NL8403050A - Modified rhenium oxide contg. catalysts - for metathesis of functionalised olefin(s), contg. co-catalyst and cpd. of molybdenum, tungsten or vanadium - Google Patents

Modified rhenium oxide contg. catalysts - for metathesis of functionalised olefin(s), contg. co-catalyst and cpd. of molybdenum, tungsten or vanadium Download PDF

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NL8403050A
NL8403050A NL8403050A NL8403050A NL8403050A NL 8403050 A NL8403050 A NL 8403050A NL 8403050 A NL8403050 A NL 8403050A NL 8403050 A NL8403050 A NL 8403050A NL 8403050 A NL8403050 A NL 8403050A
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oxide
molybdenum
tungsten
catalyst system
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/36—Rhenium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts

Abstract

Catalyst systems suitable for the metathesis of functionalised olefins comprise an aluminium oxide carrier, rhenium oxide as catalyst component, a co-catalyst (I) and at least one cpd. of Mo, W and/or V. Pref. (I) is an organometallic cpd. such as SnR4 or PbR4 where R=alkyl, esp. methyl, ethyl or butyl. Pref. the ratio of the modifying metal to Re is at least 2, esp. W oxide in a ratio W:Re=4-10, Mo oxide in a ratio Mo:Re=4-12 or V oxide in a ratio V:Re=2-10.

Description

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BtL/UP/ag/mjh STAMICARBON B.V. (Licensing subsidiary of DSM)BtL / UP / ag / mjh STAMICARBON B.V. (Licensing subsidiary of DSM)

Uitvinders: Johannes C. Mol te HeilooInventors: Johannes C. Mol in Heiloo

Xiaoding Xu te AmsterdamXiaoding Xu in Amsterdam

Godefridus C.N. van der Aardweg te Purmerend -1- PN 3580Godefridus C.N. van der Aardweg in Purmerend -1- PN 3580

KATALYSATORSYSTEEM, GESCHIKT VOOR DE METATHESE VAN GEFUNKTIOmLISEERSE OLEFINENCATALYST SYSTEM SUITABLE FOR THE METATHESIS OF FUNCTIONALIZED OLEFINS

De uitvinding heeft betrekking op een katalysatorsysteem, geschikt voor de metathese van gefunktionaliseerde olefinen, omvattende aluminiumoxide als dragermateriaal, rheniumoxide als katalysa-torkomponent» alsmede ten minste een cokatalysator.The invention relates to a catalyst system suitable for the metathesis of functionalized olefins, comprising aluminum oxide as the support material, rhenium oxide as the catalyst component and at least one cocatalyst.

5 Dergelijke katalysatorsystemen geschikt voor de metathese van gefunktionaliseerde olefinen zijn onder andere bekend uit J. Organo-met. Chem. 255 (1983) 159-171, R.H.A. Bosma et al., Heterogeneous metathesis of unsaturated esters using a rhenium-based catalyst. In dit artikel wordt een katalysatorsysteem beschreven dat een aluminium-10 oxide-drager omvat, een rheniumoxide-katalysatorkomponent en een tetraalkyltin-cokatalysator. Uit de Pranse octrooiaanvrage 2,521,872 zijn katalysatorsystemen bekend die vervaardigd worden door interaktie van een tetraalkylloodverbinding met een rheniumaluminaat op alumi-niumoxidedrager. Zulke katalysatorsystemen worden ook beschreven in de 15 Duitse octrooiaanvrage 3,229,419.Such catalyst systems suitable for the metathesis of functionalized olefins are known, inter alia, from J. Organo-met. Chem. 255 (1983) 159-171, R.H.A. Bosma et al., Heterogeneous metathesis of unsaturated esters using a rhenium-based catalyst. This article describes a catalyst system comprising an aluminum-10 oxide support, a rhenium oxide catalyst component, and a tetraalkyltin cocatalyst. Pranse patent application 2,521,872 discloses catalyst systems which are manufactured by interacting a tetraalkyl lead compound with a rhenium aluminate on an aluminum oxide support. Such catalyst systems are also described in German patent application 3,229,419.

Deze bekende katalysatorsystemen vertonen bij een hoog rhe-niumgehalte een redelijke aktiviteit terwijl de aktiviteit bij lage rheniumgehaltes slechts matig is. Het doel van de uitvinding is een katalysatorsysteem met een hoge aktiviteit en een rheniumgehalte dat, 20 in verband met de hoge kostprijs van rhenium, zo laag mogelijk is.These known catalyst systems exhibit reasonable activity at a high aluminum content, while the activity at low rhenium contents is only moderate. The object of the invention is a catalyst system with a high activity and a rhenium content which, because of the high cost price of rhenium, is as low as possible.

Verrassenderwijs is nu gevonden, dat katalysatorsystemen die op basis van een aluminiumoxide-drager naast rheniumoxide ook nog ten minste een molybdeen-, wolfraam- en/of vanadiumverbinding bevatten, aktiever zijn dan de de tot nu toe békende katalysatorsystemen. Dit is 25 des te verwonderlijker, omdat katalysatoren bestaande uit molybdeen-oxide/ aluminiumoxide of wolfraamoxide/aluminiumoxide, die bekend zijn 8403050 j> « -2- als metathese-katalysatoren werkzaam bij hoge temperatuur, onder milde reaktieomstandigheden niet aktief zijn, zelfs niet bij de metathese van niet-gefunktionaliseerde olefinen. Ook in aanwezigheid van een cokatalysator zijn deze katalysatoren niet aktief in de metathese van 5 gefunktionaliseerde olefinen. Vanadiumverbindingen op zich zijn niet bekend als metathesekatalysatoren, ook niet in kombinatie met een drager en/of cokatalysator.It has now surprisingly been found that catalyst systems which on the basis of an aluminum oxide support, in addition to rhenium oxide, also contain at least one molybdenum, tungsten and / or vanadium compound, are more active than the catalyst systems known hitherto. This is all the more surprising because catalysts consisting of molybdenum oxide / alumina or tungsten oxide / alumina, known as metathesis catalysts operating at high temperature, are not active under mild reaction conditions, even at the metathesis of unfunctionalized olefins. Even in the presence of a cocatalyst, these catalysts are not active in the metathesis of functionalized olefins. Vanadium compounds per se are not known as metathesis catalysts, not even in combination with a carrier and / or cocatalyst.

Voordelen van een katalysatorsysteem volgens de uitvinding zijn, dat deze aktiever en bovendien, door het lagere gehalte aan rhe- 10 niumoxide, aanzienlijk goedkoper is dan een ongemodificeerde rhenium-oxide-bevattende katalysator.Advantages of a catalyst system according to the invention are that it is more active and, moreover, due to the lower content of rheium oxide, considerably cheaper than an unmodified rhenium oxide-containing catalyst.

Onder gefunktionaliseerde olefinen wordt verstaan olefinen die een funktionele groep bevatten, met de algemene formule:Functionalized olefins are defined as olefins containing a functional group, having the general formula:

Rich - CH(CH2)nx 15 met Η.χ= H of alkyl, Xs* een funktionele groep, zoals bij voorkeur -COOR3 of -CN, met R2 en R3 = alkyl, n > 1.Rich - CH (CH2) nx 15 with Η.χ = H or alkyl, Xs * a functional group, such as preferably -COOR3 or -CN, with R2 and R3 = alkyl, n> 1.

Onder metathese van gefunktionaliseerde olefinen wordt verstaan zelfmetathese of cometathese met andere, al of niet gefunk- 20 tionaliseerde, olefinen.Metathesis of functionalized olefins is understood to mean self-metathesis or cometathesis with other, optionally or not, functionalized olefins.

Met katalysatorkomponenten worden bedoeld verbindingen die aan het dragermateriaal gebonden zijn. Dit kan bijvoorbeeld bewerkstelligd worden door het vaste dragermateriaal met een oplossing van de katalysatorkomponent(en) te impregneren en te kalcineren.Catalyst components are understood to mean compounds bonded to the support material. This can be accomplished, for example, by impregnating and calcining the solid support material with a solution of the catalyst component (s).

25 Cokatalysatoren zijn daarentegen niet aan het dragermateriaal gebonden. Zij kunnen apart gedoseerd worden en bevinden zich gedurende de reaktie in het reaktiemengsel waar zij, gezien hun invloed op de konversie, vermoedelijk interaktie hebben met de drager/katalysator-komponent(en) en/of het substraat.Cocatalysts, on the other hand, are not bound to the support material. They can be dosed separately and are in the reaction mixture during the reaction where, because of their influence on the conversion, they presumably interact with the support / catalyst component (s) and / or the substrate.

30 Als cokatalysator kunnen onder meer organometaalverbindingen toegepast worden, zoals bijvoorbeeld SnR4, of Pblfy, waarbij R alkyl voorstelt. Dit alkyl kan methyl, ethyl of butyl, maar ook een andere verbinding zijn. De voorkeur gaat uit naar tetraethyltin eh/of tetra-butyltin.As a cocatalyst, organometallic compounds can be used, such as, for example, SnR4, or Pblfy, wherein R represents alkyl. This alkyl can be methyl, ethyl or butyl, but also another compound. Preference is given to tetraethyltin and / or tetrabutyltin.

35 Katalysatorsystemen volgens de onderhavige uitvinding omvat ten bij voorkeur als molybdeen-, wolfraam- en/of vanadiumverbinding de 84 0 3 0 5 0 -3- oxiden van deze metalen. Katalysatoren met de hoogste aktiviteit bevatten molybdeenoxide, wolfraamoxide en/of vanadiumoxide in een zodanige hoeveelheid, dat de verhouding van ander metaal tot rhenium ten minste 2 is. In het geval van wolfraamoxide is de verhouding W : Re 5 bij voorkeur tussen 4 en 10, in het geval van molybdeenoxide Mo : Re tussen 4 en 12, en bij vanadiumoxide V : Re tussen 2 en 10.Catalyst systems according to the present invention preferably comprise, as molybdenum, tungsten and / or vanadium compound, the 84 0 3 0 5 -3-oxides of these metals. Highest activity catalysts contain molybdenum oxide, tungsten oxide and / or vanadium oxide in such an amount that the ratio of other metal to rhenium is at least 2. In the case of tungsten oxide, the ratio W: Re 5 is preferably between 4 and 10, in the case of molybdenum oxide Mo: Re between 4 and 12, and in the case of vanadium oxide V: Re between 2 and 10.

De volgorde waarin men de katalysatorkomponenten op de drager aanbrengt, is van invloed op de aktiviteit van de katalysator. De beste resultaten worden bereikt wanneer men eerst het rheniumoxide op 10 de drager aanbrengt en daarna pas de andere komponent(en). Dit aanbrengen kan op op zich bekende wijze geschieden, evenals de daarop volgende aktivering.The order in which the catalyst components are applied to the support influences the activity of the catalyst. The best results are obtained when the rhenium oxide is first applied to the carrier and only then the other component (s). This application can take place in a manner known per se, as can the subsequent activation.

De uitvinding zal nu worden toegelicht aan de hand van enige voorbeelden: 15 A. Bereiding van de katalysatoren 10 g γ-alumina (Ketjen, CK 300, 195 m^/g, 185-250 μτη) werd bij 293 K geïmpregneerd met een waterige oplossing bevattende 0,342 gr NR^ReQq.. pit mengsel werd ingedampt, gedroogd bij 383 K en gekalci-neerd gedurende 2 uur bij 823 R in een droge zuurstofstroom. Daarna 20 werd het poeder geïmpregneerd met een waterige oplossing van de andere katalysatorkomponent(en) zoals aangegeven in de tabel, kolom 2, ingedampt en gedroogd bij 383 K.The invention will now be elucidated on the basis of a few examples: 15 A. Preparation of the catalysts 10 g γ-alumina (Ketjen, CK 300, 195 m ^ / g, 185-250 μτη) was impregnated at 293 K with an aqueous solution containing 0.342 g NR ^ ReQq. kernel mixture was evaporated, dried at 383 K and calcined for 2 hours at 823 R in a dry oxygen stream. Then the powder was impregnated with an aqueous solution of the other catalyst component (s) as indicated in the table, column 2, evaporated and dried at 383 K.

Aktivering vond plaats door de katalysator gedurende 4 uur bij 823 K te kalcineren, eerst 2 uur in een droge zuurstofstroom en 25 vervolgens 2 uur in een droge stikstofstroom.Activation was effected by calcining the catalyst at 823 K for 4 hours, first 2 hours in a dry oxygen stream and then 2 hours in a dry nitrogen stream.

B. De metathesereaktieB. The metathesis reaction

De metathesereaktie werd uitgevoerd in een glazen kolf van ongeveer 30 ml inhoud waarin een argon-atmosfeer in stand werd gehouden. Aan de kolf werden onder roeren na elkaar toegevoegd: 100 mg 30 katalysator, 1 ml oplosmiddel (n-hexaan) met daarin 7,2 x 10”6 mol cokatalysator volgens de tabel, kolom 3, en 250 μΐ methyloleaat. De reaktie werd bij kamertemperatuur uitgevoerd. De gevormde reak-tieprodukten waren 9-octadeceen en dimethyl-9-octadeceendioaat.The metathesis reaction was carried out in a glass flask of about 30 ml content in which an argon atmosphere was maintained. To the flask were added successively with stirring: 100 mg of catalyst, 1 ml of solvent (n-hexane) containing 7.2 x 10 6 mol of cocatalyst according to the table, column 3, and 250 µl of methyl oleate. The reaction was carried out at room temperature. The reaction products formed were 9-octadecene and dimethyl-9-octadecenedioate.

8403050 -4- »> «»· C. Analyse8403050 -4- »>« »· C. Analysis

De reaktie werd gevolgd door middel van gas-vloeistof-chromatografie (GLG). Voor het schatten van de molekulaire respons werd de Ackman-methode gehanteerd (R.G. Ackman and J.C. Sipos, J. of 5 Chromatography, 16, 1964, 298, en R.G. Ackman, J. of Gas Chromatography, 2, 1964, 173).The reaction was monitored by gas-liquid chromatography (GLG). The Ackman method was used to estimate the molecular response (R.G. Ackman and J.C. Sipos, J. of 5 Chromatography, 16, 1964, 298, and R.G. Ackman, J. of Gas Chromatography, 2, 1964, 173).

Reaktiemengsels van esters werden geanalyseerd met behulp van een carbowax 20M- of UCC-W-982-kolom. De reaktieprodukten werden geïdentificeerd door vergelijking met de retentietijden van bekende 10 monsters.Reaction mixtures of esters were analyzed using a carbowax 20M or UCC-W-982 column. The reaction products were identified by comparison to the retention times of known samples.

De katalytische aktiviteit wordt uitgedrukt als de konversie na 90 minuten reaktietijd.The catalytic activity is expressed as the conversion after a 90 minute reaction time.

« 840 30 5 0 it i-s -5-«840 30 5 0 it i-s -5-

TA.BELTABLE

voorbeeld katalysator geïmpregneerd met} cokataly- atoonrverhouding katalytische sator: metaal : Re i A3 aktiviteit, % verg· 1 Sa(C^ )4 0 : j. : 154 1example of catalyst impregnated with} cocatalyst ratio catalytic converter: metal: Re i A3 activity,% po · 1 Sa (C ^) 4 0: y.: 154 1

2 0,579 gr NH4VO3 Sa(CH3)4 4 : 1 : 154 B2 0.579 g NH4VO3 Sa (CH3) 4 4: 1: 154 B

3 0,869 gr NS4VO3 Sa(C^4 6 : 1 : 154 15 4 1,159 gr NH4VO3 Sn(GH3)4 8 : 1 : 154 16 5 1,448 gr NH4VO3 Sn(C^)4 10 : 1 : 154 17 6 0,875 gr (NH4 )^07024 *4- H2O Sa(C^)4 4 : 1 : 154 14 7 1,312 gr (NH4 )6^07 Ο24 ·4 H2O Sa(003)4 6 : 1 : 154 23 8 1,749 gr (ΝΒ4)6Μο7θ24·4 H2O Sa(C%)4 8 : 1: 154 19 9 1,406 gr (ϊίΗ4)2»04 80(0¾)4 4 : 1 : 154 12 10 2,8B gr (NH4)2W04 Sa(C^)4 8 : 1 : 154 19 verg. 11 - Sq(C2H5)4 0 : 1 : 154 6 12 0,875 gr (NH4 )6^07024 ·4 H20 Sa(C2H5)4 4 : 1 : 154 44 B 1,312 gr (ΝΗ4)6Μο7θ24·^ H2O Sa(02^)4 6 : 1 : 154 4 6 14 1,749 gr (NH4)6^07024 ·4 H2O Sa(¢205)4 8 : 1 : 154 43 15 1,312 gr (004)6^07024«4 02Ö Sa(C4Hg)4 6 : 1 : 154 4 5 16 1,312 gr (ΝΗ4)6Μο7θ24 ·4 H2O Pb(C2H5)4 6 : 1 : 154 19 17 1,312 gr (NH4)6Mo7Ö24 ·4 H20 Pb(C4H9)4 6 : 1 : 154 22 84030503 0.869 g NS4VO3 Sa (C ^ 4 6: 1: 154 15 4 1.159 g NH4VO3 Sn (GH3) 4 8: 1: 154 16 5 1.448 g NH4VO3 Sn (C ^) 4 10: 1: 154 17 6 0.875 g ( NH4) ^ 07024 * 4- H2O Sa (C ^) 4 4: 1: 154 14 7 1,312 g (NH4) 6 ^ 07 Ο244 H2O Sa (003) 4 6: 1: 154 23 8 1,749 g (ΝΒ4) 6Μο7θ24 · 4 H2O Sa (C%) 4 8: 1: 154 19 9 1.406 gr (ϊίΗ4) 2 »04 80 (0¾) 4 4: 1: 154 12 10 2.8B gr (NH4) 2W04 Sa (C ^) 4 8: 1: 154 19 col. 11 - Sq (C2H5) 4 0: 1: 154 6 12 0.875 g (NH4) 6 ^ 07024 · 4 H20 Sa (C2H5) 4 4: 1: 154 44 B 1.312 g (ΝΗ4 ) 6Μο7θ24 · ^ H2O Sa (02 ^) 4 6: 1: 154 4 6 14 1,749 g (NH4) 6 ^ 07024 · 4 H2O Sa (¢ 205) 4 8: 1: 154 43 15 1,312 g (004) 6 ^ 07024 «4 02Ö Sa (C4Hg) 4 6: 1: 154 4 5 16 1,312 g (ΝΗ4) 6Μο7θ24 · 4 H2O Pb (C2H5) 4 6: 1: 154 19 17 1,312 g (NH4) 6Mo7Ö24 · 4 H20 Pb (C4H9 ) 4 6: 1: 154 22 8403050

Claims (10)

2. Katalysatorsysteem volgens conclusie 1, met het kenmerk, dat de molybdeen-, wolfraam- en/of vanadiumverbinding(en), molybdeen-oxide, wolfraamoxide en/of vanadiumoxide is/zijn.Catalyst system according to claim 1, characterized in that the molybdenum, tungsten and / or vanadium compound (s) is / are molybdenum oxide, tungsten oxide and / or vanadium oxide. 3. Katalysatorsysteem volgens conclusie 1-2, met het kenmerk, dat de 10 atoomverhouding van ander metaal tot rhenium ten minste 2 is.Catalyst system according to claims 1-2, characterized in that the atomic ratio of other metal to rhenium is at least 2. 4. Katalysatorsysteem volgens conclusie 2-3, met het kenmerk, dat de katalysator zoveel wolfraamoxide bevat dat de verhouding W : Re ligt tussen 4 en 10.Catalyst system according to claims 2-3, characterized in that the catalyst contains so much tungsten oxide that the ratio W: Re is between 4 and 10. 5. Katalysatorsysteem volgens conclusie 2-3, met het kenmerk, dat de 15 katalysator zoveel molybdeenoxide bevat dat de verhouding Mo : Re ligt tussen 4 en 12.Catalyst system according to claims 2-3, characterized in that the catalyst contains so much molybdenum oxide that the Mo: Re ratio is between 4 and 12. 6. Katalysatorsysteem volgens conclusie 2-3, met het kenmerk, dat de katalysator zoveel vanadiumoxide bevat dat de verhouding V : Re ligt tussen 2 en 10.Catalyst system according to claims 2-3, characterized in that the catalyst contains so much vanadium oxide that the ratio V: Re is between 2 and 10. 7. Katalysatorsysteem volgens conclusie 1-6, met het kenmerk, dat de cokatalysator tetraethyltin en/of tetrabutyltin is.Catalyst system according to claims 1-6, characterized in that the cocatalyst is tetraethyltin and / or tetrabutyltin. 8. Werkwijze voor het bereiden van een katalysatorsysteem volgens conclusie 1-7, met het kenmerk, dat eerst het rheniumoxide op de drager wordt aangebracht en daarna de molybdeen-, wolfraam- en/of 25 vanadiumverbinding(en), alvorens aktivering plaatsvindt·8. Process for preparing a catalyst system according to claims 1-7, characterized in that first the rhenium oxide is applied to the support and then the molybdenum, tungsten and / or vanadium compound (s), before activation takes place. 9. Werkwijze voorhet metathetiseren van gefunktionaliseerde olefinen onder toepassing van een katalysatorsysteem omvattende aluminium-oxide als dragermateriaal, rheniumoxide als katalysatorkomponent alsmede ten minste een cokatalysator, met het kenmerk, dat men een 30 katalysatorsysteem toepast volgens conclusie 1-7. 8403050 i -7-9. Process for metathetizing functionalized olefins using a catalyst system comprising aluminum oxide as support material, rhenium oxide as catalyst component and at least one cocatalyst, characterized in that a catalyst system according to claims 1-7 is used. 8403050 i -7- 10. Werkwijze volgens conclusie 9, met het kenmerk, dat de funktionele groep van het gefunktionaliseerde olefine een ester is.Process according to claim 9, characterized in that the functional group of the functionalized olefin is an ester. 11. Werkwijze volgens conclusie 9, met het kenmerk, dat de funktionele groep van het gefunktionaliseerde olefine een nitril is. J 840305üProcess according to claim 9, characterized in that the functional group of the functionalized olefin is a nitrile. J 840305ü
NL8403050A 1984-10-06 1984-10-06 Modified rhenium oxide contg. catalysts - for metathesis of functionalised olefin(s), contg. co-catalyst and cpd. of molybdenum, tungsten or vanadium NL8403050A (en)

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