EP3704275B1 - Zusammensetzung geeignet für vorbehandlung in wasserfreien gerben and entsprechendes gerbverfahren. - Google Patents

Zusammensetzung geeignet für vorbehandlung in wasserfreien gerben and entsprechendes gerbverfahren. Download PDF

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Publication number
EP3704275B1
EP3704275B1 EP18734308.2A EP18734308A EP3704275B1 EP 3704275 B1 EP3704275 B1 EP 3704275B1 EP 18734308 A EP18734308 A EP 18734308A EP 3704275 B1 EP3704275 B1 EP 3704275B1
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Prior art keywords
composition
range
tanning
fatliquor
water
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EP18734308.2A
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English (en)
French (fr)
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EP3704275A1 (de
Inventor
Palanisamy Thanikaivelan
Rathinam ARAVINDHAN
Balaraman Madhan
Palanivel SARAVANAN
Jonnalagadda Raghava Rao
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Council of Scientific and Industrial Research CSIR
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Council of Scientific and Industrial Research CSIR
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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
    • C14C3/08—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
    • C14C3/04—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
    • C14C3/28—Multi-step processes
    • 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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

  • the present invention relates to a composition useful for pre-treatment in waterless tanning. More particularly, the present invention relates to a composition that finds application in tanning, wherein the said composition uses the inherent water present in the substrate to be tanned, thereby eliminating the need of addition of external water.
  • the developed composition is useful in leather processing industry for making chrome or vegetable tanned leather in an eco-benign way without adding to the environmental pollution.
  • the basification is not necessary in this process ( Legesse et al, The Journal of the American Leather Chemists Association, 97, 475-486 2002 ; Rao et al, The Journal of the American Leather Chemists Association, 99, 82-94, 2004 ; WO 2012153203A1 ). Nevertheless, the disclosed process employs aqueous medium in significant quantity and discharge wastewater with fairly low pollution loads in comparison to the conventional pickle based chrome tanning system.
  • a dispersing agent composition was developed for carrying out tanning without water or any other medium ( WO 2017009867 ).
  • the dispersing agent essentially comprises polyalkylene polyhydric compound, an organic acid and a non-ionic surfactant.
  • the major constituent of the said dispersing agent is polyalkylene polyhydric compound, which would increase the cost of the composition and would limit the commercial viability.
  • Our co-pending Indian patent application No. 201611009091 provides a process for waterless chrome tanning that eliminates the use of water, salt, sulfuric acid and basification salts during the chrome tanning process. This process has been receiving more attention in global leather industries and several tanners in India have already adopted the process. However, use of more water and expensive organic acids for pre-treatment are posing problems for implementation in commercial environment. Hence, absorption of these new waterless chrome tanning technologies in worldwide leather industries has been slow thus threatening the sustainability of leather industries.
  • the inventors of the present invention realized that there exists a dire need to provide a composition and process useful for pre-treatment during waterless chrome tanning process, which helps to eliminate water from tanning process thereby reducing the wastewater discharge. Elimination of mineral tanning salt and common salt will reduce the pollution load and chemical cost of the tanning process, thereby benefiting the industry.
  • the main objective of the present invention is therefore to provide a composition useful in pre-treatment in waterless tanning process, which obviates the limitations as stated above.
  • Another objective of the present invention is to avoid the use of water both during chrome and vegetable tanning and utilize inherent water present in the substrate.
  • Still another objective of the present invention is to use auxiliary chemicals like acid stable cationic fatliquors during the tanning process.
  • Yet another objective of the present invention is to improve the uptake of chromium and vegetable tannins during the process.
  • Still another objective of the present invention is to reduce the pollution load and toxic chemicals in the effluent.
  • Yet another objective of the present invention is to reduce processing time, water and cost for pre-treatment during waterless tanning in comparison to conventional processing.
  • Still another objective of the present invention is to eliminate the use of salt, sulfuric acid and basification process in comparison to conventional processing.
  • the present invention provides a composition useful in pre-treatment in waterless tanning process, wherein the said composition comprising:
  • the present invention provides a process for the preparation of the pre-treatment composition useful in waterless tanning, which comprises mixing 90 to 95% (v/v) of organic acid having carbon chain length in the range of C1 to C3, 3 to 8% (v/v) of primary alcohol having carbon chain length in the range of C1 to C3 and 2 to 5% (v/v) of a non-ionic surfactant for a period in the range of 5 to 30 min to obtain the composition.
  • the said composition being water soluble, exhibiting a pH in the range of 1.8 to 2.6 as a 10% solution and characterized by transparent appearance.
  • the present invention provides a waterless tanning process using the developed composition, wherein the steps comprising:
  • the organic acid used may be selected from methanoic acid, ethanoic acid, propionic acid either individually or in different combinations.
  • the primary alcohol used may be selected from methanol, ethanol, propan-2-ol either individually or in different combinations.
  • the non-ionic surfactant used may be selected from 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, polyoxyethylene (20) sorbitan monooleate, [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate either individually or in different combinations.
  • the conventional fatliquor used may be selected from cationic fatliquor, acid stable fatliquor, universal fatliquor, chrome stable fatliquor either individually or in different combinations.
  • the alkali metal salt of organic acid used may be selected from sodium methanoate, sodium ethanoate either individually or in different combinations.
  • the present invention provides a process for the preparation of composition, which comprising mixing 90 to 95% (v/v) of an organic acid having carbon chain length in the range of C1 to C3, 3 to 8% (v/v) of primary alcohol having carbon chain length in the range of C1 to C3 and 2 to 5% (v/v) of a non-ionic surfactant are mixed together for a period of 5 to 30 min to obtain a composition which is useful for pre-treatment in waterless tanning processes.
  • the prepared composition has the following characteristics: pH of 10% solution: 1.8 to 2.6 Color: Transparent Solubility in water: High
  • composition is used for waterless tanning process as described below.
  • Delimed substrate is treated with 0.1 to 5% of the composition in the presence of 10-60% water.
  • the pH of the pelt is adjusted in the range of 4.8 to 5.8.
  • the float is drained and the substrate is treated with 0.2 to 2.0% of conventional fatliquor and 0.2 to 1.0% alkali metal salt of organic acid having carbon chain of length not more than two.
  • the substrate is treated with 3 to 50% of conventional tanning agent, added in one or more instalments, for a period in the range of 90 to 600 min.
  • the pH is checked to be in the range of 3.6 to 4.4 to obtain tanned substrate.
  • the inventive step of the present invention lies in preparing the composition by prudent selection and combination of key chemicals such that the resultant composition can be easily used for pre-treatment in waterless tanning, which would help in carrying out the tanning more effectively and easily utilizing the internal moisture content of raw material to reduce the effluent discharge. Further, elimination of common salt and considerable reduction in water requirement, duration of the process and cost are achieved in the new invention.
  • Composition was prepared by mixing of 45 ml of methanoic acid, 4 ml of methanol and 1 ml 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol together for a period of 5 min. pH of 10% solution of the composition was 1.80. The colour of the composition was transparent and it had good solubility in water.
  • One delimed substrate (cow hide) to be tanned weighing 3 kg was treated with the above composition diluted with 500 ml of water and drummed in the presence of 1200 ml water.
  • the pH of the pelt was checked to be 4.8.
  • the float was drained and the hide was treated with 6 g of cationic fatliquor and 6 g of sodium methanoate.
  • 90 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 90 min.
  • the pH was checked to be 3.8 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 7 ml of ethanoic acid, 0.2 ml of ethanol and 0.15 ml Polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.41. The color of the composition was transparent and it had good solubility in water.
  • Three delimed substrate (cow hide) to be tanned weighing 7.5 kg were treated with the above composition diluted with 75 ml of water and drummed in the presence of 3000 ml water.
  • the pH of the pelt was checked to be 5.2.
  • the float was drained and the hide was treated with 37.5 g of acid stable fatliquor and 15 g of sodium ethanoate.
  • 375 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 180 min.
  • the pH was checked to be 4.0 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 41 ml of propionic acid, 2.3 ml of propan-2-ol and 2.25 ml [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.58. The color of the composition was transparent and it had good solubility in water.
  • Two delimed substrate (cow hide) to be tanned weighing 5 kg were treated with the above composition diluted with 900 ml of water and drummed in the presence of 2000 ml water.
  • the pH of the pelt was checked to be 5.4.
  • the float was drained and the hide was treated with 15 g of Universal fatliquor and 27.5 g of sodium methanoate.
  • 300 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 180 min.
  • the pH was checked to be 4.10 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 45 ml of methanoic acid, 45 ml of ethanoic acid, 2.5 ml of methanol, 2.5 ml of ethanol, 2 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, 2 ml of Polyoxyethylene (20) sorbitan monooleate and 1 ml of [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.10. The color of the composition was transparent and it had good solubility in water.
  • Composition was prepared by mixing of 18 ml of methanoic acid, 18 ml of ethanoic acid, 18 ml of propionic acid, 2 ml of methanol, 2 ml of ethanol, 0.8 ml of propan-2-ol, 1 ml of Polyoxyethylene (20) sorbitan monooleate and 0.2 ml of [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.10. The color of the composition was transparent and it had good solubility in water.
  • Composition was prepared by mixing of 30 ml of methanoic acid, 15 ml of ethanoic acid, 26 ml of propionic acid, 1 ml of methanol, 0.5 ml of propan-2-ol, 0.5 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, 0.75 ml of Polyoxyethylene (20) sorbitan monooleate and 1 ml of [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.25. The color of the composition was transparent and it had good solubility in water.
  • delimed substrate to be tanned weighing 10 kg were treated with the above composition diluted with 750 ml of water and drummed in the presence of 4000 ml water.
  • the pH of the pelt was checked to be 5.0.
  • the float was drained and the hide was treated with 10 g of acid stable fatliquor, 10 g of universal fatliquor and 50 g of sodium methanoate.
  • 800 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 420 min.
  • the pH was checked to be 3.9 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 40 ml of methanoic acid, 15 ml of ethanoic acid, 50 ml of propionic acid, 4 ml of methanol, 2 ml of ethanol, 4 ml of propan-2-ol, and 2 ml of polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.6. The color of the composition was transparent and it had good solubility in water.
  • One delimed substrate (cow hide) to be tanned weighing 2 kg was treated with the above composition diluted with 1000 ml of water and drummed in the presence of 800 ml water.
  • the pH of the pelt was checked to be 5.8.
  • the float was drained and the hide was treated with 20 g of cationic fatliquor, 20 g of chrome stable fatliquor and 6 g of sodium ethanoate.
  • 60 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 120 min.
  • the pH was checked to be 4.4 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 10 ml of methanoic acid, 90 ml of ethanoic acid, 5 ml of ethanol and 5 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol together for a period of 5 min. pH of 10% solution of the composition was 2.20. The color of the composition was transparent and it had good solubility in water.
  • delimed substrate to be tanned weighing 10 kg were treated with the above composition diluted with 1000 ml of water and drummed in the presence of 4000 ml water.
  • the pH of the pelt was checked to be 4.8.
  • the float was drained and the hide was treated with 50 g of acid stable fatliquor and 50 g of sodium methanoate.
  • 600 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 300 min.
  • the pH was checked to be 4.1 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 25 ml of methanoic acid, 20 ml of propionic acid, 2.5 ml of ethanol, 2 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol and 0.5 ml of Polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.00. The color of the composition was transparent and it had good solubility in water.
  • Ten delimed substrate (cow hide) to be tanned weighing 20 kg were treated with the above composition diluted with 3000 ml of water and drummed in the presence of 8000 ml water.
  • the pH of the pelt was checked to be 4.8.
  • the float was drained and the hide was treated with 20 g of cationic fatliquor, 100 g of acid stable fatliquor, 25 g of universal fatliquor, 50 g of chrome stable fatliquor, 25 g of sodium methanoate and 25 g of sodium ethanoate.
  • 1600 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 540 min.
  • the pH was checked to be 3.7 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 41 ml of propionic acid, 2.3 ml of propan-2-ol and 2.25 ml [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.58. The color of the composition was transparent and it had good solubility in water.
  • Composition was prepared by mixing of 40 ml of methanoic acid, 15 ml of ethanoic acid, 50 ml of propionic acid, 4 ml of methanol, 2 ml of ethanol, 4 ml of propan-2-ol, and 2 ml of polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.6. The color of the composition was transparent and it had good solubility in water.
  • One delimed substrate (cow hide) to be tanned weighing 2 kg was treated with the above composition diluted with 1000 ml of water and drummed in the presence of 600 ml water.
  • the pH of the pelt was checked to be 5.6.
  • the float was drained and the hide was treated with 20 g of cationic fatliquor, 20 g of Universal fatliquor and 6 g of sodium ethanoate.
  • 1 kg of wattle GS powder was added in 4 feeds with 20 min interval and drummed for a period of 600 min.
  • the pH was checked to be 3.6 to obtain vegetable tanned leather.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Claims (8)

  1. Zusammensetzung geeignet zur Vorbehandlung bei wasserfreier Gerbung, wobei besagte Zusammensetzung umfasst:
    a) 90 bis 95% (v/v) einer organischen Säure, aufweisend eine Kohlenstoffkettenlänge im Bereich von C1 bis C3 mit einem transparenten Erscheinungsbild;
    b) 3 bis 8% (v/v) eines primären Alkohols, aufweisend eine Kohlenstoffkettenlänge im Bereich von C1 bis C3; und
    c) 2 bis 5% (v/v) eines nicht-ionischen Tensids.
  2. Zusammensetzung nach Anspruch 1, wobei die verwendete organische Säure ausgewählt ist aus Methansäure, Ethansäure, Propionsäure entweder alleinig oder in unterschiedlichen Kombinationen.
  3. Zusammensetzung nach Anspruch 1, wobei der verwendete primäre Alkohol ausgewählt ist aus Methanol, Ethanol, Propan-2-ol, entweder alleinig oder in unterschiedlichen Kombinationen.
  4. Zusammensetzung nach Anspruch 1, wobei das verwendete nicht-ionische Tensid ausgewählt ist aus 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, polyoxyethylene (20) sorbitan monooleate, [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl]octadecanoate entweder alleinig oder in unterschiedlichen Kombinationen.
  5. Verfahren zur Herstellung einer Zusammensetzung nach Anspruch 1, wobei die Schritte umfassen Mischen von 90 bis 95% (v/v) einer organischen Säure, aufweisend eine Kohlenstoffkettenlänge im Bereich von C1 bis C3, 3 bis 8% (v/v) eines primären Alkohols, aufweisend eine Kohlenstoffkettenlänge im Bereich von C1 bis C3 und 2 bis 5% (v/v) eines nicht-ionischen Tensids für eine Zeitdauer im Bereich von 5 bis 30min, um die angestrebte Zusammensetzung zu erhalten, wobei besagte Zusammensetzung wasserlöslich ist, als 10%ige Lösung einen pH-Wert im Bereich von 1,8 bis 2,6 aufweist und charakterisiert ist durch ein transparentes Erscheinungsbild.
  6. Gerbverfahren, nutzend die Zusammensetzung nach Anspruch 1, wobei die Schritte umfassen:
    a) Behandeln abgekalkten zu gerbenden Substrats mit 0,1 bis 5% w/w der Zusammensetzung nach Anspruch 1 in der Anwesenheit von 10 bis 60% Wasser, um den pH-Wert auf einen Bereich von 4,8 bis 5,8 einzustellen, gefolgt von Ablassen des Schwimmers, um vorbehandeltes Substrat zu erhalten;
    b) Behandeln des nach Schritt a) erhaltenen vorbehandelten Substrats mit 0,2 bis 2% eines konventionellen Fettlikörs und 0,2 bis 1,0% eines Alkalimetallsalzes einer organischen Säure, aufweisend eine Kohlenstoffkettenlänge von nicht mehr als zwei, für eine Zeitdauer im Bereich von 20 bis 60min;
    c) Behandeln des nach Schritt b) erhaltenen Substrats mit 3 bis 50% eines konventionellen Gerbmittels, welches in einer oder mehreren Tranchen zugegeben wird, für eine Zeitdauer im Bereich von 90 bis 600min bei gleichzeitiger Überprüfung des pH-Werts im Bereich von 3,6 bis 4,4, um gegerbtes Leder zu erhalten.
  7. Gerbverfahren nach Anspruch 6, wobei der verwendete konventionelle Fettlikör ausgewählt ist aus kationischer Fettlikör, säurestabiler Fettlikör, universaler Fettlikör, chromstabiler Fettlikör, entweder alleinig oder in unterschiedlichen Kombinationen.
  8. Gerberfahren nach Anspruch 6, wobei das verwendete Alkalimetallsalz der organischen Säure ausgewählt ist aus sodium methanoate, sodium ethanoate, entweder alleinig oder in unterschiedlichen Kombinationen.
EP18734308.2A 2017-11-24 2018-05-30 Zusammensetzung geeignet für vorbehandlung in wasserfreien gerben and entsprechendes gerbverfahren. Active EP3704275B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN201711042200 2017-11-24
PCT/IN2018/050347 WO2019102487A1 (en) 2017-11-24 2018-05-30 A composition useful for pre-treatment in waterless tanning and corresponding tanning process

Publications (2)

Publication Number Publication Date
EP3704275A1 EP3704275A1 (de) 2020-09-09
EP3704275B1 true EP3704275B1 (de) 2022-12-07

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EP18734308.2A Active EP3704275B1 (de) 2017-11-24 2018-05-30 Zusammensetzung geeignet für vorbehandlung in wasserfreien gerben and entsprechendes gerbverfahren.

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EP (1) EP3704275B1 (de)
CN (1) CN111556901B (de)
BR (1) BR112020010308A2 (de)
WO (1) WO2019102487A1 (de)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19507572A1 (de) * 1995-03-03 1996-09-12 Helmut Geihsler Verfahren zur Zurichtung von tierischen Häuten oder Fellen
CN101506341B (zh) * 2006-08-21 2012-06-20 荷兰联合利华有限公司 洗涤剂组合物
EP2336282B1 (de) * 2009-12-17 2014-07-30 The Procter and Gamble Company Flüssiges Reinigungssäuremittel für harte Oberflächen
WO2012153203A1 (en) 2011-05-10 2012-11-15 Council Of Scientific & Industrial Research Chrome tanning process for leather making reusing exhaust chrome liquor
BR112015024712A2 (pt) 2013-04-02 2017-07-18 Taminco Finland Oy método de curtimento ambientalmente vantajoso
IN2014DE00085A (de) * 2014-01-13 2015-07-17 Council Scient Ind Res
CN107109498B (zh) * 2015-07-13 2020-12-25 科学与工业研究委员会 用于对生皮/裸皮进行鞣制的分散剂组合物及其制备方法

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CN111556901B (zh) 2022-07-08
BR112020010308A2 (pt) 2020-11-17
CN111556901A (zh) 2020-08-18
WO2019102487A1 (en) 2019-05-31
EP3704275A1 (de) 2020-09-09

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