EP2601161A1 - Hydride transfer process for ketone preparation - Google Patents

Hydride transfer process for ketone preparation

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Publication number
EP2601161A1
EP2601161A1 EP11736338.2A EP11736338A EP2601161A1 EP 2601161 A1 EP2601161 A1 EP 2601161A1 EP 11736338 A EP11736338 A EP 11736338A EP 2601161 A1 EP2601161 A1 EP 2601161A1
Authority
EP
European Patent Office
Prior art keywords
formula
ketone
alcohol
iii
independently represent
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP11736338.2A
Other languages
German (de)
French (fr)
Inventor
Roland Jacquot
Philippe Marion
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
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Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP2601161A1 publication Critical patent/EP2601161A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/04—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/08—Acetone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a hydride transfer process in a reaction between an alcohol and a ketone and in the presence of a heterogeneous catalyst.
  • the simplified method according to the invention implements the transfer of a hydride from an alcohol to a ketone, thus simultaneously allowing the reduction of the ketone and the oxidation of the alcohol.
  • the invention relates to a simplified process for the simultaneous preparation of cyclohexanone and isopropanol, which allows an excellent efficiency which is very much improved.
  • the invention also relates to a mixture of compounds useful for carrying out the process according to the invention and comprising two different ketones and two alcohols.
  • Cyclohexanone is an important reagent in the context of the preparation of adipic acid used for the manufacture of polyamide, for example polyamide 6-6, or polyurethanes. It is also an important intermediate in the preparation of caprolactam, the monomer used in the manufacture of polyamide 6.
  • MPV Meerwein-Ponndorf-Verley reaction ketone
  • the present invention makes it possible, contrary to what was known from the state of the art, to prepare ketones from alcohols by a hydride transfer process in a reaction between an alcohol and a ketone and in the presence of a heterogeneous catalyst; moreover, in conditions hitherto deemed difficult or impossible to implement. Indeed, it could have been expected that an excess of ketone entails a significant risk of parasitic chemical reactions; or while the catalysts used cause reactions on the ketone produced.
  • the present invention thus proposes to provide a simplified method that provides solutions in all or part of the problems and disadvantages of the methods of the state of the art.
  • Said method also has certain other advantages, such as the fact that the preparation of an alcohol, in particular isopropanol, which is permitted by the invention is in general the product of the hydrogenation of the corresponding ketone, in particular acetone.
  • the process of the invention uses a reagent which can also serve as a reaction solvent.
  • the process according to the invention also makes it possible to use one of the reactants as hydride source or acceptor.
  • An object of the present invention is therefore to provide a process for preparing a ketone of formula (I) and an alcohol of formula (II)
  • N represents an integer ranging from 1 to 9;
  • R 1 and R 2 independently represent a hydrocarbon group at C r C 10 .
  • n advantageously represents 2, 3, 4, 5 or 9, in particular 2, 3 or 9.
  • n represents 3.
  • R 1 or R 2 independently represent CH 2 R 3 , CHR 4 R 5 or CR 6 R 7 R 8 in which: • R 3 represents a linear or branched alkyl in;
  • R 4 and R 5 independently represent a linear or branched alkyl in CC 8 ;
  • R 6 , R 7 , R 8 independently represent a linear or branched alkyl in CC 6 .
  • R 1 and R 2 independently represent methyl, ethyl, n-propyl, iso-propyl or t-butyl; in particular, R 1 and R 2 represent methyl.
  • the ketone of formula (IV) is advantageously chosen from ketones of low molecular weight, in particular from ketones whose molecular mass is less than 130 g / mol or even less than 100 g / mol.
  • the molar ratio (II) / (IV) is advantageously chosen between 1/10 and 2/1, preferably between 1/8 and 1/2.
  • said heterogeneous catalyst used in the porked preparation according to the invention is selected from zeolites, hydroxyapatites with different atomic ratio Ca / P, tricalcium phosphate, magnesium phosphates, olivine, alumina, rare earth oxides as such or mixed with other oxides.
  • the heterogeneous catalyst is generally a hydride transfer catalyst.
  • Catalysts for the process according to the invention include zeolite or zeolite catalysts.
  • zeolite is meant a crystallized tectosilicate of natural or synthetic origin whose crystals result from the three-dimensional assembly of tetrahedral units of Si0 4 and T0 4 : T representing a trivalent element such as aluminum, gallium, boron, iron preferably aluminum.
  • T representing a trivalent element such as aluminum, gallium, boron, iron preferably aluminum.
  • the aluminosilicate zeolites are the most common.
  • Zeolites have within the crystal lattice a system of cavities interconnected by channels of a well-defined diameter called pore. They can present a network of one-dimensional, two-dimensional or three-dimensional channels.
  • zeolites that may be used include, for example: chabazite, clinoptilotite, erionite, phillipsite, offretite.
  • synthetic zeolites with a one-dimensional network include zeolite ZSM-4, zeolite L, zeolite ZSM-12, zeolite ZSM-22, zeolite ZSM-23, zeolite ZSM-48.
  • mordenite and ferrierite mention may be made of mordenite and ferrierite.
  • zeolite As regards the three-dimensional network zeolites, ⁇ zeolite (BEA), titanium zeolite ⁇ , tin zeolite (SnBEA), zeolite Y, zeolite X, zeolite may be more specifically referred to as zeolite.
  • Preferential use is made of synthetic zeolites and more particularly zeolites which are in the following forms:
  • mordenite with a Si / Al molar ratio of 5 to 15; ferrierite with a Si / Al molar ratio of 3 to 10;
  • titanium ⁇ zeolites with Si / Al ratio greater than 50, preferably between 200 and
  • Ti content expressed in% by weight of TiO 2 varies between 0, 1 and 10%, preferably between 1 and 5%;
  • zeolites Y in particular zeolites obtained after dealumination treatment (for example hydrotreatment, washing with hydrochloric acid or treatment with silicon tetrachloride), and more particularly mentioning US-Y zeolites molar Si / Al greater than 2, preferably between 6 and 60;
  • mesoporous materials of the MCM type more particularly MCM-49 and MCM-41, of molar ratio Si / Al of between 10 and 100, preferably of between 15 and 40;
  • microporous materials for example MCM-22.
  • zeolites ⁇ and Y preference is given to zeolites ⁇ and Y, in particular ⁇ -zeolites.
  • zeolite it may be necessary, in order to obtain the desired Si / Al ratio, to carry out a dealumination treatment.
  • a dealumination treatment it is possible to use the methods known to those skilled in the art, among which, by way of examples, non-exhaustive examples include calcinations in the presence of steam and calcinations in the presence of water vapor. followed by attacks by mineral acids (HN0 3 , HCl, etc.), the direct dealumination treatments with reagents such as silicon tetrachloride (SiCl 4 ), ammonium hexafluorosilicate ((NH 4 ) 2 SiF 6 )), ethylenediaminetetraacetic acid (EDTA) and its mono-or disodium form.
  • reagents such as silicon tetrachloride (SiCl 4 ), ammonium hexafluorosilicate ((NH 4 ) 2 SiF 6 )), ethylenediaminetetraacetic acid (EDTA)
  • dealumination treatment by direct acid etching with solutions of inorganic acids such as, for example, hydrochloric acid, nitric acid, sulfuric acid or organic acids such as in particular acetic acid or oxalic acid.
  • inorganic acids such as, for example, hydrochloric acid, nitric acid, sulfuric acid or organic acids such as in particular acetic acid or oxalic acid.
  • organic acids such as in particular acetic acid or oxalic acid.
  • any combination of the aforementioned methods of dealumination is also possible.
  • a zeolite which has undergone activation by calcination.
  • the calcining operation is carried out at a temperature of between 200 and 800 ° C., preferably between 400 and 700 ° C., for a duration varying from 1 to 24 hours, preferably from 5 to 8 hours.
  • the zeolites used in the process of the invention are known products described in the literature. Commercially available zeolites may be used or may be synthesized according to the methods described in the literature.
  • the zeolite constitutes the catalytic phase of the process according to the invention. It can be used alone or mixed with a mineral matrix. According to the invention, the term "catalyst" will be used to refer to the catalyst made entirely of zeolite or mixed with a matrix prepared according to techniques known to those skilled in the art.
  • the matrix may be chosen from metal oxides, such as oxides of aluminum, silicon and / or zirconium, or from clays and more particularly, kaolin, talc or montmorillonite.
  • the active phase content is 5 to 100% by weight of the catalyst.
  • the catalysts may be in various forms in the process of the invention: powder, shaped products such as extruded granules or pellets, pellets, which are obtained by extrusion, molding, compacting or any other type of known process. In practice, in industrial terms, it is the forms of granules or beads that have the most advantages both in terms of efficiency and convenience of implementation.
  • the process according to the invention is athermic and therefore does not release or very little heat allowing particularly easy control of the reaction and the heating conditions.
  • the reaction temperature can be between 30 and 120 ° C, preferably between 40 and 90 ° C.
  • the pressure is generally autogenous and can advantageously be kept below 10 bar.
  • the process according to the invention is carried out in the absence of a source of hydrogen and without a particular solvent.
  • the process according to the invention can be implemented in the liquid phase.
  • the liquid phase is advantageous because the reaction is then generally very selective and can reach or exceed 96% of selectivity.
  • the invention relates to a process (P) for preparing cyclohexanone and isopropanol by transfer of a cyclohexanol hydride to acetone in a cyclohexanol / acetone molar ratio ranging from 1/10 to 2/1. preferably from 1/8 to 1/2, and in the presence of a heterogeneous catalyst.
  • the reaction can be carried out continuously or discontinuously.
  • the reaction technology can be a perfectly stirred reactor with a catalyst in suspension but also a fixed bed in which a portion of the stream is recycled to control the conversion more easily.
  • the feed streams must generally have a minimum water content, preferably less than 1% by weight, so as not to degrade the performance of the reaction with certain catalysts.
  • the invention also relates to a mixture of compounds that are useful for carrying out the process according to the invention.
  • the invention also relates to a mixture comprising a ketone of formula (I), an alcohol of formula (II), an alcohol of formula (III) and a ketone of formula (IV),
  • N represents an integer ranging from 1 to 9;
  • R and R 2 independently represent a hydrocarbon group in CC w .
  • n advantageously represents 2, 3, 4, 5 or 9, in particular 2, 3 or 9.
  • n represents 3.
  • R 1 or R 2 independently represent CH 2 R 3 , CHR 4 R 5 or CR 6 R 7 R 8 in which:
  • R 3 represents a linear or branched alkyl in ;
  • R 4 and R 5 independently represent a linear or branched C 1 -C 6 alkyl
  • R 6 , R 7 , R 8 independently represent a linear or branched alkyl in CC 6 .
  • R 1 and R 2 independently represent methyl, ethyl, n-propyl, iso-propyl or t-butyl; in particular, R 1 and R 2 represent methyl.
  • the ketone of formula (IV) is advantageously chosen from ketones of low molecular weight, in particular from ketones whose molecular mass is less than 130 g / mol or even less than 100 g / mol.
  • the compounds of formulas (I) to (IV) may be present in a wide range of ratios.
  • the alcohol of formula (III) and the ketone of formula (IV) are present in a molar ratio (III) / (IV) alcohol of formula (III) / ketone of formula (IV) ranging from 1 / 10 to 2/1.
  • the ratio (III) / (IV) is advantageously chosen between 1/8 and 1/2.
  • acetone, cyclohexanol, isopropanol and cyclohexanone mixture in particular such a mixture whose cyclohexanol / acetone molar ratio ranges from 1/10 to 2/1, preferably from 1 to / 8 to 1/2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a hydride transfer process within a reaction between an alcohol and a ketone and in the presence of a heterogeneous catalyst. The simplified process according to the invention transfers a hydride from an alcohol to a ketone, thus enabling the reduction of the ketone and the oxidation of the alcohol. In particular, the invention relates to a simplified process for the simultaneous preparation of cyclohexanone and isopropanol enabling an excellent, very significantly optimized industrial operation. The invention also relates to a mixture of compounds useful for implementing the process according to the invention and comprising two different ketones and two different alcohols.

Description

PROCÈDE DE TRANSFERT D'HYDRURE POUR LA PRÉPARATION DE CETONE  PROCESS FOR TRANSFERRING HYDRIDE FOR THE PREPARATION OF KETONE
DESCRIPTION DESCRIPTION
La présente invention concerne un procédé de transfert d'hydrure au sein d'une réaction entre un alcool et une cétone et en présence d'un catalyseur hétérogène. Le procédé simplifié selon l'invention met en œuvre le transfert d'un hydrure d'un alcool vers une cétone, permettant ainsi simultanément la réduction de la cétone et l'oxydation de l'alcool. En particulier, l'invention concerne un procédé simplifié de préparation simultanée de la cyclohexanone et d'isopropanol permettant une excellente efficacité très nettement améliorée.  The present invention relates to a hydride transfer process in a reaction between an alcohol and a ketone and in the presence of a heterogeneous catalyst. The simplified method according to the invention implements the transfer of a hydride from an alcohol to a ketone, thus simultaneously allowing the reduction of the ketone and the oxidation of the alcohol. In particular, the invention relates to a simplified process for the simultaneous preparation of cyclohexanone and isopropanol, which allows an excellent efficiency which is very much improved.
L'invention concerne également un mélange de composés utiles à la mise en œuvre du procédé selon l'invention et comprenant deux cétones et deux alcools différents. La cyclohexanone constitue un important réactif dans le cadre de la préparation de l'acide adipique utilisé pour la fabrication du polyamide, par exemple du polyamide 6-6, ou encore des polyuréthanes. Elle constitue aussi un intermédiaire important dans la préparation du caprolactame, monomère utilisé dans la fabrication du polyamide 6. On connaît la préparation simultanée d'un alcool et d'acétone ou de butanone-2 à partir d'isopropanol ou d'isobutanol et d'une cétone par réaction de Meerwein-Ponndorf-Verley (MPV).  The invention also relates to a mixture of compounds useful for carrying out the process according to the invention and comprising two different ketones and two alcohols. Cyclohexanone is an important reagent in the context of the preparation of adipic acid used for the manufacture of polyamide, for example polyamide 6-6, or polyurethanes. It is also an important intermediate in the preparation of caprolactam, the monomer used in the manufacture of polyamide 6. The simultaneous preparation of an alcohol and acetone or butanone-2 from isopropanol or isobutanol and from a Meerwein-Ponndorf-Verley reaction ketone (MPV).
On connaît la préparation de cétones et d'alcools à partir d'un alcool et d'une cétone par réaction de type Oppenauer. The preparation of ketones and alcohols from an alcohol and a ketone by reaction of the Oppenauer type is known.
Le plus souvent, les réactions de l'état de la technique ont néanmoins pour but la préparation d'alcool par hydrogénation du dérivé carbonylé ou de l'alcool insaturé correspondant.  Most often, the reactions of the state of the art nevertheless aim at the preparation of alcohol by hydrogenation of the carbonyl derivative or the corresponding unsaturated alcohol.
Ainsi, il est connu de fabriquer du cyclohexanol par hydrogénation du phénol, souvent à des pressions comprises entre 10 et 50 bar. Toutefois, cette réaction est effectuée dans des conditions difficiles liées à l'utilisation de l'hydrogène et coûteuses.  Thus, it is known to manufacture cyclohexanol by hydrogenation of the phenol, often at pressures between 10 and 50 bar. However, this reaction is carried out under difficult conditions related to the use of hydrogen and expensive.
Il est aussi connu d'obtenir de la cyclohexanone par déshydrogénation du cyclohexanol en utilisant des catalyseurs à base de cuivre, à une température comprise entre 250 et 300°C. Cette réaction est donc très énergivore et la manipulation d'hydrogène produit par la réaction est problématique.  It is also known to obtain cyclohexanone by dehydrogenation of cyclohexanol using copper catalysts at a temperature between 250 and 300 ° C. This reaction is therefore very energy intensive and the handling of hydrogen produced by the reaction is problematic.
Il est aussi connu de produire du cyclohexanol par oxydation du cyclohexane dans l'air en présence de catalyseurs à base de chrome. It is also known to produce cyclohexanol by oxidation of cyclohexane in air in the presence of chromium-based catalysts.
Il est par ailleurs connu de préparer de l'isopropanol par hydrogénation de l'acétone par une catalyse au chrome qui pose également le problème de la manipulation de l'hydrogène.  It is also known to prepare isopropanol by hydrogenation of acetone by chromium catalysis which also raises the problem of handling hydrogen.
Ainsi, la demande de brevet internationale WO-98/30517 décrit la réduction d'un composé carbonylé par réaction avec un alcool en présence d'un catalyseur, en particulier, ce document décrit la réduction de 4-alkyl-cyclohexanones en présence d'isopropanol en vue de préparer les alcools cyclohexaniques correspondants selon le schéma réactionnel suivant :  Thus, the international patent application WO-98/30517 describes the reduction of a carbonyl compound by reaction with an alcohol in the presence of a catalyst, in particular, this document describes the reduction of 4-alkyl-cyclohexanones in the presence of isopropanol in order to prepare the corresponding cyclohexane alcohols according to the following reaction scheme:
cétone A + alcool B cétone C + alcool D Il existe ainsi un besoin d'un procédé simple à mettre en œuvre et permettant la synthèse de cyclohexanone tout en évitant les inconvénients mentionnés des procédés connus. ketone A + alcohol B ketone C + alcohol D There is thus a need for a process that is simple to implement and allows the synthesis of cyclohexanone while avoiding the mentioned drawbacks of known processes.
La présente invention permet, contrairement à ce qui était connu de l'état de la technique, la préparation de cétones à partir des alcools par un procédé de transfert d'hydrure au sein d'une réaction entre un alcool et une cétone et en présence d'un catalyseur hétérogène ; qui plus est dans des conditions jusqu'alors réputées difficiles voire impossibles à mettre en œuvre. En effet, on aurait pu s'attendre à ce qu'un excès de cétone entraine un risque important de réactions chimiques parasites ; ou alors que les catalyseurs utilisés entraînent des réactions sur la cétone produite. The present invention makes it possible, contrary to what was known from the state of the art, to prepare ketones from alcohols by a hydride transfer process in a reaction between an alcohol and a ketone and in the presence of a heterogeneous catalyst; moreover, in conditions hitherto deemed difficult or impossible to implement. Indeed, it could have been expected that an excess of ketone entails a significant risk of parasitic chemical reactions; or while the catalysts used cause reactions on the ketone produced.
La présente invention se propose ainsi de fournir un procédé simplifié et qui apporte des solutions en tout ou partie aux problèmes et inconvénients des procédés de l'état de la technique. Ledit procédé présente par ailleurs certains autres avantages tels que le fait que la préparation d'un alcool, notamment l'isopropanol, permise par l'invention est en général le produit de l'hydrogénation de la cétone correspondante, notamment l'acétone. De manière avantageuse, le procédé de l'invention met en œuvre un réactif qui peut également servir de solvant de réaction. Le procédé selon l'invention permet également d'utiliser l'un des réactifs comme source ou accepteur d'hydrure. The present invention thus proposes to provide a simplified method that provides solutions in all or part of the problems and disadvantages of the methods of the state of the art. Said method also has certain other advantages, such as the fact that the preparation of an alcohol, in particular isopropanol, which is permitted by the invention is in general the product of the hydrogenation of the corresponding ketone, in particular acetone. Advantageously, the process of the invention uses a reagent which can also serve as a reaction solvent. The process according to the invention also makes it possible to use one of the reactants as hydride source or acceptor.
Un objet de la présente invention est donc de fournir un procédé de préparation d'une cétone de formule (I) et d'un alcool de formule (II) An object of the present invention is therefore to provide a process for preparing a ketone of formula (I) and an alcohol of formula (II)
(l) (II)  (l) (II)
par transfert d'un hydrure, en présence d'un catalyseur hétérogène, entre un alcool de formule (III) et une cétone de formule (IV), présents en un ratio molaire (lll)/(IV), alcool de formule (III) / cétone de formule (IV), allant de 1/10 à 2/1 , by transfer of a hydride, in the presence of a heterogeneous catalyst, between an alcohol of formula (III) and a ketone of formula (IV), present in a molar ratio (III) / (IV), alcohol of formula (III ) / ketone of formula (IV), ranging from 1/10 to 2/1,
(NI) (IV)  (NI) (IV)
dans lesquelles in which
• n représente un entier allant de 1 à 9 ;  N represents an integer ranging from 1 to 9;
· R1 et R2 représentent indépendamment un groupement hydrocarboné en CrC10. R 1 and R 2 independently represent a hydrocarbon group at C r C 10 .
Pour le procédé selon l'invention, n représente avantageusement 2, 3, 4, 5 ou 9, en particulier 2, 3 ou 9. De manière préférée, n représente 3. De manière préférée, pour le procédé selon l'invention, R1 ou R2 représentent indépendamment CH2R3, CHR4R5 ou CR6R7R8 dans lesquelles : • R3 représente un alkyl linéaire ou ramifié en ; For the process according to the invention, n advantageously represents 2, 3, 4, 5 or 9, in particular 2, 3 or 9. Preferably, n represents 3. Preferably, for the process according to the invention, R 1 or R 2 independently represent CH 2 R 3 , CHR 4 R 5 or CR 6 R 7 R 8 in which: • R 3 represents a linear or branched alkyl in;
• R4 et R5 représentent indépendamment un alkyl linéaire ou ramifié en C C8 ; R 4 and R 5 independently represent a linear or branched alkyl in CC 8 ;
• R6, R7, R8 représentent indépendamment un alkyl linéaire ou ramifié en C C6. R 6 , R 7 , R 8 independently represent a linear or branched alkyl in CC 6 .
De manière toute préférée, R1 et R2 représentent indépendamment methyl, ethyl, n-propyl, iso-propyl, t-butyl ; tout particulièrement, R1 et R2 représentent methyl. Most preferably, R 1 and R 2 independently represent methyl, ethyl, n-propyl, iso-propyl or t-butyl; in particular, R 1 and R 2 represent methyl.
Ainsi, la cétone de formule (IV) est avantageusement choisie parmi les cétones de faible masse moléculaire, en particulier parmi les cétones dont la masse moléculaire est inférieure à 130 g/mol, voire inférieure à 100 g/mol. Thus, the ketone of formula (IV) is advantageously chosen from ketones of low molecular weight, in particular from ketones whose molecular mass is less than 130 g / mol or even less than 100 g / mol.
Pour le procédé selon l'invention, le ratio molaire (l ll)/(IV) est avantageusement choisi entre 1 /10 et 2/1 , de manière préférée entre 1 /8 et 1 /2. For the process according to the invention, the molar ratio (II) / (IV) is advantageously chosen between 1/10 and 2/1, preferably between 1/8 and 1/2.
Conformément à l'invention, ledit catalyseur hétérogène mis en œuvre dans le porcédé de préparation selon l'invention est choisi parmi les zéolithes, les hydroxyapatites avec différents ratio atomique Ca/P, le phosphate tricalcique, les phosphates de magnésium, l'olivine, les alumines, oxydes de terres rares tels quels ou en mélange avec d'autres oxydes. According to the invention, said heterogeneous catalyst used in the porked preparation according to the invention is selected from zeolites, hydroxyapatites with different atomic ratio Ca / P, tricalcium phosphate, magnesium phosphates, olivine, alumina, rare earth oxides as such or mixed with other oxides.
Pour le procédé selon l'invention, le catalyseur hétérogène est généralement un catalyseur de transfert d'hydrure. Comme catalyseurs pour le procédé selon l'invention, on peut citer les catalyseurs zéolithiques ou à base de zéolithe.  For the process according to the invention, the heterogeneous catalyst is generally a hydride transfer catalyst. Catalysts for the process according to the invention include zeolite or zeolite catalysts.
Par "zéolithe", on entend un tectosilicate cristallisé d'origine naturelle ou synthétique dont les cristaux résultent de l'assemblage tridimensionnel d'unités tétraédriques de Si04 et T04 : T représentant un élément trivalent tel que aluminium, gallium, bore, fer, de préférence, l'aluminium. Les zéolithes de type aluminosilicate sont les plus communes. By "zeolite" is meant a crystallized tectosilicate of natural or synthetic origin whose crystals result from the three-dimensional assembly of tetrahedral units of Si0 4 and T0 4 : T representing a trivalent element such as aluminum, gallium, boron, iron preferably aluminum. The aluminosilicate zeolites are the most common.
Les zéolithes présentent au sein du réseau cristallin un système de cavités reliées entre elles par des canaux d'un diamètre bien défini que l'on appelle les pores. Elles peuvent présenter un réseau de canaux monodimensionnel, bidimensionnel ou tridimensionnel. Zeolites have within the crystal lattice a system of cavities interconnected by channels of a well-defined diameter called pore. They can present a network of one-dimensional, two-dimensional or three-dimensional channels.
Dans le procédé de l'invention , on peut faire appel à une zéolithe naturelle ou synthétique. Comme exemples de zéolithes naturelles susceptibles d'être utilisées, on peut citer, par exemple : la chabazite, la clinoptilotite, l'érionite, la phillipsite, l'offrétite. Comme exemples de zéolithes synthétiques à réseau monodimensionnel, on peut citer entre autres, la zéolithe ZSM-4, la zéolithe L, la zéolithe ZSM-12, la zéolithe ZSM-22, la zéolithe ZSM-23, la zéolithe ZSM-48. A titre d'exemples de zéolithes à réseau bidimensionnel mises en œuvre préférentiellement, on peut mentionner la mordénite et la ferrierite. En ce qui concerne les zéolithes à réseau tridimensionnel, on peut nommer plus particulièrement, la zéolithe β (BEA), la zéolithe β au titane, la zéolithe β à l'étain (SnBEA), la zéolithe Y, la zéolithe X, la zéolithe ZSM-5, la zéolithe ZSM-1 1 , l'offrétite. On fait appel préférentiellement aux zéolithes synthétiques et plus particulièrement aux zéolithes qui sont sous les formes suivantes :  In the process of the invention, it is possible to use a natural or synthetic zeolite. Examples of natural zeolites that may be used include, for example: chabazite, clinoptilotite, erionite, phillipsite, offretite. Examples of synthetic zeolites with a one-dimensional network include zeolite ZSM-4, zeolite L, zeolite ZSM-12, zeolite ZSM-22, zeolite ZSM-23, zeolite ZSM-48. As examples of two-dimensional network zeolites implemented preferentially, mention may be made of mordenite and ferrierite. As regards the three-dimensional network zeolites, β zeolite (BEA), titanium zeolite β, tin zeolite (SnBEA), zeolite Y, zeolite X, zeolite may be more specifically referred to as zeolite. ZSM-5, zeolite ZSM-1 1, offretite. Preferential use is made of synthetic zeolites and more particularly zeolites which are in the following forms:
- la mazzite de rapport molaire Si/AI de 3, 4 ;  the mazzite with a Si / Al molar ratio of 3.4;
- la zéolithe L de rapport molaire Si/AI de 1 , 5 à 3, 5 ;  zeolite L with an Si / Al molar ratio of 1.5 to 3.5;
- la mordénite de rapport molaire Si/AI de 5 à 1 5 ; - la ferrierite de rapport molaire Si/AI de 3 à 10 ; mordenite with a Si / Al molar ratio of 5 to 15; ferrierite with a Si / Al molar ratio of 3 to 10;
- l'offrétite de rapport molaire Si/AI de 4 à 8, 5 ;  - The offretite of Si / Al molar ratio of 4 to 8.5;
- les zéolithes β de rapport molaire Si/AI supérieur à 8, généralement compris entre 10 et 100, de préférence, entre 12 et 50, et encore plus préférentiellement entre 12 et 35 ;  the β zeolites with an Si / Al molar ratio greater than 8, generally between 10 and 100, preferably between 12 and 50, and even more preferably between 12 and 35;
- les zéolithes β au titane de rapport Si/AI supérieur à 50, de préférence, compris entre 200 et titanium β zeolites with Si / Al ratio greater than 50, preferably between 200 and
600 et la teneur en Ti exprimée en % en poids de Ti02 varie entre 0, 1 et 10 %, de préférence, entre 1 et 5 % ; 600 and the Ti content expressed in% by weight of TiO 2 varies between 0, 1 and 10%, preferably between 1 and 5%;
- les zéolithes β au titane sans aluminium ou à très faible teneur (rapport Si/AI supérieur à 100 000) ; la teneur en Ti exprimée en % en poids de Ti02 varie entre 0, 1 et 10 %, de préférence, entre 1 et 5 %, par exemple les ΤΊΒΕΑ ; β-zeolites titanium without aluminum or very low content (Si / Al ratio greater than 100,000); the Ti content expressed in% by weight of TiO 2 varies between 0.1 and 10%, preferably between 1 and 5%, for example ΤΊΒΕΑ;
- les zéolithes Y en particulier les zéolithes obtenues après traitement de désalumination (par exemple hydrotraitement, lavage à l'aide d'acide chlorhydrique ou traitement par le tétrachlorure de silicium) et l'on peut citer plus particulièrement les zéolithes US-Y de rapport molaire Si/AI supérieur à 2, de préférence compris entre 6 et 60 ;  zeolites Y, in particular zeolites obtained after dealumination treatment (for example hydrotreatment, washing with hydrochloric acid or treatment with silicon tetrachloride), and more particularly mentioning US-Y zeolites molar Si / Al greater than 2, preferably between 6 and 60;
- la zéolithe X de type faujasite de rapport molaire Si/AI de 0, 7 à 1 , 5, -les zéolithes ZSM-5 ou silicalite d'aluminium de rapport molaire Si/AI de 10 à 500 ;  the zeolite X of the faujasite type with a Si / Al molar ratio of 0.7 to 1.5, the zeolites ZSM-5 or aluminum silicalite with a Si / Al molar ratio of 10 to 500;
- la zéolithe ZSM-1 1 de rapport molaire Si/AI de 5 à 30 ;  zeolite ZSM-11 with an Si / Al molar ratio of 5 to 30;
- les matériaux mésoporeux de type MCM, plus particulièrement MCM-49 et MCM-41 de rapport molaire Si/AI compris entre 10 et 100, de préférence, compris entre 15 et 40 ;  mesoporous materials of the MCM type, more particularly MCM-49 and MCM-41, of molar ratio Si / Al of between 10 and 100, preferably of between 15 and 40;
- les matériaux microporeux, par exemple MCM-22.  microporous materials, for example MCM-22.
Parmi toutes ces zéolithes, pour procédé selon l'invention, on fait préférentiellement appel aux zéolithes β et Y, en particulier aux zéolithes β.  Among all these zeolites, for the process according to the invention, preference is given to zeolites β and Y, in particular β-zeolites.
Quelle que soit la nature de la zéolithe, il peut être nécessaire afin d'obtenir le rapport Si/AI souhaité, de faire un traitement de désalumination. Ainsi, on peut mettre en œuvre les méthodes connues de l'homme du métier parmi lesquelles on peut citer, à titre d'exemples, et de manière non exhaustive, les calcinations en présence de vapeur, les calcinations en présence de vapeur d'eau suivies d'attaques par des acides minéraux (HN03, HCI, etc), les traitements directs de désalumination par des réactifs tels que le tétrachlorure de silicium (SiCI4), l'hexafluorosilicate d'ammonium ((NH4)2SiF6)), l'éthylènediaminetétracétique (EDTA) ainsi que sa forme mono-ou disodique. On peut également faire un traitement de désalumination par attaque acide directe avec des solutions d'acides minéraux tels que par exemple l'acide chlorhydrique, l'acide nitrique, l'acide sulfurique ou d'acides organiques comme notamment l'acide acétique ou l'acide oxalique. Par ailleurs, toute combinaison des méthodes de désalumination précitées est aussi possible. Whatever the nature of the zeolite, it may be necessary, in order to obtain the desired Si / Al ratio, to carry out a dealumination treatment. Thus, it is possible to use the methods known to those skilled in the art, among which, by way of examples, non-exhaustive examples include calcinations in the presence of steam and calcinations in the presence of water vapor. followed by attacks by mineral acids (HN0 3 , HCl, etc.), the direct dealumination treatments with reagents such as silicon tetrachloride (SiCl 4 ), ammonium hexafluorosilicate ((NH 4 ) 2 SiF 6 )), ethylenediaminetetraacetic acid (EDTA) and its mono-or disodium form. It is also possible to carry out dealumination treatment by direct acid etching with solutions of inorganic acids such as, for example, hydrochloric acid, nitric acid, sulfuric acid or organic acids such as in particular acetic acid or oxalic acid. Moreover, any combination of the aforementioned methods of dealumination is also possible.
Pour le procédé selon l'invention, il est également possible de mettre en œuvre une zéolithe ayant subie une activation par calcination. L'opération de calcination est conduite à une température comprise entre 200 et 800°C, de préférence entre 400 et 700°C, pendant une durée variant de 1 à 24 heures, de préférence de 5 à 8 heures Les zéolithes mises en œuvre dans le procédé de l'invention sont des produits connus décrits dans la littérature. On peut faire appel aux zéolithes disponibles dans le commerce ou bien les synthétiser selon les procédés décrits dans la littérature.  For the process according to the invention, it is also possible to implement a zeolite which has undergone activation by calcination. The calcining operation is carried out at a temperature of between 200 and 800 ° C., preferably between 400 and 700 ° C., for a duration varying from 1 to 24 hours, preferably from 5 to 8 hours. The zeolites used in the process of the invention are known products described in the literature. Commercially available zeolites may be used or may be synthesized according to the methods described in the literature.
La zéolithe constitue la phase catalytique du procédé selon l'invention. Elle peut être utilisée seule ou en mélange avec une matrice minérale. Selon l'invention, on désignera par "catalyseur", le catalyseur réalisé entièrement en zéolithe ou en mélange avec une matrice préparée selon des techniques connues de l'homme du métier. À cet effet, la matrice peut être choisie parmi les oxydes de métaux, tels que les oxydes d'aluminium, de silicium et/ou de zirconium, ou encore parmi les argiles et plus particulièrement, le kaolin, le talc ou la montmorillonite. The zeolite constitutes the catalytic phase of the process according to the invention. It can be used alone or mixed with a mineral matrix. According to the invention, the term "catalyst" will be used to refer to the catalyst made entirely of zeolite or mixed with a matrix prepared according to techniques known to those skilled in the art. For this purpose, the matrix may be chosen from metal oxides, such as oxides of aluminum, silicon and / or zirconium, or from clays and more particularly, kaolin, talc or montmorillonite.
Dans le catalyseur, la teneur en phase active représente de 5 à 100% du poids du catalyseur. In the catalyst, the active phase content is 5 to 100% by weight of the catalyst.
Les catalyseurs peuvent se présenter sous différentes formes dans le procédé de l'invention : poudre, produits mis en forme tels que granulés par exemple extrudés ou billes, pastilles, qui sont obtenus par extrusion, moulage, compactage ou tout autre type de procédé connu. En pratique, sur le plan industriel, ce sont les formes de granulés ou de billes qui présentent le plus d'avantages tant sur le plan de l'efficacité que sur le plan de commodité de mise en œuvre.  The catalysts may be in various forms in the process of the invention: powder, shaped products such as extruded granules or pellets, pellets, which are obtained by extrusion, molding, compacting or any other type of known process. In practice, in industrial terms, it is the forms of granules or beads that have the most advantages both in terms of efficiency and convenience of implementation.
De manière avantageuse, le procédé selon l'invention est athermique et ne dégage donc pas ou très peu de chaleur permettant un contrôle particulièrement aisé de la réaction et des conditions de chauffage. Ainsi, pour le procédé selon l'invention, la température de réaction peut être comprise entre 30 et 120°C, de préférence entre 40 et 90°C. Advantageously, the process according to the invention is athermic and therefore does not release or very little heat allowing particularly easy control of the reaction and the heating conditions. Thus, for the process according to the invention, the reaction temperature can be between 30 and 120 ° C, preferably between 40 and 90 ° C.
Pour le procédé selon l'invention, la pression est généralement autogène et peut avantageusement être maintenue inférieure à 10 bar. De manière particulièrement avantageuse, le procédé selon l'invention est mis en œuvre en absence de source d'hydrogène et sans solvant particulier. For the process according to the invention, the pressure is generally autogenous and can advantageously be kept below 10 bar. In a particularly advantageous manner, the process according to the invention is carried out in the absence of a source of hydrogen and without a particular solvent.
Le procédé selon l'invention peut être mis en œuvre en phase liquide. La phase liquide est avantageuse car la réaction est alors généralement très sélective et peut atteindre ou dépasser 96% de sélectivité. The process according to the invention can be implemented in the liquid phase. The liquid phase is advantageous because the reaction is then generally very selective and can reach or exceed 96% of selectivity.
De manière particulièrement avantageuse, l'invention concerne un procédé (P) de préparation de cyclohexanone et d'isopropanol par transfert d'un hydrure du cyclohexanol sur l'acétone en un ratio molaire cyclohexanol/acétone allant de 1/10 à 2/1 , de préférence allant de 1/8 à 1/2, et en présence d'un catalyseur hétérogène. Particularly advantageously, the invention relates to a process (P) for preparing cyclohexanone and isopropanol by transfer of a cyclohexanol hydride to acetone in a cyclohexanol / acetone molar ratio ranging from 1/10 to 2/1. preferably from 1/8 to 1/2, and in the presence of a heterogeneous catalyst.
Les préférences des conditions de mise en œuvre du procédé selon l'invention concernent également le procédé (P) selon l'invention.  The preferences of the conditions of implementation of the process according to the invention also relate to the process (P) according to the invention.
Pour le procédé selon l'invention, la réaction peut être effectuée de manière continue ou discontinue. La technologie de réaction peut être un réacteur parfaitement agité avec un catalyseur en suspension mais aussi un lit fixe dans lequel une partie du flux est recyclé pour maîtriser plus facilement la conversion. Les flux alimentés doivent généralement avoir une teneur minimale en eau, avantageusement inférieure à 1 % en masse, ceci afin ne pas dégrader les performances de la réaction avec certains catalyseurs. L'invention concerne également un mélange de composés utiles à la mise en œuvre du procédé selon l'invention. Ainsi, l'invention concerne également un mélange comprenant une cétone de formule (I), un alcool de formule (II), un alcool de formule (III) et une cétone de formule (IV), For the process according to the invention, the reaction can be carried out continuously or discontinuously. The reaction technology can be a perfectly stirred reactor with a catalyst in suspension but also a fixed bed in which a portion of the stream is recycled to control the conversion more easily. The feed streams must generally have a minimum water content, preferably less than 1% by weight, so as not to degrade the performance of the reaction with certain catalysts. The invention also relates to a mixture of compounds that are useful for carrying out the process according to the invention. Thus, the invention also relates to a mixture comprising a ketone of formula (I), an alcohol of formula (II), an alcohol of formula (III) and a ketone of formula (IV),
(I) (II) (III) (IV) dans lesquelles (I) (II) (III) (IV) in which
· n représente un entier allant de 1 à 9 ;  N represents an integer ranging from 1 to 9;
• R et R2 représentent indépendamment un groupement hydrocarboné en C Cw. • R and R 2 independently represent a hydrocarbon group in CC w .
Pour le mélange selon l'invention, n représente avantageusement 2, 3, 4, 5 ou 9, en particulier 2, 3 ou 9. De manière préférée, n représente 3. For the mixture according to the invention, n advantageously represents 2, 3, 4, 5 or 9, in particular 2, 3 or 9. Preferably, n represents 3.
De manière préférée, pour le mélange selon l'invention, R1 ou R2 représentent indépendamment CH2R3, CHR4R5 ou CR6R7R8 dans lesquelles : Preferably, for the mixture according to the invention, R 1 or R 2 independently represent CH 2 R 3 , CHR 4 R 5 or CR 6 R 7 R 8 in which:
• R3 représente un alkyl linéaire ou ramifié en ; • R 3 represents a linear or branched alkyl in ;
• R4 et R5 représentent indépendamment un alkyl linéaire ou ramifié en C^Cs ; R 4 and R 5 independently represent a linear or branched C 1 -C 6 alkyl;
· R6, R7, R8 représentent indépendamment un alkyl linéaire ou ramifié en C C6. R 6 , R 7 , R 8 independently represent a linear or branched alkyl in CC 6 .
De manière toute préférée, R1 et R2 représentent indépendamment methyl, ethyl, n-propyl, iso-propyl, t-butyl ; tout particulièrement, R1 et R2 représentent methyl. Most preferably, R 1 and R 2 independently represent methyl, ethyl, n-propyl, iso-propyl or t-butyl; in particular, R 1 and R 2 represent methyl.
Ainsi, la cétone de formule (IV) est avantageusement choisie parmi les cétones de faible masse moléculaire, en particulier parmi les cétones dont la masse moléculaire est inférieure à 130 g/mol, voire inférieure à 100 g/mol. Thus, the ketone of formula (IV) is advantageously chosen from ketones of low molecular weight, in particular from ketones whose molecular mass is less than 130 g / mol or even less than 100 g / mol.
Au sein du mélange selon l'invention, les composés de formules (I) à (IV) peuvent être présents en un une large gamme de ratio. De manière avantageuse, l'alcool de formule (III) et la cétone de formule (IV) sont présents en un ratio molaire (lll)/(IV) alcool de formule (III) / cétone de formule (IV) allant de 1/10 à 2/1 . Pour le mélange selon l'invention, le ratio (lll)/(IV) est avantageusement choisi entre 1/8 et 1/2. Within the mixture according to the invention, the compounds of formulas (I) to (IV) may be present in a wide range of ratios. Advantageously, the alcohol of formula (III) and the ketone of formula (IV) are present in a molar ratio (III) / (IV) alcohol of formula (III) / ketone of formula (IV) ranging from 1 / 10 to 2/1. For the mixture according to the invention, the ratio (III) / (IV) is advantageously chosen between 1/8 and 1/2.
Comme exemple de mélange particulièrement avantageux selon l'invention, on peut citer le mélange acétone, cyclohexanol, isopropanol et cyclohexanone, notamment un tel mélange dont le ratio molaire cyclohéxanol/acétone va de 1/10 à 2/1 , de manière préférée de 1/8 à 1/2. As an example of a particularly advantageous mixture according to the invention, mention may be made of the acetone, cyclohexanol, isopropanol and cyclohexanone mixture, in particular such a mixture whose cyclohexanol / acetone molar ratio ranges from 1/10 to 2/1, preferably from 1 to / 8 to 1/2.
L'exemple suivant illustre le procédé de l'invention, en particulier les avantages de ce procédé. The following example illustrates the process of the invention, in particular the advantages of this process.
Exemple 1 Example 1
Dans un réacteur de 250 ml pouvant travailler sous pression, on introduit 100 g de cyclohexanol, soit 1 mol, et 175 g d'acétone, soit 3 mol. On agite et on ajoute 20 g de catalyseur. On chauffe alors le réacteur à 75°C et à pression autogène et on maintient pendant 3 heures dans ces conditions. Le milieu réactionnel est alors analysé par chromatographie en phase gazeuse (CPG). Les résultats obtenus sont présentés dans le tableau 1 . 250 g of cyclohexanol, ie 1 mol, and 175 g of acetone, ie 3 mol, are introduced into a 250 ml reactor capable of working under pressure. Stir and add 20 g of catalyst. We then heat the reactor at 75 ° C and autogenous pressure and maintained for 3 hours under these conditions. The reaction medium is then analyzed by gas chromatography (GC). The results obtained are shown in Table 1.
Tableau 1  Table 1
La faisabilité de la réaction est démontrée et la sélectivité est égale ou supérieure à 80%. Exemple 2 The feasibility of the reaction is demonstrated and the selectivity is equal to or greater than 80%. Example 2
Dans un réacteur pouvant travailler sous pression, on introduit 100 g de cyclohexanol, soit 1 mol, et 350 g d'acétone, soit 6 mol. On agite et on ajoute 20 g de catalyseur. On chauffe alors le milieu réactionnel à 75°C et à pression autogène, on maintient pendant 3h dans ces conditions. On analyse alors le milieu réactionnel par CPG. Les résultats obtenus sont rassemblés dans le tableau 2. In a reactor which can work under pressure, 100 g of cyclohexanol, ie 1 mol, and 350 g of acetone, ie 6 mol, are introduced. Stir and add 20 g of catalyst. The reaction medium is then heated at 75 ° C. and at autogenous pressure, and maintained under these conditions for 3 hours. The reaction medium is then analyzed by GC. The results obtained are collated in Table 2.
Tableau 2  Table 2
Pour cet essai, la conversion est très améliorée tout en gardant une excellente sélectivité.  For this test, the conversion is greatly improved while maintaining excellent selectivity.

Claims

REVENDICATIONS
1. Procédé de préparation d'une cétone de formule (I) et d'un alcool de formule (II) 1. Process for preparing a ketone of formula (I) and an alcohol of formula (II)
(l) (II)  (l) (II)
par transfert d'un hydrure, en présence d'un catalyseur hétérogène, entre un alcool de formule (III) et une cétone de formule (IV), présents en un ratio molaire (lll)/(IV), alcool de formule (III) / cétone de formule (IV), allant de 1/10 à 2/1 , ledit catalyseur étant choisi parmi les zéolithes, les hydroxyapatites avec différents ratio atomique Ca/P, le phosphate tricalcique, les phosphates de magnésium, l'olivine, les alumines, oxydes de terres rares tels quels ou en mélange avec d'autres oxydes, by transfer of a hydride, in the presence of a heterogeneous catalyst, between an alcohol of formula (III) and a ketone of formula (IV), present in a molar ratio (III) / (IV), alcohol of formula (III ) / ketone of formula (IV), ranging from 1/10 to 2/1, said catalyst being chosen from zeolites, hydroxyapatites with different atomic ratio Ca / P, tricalcium phosphate, magnesium phosphates, olivine, alumina, rare earth oxides as such or mixed with other oxides,
(NI) (IV)  (NI) (IV)
dans lesquelles in which
• n représente un entier allant de 1 à 9 ;  N represents an integer ranging from 1 to 9;
• R et R2 représentent indépendamment un groupement hydrocarboné en CrC10. • R and R 2 independently represent a hydrocarbon group C r C 10 .
2. Procédé selon la revendication 1 pour lequel n représente 2, 3, 4, 5 ou 9. 2. The method of claim 1 wherein n is 2, 3, 4, 5 or 9.
3. Procédé selon les revendications 1 et 2 pour lequel R1 ou R2 représentent indépendamment CH2R3, CHR4R5 ou CR6R7R8 dans lesquelles : 3. Process according to claims 1 and 2 for which R 1 or R 2 independently represent CH 2 R 3 , CHR 4 R 5 or CR 6 R 7 R 8 in which:
• R3 représente un alkyl linéaire ou ramifié en ; • R 3 represents a linear or branched alkyl in ;
• R4 et R5 représentent indépendamment un alkyl linéaire ou ramifié en C C8 ; R 4 and R 5 independently represent a linear or branched alkyl in CC 8 ;
• R6, R7, R8 représentent indépendamment un alkyl linéaire ou ramifié en C C6. R 6 , R 7 , R 8 independently represent a linear or branched alkyl in CC 6 .
4. Procédé selon les revendications 1 à 3 pour lequel la cétone de formule (IV) est choisie parmi les cétones de faible masse moléculaire dont la masse moléculaire est inférieure à 130 g/mol. 4. Process according to claims 1 to 3 wherein the ketone of formula (IV) is chosen from low molecular weight ketones whose molecular mass is less than 130 g / mol.
5. Procédé selon les revendications 1 à 4 pour lequel le ratio molaire (lll)/(IV) est choisi entre 1/8 et 1/2. 5. Method according to claims 1 to 4 for which the molar ratio (III) / (IV) is chosen between 1/8 and 1/2.
6. Procédé selon les revendications 1 à 5 pour lequel la température de réaction est comprise entre 30 et 120°C. 6. Process according to claims 1 to 5 for which the reaction temperature is between 30 and 120 ° C.
7. Procédé (P) de préparation de cyclohexanone et d'isopropanol par transfert d'un hydrure du cyclohexanol sur l'acétone en un ratio molaire cyclohexanol/acétone allant de 1/10 à 2/1 et en présence d'un catalyseur hétérogène. 7. Process (P) for preparing cyclohexanone and isopropanol by transfer of a cyclohexanol hydride on acetone in a cyclohexanol / acetone molar ratio ranging from 1/10 to 2/1 and in the presence of a heterogeneous catalyst .
8. Mélange comprenant une cétone de formule (I), un alcool de formule (II), un alcool de formule (III) et une cétone de formule (IV), 8. Mixture comprising a ketone of formula (I), an alcohol of formula (II), an alcohol of formula (III) and a ketone of formula (IV),
(I) (II) (III) (IV) dans lesquelles (I) (II) (III) (IV) in which
• n représente un entier allant de 1 à 9 ;  N represents an integer ranging from 1 to 9;
• R et R2 représentent indépendamment un groupement hydrocarboné en CrC10 • R and R 2 independently represent a hydrocarbon group C r C 10
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