WO2004007414A1 - Procede d'hydrogenation continue de citral permettant l'obtention de citronellal - Google Patents

Procede d'hydrogenation continue de citral permettant l'obtention de citronellal Download PDF

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Publication number
WO2004007414A1
WO2004007414A1 PCT/EP2003/007601 EP0307601W WO2004007414A1 WO 2004007414 A1 WO2004007414 A1 WO 2004007414A1 EP 0307601 W EP0307601 W EP 0307601W WO 2004007414 A1 WO2004007414 A1 WO 2004007414A1
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WIPO (PCT)
Prior art keywords
liquid phase
catalyst particles
catalyst
citral
transport
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Application number
PCT/EP2003/007601
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German (de)
English (en)
Inventor
Hans-Georg Göbbel
Günter WEGNER
Hartwig Fuchs
Signe Unverricht
Axel Salden
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2003254348A priority Critical patent/AU2003254348A1/en
Publication of WO2004007414A1 publication Critical patent/WO2004007414A1/fr

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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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds

Definitions

  • the present invention relates to a process for the continuous, selective hydrogenation of citral to citronellal (Scheme 1).
  • Citral and its hydrogenation products are used as fragrance and aroma substances.
  • GB 1 389 177, GB 1 476 818, GB 1 340 409 and US 3,971,830 describe processes for the preparation of citronellal by hydrogenating citral over a palladium-containing catalyst in the presence of borax or bases.
  • Catalytic hydrogenations on heterogeneous catalysts are often carried out using fixed bed reactors in order to obtain the advantages of a continuous process.
  • specially prepared catalysts have to be manufactured and used for this purpose, which have to be replaced or regenerated in a complex manner if activity is lost - often after a short period of idle time - which is usually not only the case when the hydrogenation system is switched off, but also afterwards Processing stages is connected.
  • a heterogeneously catalyzed hydrogenation can be carried out in the form of a suspension reaction, the hydrogenation catalyst being suspended in a liquid phase by supplying mechanical energy, for example in a stirred tank, cf. eg Ull ann's Encyclopedia of Technical Chemistry, 4th ed. Volume 13, 1997, p. 138, Verlag Chemie Weinheim.
  • mechanical energy for example in a stirred tank, cf. eg Ull ann's Encyclopedia of Technical Chemistry, 4th ed. Volume 13, 1997, p. 138, Verlag Chemie Weinheim.
  • Fluidized or fluidized bed reactors allow higher relative speeds, but require the use of significantly larger catalyst particles so that a more or less strongly expanded catalyst bed is present during operation.
  • the smaller volume-related surface area of larger catalyst particles limits the material conversion and thus compensates for the effect of the higher relative speed.
  • EP-A 798 039 discloses a process for carrying out catalytic reactions in a reactor which contains a liquid phase in which at least one catalyst is suspended. The hydrogenation of hydrodehydrolinalool to hydrolinalool and further to tetrahydrolinalool is described. Hydrodehydrolinalool contains only a triple bond as the functional group to be hydrogenated, so that the person skilled in the art would not have taken any suggestion regarding selective hydrogenation.
  • the present invention has for its object to provide a process for the selective hydrogenation of citral to citronellal, which combines the advantages of a high space-time yield and a simple catalyst exchange.
  • the object is achieved according to the invention by a process in which a liquid phase in which the citral is dissolved and suspended in the particles of a catalyst which is capable of preferential hydrogenation of carbon-carbon double bonds before carbon-oxygen double bonds , in the presence of a hydrogen-containing gas through a device which inhibits the transport of the catalyst particles.
  • a higher relative speed of the liquid phase compared to the catalyst particles is generated because the transport of the catalyst particles is inhibited by suitable means, such as internals in a reactor, i.e. the particles are held back more strongly by the surrounding liquid.
  • suitable means such as internals in a reactor, i.e. the particles are held back more strongly by the surrounding liquid.
  • high space-time yields are achieved as a result.
  • the device which inhibits the transport of the catalyst particles preferably has openings or channels whose hydraulic diameter is 2 to 2000 times, in particular 5 to 500 times, particularly preferably 5 to 100 times the average diameter of the catalyst particles.
  • the hydraulic diameter is a parameter familiar to the person skilled in the art for describing the equivalent diameter of non-circular channel structures.
  • the hydraulic diameter of an opening is defined as the quotient of 4 times the cross-section of the opening and its circumference.
  • the hydraulic diameter can be as
  • the openings or channels of suitable devices generally have a hydraulic diameter of 0.5 to 20 mm, preferably 1 to 10 mm, particularly preferably 1 to 3 mm.
  • catalyst particles with an average diameter of 0.0001 to 2 mm, preferably 0.001 to 1 mm, particularly preferably 0.005 to 0.1 mm are used.
  • the device which inhibits the transport of the catalyst particles can consist of a bed, a knitted fabric, or an open-celled one
  • Foam structure preferably made of plastic e.g. Polyurethane or melamine resin, or ceramic, or a packing element as is basically, i.e. its geometrical shape, already known from the distillation and extraction technology, exist.
  • the packs generally have a hydraulic diameter which is smaller by a factor of 2 to 10 than that of comparable internals in the area of distillation and extraction technology.
  • Metal mesh packs or wire mesh packs are particularly suitable as packing elements.
  • packs made of other woven, knitted or felted materials can also be used.
  • Packs of flat or corrugated metal sheets are also suitable, preferably without perforation or other larger openings, for example in accordance with the Montz Bl or Sulzer Mellapak types.
  • Packings made of are also advantageous Expanded metal, such as packs of the type Montz BSH. What is decisive for the suitability of a package in the context of the present invention is not its geometry, but rather the opening sizes or channel widths in the package which arise for the current conduction.
  • the surfaces of the device facing the liquid phase have a roughness in the range from 0.1 to 10 times, preferably from 0.5 to 5 times, the average diameter of the catalyst particles.
  • Materials are preferred whose surfaces have a mean roughness value R a (determined according to DIN 4768/1) of 0.001 to 0.01 mm.
  • R a determined according to DIN 4768/1
  • a corresponding surface roughness can be achieved when using wire mesh packings made of stainless steel by thermal treatment in the presence of oxygen, for example by tempering the tissue in air at a temperature of about 800 ° C.
  • the process according to the invention is generally carried out at a pressure between 1 and 100 bar, preferably 1 and 60 bar, particularly preferably 1 and 50 bar.
  • the reaction temperatures are usually between 40 and 120 ° C, preferably between 60 and 100 ° C, particularly preferably between 70 and 90 ° C.
  • the liquid phase preferably comprises an inert diluent, in particular a C 1 -C 6 -alkanol, particularly preferably a C 1 -C 4 -alkanol, such as, in particular, methanol.
  • the liquid phase further preferably comprises ammonia, a primary, secondary and / or tertiary amine, of which tertiary amines, for example tri (C (-C -alkyl) amines, in particular trimethylamine, are particularly preferred.
  • the concentration of citral in the liquid phase is preferably 50 to 90% by weight, particularly preferably 60 to 80% by weight, that of the diluent 40 to 5% by weight, preferably 20 to 35%, that of the ammonia / amine 1 up to 15% by weight, preferably 1 to 8% by weight.
  • Hydrogen gas with a purity of at least 99.5% by volume is generally used as the hydrogen-containing gas. It is used in an at least stoichiometric amount, based on the carbonyl compound contained in the liquid phase, usually in an excess of 1 to 20%.
  • a commercially available suspension catalyst which is capable of preferentially hydrogenating carbon-carbon double bonds over carbon-oxygen double bonds can be used as the catalyst.
  • Catalysts which contain at least palladium as the active component are particularly suitable.
  • the catalyst can also contain other active components, such as zinc, cadium, platinum, silver or a rare earth metal.
  • the catalyst can be used in metallic and / or oxidic form.
  • the active components are preferably applied to a carrier material. Suitable carrier materials are, for example, Si0 2 , Ti0 2 , Zr0 2 , Al 2 0 3 or carbon such as graphite, carbon black or activated carbon. Activated carbon is preferred because of its easy suspendability.
  • the palladium content is preferably 0.1 to 10% by weight, in particular 0.5 to 7% by weight and particularly preferably 2 to 6% by weight, based on the total weight of the catalyst.
  • the suspended catalyst material can be introduced into the liquid phase and distributed therein using conventional techniques.
  • the device which inhibits the transport of the catalyst particles is usually built into a reactor which is arranged in such a way that the reaction mixture is forced through the device as it passes through the reactor, i.e. the internals usually fill the entire free cross-section of the reactor.
  • the internals preferably, but not necessarily, extend over the entire extent of the reactor in the direction of flow of the liquid phase.
  • reactors such as jet nozzle reactors, bubble columns or tube bundle reactors.
  • a vertically arranged bubble column or a tube bundle reactor in which the internals are accommodated in the individual tubes are particularly suitable.
  • the hydrogen-containing gas and the liquid phase are preferably passed through the reactor in cocurrent, preferably counter to the direction of gravity.
  • the gas phase is intimately mixed with the liquid phase, for example by means of an injector nozzle.
  • the empty tube velocity of the liquid phase is preferably more than 100 m 3 / m 2 h, in particular 100 to 250 m 3 / m 2 h, that of the gas phase more than 100 Nm 3 / m 2 h, in particular 100 to 250 Nm 3 / m 2 h , In order to achieve sufficiently high empty tube velocities, it is preferred to return partial streams of the gas and liquid phase that leave the reactor.
  • the catalyst particles suspended in the hydrogenation discharge are separated off by customary methods, for example by sedimentation, centrifugation, cake filtration or crossflow filtration.
  • the hydrogenation according to the invention can be carried out either continuously or batchwise, but it is preferably continuous.
  • FIG. 1 shows schematically a plant suitable for carrying out the process according to the invention with a reactor (bubble column) 1 with a packing 2, which inhibited the transport of the catalyst particles.
  • Liquid is introduced into the reactor via lines 3 and hydrogen gas via line 4.
  • the circulating gas 5 is mixed in with the mixing nozzle 6 with fresh gas and the suspension 11 circulated by the pump 14.
  • the reactor discharge is fed via line 7 into the separating vessel 8, in which the gas phase is separated off and discharged via line 9.
  • a partial stream of this gas quantity is withdrawn via line 10 and the remaining amount is fed via line 5 into the reactor.
  • the suspended catalyst remains in the reactor system in that it is retained by a crossflow filter 12 and only catalyst-free liquid phase emerges via line 13 and is removed.
  • the temperature in the reactor system can be set in a targeted manner via the heat exchanger 15.
  • FIG. 2 shows schematically a layer of a folded fabric. Packs which can be used according to the invention are obtained if several of these layers are arranged one above the other. Each layer comprises channels with a cross section in the form of an isosceles triangle with the leg length s, the base b and the height h.
  • FIG. 1 A system was used as shown in FIG. 1, which comprised a bubble column (1000 mm long, 27.3 mm in diameter) equipped with a Montz AI 1200 type tissue pack.
  • the package consisted of layers of a fabric of stainless steel wires, which were folded so that channels with a cross section in the shape of an isosceles triangle were formed, the leg length 3.1 mm, the base 5.1 mm and the height 1.8 mm was, corresponding to a hydraulic diameter of 1.62 mm.
  • a mixture of 70% by weight of citral, 27% by weight of methanol and 3% by weight of trimethylamine was used as the feed.
  • a palladium-carbon suspension catalyst which contained 5% palladium on activated carbon and an average particle size of about 50 was suspended in the feed ⁇ m.
  • the reaction was carried out continuously under a hydrogen pressure of 10 bar and a temperature of 80 ° C.
  • the liquid with the suspended catalyst and the gas were introduced into the packed reactor from below at an empty tube speed of 200 m3 / m2h.
  • the conversion was 97% with a selectivity of more than 90% for Citronellal and about 5% for Citronellol.
  • the catalyst load was 140 kg C itrai / (kg ⁇ at (Pd) * n ) ' ⁇ - e space-time yield 930 kg cit rai / (m 3 h).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé d'hydrogénation continue de citral permettant l'obtention de citronellal. Ledit procédé consiste à amener une phase liquide, dans laquelle le citral est dissous et des particules d'un catalyseur sont en suspension, ledit catalyseur étant apte à l'hydrogénation préférentielle de liaisons doubles carbone-carbone avant des liaisons doubles carbone-oxygène, en présence d'un gaz contenant de l'hydrogène, à travers un dispositif empêchant l'acheminement des particules de catalyseur.
PCT/EP2003/007601 2002-07-15 2003-07-14 Procede d'hydrogenation continue de citral permettant l'obtention de citronellal WO2004007414A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003254348A AU2003254348A1 (en) 2002-07-15 2003-07-14 Method for the continuous hydrogenation of citral to give citronellal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10231944.8 2002-07-15
DE2002131944 DE10231944A1 (de) 2002-07-15 2002-07-15 Verfahren zur kontinuierlichen Hydrierung von Citral zu Citronellal

Publications (1)

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WO2004007414A1 true WO2004007414A1 (fr) 2004-01-22

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AU (1) AU2003254348A1 (fr)
DE (1) DE10231944A1 (fr)
WO (1) WO2004007414A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006021822A1 (fr) 2004-08-23 2006-03-02 Thalesnano Zrt. Réacteur à cartouche pour appareil d'hydrogénation de laboratoire à écoulement
DE102004047794A1 (de) * 2004-09-29 2006-04-06 Studiengesellschaft Kohle Mbh Verfahren zur Hydrierung von a,ß-ungesättigten Carbonylverbindungen
WO2011067386A2 (fr) 2009-12-04 2011-06-09 Basf Se Procédé de préparation d'aldéhydes aliphatiques
US8318985B2 (en) 2007-11-30 2012-11-27 Basf Se Method for producing optically active, racemic menthol

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1476818A (en) * 1975-06-18 1977-06-16 Rhone Poulenc Ind Process for the semihydrogenation of citral and its homo logues to citronellal and its homologues
EP0798039A2 (fr) * 1996-03-26 1997-10-01 Basf Aktiengesellschaft Procédé de réacteur pour la mise en oeuvre de la transformation de substances au moyen de catalyseurs en suspension dans des liquides
EP0947493A1 (fr) * 1998-04-02 1999-10-06 Basf Aktiengesellschaft Procédé pour l'hydrogénation sélective en phase liquide de composés carbonyles alpha,bèta-insaturés

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1476818A (en) * 1975-06-18 1977-06-16 Rhone Poulenc Ind Process for the semihydrogenation of citral and its homo logues to citronellal and its homologues
EP0798039A2 (fr) * 1996-03-26 1997-10-01 Basf Aktiengesellschaft Procédé de réacteur pour la mise en oeuvre de la transformation de substances au moyen de catalyseurs en suspension dans des liquides
EP0947493A1 (fr) * 1998-04-02 1999-10-06 Basf Aktiengesellschaft Procédé pour l'hydrogénation sélective en phase liquide de composés carbonyles alpha,bèta-insaturés

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006021822A1 (fr) 2004-08-23 2006-03-02 Thalesnano Zrt. Réacteur à cartouche pour appareil d'hydrogénation de laboratoire à écoulement
DE102004047794A1 (de) * 2004-09-29 2006-04-06 Studiengesellschaft Kohle Mbh Verfahren zur Hydrierung von a,ß-ungesättigten Carbonylverbindungen
US8318985B2 (en) 2007-11-30 2012-11-27 Basf Se Method for producing optically active, racemic menthol
US9988331B2 (en) 2007-11-30 2018-06-05 Basf Se Method for producing optically active, racemic menthol
WO2011067386A2 (fr) 2009-12-04 2011-06-09 Basf Se Procédé de préparation d'aldéhydes aliphatiques

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Publication number Publication date
DE10231944A1 (de) 2004-01-29
AU2003254348A1 (en) 2004-02-02

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