WO2004024826A2 - Method for the production of high-purity indigo - Google Patents
Method for the production of high-purity indigo Download PDFInfo
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- WO2004024826A2 WO2004024826A2 PCT/EP2003/009363 EP0309363W WO2004024826A2 WO 2004024826 A2 WO2004024826 A2 WO 2004024826A2 EP 0309363 W EP0309363 W EP 0309363W WO 2004024826 A2 WO2004024826 A2 WO 2004024826A2
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- indigo
- leucoindigo
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- 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
Definitions
- the invention is in the technical field of vat dyes.
- Indigo is a vat dye that has been known for a long time and is used for dyeing textile material containing celiulose, in particular cotton cotton for blue denim articles.
- indigo still contains impurities, for example up to 0.6% by weight of aniline and 0.4% by weight of N-methylaniline, as well as other organic impurities that one would like to remove. These impurities are firmly built into the crystal structure of the indigo and can therefore not be removed either by stirring with solvent or by steam distillation.
- the water-insoluble indigo For dyeing, the water-insoluble indigo must first be converted into the water-soluble fiber-affine leuco form by reduction, which is then oxidized again to the water-insoluble indigo after being drawn onto the material to be colored.
- An ecologically advantageous dyeing process is known from WO-A-94/23114, in which indigo is used in the form of the alkaline, aqueous leucoindigo solution obtained by catalytic reduction of an indigo suspension, and a drastic reduction in the wastewater pollution caused by sulfite / which occurs in the conventional dyeing processes. Allows sulfate or organic substances.
- the invention thus relates to a process for the production of high-purity indigo, characterized in that aromatic amines, in particular aniline and N-methylaniline up to a content of ⁇ 200 ppm, are separated from leucoindigo solutions with exclusion of air.
- aromatic amines in particular aniline and N-methylaniline up to a content of ⁇ 200 ppm
- the leucoindigo solutions obtained in this way can be used directly for dyeing or oxidized to indigo.
- all common methods for separating liquids are suitable.
- Particular embodiments of the present invention relate, on the one hand, to extraction and, on the other hand, to distillation, it being possible for the distillation to be carried out with and without steam or by stripping with an inert gas.
- a very special embodiment of the present invention relates to the separation by distillation of aromatic amines from highly concentrated leucoindigo solutions with exclusion of air at boiling temperature, high-purity leukoindigo solutions with a leukoindigo content of up to 55% by weight and A content of aromatic amines ⁇ 200 ppm are accessible.
- the distillation can be carried out under normal pressure or reduced pressure.
- Another very special embodiment of the present invention relates to steam distillation at normal pressure, high-purity dilute leucoindigo solutions containing aromatic amines below the detection limit being obtained
- a very special embodiment of the present invention relates to extraction with a water-immiscible organic solvent, such as, for example, toluene, .xylenes, perchlorethylene, chlorobenzene, methylisopropyl ether, n-hexanol, 2-ethylhexanol, cyclohexane, cyclohexanone, petroleum ether of a suitable boiling range.
- a water-immiscible organic solvent such as, for example, toluene, .xylenes, perchlorethylene, chlorobenzene, methylisopropyl ether, n-hexanol, 2-ethylhexanol, cyclohexane, cyclohexanone, petroleum ether of a suitable boiling range.
- Aqueous solutions of leukoindigo are usually obtained by reducing an indigo suspension.
- Dithionite, thiourea, hydroxyacetone and homologous organic reducing agents, electrochemical processes or hydrogen in combination with hydrogenation catalysts, such as Raney nickel, are suitable as reducing agents.
- hydrogenation catalysts such as Raney nickel
- EP 1097184 discloses highly concentrated leucoindigo solutions consisting of leukoindigo in the form of the leukoindigo salt of a mixture of at least two alkali metal hydroxides.
- the separation process according to the invention is applied to these leucoindigo solutions, it is possible to obtain high-purity leukoindigo solutions whose leukoindigo content is up to 55% by weight, with aniline and N-methylaniline content ⁇ 200 ppm.
- leuco indigo solutions purified by the processes according to the invention can be used directly for dyeing. They are advantageously suitable for dyeing cellulose-containing textile material, it being possible to proceed as described in WO-A-94/23114.
- Leucoindigo solutions according to the invention can be used by oxidation for the production of high-purity indigo.
- the leucoindigo solution thus prepared is subjected to distillation at normal pressure by passing a weak stream of nitrogen at a bath temperature of 140 ° C. to a concentration of 55% by weight of leucoindigo.
- the leucoindigo solution prepared in this way contains ⁇ 200 ppm aniline and ⁇ 20 ppm N-methylaniline. It can be used directly for dyeing or oxidized to indigo in the conventional way.
- the leucoindigo solution prepared according to Example 1 is stirred with 750 ml of toluene under nitrogen inertization for 1 hour at room temperature. Then the phases are separated. The aqueous phase contains the leuco indigo solution. It contains 1530 ppm aniline and 213 ppm N-methylaniline based on the indigo contained. The extraction is repeated twice, the aniline content dropping to 147 ppm, and N-methylaniline is no longer detectable
- the leucoindigo solution prepared according to Example 1 is heated to 85 ° C. with nitrogen inerting and stripped with nitrogen for 5 hours with stirring. 1000 ml of water are distilled off. This amount is then through Fresh water replaced again. A 23% by weight leukoindigo solution with an aniline content of 113 ppm, based on leukoindigo, is obtained. N-methylaniline is no longer detectable.
- the leucoindigo solution prepared according to Example 1 is distilled with steam for 3 hours. A 7% by weight leukoindigo solution is obtained in which neither aniline nor N-methylaniline can be detected.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
Description
BESCHREIBUNGDESCRIPTION
Verfahren zur Herstellung von hochreinem IndigoProcess for the production of high purity indigo
Die Erfindung liegt auf dem technischen Gebiet der Küpenfarbstoffe.The invention is in the technical field of vat dyes.
Indigo stellt einen seit langer Zeit bekannten Küpenfarbstoff dar, der zum Färben von celiulosehaltigem Textilmater ial, insbesondere von Baumwoll-Ke ttgamen für blue- denim Artikel, eingesetzt wird.Indigo is a vat dye that has been known for a long time and is used for dyeing textile material containing celiulose, in particular cotton cotton for blue denim articles.
Großtechnisch hergestellter Indigo enthält, trotz ausgereifter Produktionsverfahren, synthesebedingt noch Verunreinigungen, beispielsweise bis zu 0,6 Gew.% Anilin und 0,4 Gew.% N-Methylanilin sowie weitere organische Verunreinigungen, die man entfernen möchte. Diese Verunreinigungen sind fest im Kris tallgefüge des Indigos eingebaut und können daher weder durch Ausrühren mit Lösungsmittel, noch durch Wasserdampfdestillation entfernt werden.Despite the sophisticated production processes, industrial-scale indigo still contains impurities, for example up to 0.6% by weight of aniline and 0.4% by weight of N-methylaniline, as well as other organic impurities that one would like to remove. These impurities are firmly built into the crystal structure of the indigo and can therefore not be removed either by stirring with solvent or by steam distillation.
Es sind mehrfach Verfahren zur Entfernung dieser Verunreinigungen beschrieben worden, beispielsweise in EP 0 509 274 durch Überführen des Indigos in sein Sulfat, gefolgt von einem Hydrolyseschritt und anschließender Behandlung des zurückgewonnenen Indigos mit Wasserstoffperoxid, oder, wie in EP 0 509 275 oder EP 0 523 532 beschrieben, durch Reinigung der bei der Synthese anfallenden wässrig alkalischen Indoxylatlösung durch Strippen oder durch Extraktion mit einem inerten wasserunlöslichen Lösungsmittel.Processes for removing these impurities have been described several times, for example in EP 0 509 274 by converting the indigo into its sulfate, followed by a hydrolysis step and subsequent treatment of the recovered indigo with hydrogen peroxide, or as in EP 0 509 275 or EP 0 523 532, by purification of the aqueous alkaline indoxylate solution obtained in the synthesis by stripping or by extraction with an inert water-insoluble solvent.
Alle diese Verfahren sind jedoch aus ökologischen und ökonomischen Gründen nicht vertretbar, da zum einen auf der äußerst instabilen Indoxylatstufe gearbeitet wird und zum anderen zusätzliche aufwendige Verfahrensschritte zur Abtrennung der Verunreinigungen erforderlich sind. Demzufolge war es wichtig, ein Verfahren bereitzustellen, das eine kostengünstige und umweltverträgliche Entfernung der aromatischen Amine aus Indigo ermöglicht und somit die Herstellung von hochreinem Indigo erlaubt.However, all of these processes are not justifiable for ecological and economic reasons, since, on the one hand, work is carried out on the extremely unstable indoxylate stage and, on the other hand, additional complex process steps are required to remove the impurities. As a result, it was important to provide a process which enables the inexpensive and environmentally compatible removal of the aromatic amines from indigo and thus allows the production of high-purity indigo.
Mit der vorliegenden Erfindung wurde nunmehr überraschenderweise gefunden, dass eine nahezu quantitative Entfernung der aromatischen Amine durch Trennverfahren von Flüssigkeiten auf der Leukoindigostufe möglich ist.It has now surprisingly been found with the present invention that an almost quantitative removal of the aromatic amines is possible by means of separation processes from liquids on the leucoindigo stage.
Zum Färben muss der wasserunlösliche Indigo zunächst durch Reduktion in die wasserlösliche faseraffine Leukoform überführt werden, die dann nach dem Aufziehen auf das zu färbende Material wieder zum wasserunlöslichen Indigo oxidiert wird. Aus der WO-A-94/23114 ist ein ökologisch vorteilhaftes Färbeverfahren bekannt, bei dem Indigo in Form der durch katalytische Reduktion einer Indigosuspension erhaltenen, alkalischen, wässrigen Leukoindigolösung eingesetzt wird und das eine drastische Reduktion der bei den herkömmlichen Färbeverfahren auftretenden Abwasserbelastung durch Sulfit/Sulfat oder organische Substanzen ermöglicht.For dyeing, the water-insoluble indigo must first be converted into the water-soluble fiber-affine leuco form by reduction, which is then oxidized again to the water-insoluble indigo after being drawn onto the material to be colored. An ecologically advantageous dyeing process is known from WO-A-94/23114, in which indigo is used in the form of the alkaline, aqueous leucoindigo solution obtained by catalytic reduction of an indigo suspension, and a drastic reduction in the wastewater pollution caused by sulfite / which occurs in the conventional dyeing processes. Allows sulfate or organic substances.
Die Erfindung betrifft somit ein Verfahren zur Herstellung von hochreinem Indigo, dadurch gekennzeichnet, dass aromatische Amine , insbesondere Anilin und N- Methylanilin bis zu einem Gehalt < 200 ppm, aus Leukoindigolösungen unter Luftausschluss abgetrennt werden. Die auf diese Weise erhaltenen Leukoindigolösungen können unmittelbar zum Färben eingesetzt oder zu Indigo oxidiert werden. Prinzipiell eignen sich alle gängigen Verfahren zur Trennung von Flüssigkeiten.The invention thus relates to a process for the production of high-purity indigo, characterized in that aromatic amines, in particular aniline and N-methylaniline up to a content of <200 ppm, are separated from leucoindigo solutions with exclusion of air. The leucoindigo solutions obtained in this way can be used directly for dyeing or oxidized to indigo. In principle, all common methods for separating liquids are suitable.
Besondere Ausführungsformen der vorliegenden Erfindung betreffen zum einen die Extraktion und zum anderen die Destillation, wobei die Destillation mit und ohne Wasserdampf oder durch Strippung mit einem inerten Gas erfolgen kann.Particular embodiments of the present invention relate, on the one hand, to extraction and, on the other hand, to distillation, it being possible for the distillation to be carried out with and without steam or by stripping with an inert gas.
Eine ganz besondere Ausführungsform der vorliegenden Erfindung betrifft die destillative Abtrennung von aromatischen Aminen aus hochkonzentrierten Leukoindigolösungen unter Luftausschluss bei Siedetemperatur, wobei hochreine Leukoindigolösungen mit einem Gehalt an Leukoindigo von bis 55 Gew.% und einem Gehalt an aromatischen Aminen < 200 ppm zugänglich sind. Die Destillation kann dabei unter Normaldruck oder vermindertem Druck erfolgen.A very special embodiment of the present invention relates to the separation by distillation of aromatic amines from highly concentrated leucoindigo solutions with exclusion of air at boiling temperature, high-purity leukoindigo solutions with a leukoindigo content of up to 55% by weight and A content of aromatic amines <200 ppm are accessible. The distillation can be carried out under normal pressure or reduced pressure.
Eine weitere ganz besondere Ausführungsform der vorliegenden Erfindung betrifft die Wasserdampfdestillation bei Normaldruck, wobei man hochreine verdünnte Leukoindigolösungen mit einem Gehalt an aromatischen Aminen unterhalb der Nachweisgrenze erhältAnother very special embodiment of the present invention relates to steam distillation at normal pressure, high-purity dilute leucoindigo solutions containing aromatic amines below the detection limit being obtained
Weiterhin betrifft eine ganz besondere Ausführungsform der vorliegenden Erfindung die Extraktion mit einem nicht wassermischbaren organischen Lösungsmittel, wie beispielsweise Toluol,.Xylole, Perchlore thylen, Chlorbenzol, Methylisopropyle ther, n- Hexanol, 2-Ethylhexanol, Cyclohexan, Cyclohexanon, Petrolether von geeignetem Siedebereich.Furthermore, a very special embodiment of the present invention relates to extraction with a water-immiscible organic solvent, such as, for example, toluene, .xylenes, perchlorethylene, chlorobenzene, methylisopropyl ether, n-hexanol, 2-ethylhexanol, cyclohexane, cyclohexanone, petroleum ether of a suitable boiling range.
Wässrige Lösungen von Leukoindigo werden üblicherweise durch Reduktion einer Indigosuspension erhalten. Als Reduktionsmittel kommen dabei Dithionit, Thioharnstoff, Hydroxyaceton und homologe organische Reduktionsmittel, elektrochemische Verfahren oder Wasserstoff in Verbindung mit Hydrierkatalysatoren, wie zum Beispiel Raney Nickel in Frage. Dabei erhält man in Abhängigkeit vom verwendeten Reduktionsmittel unterschiedlich konzentrierte Leukoindigo-Lösungen: Mit Dithionit oder Thioharnstoff erhält man höchstens ca. 10%ige Lösungen bedingt durch die hohe Elektrolytbelastung durch das Reduktionsmittel. Höher konzentrierte Lösungen, bis ca 30 Gew.% erhält man durch katalytische Hydrierung. Aus EP 1097184 sind hochkonzentrierte Leukoindigolösungen bestehend aus Leukoindigo in Form des Leukoindigosalzes eines Gemisches mindestens zweier Alkalimetallhydroxide bekannt. Bei Anwendung der erfindungsgemäßen Trennverfahren auf diese Leukoindigolösungen können hochreine Leukoindigolösungen erhalten werden, deren Gehalt an Leukoindigo bis 55 Gew.% beträgt, mit einem Gehalt an Anilin und N-Methylanilin < 200 ppm .Aqueous solutions of leukoindigo are usually obtained by reducing an indigo suspension. Dithionite, thiourea, hydroxyacetone and homologous organic reducing agents, electrochemical processes or hydrogen in combination with hydrogenation catalysts, such as Raney nickel, are suitable as reducing agents. Depending on the reducing agent used, one obtains differently concentrated leucoindigo solutions: With dithionite or thiourea, at most approx. 10% solutions are obtained due to the high electrolyte load from the reducing agent. Highly concentrated solutions, up to about 30% by weight, are obtained by catalytic hydrogenation. EP 1097184 discloses highly concentrated leucoindigo solutions consisting of leukoindigo in the form of the leukoindigo salt of a mixture of at least two alkali metal hydroxides. When the separation process according to the invention is applied to these leucoindigo solutions, it is possible to obtain high-purity leukoindigo solutions whose leukoindigo content is up to 55% by weight, with aniline and N-methylaniline content <200 ppm.
Alle nach den erfindungsgemäßen Verfahren gereinigten Leukoindigolösungen können unmittelbar zum Färben verwendet werden. Sie eignen sich vorteilhaft zum Färben von cellulosehaltigem Textilmaterial, wobei wie in der WO-A-94/23114 beschrieben, vorgegangen werden kann. Darüber hinaus können die erfindungsgemäßen Leukoindigolösungen durch Oxidation zur Herstellung von hochreinem Indigo verwendet werden.All leuco indigo solutions purified by the processes according to the invention can be used directly for dyeing. They are advantageously suitable for dyeing cellulose-containing textile material, it being possible to proceed as described in WO-A-94/23114. In addition, the Leucoindigo solutions according to the invention can be used by oxidation for the production of high-purity indigo.
Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung:The following examples serve to explain the invention:
Beispiel 1 :Example 1 :
In einem 1 ,51 Glasautoklaven werden 1 138 g einer 23 gew.% igen Indigosuspension (1 Mol Indigo) zusammen mit 24 g Natriumhydroxid, 22 g Kaliumhydroxid unter Rühren in Gegenwart von 6g Raney-Nickel unter Stickstoff bei 70°C und 3 bar Druck hydriert. Nach Reaktionsende wird entspannt und auf Raumtemperatur abgekühlt. Man erhält nach Abdekantieren unter inerten Bedingungen eine 23 gew.%ige wässrig alkalische Leukoindigolösung, die 0.6% Anilin und 0.4% N-Methylanilin bezogen auf Indigo enthält.In a 1.51 glass autoclave, 1138 g of a 23% by weight indigo suspension (1 mol of indigo) together with 24 g of sodium hydroxide, 22 g of potassium hydroxide are stirred in the presence of 6 g of Raney nickel under nitrogen at 70 ° C. and 3 bar pressure hydrogenated. After the end of the reaction, the pressure is released and the mixture is cooled to room temperature. After decanting under inert conditions, a 23% by weight aqueous alkaline leucoindigo solution is obtained which contains 0.6% aniline and 0.4% N-methylaniline based on indigo.
Die so hergestellte Leukoindigolösung wird bei Normaldruck durch Überleiten eines schwachen Stickstoffstromes bei einer Badtemperatur von 140°C bis zu einer Konzentration von 55 Gew% Leukoindigo einer Destillation unterzogen. Die auf diese Weise hergestellte Leukoindigolösung enthält < 200 ppm Anilin und < 20 ppm N- Methylanilin. Sie kann unmittelbar zum Färben eingesetzt, oder auf herkömmlichem Weg zu Indigo oxidiert werden.The leucoindigo solution thus prepared is subjected to distillation at normal pressure by passing a weak stream of nitrogen at a bath temperature of 140 ° C. to a concentration of 55% by weight of leucoindigo. The leucoindigo solution prepared in this way contains <200 ppm aniline and <20 ppm N-methylaniline. It can be used directly for dyeing or oxidized to indigo in the conventional way.
Beispiel 2:Example 2:
Die nach Beispiel 1 hergestellte Leukoindigolösung wird mit 750 ml Toluol unter Stickstoffinertisierung 1 Stunde bei Raumtemperatur gerührt. Danach werden die Phasen getrennt. Die wässrige Phase enthält die Leukoindigolösung. Sie enthält 1530 ppm Anilin und 213 ppm N-Methylanilin bezogen auf den enthaltenen Indigo. Die Extraktion wird zweimal wiederholt, wobei der Anilingehalt auf 147 ppm sinkt, N- Methylanilin ist nicht mehr nachweisbarThe leucoindigo solution prepared according to Example 1 is stirred with 750 ml of toluene under nitrogen inertization for 1 hour at room temperature. Then the phases are separated. The aqueous phase contains the leuco indigo solution. It contains 1530 ppm aniline and 213 ppm N-methylaniline based on the indigo contained. The extraction is repeated twice, the aniline content dropping to 147 ppm, and N-methylaniline is no longer detectable
Beispiel 3Example 3
Die nach Beispiel 1 hergestellte Leukoindigolösung wird unter Stickstoffinertisierung auf 85°C erhitzt und unter Rühren 5 Stunden lang mit Stickstoff gestrippt. Hierbei werden 1000 ml Wasser abdestilliert. Diese Menge wird anschließend durch Frischwasser wieder ersetzt. Man erhält eine 23 gew.%ige Leukoindigolösung mit einem Anilingehalt von 113 ppm bezogen auf Leukoindigo. N-Methylanilin ist nicht mehr nachweisbar.The leucoindigo solution prepared according to Example 1 is heated to 85 ° C. with nitrogen inerting and stripped with nitrogen for 5 hours with stirring. 1000 ml of water are distilled off. This amount is then through Fresh water replaced again. A 23% by weight leukoindigo solution with an aniline content of 113 ppm, based on leukoindigo, is obtained. N-methylaniline is no longer detectable.
Beispiel 4Example 4
Die nach Beispiel 1 hergestellte Leukoindigolösung wird 3 Stunden lang mit Wasserdampf destilliert. Man erhält eine 7 gew.%ige Leukoindigolösung, in der weder Anilin noch N-Methylanilin nachweisbar ist. The leucoindigo solution prepared according to Example 1 is distilled with steam for 3 hours. A 7% by weight leukoindigo solution is obtained in which neither aniline nor N-methylaniline can be detected.
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003260454A AU2003260454A1 (en) | 2002-08-31 | 2003-08-23 | Method for the production of high-purity indigo |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10240258.2 | 2002-08-31 | ||
| DE10240258 | 2002-08-31 |
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| WO2004024826A2 true WO2004024826A2 (en) | 2004-03-25 |
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| AU (1) | AU2003260454A1 (en) |
| WO (1) | WO2004024826A2 (en) |
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2003
- 2003-08-23 AU AU2003260454A patent/AU2003260454A1/en not_active Abandoned
- 2003-08-23 WO PCT/EP2003/009363 patent/WO2004024826A2/en not_active Ceased
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