WO2002102742A2 - Procede de division catalytique oxidative de composes cycliques satures ou non sature - Google Patents

Procede de division catalytique oxidative de composes cycliques satures ou non sature Download PDF

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Publication number
WO2002102742A2
WO2002102742A2 PCT/EP2002/006299 EP0206299W WO02102742A2 WO 2002102742 A2 WO2002102742 A2 WO 2002102742A2 EP 0206299 W EP0206299 W EP 0206299W WO 02102742 A2 WO02102742 A2 WO 02102742A2
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WO
WIPO (PCT)
Prior art keywords
radical
catalyst
saturated
unsaturated
aliphatic
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Application number
PCT/EP2002/006299
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German (de)
English (en)
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WO2002102742A3 (fr
Inventor
Adolf KÜHNLE
Carsten Jost
Roger Arthur Sheldon
Sandrine M. M. Chatel
Isabella W. C. E. Arends
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Creavis Gesellschaft Für Technologie Und Innovation Mbh
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Application filed by Creavis Gesellschaft Für Technologie Und Innovation Mbh filed Critical Creavis Gesellschaft Für Technologie Und Innovation Mbh
Priority to AU2002314151A priority Critical patent/AU2002314151A1/en
Publication of WO2002102742A2 publication Critical patent/WO2002102742A2/fr
Publication of WO2002102742A3 publication Critical patent/WO2002102742A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof

Definitions

  • the invention relates to a process for the catalytic oxidative cleavage of cyclic hydrocarbons to the corresponding alcohols, hydroperoxides, aldehydes or ketones or carboxylic acids.
  • nitric acid process is also used in practice for the oxidative cleavage of trimethylcyclohexanol to trimethyladipic acid.
  • nitric acid route has the advantage of high selectivity, which can reach up to 96%, but requires corrosion-resistant systems.
  • Another disadvantage is the release of nitrous gases (DE 199 22 643) or the handling of nitric acid or its residues.
  • the copper and manganese-catalyzed liquid phase oxidation or the oxidation with atmospheric oxygen leads to lower selectivity values (DE 199 22 643), in contrast to the nitric acid route, but it is not very corrosive.
  • the disadvantage is the use of acetic acid and the need for pressure-resistant systems.
  • the catalyst residues and spent catalysts or the contamination of the end product with heavy metals are further disadvantageous.
  • DE 44 27 474 describes an improved one-step process for the production of adipic acid by oxidation of cyclohexane in the liquid phase with oxygen under normal pressure at 130 ° C. using a cobalt salt.
  • the disadvantage here is the use of acetic acid and the use of a very complex and costly reprocessing process.
  • the object of the present invention was to develop a nitric acid-free and environmentally friendly process - without free heavy metals - and at the same time a cost-effective process for the catalytic oxidative cleavage of hydrocarbons which has high selectivities at high conversions.
  • non-oxidizing inorganic or organic acids are suitable, such as hydrochloric acid, acetic acid or formic acid, in order to largely or completely rule out corrosion, however, it is advisable to use acid-reacting solid porous compounds as co-catalysts.
  • This porous co-catalyst from the group of zeolites, the amorphous mixed metal oxides, the silicalites, aluminosilicates, aluminum phosphates or the partially exchanged zeolites may also contain transition metals or heavy metals, but these are either incorporated into the crystal structure of the z.
  • the present invention therefore relates to a process according to claim 1 for the catalytic oxidative cleavage of saturated and unsaturated cyclic compounds of the general structural formula
  • R a and R b are the same or different and a hydrogen radical, an aromatic or aliphatic radical having 1 to 20 carbon atoms, SO 3 H, NH 2 , OH, F, Cl, Br, I and / or NO, can represent an aliphatic or aromatic alkoxy radical, carboxyl radical and the radicals R a of different C atoms can be connected to one another via an oxygen atom (Epoxy) and R and R b on a C atom can both together represent a keto radical, which is characterized in that the saturated or unsaturated cyclic compound using an acidic compound with a porosity below 100 n as a co-catalyst with simultaneous use a catalyst and the presence of a radical initiator is split into a non-cyclic compound, a catalyst of the formula I
  • R H, aliphatic or aromatic alkoxy radical, carboxyl radical, alkoxycarbonyl radical or hydrocarbon radical, each with 1 to 20 carbon atoms, SO 3 H, NH, OH, F, Cl,
  • R 1 and R 2 denote identical or different radicals or
  • R and R can be linked to one another via a covalent bond
  • Co-catalysts are used.
  • the process according to the invention is based on the catalytic oxidative cleavage of saturated and unsaturated cyclic compounds of the general structural formula
  • R a and R b are the same or different and a hydrogen radical, an aromatic or aliphatic radical having 1 to 20 carbon atoms , SO 3 H, NH 2 , OH, F, Cl, Br, I and / or NO 2 , an aliphatic or aromatic alkoxy radical, carboxyl radical and the radicals R a of different carbon atoms can be connected to one another via an oxygen atom ( Epoxy) and R a and R b on a C atom can both together form a keto radical.
  • Epoxy oxygen atom
  • This catalytic oxidative cleavage of the saturated or unsaturated cyclic compound into a non-cyclic compound is carried out using an acidic compound, preferably a porous compound comprising silicon and / or aluminum, which preferably has a porosity of less than 100 nm, while using a Catalyst and presence of a radical initiator, a catalyst of the formula I
  • cocatalysts are understood to mean cocatalysts which can be used both in the reaction vessel in which the oxidation takes place and in a downstream reaction vessel.
  • the overall process according to the invention can therefore be carried out both as a so-called one-pot reaction and as a multi-stage reaction.
  • Examples of the catalysts which can be used in the process according to the invention are N-hydroxyphthalimide, 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, tetrabromo-N-hydroxyphthalimide, tetrachloro-N-hydroxyphthalimide, N-hydroxyhetimide, N-hydroxyhimimide, N -Hydroxytrimellitimide, N-hydroxy-benzene-1, 2,4-tricarboximide, N, N'-dihydroxy-pyromellitic acid diimide, N, N'-dihydroxy-benzophenone-3,3 ', 4,4'-tetracarbonic acid diimide, N-hydroxymaleimide, N-hydroxy-pyridine-2,3-dicarboximide, N-hydroxysuccinimide, N-hydroxy tartarimide, N-hydroxy-5-norbonen-2,3-dicarboximide, exo-N-hydroxy-7-oxabicyclo [2.2.
  • R, ⁇ , R, X, Y, Z, k and 1 have the meanings defined for compounds of the formula I.
  • R 1 , R 2 , R 3 and R 4 H, aliphatic or aromatic alkoxy radical, carboxyl radical,
  • Alkoxycarbonyl radical or hydrocarbon radical each having 1 to 20 carbon atoms
  • X, Z C, S and or CH 2 ,
  • R 1 , R 2 H, aliphatic or aromatic alkoxy radical, carboxyl radical, alkoxycarbonyl radical or hydrocarbon radical, each with 1 to 20 carbon atoms, SO 3 H, NH 2 , OH, F, Cl, Br, I and / or NO 2 , where R 1 and R 2 denote identical or different radicals or
  • R and R can be linked to one another via a covalent bond
  • X, Z C, S or CH 2
  • Y O or OH
  • k 0, 1 or 2
  • 1 0, 1 or 2
  • the oxidation is preferably carried out so that the molar ratio of the catalyst to the hydrocarbon to be oxidized, that is to say the saturated and / or unsaturated cyclic hydrocarbons, is from 10 " to 1 to 0.1 to 1, preferably from 10 " to 1 to 0, 05 to 1, very particularly preferably from 10 " to 1 to 0.025 to 1 and in a special embodiment from 10 " to 100 to 1 to 100.
  • the process is preferably carried out using a porous compound containing silicon and / or aluminum as co-catalyst, which preferably has a porosity of less than 100 ⁇ m, particularly preferably less than 20 nm and very particularly preferably less than 10 nm.
  • porosity means the average pore size.
  • the pore size is usually determined according to Horvath and Kawazoe (J. Chem. Eng. Jpn. 16 (1983) 470 ff).
  • the BET surface is in accordance with W.F. Maier et al. (Tetrahedron 51 (1995) 3787 f).
  • the process according to the invention is preferably carried out in such a way that from 0.1 to 10 mol%, particularly preferably from 0.5 to 5.0 mol%, of the cocatalyst, based on the used to be cleaved and oxidized compound are used.
  • the co-catalyst comprising silicon and / or aluminum can e.g. B. a porous compound selected from the group of zeolites, the amorphous mixed metal oxides, the silicalites, aluminosilicates, aluminum phosphates, the partially exchanged zeolites or a mixture of the aforementioned compounds.
  • a zeolite, an amorphous misclimetal oxide or a silicalite with a pore size of less than 5 nm is particularly preferably used as the cocatalyst.
  • the cocatalyst containing silicon and / or aluminum can have elements of the 3rd main group, the 4th main group, the 3rd to 8th subgroup of the periodic table, including the lanthanoids and actinides, which are firmly bonded to the cocatalyst.
  • the cocatalyst used in the process according to the invention preferably has Mn, Co, Cu, Ni.
  • B. Si / Al lattice leads to so-called Bronsted acid centers.
  • the foreign metals are, for example, in the synthesis of the zeolite in the form of soluble salts, such as nitrates, citrates, oxalates or complex compounds such as.
  • the oxidation preferably takes place in the liquid phase at a temperature of 0 to 500 ° C., particularly preferably at a temperature of 50 to 200 ° C. Both a solvent or solvent mixture and the compound to be split and oxidized itself can be used as the solvent.
  • the saturated and unsaturated cyclic compounds used for the catalytic oxidative cleavage generally belong to the group of hydrocarbons.
  • a large number of cyclic organic compounds, such as aromatics, cycloaliphatics, cycloolefins can be selectively oxidized and split.
  • R a and R b are the same or different and are a hydrogen radical, an aromatic or aliphatic radical having 1 to 20 carbon atoms, SO 3 H, NH 2 , OH, F, Cl, Br, I and / or NO, an aliphatic or aromatic alkoxy radical, carboxyl radical and the radicals R a and R b of different carbon atoms can be connected to one another via an oxygen atom and both can together represent a keto radical on a carbon atom.
  • the reaction mixture contains a radical initiator, which is either itself a radical or decomposes to form radicals, such as. B. a peroxy compound or an azo compound.
  • a radical initiator such as cumene hydroperoxide, cyclohexylbenzene hydroperoxide, cyclododecylbenzene hydroperoxide, 1,4-di (2-neodecanoyl-peroxyisopropyl) benzene, acetylcyclohexanesulfonyl peroxide, cumyl-peroxyneodecanoate, dicyclohexyl-4-oxy-4-oxy-oxy-4-oxy-4-oxy-oxy-4-oxy-oxy-4-oxy-oxy-4-yl peroxydicarbonate, dimyristylperoxydicarbonate, dicetylperoxydicarbonate, ter - butylperoxyneodecanoate, tert.-amylperoxyneo
  • a radical initiator which contains an oxygen atom bonded to a primary, secondary or tertiary carbon atom is preferably used.
  • a radical initiator which is derived from the end product itself and contains at least one oxygen atom bonded to a primary, secondary or tertiary carbon atom is particularly preferably used.
  • the radical initiator is either added separately or, as mentioned above, generated during the reaction, or is even present in small quantities from previous reactions, since a production plant cannot be cleaned absolutely.
  • the concentration of the radical initiator in the process according to the invention is often lower than the concentration of the catalyst at the start of the reaction.
  • an intermediate formation of radical initiators can take place in the course of the reaction, see above that the concentration of radical-initiating compounds can increase in the course of the reaction.
  • the process according to the invention can be carried out using an oxygen-containing gas as the oxidizing agent.
  • the proportion of oxygen in the gas can be between 5 to 100% by volume.
  • Atmospheric oxygen or pure oxygen is preferably used as the oxidizing agent. It is important to ensure that the liquid and gaseous phases are thoroughly mixed. This can e.g. B. in stirred tanks by a corresponding stirring speed or by internals and in tubular reactors with packing elements and with bubble columns.
  • the process according to the invention can be carried out both under atmospheric pressure and under increased pressure up to 100 bar.
  • a pressure of 1 bar to 50 bar is preferred, a pressure of 1 bar to 20 bar is particularly preferred.
  • the process according to the invention can be carried out batchwise (in batches or in feedbatch) or continuously.
  • the method is preferably carried out continuously.
  • Oxidation and ring cleavage can be carried out both in a single reaction vessel and in different reaction vessels - that is, downstream.
  • reaction product formed by oxidative cleavage can be isolated as such, but the direct further conversion of this compound into another product is also possible.
  • isolation of the product is by any common technical process such. B. distillation possible.
  • the conversion in the oxidation reaction was determined by GC analysis with an internal standard (naphthalene).
  • the selectivity of the reaction was also determined by GC analysis an internal standard (also naphthalene).
  • Examples a and b Preparation instructions for zeolite a) and zeolite b) and silicalite 340 g of the starting mixture of a) 334.6 g tetraethyl orthosilicate, 7.94 g tetaethyl titanate,
  • 0.09 g of aluminum hydroxide and 1.11 g of ammonium hexacyanocobalt or from b) 334.6 tetraethyl orthosilicate, 1.34 g of aluminum hydroxide and 2.2 g of dimanganecacarbonyl are in a glass flask with 615 g of water containing 25% tetrapropylammonium hydroxide for 1 hour with the exclusion of air long stirred. The mixture is then carefully heated to 90 ° C over a period of 5 hours and the alcohol released is driven off. The volume is then supplemented with 1150 g of distilled water and the homogeneous liquid is introduced into an autoclave equipped with a stirrer.
  • Zeolite a or zeolite b).
  • the BET surface areas are all between 400 and 600 m 2 / g, the mean value of the pore size is approximately between 0.5 and 0.7 nm, determined according to Horvath and Kawazoe (J. Chem. Eng. Jpn. 16, 1983, 470 ff.).
  • Example 1 (according to the invention):
  • Example 2 (not according to the invention, with cobalt catalyst):
  • Example 4 (not according to the invention, with manganese catalyst):

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de division catalytique oxidative de substrats cycliques tels que des hydrocarbures cycliques et des composés hétérocycliques selon lequel on utilise un composé acide comme cocatalyseur en même temps qu'un catalyseur. Ledit catalyseur est un composé de la formule (I) dans laquelle : R1et R2 représentent H, des résidus alcoxy, carboxyle, alcoxy carboxyle ou d'hydrocarbures, chacun avec 1 à 20 atomes de carbone, SO¿3?H, NH2, OH, F, Cl, Br, I et /ou NO2, R?1 et R2¿ pouvant représenter des restes identiques ou différents ou bien R1 et R2 pouvant être combinés entre eux par une liaison covalente ; Q1et Q2 sont identiques ou différents et représentent C, CH, N ; X, Z représentent C, S ou CH¿2 ?; Y = O ou OH, k = 0, 1, ou 2, l = 0, 1, ou 2, k et l ne devant pas prendre la valeur 0 en même temps ; et m = 1 à 100. Ce catalyseur est utilisé en présence d'un amorceur radicalaire, le rapport moléculaire entre le catalyseur et l'hydrocarbure est inférieur à 10 % en moles. On peut utiliser des composés peroxy ou des composés azoïques comme amorceur radicalaire. Des substrats préférés sont des composés aliphatiques ou aromatiques cycliques
PCT/EP2002/006299 2001-06-16 2002-06-10 Procede de division catalytique oxidative de composes cycliques satures ou non sature WO2002102742A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002314151A AU2002314151A1 (en) 2001-06-16 2002-06-10 Method for the catalytic oxidative separation of cyclic saturated and unsaturated compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2001129117 DE10129117A1 (de) 2001-06-16 2001-06-16 Verfahren zur katalytischen oxidativen Spaltung zyklischer gestättigter und ungesättigter Verbindungen
DE10129117.5 2001-06-16

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WO2002102742A2 true WO2002102742A2 (fr) 2002-12-27
WO2002102742A3 WO2002102742A3 (fr) 2003-09-18

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0824962A1 (fr) * 1996-02-07 1998-02-25 Daicel Chemical Industries, Ltd. Systeme catalyseur d'oxydation et processus d'oxydation faisant appel a ce systeme
EP0858835A1 (fr) * 1997-02-17 1998-08-19 Daicel Chemical Industries, Ltd. Système catalytique d'oxydation et procédé d'oxydation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0824962A1 (fr) * 1996-02-07 1998-02-25 Daicel Chemical Industries, Ltd. Systeme catalyseur d'oxydation et processus d'oxydation faisant appel a ce systeme
EP0858835A1 (fr) * 1997-02-17 1998-08-19 Daicel Chemical Industries, Ltd. Système catalytique d'oxydation et procédé d'oxydation

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DE10129117A1 (de) 2002-12-19
AU2002314151A1 (en) 2003-01-02
WO2002102742A3 (fr) 2003-09-18

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