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WO1996032445A1 - Procede de reduction electrochimique de colorants de cuve - Google Patents

Procede de reduction electrochimique de colorants de cuve Download PDF

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Publication number
WO1996032445A1
WO1996032445A1 PCT/EP1996/001336 EP9601336W WO9632445A1 WO 1996032445 A1 WO1996032445 A1 WO 1996032445A1 EP 9601336 W EP9601336 W EP 9601336W WO 9632445 A1 WO9632445 A1 WO 9632445A1
Authority
WO
WIPO (PCT)
Prior art keywords
mediator
electrochemical reduction
vat dyes
indigo
carbon
Prior art date
Application number
PCT/EP1996/001336
Other languages
German (de)
English (en)
Inventor
Markus Frede
Eckhard Roske
Hermann Pütter
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1996032445A1 publication Critical patent/WO1996032445A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D06P1/221—Reducing systems; Reducing catalysts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B7/00—Indigoid dyes
    • C09B7/02—Bis-indole indigos
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D06P1/228—Indigo

Definitions

  • the present invention relates to an improved process for the electrochemical reduction of vat dyes in aqueous solution in the presence of a mediator system.
  • WO-A 90/15182 and WO-A 94/23114 teach a process for dyeing cellulose-containing textile material with indigo, in which leuco indigo is used in aqueous solution. According to the teaching of these documents, the proportion of the leucoindigo in the dyeing liquor oxidized by air contact during the dyeing can be reduced electrochemically using a mediator system. Metals such as copper, titanium, lead and stainless steel are used as electrode materials. This process enables optimal use of the dye present in the dye liquor.
  • the object was to provide a method which avoids the technical problems mentioned.
  • vat dyes ie to dyes which, before being drawn onto a textile fiber, are converted into the aqueous dye liquor by reaction from a form which is sparingly or not water-soluble.
  • Typical representatives of this class of substances are indanthrene dyes such as indanthrene blue ® GC, phthalocyanine and naphthalene dyes, but special mention should be made of indigo and and Hydronblau ® BR.
  • the concentration of vat dyes in typical dyeing liquors is generally 0.1 to 2% by weight, depending on the desired depth of color.
  • Suitable mediators for the method according to the invention are reversible inorganic and organic redox systems whose redox potential is more cathodic than the potential required for the reduction of vat dyes (-600 mV for indigo).
  • organic mediators examples include quinoid compounds such as anthraquinone sulfonic acids and hydroxyanthraquinones such as avic acid.
  • concentrations of 0.5 • 10 " 3 to 3 • 10" 3 preferably around 1.5 • 10 ⁇ 3 mol organic mediator / 1 dye bath are used.
  • inorganic mediators are transition metal complexes.
  • a system of iron (11 / III) / trialkanolamine / sodium hydroxide solution is preferred here.
  • Iron sulfate is preferably used as the iron compound.
  • Usual concentrations in dyebaths are 0.2 to 2, preferably 0.4 to 0.8 g FeS0 4 / l dyebath.
  • the molar ratios of the trialkanolamine to the iron component are generally 5: 1 to 15: 1 mol / mol, that of the sodium hydroxide to the iron component is 15: 1 to 40: 1 mol / mol.
  • a technical dye bath is made basic by adding 0.1 to 3% by weight of sodium hydroxide.
  • Carbon or graphite felt is used as the cathode material in the process according to the invention.
  • This felt is commercially available, for example as insulating mats for blast furnaces. It is produced, for example, from fibers made of polyacrylonitrile or viscose by tempering, carbon or graphite felt being formed depending on the tempering conditions.
  • the felt can be fastened in a metal frame, via which the current is then supplied.
  • Graphite, platinum, titanium and mixed oxide electrodes, but preferably stainless steel (RA 2 , RA 4 ) are suitable as anode materials.
  • the temperature during the reaction can be 20 to 90 ° C, preferably 20 to 40 ° C.
  • the potential can be chosen between -600 to -1100 mV, preferably -700 to -800 mV is preferred for reducing indigo, measured against a standard calomel electrode.
  • Electrolysis cells which can be designed as simple or as multicathode cells, are suitable as cells for the electrochemical reduction.
  • Divided electrolysis cells are preferred, with diaphragms, semi-permeable me- industries, especially ion exchange membranes such as Nafion ® are used for compartmentalization.
  • An embodiment of the invention is preferred in which the majority of the indigo used for coloring is reduced by catalytic hydrogenation, for example using Raney nickel as a catalyst (see WO-A 94/23114).
  • the leuco indigo solutions thus obtained are fed to the dyebath, where they are partially oxidized in the dyeing process on the top of the dyebath by air contact.
  • This part of the indigo, which does not attach to the yarn as a pigment, can preferably be electrochemically reduced according to the invention.
  • the cathodes made of carbon or graphite felt to be used according to the invention are considerably lighter and cheaper to purchase than metal electrodes of comparable surface.
  • the current strength can be multiplied compared to planar electrodes of the same footprint or weight.
  • the anode with the dimensions 200 x 100 x 3 mm and a flat area of 2 dm 2 consisted of RA 1.4571 (stainless steel).
  • the cathode with identical surface dimensions was used in different material designs.
  • An Ag / AgCl reference electrode was used to measure the cathode potential using a voltmeter.
  • the anode circuit contained 172 g mediator solution and 1028 g water, the cathode circuit 358 g mediator solution, 2142 g water and 2.5 g indigo. Both circles were pumped around at 20 ° C.
  • Example cathode current density current material [mA / cm 2 ] [A] weight ratio
  • the table shows the adjustable current densities at a cathode potential of -1180 mV (calculated on the flat cathode surface) as a function of the cathode material.
  • All cathodes had a volume of 200 100 x 3 mm with a flat area of 2 dm 2 .
  • the copper mesh in Comparative Example 3 had a surface area of 4500 m 2 / m 3
  • the stainless steel mesh in Comparative Example 4 had a surface area of 8700 m 2 / m 3 .
  • the specific surface area (BET) of the carbon felt was> 1.5 m 2 / g, for graphite felt it was ⁇ 1.0 m 2 / g.
  • Comparative Example 5 shows that a graphite plate leads to significantly poorer results.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Coloring (AREA)

Abstract

L'invention concerne un procédé de réduction électrochimique de colorants de cuve dans une solution aqueuse, en présence d'un système médiateur, à l'aide de feutre de charbon ou de graphite comme matériau cathodique.
PCT/EP1996/001336 1995-04-12 1996-03-27 Procede de reduction electrochimique de colorants de cuve WO1996032445A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19513839.2 1995-04-12
DE1995113839 DE19513839A1 (de) 1995-04-12 1995-04-12 Verfahren zur elektrochemischen Reduktion von Küpenfarbstoffen

Publications (1)

Publication Number Publication Date
WO1996032445A1 true WO1996032445A1 (fr) 1996-10-17

Family

ID=7759531

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/001336 WO1996032445A1 (fr) 1995-04-12 1996-03-27 Procede de reduction electrochimique de colorants de cuve

Country Status (2)

Country Link
DE (1) DE19513839A1 (fr)
WO (1) WO1996032445A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000031334A3 (fr) * 1998-11-24 2000-10-05 Walter Marte Procede et appareil pour la reduction de colorants de cuve et de colorants au soufre
US6767448B1 (en) 1999-04-29 2004-07-27 Dystar Textilfarben Gmbh & Co. Deutschland Kg Method for producing aqueous alkaline solutions or reduced indigoid dyes
US6790241B2 (en) 2000-03-02 2004-09-14 Dystar Textilfarben Gmbh & Co. Deutschland Kg Mediator systems based on mixed metal complexes, used for reducing dyes
US6814763B2 (en) 2000-03-02 2004-11-09 Dystar Textilfarben Gmbh & Co. Deutschland Kg Mediator systems based on mixed metal complexes, used for reducing dyes
CN102977639A (zh) * 2012-12-03 2013-03-20 吴江市鼎佳纺织有限公司 一种还原性染料调和工艺
CN116180108A (zh) * 2023-02-10 2023-05-30 浙江工业大学 一种不外加媒介和化学还原剂的高浓度靛蓝电化学还原方法
EP4065752A4 (fr) * 2019-11-25 2024-10-09 Specialty Operations France Procédé électrochimique de préparation d'une amine et/ou d'un nitrile

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19723889A1 (de) * 1997-06-06 1998-12-10 Consortium Elektrochem Ind System zur elektrochemischen Delignifizierung ligninhaltiger Materialien sowie Verfahren zu seiner Anwendung
DE10161265A1 (de) * 2001-12-13 2003-06-26 Dystar Textilfarben Gmbh & Co Verfahren zur Farbveränderung von gefärbten textilen Substraten
EP1458924A1 (fr) * 2001-12-20 2004-09-22 Tex-A-Tec Ag Procede et appareillage pour l'hydrogenation electrocatalytique de colorants de cuve et de colorants au soufre
AU2003273714A1 (en) * 2002-11-06 2004-06-07 Tex-A-Tec Ag Method for the electrochemical reduction of vat and sulphur dyes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE235955C (fr) *
FR379041A (fr) * 1906-08-28 1907-10-23 Henri Chaumat Préparation de la cuve d'indigo employée en teinturerie
FR2265901A1 (fr) * 1974-04-02 1975-10-24 Bombay Textile Res Assoc
WO1990015182A1 (fr) * 1989-06-01 1990-12-13 Verein Zur Förderung Der Forschung Und Entwicklung In Der Textilwirtschaft Procede de reduction pour colorants
DE4218399A1 (de) * 1992-06-04 1993-12-09 Rhone Poulenc Rorer Gmbh Verfahren zur Reduzierung der Peroxidzahl
WO1994023114A1 (fr) * 1993-03-30 1994-10-13 Basf Aktiengesellschaft Procede permettant de teindre un materiau textile contenant de la cellulose avec de l'indigo hydrogene

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE235955C (fr) *
FR379041A (fr) * 1906-08-28 1907-10-23 Henri Chaumat Préparation de la cuve d'indigo employée en teinturerie
FR2265901A1 (fr) * 1974-04-02 1975-10-24 Bombay Textile Res Assoc
WO1990015182A1 (fr) * 1989-06-01 1990-12-13 Verein Zur Förderung Der Forschung Und Entwicklung In Der Textilwirtschaft Procede de reduction pour colorants
DE4218399A1 (de) * 1992-06-04 1993-12-09 Rhone Poulenc Rorer Gmbh Verfahren zur Reduzierung der Peroxidzahl
WO1994023114A1 (fr) * 1993-03-30 1994-10-13 Basf Aktiengesellschaft Procede permettant de teindre un materiau textile contenant de la cellulose avec de l'indigo hydrogene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
OREN Y ET AL: "GRAPHITE FELT AS AN EFFICIENT POROUS ELECTRODE FOR IMPURITY REMOVAL AND RECOVERY OF METALS", ELECTROCHIMICA ACTA, vol. 28, no. 11, 1 January 1983 (1983-01-01), pages 1649 - 1654, XP000561152 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000031334A3 (fr) * 1998-11-24 2000-10-05 Walter Marte Procede et appareil pour la reduction de colorants de cuve et de colorants au soufre
US6627063B1 (en) 1998-11-24 2003-09-30 Walter Marte Method and apparatus for reducing vat and sulfur dyes
US6767448B1 (en) 1999-04-29 2004-07-27 Dystar Textilfarben Gmbh & Co. Deutschland Kg Method for producing aqueous alkaline solutions or reduced indigoid dyes
US6790241B2 (en) 2000-03-02 2004-09-14 Dystar Textilfarben Gmbh & Co. Deutschland Kg Mediator systems based on mixed metal complexes, used for reducing dyes
US6814763B2 (en) 2000-03-02 2004-11-09 Dystar Textilfarben Gmbh & Co. Deutschland Kg Mediator systems based on mixed metal complexes, used for reducing dyes
CN102977639A (zh) * 2012-12-03 2013-03-20 吴江市鼎佳纺织有限公司 一种还原性染料调和工艺
EP4065752A4 (fr) * 2019-11-25 2024-10-09 Specialty Operations France Procédé électrochimique de préparation d'une amine et/ou d'un nitrile
CN116180108A (zh) * 2023-02-10 2023-05-30 浙江工业大学 一种不外加媒介和化学还原剂的高浓度靛蓝电化学还原方法

Also Published As

Publication number Publication date
DE19513839A1 (de) 1996-10-17

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