IE37389L

IE37389L - Epoxidation catalyst.

Info

Publication number: IE37389L
Application number: IE730388A
Authority: IE
Original assignee: Shell Int Research
Priority date: 1972-03-13
Filing date: 1973-03-09
Publication date: 1973-09-13
Also published as: NO143520C; IT1053715B; JPS492795A; GB1424284A; ZA731655B; ES423071A1; AR196234A1; DK150593C; DE2311822A1; ES412496A2; FR2175844B2; JPS5635941B2; NO143520B; BR7301701D0; IE37389B1; FR2175844A2; NL168835C; NL7303415A; AU5316473A; CA1015761A

Abstract

1424284 Epoxidizing olefins SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ BV 9 March 1973 [13 March 1972] 11456/73 Addition to 1339309 Heading C2C [Also in Division B1] Oxiranes are produced by the reaction of one or more olefinic compounds with one or more hydroperoxides in the presence of solid catalyst comprising an inorganic oxygen compound of silicon and an oxide or hydroxide of Ti, Mo, V, Zr or B which has been contacted with an organodisilazane at elevated temperature. The olefinic compound suitably contains 2 to 60 carbon atoms and may be a C 3 to C 40 alkene which may be substituted with a hydroxyl group or halogen atom, e.g. propylene, allyl alcohol or allyl chloride. The hydroperoxide may contain 3 to 20 carbon atoms, e.g. tertbutyl- or tert-pentyl-hydroperoxide or aralkylhydroperoxides in which the hydroperoxy group is linked to that carbon atom of an alkyl side chain which is attached directly to an aromatic ring such as 1-phenylethyl-1-hydroperoxide (ethyl benzene hydroperoxide) and 2-phenylpropyl - 2 - hydroperoxide (cumene hydroperoxide). The reaction may be carried out at 0-200‹ C. The example describes the reaction of octene-1 and ethyl benzene hydroperoxide. [GB1424284A]

Description

37388 The present invention is an improvement, in or modification of the invention claimed in Patent specificat ion So. 35681 which relates to iaproved solid catalysts. their preparation, and their use for producing 5 ox irans compounds by epoxidising olefin ically unsaturated coat pound » with organic hydroperoxide coopounds according to the following general equation: \ / I \ /°\ / ! C » C + -C-O-O-H > C C + -C-O-H •/ X I / \ | olefin ic hydroperoxide oxirane hydroxyl group group group group The improved catalysts claimed in claim I of Specificat-10 ion No. 35681 comprise an inorganic oxygen compound of silicon and an oxide or hydroxide of titanium, molybdenum, vanadium, zirconium or boron, which have been treated prior to use by contact with an organic silylating agent at elevated temperatures. By using the solid catalysts of the metal/siliceous 15 oxide type as described and claiaed in Specification No. 35681 the selectivity to the desired olefin epoxides may be materially increased.

Olefinic compounds having from 2 to 60 carbon atoms can be employed in the epoxidat.ion process as referred to above. 20 Preference is given to the use of alkenes having of from 3 t.o 40 carbon atoms which may or may not be mibHt.ituted with J 7 10 a hydroxy! group or * halogen «toa, such a •» propylene, allyl Alcohol and allyl chloride. Preference u given to the use of propylene.

Suitable or gan lc hydroperoxfdeia'-e hydrocarbon hydroperoxides having of from > to 20 carbon at.om.s, such ,i s tertiary butyl hydroperox Ldi.' and irrn jiy pr-ntyl hvdri. oxide, and aralkyl hydroperoxides in which the hydropi-:-i.»y group is linked to that carbon atom of an alWvl side chain which is attached directly to an aromatic rinsj, such as, 1-phenylethyl-l-hydroperoxide and 2-phenylpropyl-2-hydr>.>-peroxide (often called ethylben/ene hydroperoxide and cuaene hydroperoxide, respectively).

Oxirane compounds are materials of established utility and many are chemicals of coanercr, in particular olefin oxides, for example, ethylene oxide and propylene oxide. Propylene oxide, for instance, may be converted into useful polymeric products by po1ymerisation or co-polynerisation.

The hydroxyl compounds resulting from the reaction aay, if so desired, be reconverted into the hydroperoxide 20 compound by dehydration, hydrogenat. ion and oxidation processes.

Catalysts consisting of a solid inortjanic oxygen compound of silicon in chemical combination with at least O.li. by weight, of an oxide or hydroxide of titanium, 25 molybdenum, vanadium, zirconium or boron show improved catalytic properties when treated with an organic silylati:ig agent. Advantageously, the siliceous solids have an 1 average specific surface of at least 1 m~/g and, preferably, 2 / 2 , ot from 2 S m /g to S00 in*/g. Preferred siliceous solids 10 contain at least wt silica. 3 7 3 8 9 Preferably, the catalysts contain t'roa 0.2? to SOl, by weight, of oxide* or hydroxides of titaniura, vanadiua, boron. molybdenum and zirconium. Catalysts which contain from 0.5 to 10%, by weight, of an oxide or hydroxide of titania on silica are preferred.

The catalysts cay jUo incbrpor.it «- i The catalysts can be prepared by a variety ot »«th Suitable impregnating solvents are non-basic oxygen-containing hydrocarbons which are substantially inert under impregnation conditions and which comprise generally from 1 to 12 carbon atoms, such as alkanols, ketones, ethers (acyclic and cyclic) and esters. Hydroxy- or oxo-sufcstituted hydrocarbons having from 1 to 8 carbon atoa.i are preferred solvents. Mono-functional alkanols having from 1 to 8 carbon atoms, such as methanol, ethanol, isopropanol and n-butanol are particularly preferred- Preferably, at least 80"i trt of the solvent is removed from the Impregnated solid before calcination.

Silylating agents suitable for use in the silyiating treatment disclosed in Specification No. 356^1 are defined therein as agents capable of binding organo-si 1 icon groups to the catalysts and include the organosilanes, organo-silylaainen and organosl lazanert.

■I 7 3 s it It has now been found thai vei> tfourl rKnilt e obtained bv using orffanos i. 1 j/anes a* the s i I y I at i nj{ agent* In accordance wit.h the process claimed in c 1 a La 1 of Specification So. 35'',!*1 Th ■ use of or ganosi 1 ^ /.ant s as silvlatinc agents is advantageous in that no corrosive components are generated when the metal uxide-un-siiioa catalyst is silylated (which is a drawback inherent in the use of chlorosilanes), and, in general, silylation using organo silazanes can be effected at lower temperatures than when using organosilanes. The selectivity towards epoxide formed using a catalyst which has been silylated with an oreanodisilazane in accordance with the present invention has proved to be excellent.

According to t.he present invention a solid catalyst comprises an inorganic oxygen compound of silicon and an oxide or hydroxide of titanium, molybdenum, vanadium, zirconium or boron, which catalyst has been contacted with an organo-disilazane at an elevated temperature. Oraano-disilazanes can be represented by the following molecular formu la: R,\ R, Si - N - Si R V I \ R1 H K6 in which RJt K,, R ^, R^, R . and R^ each independently represent a hydrogen atom or an organic tfioup providing at least one organic group is present. Preference is given to or ganod i s I la zane s in which, the various R-groups are hydronen or alkyl group* with up to " carbon atoms. such as methyl, ethyl or- isopropyl groups. 37380 Exaaplea of suitable organo-disi la'onea are 1,2-diethyld isilazane; 1,1,2,2-tetramethyId is ilazane; 1,1,1,2,2,2-hexaa«thyldisilasane; 1,1,2,2-tetraethyldi-silazane and 1,2-diisopropyldisilazane. Organodisilazanes containing as R-groupa 4 or 6 lower alkyl groups, each R-group having t'rcan 1 t-o 4 carbon atamK, are preferred, hexamethy Id is i la /.anc being particularly preferred.

Generally, the catalysts to be silylatod in accordance with the present invention contain from 0.2% to 10$, by weight, based on the entire catalyst., of an oxide or hydroxide of titanium, vanadium, boron, molybdenum and zirconium, in cheaical combination with silica and/or inorganic silicate. Very suitable catalysts contain froai 0.5^ to 8%, by weight, of an oxide or hydroxide of titanium in cheaical combination with silica. A preferred catalytt for treataent with an organodisilazane consists substantially of ailica chemically combined with from O.S£ to $%, by weight, of titanium oxide.

The catalysts to be treated may contain non-interfering and/or catalyst-promoting substances. Suitable promoters are, for exraple, the alkali metals or alkaline earth metals as oxides or hydroxides. Preferred amounts of alkali metal additions are in the range 0.01X to $f, by weight, based on the entire catalyart. An excellent catalyst contains substantially silica in cheaical combination with from 0.5^ to 5%, by weight, of titanium oxide and from O.OlJ to 5%. by weight, of calcium, in the form of calcium oxide, as proaoter.

The silylation may be accomplished in a variety of aanners as described in Specification No. 35681. The .! 73s silylation may be cairird out liatch-m or a* o'"C to ^^0UC iwin^ particularly preferred.

The length of tine required for the silylat inif agent to react/ with the catalyst nurf«cr depends in part on the temperature easployed. Generally, times of from 0.1 to 4-hours are applicable; from 0.1 to s hours being particularly suitable.

The amount of silylating agent employed can vary widely. Amounts of silylating agent ot' from 1<. by weight. , based on the entire catalyst composition, to 75<, by weight, are suitable, amounts of from 2< to >04, by weight, being preferred. The silylating treatment may be repeated several t imps. For reasons of oper.it ing economy j single treatment is generally preferred.

It ha.s been found that best results are often achieved by applying a hydrating treatment to the metal/silica catalyst prior to silylation. The hydrating treatment involves contacting the catalyst (prior to silylation) with water and then heating it. or by contacting the catalyst with steam at elevated temperatures, in general above 100°C, preferably in the range 1S0°C to 450°C , for tram 0.5 to 6 hours. Good results have been obtained by effecting the hydrat.ing treatment hv steaming at a temperature of 100°C - 4 >0°C tor from 1 to ti hours.

The preiwnt invent ion in illustrated by the l'»l lowing Bxuples EXAMPLE.

A 1480 ( batch of coaaercla I silica gel (Davison I.D. j grade silica 14-30 aeah) wa* contacted with a solution uf 130 g of tetra iaopropyi t. i tanj t.e .ami '>7 u ol jci-t.y l.ici.-t orm in 1.2S litre* of ixoprcipanul . The impreifnati-it silica 1 was charged t.o an electrically hinted calcination and dried to a bed temperature of 500°C under a nitrogen blanket 10 Air was then admitted and the tempera!.ur« wax raised t.o 800°C. Thia tempera ture wan maintained during i'our hours in order to burn off rewldual carbon and to chemically combine thoroughly the ailica and titania, 1183 g of this material were then rehydrated by contact with steam at 1$ 400°C for 3 hours. This rehydrated aiaterial was cooled to 200°C and then contacted with hexamethyldisilazane vapour at 200°C for 1 hour to give a silylated catalyst according to the present invention. 75 ( of hexamethyldisilazane were taken up by the catalyst. 20 The catalyst as described above as well as a similar catalyst which had, however, not been treated with hexamethyldisilazane were comparatively tested as catalysts for the epoxidation of olefins. In each test a 1 g sample of catalyst was contacted with 17 g of octene-1 and 28.6 g of 25 a 12% by weight solution of ethyl/benzene hydroperoxide in ethyl/benzene in a 100 ml glass reactor. The reaction temperature was 100°C and the reaction time was 1 hour. The results are given in the Table: - 8 - 3 7 3 s !i TABLE Hydroperox ld«; K|>oi ide Catalyst conversion {%) selectivity (<) Onsil ylatetl 72 Silylated 9S The da+a given in the Tahl<* clearly ilemon.strati: that, the silylated catalyst given a markedly higher selectivity to the desired epoxide.

Claims

1. CLAIMS 5 1. A solid catalyst comprising an inorganic oxygen coapound of silicon and an oxide or hydroxide of titanium, molybdenum, vanadium, zirconium or horon, which catalyst, has been contacted with an organo-disilazane at an elevated temperature. 10

2. A catalyst as claiaed in claim 1, wherein said elevated temperature is a temperature of up to 4 50°C. 3- A catalyst as claimed in claim 1 or claim 2, which comprises, prior to said contacting, at least. 0.1%. by weight, of said oxide or hydroxide. 15 4. A catalyst, as claiaed in any one ot the preceding claims wherein said inorganic oxygen compound of Hi 1 icon contains a ma.ior proportion of silica and has an average 2 , specific surface area of at least 1 m /g. 5. A catalyst as claimed in claim 4, wherein said 20 inorganic oxygen compound of silicon contains at least 99%, by weight, of silica, and has a specific surface area in 2 the range 25 to 800 m /g. 6. A catalyst as cleimed in any one of the preceding claimc, which comprises, prior to said contacting, 0.2 to 25 10t, by weight, of said oxide or hydroxide. _ <) - 3 7 3 8 D 7. A c»t4ly*t as cliiited in clu ia 6, which cuaprlseN prior to said contacting froa 0.5 to 81, by weight, of r*a id oxide or hydroxide. 8. A catalyst as claiaed in any one of the preceding 5 claias. wherein said organodisilazane contains at leant one* hyclrocar l>y 1 i t u oi •: witn up t<> "> tjrhuii alous. 9 . A cataly.it as c i a ined in cl jla .*■, fcnerma said organodisilazane contains 4 or 6 hydrocarbyl subrtt.it ucrits . 10. A catalyst as claiaed in claira wherein said 10 disilazane is hexaaethyldisila/ane. 11. A catalyst as claiaed in any one of the preceding clalas, wherein the aaount of organodisilazane silylating agent is froa 1% to 7S%, by weight, with respect to the total aaount of catalyst with which it is brought into 1 5 contact. 12. A catalyst an claiaed in claia 11, wherein said aaount is in the range 22 to 50f, by weight . 13. A catalyst as claiaed in any one of the preceding claias, which catalyst prior to the silylating treataent 20 has been sujbected to a hydrating treataent. 14. A catalyst as clsiaed in claia 13. wherein said hydration treataent is effected by contacting the catalyst with water, and then heating it. 1$. A catalyst as claiaed in claia 13. wherein said 2 5 hydration treataent is effected by contacting the catalyst with steaa at a tesperature above 100°C. 16. A catalyst as claiaed in claia 1 and substantially as hereinbefore described with particular reference to the Example. 30 17. A process for preparing a catalyst as claiaed in - 10 - any on>' nf ♦ Im eta late, when- in a nUtuin ol am Inorfiiiilr nllicMOua aol Id and *aid oiiiln or hydroxide in calcln« prrcrrtnl by a hydratinij I I'Cjtarni . 1 ^ . A procens ah claiaed in claim 17, wherein a MiltceouM support if* Impregnated with a suitable titanium, nolybdenum, vanadium, zirconium or boron-containing solution, and the resulting product after calcination is subjected to said silylating treatment with an organodi-silizane, which may be preceded by a hydrating treatment. 19. A process as claimed in claim IS, wherein an inorganic siliceous solid is impregnated with a substantially non-aqueous solution of a titanium compound in a non-basic, substantially inert, o*ygen-substitut.ed hydrocarbon solvent.. 20. A process n* claimed in claim 19, wherein the organic solution contains from 0.01 to 1.0 mole of titanium p«r litre. 21. A process a* claimed in claim 19 or claim 20, wherein the organic solution additionally contains at least one alkali metal or alkaline earth metal. 22. A process as claimed in any one of claims 19-21, wherein at least 80< w of the solvent is removed from the impregnated solid before calcination. 2.1. A process aa claimed in any one of claims 17-22, wherein the organo-disilazane has at least four hydrocarbvl substitiients each with from 1 to S carbon atoms, and the flilylatlntf temperature is in the rani{e 1.00°C to 4 $0°C „ 24- A process as claiaed in claia 23, »h«rrln the orgwio-disilasane containa at least four methyl groups. 25. A process as claiaed in claim 23 or claia 24, wherein the silylating temperature in in the range 100°C to 300°C. 26. A process as clainx.-d 111 any one «t claim* - >—j. wherein the organodusi lazane is hcxamet hy 1 d i s 1 la/.ai:c . 27. A process as claiaed in any one of claias 17-26, wherein the amount of organo-disilazane used is in the range 1< to 75%, by weight, with respect t.o the total amount of catalyst with which it is brought into contact. 28. A process as claimed in claim 27, wherein the aaount of organodisilazane used is in the range 2% to $0%, by weight, with respect to the total amount of catalyst with which it is brought into contact. 29* A process as claimed in any one of clains 17-25, wherein prior to the contacting the catalyst io subjected to a hydrating treataent. 30. A process as claimed in claim 29, wherein said hydrating treatment is effected by contacting the catalyst with water, and then heating it. 11. A process as claimed in claim 29, wherein said hydrating treataent is effected by contacting the catalyst with steam at a temperature above 100°C. 32. A process as claiaed in claim 17 for preparing a catalyst and substantially as hereinbefore described with particular reference to the Example. 33- A catalytic process for reacting one or more olefinic compounds with one or more organic hydroperoxides so as to produce one or more oxirane compounds, wherein a :t 7 :t s rat* I y»t ax c l« iar<1 in any n»p ol claim* l-lh t •. uwil. 14 ■ A process am claiaed in claim I !, whorrin the reaction Is carried out at a temperature in the range 0"f to 200°C. S 3 S • A process an clai.med in claim <3 or claim <4, wherein an nlof inic compound having I'nia _ i »i no i-ji-hi.n atoms in employed. 16. A process as claimed in claim : . whi'i-cin said olefinic compound in an alkene of from "to 40 carbon atoms, 10 which may or may not bo substituted wit.h a hydroxyl jjroup or a halogrn atom. 37. A process as claimed in claim «t>. wherein sa id olefinic compound is propylene. 38. A process as claiaed in claim ?t>. wherein sa id 15 olefinic compound is allyl chloride. 39. A process a«» claimed in claim 36. wherein said olefinic compound is allyl alcohol. 40. A proccgd as claimed in any one ui' claims 11-19, wherein a hydrocarbon hydroperoxide of from 3 to 20 carbon 20 atoms is employed. 41. A process as claimed in claim 40, wherein said hydroperoxide is tertiary butyl hydroperoxide. 42. A process as claimed in claim 40, wherein said hydroperoxide is an aralkyl hydroperoxide the hydroperoxy 25 group of which is on a carbon atom attached directly to an aromatic rini(. 43. A process as claimed in claim 4~. wherein said hydroperoxide is ethyl hen/ene hydroperoxide. 44. A process as claimed in claim 1' and xuhst.an-10 tially as hereinbefore described with particulai reference to the Example. I 1 - 3 7 3 N U 4S- Oxirane coapounda prepared by the procrnn claiaed in any one of the claia a

3.H—4

4. F. R . KELLY If CO. AGENTS FOR THE APPLICANTS. -14-