tanning
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 39
- 239000000203 mixture Substances 0.000 title claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 14
- 235000021110 pickles Nutrition 0.000 title claims description 5
- 238000000034 method Methods 0.000 claims description 22
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 claims description 18
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 claims description 18
- 239000011696 chromium(III) sulphate Substances 0.000 claims description 18
- 235000015217 chromium(III) sulphate Nutrition 0.000 claims description 18
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 16
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- -1 alkali metal salt Chemical class 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 235000010356 sorbitol Nutrition 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 238000005554 pickling Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000283707 Capra Species 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
Definitions
- the present disclosure relates to a composition for water free, pickle free chrome tanning of hides/skins for improved chrome tanning process.
- the present disclosure further relates to a process for chrome tanning using the said composition, whereby the tanning process is carried out as a waterless, salt free system without adding any additional medium.
- the present disclosure is envisaged to have tremendous application potential in the tanning industry to ensure eco-benign leather processing that does not add to environmental pollution.
- the present disclosure is therefore envisaged to play a crucial role in enhancing the economic and environmental benefits associated with chrome tanning.
- Salted hides and skins are the major raw materials for the tanning industry.
- the first operation carried out is the removal of salt in the hides and skins through repeated washings.
- the hair and flesh are loosened by treatment with lime and sodium sulfide or enzyme and then removed using knives.
- the hides and skins are then agitated with acid salts like ammonium chloride for removal of residual lime.
- the operation is called deliming, which is usually carried out in tanning drum.
- the resulting delimed hides and skins are subjected to pickling using 10% salt (all percentages mentioned are on the basis of weight of hides and skins) and 1% mineral acid in the hitherto known process, in order to bring down the pH of the delimed stock, which is around 8.0 to 2.8 to 3.0 to facilitate uptake as well as penetration of chrome tanning salt (commonly known as basic chromium sulfate - BCS) in the cross section of the hides and skins to be tanned. While the penetration of BCS in hides and skins during chrome tanning is carried out at pH 2.8 to 3.0, the same is raised to 3.8 to 4.0 for fixation, which is known as basification in the industry.
- 10% salt all percentages mentioned are on the basis of weight of hides and skins
- mineral acid in the hitherto known process
- Alkaline salts of weak organic acids which are normally referred to as masking salts are added during chrome tanning process to prevent surface fixation of chromium in hides and skins. All these operations are carried out in aqueous medium. It is very important in this regard that a significant portion of the chemicals used in the process is let out in the effluent.
- the conventional chrome tanning process is associated with generation of enormous amount of waste water containing a lot of unabsorbed chemicals leading to significant pollution as well as disposal problem. This obviously leads to an alarming situation especially in view of the ever growing scarcity of usable water.
- Indian patent application no. 2108/DEL/2008 describes a novel chrome composition
- a novel chrome composition comprising essentially three components - [a] basic chromium sulfate, having Cr 2 O 3 content in the range of 21-25% (weight / weight of basic chromium sulfate), [b] alkali earth metal oxide; and[c] alkali metal salt of organic acid having carbon chain of length in the range of one to three; wherein the ratio of [a] : [b] : [c] is in the range of 10:0.25:0.88 to 10:0.38:1.25.
- the method of using this composition for tanning purpose involves use of alkali dissolved in water and added in feeds of equal installments to attain a pH of 4.0 - 4.2 in aqueous medium for completion of tanning wherein the acid liberated during hydrolysis of chromium is neutralized.
- the major feature of using this composition in chrome tanning involves avoiding pickling operation, thereby ensuring that effluent is not loaded with enormous salinity as well as TDS.
- the main objective of the present disclosure is to provide a composition for water free, pickle free chrome tanning of hides/skins for improved chrome tanning process which obviates the limitations as stated above.
- Another objective of the present disclosure is to provide a process for chrome tanning without resorting to use of water for tanning.
- Yet another objective of the present disclosure is to provide a tanning process without resorting to pickling.
- compositions for water free, pickle free chrome tanning of hides/skins wherein said composition comprises:
- the composition has pH iin the range of 1-6.
- Cr 2 O 3 : SO 4 ratio is in the range of 1:2.2 to 1:2.6.
- the alkali metal salt of organic acid used is selected from sodium formate, sodium acetate, sodium citrate.
- the polyhydric alcohol used is selected from sorbitol, mannitol, glycerine.
- the ratio of polyhydric alcohol and basic chromium sulfate is in the range of 0.3:1 to 1:1.
- the acid used for acidification of polyhydric alcohol is selected from sulfuric acid, acetic acid, formic acid.
- a process for chrome tanning characterized in that it uses the said composition, wherein the steps comprise treatment of delimed hide/skin with 10 to 20% w/w of the said composition for a period in the range of 1-12 hours, preferably under stirring condition to obtain the chrome tanned hide/skin.
- Basic chromium sulfate is mixed with alkali metal salt of organic acid having carbon chain of length one to three in a ratio in the range of 1:0.25 to 1:0.5 and then mixed with acidified polyhydric alcohol, characterized by carbon chain length of 3-6, adjusted at a pH in the range of 1-6.
- the amount of polyhydric alcohol is in a ratio 0.3:1 to 1:1 with basic chromium sulfate.
- the mixture is preferably subjected to stirring for a period of 20 minutes to obtain the novel tanning composition.
- the composition exhibits the following characteristics:
- the composition is used for chrome tanning. Delimed hides and skins are treated with 10-20 % w/w, of the novel tanning composition without addition of water under agitation for a period of 1-12 hrs to get chrome tanned hide/skin.
- the inventive step of the present invention lies in providing a dispersion to enable the chrome tanning process to be carried out not only without adding water, but also eliminating the pickling and basification operations.
Landscapes
- 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 (6)
- Composition destinée au tannage au chrome sans picklage et sans eau de cuirs/peaux, comprenant :[a] du sulfate de chrome basique, ayant une teneur en Cr2O3 dans la plage de 21-25% (poids/poids de sulfate de chrome basique) ;[b] un sel de métal alcalin d'un acide organique ayant une chaîne carbonée d'une longueur dans la plage allant d'un à trois ;[c] un alcool polyhydrique préalablement acidifié par un acide ;où le rapport de [a] : [b] : [c] se trouve dans la plage allant de 1:0,25:0,3 à 1:0,5:1.
- Composition selon la revendication 1, où la composition possède un pH dans la plage de 1-6.
- Composition selon la revendication 1, où le sel de métal alcalin d'un acide organique est choisi parmi le formiate de sodium, l'acétate de sodium, le citrate de sodium.
- Composition selon la revendication 1, où l'alcool polyhydrique est choisi parmi le sorbitol, le mannitol, le glycérol.
- Composition selon la revendication 1, où l'acide utilisé pour l'acidification de l'alcool polyhydrique est choisi parmi l'acide sulfurique, l'acide acétique, l'acide formique.
- Procédé de tannage au chrome de cuirs/peaux, par le traitement de cuir/peau déchaulé(e) par de 10 à 20% p/p de la composition selon la revendication 1 pendant une période dans la plage de 1-12 heures, préférablement dans des conditions d'agitation, afin d'obtenir le cuir/la peau tanné(e) au chrome.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IN85DE2014 IN2014DE00085A (fr) | 2014-01-13 | 2014-01-13 | |
PCT/IN2014/000555 WO2015104716A1 (fr) | 2014-01-13 | 2014-08-29 | Composition pour le tannage au chrome sans piclage et sans eau de cuirs/peaux |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3094754A1 EP3094754A1 (fr) | 2016-11-23 |
EP3094754B1 true EP3094754B1 (fr) | 2018-03-28 |
Family
ID=51753266
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14786723.8A Not-in-force EP3094754B1 (fr) | 2014-01-13 | 2014-08-29 | Composition pour le tannage de chrome des peaux sans eau et sans picklage |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP3094754B1 (fr) |
CN (1) | CN106414777B (fr) |
BR (1) | BR112016016270A2 (fr) |
IN (1) | IN2014DE00085A (fr) |
TR (1) | TR201809066T4 (fr) |
WO (1) | WO2015104716A1 (fr) |
ZA (1) | ZA201605336B (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT201600130372A1 (it) * | 2016-12-22 | 2018-06-22 | Conceria Giardini S R L | Processo ci conciatura di pelli |
WO2018216029A1 (fr) * | 2017-05-25 | 2018-11-29 | Council Of Scientific And Industrial Research | Composition d'agent dispersant destinée à être utilisée pour le tannage et procédé pour sa préparation |
EP3704275B1 (fr) * | 2017-11-24 | 2022-12-07 | Council of Scientific and Industrial Research | Composition convenant au traitement préalable de tannage exempt d'eau et procédé de tannage correspondant |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2134070C3 (de) * | 1971-07-08 | 1975-09-25 | Bayer Ag, 5090 Leverkusen | Pulverförmige Mischungen zum Gerben von tierischen Häuten oder Nachgerben von Leder |
FR2649413B1 (fr) * | 1989-07-10 | 1993-05-28 | Toulouse Inst Nat Polytech | Procede de tannage de peaux |
AU2003209672A1 (en) | 2002-02-28 | 2003-09-09 | Council Of Scientific And Industrial Research | A process for making chrome tanned leathers |
-
2014
- 2014-01-13 IN IN85DE2014 patent/IN2014DE00085A/en unknown
- 2014-08-29 WO PCT/IN2014/000555 patent/WO2015104716A1/fr active Application Filing
- 2014-08-29 TR TR2018/09066T patent/TR201809066T4/tr unknown
- 2014-08-29 CN CN201480073078.4A patent/CN106414777B/zh not_active Expired - Fee Related
- 2014-08-29 BR BR112016016270A patent/BR112016016270A2/pt not_active Application Discontinuation
- 2014-08-29 EP EP14786723.8A patent/EP3094754B1/fr not_active Not-in-force
-
2016
- 2016-08-02 ZA ZA2016/05336A patent/ZA201605336B/en unknown
Also Published As
Publication number | Publication date |
---|---|
IN2014DE00085A (fr) | 2015-07-17 |
EP3094754A1 (fr) | 2016-11-23 |
TR201809066T4 (tr) | 2018-07-23 |
ZA201605336B (en) | 2017-11-29 |
BR112016016270A2 (pt) | 2017-08-08 |
CN106414777A (zh) | 2017-02-15 |
WO2015104716A1 (fr) | 2015-07-16 |
CN106414777B (zh) | 2018-04-10 |
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