EP1563137A1 - Procede de reduction electrochimique de colorants de cuve et au soufre - Google Patents

Procede de reduction electrochimique de colorants de cuve et au soufre

Info

Publication number
EP1563137A1
EP1563137A1 EP03757624A EP03757624A EP1563137A1 EP 1563137 A1 EP1563137 A1 EP 1563137A1 EP 03757624 A EP03757624 A EP 03757624A EP 03757624 A EP03757624 A EP 03757624A EP 1563137 A1 EP1563137 A1 EP 1563137A1
Authority
EP
European Patent Office
Prior art keywords
dye
carrier
redox
vat
graphite
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.)
Withdrawn
Application number
EP03757624A
Other languages
German (de)
English (en)
Inventor
Walter Marte
Albert Roessler
Paul Rys
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TEX-A-TEC AG
TEX A TEC AG
Original Assignee
TEX-A-TEC AG
TEX A TEC AG
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 TEX-A-TEC AG, TEX A TEC AG filed Critical TEX-A-TEC AG
Publication of EP1563137A1 publication Critical patent/EP1563137A1/fr
Withdrawn legal-status Critical Current

Links

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
    • D06P1/30—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 sulfur dyes
    • 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
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2016—Application of electric energy

Definitions

  • the present invention relates to a method for the electrochemical reduction of vat and sulfur dyes according to claim 1 and to a use of the dyes reduced in this way according to claim 17.
  • Reducing agents play a crucial role in the application of vat and sulfur dyes, since their reduced form is water-soluble and has a substrate affinity. As a result of the oxidation carried out after dyeing, the dye is converted from its leuco form back into the water-soluble pigment structure.
  • the main reducing agent for vat dyes is sodium dithionite Na 2 S 2 0 4 .
  • Na 2 S 2 0 4 The main reducing agent for vat dyes is sodium dithionite Na 2 S 2 0 4 .
  • This leads to a high sulfite and sulfate load in the wastewater, since it is a non-regenerable reducing agent.
  • These salt loads are both toxic and corrosive and lead to the destruction of concrete pipes.
  • coal, graphite and similar materials are not absolutely inert to chemical reactions.
  • the properties of carbon-containing products depend very much on the presence of functional groups on the surface.
  • a wide variety of classes have been identified, whereby oxygen-carbon complexes, conjugated CC multiple bonds and intercalates are essential with regard to the redox properties of coal.
  • the following classes can usually be observed: phenols, carbonyls, carboxyls, quinones and lactones.
  • the redox properties of the carbon-containing products in the Essentially caused by the presence of quinoid groups. It is also state of the art to increase the proportion of redox-active quinoid groups by means of various pretreatments of the coal.
  • the reactions with nitric acid, mixtures of nitric acid with sulfuric acid, potassium permanganate, potassium dichromate and oxygen are worth mentioning.
  • the object is achieved by a method according to claim 1.
  • the method is described below.
  • the dye is reduced in an oxygen-free, electrochemical reaction cell.
  • many cell types that are common in electrochemistry can be used.
  • work is preferably carried out in a fixed bed reactor in which the cathode material is in a flow channel and the electrical contact is ensured via a feed electrode.
  • a modified cathode 2 comprising a carrier 3 made of an electrically conductive, large-area material and a redox-active substance 4, which is permanently fixed on the carrier.
  • all electrically conductive, large-area materials that are stable in the alkaline range (pH 9 to 14) can be used as the carrier material for the carrier 3 become.
  • Examples are metals such as platinum and gold, metal oxides such as tin dioxide, titanium dioxide and ruthenium oxide, semiconductors such as silicon and germanium, graphite and graphite-like materials, conductive composite materials and conductive polymers such as polyacetylene, polypyrrole, polyaniline, polyfuran or polyazulene.
  • Doping of the polymer with alkali metal or halogens is also possible.
  • redox-active substances 4 can be fixed on the carrier or on the carrier material and used for direct electrochemical dye reduction.
  • Molecules with at least two carbonyl groups conjugated with one another are used as organic compounds with which the redox system can be implemented.
  • quinoid and anthraquinoid structures are to be designated. Examples are benzoquinone, naphthoquinone, anthraquinone, acenphthalene quinone, 1, 8-dihydroxyanthraquinone.
  • metal salt complexes can also be immobilized on the carrier material.
  • metal salt complexes can also be immobilized on the carrier material. Examples are Ru (III) ethylenediaminetetraacetate or cobalt (II) tetrakis (p-aminophenyl) porphyrin.
  • these redox-active substances 4 are immobilized on the carrier 3 or on the carrier material, ie permanently fixed. This implies both covalent and coordinative bonds as well as irreversible adsorption.
  • a covalent bond is formed between the carrier material and the redox-active substance, it is possible, for example, to utilize surface functionalities of the carrier material, such as carboxylic acid groups, hydroxide groups or amino groups in the case of graphite or polymers, and the oxide or hydroxide groups in the case of metals, in order to use a chemical to mediator molecule To fix ties.
  • bifunctional anchor molecules such as, for example, aminopropyltriethoxysilane, which covalently bond the support to the redox-active substances.
  • Typical functional groups of such anchor molecules for the formation of covalent or coordinative bonds are amino, carboxyl, cyanide, sulfide and pyridine groups.
  • Modification via activated carrier surfaces is also known. The activation can take place, for example, by vacuum pyrolysis or plasma treatment. In particular, substances with vinyl or amino groups can be bound in this way.
  • the irreversible adsorption of mediator molecules is less preferred because of the lower stability, but has advantages due to the simplicity of the preparation.
  • Various techniques for immobilization on or in the carrier such as sublimation or precipitation processes from the solution, are conceivable.
  • phthalocyanine systems and porphyrin systems can be irreversibly adsorbed on coal.
  • the modification of platinum with functionalized vinyl components is also known.
  • bifunctional anchor molecules e.g. Phenanthrene substituted with pyridine is conceivable.
  • modified cathode 2 The system consisting of carrier 3 and redox-active substance 4 immobilized thereon is referred to as modified cathode 2.
  • vat dyes and sulfur dyes - abbreviated to dye 1 - can be reduced within the scope of the method according to the invention.
  • indigo dyes such as e.g. Indigo, 5,5'-dibromo indigo, ⁇ . ⁇ '' tetrabromo indigo and thioindigo
  • anthraquinone dyes such as e.g. Acylaminoanthraquinones, anthraquinonazoles, anthramides and other branched anthraquinones, anthrimidecarbazoles, phthaloylacridones, quinacridones, indanthrones and highly condensed ring systems such as e.g. Flavanthron, Violanthron, Isoviolanthron, Dibenzpyrenchinon, Anthron and Pyranthron to name.
  • the dye is thus reduced directly on the electrode or on the modified cathode and not via dissolved mediator molecules. Rather, these redox-active centers are permanently on the surface of the modified cathode.
  • anode material is not very critical. However, materials with low oxygen overvoltage are preferably used, e.g. Iron, nickel, platinum, titanium coated with platinum and titanium coated with ruthenium oxide.
  • Ion exchange membranes In order to keep oxygen as far as possible from the cathode compartment, a divided cell must be used. Ion exchange membranes, diaphragms, glass frits, etc. are used as the separation medium. Ion exchange membranes, in particular cation exchange membranes, are preferably used, wherein, in turn, preference is given to using membranes which consist of a copolymer, tetrafluoroethylene and a perfluorinated monomer which contains sulfo groups.
  • the dye is introduced on the cathode side into an electrolysis vessel in an aqueous suspension containing various additives.
  • the alkaline pH required for the reduction is pH 9 to 14, preferably 12 to 14, and is adjusted with alkali hydroxide, in particular sodium hydroxide.
  • the acidic or alkaline anolyte spatially separated by a separator preferably consists of an aqueous solution of sulfuric acid or alkali hydroxide.
  • dye-related solubilizing or dispersing agents are used as additives:
  • Alcohols e.g. Methanol, ethanol, isopropanol, with methanol being preferred,
  • Naphthalenesulfonic acid derivatives e.g. Setamol WS
  • additives are used in amounts of approximately 0.1 to 90%, preferably 1 to 30%, based on the dye composition used.
  • the use of ultrasound has also proven itself to support the dispersion.
  • surfactants and solvents are also used as additives.
  • Typical representatives are alcohol propoxylates such as Lavotan SFJ, alcohol sulfates such as Subitol MLF and alkyl sulfonates such as Levapon ML.
  • the amounts used are in the range from 0.1 to 10 g / l, preferably between 1 and 5 g / l.
  • the voltage applied to the electrodes is a function of the hydrogen overvoltage of the respective electrode material and also depends on the reaction medium. Usually cell voltages between 1 and 5 V, preferably between 2 and 3 V, are applied.
  • the process is usually carried out at atmospheric pressure and temperatures between 20 and 100 ° C, preferably between 50 and 70 ° C.
  • dye concentrations of up to 200 g / l, but preferably 80 to 120 g / l, can be achieved in the stock vats.
  • the high level of dye solubility is of particular importance, as the overflowing of the dye in the dye baths can be prevented by means of more concentrated stock pools. This tying technique also leads to largely salt-free dyeing, which automatically ensures higher reproducibility and better fabric or yarn quality. Further advantages are the high stability of the reduced stem vat fleet in the oxygen-free electrolysis vessel, the high dye solubility of the linked species, the continuous dye reduction and thus the "just in time" preparation of the dye solution.
  • the present invention relates to the use of an electrochemically reduced dye produced by the process according to the invention for dyeing substrates.
  • the term “substrates” in the context of the present invention encompasses all substrates which can be colored with the dye according to the invention.
  • knitted fabric and knitted fabric made of natural or synthetic fibers, wood, plastic, glass and metal objects can also be dyed. It is also possible to dye the skin and tissue.
  • Example 1 describes the electrochemical reduction of indigo on graphite electrodes modified with benzoquinone.
  • the electrochemical reactor consists of a bed electrode; the previously produced modified graphite granulate with a diameter of 2 - 4 mm serves as the electrode material.
  • a centrally arranged platinum wire serves as the contact electrode.
  • the balls are located in a flow channel made of glass (cross section 7 cm 2 ) on a perforated glass plate.
  • An anode (DeNora DSA: electrode area 20 cm 2 ) is located in the anode space, which is spatially separated by a membrane (Nation 324, DuPont).
  • Sodium hydroxide solution with a concentration of 40 g / l serves as the anolyte.
  • indigo In the catholyte tank, 0.4 g of indigo is dispersed in 2000 ml of water, which also contains 80 g of sodium hydroxide solution.
  • the working current is 10 mA.
  • the catholyte flows vertically from bottom to top at 1.23 l / h. These conditions are maintained for 4 hours to completely reduce the dye.
  • Example 2 describes the electrochemical reduction of indigo on graphite electrodes modified with 1,8-dihydroxyanthraquinone.
  • Dicyclohexylcarbodiimide activated This was followed by the addition of 1,8-dihydroxyanthraquinone and further stirring for 24 h.
  • the concentration of quinone was 0.2 mol / l, the molar ratio quinone to N.N'-dicyclohexylcarbodiimide 1: 1.1.
  • the electrochemical reactor consists of a bed electrode; the previously produced modified graphite granulate with a diameter of 2 - 4 mm serves as the electrode material.
  • a centrally arranged platinum wire serves as the contact electrode.
  • the balls are located in a flow channel made of glass (cross section 7 cm 2 ) on a perforated glass plate.
  • An anode (DeNora DSA: electrode area 20 cm 2 ) is located in the anode space, which is spatially separated by a membrane (Nation 324, DuPont). 1.5% sulfuric acid is used as the anolyte.
  • indigo In the catholyte tank, 1 g of indigo is dispersed in 2000 ml of water, which also contains 80 g of sodium hydroxide solution.
  • the working current is 10 mA.
  • the catholyte flows vertically from bottom to top at 1.23 l / h. These conditions are maintained for 8 hours to completely reduce the dye.
  • Example 3 describes the electrochemical reduction of Vat green 1 on graphite electrodes modified with acenaphthenequinone.
  • the electrochemical reactor consists of a bed electrode; the previously produced modified graphite granulate with a diameter of 2 - 4 mm serves as the electrode material.
  • a centrally arranged platinum wire serves as the contact electrode.
  • the balls are located in a flow channel made of glass (cross section 7 cm 2 ) on a perforated glass plate.
  • An anode (DeNora DSA: electrode area 20 cm 2 ) is located in the anode space, which is spatially separated by a membrane (Nation 324, DuPont).
  • Sodium hydroxide solution with a concentration of 40 g / l serves as the anolyte.
  • Vat green 1 In the catholyte tank, 0.4 g of Vat green 1 is dispersed in 2000 ml of water, which also contains 80 g of sodium hydroxide solution. The reduction of the dye suspension is carried out at 70 ° C in the reactor after appropriate degassing with nitrogen (99%) by simply applying a cathode potential of -1100 mV vs. Ag / AgCI reached in 3 M KCI solution. The working current is 10 mA. The catholyte flows vertically from bottom to top at 1.23 l / h. These conditions are maintained for 5.5 hours to completely reduce the dye.
  • Example 4 describes the electrochemical reduction of indigo on graphite electrodes modified with anthraquinone carboxylic acid.
  • Anthraquinone carboxylic acid was mixed in a molar ratio of 1: 1.1 with N, N'-dicyclohexylcarbodiimide in dry THF for 24 h, the quinone concentration being 0.2 mol / l. Then the graphite was added and the whole batch for more Stirred for 24 h.
  • the electrochemical reactor consists of a bed electrode; the previously produced modified graphite granulate with a diameter of 2 - 4 mm serves as the electrode material.
  • the balls are located in an annular flow channel made of PVC (diameter 20 cm) around the central anode compartment on a perforated PVC plate.
  • Sodium hydroxide solution with a concentration of 40 g / l serves as the anolyte.
  • This stock vise is used as a coloring solution with a dye concentration of 10 g / l.
  • the dyeing is carried out in the absence of oxygen using 10 g of cotton fabric at a temperature of 30 ° C. for 10 minutes. After the dyeing process is completed, the sample is oxidized in air, rinsed and finally washed at 50 ° C.
  • the sample produced in this way shows a brilliant shade of blue, the color depth is identical to that of a color sample produced by the conventional dyeing method with sodium hydrosulfite.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Procédé de réduction électrochimique de colorants de cuve ou au soufre par mise en contact du colorant (1) avec une cathode modifiée (2). Cette dernière comprend un support (3) constitué d'une matière électro-conductrice à grande surface sur laquelle est fixée à demeure une substance active (4) d'oxydoréduction. Les substances utilisées possèdent de préférence des structures quinoïdes, en particulier une structure anthraquinoïde. Les eaux usées résultant de la mise en oeuvre du procédé selon la présente invention ne présentent pas de contamination toxique et possèdent une charge en sel fortement réduite.
EP03757624A 2002-11-06 2003-11-05 Procede de reduction electrochimique de colorants de cuve et au soufre Withdrawn EP1563137A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH18632002 2002-11-06
CH186302 2002-11-06
PCT/CH2003/000723 WO2004042138A1 (fr) 2002-11-06 2003-11-05 Procede de reduction electrochimique de colorants de cuve et au soufre

Publications (1)

Publication Number Publication Date
EP1563137A1 true EP1563137A1 (fr) 2005-08-17

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EP03757624A Withdrawn EP1563137A1 (fr) 2002-11-06 2003-11-05 Procede de reduction electrochimique de colorants de cuve et au soufre

Country Status (3)

Country Link
EP (1) EP1563137A1 (fr)
AU (1) AU2003273714A1 (fr)
WO (1) WO2004042138A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004040601A1 (de) * 2004-08-21 2006-03-02 Dystar Textilfarben Gmbh & Co. Deutschland Kg Neuartige flüssige Chinonimin-Schwefelfarbstoff-Zusammensetzungen sowie Verfahren zu ihrer Herstellung und ihre Verwendung zum Färben von cellulosehaltigem Material
DE102005040468A1 (de) * 2005-08-26 2007-03-01 Dystar Textilfarben Gmbh & Co. Deutschland Kg Mediatorsysteme zur elektrochemischen Reduktion organischer Verbindungen in wässriger Lösung
CN103367696A (zh) * 2012-03-29 2013-10-23 海洋王照明科技股份有限公司 正极片、其制备方法及锂离子电池
CN103835164B (zh) * 2014-03-10 2016-01-13 江南大学 一种电化学间接还原染色中阴极介质续用方法

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Publication number Priority date Publication date Assignee Title
US4595479A (en) * 1982-11-09 1986-06-17 Ajinomoto Co., Inc. Modified electrode
GB8508053D0 (en) * 1985-03-28 1985-05-01 Genetics Int Inc Graphite electrode
AT398316B (de) * 1989-06-01 1994-11-25 Verein Zur Foerderung Der Fors Verfahren zur reduktion von farbstoffen
DE4320867A1 (de) * 1993-06-24 1995-01-05 Basf Ag Verfahren zum Färben von cellulosehaltigen Textilmaterialien mit Küpenfarbstoffen oder Schwefelfarbstoffen
DE19513839A1 (de) * 1995-04-12 1996-10-17 Basf Ag Verfahren zur elektrochemischen Reduktion von Küpenfarbstoffen
AU1146500A (en) * 1998-11-24 2000-06-13 Otmar Dossenbach Method and apparatus for reducing vat and sulfur dyes
DE19919746A1 (de) * 1999-04-29 2000-11-02 Basf Ag Verfahren zur Herstellung von wäßrig-alkalischen Lösungen reduzierter indigoider Farbstoffe
DE19962155A1 (de) * 1999-12-22 2001-06-28 Basf Ag Verfahren zur elektrochemischen Reduktion von Küpenfarbstoffen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004042138A1 *

Also Published As

Publication number Publication date
WO2004042138A1 (fr) 2004-05-21
AU2003273714A1 (en) 2004-06-07

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