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EP0906298A1 - Process for producing epoxides from olefines and hydrogen peroxide or hydroperoxides using a zeolithic oxidation catalyst - Google Patents

Process for producing epoxides from olefines and hydrogen peroxide or hydroperoxides using a zeolithic oxidation catalyst

Info

Publication number
EP0906298A1
EP0906298A1 EP97925967A EP97925967A EP0906298A1 EP 0906298 A1 EP0906298 A1 EP 0906298A1 EP 97925967 A EP97925967 A EP 97925967A EP 97925967 A EP97925967 A EP 97925967A EP 0906298 A1 EP0906298 A1 EP 0906298A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen peroxide
hydroperoxides
titanium
sources
oxidation catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97925967A
Other languages
German (de)
French (fr)
Inventor
Ulrich Müller
Georg Heinrich Grosch
Bernhard Hauer
Michael Schulz
Norbert Rieber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0906298A1 publication Critical patent/EP0906298A1/en
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Classifications

    • 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
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids

Definitions

  • the present invention relates to an improved process for the production of epoxides from olefins and hydrogen peroxide or hydroperoxides using an oxidation catalyst based on titanium or vanadium silicates with a zeolite structure.
  • the epoxidation of ethylene, propene, allyl chloride, 2-butene, 1-octene, 1-tridecene, mesityl oxide, isoprene, 0 cyclooctene and cyclohexene by means of dilute aqueous hydrogen peroxide in the presence of a titanium silicalite in an autoclave ven carried out.
  • the hydrogen peroxide concentration in the reaction mixture can be reduced by up to 10% by weight.
  • the object of the present invention was therefore to provide a simple, efficient and, in particular, economical epoxidation process for olefins which no longer has the disadvantages of the prior art.
  • organic hydroperoxides of the formula R-O-O-H used as customary oxidizing agents for such epoxidations can be used as hydroperoxides, where R generally represents an organic radical having 1 to 30 C atoms. Cumene and diisopropylbenzene hydroperoxide are of particular interest.
  • the hydrogen peroxide sources used for the epoxidation according to the invention are aqueous hydrogen peroxide solutions, in particular technical (ie not purified) hydrogen peroxide solutions with a content of 0.1 to 10% by weight, in particular 0.15 up to 5% by weight, especially 0.2 to
  • Such technical hydrogen peroxide sources are particularly suitable as extraction solutions containing hydrogen peroxide from an anthraquinone working solution for the production of hydrogen peroxide.
  • Such technical hydrogen peroxide sources are furthermore suitable hydrogen peroxide-containing streams or residues, for example vapors or bottoms, from a hydrogen peroxide distillation, these streams or residues mostly not having been further concentrated in their H 2 0 2 content.
  • Such technical hydrogen peroxide sources are also particularly suitable extraction solutions containing fermenter broths or enzyme mixtures containing hydrogen peroxide, ie from naturally occurring or biotechnologically accessible sources.
  • the oxidation catalysts based on titanium or vanadium silicates with a zeolite structure are known from the prior art.
  • zeolites are crystalline alumino-silicates with ordered channel and cage structures, the pore openings of which are in the range of micropores which are smaller than 0.9 nm.
  • the network of such zeolites is made up of Si0 4 and A10 4 tetrahedra, which are connected via common oxygen bridges.
  • Zeolites are now also known which do not contain aluminum and in which titanium (Ti) is used instead of Si (IV) in the silicate lattice. These titanium zeolites, in particular those with an MFI-type crystal structure, and possibilities for their production are described, for example in EP-A 311 983 or EP-A 405 978.
  • silicon and titanium such materials can also contain additional elements such as aluminum, Contain zirconium, tin, iron, cobalt, nickel, gallium, boron or small amounts of fluorine.
  • the titanium of the zeolite can be partially or completely replaced by vanadium.
  • the molar ratio of titanium and / or vanadium to the sum of silicon plus titanium and / or vanadium is generally in the range from 0.01: 1 to 0.1: 1.
  • Titanium zeolites with an MFI structure are known to have a certain pattern when determining their X-ray diffraction images and also a framework vibration band in the
  • Infrared range can be identified at about 960 cm "1 and thus differ from alkali metal titanates or crystalline and amorphous Ti0 2 phases.
  • the titanium and also vanadium zeolites mentioned are prepared by adding an aqueous mixture of an SiO 2 source, a titanium or vanadium source such as titanium dioxide or a corresponding vanadium oxide and a nitrogenous organic base ( "Template compound”), for example tetrapropylammonium hydroxide, optionally with the addition of alkali metal compounds, in a pressure vessel under elevated temperature over a period of several hours or a few days, the crystalline product being formed. This is filtered off, washed, dried and fired at elevated temperature to remove the organic nitrogen base.
  • the titanium or the vanadium is at least partially in varying proportions within the zeolite framework with four, five or six-fold coordination.
  • a repeated washing treatment with sulfuric acid hydrogen peroxide solution can follow, after which the titanium or vanadium zeolite powder must be dried and fired again; this can be followed by treatment with alkali metal compounds in order to convert the zeolite from the H form into the cation form.
  • Preferred titanium or vanadium zeolites are those with a pentasil zeolite structure, in particular the types with X-ray assignment to the BEA, MOR, TON, MTW, FER, MFI, MEL or MFI / MEL mixed structure. Zeolites of this type are described, for example, in W.M. Meier and D.H. Olson, "Atlas of Zeolite Structure Types", Butterworths, 2nd Ed., London 1987. Titanium-containing zeolites with the structure of ZSM-48, ZSM-12, ferrierite or ⁇ -zeolite and mordenite are also conceivable for the present invention.
  • the process according to the invention for the preparation of epoxides can be carried out using all customary reaction procedures and in all customary reactor types, for example using the suspension procedure or in a fixed bed arrangement. You can work continuously or discontinuously.
  • the epoxidation according to the invention is expediently carried out in the liquid phase in water alone or in a mixture of water and water-miscible organic solvents.
  • organic solvents are particularly suitable alcohols such as methanol, ethanol, iso-propanol, tert. -Butanol or mixtures thereof. If such organic solvents are used in a mixture with water, their proportion of the total mixture is usually 5 to 95% by volume, in particular 30 to 85% by volume.
  • the epoxidation according to the invention is generally carried out at a temperature of from -20 to 70 ° C., in particular from -5 to 50 ° C., and at a pressure of 1 to 10 bar.
  • the olefin used can be any organic compound which contains at least one ethylenically unsaturated double bond. It can be aliphatic, aromatic or cycloaliphatic in nature, it can consist of a linear or a branched structure.
  • the olefin preferably contains 2 to 30 carbon atoms. There may be more than one ethylenically unsaturated double bond, for example in dienes or trienes.
  • the olefin can additionally contain functional groups such as halogen atoms, carboxyl groups, carboxylic ester functions, hydroxyl groups, ether bridges, sulfide bridges, carbonyl functions, cyano groups, nitro groups or amino groups.
  • Typical examples of such olefins are ethylene, propene, 5 1-butene, ice and trans-2-butene, 1, 3-butadiene, pentene, isoprene, hexene, octene, nonene, decene, undecene, dodecene, cyclopentene, cyclohexene, Dicyclopentadiene, methylene cyclopropane, vinyl cyclohexane, vinyl cyclohexene, allyl chloride, acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, allyl alcohol, alkyl acrylates, alkyl
  • the process according to the invention is particularly suitable for the epoxidation of propene to propylene oxide.
  • the present invention it is possible to successfully epoxidize olefins far below the hydrogen peroxide concentration known in the prior art by means of titanium or vanadium silicalites. Because of the low concentration of hydrogen peroxide in the system, there are no longer any safety problems. Furthermore, hydrogen peroxide solutions can be used without disturbing stabilizers, which are necessary at high concentrations.
  • the process according to the invention has the advantage that inexpensive technical hydrogen peroxide sources can be used as feedstock; the impurities present in such sources surprisingly do not interfere with the epoxidation according to the invention.
  • the sealed autoclave (anchor stirrer, 200 rpm) was brought to a reaction temperature of 175 ° C. at a heating rate of 3 ° / min. The reaction was complete after 92 hours.
  • the cooled reaction mixture (white suspension) was centrifuged off and washed neutral with water several times. The solid obtained was dried at 110 ° C. in the course of 24 hours (weight 149 g).
  • the pure white product had a Ti content of 1.5% by weight and a residual alkali content below 100 ppm.
  • the yield on Si0 2 used was 97%.
  • the crystallites had a size of 0.05 to 0.25 ⁇ m and the product showed a typical band at approx. 960 cm 1 in the IR.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Epoxy Compounds (AREA)

Abstract

A process for producing epoxides from olefines and hydrogen peroxide or hydroperoxides in the liquid phase using an oxidation catalyst based on titanium or vanadium silicalites with a zeolithic structure, in which the concentration of the hydrogen peroxide or hydroperoxides in the reaction mixture is in the range from 0.05 to less than 1 wt.% during the reaction.

Description

VERFAHREN ZUR HERSTELLUNG VON EPOXIDEN AUS OLEFINEN UND WASSERSTOFFPEROXIDODER HYDROPEROXIDEN UNTER VERWENDUNG EINES ZEOLITH-OXIDAΗONSKATALYSATORSMETHOD FOR PRODUCING EPOXIES FROM OLEFINES AND HYDROGEN PEROXIDES OR HYDROPEROXIDES USING A ZEOLITE OXIDAΗON CATALYST
5 Beschreibung5 Description
Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Herstellung von Epoxiden aus Olefinen und Wasserstoffperoxid oder Hydroperoxiden unter Verwendung eines Oxidationskatalysators auf 0 Basis von Titan- oder Vanadiumsilikaten mit Zeolith-Struktur.The present invention relates to an improved process for the production of epoxides from olefins and hydrogen peroxide or hydroperoxides using an oxidation catalyst based on titanium or vanadium silicates with a zeolite structure.
Verfahren zur Herstellung von Epoxiden aus Olefinen und wäßrigem Wasserstoffperoxid unter Verwendung von Titansilikaten als Epoxi - dierungskatalysatoren sind aus der EP-A 100 119 (1) und der 5 Literaturstelle M.G. Clerici et al., J. Catal. 129, 159-167 (1991) (2) bekannt.Processes for the preparation of epoxides from olefins and aqueous hydrogen peroxide using titanium silicates as epoxidation catalysts are described in EP-A 100 119 (1) and the 5 literature reference M.G. Clerici et al., J. Catal. 129, 159-167 (1991) (2).
Gemäß (1) wird die Epoxidierung von Ethylen, Propen, Allyl- chlorid, 2-Buten, 1-Octen, 1-Tridecen, Mesityloxid, Isopren, 0 Cycloocten und Cyclohexen mittels verdünntem wäßrigem Wasser¬ stoffperoxid in Gegenwart eines Titansilikalits in einem Autokla¬ ven durchgeführt. Die Wasserstoffperoxidkonzentration in der Re¬ aktionsmischung kann dabei bis zu 10 Gew. -% abgesenkt werden.According to (1), the epoxidation of ethylene, propene, allyl chloride, 2-butene, 1-octene, 1-tridecene, mesityl oxide, isoprene, 0 cyclooctene and cyclohexene by means of dilute aqueous hydrogen peroxide in the presence of a titanium silicalite in an autoclave ven carried out. The hydrogen peroxide concentration in the reaction mixture can be reduced by up to 10% by weight.
5 Aus (2) ist bekannt, daß die Wasserstoffperoxidkonzentration bei solchen Epoxidierungen sogar bis zu 1 % heruntergefahren werden kann. Als Wasserstoffperoxidquellen für die in (2) beschriebenen Titansilikalit-katalysierten Epoxidierungen von Propen zu Propylenoxid werden 30 bis 35 %ige wäßrige H202-Lösungen einge- 0 setzt.5 From (2) it is known that the hydrogen peroxide concentration can even be reduced by up to 1% in such epoxidations. 30 to 35% strength aqueous H 2 0 2 solutions are used as hydrogen peroxide sources for the titanium silicalite-catalyzed epoxidations of propene to propylene oxide described in (2).
Derartige aus dem Stand der Technik bekannte Epoxidierungsverfah- ren weisen jedoch Nachteile auf. Bei Verwendung von konzentrier¬ ten Wasserstoffperoxid-Lösungen (mit ca. 10 bis 70 Gew. -% H202) 5 können erhebliche Sicherheitsprobleme bei der Reaktionsführung wegen möglicher spontaner Zersetzungen des Wasserstoffperoxids oder von dessen Nebenprodukten (z.B. Hydroperoxiden), ins¬ besondere in Gegenwart bestimmter organischer Lösungsmittel, auf¬ treten. Die Beseitigung solcher Sicherheitsprobleme führt zu er- 0 heblich größerem Aufwand und höheren Verfahrenskosten. Auch ohne den genannten Sicherheitsaspekt sind die Verfahrenskosten ohnehin schon groß, da mittel- bis hochkonzentrierte Wasserstoffperoxid- Lösungen relativ teuer sind.However, such epoxidation processes known from the prior art have disadvantages. When using concentrated hydrogen peroxide solutions (with approx. 10 to 70% by weight H 2 0 2 ) 5, considerable safety problems in the course of the reaction can occur, in particular because of possible spontaneous decomposition of the hydrogen peroxide or its by-products (eg hydroperoxides) in the presence of certain organic solvents. The elimination of such security problems leads to considerably more effort and higher process costs. Even without the safety aspect mentioned, the process costs are already high, since medium to highly concentrated hydrogen peroxide solutions are relatively expensive.
5 Aufgabe der vorliegenden Erfindung war es daher, ein einfaches, effizientes und insbesondere wirtschaftliches Epoxidierungsver- fahren von Olefinen bereitzustellen, das die Nachteile des Standes der Technik nicht mehr aufweist.5 The object of the present invention was therefore to provide a simple, efficient and, in particular, economical epoxidation process for olefins which no longer has the disadvantages of the prior art.
Demgemäß wurde ein Verfahren zur Herstellung von Epoxiden aus Olefinen und Wasserstoffperoxid oder Hydroperoxiden in flüssiger Phase unter Verwendung eines Oxidationskatalysators auf Basis von Titan- oder Vanadiumsilikaliten mit Zeolith-Struktur gefunden, welches dadurch gekennzeichnet ist, daß die Konzentration des Wasserstoffperoxids oder der Hydroperoxide in der Reaktions- mischung bei der Umsetzung im Bereich von 0,05 bis kleinerAccordingly, a process for the production of epoxides from olefins and hydrogen peroxide or hydroperoxides in the liquid phase using an oxidation catalyst based on titanium or vanadium silicates with a zeolite structure was found, which is characterized in that the concentration of the hydrogen peroxide or the hydroperoxides in the reaction - Mix in the implementation in the range of 0.05 to less
1 Gew. -%, insbesondere von 0,1 bis 0,8 Gew. -%, vor allem von 0,2 bis 0,6 Gew. -%, liegt.1% by weight, in particular from 0.1 to 0.8% by weight, especially from 0.2 to 0.6% by weight.
Als Hydroperoxide können alle als übliche Oxidationsmittel für derartige Epoxidierungen verwendeten organischen Hydroperoxide der Formel R-O-O-H eingesetzt werden, wobei R in der Regel für einen organischen Rest mit 1 bis 30 C-Atomen steht. Von besonde- rem Interesse sind hierbei Cumol- und Diisopropylbenzol-Hydro¬ peroxid.All of the organic hydroperoxides of the formula R-O-O-H used as customary oxidizing agents for such epoxidations can be used as hydroperoxides, where R generally represents an organic radical having 1 to 30 C atoms. Cumene and diisopropylbenzene hydroperoxide are of particular interest.
In einer bevorzugten Ausführungsform setzt man als Wasserstoff¬ peroxidquellen für die erfindungsgemäße Epoxidierung wäßrige Was- serstoffperoxid-Lösungen, insbesondere technische (also nicht gereinigte) Wasserstoffperoxid-Lösungen, mit einem Gehalt an 0,1 bis 10 Gew. -%, insbesondere 0,15 bis 5 Gew. -%, vor allem 0,2 bisIn a preferred embodiment, the hydrogen peroxide sources used for the epoxidation according to the invention are aqueous hydrogen peroxide solutions, in particular technical (ie not purified) hydrogen peroxide solutions with a content of 0.1 to 10% by weight, in particular 0.15 up to 5% by weight, especially 0.2 to
2 Gew. -% Wasserstoffperoxid ein.2% by weight of hydrogen peroxide.
Als derartige technische Wasserstoffperoxidquellen eignen sich vor allem wasserstoffperoxidhaltige Extraktionslösungen aus einer Anthrachinon-Arbeitslösung zur Wasserstoffperoxid-Herstellung.Such technical hydrogen peroxide sources are particularly suitable as extraction solutions containing hydrogen peroxide from an anthraquinone working solution for the production of hydrogen peroxide.
Als derartige technische Wasserstoffperoxidquellen eignen sich weiterhin gut wasserstoffperoxidhaltige Ströme oder Rückstände, z.B. Brüden oder Sumpfausträge, aus einer Wasserstoffperoxid- Destillation, wobei diese Ströme oder Rückstände meist nicht weiter in ihrem H202-Gehalt aufkonzentriert worden sind.Such technical hydrogen peroxide sources are furthermore suitable hydrogen peroxide-containing streams or residues, for example vapors or bottoms, from a hydrogen peroxide distillation, these streams or residues mostly not having been further concentrated in their H 2 0 2 content.
Als derartige technische Wasserstoffperoxidquellen eignen sich insbesondere auch wasserstoffperoxidhaltige Extraktionslösungen von Fermenterbrühen oder von enzymhaltigen Mischungen, also aus natürlich vorkommenden oder biotechnologisch zugänglichen Quellen. Die eingesetzten Oxidationskatalysatoren auf Basis von Ti¬ tan- oder Vanadiumsilikaten mit Zeolith-Struktur sind aus dem Stand der Technik bekannt. Zeolithe sind bekanntermaßen kristal¬ line Alumosilikate mit geordneten Kanal- und Käfigstrukturen, deren Porenöffnungen im Bereich von Mikroporen, die kleiner als 0,9 nm sind, liegen. Das Netzwerk solcher Zeolithe ist aufgebaut aus Si04- und A104-Tetraedern, die über gemeinsame Sauerstoffbrük- ken verbunden sind. Eine Übersicht der bekannten Strukturen fin¬ det sich beispielsweise bei W.M. Meier und D.H. Olson, "Atlas of Zeolite Structure Types" , Butterworth, 2nd Ed., London 1987.Such technical hydrogen peroxide sources are also particularly suitable extraction solutions containing fermenter broths or enzyme mixtures containing hydrogen peroxide, ie from naturally occurring or biotechnologically accessible sources. The oxidation catalysts based on titanium or vanadium silicates with a zeolite structure are known from the prior art. As is known, zeolites are crystalline alumino-silicates with ordered channel and cage structures, the pore openings of which are in the range of micropores which are smaller than 0.9 nm. The network of such zeolites is made up of Si0 4 and A10 4 tetrahedra, which are connected via common oxygen bridges. An overview of the known structures can be found, for example, in WM Meier and DH Olson, "Atlas of Zeolite Structure Types", Butterworth, 2nd Ed., London 1987.
Es sind nun auch Zeolithe bekannt, die kein Aluminium enthalten und bei denen im Silikatgitter anstelle des Si(IV) teilweise Titan als Ti(IV) steht. Diese Titanzeolithe, insbesondere solche mit einer Kristallstruktur vom MFI-Typ, sowie Möglichkeiten zu ihrer Herstellung sind beschrieben, beispielsweise in der EP-A 311 983 oder der EP-A 405 978. Außer Silizium und Titan können solche Materialien auch zusätzliche Elemente wie Aluminium, Zirkonium, Zinn, Eisen, Kobalt, Nickel, Gallium, Bor oder geringe Mengen an Fluor enthalten.Zeolites are now also known which do not contain aluminum and in which titanium (Ti) is used instead of Si (IV) in the silicate lattice. These titanium zeolites, in particular those with an MFI-type crystal structure, and possibilities for their production are described, for example in EP-A 311 983 or EP-A 405 978. In addition to silicon and titanium, such materials can also contain additional elements such as aluminum, Contain zirconium, tin, iron, cobalt, nickel, gallium, boron or small amounts of fluorine.
Im beschriebenen Oxidationskatalysator kann das Titan des Zeoliths teilweise oder vollständig durch Vanadium ersetzt sein. Das molare Verhältnis von Titan und/oder Vanadium zur Summe aus Silicium plus Titan und/oder Vanadium liegt in der Regel im Be¬ reich von 0,01:1 bis 0,1:1.In the oxidation catalyst described, the titanium of the zeolite can be partially or completely replaced by vanadium. The molar ratio of titanium and / or vanadium to the sum of silicon plus titanium and / or vanadium is generally in the range from 0.01: 1 to 0.1: 1.
Titanzeolithe mit MFI-Struktur sind dafür bekannt, daß sie über ein bestimmtes Muster bei der Bestimmung ihrer Röntgenbeugungs- aufnahmen sowie zusätzlich über eine Gerüstschwingungsbande imTitanium zeolites with an MFI structure are known to have a certain pattern when determining their X-ray diffraction images and also a framework vibration band in the
Infrarotbereich (IR) bei etwa 960 cm"1 identifiziert werden können und sich damit von Alkalimetalltitanaten oder kristallinen und amorphen Ti02-Phasen unterscheiden.Infrared range (IR) can be identified at about 960 cm "1 and thus differ from alkali metal titanates or crystalline and amorphous Ti0 2 phases.
Typischerweise stellt man die genannten Titan- und auch Vanadium- zeolithe dadurch her, daß man eine wäßrige Mischung aus einer Si02-Quelle, einer Titan- bzw. Vanadium-Quelle wie Titandioxid bzw. einem entsprechenden Vanadiumoxid und einer stickstoff¬ haltigen organischen Base ("Schablonen-Verbindung") , z.B. Tetra- propylammoniumhydroxid, gegebenenfalls noch unter Hinzufügen von Alkalimetallverbindungen, in einem Druckbehälter unter erhöhter Temperatur im Zeitraum mehrerer Stunden oder einiger Tage um¬ setzt, wobei das kristalline Produkt entsteht. Dieses wird ab- filtriert, gewaschen, getrocknet und zur Entfernung der organi - sehen Stickstoffbase bei erhöhter Temperatur gebrannt. In dem so erhaltenen Pulver liegt das Titan bzw. das Vanadium zumindest teilweise innerhalb des Zeolithgerüsts in wechselnden Anteilen mit vier-, fünf- oder sechsfacher Koordination vor. Zur Verbesse¬ rung des katalytischen Verhaltens kann sich noch eine mehrmalige Waschbehandlung mit schwefelsaurer Wasserstoffperoxidlösung an¬ schließen, worauf das Titan- bzw. Vanadiumzeolith-Pulver erneut getrocknet und gebrannt werden muß; daran kann sich eine Behand¬ lung mit Alkalimetallverbindungen anschließen, um den Zeolith von der H-Form in die Kation-Form zu überführen.Typically, the titanium and also vanadium zeolites mentioned are prepared by adding an aqueous mixture of an SiO 2 source, a titanium or vanadium source such as titanium dioxide or a corresponding vanadium oxide and a nitrogenous organic base ( "Template compound"), for example tetrapropylammonium hydroxide, optionally with the addition of alkali metal compounds, in a pressure vessel under elevated temperature over a period of several hours or a few days, the crystalline product being formed. This is filtered off, washed, dried and fired at elevated temperature to remove the organic nitrogen base. In the powder thus obtained, the titanium or the vanadium is at least partially in varying proportions within the zeolite framework with four, five or six-fold coordination. In order to improve the catalytic behavior, a repeated washing treatment with sulfuric acid hydrogen peroxide solution can follow, after which the titanium or vanadium zeolite powder must be dried and fired again; this can be followed by treatment with alkali metal compounds in order to convert the zeolite from the H form into the cation form.
Bevorzugte Titan- oder Vanadiumzeolithe sind solche mit Pentasil- Zeolith-Struktur, insbesondere die Typen mit röntgenographischer Zuordnung zur BEA- , MOR-, TON-, MTW- , FER-, MFI-, MEL- oder MFI/ MEL-Mischstruktur. Zeolithe dieses Typs sind beispielsweise in W.M. Meier und D.H. Olson, "Atlas of Zeolite Structure Types", Butterworths, 2nd Ed., London 1987, beschrieben. Denkbar sind für die vorliegende Erfindung weiterhin titanhaltige Zeolithe mit der Struktur des ZSM-48, ZSM-12, Ferrierit oder ß-Zeolith und des Mor- denits .Preferred titanium or vanadium zeolites are those with a pentasil zeolite structure, in particular the types with X-ray assignment to the BEA, MOR, TON, MTW, FER, MFI, MEL or MFI / MEL mixed structure. Zeolites of this type are described, for example, in W.M. Meier and D.H. Olson, "Atlas of Zeolite Structure Types", Butterworths, 2nd Ed., London 1987. Titanium-containing zeolites with the structure of ZSM-48, ZSM-12, ferrierite or β-zeolite and mordenite are also conceivable for the present invention.
Das erfindungsgemäße Verfahren zur Herstellung von Epoxiden kann im Prinzip mit allen üblichen Umsetzungsfahrweisen und in allen üblichen Reaktortypen durchgeführt werden, beispielsweise in Suspensionsfahrweise oder in einer Festbettanordnung. Mann kann kontinuierlich oder diskontinuierlich arbeiten.In principle, the process according to the invention for the preparation of epoxides can be carried out using all customary reaction procedures and in all customary reactor types, for example using the suspension procedure or in a fixed bed arrangement. You can work continuously or discontinuously.
Die erfindungsgemäße Epoxidierung wird in flüssiger Phase zweck¬ mäßigerweise in Wasser allein oder in einer Mischung aus Wasser und wassermischbaren organischen Lösungsmitteln durchgeführt. Als derartige organische Lösungsmittel eignen sich insbesondere Alkohole wie Methanol, Ethanol, iso-Propanol, tert. -Butanol oder Mischungen hieraus. Werden solche organische Lösungsmittel in Mischung mit Wasser verwendet, beträgt ihr Anteil an der Gesamt- mischung meist 5 bis 95 Vol.-%, insbesondere 30 bis 85 Vol.-%.The epoxidation according to the invention is expediently carried out in the liquid phase in water alone or in a mixture of water and water-miscible organic solvents. Such organic solvents are particularly suitable alcohols such as methanol, ethanol, iso-propanol, tert. -Butanol or mixtures thereof. If such organic solvents are used in a mixture with water, their proportion of the total mixture is usually 5 to 95% by volume, in particular 30 to 85% by volume.
Die erfindungsgemäße Epoxidierung wird in der Regel bei einer Temperatur von -20 bis 70°C, insbesondere -5 bis 50°C, und bei einem Druck von 1 bis 10 bar vorgenommen.The epoxidation according to the invention is generally carried out at a temperature of from -20 to 70 ° C., in particular from -5 to 50 ° C., and at a pressure of 1 to 10 bar.
Das eingesetzte Olefin kann eine beliebige organische Verbindung sein, die mindestens eine ethylenisch ungesättigte Doppelbindung enthält. Sie kann aliphatischer, aromatischer oder cycloali- phatischer Natur sein, sie kann aus einer linearen oder einer verzweigten Struktur bestehen. Vorzugsweise enthält das Olefin 2 bis 30 C-Atome. Mehr als eine ethylenisch ungesättigte Doppelbin¬ dung kann vorhanden sein, so etwa in Dienen oder Trienen. Das Olefin kann zusätzlich funktioneile Gruppen wie Halogenatome, Carboxylgruppen, Carbonesterfunktionen, Hydroxylgruppen, Ether- brücken, Sulfidbrücken, Carbonylfunktionen, Cyanogruppen, Nitro- gruppen oder Aminogruppen enthalten.The olefin used can be any organic compound which contains at least one ethylenically unsaturated double bond. It can be aliphatic, aromatic or cycloaliphatic in nature, it can consist of a linear or a branched structure. The olefin preferably contains 2 to 30 carbon atoms. There may be more than one ethylenically unsaturated double bond, for example in dienes or trienes. The olefin can additionally contain functional groups such as halogen atoms, carboxyl groups, carboxylic ester functions, hydroxyl groups, ether bridges, sulfide bridges, carbonyl functions, cyano groups, nitro groups or amino groups.
Typische Beispiele für derartige Olefine sind Ethylen, Propen, 5 1-Buten, eis- und trans-2-Buten, 1, 3 -Butadien, Pentene, Isopren, Hexene, Octene, Nonene, Decene, Undecene, Dodecene, Cyclopenten, Cyclohexen, Dicyclopentadien, Methylencyclopropan, Vinylcyclo- hexan, Vinylcyclohexen, Allylchlorid, Acrylsäure, Methacrylsäure, Crotonsäure, Vinylessigsäure, Allylalkohol, Alkylacrylate, Alkyl-Typical examples of such olefins are ethylene, propene, 5 1-butene, ice and trans-2-butene, 1, 3-butadiene, pentene, isoprene, hexene, octene, nonene, decene, undecene, dodecene, cyclopentene, cyclohexene, Dicyclopentadiene, methylene cyclopropane, vinyl cyclohexane, vinyl cyclohexene, allyl chloride, acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, allyl alcohol, alkyl acrylates, alkyl
10 methacrylate, Ölsäure, Linolsäure, Linolensäure, Ester und Glyce- ride derartiger ungesättigter Fettsäuren, Styrol, α-Methylstyrol, Divinylbenzol, Inden und Stilben. Auch Mischungen der genannten Olefine können nach dem erfindungsgemäßen Verfahren epoxidiert werden.10 methacrylates, oleic acid, linoleic acid, linolenic acid, esters and glycerides of such unsaturated fatty acids, styrene, α-methylstyrene, divinylbenzene, indene and stilbene. Mixtures of the olefins mentioned can also be epoxidized by the process according to the invention.
1515
Das erfindungsgemäße Verfahren eignet sich in besonderem Maße für die Epoxidierung von Propen zu Propylenoxid.The process according to the invention is particularly suitable for the epoxidation of propene to propylene oxide.
Gemäß der vorliegenden Erfindung kann man weit unterhalb der im 20 Stand der Technik bekannten Wasserstoffperoxid-Konzentration mittels Titan- oder Vanadiumsilikaliten erfolgreich Olefine epoxidieren. Aufgrund der niedrigen Konzentration an Wasserstoff¬ peroxid im System treten keine Sicherheitsprobleme mehr auf. Weiterhin können Wasserstoffperoxid-Lösungen ohne störende Stabi- 25 lisatoren, welche bei hohen Konzentrationen notwendig sind, ein¬ gesetzt werden. Zudem hat das erfindungsgemäße Verfahren den Vor¬ teil, daß preiswerte technische Wasserstoffperoxidquellen als Einsatzmaterial herangezogen werden können; die in solchen Quellen vorhandenen Verunreinigungen stören überraschenderweise 30 bei der erfindungsgemäßen Epoxidierung nicht.According to the present invention, it is possible to successfully epoxidize olefins far below the hydrogen peroxide concentration known in the prior art by means of titanium or vanadium silicalites. Because of the low concentration of hydrogen peroxide in the system, there are no longer any safety problems. Furthermore, hydrogen peroxide solutions can be used without disturbing stabilizers, which are necessary at high concentrations. In addition, the process according to the invention has the advantage that inexpensive technical hydrogen peroxide sources can be used as feedstock; the impurities present in such sources surprisingly do not interfere with the epoxidation according to the invention.
Die nachstehenden Beispiele sollen das erfindungsgemäße Verfahren näher erläutern, ohne daß dadurch eine Einschränkung zu verstehen wäre.The following examples are intended to explain the process according to the invention in more detail, without any limitation being understood thereby.
3535
Beispiel 1example 1
In einem Vierhalskolben (2 1 Inhalt) wurden 455 g Tetraethyl- orthosilikat vorgelegt und aus einem Tropftrichter innerhalb von455 g of tetraethyl orthosilicate were placed in a four-necked flask (2 1 contents) and from a dropping funnel within
40 30 min mit 15 g Tetraisopropylorthotitanat unter Rühren40 30 min with 15 g tetraisopropyl orthotitanate with stirring
(250 U/min, Blattrührer) versetzt. Es bildete sich eine farblose, klare Mischung. Abschließend versetzte man mit 800 g einer(250 rpm, blade stirrer) added. A colorless, clear mixture was formed. Finally, 800 g was added to one
20 gew. -%igen Tetrapropylammoniumhydroxid-Lösung (Alkaligehalt20 wt. -% tetrapropylammonium hydroxide solution (alkali content
< 10 ppm) und rührte noch eine Stunde nach. Bei 90 bis 100°C wurde<10 ppm) and stirred for another hour. Was at 90 to 100 ° C
45 das aus der Hydrolyse gebildete Alkoholgemisch (ca. 450 g) ab- destilliert. Man füllte mit 1,5 1 deionisiertem Wasser auf und gab das mittlerweile leicht opaque Sol in einen 2,5 1 fassenden Rührautoklaven aus Edelstahl.45 distilled off the alcohol mixture formed from the hydrolysis (approx. 450 g). It was filled with 1.5 l of deionized water and placed the now slightly opaque sol in a 2.5 liter stirred autoclave made of stainless steel.
Mit einer Heizrate von 3°/min wurde der verschlossene Autoklav (Ankerrührer, 200 U/min) auf eine Reaktionstemperatur von 175°C gebracht. Nach 92 Stunden war die Reaktion beendet. Das erkaltete Reaktionsgemisch (weiße Suspension) wurde abzentrifugiert und mehrfach mit Wasser neutral gewaschen. Der erhaltene Feststoff wurde bei 110°C innerhalb von 24 Stunden getrocknet (Auswaage 149 g) .The sealed autoclave (anchor stirrer, 200 rpm) was brought to a reaction temperature of 175 ° C. at a heating rate of 3 ° / min. The reaction was complete after 92 hours. The cooled reaction mixture (white suspension) was centrifuged off and washed neutral with water several times. The solid obtained was dried at 110 ° C. in the course of 24 hours (weight 149 g).
Abschließend wurde unter Luft bei 550°C in 5 Stunden das im Zeolithen noch verbliebene Templat abgebrannt (Kalzinierungs- Verlust: 14 Gew. -%) .Finally, the template still remaining in the zeolite was burned off in air at 550 ° C. in 5 hours (loss of calcination: 14% by weight).
Das reinweiße Produkt hatte nach naßchemischer Analyse einen Ti - Gehalt von 1,5 Gew. -% und einen Gehalt an Restalkali unterhalb 100 ppm. Die Ausbeute auf eingesetztes Si02 betrug 97 %. Die Kristallite hatten eine Größe von 0,05 bis 0,25 μm und das Produkt zeigte im IR eine typische Bande bei ca. 960 cm 1.According to wet chemical analysis, the pure white product had a Ti content of 1.5% by weight and a residual alkali content below 100 ppm. The yield on Si0 2 used was 97%. The crystallites had a size of 0.05 to 0.25 μm and the product showed a typical band at approx. 960 cm 1 in the IR.
Beispiel 2Example 2
In einen 250 ml Glasautoklaven wurden 45 ml Methanol und 0,5 g Titansilikatpulver aus Beispiel 1 eingefüllt und die Suspension wurde mit einem Magnetrührer gerührt. Der verschlossene Glasauto¬ klav wurde danach auf -30°C abgekühlt und 20,7 g Propen wurden aufgepreßt. Danach wurde der Glasautoklav auf 0°C erwärmt und 23 g 0,5 gew. -%ige Wasserstoffperoxidlösung wurde zudosiert. Die Reaktionsmischung wurde 5 h bei 0°C unter Eigendruck gerührt. Danach wurde der Katalysator abzentrifugiert und der Gehalt an Propylenoxid gaschromatographisch bestimmt. Der Gehalt an Propylenoxid betrug 0,3 Gew.-%.45 ml of methanol and 0.5 g of titanium silicate powder from Example 1 were introduced into a 250 ml glass autoclave and the suspension was stirred with a magnetic stirrer. The sealed glass autoclave was then cooled to -30 ° C. and 20.7 g of propene were pressed on. The glass autoclave was then heated to 0 ° C. and 23 g of 0.5 wt. -% hydrogen peroxide solution was added. The reaction mixture was stirred at 0 ° C. under autogenous pressure for 5 h. The catalyst was then centrifuged off and the propylene oxide content was determined by gas chromatography. The propylene oxide content was 0.3% by weight.
Beispiel 3Example 3
In einen 250 ml Glasautoklaven wurden 45 ml Methanol und 0,5 g Titansilikalit aus Beispiel 1 eingefüllt und die Suspension wurde mit einem Magnetrührer gerührt. Der verschlossene Glasautoklav wurde danach auf -30°C abgekühlt und 20,2 g Propen wurde aufge¬ preßt. Danach wurde Glasautoklav auf 0°C erwärmt und 23 g 0,5 gew. -%ige Wasserstoffperoxidlösung zudosiert. Die Reaktions¬ mischung wurde 30 Minuten bei 0°C unter Eigendruck gerührt. Danach wurde der Katalysator abzentrifugiert und der Gehalt an Propylen- oxid gaschromatographisch bestimmt. Der Gehalt an Propylenoxid betrug 0, 18 Gew. -%. 45 ml of methanol and 0.5 g of titanium silicalite from Example 1 were introduced into a 250 ml glass autoclave and the suspension was stirred with a magnetic stirrer. The sealed glass autoclave was then cooled to -30 ° C. and 20.2 g of propene were pressed on. The glass autoclave was then heated to 0 ° C. and 23 g of 0.5 wt. -% hydrogen peroxide solution metered. The reaction mixture was stirred at 0 ° C. under autogenous pressure for 30 minutes. The catalyst was then centrifuged off and the content of propylene oxide was determined by gas chromatography. The propylene oxide content was 0.18% by weight.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Epoxiden aus Olefinen und Wasserstoffperoxid oder Hydroperoxiden in flüssiger Phase unter Verwendung eines Oxidationskatalysators auf Basis von Titan- oder Vanadiumsilikaten mit Zeolith-Struktur, dadurch gekennzeichnet, daß die Konzentration des Wasserstoffperoxids oder der Hydroperoxide in der Reaktionsmischung bei der Um- setzung im Bereich von 0,05 bis kleiner 1 Gew. -% liegt.1. A process for the preparation of epoxides from olefins and hydrogen peroxide or hydroperoxides in the liquid phase using an oxidation catalyst based on titanium or vanadium silicates with a zeolite structure, characterized in that the concentration of the hydrogen peroxide or the hydroperoxides in the reaction mixture during the settlement is in the range from 0.05 to less than 1% by weight.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Wasserstoffperoxidquellen für die Epoxidierung wäßrige Wasserstoffperoxid-Lösungen mit einem Gehalt von 0,1 bis 10 Gew. -% an Wasserstoffperoxid einsetzt.2. The method according to claim 1, characterized in that aqueous hydrogen peroxide solutions containing 0.1 to 10% by weight of hydrogen peroxide are used as the hydrogen peroxide sources for the epoxidation.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man als Wasserstoffperoxidquellen wasserstoffperoxidhaltige Ex¬ traktionslösungen aus einer Anthrachinon-Arbeitslösung zur Wasserstoffperoxid-Herstellung einsetzt.3. The method according to claim 2, characterized in that hydrogen peroxide sources used hydrogen peroxide-containing extraction solutions from an anthraquinone working solution for the production of hydrogen peroxide.
4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man als Wasserstoffperoxidquellen wasserstoffperoxidhaltige Ströme oder Rückstände aus einer Wasserstoffperoxid-Destilla- tion einsetzt.4. The method according to claim 2, characterized in that hydrogen peroxide sources are used as hydrogen peroxide sources or residues from a hydrogen peroxide distillation.
5. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man als Wasserstoffperoxidquellen wasserstoffperoxidhaltige Ex¬ traktionslösungen von Fermenterbrühen oder von enzymhaltigen Mischungen einsetzt.5. The method according to claim 2, characterized in that hydrogen peroxide sources used hydrogen peroxide-containing extraction solutions from fermenter broths or from enzyme-containing mixtures.
6. Verfahren zur Herstellung von Propylenoxid aus Propen und Wasserstoffperoxid oder Hydroperoxiden nach den Ansprüchen 1 bis 5. 6. A process for the preparation of propylene oxide from propene and hydrogen peroxide or hydroperoxides according to claims 1 to 5.
EP97925967A 1996-06-13 1997-05-30 Process for producing epoxides from olefines and hydrogen peroxide or hydroperoxides using a zeolithic oxidation catalyst Withdrawn EP0906298A1 (en)

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