WO1999039826A1 - Method for improving the operational life of supported catalysts covered with gold particles and used for oxidising unsaturated hydrocarbons - Google Patents
Method for improving the operational life of supported catalysts covered with gold particles and used for oxidising unsaturated hydrocarbons Download PDFInfo
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- WO1999039826A1 WO1999039826A1 PCT/EP1999/000034 EP9900034W WO9939826A1 WO 1999039826 A1 WO1999039826 A1 WO 1999039826A1 EP 9900034 W EP9900034 W EP 9900034W WO 9939826 A1 WO9939826 A1 WO 9939826A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
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- the invention relates to a process for the treatment of supported catalysts with nanoscale gold particles for the catalytic production of epoxides from unsaturated hydrocarbons in the gas phase by oxidation of unsaturated hydrocarbons with molecular oxygen in the presence of molecular hydrogen, and the use of these treated catalysts for the preparation of Epoxies.
- Direct oxidation of unsaturated hydrocarbons with molecular oxygen in the gas phase normally does not proceed below 200 ° C., even in the presence of catalysts, and it is therefore difficult to process oxidation-sensitive oxidation products such as e.g. B. selectively produce epoxies, alcohols or aldehydes, since the further reaction of these products often proceeds faster than the oxidation of the olefins used themselves.
- oxidation-sensitive oxidation products such as e.g. B. selectively produce epoxies, alcohols or aldehydes
- Propene oxide is one of the most important basic chemicals in the chemical industry.
- the area of application with a share of over 60% is in the plastics sector, especially for the production of polyether polyols for the synthesis of polyurethanes.
- even larger market shares in the area of glycols, especially lubricants and antifreezes, are occupied by propene oxide derivatives.
- organic compounds were chosen to transfer oxygen to propene (oxirane process).
- Indirect epoxidation is based on the fact that organic peroxides such as hydroperoxides or peroxycarboxylic acids in the liquid phase can selectively transfer their peroxide oxygen to olefins to form epoxides.
- the hydroperoxides are converted into alcohols, the peroxycarboxylic acids into acids.
- Hydroperoxides or peroxycarboxylic acids are generated from the corresponding hydrocarbon or aldehyde by autoxidation with air or molecular oxygen.
- a serious disadvantage of indirect oxidation is the economic dependence of the propene oxide value on the market of the co-product.
- the propene oxidation takes place with low yield in the liquid phase of platinum metal-containing titanium silicalites with a gas mixture consisting of molecular oxygen and molecular hydrogen (JP-A 92/352771).
- EP-A 0 709 360 AI (Haruta et al.) Describes for the first time a gas-phase direct oxidation of propene to propene oxide with 100% selectivity. It is a catalytic gas phase oxidation with molecular oxygen in the presence of the reducing agent hydrogen. Special titanium dioxide with an anatase modification, which is coated with nanoscale gold particles, is used as the catalyst.
- the Au / TiO 2 catalysts described achieve the initial pro- pen turnover only for a very short time; z. B. the typical half-lives at moderate temperatures (40-50 ° C) are only 100-200 min.
- the invention relates to a method for increasing the catalyst life of supported catalysts coated with nanoscale gold particles for the catalytic production of epoxides from unsaturated hydrocarbons in the gas phase.
- the invention therefore relates to a process for extending the service life of supported catalysts for the oxidation of unsaturated hydrocarbons coated with gold particles, in which the catalyst is contacted before or during its use for the oxidation of unsaturated hydrocarbons with the aqueous or alcoholic solution of a neutral, acidic or basic reacting reagent brings, washes and if necessary dries.
- Reagents from the group .... are preferably used here.
- the neutral reacting reagents from the group CsF, Na 2 SO 4 are particularly preferred.
- the prolongation of the service life can advantageously be achieved with all carrier catalysts coated with gold particles based on titanium silicalite, titanium oxide (rutile and / or analog modification) or titanium oxide hydrate. These catalysts were preferably produced using the “deposition-precipitation” method.
- the treatment of the catalysts with neutral reacting salts eg sodium sulfate
- the catalyst containing gold atoms before it is used for epoxidation, is reacted with a solution of a neutral-reacting inorganic or organic salt in water or an alcohol, separated from this solution, optionally washed with water and / or a solvent, optionally dried and then for the epoxidation of a Olefins used.
- concentration of the salt solution used to treat the catalyst can be varied between 0.0001 mol / 1 and the saturation limit, preferably between 0.01 and 1 mol / 1.
- the temperature and duration of the catalyst treatment can be chosen within wide limits and are only limited by the rate of mass exchange between catalyst and saline solution at low temperature and short treatment time and the stability of the catalyst against hydrolysis at high temperatures and long treatment times.
- the salt solution used to treat the catalyst can advantageously be reused several times, the number of possible reuses depending on the concentration of the salt solution and the ratio of the salt solution and the treated catalyst.
- the treatment of the catalyst takes place during the epoxidation reaction.
- the salt or the organic compound optionally as a solution in water or another solvent, is added either directly to the reaction mixture of the epoxidation or to the feed mixture of the epoxidation reaction.
- the amount of salt can be chosen so that the salt concentration in the reaction mixture is between 0.0001 and 1 mol / 1, preferably between 0.001 and 1 mol / 1.
- the treatment of the catalyst with the above salts or organics according to the invention can be added either continuously or in batches.
- the epoxidation according to the invention in the presence of a catalyst containing gold atoms, which is treated with a neutral, acidic or basic reagent before or during the epoxidation reaction, has known th process the advantage that with reduced by-product formation, a variation in the amount of the substance used to treat the catalyst does not adversely affect the catalytic activity of the catalyst in the epoxidation reaction.
- the catalysts treated in this way are preferably used for the epoxidation of ether, propene, 1-butene or 2-butene.
- the epoxidation of propene is preferred.
- the catalysts treated according to the invention are used for the epoxidation of
- the main products water, propane and CO 2 as well as the oxygenates propylene oxide and acetone are found at 150 ° C.
- the reaction temperature is reduced to ⁇ 100 ° C., preferably 30-60 ° C.
- the water formation becomes strong and the CO 2 formation is completely suppressed.
- acetone approximately 1% based on PO
- the water content is twice (molar) the propene oxide content.
- composition of the gas phase consisting of propene, oxygen, hydrogen and possibly an inert gas
- propene is not only important for the space-time yield, but also for safety.
- all molar compositions of the gases propene / oxygen / hydrogen / nitrogen can be used. Therefore, preferred gas ratios for the oxidation reaction of propene are as follows: H 2 / hydrocarbon / oxygen nitrogen: 10-50% / 5 - 50% / 0.1 -10%
- the molecular oxygen used for the reaction can be of various origins, e.g. B. pure oxygen, air or other oxygen / inert gas mixtures. Examples
- the reactor is a fixed-bed tube reactor (1 cm in diameter, 20 cm in length) made of double-walled glass, which is heated to 46 ° C. by means of a water thermostat. A static mixing and temperature control section is connected upstream of the reactor. The gold supported catalyst is placed on a glass frit. The catalyst load is 1.8 1 / g cat. H. The reactant gases are metered into the reactor from top to bottom by means of mass flow controllers.
- the starting gas ratios are O 2 / H 2 / C 3 H 6 : 0.1 / 1.3 / 0.4 1 / h.
- reaction gas mixture is analyzed by means of gas chromatography with an FID (all oxygen-containing organic compounds, with the exception of CO 2 ) and a TCD detector (permanent gases, CO, CO 2 , H 2 O).
- FID all oxygen-containing organic compounds, with the exception of CO 2
- TCD detector permanent gases, CO, CO 2 , H 2 O
- a solution of 0.104 g HAuCl 4 x 4 H 2 O in 400 ml distilled water is heated to 70 ° C., brought to pH 7.5 with an aqueous 0.1 N NaOH solution and 5 g titanium dioxide (anatase- Rutile mixed oxide; P 25 from Degussa) added in one portion and stirring continued for 1 h.
- the solid is washed 5 times with 3 liters of distilled water, dried at room temperature in a vacuum for 12 hours and calcined at 400 ° C. for 4 hours.
- a gold-titanium dioxide catalyst with 1% by weight of gold is obtained.
- Catalyst preparation analogous to catalyst preparation 1 or catalyst preparation 2, but the calcined catalyst (2 g) is suspended in 500 ml H 2 O, 10 mmol salt added, stirred at room temperature for 1 h, separated and dried at 150 ° C. for 1 hour. The contact thus obtained is used for propene oxidation according to the standard procedure.
- the catalyst is suspended in ethanol, suspended with the organics, stirred for 1 h at room temperature, separated and dried at 150 ° C. for 1 hour. The contact thus obtained is used for propene oxidation according to the standard procedure.
- silylation reagents are used, the catalyst is suspended in anhydrous pentane, 1 mmol of silylation reagent is added, the mixture is stirred for 1 h, separated and dried at 150 ° C. for 1 h. The contact thus obtained is used for propene oxidation according to the standard procedure.
- Triethylamine 30 0.9 0.9> 97
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Abstract
Description
Verfahren zur Standzeitverlängerung von mit Goldteilen belegten Trägerkatalysatoren für die Oxidation ungesättigter KohlenwasserstoffeProcess for extending the service life of supported gold-coated catalysts for the oxidation of unsaturated hydrocarbons
Die Erfindung betrifft ein Verfahren zur Behandlung von mit nanoskaligen Goldpartikeln belegten Trägerkatalysatoren für die katalytische Herstellung von Epoxiden aus ungesättigten Kohlenwasserstoffen in der Gasphase durch Oxidation ungesättigter Kohlenwasserstoffe mit molekularem Sauerstoff in Gegenwart von molekularem Wasserstoff, sowie die Verwendung dieser behandelten Katalysatoren für die Her- Stellung von Epoxiden.The invention relates to a process for the treatment of supported catalysts with nanoscale gold particles for the catalytic production of epoxides from unsaturated hydrocarbons in the gas phase by oxidation of unsaturated hydrocarbons with molecular oxygen in the presence of molecular hydrogen, and the use of these treated catalysts for the preparation of Epoxies.
Direktoxidationen von ungesättigten Kohlenwasserstoffen mit molekularem Sauerstoff in der Gasphase verlaufen normalerweise - selbst in Gegenwart von Katalysatoren - nicht unterhalb von 200°C, und es ist daher schwierig, oxidationsempfmdliche Oxidationsprodukte, wie z. B. Epoxide, Alkohole oder Aldehyde, selektiv herzustellen, da die Weiterreaktion dieser Produkte häufig schneller als die Oxidation der eingesetzten Olefine selbst verläuft.Direct oxidation of unsaturated hydrocarbons with molecular oxygen in the gas phase normally does not proceed below 200 ° C., even in the presence of catalysts, and it is therefore difficult to process oxidation-sensitive oxidation products such as e.g. B. selectively produce epoxies, alcohols or aldehydes, since the further reaction of these products often proceeds faster than the oxidation of the olefins used themselves.
Propenoxid stellt eine der wichtigsten Grundchemikalien der Chemischen Industrie dar. Das Einsatzgebiet liegt mit einem Anteil von über 60 % im Kunststoffsektor, speziell zur Herstellung von Polyetherpolyolen für die Synthese von Polyurethanen. Daneben werden noch größere Marktanteile im Bereich der Glykole, besonders bei den Schmier- und Frostschutzmitteln, von den Propenoxid-Derivaten belegt.Propene oxide is one of the most important basic chemicals in the chemical industry. The area of application with a share of over 60% is in the plastics sector, especially for the production of polyether polyols for the synthesis of polyurethanes. In addition, even larger market shares in the area of glycols, especially lubricants and antifreezes, are occupied by propene oxide derivatives.
Heute werden weltweit etwa 50 % des Propenoxids über das „Chlorhy drin- Verfahren" synthetisiert. Weitere 50 %, mit steigender Tendenz, liefern die „Oxiran-Verfah- ren.Today around 50% of the propene oxide is synthesized worldwide using the "chlorohydrin process". Another 50%, and the trend is increasing, is provided by the "oxirane processes".
Beim Chlorhydrinverfahren (F. Andreas et al.; Propylenchemie, Berlin 1969) wird durch Reaktion von Propen mit HOC1 (Wasser und Chlor) zuerst das Chlorhy drin und anschließend hieraus durch Abspaltung von HC1 mit Kalk das Propenoxid gebil- det. Das Verfahren ist kostenintensiv, weist aber bei entsprechender Optimierung eine hohe Selektivität (> 90 %) bei hohen Umsätzen auf. Der Chlorverlust beim Chlorhydrin-V erfahren in Form wertloser Calciumchlorid- bzw. Natriumchlorid-Lösungen hat frühzeitig zur Suche nach chlorfreien Oxidationssystemen geführt.In the chlorohydrin process (F. Andreas et al .; Propylenchemie, Berlin 1969) the reaction of propene with HOC1 (water and chlorine) first creates the chlorine in it and then by splitting off HC1 with lime the propene oxide is formed. det. The process is cost-intensive, but with appropriate optimization, it has a high selectivity (> 90%) with high sales. The loss of chlorine in chlorohydrin V in the form of worthless calcium chloride or sodium chloride solutions led to the search for chlorine-free oxidation systems at an early stage.
Anstelle des anorganischen Oxidationsmittels HOC1 wurden organische Verbindungen zur Übertragung von Sauerstoff auf Propen gewählt (Oxiranverfahren). Die indirekte Epoxidation beruht auf der Tatsache, daß organische Peroxide wie Hydroperoxide oder Peroxycarbonsäuren in flüssiger Phase ihren Peroxidsauerstoff selektiv auf Olefine unter Bildung von Epoxiden übertragen können. Die Hydroperoxide gehen dabei in Alkohole, die Peroxycarbonsäuren in Säuren über. Hydroperoxide bzw. Peroxycarbonsäuren werden durch Autoxidation mit Luft oder molekularen Sauerstoff aus dem entsprechenden Kohlenwasserstoff bzw. Aldehyd erzeugt. Ein gravierender Nachteil der indirekten Oxidation ist die wirtschaftliche Abhängigkeit des Propenoxidwertes vom Markt des Koppelproduktes.Instead of the inorganic oxidizing agent HOC1, organic compounds were chosen to transfer oxygen to propene (oxirane process). Indirect epoxidation is based on the fact that organic peroxides such as hydroperoxides or peroxycarboxylic acids in the liquid phase can selectively transfer their peroxide oxygen to olefins to form epoxides. The hydroperoxides are converted into alcohols, the peroxycarboxylic acids into acids. Hydroperoxides or peroxycarboxylic acids are generated from the corresponding hydrocarbon or aldehyde by autoxidation with air or molecular oxygen. A serious disadvantage of indirect oxidation is the economic dependence of the propene oxide value on the market of the co-product.
Mit Titansilicalit (TS 1) als Katalysator (Notari et al., US 44 10 501 (1983) und US 47 01 428) war es erstmalig möglich, Propen mit Wasserstoffperoxid in der Flüssigphase unter sehr milden Reaktionsbedingungen mit Selektivitäten > 90 % zu epoxi- dieren (Clerici et al., EP-A 230 949).With titanium silicalite (TS 1) as a catalyst (Notari et al., US 44 10 501 (1983) and US 47 01 428) it was possible for the first time to propylene with hydrogen peroxide in the liquid phase under very mild reaction conditions with selectivities> 90% dieren (Clerici et al., EP-A 230 949).
Die Propenoxidation gelingt mit geringer Ausbeute in der Flüssigphase an platinmetallhaltigen Titansilikaliten mit einem Gasgemisch bestehend aus molekularem Sauerstoff und molekularem Wasserstoff (JP-A 92/352771).The propene oxidation takes place with low yield in the liquid phase of platinum metal-containing titanium silicalites with a gas mixture consisting of molecular oxygen and molecular hydrogen (JP-A 92/352771).
In EP-A 0 709 360 AI (Haruta et al.) wird erstmalig eine Gasphasen-Direktoxidation von Propen zu Propenoxid mit 100%iger Selektivität beschrieben. Es handelt sich hierbei um eine katalytische Gasphasenoxidation mit molekularem Sauerstoff in Gegenwart des Reduktionsmittels Wasserstoff. Als Katalysator wird spezielles Titan- dioxid mit einer Anatas-Modifikation verwendet, das mit nanoskaligen Goldteilchen belegt ist. Die beschriebenen Au/TiO2-Katalysatoren erreichen den anfänglichen Pro- penumsatz nur für sehr kurze Zeit; z. B. liegen die typischen Halbwertszeiten bei moderaten Temperaturen (40-50°C) bei lediglich 100-200 min.EP-A 0 709 360 AI (Haruta et al.) Describes for the first time a gas-phase direct oxidation of propene to propene oxide with 100% selectivity. It is a catalytic gas phase oxidation with molecular oxygen in the presence of the reducing agent hydrogen. Special titanium dioxide with an anatase modification, which is coated with nanoscale gold particles, is used as the catalyst. The Au / TiO 2 catalysts described achieve the initial pro- pen turnover only for a very short time; z. B. the typical half-lives at moderate temperatures (40-50 ° C) are only 100-200 min.
Für eine wirtschaftliche Nutzung ist daher die Entwicklung von Katalysatoren mit stark erhöhter Katalysatorstandzeit unbedingt weiter notwendig.For economic use, the development of catalysts with a greatly increased catalyst life is therefore absolutely necessary.
Die Erfindung betrifft ein Verfahren zur Erhöhung der Katalysatorstandzeiten von mit nanoskaligen Goldpartikeln belegten Trägerkatalysatoren für die katalytische Herstellung von Epoxiden aus ungesättigten Kohlenwasserstoffen in der Gasphase.The invention relates to a method for increasing the catalyst life of supported catalysts coated with nanoscale gold particles for the catalytic production of epoxides from unsaturated hydrocarbons in the gas phase.
Gegenstand der Erfindung ist daher ein Verfahren zur Standzeitverlängerung von mit Goldteilchen belegten Trägerkatalysatoren für die Oxidation ungesättigter Kohlenwasserstoffe, bei dem man den Katalysator vor oder während seiner Verwendung zur Oxidation ungesättigter Kohlenwasserstoffe mit der wäßrigen oder alkoholischen Lösung eines neutral, sauer oder basisch reagierenden Reagens in Kontakt bringt, wäscht und gegebenenfalls trocknet.The invention therefore relates to a process for extending the service life of supported catalysts for the oxidation of unsaturated hydrocarbons coated with gold particles, in which the catalyst is contacted before or during its use for the oxidation of unsaturated hydrocarbons with the aqueous or alcoholic solution of a neutral, acidic or basic reacting reagent brings, washes and if necessary dries.
Bevorzugt werden hierbei Reagenzien aus der Gruppe .... eingesetzt.Reagents from the group .... are preferably used here.
Besonders bevorzugt sind die neutral reagierenden Reagenzien aus der Gruppe CsF, Na2SO4.The neutral reacting reagents from the group CsF, Na 2 SO 4 are particularly preferred.
Die Verlängerung der Standzeit kann bei allen mit Goldteilchen belegten Trägerkata- lysatoren auf der Basis von Titansilicalit, Titanoxid (Rutil und/oder Analog-Modifi- kation) oder Titanoxidhydrat vorteilhaft erreicht werden. Bevorzugt wurden diese Katalysatoren dabei nacfh der „deposition-precipitation" -Methode hergestellt.The prolongation of the service life can advantageously be achieved with all carrier catalysts coated with gold particles based on titanium silicalite, titanium oxide (rutile and / or analog modification) or titanium oxide hydrate. These catalysts were preferably produced using the “deposition-precipitation” method.
Es ist überraschend, daß insbesondere die Behandlung der Katalysatoren mit neutral reagierenden Salzen (z.B. Natriumsulfat) eine deutliche Standzeitverlängerung bei höheren Aktivitäten ermöglicht. In einer bevorzugten Ausführung der Erfindung wird der Goldatome enthaltene Katalysator vor seiner Verwendung zur Epoxidierung mit einer Lösung eines neutral reagierenden anorganischen oder organischen Salzes in Wasser oder einem Alkohol umgesetzt, von dieser Lösung abgetrennt, gegebenenfalls mit Wasser und/oder einem Lösungsmittel gewaschen, gegebenenfalls getrock- net und anschließend zur Epoxidierung eines Olefins eingesetzt. Die Konzentration der zur Behandlung des Katalysators verwendeten Salzlösung kann zwischen 0,0001 mol/1 und der Sättigung- grenze, vorzugsweise zwischen 0,01 und 1 mol/1, variiert werden. Temperatur und Dauer der Katalysatorbehandlung können in weiten Grenzen gewählt werden und werden nur begrenzt durch die Geschwindigkeit des Stoffaustausches zwischen Katalysator und Salzlösung bei niedriger Temperatur und kurzer Behandlungszeit und die Stabilität des Katalysators gegenüber Hydrolyse bei hohen Temperaturen und langen Behandlungszeiten. Die zur Behandlung des Katalysators verwendete Salzlösung kann vorteilhaft mehrfach wieder eingesetzt werden, wobei die Zahl der möglichen Wiederverwendungen von der Konzentration der Salzlösung und dem Mengenverhältnis von Salzlösung und behandeltem Katalysator abhängt.It is surprising that in particular the treatment of the catalysts with neutral reacting salts (eg sodium sulfate) enables a significant increase in service life for higher activities. In a preferred embodiment of the invention the catalyst containing gold atoms, before it is used for epoxidation, is reacted with a solution of a neutral-reacting inorganic or organic salt in water or an alcohol, separated from this solution, optionally washed with water and / or a solvent, optionally dried and then for the epoxidation of a Olefins used. The concentration of the salt solution used to treat the catalyst can be varied between 0.0001 mol / 1 and the saturation limit, preferably between 0.01 and 1 mol / 1. The temperature and duration of the catalyst treatment can be chosen within wide limits and are only limited by the rate of mass exchange between catalyst and saline solution at low temperature and short treatment time and the stability of the catalyst against hydrolysis at high temperatures and long treatment times. The salt solution used to treat the catalyst can advantageously be reused several times, the number of possible reuses depending on the concentration of the salt solution and the ratio of the salt solution and the treated catalyst.
In einer weiteren ebenfalls bevorzugten Ausführungsform der Erfindung erfolgt die Behandlung des Katalysators während der Epoxidierungsreaktion. Dazu wird das Salz oder die organische Verbindung, gegebenenfalls als Lösung in Wasser oder einem anderen Lösungsmittel, entweder direkt der Reaktionsmischung der Epoxidierung oder dem Einsatzgemisch der Epoxidierungsreaktion zugesetzt. Die Salzmenge kann dabei so gewählt werden, daß die Salzkonzentration in der Reaktionsmischung zwischen 0,0001 und 1 mol/1, vorzugsweise zwischen 0,001 und 1 mol/1, liegt. Die erfindungsgemäße Behandlung des Katalysators mit den obigen Salzen oder Organika kann sowohl kontinuierlich als auch in diskontinuierlichen Portionen zugesetzt werden.In a further likewise preferred embodiment of the invention, the treatment of the catalyst takes place during the epoxidation reaction. For this purpose, the salt or the organic compound, optionally as a solution in water or another solvent, is added either directly to the reaction mixture of the epoxidation or to the feed mixture of the epoxidation reaction. The amount of salt can be chosen so that the salt concentration in the reaction mixture is between 0.0001 and 1 mol / 1, preferably between 0.001 and 1 mol / 1. The treatment of the catalyst with the above salts or organics according to the invention can be added either continuously or in batches.
Die erfindungsgemäße Epoxidierung in Gegenwart eines Goldatome enthaltenen Katalysators, der vor oder während der Epoxidationsreaktion mit einem neutral, sauer oder basisch reagierenden Reagens behandelt wird, besitzt gegenüber bekann- ten Verfahren den Vorteil, daß bei verringerter Nebenproduktbildung eine Variation der Menge des zur Behandlung des Katalysators eingesetzten Stoffes sich nicht nachteilig auf die katalytische Aktivität des Katalysators bei der Epoxidierungsreaktion auswirkt.The epoxidation according to the invention in the presence of a catalyst containing gold atoms, which is treated with a neutral, acidic or basic reagent before or during the epoxidation reaction, has known th process the advantage that with reduced by-product formation, a variation in the amount of the substance used to treat the catalyst does not adversely affect the catalytic activity of the catalyst in the epoxidation reaction.
Bevorzugt werden die so behandelten Katalysatoren zur Epoxidierung von Ether, Propen, 1 -Buten oder 2-Buten eingesetzt. Die Epoxidierung von Propen ist dabei bevorzugt.The catalysts treated in this way are preferably used for the epoxidation of ether, propene, 1-butene or 2-butene. The epoxidation of propene is preferred.
Die erfindungsgemäß behandelten Katalysatoren werden zur Epoxidierung vonThe catalysts treated according to the invention are used for the epoxidation of
Propen in Gegenwart der Gase Sauerstoff und Wasserstoff eingesetzt. In Gegenwart dieser Gase werden bei 150°C neben den Hauptprodukten Wasser, Propan und CO2 auch die Oxygenate Propylenoxid und Aceton gefunden. Bei Senkung der Reaktionstemperatur auf < 100°C, bevorzugt 30-60°C, wird die Wasserbildung stark, die CO2- Bildung vollständig zurückgedrängt. Bei einer Temperatur zwischen 30-60°C werden neben dem Hauptprodukt Propylenoxid (ca. 4 % Ausbeute) nur noch Spuren von Aceton (ca. 1 % bezogen auf PO) gefunden. Der Wasseranteil beträgt das 2fache (molar) des Propenoxidanteils.Propene used in the presence of the gases oxygen and hydrogen. In the presence of these gases, the main products water, propane and CO 2 as well as the oxygenates propylene oxide and acetone are found at 150 ° C. When the reaction temperature is reduced to <100 ° C., preferably 30-60 ° C., the water formation becomes strong and the CO 2 formation is completely suppressed. At a temperature between 30-60 ° C only traces of acetone (approx. 1% based on PO) are found in addition to the main product propylene oxide (approx. 4% yield). The water content is twice (molar) the propene oxide content.
Die Zusammensetzung der Gasphase, bestehend aus Propen, Sauerstoff, Wasserstoff und eventuell eines Inertgases ist nicht nur für die Raum-Zeit-Ausbeute wichtig, sondern auch für die Sicherheit. Theoretisch können alle molaren Zusammensetzungen der Gase Propen/ Sauerstoff/Wasserstoff/Stickstoff eingesetzt werden. Daher sind bevorzugte Gasverhältnisse für die Oxidationsreaktion von Propen folgende Verhält- nisse: H2 / Kohlenwasserstoff / Sauerstoff Stickstoff: 10-50 % / 5 - 50 % / 0,1 -10 %The composition of the gas phase, consisting of propene, oxygen, hydrogen and possibly an inert gas, is not only important for the space-time yield, but also for safety. Theoretically, all molar compositions of the gases propene / oxygen / hydrogen / nitrogen can be used. Therefore, preferred gas ratios for the oxidation reaction of propene are as follows: H 2 / hydrocarbon / oxygen nitrogen: 10-50% / 5 - 50% / 0.1 -10%
/ 5-50 %; bevorzugt H2 / Kohlenwasserstoff / Sauerstoff / Stickstoff: 20-40 % / 6- 20 / 1-5 % / 0-10 %. Der molekulare Sauerstoff, der für die Reaktion eingesetzt wird, kann vielfältiger Herkunft sein, z. B. reiner Sauerstoff, Luft oder andere Sauerstoff/Inertgasmischungen. Beispiele/ 5-50%; preferably H 2 / hydrocarbon / oxygen / nitrogen: 20-40% / 6- 20 / 1-5% / 0-10%. The molecular oxygen used for the reaction can be of various origins, e.g. B. pure oxygen, air or other oxygen / inert gas mixtures. Examples
Die Verlängerung der Standzeit wird am Beispiel der Epoxidierung von Propen gezeigt.The extension of the service life is shown using the example of the epoxidation of propene.
Direktoxidation von Propen zu PropenoxidDirect oxidation of propene to propene oxide
Standardreaktionsbedingungen: Bei dem Reaktor handelt es sich um einen Festbettrohrreaktor (1 cm Durchmesser, 20 cm Länge) aus doppelwandigem Glas, der mittels eines Wasser-Thermostaten auf 46°C temperiert wird. Dem Reaktor ist eine statische Misch- und Temperierstrecke vorgeschaltet. Der Gold-Trägerkatalysator wird auf einer Glasfritte vorgelegt. Die Katalysatorbelastung beträgt 1,8 1 / g Kat. h. Die Eduktgase werden mittels Massendurchflußregler in den Reaktor von oben nach unten eindosiert. Die Eduktgasverhältnisse sind O2 / H2 / C3H6 : 0,1 / 1,3 / 0,4 1/h. Das Reaktionsgasgemisch wird mittels Gaschromatographie mit einem FID- (alle sauerstoffhaltigen organischen Verbindungen, Ausnahme CO2) und WLD-Detektor (Permanentgase, CO, CO2, H2O) analysiert. Die Anlage wird über ein zentrales Meßwerterfassungssystem gesteuert.Standard reaction conditions: The reactor is a fixed-bed tube reactor (1 cm in diameter, 20 cm in length) made of double-walled glass, which is heated to 46 ° C. by means of a water thermostat. A static mixing and temperature control section is connected upstream of the reactor. The gold supported catalyst is placed on a glass frit. The catalyst load is 1.8 1 / g cat. H. The reactant gases are metered into the reactor from top to bottom by means of mass flow controllers. The starting gas ratios are O 2 / H 2 / C 3 H 6 : 0.1 / 1.3 / 0.4 1 / h. The reaction gas mixture is analyzed by means of gas chromatography with an FID (all oxygen-containing organic compounds, with the exception of CO 2 ) and a TCD detector (permanent gases, CO, CO 2 , H 2 O). The system is controlled by a central data acquisition system.
Alle Katalysatoren werden mit TEM (Trasmission Elctron Microscopy) hinsichtlich der Goldpartikelgröße untersucht.All catalysts are examined with TEM (Trasmission Elctron Microscopy) for the gold particle size.
Katalysatorpräparation 1:Catalyst preparation 1:
Zur Suspension von 10 g Titanoxidhydrat (0,6 % Sulfatanteil, 12 % Wasser; Vorstufe zum Anatas) in 0,3 1 VE- Wasser werden bei RT unter Rühren 100 mg H(AuCl4), gelöst in 100 ml VE- Wasser, innerhalb von 60 min zugetropft. Zur Fällung des Goldhydroxides wird mit einer 0,5 molaren Na2CO3-Lösung der pH- Wert auf 8 eingestellt; die schwach gelbe Suspension entfärbt sich. Die Suspension wird 3 h bei RT gerührt, der Feststoff abgetrennt und 4 mal mit je 25 ml VE- Wasser gewaschen. Zur Trocknung wird der Feststoff 2 h bei 150°C und 1 h bei 200°C gehalten, und anschließend wird der getrocknete Kontakt an der Luft 2 h bei 250°C und 5 h bei 400°C kalziniert. Man erhält einen Katalysator mit 0,5 Gew.-% Gold. Die Charakterisierung mit TEM ergibt nanoskalige Goldpartikel mit mittleren Teilchen-durchmessern von ca. 1 -6 nm.100 mg of H (AuCl 4 ), dissolved in 100 ml of demineralized water, are added at RT to the suspension of 10 g of titanium oxide hydrate (0.6% sulfate, 12% water; precursor to anatase) in 0.3 l demineralized water with stirring. added dropwise within 60 min. To precipitate the gold hydroxide, the pH is adjusted to 8 using a 0.5 molar Na 2 CO 3 solution; the pale yellow suspension becomes discolored. The suspension is stirred at RT for 3 h, the solid is separated off and washed 4 times with 25 ml of demineralized water. For drying, the solid is kept at 150 ° C. for 2 hours and at 200 ° C. for 1 hour, and then the dried contact in air is at 250 ° C. for 2 hours and at 400 ° C. for 5 hours calcined. A catalyst with 0.5% by weight of gold is obtained. Characterization with TEM reveals nanoscale gold particles with average particle diameters of approx. 1 -6 nm.
Ergebnisse der katalytischen Reaktion analog den Standardreaktionsbedingungen sind in Tabelle 1 zusammengefaßt.Results of the catalytic reaction analogous to the standard reaction conditions are summarized in Table 1.
Katalysatorpräparation 2:Catalyst preparation 2:
Eine Lösung von 0,104 g HAuCl4 x 4 H2O in 400 ml destilliertem Wasser wird auf 70 °C aufgeheizt, mit einer wäßrigen 0,1 N NaOH-Lösung auf pH 7,5 gebracht und bei intensiven Rühren 5 g Titandioxid (Anatas-Rutil-Mischoxid; P 25 der Firma Degussa) in einer Portion hinzugefügt und 1 h weiter gerührt. Der Feststoff wird 5 mal mit je 3 Liter destilliertem Wasser gewaschen, bei Raumtemperatur im Vakuum für 12 Stunden getrocknet und 4 h bei 400 °C kalziniert. Man erhält einen Gold-Titandi- oxid-Katalysator mit 1 Gew.-% Gold.A solution of 0.104 g HAuCl 4 x 4 H 2 O in 400 ml distilled water is heated to 70 ° C., brought to pH 7.5 with an aqueous 0.1 N NaOH solution and 5 g titanium dioxide (anatase- Rutile mixed oxide; P 25 from Degussa) added in one portion and stirring continued for 1 h. The solid is washed 5 times with 3 liters of distilled water, dried at room temperature in a vacuum for 12 hours and calcined at 400 ° C. for 4 hours. A gold-titanium dioxide catalyst with 1% by weight of gold is obtained.
Beispiel 1 bis 8:Examples 1 to 8:
Katalytische Aktivität von erfindungsgemäß behandelten Gold-enthaltenen KatalysatorenCatalytic activity of gold-containing catalysts treated according to the invention
Katalysatorpräparation analog Katalysatorpräparation 1 bzw. Katalysatorpräparation 2, aber es wird der kalzinierte Katalysator (2 g) in 500 ml H2O suspendiert, 10 mmol Salz hinzugegeben, 1 h bei Raumtemperatur gerührt, abgetrennt und lh bei 150°C getrocknet. Der so erhaltene Kontakt wird zur Propenoxidation nach der Stan- dardfahrweise eingesetzt.Catalyst preparation analogous to catalyst preparation 1 or catalyst preparation 2, but the calcined catalyst (2 g) is suspended in 500 ml H 2 O, 10 mmol salt added, stirred at room temperature for 1 h, separated and dried at 150 ° C. for 1 hour. The contact thus obtained is used for propene oxidation according to the standard procedure.
Im Falle von Organika (z.B. Amine) wird der Katalysator in Ethanol suspendiert, mit der Organika suspendiert, 1 h bei Raumtemperatur gerührt, abgetrennt und lh bei 150°C getrocknet. Der so erhaltene Kontakt wird zur Propenoxidation nach der Stan- dardfahrweise eingesetzt. Bei der Verwendung von Silylierungsreagenzien wird der Katalysator in wasserfreiem Pentan suspendiert, 1 mmol Silylierungsreagenz hinzugefügt, 1 h gerührt, abgetrennt und 1 h bei 150°C getrocknet. Der so erhaltene Kontakt wird zur Propenoxidation nach der Standardfahrweise eingesetzt.In the case of organics (eg amines), the catalyst is suspended in ethanol, suspended with the organics, stirred for 1 h at room temperature, separated and dried at 150 ° C. for 1 hour. The contact thus obtained is used for propene oxidation according to the standard procedure. If silylation reagents are used, the catalyst is suspended in anhydrous pentane, 1 mmol of silylation reagent is added, the mixture is stirred for 1 h, separated and dried at 150 ° C. for 1 h. The contact thus obtained is used for propene oxidation according to the standard procedure.
Ergebnisse der katalytischen Reaktion analog den Standardreaktionsbedingungen sind in Tabelle 1 zusammengefaßt. Results of the catalytic reaction analogous to the standard reaction conditions are summarized in Table 1.
Tabelle 1Table 1
Katalysator t PropenumPO-Ausbeute PO-SelektivitätCatalyst t propene PO PO yield PO selectivity
Präparation 1 (min) satz (%) (%) (%) unbehandelt 30 5,5 5,4 >97Preparation 1 (min) set (%) (%) (%) untreated 30 5.5 5.4> 97
300 1,5 1,5 >97300 1.5 1.5> 97
Wasser 30 5,3 5,2 >97Water 30 5.3 5.2> 97
300 1,6 1,6 >97300 1.6 1.6> 97
Na2SO4 30 4,5 4,4 >97Na 2 SO 4 30 4.5 4.4> 97
300 2,8 2,8 >97300 2.8 2.8> 97
NaH2PO4 30 2,5 2,3 >97NaH 2 PO 4 30 2.5 2.3> 97
300 1,0 0,8 >97300 1.0 0.8> 97
Na2CO3 30 2,6 2,5 >97Na 2 CO 3 30 2.6 2.5> 97
300 0,9 0,9 >97300 0.9 0.9> 97
NH4NO3 30 4,7 4,5 >97NH 4 NO 3 30 4.7 4.5> 97
300 1,6 1,5 >97300 1.6 1.5> 97
NaOAc 30 2,7 2,6 >97NaOAc 30 2.7 2.6> 97
300 0,8 0,8 >97300 0.8 0.8> 97
CsF 30 2,7 2,6 >97CsF 30 2.7 2.6> 97
300 2,0 2,0 >97300 2.0 2.0> 97
Hydroxylamin 30 2,3 2,3 >97Hydroxylamine 30 2.3 2.3> 97
300 1,5 1,5 >97300 1.5 1.5> 97
Triethylamin 30 0,9 0,9 >97Triethylamine 30 0.9 0.9> 97
300 0,8 0,8 >97300 0.8 0.8> 97
Benzylidenanilin 30 0,6 0,6 >97Benzylidenaniline 30 0.6 0.6> 97
300 0,6 0,6 >97300 0.6 0.6> 97
Hexamethyldisilan 30 1,2 1,2 >97Hexamethyldisilane 30 1.2 1.2> 97
300 0,9 0,9 >97300 0.9 0.9> 97
Hexamethyldisilazan 30 1,4 1,4 >97 300 1,0 1,0 >97Hexamethyldisilazane 30 1.4 1.4> 97 300 1.0 1.0> 97
Hexamethyldisiloxan 30 1,1 1,1 >97 300 0,9 0,9
Präparation 2 (min) (%) (%) tät (%) unbehandelt 30 1,4 1,3 >97Preparation 2 (min) (%) (%) activity (%) untreated 30 1.4 1.3> 97
300 0,5 0,5 >97300 0.5 0.5> 97
Na2SO4 30 1,0 1,0 >97Na 2 SO 4 30 1.0 1.0> 97
300 0,8 0,8 >97
Claims
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU27159/99A AU2715999A (en) | 1998-02-06 | 1999-01-07 | Method for improving the operational life of supported catalysts covered with gold particles and used for oxidising unsaturated hydrocarbons |
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| Application Number | Priority Date | Filing Date | Title |
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| DE19804712.6 | 1998-02-06 | ||
| DE19804712A DE19804712A1 (en) | 1998-02-06 | 1998-02-06 | Process for extending the service life of supported gold-coated catalysts for the oxidation of unsaturated hydrocarbons |
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| AU (1) | AU2715999A (en) |
| DE (1) | DE19804712A1 (en) |
| WO (1) | WO1999039826A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000064582A1 (en) * | 1999-04-23 | 2000-11-02 | Bayer Aktiengesellschaft | Surface-modified mixed oxides containing precious metal and titanium, for the selective oxidation of hydrocarbons |
| WO2009061623A3 (en) * | 2007-11-07 | 2009-06-18 | Dow Global Technologies Inc | Hydro-oxidation process using a catalyst containing gold and a halogen-containing compound |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60008933T2 (en) | 1999-12-09 | 2005-01-05 | Dow Global Technologies, Inc., Midland | ACTIVATION AND REGENERATION OF A HYDRO-OXYDATION CATALYST |
| EP1125632A1 (en) | 2000-02-07 | 2001-08-22 | Bayer Aktiengesellschaft | Process for the epoxidation of olefins using gold-containing catalysts |
| CN1231296C (en) | 2001-08-01 | 2005-12-14 | 陶氏环球技术公司 | Method for prolonging the life of hydrogenation-oxidation catalysts |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1107495A (en) * | 1966-01-15 | 1968-03-27 | Knapsack Ag | Process for regenerating palladium carrier catalysts for use in the manufacture of vinyl acetate |
| DE1667212A1 (en) * | 1966-06-10 | 1971-06-09 | Nat Distillers Chem Corp | Catalyst reactivation |
| EP0709360A1 (en) * | 1994-10-28 | 1996-05-01 | AGENCY OF INDUSTRIAL SCIENCE & TECHNOLOGY MINISTRY OF INTERNATIONAL TRADE & INDUSTRY | Method for production of alcohol, ketone, and alderhyde by oxidation of hydrocarbon |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19528219A1 (en) * | 1995-08-01 | 1997-02-06 | Degussa | Process for the preparation of epoxides from olefins |
| US5932750A (en) * | 1996-03-21 | 1999-08-03 | Agency Of Industrial Science And Technology | Catalysts for partial oxidation of hydrocarbons and method of partial oxidation of hydrocarbons |
-
1998
- 1998-02-06 DE DE19804712A patent/DE19804712A1/en not_active Ceased
-
1999
- 1999-01-07 WO PCT/EP1999/000034 patent/WO1999039826A1/en not_active Ceased
- 1999-01-07 AU AU27159/99A patent/AU2715999A/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1107495A (en) * | 1966-01-15 | 1968-03-27 | Knapsack Ag | Process for regenerating palladium carrier catalysts for use in the manufacture of vinyl acetate |
| DE1667212A1 (en) * | 1966-06-10 | 1971-06-09 | Nat Distillers Chem Corp | Catalyst reactivation |
| EP0709360A1 (en) * | 1994-10-28 | 1996-05-01 | AGENCY OF INDUSTRIAL SCIENCE & TECHNOLOGY MINISTRY OF INTERNATIONAL TRADE & INDUSTRY | Method for production of alcohol, ketone, and alderhyde by oxidation of hydrocarbon |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000064582A1 (en) * | 1999-04-23 | 2000-11-02 | Bayer Aktiengesellschaft | Surface-modified mixed oxides containing precious metal and titanium, for the selective oxidation of hydrocarbons |
| US6734133B1 (en) | 1999-04-23 | 2004-05-11 | Bayer Aktiengesellschaft | Surface-modified mixed oxides containing precious metal and titanium, for the selective oxidation of hydrocarbons |
| WO2009061623A3 (en) * | 2007-11-07 | 2009-06-18 | Dow Global Technologies Inc | Hydro-oxidation process using a catalyst containing gold and a halogen-containing compound |
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| DE19804712A1 (en) | 1999-08-12 |
| AU2715999A (en) | 1999-08-23 |
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