EP1056900B1 - Procede et appareil pour la reduction de colorants de cuve et de colorants au soufre - Google Patents

Procede et appareil pour la reduction de colorants de cuve et de colorants au soufre Download PDF

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EP1056900B1
EP1056900B1 EP99972704A EP99972704A EP1056900B1 EP 1056900 B1 EP1056900 B1 EP 1056900B1 EP 99972704 A EP99972704 A EP 99972704A EP 99972704 A EP99972704 A EP 99972704A EP 1056900 B1 EP1056900 B1 EP 1056900B1
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dye
reaction
fact
process according
vessel
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EP1056900A2 (fr
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Walter Marte
Otmar Dossenbach
Ulrich Meyer
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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
    • 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
    • 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
    • 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
    • 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 process for the electrochemical reduction of Vat and sulfur dyes in aqueous solutions according to claim 1 and an apparatus for carrying out this method according to claim 11.
  • vat and sulfur dyes on cellulosic materials takes place in the reduced form, since only this is water-soluble and a high Has substrate affinity.
  • vat and sulfur dyes for printing and dyeing cellulosic fibers is until now the use of superstoichiometric Reducing agent amounts (based on the amount of dye to be reduced) bound.
  • the reduction of the vat dyes is usually carried out in alkaline (pH> 9), aqueous solutions with sodium dithionite (hydrosulfite) or derived therefrom Reducing agents (RONGALIT C, BASF) in conjunction with wetting agents and complexing agents.
  • Other reducing agents such as thiourea dioxide or endiolates have become available for price reasons hardly enforced, in the case of thiourea dioxide a similar environmental problem exists with hydrosulfite.
  • the reducing agents suitable for the reduction of the vat dyes show among the conditions necessary for vatting the dyes a redox potential of -400 mV to -1,000 mV.
  • Both the use of hydrosulfite and thiourea dioxide lead to a high sulfite or sulfate pollution of the wastewater.
  • These salt loads On the one hand toxic and on the other hand corrosive and lead to the destruction of Concrete pipes.
  • Another problem of sulfite from the sulfite in the Wastewater is the hydrogen sulphide formation caused by anaerobic organisms in the schedule tubes.
  • the reducing agent or mediator used is the dye-reducing agent.
  • the mediator system is electrochemically regenerated cathodically according to the example mentioned above (eg Fe 2+ ⁇ -> Fe 3+ ). Due to the high quantities used and the environmental concern of such mediators, there is still an acute environmental problem that can only be solved by additional investment in adequate wastewater technology or a recycling process. Another disadvantage of these methods is the permanent Mediatornachsatz for maintaining the redox cycle in the Kontinuefärbetechnik. The post-dose metering of the mediator system results from the fabric or yarn flow proportional fleet discharge.
  • the object of the present invention is therefore to avoid the mentioned Disadvantages of known reduction methods a largely reducing agent-free Vatting process for the preparation of fully reduced dye solutions for Dyeing of cellulosic textile materials.
  • the object is achieved by a method according to claim 1 and a Apparatus according to claim 11.
  • vat dyes in the context of the present invention except the indigoid dyes, with indigo itself being preferred, including anthraquinoids Dyes and optionally also not prereduced sulfur dyes understand.
  • Dye A reacts with the reduced dye species P, in the following briefly with Species P, which represents the leuco form of Dye A, in a comproportionation reaction (I) in which two dye radical anions form 2R.
  • the two dye-radical anions 2R due to their charge are water-soluble, electrochemically according to the reaction equation (II) the cathode to the dianions, resp. reduced species 2P.
  • the redox potential of the dye radical anions is increased 2R adapted DC voltage applied.
  • Fig. 1 shows a schematic representation of the just described electrochemical Vatting.
  • the dye reduction takes place in an oxygen-free electrolysis vessel which contains both the electrodes and a possible mixing unit.
  • Various cell connections allow on the one hand the continuous and on the other hand the batch operation of the electrolysis apparatus.
  • the dye pigment A is introduced into the electrolysis vessel in an aqueous suspension containing various additives.
  • the alkaline pH necessary for dye reduction is 10.5-13, which is adjusted with alkali metal hydroxide, in particular sodium hydroxide solutions.
  • additives according to the desired reaction start conditions, surfactants, reducing agents and solvents are used in low concentrations. According to the invention, the additives used can be discontinued after the start of the reaction or their concentration can be changed.
  • reaction equation (IIIA) shows a first start reaction: A + B ⁇ P
  • reaction starter is in the simplest case, a commercial, for the reduction of Vat dyes suitable reducing agent B such. Hydrosulfite or an endiolate used in substoichiometric ratio with respect to the dye A.
  • the reducing agent B called starter or reduction starter for short, reduces an amount corresponding to its amount of the dye A to the species P, or to the Dianion.
  • the inventive method differs quite significantly from one Reaction management using a mediator system that is permanently in mandatory Way must be present.
  • reaction equations (IIIB) show a second start reaction: A + X ⁇ (AX) sol (AX) sol + 2e - ⁇ P
  • auxiliaries are used in amounts of about 1 to 90%, preferably 5 to 30%, used based on the dye composition used.
  • the auxiliaries In support of the Solubilization or dispersion by the described auxiliaries has the Use of ultrasound proven as a dispersing aid. This is during or before the Reduction of the dye applied to the suspension with ultrasonic energy.
  • reaction equations (IIIC) show a third start reaction: S ⁇ S * S * + A ⁇ R
  • a radical initiator S is activated by the action of physical means such as ultraviolet radiation, cobalt radiation and / or ultrasound, whereby it is converted to an excited state S * of the radical initiator (IIIC.1). This reacts with the dye A, from which a radical anion R is formed (IIIC.2).
  • Radical starters used are benzophenones, its diaryl ketone derivatives, anthraquinones and xanthones.
  • Further classes of compounds which are suitable as free-radical initiators are azo compounds and diazonium salts (eg azoisobutyronitrile).
  • UV burners or any radiation sources, even for harder radiation, and ultrasound in a known manner.
  • the ultrasonic waves which are used in accordance with the method, are produced with conventional ultrasound generators. Their frequency is in the range of 16 kHz and above, preferably at 20 to 30 kHz.
  • the ultrasound energy to be used depends on the dye or on the radical-forming substance and the size of the reaction vessel. Usually, powers between 0.5 and 1 kW are used to generate the cavitation required for radical formation in the reaction medium.
  • Combinations of reducing starters with solubilizing or dispersing agents show synergistic effects in such a way that to be achieved in the starting phase Reaction rate is greater than that with the reduction starter or with the Solubilizing or dispersing agent alone. With increasing reaction conversion the rate of reaction increases by the superposition of the Komproportionierungsrepress and the reaction sequence described above with the used Solubilizing or dispersing agent.
  • Preferred combinations for starting the Reaction are sodium hydrosulfite as a starter and certain Naphthalinsulfonkla (Setamol WS from BASF Ludwigshafen) or combinations thereof as dispersants.
  • ionic or nonionic are also used Surfactants and protic and aprotic solvents (as described above) used as additives, which have both a dye and electrode affinity have and do not self-reducing.
  • Typical representatives of this Substances are alcohol propoxylates such as e.g. Lavotan SFJ, alcohol sulfates, e.g. Sandopan WT, Subitol MLF and alkyl sulfonates such as e.g. Levapon ML.
  • the amounts of these additives are in the range of 0.1 to 10 g / l, preferred Concentrations are between 1 and 5 g / l.
  • Electrode material it is possible in principle to use all electrically conductive materials which are stable in the alkaline range (pH 9 to 14) and which have no hydrogen formation at the redox potential necessary for the dye reduction.
  • These include electrodes which have been modified by special surface treatments. This can be done by adsorbing specific surfactants with a typical HLB value (hydrophilic / hydrophobic balance) of 8 to 14 or by partial coating with a hydrophobic polymer suspension. Typical substances are polytetrafluoroethylene, tetrafluoroethene oligomers and polystyrene.
  • the size of the electrode surface is determined by the required Verkupp amalgam and is designed reactor-specific.
  • the voltage applied to the electrodes is a function of the vatting potential of the dye (taking into account the comproportionation reaction) and also depends on the nature of the electrode. Usually voltages of 2.3 V to 2.6 V are applied.
  • Fig. 2 shows an apparatus for continuous, electrochemical dye reduction in a schematic representation.
  • An electrolysis vessel 1 with lid 1 ', tightly sealed by seals 2, is part of a circuit with the line 13, with a pump P1, a line 13', a steel tube spiral 3, a line 13 "and an inlet tube 4, via the lid 1 'is returned to the electrolysis vessel 1.
  • the steel tube spiral 3 is located on an ultrasonic oscillator 5.
  • the energy input via the ultrasound oscillator 5 is 100-1000 watts and serves to form radicals and to disperse the dye Selected start reaction dependent additives is circulated throughout the Verüpungszeit in a circulation flow V1 'by means of the pump P1, the steel tube spiral 3 with the ultrasonic vibrator 5 act as a dispersing aid.
  • the electrolysis vessel 1 there is a further electrode pair 6, 6 ', to which an electrical voltage of approximately 2.2 V is applied after the start reaction has been completed. This condition is maintained until the total amount of dye introduced is completely reduced.
  • stationary reaction conditions set by the electrolysis vessel 1 is continuously supplied to a volume flow V2 'of the dye suspension and an equivalent volume flow V3' reduced dye is removed.
  • a pump P2 in a volume flow V2' via lines 14, 14 'in the line 13 and thus supplied to the circulation flow V1'.
  • a volumetric flow V2 'corresponding volume flow V3' removed and metered by means of a pump P3 via lines 15, 15 'and an inlet pipe 16 into an oxygen-free storage vessel 21, which with a lid 21' and seals 22 sealed is.
  • the reduction agent-free, electrochemical Farbstoffverküpung carried out in this way corresponds to the principles of continuous reaction in an ideal mixed stirred tank.
  • Example 1 describes an electrochemical Batchverküpung with a reducing agent B according to start reaction (IIIA). 10 g of indigo are dispersed in 100 ml of water which simultaneously contains 4.0 g of sodium hydroxide solution and 1 ml of a 10% Subitol SE solution (BEZEMA AG) as wetting agent and added to an electrolysis vessel thermostated at 40 ° C. Subsequently, a hydrosulfite addition of 1.7 g takes place under exclusion of oxygen. This corresponds to about 0.25 redox equivalents based on the amount of indigo present.
  • IIIA start reaction
  • the start reaction is complete and the dye is present in a proportional to the reducing agent stoichiometric amount as dianion, according to the adjusted pH of about 12.5.
  • a voltage of 2.3 V is applied to the existing electrodes.
  • the working current is about 1.5 A.
  • Example 2 describes a first continuous electrochemical vatting according to the starting reactions (IIIB) with solubilizing and dispersing aids.
  • the electrochemical vatting is carried out in an apparatus according to FIG. 2.
  • 5 g of indigo are dispersed in 100 ml of water which simultaneously contains 3.5 g of sodium hydroxide solution and 2 g of Setamol SW as a dispersant.
  • the dye suspension is placed in a thermostated at 40 ° C, stirred, oxygen-free and equipped with electrodes 6, 6 'electrolysis vessel 1.
  • the dye suspension is circulated throughout the vatting time with a circulation flow V1 'of 20 ml / min.
  • the working voltage applied to the electrodes is 2.0 V at a current flow of 2.0 A. After about 40 minutes under the conditions specified in the electrolysis vessel results in a 100% reduced color solution.
  • the registered via the ultrasonic transducer 5 power is about 150 watts and is used for radical formation and dye dispersion.
  • a 5% indigo suspension is conveyed from the second vessel 11 into the circulation stream V1 'by means of the pump P2 with a volume flow V2' of 1.5 ml / min.
  • the indigo suspension present in the storage vessel 11 has the same composition as was described at the beginning.
  • a volume flow V3 'corresponding to the paint inlet V2' of 1.5 ml / min is withdrawn from the electrolysis vessel 1 and metered into the oxygen-free supply vessel 21 by means of the pump P3.
  • the liquor content of the electrolysis vessel is exchanged so far that no more starter chemicals are present and the further reduction is carried out by the reactions described in the reaction equations (I) and (II). This mode of operation is maintained for an additional hour to demonstrate the absolutely starter-free, electrochemical direct coving.
  • vatting levels analyzed within this time show values> 95%.
  • the Dyeings made with this solution meet all criteria (Color depth and fastness properties) as with conventionally produced vat dye fleets be achieved.
  • Example 3 describes a second continuous electrochemical vatting of indigo with the aid of solubilizing or dispersing aids according to the starting reactions (IIIB).
  • 5 g of indigo are dispersed in 100 ml of water, in which previously 2 g of Setamol WS and 5 ml of methanol were added.
  • 3 g of sodium hydroxide solution are added to the suspension, which is then added to the nitrogen-purged and stirred electrolysis vessel.
  • the heatable electrolysis vessel is thermostated at 35 ° C. After reaching the temperature (35 ° C), the power connection (2.2 V, 2.0 A) takes place for electrochemical Farbstoffverküpung.
  • Example 4 describes an electrochemical vatting with photochemical starting reaction according to the starting reactions (IIIC).
  • 5 g of indigo are dispersed in 200 ml of water containing 2 g of sodium hydroxide solution and 10 ml of methanol with the aid of ultrasound.
  • the dye suspension 0.5 g Michler's ketone [4,4-bis (N, N-dimethyl-amino) benzophenone] is added as a radical initiator.
  • the reaction mixture is placed in a nitrogen-purged, thermostated at 30 ° C and stirred electrolysis vessel, which is equipped parallel to the electrode with a UV burner. After complete exchange of oxygen (after approx. 10 - 15 minutes), both the UV burner and the electrolysis are switched on.
  • the UV burner operates with a radiator output of 150 W, whereby the maximum of the spectral energy distribution is around 250 nm.
  • the voltage applied to the electrodes is 2.0 V with a current flow of 1.7 A.
  • a photochemical excitation of Michler's ketone occurs to form a radical.
  • the electron of the radical initiator is transferred to a dye molecule, forming the Farbstoffmonoanionradikals, which is reduced according to the reaction scheme (IIIC.2) electrochemically to the dye dianion.
  • the UV burner is switched off and started the continuous vatting, which is performed exclusively electrochemically.
  • a dye volume flow of 1 ml / min of a dye suspension with 25 g / l of indigo and 3 g / l of caustic soda (without free-radical initiator and methanol) is fed to the electrolysis vessel and at the same time a volume flow of 1 ml / min is removed from the electrolysis vessel.
  • the reaction vessel is operated as an ideally mixed stirred tank, whereby under the given conditions in the reactor effluent a Verüpungsgrad of> 95% was determined.
  • the thus continuously prepared vat stock solution contains only dye and sodium hydroxide, since the initially used radical starter and the methanol are completely discharged after about 6 ⁇ and the dye reduction takes place directly, without further auxiliaries.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Treating Waste Gases (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (14)

  1. Procédé permettant la réduction électrochimique de colorants au cupe et au soufre dans des solutions aqueuses, caractérisé en ce que deux anions radicaux de colorant (2R) sont formés dans une réaction de comproportionation entre un colorant (A) et sa forme (P) ou son espèce (P) réduite (équation de réaction I), que les deux anions radicaux de colorant (2R) sont réduits de manière électrochimique à la même espèce (2P) (équation de réaction II), A + P -> 2R 2R + 2e -> 2P que les équations de réaction (I) et (II) forment un cycle stationnaire, que l'obtention des conditions stationnaires de réaction résulte d'une réaction initiale et que le cycle stationnaire est préservé, l'espèce (P) formée étant, d'une part, nécessaire pour la préservation du cycle et, d'autre part, utilisée pour le processus de coloration.
  2. Procédé selon la revendication 1, caractérisé en ce que la réaction initiale s'effectue selon l'équation de réaction (IIIA) A + B -> P par la formation du colorant (A) avec une faible quantité sous-stoechiométrique par rapport au colorant d'un agent réducteur (B) d'une faible quantité de l'espèce (P), le cycle des équations de réaction (I) et (II) étant ainsi amené dans des conditions stationnaires de réaction.
  3. Procédé selon la revendication 1, caractérisé en ce que la réaction initiale s'effectue selon les équations de réaction (IIIB) A + X -> (AX)sol (AX)sol + 2e -> P par la solubilisation du colorant (A) avec une substance auxiliaire (X) et par la réduction électrochimique sous la forme solubilisée, ce qui permet de former une faible quantité de l'espèce (P) et d'amener le cycle des équations de réaction (I) et (II) dans les conditions stationnaires de réaction.
  4. Procédé selon la revendication 1, caractérisé en ce que la réaction initiale s'effectue selon les équations de réaction (IIIC) S -> S* S* + A -> R par l'activation d'un initiateur radicalaire (S) sous l'influence de moyens physiques, l'initiateur radicalaire (S) étant amené dans un état excité (S*) de sorte que ce dernier réagit avec le colorant (A) et forme un anion radical (R), ce qui permet d'amener le cycle des équations de réaction (I) et (II) dans les conditions stationnaires de réaction.
  5. Procédé selon une des revendications 1 à 4, caractérisé en ce que les colorants (A) utilisés sont des colorants indigoides et anthraquinoniques ainsi que des colorants au soufre.
  6. Procédé selon la revendication 2, caractérisé en ce que les agents réducteurs (B) utilisés en quantités sous-stoechiométriques sont l'hydrosulfite et ses dérivés, le dioxyde de thio-urée, la glucose, l'α-hydroxycétone, l'α-hydroxyaldéhyde, la réduction de triose ou l'acide de réductine.
  7. Procédé selon la revendication 3, caractérisé en ce que les substances auxiliaires (X) utilisées sont des cétones, des alcools, de préférence le méthanol et l'isopropanol, des acétales, des glycols et des glycoléthers, des pyridines, des lactames, des acides, des dérivés des acides naphthaline-sulfoniques et des amides d'acide.
  8. Procédé selon la revendication 3, caractérisé en ce que les initiateurs radicalaires (S) utilisés sont des benzophénones, ses dérivés de diarylcétone, des anthraquinones, des xanthones ainsi que des composés azoïques et des sels de diazonium.
  9. Procédé selon la revendication 4, caractérisé en ce que les moyens physiques utilisés sont un rayonnement riche en énergie, de préférence un rayonnement UV, une radiation au cobalt, et/ou des ultrasons.
  10. Procédé selon une des revendications 1 à 9, caractérisé en ce qu'un débit volumétrique (V3') est directement transféré dans le cadre d'une réduction continue de colorant de la cuve d'électrolyse (1) vers le bain de coloration et que ceci s'effectue en fonction de la part de colorant consommée par la matière à colorer par une addition 'juste-à-temps'.
  11. Appareillage permettant de réaliser le procédé selon une des revendications 1 à 10, caractérisé en ce qu'un cycle avec un débit de circulation (V1') est prévu pour une suspension de colorant (A) contenue dans une cuve d'électrolyse (1), la cuve d'électrolyse (1) étant équipée d'électrodes (6, 6'), qu'une suspension de colorant identique contenu dans une deuxième cuve (11) est prévue pour l'introduction avec un premier débit volumétrique (V2') par des conduites (14, 14') et une pompe (P2) dans le cycle, que la cuve d'électrolyse (1) est équipée de deuxièmes conduites (15, 15') et d'une seconde pompe (P3) pour l'extraction d'une quantité d'un second débit volumétrique (V3') équivalent au premier débit volumétrique (V2'), la seconde conduite (15') étant reliée à une troisième cuve (21).
  12. Appareillage selon la revendication 11, caractérisé en ce que le cycle est composé d'une première pompe (P1), d'une spirale en acier (3), d'un tuyau d'entrée (4) et de conduites (13, 13', 13"), la spirale en acier (3) étant disposée sur un émetteur d'ultrasons (5) servant à la formation radicalaire et à la dispersion de colorant.
  13. Appareillage selon une des revendications 11 ou 12, caractérisé en ce que la cuve d'électrolyse (1) et la troisième cuve (21) sont hermétiquement fermées et exemptes d'oxygène.
  14. Appareillage selon les revendications 11-13, caractérisé en ce que le débit volumétrique (V3') évacué dans le cadre d'une réduction continue de colorant de la cuve d'électrolyse (1) est prévu pour le transfert direct vers le bain de coloration, en fonction de la part de colorant consommée par la matière à colorer, ce qui permet de remplir les conditions d'une addition 'juste-à-temps'.
EP99972704A 1998-11-24 1999-11-24 Procede et appareil pour la reduction de colorants de cuve et de colorants au soufre Expired - Lifetime EP1056900B1 (fr)

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CH233898 1998-11-24
CH233898 1998-11-24
PCT/CH1999/000562 WO2000031334A2 (fr) 1998-11-24 1999-11-24 Procede et appareil pour la reduction de colorants de cuve et de colorants au soufre

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EP1056900A2 EP1056900A2 (fr) 2000-12-06
EP1056900B1 true EP1056900B1 (fr) 2005-09-07

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US (1) US6627063B1 (fr)
EP (1) EP1056900B1 (fr)
AT (1) ATE304075T1 (fr)
AU (1) AU1146500A (fr)
CA (1) CA2318796A1 (fr)
DE (1) DE59912528D1 (fr)
WO (1) WO2000031334A2 (fr)

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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
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

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CN109082685A (zh) * 2018-08-28 2018-12-25 河南师范大学 一种在低共熔溶剂中制备花状AuPt合金纳米粒子的方法及其电氧化合成氧杂蒽酮的应用
CN109082685B (zh) * 2018-08-28 2020-04-21 河南师范大学 一种在低共熔溶剂中制备花状AuPt合金纳米粒子的方法及其电氧化合成氧杂蒽酮的应用

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EP1056900A2 (fr) 2000-12-06
ATE304075T1 (de) 2005-09-15
WO2000031334A2 (fr) 2000-06-02
CA2318796A1 (fr) 2000-06-02
US6627063B1 (en) 2003-09-30
DE59912528D1 (de) 2005-10-13
WO2000031334A3 (fr) 2000-10-05

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