EP0426832B1 - Procede de reduction pour colorants - Google Patents

Procede de reduction pour colorants Download PDF

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Publication number
EP0426832B1
EP0426832B1 EP90908918A EP90908918A EP0426832B1 EP 0426832 B1 EP0426832 B1 EP 0426832B1 EP 90908918 A EP90908918 A EP 90908918A EP 90908918 A EP90908918 A EP 90908918A EP 0426832 B1 EP0426832 B1 EP 0426832B1
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EP
European Patent Office
Prior art keywords
potential
dye
reducing agent
cathode
reduction
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.)
Expired - Lifetime
Application number
EP90908918A
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German (de)
English (en)
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EP0426832A1 (fr
Inventor
Thomas Bechtold
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.)
Verein Zur Forderung der Forschung u Entwicklung der Textilwirts
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Verein Zur Forderung der Forschung u Entwicklung der Textilwirts
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Priority to AT9090908918T priority Critical patent/ATE105345T1/de
Publication of EP0426832A1 publication Critical patent/EP0426832A1/fr
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Publication of EP0426832B1 publication Critical patent/EP0426832B1/fr
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    • 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 invention relates to a process for the reduction of dyes in aqueous solution with pH> 9, using a reducing agent with a redox potential of over 400 mV, which is present in a reduced and oxidized form, a pair of electrodes being introduced into the solution, the Cathode potential is kept below the value at which hydrogen evolution occurs.
  • vat dyes for dyeing cellulose fibers have a considerable market share (approx. 12.5%, world consumption approx. 25,000 t / year).
  • This dye class is one of the high-quality dyes, particularly due to its high fastness properties.
  • the primarily non-fiber-insoluble dye particles are reduced to their alkali-soluble leuco form by reduction.
  • the reduced dye has a high affinity for the substrate and is now quickly absorbed by the dye.
  • the pull-up phase has ended, the leuco form is oxidized to fix the dye, forming the water-insoluble pigment.
  • the basic chemical structure of the dyes is often anthraquinone or indigoide.
  • sulfur dyes are inferior to vat dyes, but their price is very cheap, so that they have a relatively large market share in cellulose dyeing (25%, 50,000 t / year).
  • the sulfur dyes are used analogously to the vat dyes, with the reduction of the sulfur dyes being possible even at lower redox potentials.
  • Reducing agents are also used to destroy excess bleaching agents, reductive bleaching (wool) and reductive wastewater treatment (decolorization).
  • the main reducing agent for vat dyeing and for the reductive cleavage of azo dyes is Na2S2O4 sodium dithionite ("Hydro"), which has a reduction potential of approximately -1000 mV in an alkaline environment.
  • Sulfinic acid derivatives (Rongalit types BASF) are used for reductions at higher temperatures (steaming processes, HT processes) (reduction potential at 50 o C approx. -1000 mV).
  • Sulfinic acid derivatives can be activated through the use of heavy metal compounds such as Ni-cyano complexes, Co complexes etc.
  • the use of anthraquinone compounds as accelerators for the reducing agents used has been proposed, but is practically not carried out.
  • reducing agents are thiourea dioxide (-1100 mV), hydroxyacetone (-810 mV) and sodium borohydride (-1100 mV).
  • indigo lies between the vat dyes and sulfur dyes.
  • hydroxyacetone / sodium hydroxide solution can also be used here as a reducing agent.
  • iron vitriol (FeSO4) lime vats, zinc lime vats and fermentation vats were used.
  • other reducing agents can also be used for sulfur dyeing.
  • the main reducing agents are Na2S and NaHS (reduction potential approx. -500 mV). Mixtures of glucose and sodium hydroxide were also used.
  • Na2S2O4 is a relatively expensive chemical that has to be imported by many countries.
  • a large excess of Na2S2O4 based on the amount theoretically required for the reduction, must be used.
  • the oxygen present in the liquor must first be removed, only then can the dye reduction begin.
  • atmospheric oxygen from the environment continuously consumes Na2S2O4.
  • the quantities used are approx. 1.25 to 2.5 kg of reducing agent per kg of dye.
  • the amount of reducing agent must be in the dyebath sufficient for complete reduction to complete the dyeing process.
  • the dye bath is therefore drained off with a relatively large amount of reducing agent. The oxidation therefore takes place in a new treatment bath, since otherwise the entire excess of reducing agent still present in the dye bath must also be oxidized.
  • the reducing agent bath leads to considerable oxygen consumption in the wastewater, which leads to wastewater problems.
  • the procurement costs are relatively low, but the wastewater problem is becoming increasingly important here, since not only oxygen depletion, but also considerable toxicity and odor problems occur.
  • the invention has for its object to avoid the disadvantages of the previous reducing agents. This is achieved in that a reducing agent is used whose redox potential (half-stage potential), increased by the charge transfer overvoltage for the return of the oxidized form of the reducing agent to the reduced one below the cathode potential.
  • the dye is therefore not reduced directly at the electrode, which has already been proposed, but has not proven successful. Rather, a reducing agent is used which reduces the dye in a conventional manner, is oxidized in the process and reaches the cathode in this oxidized form, where it is returned to its original state.
  • Redox systems of this type are called mediators in electrochemistry. The use of such mediators for the reduction of dyes was not obvious for several reasons. So far, mediators have hardly been watery per se
  • the cathode thus reduces the reversible redox system which, in turn, is able to reduce the dye after the reduction potential of the dye has been reached.
  • the upstream reversible redox system has the task of generating a continuously regenerable reduction potential in the dye liquor, as a result of which no further reducing agent has to be added to the dye liquor.
  • the proportion of reducing agent consumed by air oxidation is continuously renewed at the cathode. There are no secondary products from the addition of reducing agents in the dyeing liquor. Enrichment by the usually necessary addition of reducing agent does not occur either.
  • the dye bath After removing the unfixed dye (centrifugation, filtration, ..), the dye bath can be reused, only the liquor volume lost with the goods having to be replaced. Chemical consumption in the usual sense does not occur. Even the dye reoxidation can be carried out in the dye bath, which according to the literature should lead to an improvement in the rub fastness of the dye (doubtful). This procedure is not economically justifiable with the reducing agents currently used, since at the end of the dyeing process large amounts of reducing agent remain in the dye liquor and draining the dye liquor is more cost-effective. A closed recycling of the entire dyeing liquor without time-consuming reprocessing is out of the question, also because of the ongoing enrichment with secondary reducing agent products.
  • Various upstream redox systems can be used for indirect electrochemical dye reduction:
  • organic compounds with which the redox system can be implemented in particular those with an anthrachinoid basic structure have been investigated.
  • Experiments with anthraquinone mono- and disulfonic acids, hydroxyanthraquinones and mixed substituted products enabled the reduction of sulfur dyes and vat dyes with the corresponding potential.
  • the quantities of anthrachinoid compound used are between 0.5. 10 ⁇ 3 mol / l and 3. 10 ⁇ 3 mol / l, with concentrations of about 1.5. 10 ⁇ 3 mol / l are cheap.
  • the oxygen input from the air must also be taken into account. The amount of catalyst required can be reduced by a closed apparatus.
  • Inorganic compounds for the invention Can be used, one has to look above all under the metal complex salts.
  • the system Fe (II / III) triethanolamine sodium hydroxide solution is suitable as a reduction mediator.
  • the achievable potentials of up to -980 mV enable the reduction of all common vat dyes, indigoid dyes, sulfur dyes, azo dyes without the use of other reducing substances.
  • the device shown comprises a container 11, on the bottom of which there is a working cathode 1 made of copper.
  • a magnetic stirrer 8 is located above the working cathode 1 to accelerate the removal of the reduction products.
  • a reference electrode 4 (Ag / AgCl) is provided for measuring the cathode potential by means of the voltmeter 5.
  • the potential in solution is measured using a separate measuring electrode 3 made of copper or platinum, which is connected to the reference electrode. As a result, the potential increase in the solution can be tracked as a result of the reduction system that is building up.
  • a container 10 filled with textiles to be dyed is introduced into the electrolysis chamber on the cathode side with respect to the diaphragm 7, through which the solution is sucked by means of the liquor circulation pump 9, whereupon it returns to the container 11.
  • the temperatures were between 40 and 50 o C, but in itself the entire temperature range from 20 to 90 o C could be used.
  • the potential in the solution rises to -940 mV within 20 minutes and is held there for 1 hour.
  • the reduced dye on the goods is oxidized by rinsing.
  • the dyeing is completed by boiling soap according to the dye manufacturer's instructions.
  • the color depth achieved during coloring corresponds to the guide values of the dye manufacturers.
  • the potential in the solution rises to over -800 mV within 20 min and is held there for 40 min.
  • the dyeing temperature was increased to approx. 60 ° C
  • the working current rises to 60 mA
  • the potential in the solution reaches -870 mV.
  • the reduced dye on the goods is oxidized by rinsing.
  • the dyeing is completed by boiling soap according to the instructions of the dye manufacturer The color depth achieved corresponds to the guide values of the dye manufacturers.
  • the potential in the solution rises to over -870 mV within 60 min, especially after the addition of Na2SO4.
  • the dyeing temperature is increased to approx. 45 ° C.
  • the reduced dye on the goods is oxidized by rinsing.
  • the dyeing is completed by boiling soap according to the dye manufacturer's instructions.
  • the color depth achieved during coloring corresponds to the guide values of the dye manufacturers.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)

Abstract

Procédé de réduction de colorants en solution aqueuse. On introduit une paire d'électrodes dans la solution et on maintient le potentiel de la cathode en dessous du niveau où de l'hydrogène commence à se former; on utilise ensuite un agent de réduction dont le potentiel redox est inférieur au potentiel de la cathode, lorsqu'on y ajoute l'excédent de potentiel de transfert de charge pour ramener l'agent de réduction de sa forme oxydée à sa forme réduite sur l'électrode.

Claims (6)

  1. Procédé de réduction de substances colorantes en solution aqueuse à un pH supérieur à 9, en utilisant un agent réducteur ayant un potentiel redox supérieur à 400 mV, Présent en solution sous forme réduite ou oxydée, dans lequel procédé une paire d'électrodes est plongée dans la solution, le potentiel cathodique de ladite paire d'électrodes étant maintenu à une valeur inférieure à celle où se produit un dégagement d'hydrogène,
    caractérisé en ce qu'on utilise un agent réducteur dont le potentiel redox (potentiel au milieu de l'échelle) augmenté de la surtension de transfert de charge pour le retour, ayant lieu à la cathode, de la forme oxydée de l'agent réducteur à la forme réduite, est inférieur au potentiel de la cathode.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise une cathode en Cu, Zn, Pb ou en acier fin.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise un agent réducteur à structure de base anthraquinoïde.
  4. Procédé selon la revendication 3, caractérisé en ce qu'on utilise de 0,5.10⁻³ mol/l à 3.10⁻³ mol/l, de préférence environ 1,5.10⁻³ mol/l, du composé anthraquinoïde.
  5. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise comme agent réducteur un sel métallique complexe.
  6. Procédé selon la revendication 5, caractérisé en ce qu'on utilise un mélange de 0,5.10⁻³ mol/l à 5.10⁻³ mol/l d'un sel de fer (II) ou de fer (III) et de triéthanolamine.
EP90908918A 1989-06-01 1990-05-31 Procede de reduction pour colorants Expired - Lifetime EP0426832B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT9090908918T ATE105345T1 (de) 1989-06-01 1990-05-31 Verfahren zur reduktion von farbstoffen.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT1329/89 1989-06-01
AT0132989A AT398316B (de) 1989-06-01 1989-06-01 Verfahren zur reduktion von farbstoffen
PCT/AT1990/000052 WO1990015182A1 (fr) 1989-06-01 1990-05-31 Procede de reduction pour colorants

Publications (2)

Publication Number Publication Date
EP0426832A1 EP0426832A1 (fr) 1991-05-15
EP0426832B1 true EP0426832B1 (fr) 1994-05-04

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EP90908918A Expired - Lifetime EP0426832B1 (fr) 1989-06-01 1990-05-31 Procede de reduction pour colorants

Country Status (6)

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US (1) US5244549A (fr)
EP (1) EP0426832B1 (fr)
AT (1) AT398316B (fr)
DE (1) DE59005612D1 (fr)
ES (1) ES2054358T3 (fr)
WO (1) WO1990015182A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046497A2 (fr) * 1999-12-22 2001-06-28 Dystar Textilfarben Gmbh & Co. Deutschland Kg Procede de reduction electrochimique de colorants reductibles
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

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ATE135765T1 (de) * 1990-12-03 1996-04-15 Verein Zur Foerderung Der Fors Verfahren zur reduktion von textilfarbstoffen
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DE19513839A1 (de) * 1995-04-12 1996-10-17 Basf Ag Verfahren zur elektrochemischen Reduktion von Küpenfarbstoffen
DE19723889A1 (de) * 1997-06-06 1998-12-10 Consortium Elektrochem Ind System zur elektrochemischen Delignifizierung ligninhaltiger Materialien sowie Verfahren zu seiner Anwendung
AT408455B (de) * 1997-09-04 2001-12-27 Basf Ag Verfahren zur reduktion von schwefelfarbstoffen
ATE304075T1 (de) 1998-11-24 2005-09-15 Walter Marte Verfahren und apparatur zur reduktion von küpen- und schwefelfarbstoffen
DE19919746A1 (de) * 1999-04-29 2000-11-02 Basf Ag Verfahren zur Herstellung von wäßrig-alkalischen Lösungen reduzierter indigoider Farbstoffe
DE10010060A1 (de) 2000-03-02 2001-09-06 Dystar Textilfarben Gmbh & Co Mediatorsysteme auf Basis gemischter Metallkomplexe zur Reduktion von Farbstoffen
DE10010059A1 (de) 2000-03-02 2001-09-06 Dystar Textilfarben Gmbh & Co Mediatorsysteme auf Basis gemischter Metallkomplexe zur Reduktion von Farbstoffen
DE10161265A1 (de) * 2001-12-13 2003-06-26 Dystar Textilfarben Gmbh & Co Verfahren zur Farbveränderung von gefärbten textilen Substraten
DE10234825A1 (de) * 2002-07-31 2004-02-19 Dystar Textilfarben Gmbh & Co. Deutschland Kg Verfahren zum Färben mit Schwefel- und Schwefelküpenfarbstoffen
WO2004042138A1 (fr) * 2002-11-06 2004-05-21 Tex-A-Tec Ag Procede de reduction electrochimique de colorants de cuve et au soufre
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HK1067926A2 (en) * 2004-01-20 2005-03-24 Hong Kong Productivity Council An electrochemical dye reducing method.
DE102005040469A1 (de) * 2005-08-26 2007-03-01 Dystar Textilfarben Gmbh & Co. Deutschland Kg Farbstoffzubereitungen von indigoiden Farbstoffen, von Küpen- und Schwefelfarbstoffen enthaltend anorganische und/oder organische elektrochemisch aktive Mediatorsysteme sowie deren Verwendung
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CN102174731B (zh) * 2011-03-04 2012-11-07 东华大学 一种电化学还原的染色装置
CN102154793A (zh) * 2011-03-23 2011-08-17 东华大学 一种用于棉纱线电化学还原的染色装置
CN102433770A (zh) * 2011-08-31 2012-05-02 常州耀春格瑞纺织品有限公司 还原染料电化学快速清洁染色工艺
BR112015004395A2 (pt) 2012-08-30 2016-02-16 Cargill Inc agente redutor para corantes de enxofre, processo para fabricar o agente redutor, uso do agente, método para reduzir os corantes de enxofre e método para tingir tecidos
CN108691116A (zh) * 2018-05-24 2018-10-23 武汉纺织大学 一种导电纱线电化学还原染色装置及方法
CN113166954B (zh) 2018-11-30 2024-07-26 赛杜工程股份有限公司 电化学反应器和它的清洁或再生
CN113166953A (zh) 2018-11-30 2021-07-23 赛杜工程股份有限公司 副产物(杂质)的除去
US11753730B2 (en) 2018-11-30 2023-09-12 Sedo Engineering Sa Leucodye (such as leucoindigo) as dispersing aid
CN113549938B (zh) * 2021-06-17 2022-06-21 武汉纺织大学 一种回收废旧牛仔激光废灰中靛蓝的方法
CN113416967B (zh) * 2021-06-17 2022-09-06 武汉纺织大学 一种回收废旧牛仔中靛蓝染料的方法和织物染色方法
WO2023161441A2 (fr) 2022-02-25 2023-08-31 Laboratoire Biosthetique Kosmetik Gmbh & Co. Kg Composition colorante comprenant du leuco-indigo pour colorer des fibres et des tissus

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046497A2 (fr) * 1999-12-22 2001-06-28 Dystar Textilfarben Gmbh & Co. Deutschland Kg Procede de reduction electrochimique de colorants reductibles
WO2001046497A3 (fr) * 1999-12-22 2001-12-13 Dystar Textilfarben Gmbh & Co Procede de reduction electrochimique de colorants reductibles
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

Also Published As

Publication number Publication date
ES2054358T3 (es) 1994-08-01
EP0426832A1 (fr) 1991-05-15
AT398316B (de) 1994-11-25
DE59005612D1 (de) 1994-06-09
US5244549A (en) 1993-09-14
ATA132989A (de) 1994-03-15
WO1990015182A1 (fr) 1990-12-13

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