CA1312626C - Preparation of phenylacetyldehydes - Google Patents
Preparation of phenylacetyldehydesInfo
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- CA1312626C CA1312626C CA000583933A CA583933A CA1312626C CA 1312626 C CA1312626 C CA 1312626C CA 000583933 A CA000583933 A CA 000583933A CA 583933 A CA583933 A CA 583933A CA 1312626 C CA1312626 C CA 1312626C
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- zeolite
- general formula
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- catalyst used
- phosphate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
- 28 - O.Z. 0050/39603/40063 Abstract of the Disclosure: Phenylacetaldehydes of the general formula I
(I) where R1 to R5 are each independently of the others hydrogen, halogen or unsubstitutad or halogen-substituted alkyl, alkenyl, alkoxy, alkylthio or cycloalkyl, are prepared by a) reacting an epoxy of the general formula II or a phenylglycol of the general formula III
(II) or (III) where R1 to R5 are each as defined above and Y and Z can be identical to or different from each other and are each hydroxyl, alkoxy, aryloxy or acyloxy, in the gas phase over a borosilicate zeolite catalyst at from 70 to 200°C
under reduced pressure, or b) reacting a glycidic ester of the general formula IV
(I) where R1 to R5 are each independently of the others hydrogen, halogen or unsubstitutad or halogen-substituted alkyl, alkenyl, alkoxy, alkylthio or cycloalkyl, are prepared by a) reacting an epoxy of the general formula II or a phenylglycol of the general formula III
(II) or (III) where R1 to R5 are each as defined above and Y and Z can be identical to or different from each other and are each hydroxyl, alkoxy, aryloxy or acyloxy, in the gas phase over a borosilicate zeolite catalyst at from 70 to 200°C
under reduced pressure, or b) reacting a glycidic ester of the general formula IV
Description
~3~66~J~
Preparation oE phenylacetaldehydes The present inven-tion relates to a process for preparing phenylacetaldehydes Erom styrene oxides, phenylglycols or glycidic esters in -the presence of zeolites or other ca-talysts.
It is known to prepare phenylace-taldehydes by dehydrogenation of phenylethanols with par-tial conversion and high-loss separation of starting materials and end product. Owing to the thermolability of phenylace-tal-dehydes, the frac-tionating step of the process leads to the formation of self-condensation products and thus to yield losses. Nor is it possible to prepare halogen-containing phenylacetaldehydes in -this way, since halogen is eliminated under the reaction conditions.
Furthermore, the prepara-tion of phenylace-tal-dehydes by catalytic rearrangemen-t of styrene oxides is known. In general, again the reaction does not go to completion and difficult--to-remove by-products are obtained.
2Q EP-A-100,117 published on Feb. 8, 1984 to ANIC
S.P.A. describes the reaction of styrene oxide and of styrene oxides with alkyl or alkoxy substi-tution on the aromatic nucleus over titanium-containing zeolites in -the liquid phase at 30 to 100C to give ~-phenylacetaldehydes.
The catalys-t has to be expensively prepared from costly high-purity starting materials such as tetraalkyl or-thosilicate, tetraalkyl orthotitana-te and tetrapropyl-ammonium hydroxide. There are other prior art methods for rearranging epoxies to carbonyl compounds. For instance, cyclododecanone is obtained over Pd- or Rd- doped A12O3 from epoxycyclododecane (Neftekhimiya 16 (1976), 250-254). It is expressly pointed out that zeolites are not suitable for this reaction. Similarly, the use of A-zeolites for the rearrangemen-t of butylene oxide to butyraldehyde has been . ~
.~
~3~2~
described (~lokkaido Daigaku Kogakybu Hokuku 67 (1973) 171-178). The Selec-tivity (55-72%) leaves something to be desired. Azeolite ca-talysts are diEficult -to regenerate following deactivation by coking, since at the temperatures of about 500C required for regeneration the crystal structure of these æeolites is destroyed.
Furthermore, EP-A-228,675 published on July 1~, 1987 to BASF A.G. discloses a process for preparing phenylacetaldehydes from styrene oxides or phenylethylene glycols wherein zeolites of the pentasil, mordenite, erionite, chabazite or L type are used and the reaction is carried out a-t from 200 to 500C, preferably at from 200 to 400 C, under atmospheric pressure. The selec-tivities and lifetimes of the catalysts leave some-thing -to be desired, in particular if halogenated styrene oxides or phenylethylene glycols are used.
It is also known that phenylace-taldehydes can be obtained by rearrangement of styrene glycol over aluminum silicates having an SiO2:A12O3 ratio of from 80:20 to 93:7 and mixed Eor example with iron oxide, calcium oxide or magnesium oxide or over activa-ted clay in suspension under reduced pressure. Common to these two processes is that the yields of from 50 to 86~ are still deserving of improvement.
Nor is this process flexible, since halogenated compounds are not obtained. Clay is a na-tural mineral of which, depending on its provenience, has different compositions and hence different cataly-tic properties and selectivities.
This is an obstacle in particular to a continuous industrial process.
Aldehydes can also be obtained in a Rosenmund reduction from carbonyl chlorides. Such reactions proceed smoothly in the liquid phase with acryloyl chloride. With other acid chlorides, eg. aralkylcarbonyl chlorides, the yields are in general lower and the catalyst is poisoned.
~-3:~$~
- 2a -I-t is an object of the present inven-tion -to develop a process for preparing the phenylacetaldehydes of the formula I from readily accessible s-tarting ma-terials with high conversions in the presence of a catalyst which shall be readily available and show high activity and high selectivity coupled with long times on stream. Moreover, the catalys-t shall be readily ///
/
/
~ 3~2~
- 3 - O.Z. 0050/39603/40063 regenerable in thi~ proces~.
We hav~ found that this ob~ect i3 achieved with a p~oce~ for preparing a phenylacetaldehydQ of the general formula I
- R2 Rl o R 3~CH 2--C~
R4 R5 H (I~
whero Rl to Rs are each indepe~dently of the o~hers hydrog~n, halogen or un3ub3titutQd or halogen-sub~tituted alkyl, alkenyl, alkoxy, alkylthio or cycloalkyl, which comprisa~ reacting an epoxy of the gan~ral formula II or a phanylglycol of the general formula III
R3 ~ CH~C~2 (II) o~ R3 ~ c iH2 (III) R4 RS R~ Rj whare R~ to Rg are each a~ defined above and ~ a~d Z can be identical to or different fro~ e~ch other and are each hydroxyl, alkoxy, arylo~y or acylo~y, in th~ ga~ phasa over a boro~ilicate zeolit0 cat~lyst at fro~ 70 to 200C
under recluc0d pre~ure, or react~ng a glycidic estex of the general fonmula IV
R2 Rl o o R ~/H--C\l~C//
R~R 5 oR6 ( I~l ) 20 wher~ o Rs ~re each as defined above and R6 is tert butyl or i-propyl, in the liguid or gas pha~e in the pre3ence of a zeolitQ and~or phosphate and/or phosphoric or boric acid on 8 carrier material and/or an acidic metal oxide at fro~ 50 to ~OQC under a pre~ure of from 0.01 to 50 mbar.
The proce~3 according to the invention h~lp~ to overcome the abovementloned di~dvantage~ of the prior 2 ~ 2 ~i _ 4 _ O.Z. 0050/39603t40063 art proce~es.
Tha present invention makeh it po~sible to prepare phenylacetaldehyde~ I fxom readily acce~ible starting material~ in the presen~e of a ca-talyst which i3 notable for ready availability, high activity and ea~y regenerability. Furthermore, the cataly3t ha3 a long life, give~ high conver~ions and high -~electivitie.~ and i~ ver~atila with respect to fea~ible ~arting material~.
Advantage~ of th~ proce~ and cataly~t according to the invention are. complete conversion, no separating probl~ms, long time~ on stream, ~electivities >90~, including very good yialds from halogen-containing ~tarting materialq~ sLmpla isolAtion of the end produc~s, in general further use without ~dditional purificat~on, and ~asy regenerability of the cataly8~8 in the event o coking.
Phenylacetaldehydes I are obtainable a) by conver~ion of styTene oxide~ or phenylethylene glycols or 20 b) by conver~ion of glycidic e~ters over zeolite~ or other c~t~ly~t~.
In proce~ v~rLant ~, conver~ion i8 affected by contacting a ~tyrene o~ida ~I or a phenylglycol III with a borosilic~te zeolite at ro~ 70 to 200C under reduced pre~sure in the ga~ phaRe in ~ccord~nca with the follow-ing reactlon schQ~e:
R3 ~ /H-\H2 R ~ ~2 1 (I) R2 RIY Z R2 Rl o R 3~H--CH 2 R 3~H 2~
R4 R5 (III)R4~ R5 H (I) The re~idence tim~ ov~r ~ho cat~ly~t in the course of reaction 3hould be 1e88 than 4 econd~ (for e~2mple fro~
0.001 to 3.99 saconds), pre~rably le8~ than one econd (for ~xample from 0.001 to 0.99 seconds). Pre$er~nc~
L ~
given ~o borosilicate zeoll.tes without Al-contalning binder~.
Th~ ~ubstituentq R~ to Rs in the formulae I to III
are each lndependently of the other~ hydrogen, alkyl, alkenyl, alkoxy, alkylthio, cycloalkyl, halogen, halo-alkyl, haloalXenyl, haloalkoxy, haloalkylthio or halo-cycloalkyl.
The sub~tituent3 Y and Z in the formula III can be identical to or different from each othar and each be hydroxyl, alkoxy, aryloxy or acyloxy.
Epoxies used for the proces~ accordlny to the inventlon are for example styrene oxide, p-fluoro~tyrene oxld~, p-chloroatyrane oxide, 2t4-difluorostyrene oxlda, 3,4-dlfluoro~tyrene oxida, 2,4,5-trlfluoroatyrene oxide, o-, m- or p-trifluoromethylstyrene oxide, o-, m- or p-methyl~tyrene oxide, o-, m- or p-methoxy~tyIene oxide, 2,3,4,5-tetrafluorostyTene oxldQ, p-trifluoromethoxy-styrene oxlde, p-trifluoromethylthio~tyreno oxide, ~-fluoro-6-chlorofftyrene ox~de, 2~fluoro-4-trifluoro-methylstyrene oxide, 2-fluoro-4-trlfluoromethoxystyrena oxide and 2-mothyl-4-fluorostyrene oxida.
The phenylglycols u~ed for the procss~ aceording to the ~nvantion are for example phenylglycol, phenyl-glycol monomethyl e~her, phenyl~lycol acetate and ph~nyl-glycol monophenyl ether.
The catalyst~ used are boro~ilicate ~eolite~.
The~e c~n be ~ynthe~lzed for a~ample ~t ~rom 90 to 200~C
under autogenous pre~su~o by reactlng a boron compound, for oxample H~BO~ with a ~ilicon compound, proferably flnoly divided ~ilica, ln an aqueou~ amlne ~olution, in particular in a 1,6-hexnnedlamlna or 1 t 3-propanediamine or triethylenetetra~ine 001utlon, in the presence or absence of alkali metal or alkallne sarth metal. It i9 also pos~ible to u~e tha i~otac~ic 2eollte8 de~cribed in DE-A-3,006,471 published on August 27, 1981 to sAsF A.G.
Instead of in a~ueous amine solution the reaction can also.-take place in an ether solution, for example in diethylene glycol dimethyl ether, or in an --s_`
=1, ~, ~ 3~ 2 i~3 2~
- 6 - O.~. 0050/39603/40063 alcohol ~olution, for example in 1,fi-hexanedlol.
The boro~ilic~te ~eolite obtained af~er i~ola-tion, drying at from 100 to 160C, in particular at 110C, and calcination at from 450 to 550C, in particular at 500C to 5~0C, can be molded with a binder in a ratio of 90:10 to 40:60~ by weight, to extrudate3 or tablet~. A
suitable binder is ~ilicon dioxide, preferably finely divided SiO2. After molding, the extrudateY or ~ablet8 are dried at 110C/16 h and calcined at 500C/16 h.
Suitable catalysts are al~o obtained ~hen the i.~olated borosilicate zeolit~ is molded directly after drying and not sub~ected to a calcination until after molding. The borosilicate zeolite can be used in the pure form, without binder, as extrudate0 or tablets, the extru~ion or peptizatlon ~id~ usod b~ing for exampls ~ hylcellulose, nitric a~d, ammo~ia, amine~, 8ilico-e~t~r and graphite or mixtures thereof.
If the borosilicate zeolit~, on account of its manner of pr~para~ion, is present no~ in the catalyti-cally active, acidi~ H ~orm but in the N~ fosm, thelatter can be co~pletely vr p~rtially convarted into ~he de3ired H-for~ by ion exch~nge wikh a~moniu~ ions and ~ubsequont ealc~n~ion, or by treatment with acid30 When ~he zeoli~i~ cataly~ become d~ac~iva~0d in tha cour8e 0~ th~ r~action duQ to coklng, it i~ ad~i~able to regen~rat~ ~he catalys~ by burninq off the coke deps~it wikh ~ir or with an air~N2 mixture at from 4Q0 to 500C, in par~icular a~ fro~ 500C to 540C. This restore~
tho c~t~lyst to its initial ac~ivity level. By partial precoking it 1~ po~aible tc ad~us~ tho activity of ~he cataly~t to optimu~ selectiv$ty in r98pQCt of the desired reaction product.
To obt~in a~ high a ~electivity as po~ibl~, high conver~ion and a long tLme on ~tre~m, it i8 occasionally ad~antageous to modi~y the borosilicate zeolite. A
~uitable method of ~odifying compri8e~ for example dopins th~ molded cr unmoldod zeol~e with matal salt by ion ~ 3 2 ~
- 7 - o.z. 0050/39603/40063 exchange or by Lmpregnation.
Advantageou~lyt doping i9 CarriQd OU~ by intro-ducing the molded boro~ilicate zeolite into a riser pipe and pa~ing an a~ueou~ or ~moniacal ~olution of a halide or nitrite o the metal o~rer it a~ from 20 to 100C. Such an ion exchange can take place, for example, with the hydrogen, ammonium or al3cali m~t~l form of the zeolite.
Another way of applying metal to the zeolite compri~e~
~mpregnating the zeolitic material with an aqueouR, alcoholic or aIm~oniacal 301u~ion of the metal or metal ~alt. Both ion exchange and impregnation are followed by at l~ast one drying ~tep, optionally by a further cal-cination .
An embodiment compri~es for ~xainple dissolving C~2CO3 in-water and impregn~ting th~ molded or unmolded zeolite with thi~ ~olution for a certain period, for example 30 minut~, and str~ pping the supernatant liquor of water in a rotary ~vaporator. Therea f ter thQ Lmpreg-nated zQolite i~ dried at about 150C and calcined a~
~0 about 550C~ This i~pregnating 8tQp can be carried out rapeatedly until the de~irad metal content i8 obtained.
It is al~o pos8ibl~ to prepare an ~m~oniacal Pd(NO3) 2 301ution and to susp~nd t~e pure pulverulent ~eolit~ th0re~n at fro~ 40 to 100C by stirring for about 2 h. After filtr~tlon, drying ~ abou~ 150C an~ calcina-tion a~ ~bout 500~C, the zeoli~ic m~t~rial thus ob~ained can be furthe~ proce~s~d with or without binders into oxtxuda~e~, pell~t8 or fluidizable m~terial.
An ~on ~xchange on the 23011te preaent in the ~-form can ~180 be carried out by lntroducing the ~eolite in extruded or pell~t for~ into a column and for example passing an ammoniacal Pd(NO3)2 801ution over it in a recycla loop at ~lightly ~levated t~mper~ture~ of from 30 to 80C for fro~ 15 ~o 20 hours. ~hi~ i8 followed by washing with watsr, drying at about 150C and calcination about 550C.
For 80me metal-dop~d 2eoli~e3 an af~ertreatment 3~
- 8 - O. æ . OOS0/39603/40063 hydrogen i~ advantageous.
A fuxther method o~ modifying the zeolite com-prise3 treating the zaolitic material, which may be in molded or unmolded form, with an acid ~uch a~ hydro-chloric acid, hydrofluoric acid or phosphoric acid and/or steam.
The cataly3t~ described here can optionally b8 u~d as from 2 to 4 ~m axtxudates or a~ tablat3 from 3 to 5 mm in diamet~r or as powders from 0.1 to 0.5 mm in particle size or in fluidizablo form.
The conver~ion of th~ epoxies or glycols i~
carried out in tha g~s pha~e at from 70 to 200C, in particular at from 120 to 170~C~ u8ing ~ weight hourly ~paca velocity (WHSV) of from Qol to 30 h-~, in particular of from 0.5 to 15 h~1 ~g of ~poxy per g of cataly~t psr hour). In gen~ral, conver~ion and selectivity remain cQnstant at increasing tempsrature, but decæease with incraa~ing residence time over the cat~ly~t. The re~ction can ba carriad out i~ a fixed bed or fluidlzed bad.
Th~ raaction is carrisd out und~r a reduced pre~sure of le~ than 1000 mbar, i~. at fro~ 0.1 ~o 999 mbar, preerably at fro~ 1 to 300 mbar.
Th~ pres~ur~ range can ba chosen in accordance with ~he boiling point o the subs~an~Q~ to be conver~ed.
If for exampl~ ~ubstance~ h~vl~g boiling point~ abova 200C u~der atmosph~ric prQ~sur~ are u~ed~ reduced pres~
sure ~ke~ it pos~ible to low~r the boiling point along the Yapor prs~3ura curve to w~thin th~ t~parature range of from 70 to 200~C. For this rea~on the reduced pr~ssure proce~ure wid~ns tho scope of application of the reaction in ~he ga~ pha3~.
Howe~sr, in tha casa of s~arting material~ who~e boiling point under atmosphsri~ pr~0sure i3 below 200C, ~he proces~ under reduced pr~s~ure i~ advantageous becau~e thi~ reduce~ th~ re~idenca ti~a o~er the cataly3t to 1s~s t~an one second. Thi~ can h~ a f~vorable effect on tAa electiv~ty.
~3~2t'~
- 9 - O.Z. 0050/39603/40063 The epoxie3 can be prepared either by epoxidation of the corre~ponding ~tyrenas or from haloacetophenone~
by hydrogenation to chlorohydrin~ or bromohydrins and by ~ub~aquent cyclization in an alkaline medium. By reac~ing S the epoxie3 with water, alcohol~, carboxylic acids or phenol~, it is po~sible to prepare further intermediates suitable for forming phenylacetaldehydes by rearrange-ment.
In process variant b), the conversion i9 effec~ed by contacting a glycidic ester IV with a zeolite and/or pho~pha~e and/or pho~phoric or boric acid on a carrier material and/or acidic metal oxide in the liquid or gaY
phas~ at from 50 to 500C under a pre33ure of from 0.01 to 50 bar in accordanc~ with the following reaction scheme:
R 3~C~CI~C ---- R 3~CH 2--C~
R4 R5 OR~ R4 R5 H
(IV~
The reaction can ba carried out not only in the liquid phase but al~o in the dLscontinuou~ or prefer~bly the continuou~ gas phase at from 50 to S00C under from 0.01 ~0 to 50 bar.
Th~ liguid pha~e reaction can be carried out for ~xampl~ by the 8uspen~ion, trickle bed or liquid-pha~e procedure a~ from 50 to 200C under fro~ 0.5 to 20 bar, pr~er~bly at fro~ 70 ~o 170C and fro~ 1 to 5 bar.
The prefarred gas pha8e react~on can be carried out for exa~ple at from 100 to 530C, preferably at from 150 to 400~, under from 0.1 to 50 bar, particularly preferably at from 200 to 350C und2r from 0.5 to 5 bar, in the pre~Qnce or ab~onc~ o~ inert ga8e8 3uch as nitro-y n or argon, in com~ cases even oxygen or ~13e for exampla ~taam. I ~he converaion i8 carried out in the gas phase, the w~ight hourly space velocity ovar the ~13~2~
- 10 - O.Z. 0050~39603/~0063 catalyst i3 advantageou~ly maintained at from 0.1 to 20, in particular at from 0.5 to S, g o~ glycidic e3ter per g o~ catalyst per hour. The gas pha~e reaction can be carried out in a fix~d bed or in a fluidized bed.
The radical~ R1 to R5, which can be identical to or different from one another, are each for example methyl, ethyl, n-ti-propyl, n~ t-butyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, trifluoromethyl, trichloromethyl, trifluoromethoxy, fluoromethyl, chloro-methyl, fluorocyclopentyl, athenyl, propenyl, butenyl, hexenyl, octenyl, decenyl, dodecenyl, cyclopentenyl, cyclohexenyl, fluorocyclopentenyl, trifluoromethylthio, fluorine or chlorine.
The radical R6 i8 tart-butyl or i-propyl.
Tho catalysts used for the proce8~ ~ccording to the inven~ion ar~ acidic z~olitic ~ataly~. Zeolites are cry~talline aluminosilicates which have a highly ordered ~tructure comprising a rigid three-dLmensional nstwork of SiO~ and AlO~ tetrahedra linXed by common oxygen atom3.
The ratio of the Si and Al ato~:oxyg~n i~ 1:2 (seo Ullmann's Encyclop~die der technischen Chemie, 4th edition, vol~me 24, p~g~ 575 ~1983)). The olectrovalence of the alu~inu~ containlng tetrahedra ia balanced by the inclu~ion of cations, for example an alkali metal or hydrogen ion, in the crystal. Cation e~change i8 pO8-~ibla. ~he spaces between the tetrahedra are occupied by wat~r ~olecule~ prior to dehydration through drying or calcination, In zeolite~, ~he alum~n~m in the lattice may al~o be raplaced by other el~ents, such 28 ~, ~a, FQ, Cr, V, A~, Sb, B~ or Be, or mixture~ thereo, or tho silicon may be repl~ced by another tetravalent element ~uch a~ Ge, Ti, Zr or Hf.
According to their structura, 2aolites are divi-ded into variou~ group~ (loc. cit.). For in~tanc~, the zeolit~ structure in th~ mordenite group is formed by tetrahedra arranged in ch~ins and in the chabasite group :~ 3 ~ ^3 ~ O.Z. 0050/39603/40063 by t~trahedra arranged in layer~, wh.ile in the fau~asite group ~hs tetrahedra form polyhedra, for e~ample in the form of a cuboctahedron which i~ composed of tetragon~
and hexagon~. Depending on the way ~he cuboctahedra are linked, which produce~ differently sized voids and pores, z~olite~ are clas~ed as type A, L, ~ or Y.
Catalyst~ suitable for the proce3s according to the invention are zeolite~ of the mordenite group or narrow-pored zeolites of the erionite or chabasite type or zeolites of the fau~a~ite type for example Y-, X- or L-zeolites. The~a groups of zeolites al o include the ultrastabla zeoli~es of the fau~a~ite typ~, ie. dealumi-nized zeolites. Method~ for preparing such zeolites ar~
described in Cataly~is by Z olites volume 5 of Studi~s Ln Surface Scionce and Catalysi~ od. B. Imelik et al.
Els~vier Scientifi~ Publishing Comp~, 1980, page 203, ~nd Cryst~l Structure~ of Ultra-stable Fau~asit~, Advances in Che~istry S~rie~ No. 1~1, Amer~can Ch~mical Society Washington DC, p2ges 226 ff ~1971), and in US Paten~
Preparation oE phenylacetaldehydes The present inven-tion relates to a process for preparing phenylacetaldehydes Erom styrene oxides, phenylglycols or glycidic esters in -the presence of zeolites or other ca-talysts.
It is known to prepare phenylace-taldehydes by dehydrogenation of phenylethanols with par-tial conversion and high-loss separation of starting materials and end product. Owing to the thermolability of phenylace-tal-dehydes, the frac-tionating step of the process leads to the formation of self-condensation products and thus to yield losses. Nor is it possible to prepare halogen-containing phenylacetaldehydes in -this way, since halogen is eliminated under the reaction conditions.
Furthermore, the prepara-tion of phenylace-tal-dehydes by catalytic rearrangemen-t of styrene oxides is known. In general, again the reaction does not go to completion and difficult--to-remove by-products are obtained.
2Q EP-A-100,117 published on Feb. 8, 1984 to ANIC
S.P.A. describes the reaction of styrene oxide and of styrene oxides with alkyl or alkoxy substi-tution on the aromatic nucleus over titanium-containing zeolites in -the liquid phase at 30 to 100C to give ~-phenylacetaldehydes.
The catalys-t has to be expensively prepared from costly high-purity starting materials such as tetraalkyl or-thosilicate, tetraalkyl orthotitana-te and tetrapropyl-ammonium hydroxide. There are other prior art methods for rearranging epoxies to carbonyl compounds. For instance, cyclododecanone is obtained over Pd- or Rd- doped A12O3 from epoxycyclododecane (Neftekhimiya 16 (1976), 250-254). It is expressly pointed out that zeolites are not suitable for this reaction. Similarly, the use of A-zeolites for the rearrangemen-t of butylene oxide to butyraldehyde has been . ~
.~
~3~2~
described (~lokkaido Daigaku Kogakybu Hokuku 67 (1973) 171-178). The Selec-tivity (55-72%) leaves something to be desired. Azeolite ca-talysts are diEficult -to regenerate following deactivation by coking, since at the temperatures of about 500C required for regeneration the crystal structure of these æeolites is destroyed.
Furthermore, EP-A-228,675 published on July 1~, 1987 to BASF A.G. discloses a process for preparing phenylacetaldehydes from styrene oxides or phenylethylene glycols wherein zeolites of the pentasil, mordenite, erionite, chabazite or L type are used and the reaction is carried out a-t from 200 to 500C, preferably at from 200 to 400 C, under atmospheric pressure. The selec-tivities and lifetimes of the catalysts leave some-thing -to be desired, in particular if halogenated styrene oxides or phenylethylene glycols are used.
It is also known that phenylace-taldehydes can be obtained by rearrangement of styrene glycol over aluminum silicates having an SiO2:A12O3 ratio of from 80:20 to 93:7 and mixed Eor example with iron oxide, calcium oxide or magnesium oxide or over activa-ted clay in suspension under reduced pressure. Common to these two processes is that the yields of from 50 to 86~ are still deserving of improvement.
Nor is this process flexible, since halogenated compounds are not obtained. Clay is a na-tural mineral of which, depending on its provenience, has different compositions and hence different cataly-tic properties and selectivities.
This is an obstacle in particular to a continuous industrial process.
Aldehydes can also be obtained in a Rosenmund reduction from carbonyl chlorides. Such reactions proceed smoothly in the liquid phase with acryloyl chloride. With other acid chlorides, eg. aralkylcarbonyl chlorides, the yields are in general lower and the catalyst is poisoned.
~-3:~$~
- 2a -I-t is an object of the present inven-tion -to develop a process for preparing the phenylacetaldehydes of the formula I from readily accessible s-tarting ma-terials with high conversions in the presence of a catalyst which shall be readily available and show high activity and high selectivity coupled with long times on stream. Moreover, the catalys-t shall be readily ///
/
/
~ 3~2~
- 3 - O.Z. 0050/39603/40063 regenerable in thi~ proces~.
We hav~ found that this ob~ect i3 achieved with a p~oce~ for preparing a phenylacetaldehydQ of the general formula I
- R2 Rl o R 3~CH 2--C~
R4 R5 H (I~
whero Rl to Rs are each indepe~dently of the o~hers hydrog~n, halogen or un3ub3titutQd or halogen-sub~tituted alkyl, alkenyl, alkoxy, alkylthio or cycloalkyl, which comprisa~ reacting an epoxy of the gan~ral formula II or a phanylglycol of the general formula III
R3 ~ CH~C~2 (II) o~ R3 ~ c iH2 (III) R4 RS R~ Rj whare R~ to Rg are each a~ defined above and ~ a~d Z can be identical to or different fro~ e~ch other and are each hydroxyl, alkoxy, arylo~y or acylo~y, in th~ ga~ phasa over a boro~ilicate zeolit0 cat~lyst at fro~ 70 to 200C
under recluc0d pre~ure, or react~ng a glycidic estex of the general fonmula IV
R2 Rl o o R ~/H--C\l~C//
R~R 5 oR6 ( I~l ) 20 wher~ o Rs ~re each as defined above and R6 is tert butyl or i-propyl, in the liguid or gas pha~e in the pre3ence of a zeolitQ and~or phosphate and/or phosphoric or boric acid on 8 carrier material and/or an acidic metal oxide at fro~ 50 to ~OQC under a pre~ure of from 0.01 to 50 mbar.
The proce~3 according to the invention h~lp~ to overcome the abovementloned di~dvantage~ of the prior 2 ~ 2 ~i _ 4 _ O.Z. 0050/39603t40063 art proce~es.
Tha present invention makeh it po~sible to prepare phenylacetaldehyde~ I fxom readily acce~ible starting material~ in the presen~e of a ca-talyst which i3 notable for ready availability, high activity and ea~y regenerability. Furthermore, the cataly3t ha3 a long life, give~ high conver~ions and high -~electivitie.~ and i~ ver~atila with respect to fea~ible ~arting material~.
Advantage~ of th~ proce~ and cataly~t according to the invention are. complete conversion, no separating probl~ms, long time~ on stream, ~electivities >90~, including very good yialds from halogen-containing ~tarting materialq~ sLmpla isolAtion of the end produc~s, in general further use without ~dditional purificat~on, and ~asy regenerability of the cataly8~8 in the event o coking.
Phenylacetaldehydes I are obtainable a) by conver~ion of styTene oxide~ or phenylethylene glycols or 20 b) by conver~ion of glycidic e~ters over zeolite~ or other c~t~ly~t~.
In proce~ v~rLant ~, conver~ion i8 affected by contacting a ~tyrene o~ida ~I or a phenylglycol III with a borosilic~te zeolite at ro~ 70 to 200C under reduced pre~sure in the ga~ phaRe in ~ccord~nca with the follow-ing reactlon schQ~e:
R3 ~ /H-\H2 R ~ ~2 1 (I) R2 RIY Z R2 Rl o R 3~H--CH 2 R 3~H 2~
R4 R5 (III)R4~ R5 H (I) The re~idence tim~ ov~r ~ho cat~ly~t in the course of reaction 3hould be 1e88 than 4 econd~ (for e~2mple fro~
0.001 to 3.99 saconds), pre~rably le8~ than one econd (for ~xample from 0.001 to 0.99 seconds). Pre$er~nc~
L ~
given ~o borosilicate zeoll.tes without Al-contalning binder~.
Th~ ~ubstituentq R~ to Rs in the formulae I to III
are each lndependently of the other~ hydrogen, alkyl, alkenyl, alkoxy, alkylthio, cycloalkyl, halogen, halo-alkyl, haloalXenyl, haloalkoxy, haloalkylthio or halo-cycloalkyl.
The sub~tituent3 Y and Z in the formula III can be identical to or different from each othar and each be hydroxyl, alkoxy, aryloxy or acyloxy.
Epoxies used for the proces~ accordlny to the inventlon are for example styrene oxide, p-fluoro~tyrene oxld~, p-chloroatyrane oxide, 2t4-difluorostyrene oxlda, 3,4-dlfluoro~tyrene oxida, 2,4,5-trlfluoroatyrene oxide, o-, m- or p-trifluoromethylstyrene oxide, o-, m- or p-methyl~tyrene oxide, o-, m- or p-methoxy~tyIene oxide, 2,3,4,5-tetrafluorostyTene oxldQ, p-trifluoromethoxy-styrene oxlde, p-trifluoromethylthio~tyreno oxide, ~-fluoro-6-chlorofftyrene ox~de, 2~fluoro-4-trifluoro-methylstyrene oxide, 2-fluoro-4-trlfluoromethoxystyrena oxide and 2-mothyl-4-fluorostyrene oxida.
The phenylglycols u~ed for the procss~ aceording to the ~nvantion are for example phenylglycol, phenyl-glycol monomethyl e~her, phenyl~lycol acetate and ph~nyl-glycol monophenyl ether.
The catalyst~ used are boro~ilicate ~eolite~.
The~e c~n be ~ynthe~lzed for a~ample ~t ~rom 90 to 200~C
under autogenous pre~su~o by reactlng a boron compound, for oxample H~BO~ with a ~ilicon compound, proferably flnoly divided ~ilica, ln an aqueou~ amlne ~olution, in particular in a 1,6-hexnnedlamlna or 1 t 3-propanediamine or triethylenetetra~ine 001utlon, in the presence or absence of alkali metal or alkallne sarth metal. It i9 also pos~ible to u~e tha i~otac~ic 2eollte8 de~cribed in DE-A-3,006,471 published on August 27, 1981 to sAsF A.G.
Instead of in a~ueous amine solution the reaction can also.-take place in an ether solution, for example in diethylene glycol dimethyl ether, or in an --s_`
=1, ~, ~ 3~ 2 i~3 2~
- 6 - O.~. 0050/39603/40063 alcohol ~olution, for example in 1,fi-hexanedlol.
The boro~ilic~te ~eolite obtained af~er i~ola-tion, drying at from 100 to 160C, in particular at 110C, and calcination at from 450 to 550C, in particular at 500C to 5~0C, can be molded with a binder in a ratio of 90:10 to 40:60~ by weight, to extrudate3 or tablet~. A
suitable binder is ~ilicon dioxide, preferably finely divided SiO2. After molding, the extrudateY or ~ablet8 are dried at 110C/16 h and calcined at 500C/16 h.
Suitable catalysts are al~o obtained ~hen the i.~olated borosilicate zeolit~ is molded directly after drying and not sub~ected to a calcination until after molding. The borosilicate zeolite can be used in the pure form, without binder, as extrudate0 or tablets, the extru~ion or peptizatlon ~id~ usod b~ing for exampls ~ hylcellulose, nitric a~d, ammo~ia, amine~, 8ilico-e~t~r and graphite or mixtures thereof.
If the borosilicate zeolit~, on account of its manner of pr~para~ion, is present no~ in the catalyti-cally active, acidi~ H ~orm but in the N~ fosm, thelatter can be co~pletely vr p~rtially convarted into ~he de3ired H-for~ by ion exch~nge wikh a~moniu~ ions and ~ubsequont ealc~n~ion, or by treatment with acid30 When ~he zeoli~i~ cataly~ become d~ac~iva~0d in tha cour8e 0~ th~ r~action duQ to coklng, it i~ ad~i~able to regen~rat~ ~he catalys~ by burninq off the coke deps~it wikh ~ir or with an air~N2 mixture at from 4Q0 to 500C, in par~icular a~ fro~ 500C to 540C. This restore~
tho c~t~lyst to its initial ac~ivity level. By partial precoking it 1~ po~aible tc ad~us~ tho activity of ~he cataly~t to optimu~ selectiv$ty in r98pQCt of the desired reaction product.
To obt~in a~ high a ~electivity as po~ibl~, high conver~ion and a long tLme on ~tre~m, it i8 occasionally ad~antageous to modi~y the borosilicate zeolite. A
~uitable method of ~odifying compri8e~ for example dopins th~ molded cr unmoldod zeol~e with matal salt by ion ~ 3 2 ~
- 7 - o.z. 0050/39603/40063 exchange or by Lmpregnation.
Advantageou~lyt doping i9 CarriQd OU~ by intro-ducing the molded boro~ilicate zeolite into a riser pipe and pa~ing an a~ueou~ or ~moniacal ~olution of a halide or nitrite o the metal o~rer it a~ from 20 to 100C. Such an ion exchange can take place, for example, with the hydrogen, ammonium or al3cali m~t~l form of the zeolite.
Another way of applying metal to the zeolite compri~e~
~mpregnating the zeolitic material with an aqueouR, alcoholic or aIm~oniacal 301u~ion of the metal or metal ~alt. Both ion exchange and impregnation are followed by at l~ast one drying ~tep, optionally by a further cal-cination .
An embodiment compri~es for ~xainple dissolving C~2CO3 in-water and impregn~ting th~ molded or unmolded zeolite with thi~ ~olution for a certain period, for example 30 minut~, and str~ pping the supernatant liquor of water in a rotary ~vaporator. Therea f ter thQ Lmpreg-nated zQolite i~ dried at about 150C and calcined a~
~0 about 550C~ This i~pregnating 8tQp can be carried out rapeatedly until the de~irad metal content i8 obtained.
It is al~o pos8ibl~ to prepare an ~m~oniacal Pd(NO3) 2 301ution and to susp~nd t~e pure pulverulent ~eolit~ th0re~n at fro~ 40 to 100C by stirring for about 2 h. After filtr~tlon, drying ~ abou~ 150C an~ calcina-tion a~ ~bout 500~C, the zeoli~ic m~t~rial thus ob~ained can be furthe~ proce~s~d with or without binders into oxtxuda~e~, pell~t8 or fluidizable m~terial.
An ~on ~xchange on the 23011te preaent in the ~-form can ~180 be carried out by lntroducing the ~eolite in extruded or pell~t for~ into a column and for example passing an ammoniacal Pd(NO3)2 801ution over it in a recycla loop at ~lightly ~levated t~mper~ture~ of from 30 to 80C for fro~ 15 ~o 20 hours. ~hi~ i8 followed by washing with watsr, drying at about 150C and calcination about 550C.
For 80me metal-dop~d 2eoli~e3 an af~ertreatment 3~
- 8 - O. æ . OOS0/39603/40063 hydrogen i~ advantageous.
A fuxther method o~ modifying the zeolite com-prise3 treating the zaolitic material, which may be in molded or unmolded form, with an acid ~uch a~ hydro-chloric acid, hydrofluoric acid or phosphoric acid and/or steam.
The cataly3t~ described here can optionally b8 u~d as from 2 to 4 ~m axtxudates or a~ tablat3 from 3 to 5 mm in diamet~r or as powders from 0.1 to 0.5 mm in particle size or in fluidizablo form.
The conver~ion of th~ epoxies or glycols i~
carried out in tha g~s pha~e at from 70 to 200C, in particular at from 120 to 170~C~ u8ing ~ weight hourly ~paca velocity (WHSV) of from Qol to 30 h-~, in particular of from 0.5 to 15 h~1 ~g of ~poxy per g of cataly~t psr hour). In gen~ral, conver~ion and selectivity remain cQnstant at increasing tempsrature, but decæease with incraa~ing residence time over the cat~ly~t. The re~ction can ba carriad out i~ a fixed bed or fluidlzed bad.
Th~ raaction is carrisd out und~r a reduced pre~sure of le~ than 1000 mbar, i~. at fro~ 0.1 ~o 999 mbar, preerably at fro~ 1 to 300 mbar.
Th~ pres~ur~ range can ba chosen in accordance with ~he boiling point o the subs~an~Q~ to be conver~ed.
If for exampl~ ~ubstance~ h~vl~g boiling point~ abova 200C u~der atmosph~ric prQ~sur~ are u~ed~ reduced pres~
sure ~ke~ it pos~ible to low~r the boiling point along the Yapor prs~3ura curve to w~thin th~ t~parature range of from 70 to 200~C. For this rea~on the reduced pr~ssure proce~ure wid~ns tho scope of application of the reaction in ~he ga~ pha3~.
Howe~sr, in tha casa of s~arting material~ who~e boiling point under atmosphsri~ pr~0sure i3 below 200C, ~he proces~ under reduced pr~s~ure i~ advantageous becau~e thi~ reduce~ th~ re~idenca ti~a o~er the cataly3t to 1s~s t~an one second. Thi~ can h~ a f~vorable effect on tAa electiv~ty.
~3~2t'~
- 9 - O.Z. 0050/39603/40063 The epoxie3 can be prepared either by epoxidation of the corre~ponding ~tyrenas or from haloacetophenone~
by hydrogenation to chlorohydrin~ or bromohydrins and by ~ub~aquent cyclization in an alkaline medium. By reac~ing S the epoxie3 with water, alcohol~, carboxylic acids or phenol~, it is po~sible to prepare further intermediates suitable for forming phenylacetaldehydes by rearrange-ment.
In process variant b), the conversion i9 effec~ed by contacting a glycidic ester IV with a zeolite and/or pho~pha~e and/or pho~phoric or boric acid on a carrier material and/or acidic metal oxide in the liquid or gaY
phas~ at from 50 to 500C under a pre33ure of from 0.01 to 50 bar in accordanc~ with the following reaction scheme:
R 3~C~CI~C ---- R 3~CH 2--C~
R4 R5 OR~ R4 R5 H
(IV~
The reaction can ba carried out not only in the liquid phase but al~o in the dLscontinuou~ or prefer~bly the continuou~ gas phase at from 50 to S00C under from 0.01 ~0 to 50 bar.
Th~ liguid pha~e reaction can be carried out for ~xampl~ by the 8uspen~ion, trickle bed or liquid-pha~e procedure a~ from 50 to 200C under fro~ 0.5 to 20 bar, pr~er~bly at fro~ 70 ~o 170C and fro~ 1 to 5 bar.
The prefarred gas pha8e react~on can be carried out for exa~ple at from 100 to 530C, preferably at from 150 to 400~, under from 0.1 to 50 bar, particularly preferably at from 200 to 350C und2r from 0.5 to 5 bar, in the pre~Qnce or ab~onc~ o~ inert ga8e8 3uch as nitro-y n or argon, in com~ cases even oxygen or ~13e for exampla ~taam. I ~he converaion i8 carried out in the gas phase, the w~ight hourly space velocity ovar the ~13~2~
- 10 - O.Z. 0050~39603/~0063 catalyst i3 advantageou~ly maintained at from 0.1 to 20, in particular at from 0.5 to S, g o~ glycidic e3ter per g o~ catalyst per hour. The gas pha~e reaction can be carried out in a fix~d bed or in a fluidized bed.
The radical~ R1 to R5, which can be identical to or different from one another, are each for example methyl, ethyl, n-ti-propyl, n~ t-butyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, trifluoromethyl, trichloromethyl, trifluoromethoxy, fluoromethyl, chloro-methyl, fluorocyclopentyl, athenyl, propenyl, butenyl, hexenyl, octenyl, decenyl, dodecenyl, cyclopentenyl, cyclohexenyl, fluorocyclopentenyl, trifluoromethylthio, fluorine or chlorine.
The radical R6 i8 tart-butyl or i-propyl.
Tho catalysts used for the proce8~ ~ccording to the inven~ion ar~ acidic z~olitic ~ataly~. Zeolites are cry~talline aluminosilicates which have a highly ordered ~tructure comprising a rigid three-dLmensional nstwork of SiO~ and AlO~ tetrahedra linXed by common oxygen atom3.
The ratio of the Si and Al ato~:oxyg~n i~ 1:2 (seo Ullmann's Encyclop~die der technischen Chemie, 4th edition, vol~me 24, p~g~ 575 ~1983)). The olectrovalence of the alu~inu~ containlng tetrahedra ia balanced by the inclu~ion of cations, for example an alkali metal or hydrogen ion, in the crystal. Cation e~change i8 pO8-~ibla. ~he spaces between the tetrahedra are occupied by wat~r ~olecule~ prior to dehydration through drying or calcination, In zeolite~, ~he alum~n~m in the lattice may al~o be raplaced by other el~ents, such 28 ~, ~a, FQ, Cr, V, A~, Sb, B~ or Be, or mixture~ thereo, or tho silicon may be repl~ced by another tetravalent element ~uch a~ Ge, Ti, Zr or Hf.
According to their structura, 2aolites are divi-ded into variou~ group~ (loc. cit.). For in~tanc~, the zeolit~ structure in th~ mordenite group is formed by tetrahedra arranged in ch~ins and in the chabasite group :~ 3 ~ ^3 ~ O.Z. 0050/39603/40063 by t~trahedra arranged in layer~, wh.ile in the fau~asite group ~hs tetrahedra form polyhedra, for e~ample in the form of a cuboctahedron which i~ composed of tetragon~
and hexagon~. Depending on the way ~he cuboctahedra are linked, which produce~ differently sized voids and pores, z~olite~ are clas~ed as type A, L, ~ or Y.
Catalyst~ suitable for the proce3s according to the invention are zeolite~ of the mordenite group or narrow-pored zeolites of the erionite or chabasite type or zeolites of the fau~a~ite type for example Y-, X- or L-zeolites. The~a groups of zeolites al o include the ultrastabla zeoli~es of the fau~a~ite typ~, ie. dealumi-nized zeolites. Method~ for preparing such zeolites ar~
described in Cataly~is by Z olites volume 5 of Studi~s Ln Surface Scionce and Catalysi~ od. B. Imelik et al.
Els~vier Scientifi~ Publishing Comp~, 1980, page 203, ~nd Cryst~l Structure~ of Ultra-stable Fau~asit~, Advances in Che~istry S~rie~ No. 1~1, Amer~can Ch~mical Society Washington DC, p2ges 226 ff ~1971), and in US Paten~
4,512~961.
It is particu~arly advantageous to usa zeolite8 of ths p~nt~sil typa. Th~ir baæic bu~lding block i~ a pentagon co~po~ad of SiO~ t~trahedx~. They are charac-terizad by ~ hi~h SiO2~Al2O3 r~tio and by pore ~izes be~ws2~ those o~ zeolite~ o~ t ~ A and tho~e of type or Y (cf. UlL~nn'~ a~ cited).
The~e zeolit0~ c~n havQ different chemical compo~ition~ They can be alumino~ilicate, borosllicate or i ron, beryllium, g~llium, chro~ium, arsenic, antimony or bi~mu~h silic~te ~eolita~ or ~ixtura~ thereof and aluminogerminat~, ~orogermin~e and gallium or iron germinate zeolites or mi~tures ther20f. Particularly ~uitable for the proces~ according ~o the invention are the aluminoRilicate, boro~ilicate and iron ~ilicate zeolite~ of the pentasil type. The aluminosilicate zeolite i8 prepared for e~amplo fro~ an aluminum compound preferably Al(QH)3 or Al2(S04)3, and a silicon component, ~ 3 ~ ii2~
preferably finely divided silicon dioxide, in an aqueous amine solution, in particular in polyamines such as 1,6-hexanediamine or l,3-propanediamine or trie-thylenetetramine solution, in the presence or in particular in the absence of alkali or alkaline earth metal at from 100 to 220C under autogenous pressure. This also includes the isotactic zeolites described in EP-A- 34,727 published on September 2, 19~1 and EP-A-46,504 published on March 3, 1982, both to BASF A.G. The aluminosilica-te zeolites obtained have an SiO2/Al2O3 ratio of from 10 -to 40,000, depending on the mixing ratio of the starting materials. Such alumino-silicate zeolites can also be synthesized in an ether medium such as diethylene glycol dimethyl ether, in an alcohol medium such as me-thanol or 1,4 butanediol, or in water.
Borosilicate zeolite is synthesized under auto-genous pressure, for example at from 90 to 200C, by reacting a boron compound, for example H3BO3, with a silicon compound, preferably finely divided silicon dioxide, in an aqueous amine solution, in particular in 1,6-hexanediamine, 1,3-propanediamine or triethylene -te-tramine solution, in the presence or in particular in the absence of alkali or alkaline earth metal. They also inc~ude the isotac tic zeolites described in the above men-tioned EP-A-34,727 and EP-A-46,504. These borosilicate zeolites can also be prepared by carrying out -the reaction not in an aqueous amine solution bu-t alterna-tively in an ether solution, for example diethylene glycol dimethyl ether, or in an alcohol solution, for example 1,6-hexanediol.
Iron silicate zeolites are obtained for example from an iron compound, preferably Fe2(SO4)3, and a silicon compound, preferably finely divided silicon dioxide, in an aqueous amine solution, in particular 1,6-hexanediamine, in the presence or absence of alkali or alkaline eart metal at from 100 to 220C under autogenous pressure.
The usable high-silicon zeolites (SiO2/Al2O3 > 10) also include the various ZSM types, ferrierite,Nu-l and . ~
c~ -12 ~ ?.. ~
- 13 - O.Z. 0050~39603/400b3 Silicalit~, a silica polymorph molecular 3ieve.
The aluminosilicate, boro~ilicate and iron sili-cate zeolites thu~ prepared, after they have been i80-lated, dried at from 100 to 160C, preferably at 110C, and calcined at from 450 to 550C, preferably at 500C, can be combined with a binder in a ra~io of ~rom 90:10 to 40:60 % by weight and molded into extrudates or table~4.
Suitable binder~ are v~rious aluminum o~ides, preferably boehmite, amorphous aluminoRilicates havin~ an SiO2/Al~O3 ratio of from 25:75 to 90s5, preferably 75:25~ ~ilicon dioxidQ, preferably finely divid~d SiO~, mi~tur~s of finely divided SiO2 and finely divided ~1203, TiO2, Zr2~
and clay. After molding, th~ ~xtrudate~ or tablet~ are dried at 110C/16 h and calcined ~t 500C~16 h.
It i8 al80 po~sible to obtain advantageous cata-ly~ts by molding the i~ol~t~d al~mino~ilicAte or boro-silicate zeolit~ Lmmediately after drying ~nd ~ub~ecting it to calcination only aftar the molding. ~he alumino-~ilicats and boro~ilicate zeolito~ prepared can ~e u~e~
in ~he pure fonm, without bindar, as o~trudate~ or tab-let~, the extrusion or pepti~ation ai~æ used being for example ~thylcellulo e, ste~rlc acidt potato starch, for-mic acid, ox~lic aoid, acetic ~cidO nitric acld, ammonia, amine~, 311icoe ters and graphite or mi~ture8 th~reof, If the zeolîta, on aecount o~ i~8 m~ner of pre-paration i8 pr~sent not in th~ c~talytic~lly activa, a~idic H-form but, for s~ample, in the Na-form, it can ~e co~pletely or partially con~erted into the d~sired H~form by ~on exchange, for exa~ple with a~onium ions and 8ub8~quent calcination, or by ~reatmen~ with acids.
Should the zeolitic catalyst u~ed accordiny to the inven~ion und.ergo dea~ivation du~ ~o coking, it i advi~abl~ to regenera~e the zaoli~e by burning of f the coke d~po it with air or with ~n ~ir/N~ m~xture at from 400 to 500C, preferably at 500~C. Thi~ re~tore~ the initial activity level of the zeolite~
By partial precoking it i~ pos~ibl~ to 8Qt the - 14 - O.Z. 0050/39603/40063 activity of the catalyst for optLmum selectivity in resp~ct of the desired r~action product.
To obtain a high ~electivity, high conversions and long time~ on ~tream, it may be advantageous to modify the zeolites. A suitable method of modifying the catalysts comprises for example doping the molded or unmolded zeolite with metal salt3 by ion exchange or impregnation. The metal~ used are alkali metal~ such as Li, C~ or R, alkaline earth metals ~uch a3 Mg, Ca or Sr, metals of main groups III, IV and V, such as ~l, Ga, Ge, Sn, Pb or Bi, transition metalQ of ~ubgroups IV-VIII, such as Ti, Zr, V, Nb, Cr, Mo, W, Mn, Re, Fe, Ru, 08, Co, Rh, Sr, Ni, Pd or Pt, tran~ition metal~ of secondary group~ I or II, ~uch a3 Cu, Ag or Znl and rare ~arth metal~ Quch a~ La, Ce, Pr, Nd, Fr, Yb or U.
Advantageou~ly, doping is carried out by intro-ducing the molded zeolite into a ri~er pip~ and pa3~ing an aqueous or ammoniacAl ~olution of a halide or ni.trate of one of thQ abovementioned metal~ over it a~ from 20 to 100C. Such an ion exchange can taka place, for example, with the hydrogen, a~monium, or alkali met~l form of the zeolite. ~nothQr way of applying metal to the zeolite compri~es Lmpregnati~g the zeolitic material with, for example, a halid~, nitrate or oxide of one of the abovem0ntioned metal3 in aqueou~, alcoholic or ammoniacal solu~ion. Bo~h ion ax~hange and impregnation are folowed by at lea~t one dryinq ~tep, optionally by another calcina~ion.
A po~sible embodL~ent compri~a3 for example diY-solving Cu(NO3)2 x 3 H2O or Ni(NO3~ 2 X 6 HzO or Ce(NO~)3 x 6 H20 or La(NO3~3 x 6 H20 or Cs2C03 in water and Lmpreg-nating the molded or unmold~d zeolite with this solution for a certain period, for example 30 minutes. Any supernatant solution i~ stripp~d of water in a rotary evaporator. The impreynated zeolite i3 then dried at about 150C and calcined at about 550C~ ~his L~pregnat-ing step can b~ carried out repeatedly in succession ~ 3 ~ 3 - 15 - O.Z. 0050/39603/40063 until the de~ired metal content is obtained.
It is also poq~ibla to prepare, for example, an aqueou3 Ni( C03 ) 2 solution or ammoniacal Pd(NO3) 2 solution and to suqp~nd the pure pulverulent zeolite therein at from 40 to 100C by qtirring for about 24 hours. After filtration, drying at about 150C and calcination at about 500C, the zeolitic mat~rial thus obtained can be further processed with or without binders into extru-dates, pellets or fluidizable material.
An ion exchange on the zeolit~ peresent in the H-form or ammonium form or alkali metal form ~an be car-ried out by introducing the zeolite in extruded or pellet form into a column and for example pa~ing an aqueous Ni(N03)2 olution or ammoniacal Pd~NO3)2 301ution over i~
in a recycle loop and at ~lightly ~levated temperature~
of from 30 to 80C for fro~ 15 to 20 hour~. Thi~ i~
followed by wa~hlng out with wster, drying at about 150C
and calcination at abou~ 550C. With som~ metal-doped zeoliteq/ for exampls Pd-, Cu- or Ni-doped zeolit~, an aftertreatment with hydrog0n i~ advantageou~.
A further method of modifying the zeolite com-prises treating the zeolitic matarial, which may ba in molded or unmolded ~orm, with an acid 3uch a~ hydro chloric acid, hydrofluoric acid or phc)sphoric acid and/or steam, ad~antageou~ly, for ~xa~ple, by treating the zeolite in pulverulent form with 1 N pho~phoric acid at 80C for 1 hour and then wa~hing with water and drying at 110C for 16 hour~ and calcining at 500C in 29 hour3.
Alternatively, before or after being molded together with a binder, the zeolite is treated for example at from 60 to 80C with from 3 to 25% ~trength by weight, in par-ticular from 12 to 20~ ~trength by weight aqueou~ hydro-chloric acid for from 1 to 3 hour~. Afterwards, the zeolite thu~ treated i~ wa~hed with water, dried and calcined at from 400C to 500C.
In a particular embodiment, the acid treatment compri e~ treating the zeolitic material~ before it i~
.3~ ~
~ 16 - O.~. 0050/39603~40063 molded, ~ith in general 0.001 N to 2N, preferably 0.05 N
to 0.5 N, hydrofluoric acid at elevated temperature~l for exampl2, by refluxiny for from 0.5 to 5, preferably from 1 ~o 3, hour~. After the zeolitic material ha~ been isolated by filtering and wa~hing, it i3 advantageously dried, for example, at from 100 ~o 160C and calcined at from 450C to 600C in general. In a further praferred form of the acid trea~ment, the z~olitic material, after it ha~ been molded tog~ther with a binder, is treated a~
elevated temperatures, advantageou~ly at from 50 to 90C, preferably at from 60 to 80C, for from 0.5 to 5 hour~
with, preferably, from 12 to 20% ~trength by weight hydrochloric acid. The zeolitic material i~ in general sub3equently washed and expediently dried at, for example, from lQ0 to 160C and calcined at in general from 450 to 600C. An HF treatment can al~o be followed by an HCl treat~ent.
In anoth~r procedure, zeolite~ can be modified by applyi~g pho3phorus compoundq, ~uch a~ trimethoxyphos-phate~ trLm~tho~ypho~phine or primary, 3econdary or tertiary sodium pho~phate. Treatment with primary sodium pho~phate haq proved particularly advantageou~. To thi~
end, the ~eolit~ are Lmpregnated in extruded, tablet or fluidizable form with aqueou~ NaH2PO~ solution, dried at 110C and calcined at 500C.
Further ~ataly~ts for the proces~ according to the invantisn arQ phosphate~, in particular aluminum phosphates, silicon aluminum phosphates, ~ilicon iron alu~inu~ phosphates, ceriu~ pho~phate, zirconium phos-phate~, boron pho4pha~e, iron phospAate or mixtures thereof.
The aluminum pho~phate catalysts used for the proces~ according to the invention are in particular tho~e aluminum pho~phates which have been synthesized under hydrothermal condition~ and have a zeolite struc-ture.
Hydrothermally ~ynthe~ized aluminum phosphate are 1 3 1 2 ~ 2 i~`3 - 17 - O.~. 0050/39603/~0063 for exampla APO-5, AP0~9, APO-11, AP0-12, ~P0-14, AP0-21, AP0-25, AP0-31 and ~PO-33. Synthese~ of these compound~
are described in EP 132,708, US 4~310,440 and US
4,4~3,663.
For in~tance, AlPO~-5 (APO-5~ i~ synthesi2ed by preparing a homogeneou~ mixture of orthophosphoric acid with pseudoboehmite (Catapal SBR) in water, adding tetra-propylammonium hydroxide and then heating at about 150C
under autogenou~ pressure in an autocla~e for from 20 to 60 hours. The AlPO~ i9 filtered off, dried at from 100 to 160C and calcined at from 450 to 550C.
AlPO~-9 (APO-9) i~ likewise ~ynthesi22d from orthopho~phoric acid and pseudoboehmito but in an aqueou~
DABC0 solution (1,4-diazabicyclo[2.2.23Octane) at about 200C under autogenou3 pres~ura in th~ cour~e of from 200 to 400 hour~.
AlPO4-21 (ARO-21~ ynthesizqd from orthophos phoric acid and p~eudoboekmit~ in an aqueous pyrrolidone solution at fro~ 150 to 200C under autogenous pressure in the courqe of from 50 to 200 hour~.
Silicon aluminu~ pho~phatea ~uitable for the proce.~s according to tha invention are for exampla SAP0-5, SAPO ll, SAP0-31 and SAPO~34. ~ho synthe~i~ of thi3 compound i3 described, for axampl~, in ~ Patent 103,117 and US Patent 4,440,8~1. SAPO~ aro prepared by cry~allization from an aqueou~ mixture at fro~ 100 to 250C under autog~nou~ pres~ure in the course of from 2 hours to 2 week~ during which the reaction mixture compri~ing a silicon, aluminum and pho phorus component i~ converted into aqueou~ organoamine ~olutions.
SAP0-5, for example, i~ obtained by ~ixing a ~U9-pen3ion of SiO2 in aqueous tetrapropylammonium hydroxide solu~ion with an aqueous ~u~pension of p~eudoboahmite and orthopho phoric acid and subsequant reaction at from 150 to 200C under autogenou~ prQ~sur~ in a ~tirred auto-clave for from 20 to 200 hours. Aftsr the powder ha~
be~n filtered off, it i~ dried at from 110 to 160C and 2 ~ ~ 6 ~ O.Z. 0050/39603/40063 calcine~ at from 450 to 550~C.
Suitable pho~phoru cataly~t~ for the proce~s also includa precipitated aluminum pho~phate~. Such an aluminum pho~phate is preparad for example by dissolving 92 g of diammonium hydrog~npho~phate in 700 ml of water.
260 g of Al(NO3)3 x H2O in 700 ml of water axe added drop-wise in the cour~e of 2 hours during which pH 8 i~
maintained by the ~imultaneouQ addition of 25% ~trength NX3 solution. The resul~ing precipitate i~ subsequently stirred for 12 hour~ and then filtered off with ~uction and washed. It i~ drie~ at 60C/16 h.
Boron phosphates for the proces~ according to ~he invention are preparable for example by mixing and knead-ing concentrated boric acid and phosphoric acid and by sub~equent drying an~ calcination in inert ga~, aix or 3team atmosphere at fro~ 250 to 650C, in particul~r at from 300 to 550C.
The~e phosphat~ may b~ modified by impr~gnation (~aturation or spraying3 or in some ca~es even by ion exchange with modifying component~ as de~cribed ~bove for zeolites. As with the zeolite cataly~t~, a modification with an acid is also pos~ible.
Suitable acidic cat~ly~t~ al~o include for example the acidic oxid~ of element o~ m~in groups III
an~ I~ and of subgroups IV to VI of the periodic table, in par~icular oxides ~uch as ~ilicon ~loxide in the form of sili~a gel, diatomaceou~ earth, quartz and also titanium dioxide, zir~onium dioxid~, phosphoru~ oxides, vanadium oxide~, niobium ox1dea, boron oxide~, chromium oxide~, molybdenum oxides 9 tungsten o~idos or pumice or mixtures thereof. Similarly, thefie oxido~ may be dop~d by applying modifying componsnt~ as de~cribed above for zeolite ca~alyst3~ The treatment with acids a~ de~cribed above for zeolita catalyst i9 another pos~ible modifying treatm~nt.
It i~ al~o poR~ible to use cataly8t8 impregnated wi~h pho3phoric acid or boric acid. Phosphoric acid or ~3~2~2~
- 19 - O.Z. 0050~39603/~0063 boric acid i~ applied to SiO2, A12l or pumice carriers, for ax~mple by ~pregnating or qprayingO A phosphoric acid-containing catalys~ can be obtainQd for e~ampl~ by Lmpregna~ing SiO2 with H3P0, or N~H2~0~ o~ Na2XPO~ solution and then drying or calcini~g. ~owever, phoaphoric acid can al~o be ~prayed togeth~r with 3ilica gel in a 3pray tower, followed by drying and usually calcination.
Phosphoric acid can al80 ba ~prayed onto the carrier material in an Lmpregnating mill.
The catalysts described h~re ca~ optionally be u~ed in the form of from 2 to 4 m~ extrudate~ or as tab-lets from 3 to 5 mm in diameter or ~h chip3 h~Ylng particl~ ~izes of from 0.1 to 0.5 ~m, or in a fluidiz~lblo form.
In both ver~ioll~ of th~ proce~s a) and b) in-volatile or solid s~ar~ing ma~erial~ ~an be u~ad ln ~
dis~olved ~o~ for exampl~ in q~, toluene ar petroleum ether ~olution. A dilution w~th th~s ~olvent~ m~ntion~d i~
al~o po~sible, from 100 to 500 ~al, p:re~er~bly frolz 150 to 350 ml, of one of thes0 ss~lv0nt~ being in general su~fi-cient per ~ol~ of II, III or TV.
~f~ar the r~action ~h~ phenylace~aldehydes are isolated froD~ th~ reac~ion mixture in a conventional mann~r, for ~axan~ple by distlll~tion; u3lconver~ed ~tarting ma~erial~ D~y bs recyclad in~o th~ rea~tlo~l. Dlr~#:t u8e of ~he r~ac~ion procluc~ al~o po~ible o~ing to the very high y~ld~. The proc~ pr2fl3ren~1ally producss the co~pound~ in ~nouler f o~. If oligoDIeric ~ for e~ca~ple trl~ric, phe~ylacetalldehyd~ hould al~o be fona~d thay can b@ prec:ipit~ted off and ~plit lnlto the deslred monoD~er~ ln a convention~l ~nner.
The co~pound~ acces~lble by ~hs proces~ accorcling to the inlr~ntlon ar~ ~portant inte~mediate~ for bio-acti~re compounds, for exa~nple ins3cticides (resmethrin), fungicide~, herbicides and drug~. ~hey c~n al80 b4 procesaed by conventional ~0thod~, for e~c~aple by oxida-tion with oxygen or by re~du~:tion, for e~pl~ by ~lC~12~2~
- 20 - O.Z. 0050/39603/~0063 catalytic hydrogenation or hydrogenating amination, in~o amines, alcohols and acids which in turn are useful inte~mediates.
The following Examples illustrate the invention:
~xamples of proces~ variant a) p-Fluorostyrene oxide i~ isomerized over catalyst A to give p~fluorophenylacetaldehyde. The reactions are carried out under isothenmal conditions in a tubular reactor (1.9 cm in internal diameter, 50 cm in length) in the gas phase. The weight hourly space velocity is 2.5 g of epoxy per g of cataly~t per hour. The length of run is in each case 4 hours. The flow velocity in the t~bular reactor is either ad~ust~d by mean~ of an N2 ~tream in such a way that the residenc~ timo i5 2 Qecond~, 1.5 second~, or 1 second or ad~u~tsd in ~uch a way by apply-ing a water jet vacuum so that ~he re idence time i~
< O.3 3econds (see Table~ 1 and 2).
Selectivity of 2eolite-catalyzed rearrangement of p-20 fluorostyrena oxide to p-~luorophenylacetaldehyde Re~idence T
time I180C I 160C I 14dC
2 second3 182% 1 _ I _ 1.5 econd3 190% i 90% 1 92%
l.0 s~cond 192~ i ~ I _ Selectivity of zeoli~e-ca~alyzed rearrangement of p-fluorostyrene oxide to p--fluorophanylacetaldehyde:
dependence of selectivity on weight hourly space velocity using cataly~t Q
Residence time 1 180~C, WHSV = 5 h-l I lgO, WHSY = lO h-l _________l_______________L_____________ ______ < 0.3 second 1 96.4% 1 96.6%
- :~ 3:iL2~;32~ ' - 21 - O.Z. 0050/39603/40063 Cataly~t Q
A boro~ilicate zeolita of the penta~il type i~
prepared by hydrothermal iynthe_i~ from 640 g of finely divided SiO2, 122 g of H3BO3 and 8 kg of an aqueou~ 1,6-hexanediamine solution (mixture 5D:50% by weight) at170C under autogenous pre~ure in a ~tirred autoclave.
After filtering and washing, the crystalline reaction product is dried at 100C~24 h and calcined at 500C/24 h.
This borosilicate zeolite i3 composed of 94.2~ by weight of SiO2 and 2.3~ by weight of ~23~
Thi~ material iq molded with a molding aid into 2 mm extrudate~ which are dried at 110C/16 h and cal-cined at 500C/24 h.
The cataly~t~ ussd for ver~ion b) for the proc~s~
according to ths invention ares CatalyRt A
The borosilicate zeolite of the pen~a~il type is prepared in a hydrothsrmal ~ynthesis from 640 g of finely divid~d SiO2, 122 g of H3B03 and 8,000 g of an aqueous 1,6-hexan~diaminQ solution (mixture 50:50~ by weight) at 170C under autoganou~ pressura in a ~tirred autoclave.
After filtering and washingr the crystallins reaction product i~ dried at 100C/24 h and calcinad at 500C/24 h.
Thi~ borosilicate zeolita comprises 94.2~ by weight of SiO2 and 2.3~ by weight of B2Ol.
Thl~ m~tarial i~ molded with a mol~ing aid into 2 mm extrud~te~ which are dried at 110C~16 h and cal-cined at 500C~24 h.
Ca~aly~t B
An alu~inosili~at~ zeolite of the penta~il type i3 pr~pared u~der hydrothermal conditions and autogenou~
pressure at 150C fro~ 65 g of finely divided SiO2t 20.3 g of A12(SO4~ x 18 HlO in 1 kg of an aqueous 1,6 hexane-diamine solution (mixture 50s50~ by waight) in a stirred autoclave. After filtering and wa hinq, the cry~talline reaction product i~ dried at 110C/24 h and calcined at 500Ct24 h. Thi~ alumino~ilicate zeolite contains 91.6%
2~2.6 - ~2 - O. Z . û050/39603/40063 by weight of SiO2 and 4 . 6~ by weight of A12O3.
The catalyst i~ molded wikh a molding aid into 2 mm extrudate~, dried at 110C~16 h and calcined at 500/24h .
Catalyst C
Catalyst C iq obtained by impregnating the extrudates of Cataly~t A with aqueou~ C~2CO3 solution, drying at 130C/2 h and calcining at 540C/2 h. The C9 content i9 0 . 6 % by weight .
Catalyst D
The iron silicate zeolite of th~ pqnta~il type i~
synthe~ized under hydrothermal condition~ and autogenou~
pre~sure at 165C from 273 g o~ sodium ~ilicate, dis-solved in 253 g of aqueous 1, 6-hexanediamine ~olution (mixture 50:50% by w~ight), and 31 g of iron ~ulfate, dis~olved in 21 g of 96~6 ~trength sulfuric acid and 425 g of water in a tirred au~oclav~ in the cour~e of 4 days.
The zeolite is filtered off ~ wa~h~d, dried at 110C/24 h and calcined at 500C/24 h. An iron silicate zeolita i~
~0 obtained having an SiO2/Fe2O3 ratio of 1~.7 and an Na2O
content of 1.2% by w~igh~. ~he cataly~t i~ extruded tog~her with finely divid~d SiO2 in a waight ratio o f 70:30 into 2.5 mm e~trudate~, dried at 110CJ16 h and calcined at 500C/24 h. Thes~ extrudates are ion exchanged with a 20% 3trength NH4Cl ~olu~ion at 80C and then washed until chloride-fre0, dried at 110C and calcined at 500C~5 h. Th~ ion sxchange i~ continued until the Na content is 0.002% by w~ight.
Cataly~t E
Cataly~t E i8 prepared in the ~ame way a~ cata ly~t C, except that C32CO3 i~ replaced by Ce(NO3) 2 . The Ce content i8 1.89~ by weight.
Catalyst F
Silicon aluminum phosphates-5 ( 5APO-5 ~ i~ prepared from a mixture of 200 g of 93% ~trength pho~phoric a~id, 136 g of boehmit~, 50 g of silica ~ol (30% strenqth), 287 g of tripropylamine and 587 g of H20. Thi~ mixture i~
~ 3 ~ 2 ~
- 23 - O.Z. 0050/39603/40063 reacted at lSO~C under autogenous pre~ure for 168 hour~.
After filtration, tha cry~talline product i~ dried a~
120C and calcined at 500C. SAP0-5 contain~ 49.8% by weight of P2O~, 33.0% by weight of Al2O3, and 6.2~ by weight of SiO2. SAP0-5 is molded together with an extru~ion aid into 3 mm Pxtrudate~, dried at 120C and calcined at 500C.
Cataly~t G
Commercially available zirconium pho~pha~e Zr3(PO~)4 i~ molded in the form of a pure ~ubstanc~.
Catalyst H
BPO4 i~ preparad by adding 49 g of H3aO3 to a kneader together with 117 g of H3PO~ (75% ~trQngth~, eva-porating off e~ces~ water and molding the re~ction pro-duct into 3 mm extrudates. The~e ex~rudat2s are dried at 100C and calcined a~ 350C. Cataly~t H contain~ 8.77~ by weight of B and 28.3% by waight of P.
Cataly~t I
TiO2 P 2 ~ i~ molded into 2 mm extrudates, dri~d a~ 110C and calcined at 500Ctl6 h.
Cataly~ J
D 10-l ~ Al20~ i~ impregnated with H3~03, dried at 110C and calcined at 500Ci5 h. Catalyst J i3 co~posed of 85~ of Al2O3 and 15% of B2O3-The experLmental xQsul~ ob~ained wi~h the~e cataly3t~ and experLmental condi ions are givQn in ~ables 3 and 4.
EX~MPL~S 1 TO 15 The reactions were carried out in the q~ pha~e under isothenmal condi~ion3 in a ~ubular reactor (coil~
O.6 cm in in~ernal diamater, 90 c~ in length) for not les~ than 6 hour~. Th~ reac~ion products w2ra separated off and characterized in a conventional manner. The reaction product~ and ~tarting matarial~ were analyzed quantitatively by gas chroma~ography.
The re~ult~ ar~ given in T~bles 3 and 4.
~ 2~
o ~o .c o ~
o ~ . ,, o ~
~ - ~ O ~ 0 Cl~^
~ ~ ~ o ~ ~ o ~, o Qo 6 a~ o ~, ~æ
w~ ~ ~ ~ ~v ~ c~ o ~ oo ~ ~, p~ ~ c~o~ooo~ ~ :~c S~ ~ al ~ o i~' ~ 2 ~ _ oo ~ o o .
w ~ ~ ~ o _ C ~ S~ ' D ~
_ O ~ g ~ O
C~ o~ O
O ~ , Ql ~ U~ V _-~ ,~ ~ V
_ ~ 1: L
E ~ n ~1~ E ;/~ ~ _ x ~ ~ O
x ~ J g t~ IJ v~ 3 t.~ v~
~ 2~2~
- 25 ~ O. Z . oO!iO/'39603/40063 EX~?LE 1 6 ~ 2 r ~H
100 g of tert-butyl p-tert-butylphenylglycidats were pas~ed per hour in cocurrant flow with 400 1 ~S.T.P) of nitrogen per hour over a hot borozeolite catalyst A at 260C in~ide an electrically heated 1-1 tubular reactor.
The reaction-products lea~ng the reactor were condensed and worked up by di~tillation. p tert-Butylphenylacet-aldehyde (~.p. 87C/0.4 mb~r) i~ obt~ned in a yield of 92% by waight.
It is particu~arly advantageous to usa zeolite8 of ths p~nt~sil typa. Th~ir baæic bu~lding block i~ a pentagon co~po~ad of SiO~ t~trahedx~. They are charac-terizad by ~ hi~h SiO2~Al2O3 r~tio and by pore ~izes be~ws2~ those o~ zeolite~ o~ t ~ A and tho~e of type or Y (cf. UlL~nn'~ a~ cited).
The~e zeolit0~ c~n havQ different chemical compo~ition~ They can be alumino~ilicate, borosllicate or i ron, beryllium, g~llium, chro~ium, arsenic, antimony or bi~mu~h silic~te ~eolita~ or ~ixtura~ thereof and aluminogerminat~, ~orogermin~e and gallium or iron germinate zeolites or mi~tures ther20f. Particularly ~uitable for the proces~ according ~o the invention are the aluminoRilicate, boro~ilicate and iron ~ilicate zeolite~ of the pentasil type. The aluminosilicate zeolite i8 prepared for e~amplo fro~ an aluminum compound preferably Al(QH)3 or Al2(S04)3, and a silicon component, ~ 3 ~ ii2~
preferably finely divided silicon dioxide, in an aqueous amine solution, in particular in polyamines such as 1,6-hexanediamine or l,3-propanediamine or trie-thylenetetramine solution, in the presence or in particular in the absence of alkali or alkaline earth metal at from 100 to 220C under autogenous pressure. This also includes the isotactic zeolites described in EP-A- 34,727 published on September 2, 19~1 and EP-A-46,504 published on March 3, 1982, both to BASF A.G. The aluminosilica-te zeolites obtained have an SiO2/Al2O3 ratio of from 10 -to 40,000, depending on the mixing ratio of the starting materials. Such alumino-silicate zeolites can also be synthesized in an ether medium such as diethylene glycol dimethyl ether, in an alcohol medium such as me-thanol or 1,4 butanediol, or in water.
Borosilicate zeolite is synthesized under auto-genous pressure, for example at from 90 to 200C, by reacting a boron compound, for example H3BO3, with a silicon compound, preferably finely divided silicon dioxide, in an aqueous amine solution, in particular in 1,6-hexanediamine, 1,3-propanediamine or triethylene -te-tramine solution, in the presence or in particular in the absence of alkali or alkaline earth metal. They also inc~ude the isotac tic zeolites described in the above men-tioned EP-A-34,727 and EP-A-46,504. These borosilicate zeolites can also be prepared by carrying out -the reaction not in an aqueous amine solution bu-t alterna-tively in an ether solution, for example diethylene glycol dimethyl ether, or in an alcohol solution, for example 1,6-hexanediol.
Iron silicate zeolites are obtained for example from an iron compound, preferably Fe2(SO4)3, and a silicon compound, preferably finely divided silicon dioxide, in an aqueous amine solution, in particular 1,6-hexanediamine, in the presence or absence of alkali or alkaline eart metal at from 100 to 220C under autogenous pressure.
The usable high-silicon zeolites (SiO2/Al2O3 > 10) also include the various ZSM types, ferrierite,Nu-l and . ~
c~ -12 ~ ?.. ~
- 13 - O.Z. 0050~39603/400b3 Silicalit~, a silica polymorph molecular 3ieve.
The aluminosilicate, boro~ilicate and iron sili-cate zeolites thu~ prepared, after they have been i80-lated, dried at from 100 to 160C, preferably at 110C, and calcined at from 450 to 550C, preferably at 500C, can be combined with a binder in a ra~io of ~rom 90:10 to 40:60 % by weight and molded into extrudates or table~4.
Suitable binder~ are v~rious aluminum o~ides, preferably boehmite, amorphous aluminoRilicates havin~ an SiO2/Al~O3 ratio of from 25:75 to 90s5, preferably 75:25~ ~ilicon dioxidQ, preferably finely divid~d SiO~, mi~tur~s of finely divided SiO2 and finely divided ~1203, TiO2, Zr2~
and clay. After molding, th~ ~xtrudate~ or tablet~ are dried at 110C/16 h and calcined ~t 500C~16 h.
It i8 al80 po~sible to obtain advantageous cata-ly~ts by molding the i~ol~t~d al~mino~ilicAte or boro-silicate zeolit~ Lmmediately after drying ~nd ~ub~ecting it to calcination only aftar the molding. ~he alumino-~ilicats and boro~ilicate zeolito~ prepared can ~e u~e~
in ~he pure fonm, without bindar, as o~trudate~ or tab-let~, the extrusion or pepti~ation ai~æ used being for example ~thylcellulo e, ste~rlc acidt potato starch, for-mic acid, ox~lic aoid, acetic ~cidO nitric acld, ammonia, amine~, 311icoe ters and graphite or mi~ture8 th~reof, If the zeolîta, on aecount o~ i~8 m~ner of pre-paration i8 pr~sent not in th~ c~talytic~lly activa, a~idic H-form but, for s~ample, in the Na-form, it can ~e co~pletely or partially con~erted into the d~sired H~form by ~on exchange, for exa~ple with a~onium ions and 8ub8~quent calcination, or by ~reatmen~ with acids.
Should the zeolitic catalyst u~ed accordiny to the inven~ion und.ergo dea~ivation du~ ~o coking, it i advi~abl~ to regenera~e the zaoli~e by burning of f the coke d~po it with air or with ~n ~ir/N~ m~xture at from 400 to 500C, preferably at 500~C. Thi~ re~tore~ the initial activity level of the zeolite~
By partial precoking it i~ pos~ibl~ to 8Qt the - 14 - O.Z. 0050/39603/40063 activity of the catalyst for optLmum selectivity in resp~ct of the desired r~action product.
To obtain a high ~electivity, high conversions and long time~ on ~tream, it may be advantageous to modify the zeolites. A suitable method of modifying the catalysts comprises for example doping the molded or unmolded zeolite with metal salt3 by ion exchange or impregnation. The metal~ used are alkali metal~ such as Li, C~ or R, alkaline earth metals ~uch a3 Mg, Ca or Sr, metals of main groups III, IV and V, such as ~l, Ga, Ge, Sn, Pb or Bi, transition metalQ of ~ubgroups IV-VIII, such as Ti, Zr, V, Nb, Cr, Mo, W, Mn, Re, Fe, Ru, 08, Co, Rh, Sr, Ni, Pd or Pt, tran~ition metal~ of secondary group~ I or II, ~uch a3 Cu, Ag or Znl and rare ~arth metal~ Quch a~ La, Ce, Pr, Nd, Fr, Yb or U.
Advantageou~ly, doping is carried out by intro-ducing the molded zeolite into a ri~er pip~ and pa3~ing an aqueous or ammoniacAl ~olution of a halide or ni.trate of one of thQ abovementioned metal~ over it a~ from 20 to 100C. Such an ion exchange can taka place, for example, with the hydrogen, a~monium, or alkali met~l form of the zeolite. ~nothQr way of applying metal to the zeolite compri~es Lmpregnati~g the zeolitic material with, for example, a halid~, nitrate or oxide of one of the abovem0ntioned metal3 in aqueou~, alcoholic or ammoniacal solu~ion. Bo~h ion ax~hange and impregnation are folowed by at lea~t one dryinq ~tep, optionally by another calcina~ion.
A po~sible embodL~ent compri~a3 for example diY-solving Cu(NO3)2 x 3 H2O or Ni(NO3~ 2 X 6 HzO or Ce(NO~)3 x 6 H20 or La(NO3~3 x 6 H20 or Cs2C03 in water and Lmpreg-nating the molded or unmold~d zeolite with this solution for a certain period, for example 30 minutes. Any supernatant solution i~ stripp~d of water in a rotary evaporator. The impreynated zeolite i3 then dried at about 150C and calcined at about 550C~ ~his L~pregnat-ing step can b~ carried out repeatedly in succession ~ 3 ~ 3 - 15 - O.Z. 0050/39603/40063 until the de~ired metal content is obtained.
It is also poq~ibla to prepare, for example, an aqueou3 Ni( C03 ) 2 solution or ammoniacal Pd(NO3) 2 solution and to suqp~nd the pure pulverulent zeolite therein at from 40 to 100C by qtirring for about 24 hours. After filtration, drying at about 150C and calcination at about 500C, the zeolitic mat~rial thus obtained can be further processed with or without binders into extru-dates, pellets or fluidizable material.
An ion exchange on the zeolit~ peresent in the H-form or ammonium form or alkali metal form ~an be car-ried out by introducing the zeolite in extruded or pellet form into a column and for example pa~ing an aqueous Ni(N03)2 olution or ammoniacal Pd~NO3)2 301ution over i~
in a recycle loop and at ~lightly ~levated temperature~
of from 30 to 80C for fro~ 15 to 20 hour~. Thi~ i~
followed by wa~hlng out with wster, drying at about 150C
and calcination at abou~ 550C. With som~ metal-doped zeoliteq/ for exampls Pd-, Cu- or Ni-doped zeolit~, an aftertreatment with hydrog0n i~ advantageou~.
A further method of modifying the zeolite com-prises treating the zeolitic matarial, which may ba in molded or unmolded ~orm, with an acid 3uch a~ hydro chloric acid, hydrofluoric acid or phc)sphoric acid and/or steam, ad~antageou~ly, for ~xa~ple, by treating the zeolite in pulverulent form with 1 N pho~phoric acid at 80C for 1 hour and then wa~hing with water and drying at 110C for 16 hour~ and calcining at 500C in 29 hour3.
Alternatively, before or after being molded together with a binder, the zeolite is treated for example at from 60 to 80C with from 3 to 25% ~trength by weight, in par-ticular from 12 to 20~ ~trength by weight aqueou~ hydro-chloric acid for from 1 to 3 hour~. Afterwards, the zeolite thu~ treated i~ wa~hed with water, dried and calcined at from 400C to 500C.
In a particular embodiment, the acid treatment compri e~ treating the zeolitic material~ before it i~
.3~ ~
~ 16 - O.~. 0050/39603~40063 molded, ~ith in general 0.001 N to 2N, preferably 0.05 N
to 0.5 N, hydrofluoric acid at elevated temperature~l for exampl2, by refluxiny for from 0.5 to 5, preferably from 1 ~o 3, hour~. After the zeolitic material ha~ been isolated by filtering and wa~hing, it i3 advantageously dried, for example, at from 100 ~o 160C and calcined at from 450C to 600C in general. In a further praferred form of the acid trea~ment, the z~olitic material, after it ha~ been molded tog~ther with a binder, is treated a~
elevated temperatures, advantageou~ly at from 50 to 90C, preferably at from 60 to 80C, for from 0.5 to 5 hour~
with, preferably, from 12 to 20% ~trength by weight hydrochloric acid. The zeolitic material i~ in general sub3equently washed and expediently dried at, for example, from lQ0 to 160C and calcined at in general from 450 to 600C. An HF treatment can al~o be followed by an HCl treat~ent.
In anoth~r procedure, zeolite~ can be modified by applyi~g pho3phorus compoundq, ~uch a~ trimethoxyphos-phate~ trLm~tho~ypho~phine or primary, 3econdary or tertiary sodium pho~phate. Treatment with primary sodium pho~phate haq proved particularly advantageou~. To thi~
end, the ~eolit~ are Lmpregnated in extruded, tablet or fluidizable form with aqueou~ NaH2PO~ solution, dried at 110C and calcined at 500C.
Further ~ataly~ts for the proces~ according to the invantisn arQ phosphate~, in particular aluminum phosphates, silicon aluminum phosphates, ~ilicon iron alu~inu~ phosphates, ceriu~ pho~phate, zirconium phos-phate~, boron pho4pha~e, iron phospAate or mixtures thereof.
The aluminum pho~phate catalysts used for the proces~ according to the invention are in particular tho~e aluminum pho~phates which have been synthesized under hydrothermal condition~ and have a zeolite struc-ture.
Hydrothermally ~ynthe~ized aluminum phosphate are 1 3 1 2 ~ 2 i~`3 - 17 - O.~. 0050/39603/~0063 for exampla APO-5, AP0~9, APO-11, AP0-12, ~P0-14, AP0-21, AP0-25, AP0-31 and ~PO-33. Synthese~ of these compound~
are described in EP 132,708, US 4~310,440 and US
4,4~3,663.
For in~tance, AlPO~-5 (APO-5~ i~ synthesi2ed by preparing a homogeneou~ mixture of orthophosphoric acid with pseudoboehmite (Catapal SBR) in water, adding tetra-propylammonium hydroxide and then heating at about 150C
under autogenou~ pressure in an autocla~e for from 20 to 60 hours. The AlPO~ i9 filtered off, dried at from 100 to 160C and calcined at from 450 to 550C.
AlPO~-9 (APO-9) i~ likewise ~ynthesi22d from orthopho~phoric acid and pseudoboehmito but in an aqueou~
DABC0 solution (1,4-diazabicyclo[2.2.23Octane) at about 200C under autogenou3 pres~ura in th~ cour~e of from 200 to 400 hour~.
AlPO4-21 (ARO-21~ ynthesizqd from orthophos phoric acid and p~eudoboekmit~ in an aqueous pyrrolidone solution at fro~ 150 to 200C under autogenous pressure in the courqe of from 50 to 200 hour~.
Silicon aluminu~ pho~phatea ~uitable for the proce.~s according to tha invention are for exampla SAP0-5, SAPO ll, SAP0-31 and SAPO~34. ~ho synthe~i~ of thi3 compound i3 described, for axampl~, in ~ Patent 103,117 and US Patent 4,440,8~1. SAPO~ aro prepared by cry~allization from an aqueou~ mixture at fro~ 100 to 250C under autog~nou~ pres~ure in the course of from 2 hours to 2 week~ during which the reaction mixture compri~ing a silicon, aluminum and pho phorus component i~ converted into aqueou~ organoamine ~olutions.
SAP0-5, for example, i~ obtained by ~ixing a ~U9-pen3ion of SiO2 in aqueous tetrapropylammonium hydroxide solu~ion with an aqueous ~u~pension of p~eudoboahmite and orthopho phoric acid and subsequant reaction at from 150 to 200C under autogenou~ prQ~sur~ in a ~tirred auto-clave for from 20 to 200 hours. Aftsr the powder ha~
be~n filtered off, it i~ dried at from 110 to 160C and 2 ~ ~ 6 ~ O.Z. 0050/39603/40063 calcine~ at from 450 to 550~C.
Suitable pho~phoru cataly~t~ for the proce~s also includa precipitated aluminum pho~phate~. Such an aluminum pho~phate is preparad for example by dissolving 92 g of diammonium hydrog~npho~phate in 700 ml of water.
260 g of Al(NO3)3 x H2O in 700 ml of water axe added drop-wise in the cour~e of 2 hours during which pH 8 i~
maintained by the ~imultaneouQ addition of 25% ~trength NX3 solution. The resul~ing precipitate i~ subsequently stirred for 12 hour~ and then filtered off with ~uction and washed. It i~ drie~ at 60C/16 h.
Boron phosphates for the proces~ according to ~he invention are preparable for example by mixing and knead-ing concentrated boric acid and phosphoric acid and by sub~equent drying an~ calcination in inert ga~, aix or 3team atmosphere at fro~ 250 to 650C, in particul~r at from 300 to 550C.
The~e phosphat~ may b~ modified by impr~gnation (~aturation or spraying3 or in some ca~es even by ion exchange with modifying component~ as de~cribed ~bove for zeolites. As with the zeolite cataly~t~, a modification with an acid is also pos~ible.
Suitable acidic cat~ly~t~ al~o include for example the acidic oxid~ of element o~ m~in groups III
an~ I~ and of subgroups IV to VI of the periodic table, in par~icular oxides ~uch as ~ilicon ~loxide in the form of sili~a gel, diatomaceou~ earth, quartz and also titanium dioxide, zir~onium dioxid~, phosphoru~ oxides, vanadium oxide~, niobium ox1dea, boron oxide~, chromium oxide~, molybdenum oxides 9 tungsten o~idos or pumice or mixtures thereof. Similarly, thefie oxido~ may be dop~d by applying modifying componsnt~ as de~cribed above for zeolite ca~alyst3~ The treatment with acids a~ de~cribed above for zeolita catalyst i9 another pos~ible modifying treatm~nt.
It i~ al~o poR~ible to use cataly8t8 impregnated wi~h pho3phoric acid or boric acid. Phosphoric acid or ~3~2~2~
- 19 - O.Z. 0050~39603/~0063 boric acid i~ applied to SiO2, A12l or pumice carriers, for ax~mple by ~pregnating or qprayingO A phosphoric acid-containing catalys~ can be obtainQd for e~ampl~ by Lmpregna~ing SiO2 with H3P0, or N~H2~0~ o~ Na2XPO~ solution and then drying or calcini~g. ~owever, phoaphoric acid can al~o be ~prayed togeth~r with 3ilica gel in a 3pray tower, followed by drying and usually calcination.
Phosphoric acid can al80 ba ~prayed onto the carrier material in an Lmpregnating mill.
The catalysts described h~re ca~ optionally be u~ed in the form of from 2 to 4 m~ extrudate~ or as tab-lets from 3 to 5 mm in diameter or ~h chip3 h~Ylng particl~ ~izes of from 0.1 to 0.5 ~m, or in a fluidiz~lblo form.
In both ver~ioll~ of th~ proce~s a) and b) in-volatile or solid s~ar~ing ma~erial~ ~an be u~ad ln ~
dis~olved ~o~ for exampl~ in q~, toluene ar petroleum ether ~olution. A dilution w~th th~s ~olvent~ m~ntion~d i~
al~o po~sible, from 100 to 500 ~al, p:re~er~bly frolz 150 to 350 ml, of one of thes0 ss~lv0nt~ being in general su~fi-cient per ~ol~ of II, III or TV.
~f~ar the r~action ~h~ phenylace~aldehydes are isolated froD~ th~ reac~ion mixture in a conventional mann~r, for ~axan~ple by distlll~tion; u3lconver~ed ~tarting ma~erial~ D~y bs recyclad in~o th~ rea~tlo~l. Dlr~#:t u8e of ~he r~ac~ion procluc~ al~o po~ible o~ing to the very high y~ld~. The proc~ pr2fl3ren~1ally producss the co~pound~ in ~nouler f o~. If oligoDIeric ~ for e~ca~ple trl~ric, phe~ylacetalldehyd~ hould al~o be fona~d thay can b@ prec:ipit~ted off and ~plit lnlto the deslred monoD~er~ ln a convention~l ~nner.
The co~pound~ acces~lble by ~hs proces~ accorcling to the inlr~ntlon ar~ ~portant inte~mediate~ for bio-acti~re compounds, for exa~nple ins3cticides (resmethrin), fungicide~, herbicides and drug~. ~hey c~n al80 b4 procesaed by conventional ~0thod~, for e~c~aple by oxida-tion with oxygen or by re~du~:tion, for e~pl~ by ~lC~12~2~
- 20 - O.Z. 0050/39603/~0063 catalytic hydrogenation or hydrogenating amination, in~o amines, alcohols and acids which in turn are useful inte~mediates.
The following Examples illustrate the invention:
~xamples of proces~ variant a) p-Fluorostyrene oxide i~ isomerized over catalyst A to give p~fluorophenylacetaldehyde. The reactions are carried out under isothenmal conditions in a tubular reactor (1.9 cm in internal diameter, 50 cm in length) in the gas phase. The weight hourly space velocity is 2.5 g of epoxy per g of cataly~t per hour. The length of run is in each case 4 hours. The flow velocity in the t~bular reactor is either ad~ust~d by mean~ of an N2 ~tream in such a way that the residenc~ timo i5 2 Qecond~, 1.5 second~, or 1 second or ad~u~tsd in ~uch a way by apply-ing a water jet vacuum so that ~he re idence time i~
< O.3 3econds (see Table~ 1 and 2).
Selectivity of 2eolite-catalyzed rearrangement of p-20 fluorostyrena oxide to p-~luorophenylacetaldehyde Re~idence T
time I180C I 160C I 14dC
2 second3 182% 1 _ I _ 1.5 econd3 190% i 90% 1 92%
l.0 s~cond 192~ i ~ I _ Selectivity of zeoli~e-ca~alyzed rearrangement of p-fluorostyrene oxide to p--fluorophanylacetaldehyde:
dependence of selectivity on weight hourly space velocity using cataly~t Q
Residence time 1 180~C, WHSV = 5 h-l I lgO, WHSY = lO h-l _________l_______________L_____________ ______ < 0.3 second 1 96.4% 1 96.6%
- :~ 3:iL2~;32~ ' - 21 - O.Z. 0050/39603/40063 Cataly~t Q
A boro~ilicate zeolita of the penta~il type i~
prepared by hydrothermal iynthe_i~ from 640 g of finely divided SiO2, 122 g of H3BO3 and 8 kg of an aqueou~ 1,6-hexanediamine solution (mixture 5D:50% by weight) at170C under autogenous pre~ure in a ~tirred autoclave.
After filtering and washing, the crystalline reaction product is dried at 100C~24 h and calcined at 500C/24 h.
This borosilicate zeolite i3 composed of 94.2~ by weight of SiO2 and 2.3~ by weight of ~23~
Thi~ material iq molded with a molding aid into 2 mm extrudate~ which are dried at 110C/16 h and cal-cined at 500C/24 h.
The cataly~t~ ussd for ver~ion b) for the proc~s~
according to ths invention ares CatalyRt A
The borosilicate zeolite of the pen~a~il type is prepared in a hydrothsrmal ~ynthesis from 640 g of finely divid~d SiO2, 122 g of H3B03 and 8,000 g of an aqueous 1,6-hexan~diaminQ solution (mixture 50:50~ by weight) at 170C under autoganou~ pressura in a ~tirred autoclave.
After filtering and washingr the crystallins reaction product i~ dried at 100C/24 h and calcinad at 500C/24 h.
Thi~ borosilicate zeolita comprises 94.2~ by weight of SiO2 and 2.3~ by weight of B2Ol.
Thl~ m~tarial i~ molded with a mol~ing aid into 2 mm extrud~te~ which are dried at 110C~16 h and cal-cined at 500C~24 h.
Ca~aly~t B
An alu~inosili~at~ zeolite of the penta~il type i3 pr~pared u~der hydrothermal conditions and autogenou~
pressure at 150C fro~ 65 g of finely divided SiO2t 20.3 g of A12(SO4~ x 18 HlO in 1 kg of an aqueous 1,6 hexane-diamine solution (mixture 50s50~ by waight) in a stirred autoclave. After filtering and wa hinq, the cry~talline reaction product i~ dried at 110C/24 h and calcined at 500Ct24 h. Thi~ alumino~ilicate zeolite contains 91.6%
2~2.6 - ~2 - O. Z . û050/39603/40063 by weight of SiO2 and 4 . 6~ by weight of A12O3.
The catalyst i~ molded wikh a molding aid into 2 mm extrudate~, dried at 110C~16 h and calcined at 500/24h .
Catalyst C
Catalyst C iq obtained by impregnating the extrudates of Cataly~t A with aqueou~ C~2CO3 solution, drying at 130C/2 h and calcining at 540C/2 h. The C9 content i9 0 . 6 % by weight .
Catalyst D
The iron silicate zeolite of th~ pqnta~il type i~
synthe~ized under hydrothermal condition~ and autogenou~
pre~sure at 165C from 273 g o~ sodium ~ilicate, dis-solved in 253 g of aqueous 1, 6-hexanediamine ~olution (mixture 50:50% by w~ight), and 31 g of iron ~ulfate, dis~olved in 21 g of 96~6 ~trength sulfuric acid and 425 g of water in a tirred au~oclav~ in the cour~e of 4 days.
The zeolite is filtered off ~ wa~h~d, dried at 110C/24 h and calcined at 500C/24 h. An iron silicate zeolita i~
~0 obtained having an SiO2/Fe2O3 ratio of 1~.7 and an Na2O
content of 1.2% by w~igh~. ~he cataly~t i~ extruded tog~her with finely divid~d SiO2 in a waight ratio o f 70:30 into 2.5 mm e~trudate~, dried at 110CJ16 h and calcined at 500C/24 h. Thes~ extrudates are ion exchanged with a 20% 3trength NH4Cl ~olu~ion at 80C and then washed until chloride-fre0, dried at 110C and calcined at 500C~5 h. Th~ ion sxchange i~ continued until the Na content is 0.002% by w~ight.
Cataly~t E
Cataly~t E i8 prepared in the ~ame way a~ cata ly~t C, except that C32CO3 i~ replaced by Ce(NO3) 2 . The Ce content i8 1.89~ by weight.
Catalyst F
Silicon aluminum phosphates-5 ( 5APO-5 ~ i~ prepared from a mixture of 200 g of 93% ~trength pho~phoric a~id, 136 g of boehmit~, 50 g of silica ~ol (30% strenqth), 287 g of tripropylamine and 587 g of H20. Thi~ mixture i~
~ 3 ~ 2 ~
- 23 - O.Z. 0050/39603/40063 reacted at lSO~C under autogenous pre~ure for 168 hour~.
After filtration, tha cry~talline product i~ dried a~
120C and calcined at 500C. SAP0-5 contain~ 49.8% by weight of P2O~, 33.0% by weight of Al2O3, and 6.2~ by weight of SiO2. SAP0-5 is molded together with an extru~ion aid into 3 mm Pxtrudate~, dried at 120C and calcined at 500C.
Cataly~t G
Commercially available zirconium pho~pha~e Zr3(PO~)4 i~ molded in the form of a pure ~ubstanc~.
Catalyst H
BPO4 i~ preparad by adding 49 g of H3aO3 to a kneader together with 117 g of H3PO~ (75% ~trQngth~, eva-porating off e~ces~ water and molding the re~ction pro-duct into 3 mm extrudates. The~e ex~rudat2s are dried at 100C and calcined a~ 350C. Cataly~t H contain~ 8.77~ by weight of B and 28.3% by waight of P.
Cataly~t I
TiO2 P 2 ~ i~ molded into 2 mm extrudates, dri~d a~ 110C and calcined at 500Ctl6 h.
Cataly~ J
D 10-l ~ Al20~ i~ impregnated with H3~03, dried at 110C and calcined at 500Ci5 h. Catalyst J i3 co~posed of 85~ of Al2O3 and 15% of B2O3-The experLmental xQsul~ ob~ained wi~h the~e cataly3t~ and experLmental condi ions are givQn in ~ables 3 and 4.
EX~MPL~S 1 TO 15 The reactions were carried out in the q~ pha~e under isothenmal condi~ion3 in a ~ubular reactor (coil~
O.6 cm in in~ernal diamater, 90 c~ in length) for not les~ than 6 hour~. Th~ reac~ion products w2ra separated off and characterized in a conventional manner. The reaction product~ and ~tarting matarial~ were analyzed quantitatively by gas chroma~ography.
The re~ult~ ar~ given in T~bles 3 and 4.
~ 2~
o ~o .c o ~
o ~ . ,, o ~
~ - ~ O ~ 0 Cl~^
~ ~ ~ o ~ ~ o ~, o Qo 6 a~ o ~, ~æ
w~ ~ ~ ~ ~v ~ c~ o ~ oo ~ ~, p~ ~ c~o~ooo~ ~ :~c S~ ~ al ~ o i~' ~ 2 ~ _ oo ~ o o .
w ~ ~ ~ o _ C ~ S~ ' D ~
_ O ~ g ~ O
C~ o~ O
O ~ , Ql ~ U~ V _-~ ,~ ~ V
_ ~ 1: L
E ~ n ~1~ E ;/~ ~ _ x ~ ~ O
x ~ J g t~ IJ v~ 3 t.~ v~
~ 2~2~
- 25 ~ O. Z . oO!iO/'39603/40063 EX~?LE 1 6 ~ 2 r ~H
100 g of tert-butyl p-tert-butylphenylglycidats were pas~ed per hour in cocurrant flow with 400 1 ~S.T.P) of nitrogen per hour over a hot borozeolite catalyst A at 260C in~ide an electrically heated 1-1 tubular reactor.
The reaction-products lea~ng the reactor were condensed and worked up by di~tillation. p tert-Butylphenylacet-aldehyde (~.p. 87C/0.4 mb~r) i~ obt~ned in a yield of 92% by waight.
Claims (10)
1. A process for preparing a phenylacetaldehyde of the general formula I
(I) where R1 to R5 are each independently of the others hydrogen, halogen or unsubstituted or halogen-substituted alkyl, alkenyl, alkoxy, alkylthio or cycloalkyl, which comprises a) reacting an epoxy of the general formula II or phenylglycol of the general formula III
(II) or (III) where R1 to R5 are each as defined above and Y and Z can be identical to or different from each other and are each hydroxyl, alkoxy, aryloxy or acyloxy, in the gas phase over a borosilicate zeolite catalyst at from 70 to 200°C
under reduced pressure, or b) reacting a glycidic ester of the general formula IV
(IV) where R1 to R5 are each as defined above and R6 is tert-butyl or i-propyl, in the liquid or gas phase in the presence of a zeolite and/or phosphate and/or phosphoric or boric acid on a carrier material and/or an acidic metal oxide at from 50 to 500°C under a pressure of from 0.01 to 50 bar.
- 27 - O.Z. 0050/39603/40063
(I) where R1 to R5 are each independently of the others hydrogen, halogen or unsubstituted or halogen-substituted alkyl, alkenyl, alkoxy, alkylthio or cycloalkyl, which comprises a) reacting an epoxy of the general formula II or phenylglycol of the general formula III
(II) or (III) where R1 to R5 are each as defined above and Y and Z can be identical to or different from each other and are each hydroxyl, alkoxy, aryloxy or acyloxy, in the gas phase over a borosilicate zeolite catalyst at from 70 to 200°C
under reduced pressure, or b) reacting a glycidic ester of the general formula IV
(IV) where R1 to R5 are each as defined above and R6 is tert-butyl or i-propyl, in the liquid or gas phase in the presence of a zeolite and/or phosphate and/or phosphoric or boric acid on a carrier material and/or an acidic metal oxide at from 50 to 500°C under a pressure of from 0.01 to 50 bar.
- 27 - O.Z. 0050/39603/40063
2. A process as claimed in claimed 1a, wherein the residence time over the catalyst in the course of the reaction is less than four seconds.
3. A process as claimed in claim 1a, wherein a borosilicate zeolite without Al-containing binder is used.
4. A process as claimed in claim 1b, wherein the catalyst used is a zeolite of the pentasil or faujasite type.
5. A process as claimed in claim 1b, wherein the catalyst used is an aluminosilicate zeolite, borosilicate zeolite or iron silicate zeolite of the pentasil type.
6. A process as claimed in claim 1b, wherein the catalyst used is a zeolite doped with an alkali metal, a transition metal or a rare earth metal.
7. A process as claimed in claim 1b, wherein the catalyst used is a phosphate of the elements B, Al, Zr, Ce, Fe, Sr or a mixture thereof or a hydrothermally synthesized phosphate.
8. A process as claimed in claim 1b, wherein the catalyst used is a hydrothermally synthesized aluminum phosphate or silicon aluminum phosphate or silicon iron aluminum phosphate or boron aluminum phosphate.
9. A process as claimed in claim 1b, wherein the catalyst used is an acidic oxide of Ti, Zr, Al, Si, V, W, Nb, Cr or phosphoric acid or boric acid on SiO2, Al2O3, TiO2 or pumice as carrier.
10. A process as claimed in claim 1b, wherein the reaction is carried out in the gas phase.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3740270.6 | 1987-11-27 | ||
| DE19873740270 DE3740270A1 (en) | 1987-11-27 | 1987-11-27 | METHOD FOR PRODUCING PHENYL ACETALDEHYDES |
| DE3824725A DE3824725A1 (en) | 1988-07-21 | 1988-07-21 | METHOD FOR PRODUCING PHENYL ACETALDEHYDES |
| DEP3824725.9 | 1988-07-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1312626C true CA1312626C (en) | 1993-01-12 |
Family
ID=25862226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000583933A Expired - Lifetime CA1312626C (en) | 1987-11-27 | 1988-11-23 | Preparation of phenylacetyldehydes |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0317911B1 (en) |
| JP (1) | JP2610970B2 (en) |
| CA (1) | CA1312626C (en) |
| DE (1) | DE3881649D1 (en) |
| HU (1) | HU203310B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3808512A1 (en) * | 1988-03-15 | 1989-09-28 | Basf Ag | METHOD FOR PRODUCING (ALPHA) KETOCARBONIC ACID ESTERS |
| CN115155650B (en) * | 2022-08-01 | 2024-03-19 | 浙江医药股份有限公司新昌制药厂 | Catalyst and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61112040A (en) * | 1984-11-07 | 1986-05-30 | Mitsubishi Gas Chem Co Inc | Production of phenylacetaldehyde |
| DE3546372A1 (en) * | 1985-12-31 | 1987-07-02 | Basf Ag | NEW PHENYLACETALDEHYDE AND METHOD FOR PRODUCING PHENYLACETALDEHYDE |
| DE3632529A1 (en) * | 1986-09-25 | 1988-04-07 | Basf Ag | METHOD FOR PRODUCING ALDEHYDES AND / OR KETONES BY REALIZING EPOXIES |
-
1988
- 1988-11-18 EP EP88119194A patent/EP0317911B1/en not_active Expired - Lifetime
- 1988-11-18 DE DE8888119194T patent/DE3881649D1/en not_active Expired - Lifetime
- 1988-11-23 CA CA000583933A patent/CA1312626C/en not_active Expired - Lifetime
- 1988-11-25 HU HU886074A patent/HU203310B/en unknown
- 1988-11-28 JP JP63298440A patent/JP2610970B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01265053A (en) | 1989-10-23 |
| EP0317911A2 (en) | 1989-05-31 |
| HU203310B (en) | 1991-07-29 |
| EP0317911A3 (en) | 1990-05-02 |
| EP0317911B1 (en) | 1993-06-09 |
| JP2610970B2 (en) | 1997-05-14 |
| DE3881649D1 (en) | 1993-07-15 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |