EP1603852A2

EP1603852A2 - Metallic compound fixed to a support, method for production and use of said compound in hydrocarbon metathesis reactions

Info

Publication number: EP1603852A2
Application number: EP04742338A
Authority: EP
Inventors: Jean-Marie Basset; Christophe Coperet; Daravong Soulivong; Mostafa Taoufik; Jean Thivolle-Cazat
Original assignee: CPE Lyon FCR SAS; CPE Lyon Formation Continue et Recherche SAS
Current assignee: CPE Lyon FCR SAS; CPE Lyon Formation Continue et Recherche SAS
Priority date: 2003-03-25
Filing date: 2004-03-24
Publication date: 2005-12-14
Also published as: FR2852866B1; US20070129584A1; WO2004089541A2; WO2004089541A3; FR2852866A1; CN1795153B; CN1795153A

Abstract

The invention relates to a supported metal compound, comprising a support made from aluminium oxide to which a tungsten hydride is grafted. The support may be selected from the homogeneous supports with a composition based on aluminum oxide and from heterogeneous supports made from aluminium oxide with aluminum oxide essentially on the surface of said support. The support may in particular comprise aluminium oxide, mixed aluminium oxides and modified aluminium oxides particularly comprising one or more elements of groups 15 to 17 of the periodic table of the elements, such as phosphorus, sulphur, fluorine or chlorine. A support made from porous, non-porous or mesoporous aluminas is preferred. The degree of oxidation of the tungsten may have a value of from 2 to 6. The tungsten atom is generally bonded to one or several hydrogen atoms and optionally to one or several hydrocarbon groups. According to the invention, the compound may be prepared by a dispersion step and grafting of a tungsten organometallic precursor to the support made from aluminium oxide then hydrogenation of the resulting product. The product may be used as catalyst in reactions of cleavage and recombination of hydrocarbons, particularly in hydrocarbon metathesis reactions most particularly of alkanes. The product has a surprising, extremely high catalytic activity in this type of reaction and in particular, a high selectivity for the formation of n-alkanes with relation to iso-alkanes.

Description

The present invention relates to a metal compound fixed on a solid support, to a process for the preparation and to uses of the compound in particular as a reaction catalyst for the metathesis of hydrocarbon compounds.

International patent application WO 98/02244 describes a process for metathesis of alkanes in which one or more alkanes are reacted on a solid compound comprising a metal hydride grafted on a solid support. The preparation of the solid compound comprises firstly a grafting of an organometallic compound onto a solid support so as to form an organometallic compound grafted, then a treatment by hydrogenolysis of the said compound with hydrogen or another reducing agent so as to melt a metal hydride grafted on the support. The metal hydride thus prepared is used as a catalyst in alkane metathesis reactions. The metal of the metal hydride can be chosen from the transition metals from Groups 5 to 6 of the Table of the Periodic Classification of the Elements, and the support can be chosen from many solid oxides. Typically, the examples of the international patent application describe the preparation of a tantalum hydride grafted onto silica and the use of this hydride in metathesis reactions of emane, propane, butane or isobutane. The examples also describe the preparation of a tungsten hydride grafted onto silica and the use of this hydride in a propane metathesis reaction. These tantalum or tungsten hydrides grafted onto silica are active in alkane metathesis reactions. However, it appeared as an important objective to find reaction catalysts for metathesis of hydrocarbons having an even higher activity in this field.

It was surprisingly found that all the possible combinations between the transition metals of Groups 5 and 6 on the one hand and the supports based on solid oxides on the other, nothing suggested that the specific choices bearing on tungsten as a transition metal and on aluminum oxide as a solid support could lead to a metal hydride grafted on a solid support capable of considerably improving the catalysis of the reactions of hydrocarbon metathesis. This improvement concerns both a considerable increase in the catalytic activity and an increase in the selectivity towards normal hydrocarbons formed in comparison with hydrocarbons of “iso” form in the metathesis reactions of hydrocarbons.

The present invention relates first of all to a supported metallic compound comprising a support based on aluminum oxide onto which a tungsten hydride is grafted. The term “tungsten hydride grafted onto a support based on aluminum oxide” generally means a tungsten atom linked to at least one hydrogen atom and, in particular by at least one single bond, to said support.

The Table of the Periodic Classification of the Elements quoted previously and later is that presented by IUPAC in 1991 in which the groups are numbered from 1 to 18 and which one finds for example in “CRC Handbook of Chemistry and Physics”, 76th Edition (1995-1996), by David R. Lide, published by CRC Press, hic. (USA).

The compound according to the invention essentially comprises a tungsten hydride grafted on a support based on aluminum oxide. In this compound, the support can be any support based on aluminum oxide, and more particularly any support where aluminum oxide is accessible in particular on the surface of said support. Thus the support can be chosen from relatively homogeneous supports in composition based on aluminum oxide, having in particular a composition based on aluminum oxide relatively homogeneous throughout the whole mass of the support, that is to say say from the heart to the surface of the support, and also among heterogeneous supports based on aluminum oxide comprising aluminum oxide essentially on the surface of the supports. In the case of a heterogeneous support, the support can comprise aluminum oxide deposited, supported or grafted on an inorganic solid which can itself be an inorganic solid support, in particular chosen from metals, oxides or sulfides and salts, for example from silica and metal oxides.

The support can have a specific surface (BET) chosen in a range going from 0.1 to 1000 m ² / g, preferably from 0.5 to 800 m ² / g. The specific surface (BET) is measured according to standard ISO 9277 (1995). The support may in particular comprise aluminum oxide, mixed aluminum oxides or aluminum oxides modified, in particular by one or more elements from Groups 15 to 17 of the Table of the Periodic Table of the Elements. By aluminum oxide (also called simple alumina), is generally meant an aluminum oxide substantially free of any other oxide (or containing less than 2% by weight of one or more other oxides, present in the form of impurities) . If it contains more than 2% by weight of one or more other oxides, then it is generally agreed to consider the oxide as a mixed oxide of alummiu, i.e. an aluminum oxide combined with at least one other oxide.

The support may preferably comprise aluminum oxide chosen from porous aluminas, non-porous aluminas and mesoporous aluminas.

Porous aluminas are often called "activated aluminas" or "transition aluminas". They generally correspond to different aluminum oxides, A1 ₂ 0 ₃ , partially hydroxylated. These are porous supports generally obtained by a so-called “activation” treatment comprising in particular a heat treatment (or dehydration) of a precursor chosen from aluminum hydroxides, such as aluminum tri-hydroxides, aluminum oxide hydroxides or gelatinous aluminum hydroxides. The activation treatment makes it possible to remove the water contained in the precursor, but also in part the hydroxyl groups, thus leaving a few residual hydroxyl groups and a specific porous structure. The surface of porous aluminas generally comprises a complex mixture of aluminum and oxygen atoms and hydroxyl ions which combine according to specific crystalline forms and which in particular produce both acid and basic sites. One can thus choose as solid support a porous alumina among Talumine-γ (alumina-gamma), alumina-T (alumina-eta), alumina-δ (alumina-delta), alumina-fl (alumina- theta), alumina-c (alumina-kappa), alumina-p (alumina-ro) and alumina-χ (alumina-ksi or -chi), and preferably from alumina-7 and l alumina-η. These different crystalline forms depend essentially on the choice of the precursor and the conditions of the activation treatment, in particular the temperature and the pressure. Activation processing can be performed by example under a stream of air or a stream of another gas, in particular an inert gas, at a temperature which can be chosen in a range going from 100 to 1000 ° C., preferably from 200 to 1000 ° C.

It is also possible to use porous or even semi-porous aluminas, prepared by an activation treatment as previously described, in particular at a temperature ranging from 600 to 1000 ° C. These porous or semi-porous aluminas can comprise mixtures of porous aluminas under at least one of the crystalline foundations previously described, such as alumina-γ, alumina-77, alumina-δ, alumina - ^, alumina- * :, alumina-p or alumma-χ, with a non-porous alumina, in particular alumina-α, in particular in a proportion of 20 to 80% by weight.

Porous aluminas are generally the decomposition products of aluminum tri-hydroxides, hydroxides of aluminum oxide (or hydrates of aluminum oxide) and gelatinous hydroxides of aluminum (or gels of alumina). Aluminum tri-hydroxides of general formula Al (OH) ₃ = A1 ₂ 0 ₃ ,

3H ₂ 0 can exist in different crystalline forms, such as gibbsite or hydrargillite (Al (OH) -a), bayerite (Al (OH) ₃ -j8), or nordstrandite. Aluminum trihydroxides can be obtained by precipitation from aluminum salts in generally alkaline solutions. Aluminum oxide hydroxides of general formula AIO (OH) =

A1 ₂ 0 ₃ , H ₂ 0 can also exist in different crystalline forms, such as diaspore (A10 (OH) - / 3) or boehmite (or AIO (OH) -CÏ). Diaspore can be found in certain types of clay and bauxite, and can be synthesized by a heat treatment of gibbsite at around 150 ° C, or by a hydrothermal treatment of boehmite at 380 ° C under a pressure of 50MPa. Boehmite can be easily obtained by heating the gelatinous precipitate formed by cold treating solutions of aluminum salts with ammonia. Aluminum oxide hydroxides can also be obtained by hydrolysis of aluminum alcoholates.

Gelatinous aluminum hydroxides (or alumina gels) are generally aluminum polyhydroxides, in particular of general formula: nAl (OH) ₃ , (nl) H ₂ 0 (1) in which n is a number varying from 1 to 8. The gelatinous aluminum hydroxides can be obtained by one of the methods chosen from the thermal decomposition of an aluminum salt, such as aluminum chloride, electrolysis of aluminum salts, such as a mixture of aluminum sulphate and alkaline sulphate, hydrolysis of aluminum alcoholates, such as aluminum methylate, precipitation from aluminates, such as alkali or alkaline-alkali aluminates, and precipitation from aluminum salts, for example by contacting aqueous solutions of A1 ₂ (S0) ₃ and ammonia, or NaA10 ₂ and an acid, or NaA10 ₂ and Al ₂ (S0 ₄ ) _3ι the precipitates thus obtained can then undergo aging and drying i to remove the water. Gelatinous aluminum hydroxides are generally present in the form of an amorphous alumina gel, in particular in the form of a pseudoboehmite.

Porous aluminas may have a specific surface (BET) chosen from a range from 100 to 1000 m ² / g, preferably from 300 to 1000 m ² / g, in particular from 300 to 800 m ² / g, in particular from 300 at 600 m ² / g. They can also have a specific pore volume equal to or less than 1 cm ³ / g, preferably equal to or less than 0.9 cm ³ / g, in particular equal to or less than 0.6 cm ³ / g.

The support can also comprise non-porous aluminas, preferably α-alumina (alpha-alumina), generally known under the term of "calcined alumina" or of "flame alumina". Alumina-α exists naturally under the term "corundum". It can generally be synthesized by heat treatment or calcination of a precursor chosen in particular from aluminum salts, aluminum oxide hydroxides, aluminum tri-hydroxides and aluminum oxides, such as alumina-γ, at a temperature above 1000 ° C, preferably above 1100 ° C. It can contain impurities such as other oxides, for example Fe ₂ 0 ₃ , Si0 ₂ , Ti0 ₂ , CaO, Na ₂ 0, K ₂ 0, MgO, SrO, BaO and Li ₂ O, in proportions lower than 2%, preferably 1% by weight. Non-porous aluminas, such as Talumine-α, can have a specific surface (BET) chosen in a range going from 0.1 to less than 300 m ² / g, preferably from 0.5 to 300 m ² / g , in particular from 0.5 to 250 m ² / g. The support can also comprise mesoporous aluminas, in particular having a specific surface (BET) chosen from a range going from 100 to 800 m ² / g. Mesoporous aluminas generally have pores ranging from 2 nm to 0.05 μm in width. The support can also include mixed aluminum oxides. By mixed aluminum oxides is generally meant aluminum oxides combined with at least one other oxide in a proportion by weight preferably of 2 to less than 80%, in particular from 2 to less than 50%, in particular from 2 to less than 40% or even 2 to less than 30%. The other oxide or oxides may be oxides of the elements, M, chosen by the metals from Groups 1 to 13 and the elements from Group 14, with the exception of carbon, from the Table of the Periodic Table of the Elements. More particularly, they can be oxides of the elements M chosen from alkali metals, alkaline earth metals, transition metals and elements from Groups 13 and 14 of said Table, with the exception of carbon. The transition metals generally include the metals of Groups 3 to 11 of said Table, in particular the elements 21 to 29, 39 to 47, 57 to 79 (including the lanthanides) and the actinides. The other oxide (s) of the elements M are preferably chosen from the transition metals from Groups 3 to 1, the lanthanides, the actinides and the elements from Groups 13 and 14 of said Table, with the exception of carbon. More particularly, they can be chosen from oxides of silicon, boron, gallium, germanium, titanium, zirconium, cerium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten.

Mixed aluminum oxides can be chosen from anhydrous aluminates, spinels and aluminosilicates. In particular, anhydrous aluminates can be chosen from anhydrous alkaline aluminates, such as anhydrous lithium aluminate (LiA10 ₂ ) or anhydrous sodium aluminate (Na 0, A1 0 ₃ ), and anhydrous alkaline earth aluminates , such as anhydrous tricalcium aluminate (3CaO, A1 ₂ 0) or anhydrous beryllium aluminate (BeO, A1 ₂ 0 ₃ ). The spinels can be chosen in particular from the aluminum oxides combined with the oxides of the divalent metals, and in particular from the magnesium spinel (MgAl ₂ 0 ₄ ), the calcium spinel (CaAl ₂ 0), the zinc spinel (ZnAl ₂ 0), the manganese spinel (MnAl ₂ O), iron spinel (FeAl ₂ 0) and cobalt spinel (CoAl ₂ 0). We can choose in particular aluminosilicates panni clays, talc, micas, feldspar, micro-porous aluminosilicates, in particular molecular sieves, and zeolites. The support can also comprise modified aluminum oxides, in particular modified by one or more elements from Groups 15 to 17, preferably from Groups 16 to 17 of the Table of the Periodic Classification of the Elements, for example phosphorus, sulfur, fluorine or chlorine. The support may in particular comprise alumina super acids or sulphated, sulphurized, chlorinated or fluorinated aluminum oxides.

The support can be a homogeneous support in composition, in particular across the whole mass of the support. It can also be a heterogeneous support based on aluminum oxide, support in which aluminum oxide, mixed aluminum oxides or modified aluminum oxides, as described above, are essentially arranged on the surface of the support, and the core of the support consists essentially of an inorganic solid chosen in particular from metals, oxides or sulfides, and salts, such as silica or metal oxides. The heterogeneous support can be prepared by dispersion, by precipitation and / or by grafting onto the mineral solid of one of the precursors of the compounds based on aluminum oxide mentioned above. The precursors can in particular be chosen from aluminum hydroxides, in particular from aluininium tri-hydroxides, aluminum oxide hydroxides and gelatinous aluminum hydroxides. Preferred are the gelatinous hydroxides of alumimum, as described above, known as alumina gels or amorphous alumina. The preparation of a heterogeneous support can be carried out in particular by using such a precursor by means of a sol-gel or using an organometallic compound which in particular facilitates grafting on the mineral solid.

The compound according to the invention is generally in the form of particles which can have any shape and any size, in particular an average size ranging from 10 to 5 mm, preferably from 20 nm to 4 mm. The particles of the support can be presented as they are or can be shaped so as to have a specific faith, in particular a spherical, spheroidal, hemispherical, hemispheroidal, cylindrical or cubic shape, or a form of rings, pellets, discs or granules.

The compound according to the invention essentially comprises a tungsten hydride grafted on the support based on aluminum oxide. The degree of oxidation of tungsten in the supported metal compound can have a value chosen from a range from 2 to 6, preferably from 4 to 6. The tungsten atom is linked in particular to the solid support, in particular by at least one single bond. It can also be linked to one or more hydrogen atoms by single bonds (W - H) and optionally to one or more hydrocarbon radicals, R, in particular by simple or multiple carbon-tungsten bonds. The number of hydrogen atoms linked to a tungsten atom depends on the degree of oxidation of the tungsten, on the number of single bonds linking said tungsten atom to the support and possibly on the number of single or multiple bonds linking said tungsten atom to hydrocarbon radical, R. Thus, the number of hydrogen atoms linked to a tungsten atom can be at least 1 and at most 5, and can preferably range from 1 to 4, preferably from 1 to 3. By grafting tungsten hydride to the solid support based on aluminum oxide, it is generally understood that the tungsten atom is linked by at least one single bond to said support, and more particularly by at least one bond single (W-OA1) to at least one oxygen atom of aluminum oxide. The number of single bonds linking the tungsten atom to the support, in particular by a single bond (W-OA1), depends on the degree of oxidation of the tungsten and on the number of the other bonds binding the tungsten atom, and is generally equal to 1, 2 or 3.

The tungsten atom of the compound according to the invention may optionally be linked to one or more hydrocarbon radicals, R, by one or more simple, double or triple carbon-tungsten bonds. The hydrocarbon radical (s), R, can be hydrocarbon radicals, identical or different, saturated or unsaturated, in particular comprising from 1 to 20, preferably from 1 to 10 carbon atoms, and optionally comprising silicon, in particular in a group organo-silane. They can be chosen in particular from alkyl radicals, in particular linear or branched, aliphatic or alicyclic, for example alkyl radicals, alkylidene or alkylidyne, in particular from Ci to Cio, pamii aryl radicals, in particular from C ₆ to Ci ₂ , and panni aralkyl, aralkylidene or aralkylidyne radicals, notaimxient from C ₇ to Cι ₄ .

The tungsten atom of the grafted tungsten hydride can be linked to the hydrocarbon radical, R, by one or more simple, double or triple carbon-tungsten bonds. It may be a simple carbon-tungsten bond, in particular of the σ type: in this case, the hydrocarbon radical, R, may be an alkyl radical, in particular linear or branched, or an aryl radical, for example the phenyl radical , or an aralkyl radical, for example the benzyl radical or the radical of formula (C6H5-CH2-CH2-). The term “alkyl radical” generally means a monovalent aliphatic radical originating from the removal of a hydrogen atom from a carbon atom of the molecule of an alkane, or of an alkene, or of an alkyne, or even an organosilane, for example a methyl (CH3-), ethyl (C2H5-), propyl (C2H5-CH2-), neopentyl ((CH3) 3C- CH2-), allyl (CH2 = CH-CH2-) radical ), alkynyl (RC ≡C-), in particular ethynyl (CFI≡ € -), or neosilyl ((CH ^ Si-CFL: -). The alkyl radical can be for example of formula (R'- CH2-) where R 'represents an alkyl radical, linear or branched.

It can also be a double carbon-tungsten bond, in particular of the 7τ type: in this case, the hydrocarbon radical, R, can be an alkylidene radical, in particular linear or branched, or an aralkylidene radical. The term “alkylidene radical” generally means a bivalent aliphatic radical originating from the removal of two hydrogen atoms from the same carbon atom of the molecule of an alkane, or of an alkene, or of an alkyne, or even an organosilane, for example a methylidene (CH2 =), ethylidene (CH3-CH =), propylidene (C2H5-CH =), neopentylidene ((CH3) 3C-CH =), or allylidene (CH2 = CH) radical -CH =). The alkylidene radical may for example be of formula (R'-CH =) where R 'represents an alkyl radical, linear or branched. The term “aralkylidene radical” generally means a bivalent aliphatic radical originating from the removal of two hydrogen atoms on the same carbon from an alkyl, alkenyl or alkynyl radical connected to an aromatic group. It can also be a triple carbon-tungsten bond: in this case, the hydrocarbon radical, R, can be an alkylidyne radical, in particular linear or branched, or an aralkylidyne radical. The term “alkylidyne radical” generally means a trivalent aliphatic radical originating from the removal of three hydrogen atoms from the same carbon atom of the molecule of an alkane, or of an alkene, or of an alkyne, or even of an organosilane, for example an ethylidyne radical (CH3-C, propylidyne (C2H5-C ^, neopentylidyne ((CΗ3) 3C-C OR allylidyne (CH2 = CH-C ^). The alkylidyne radical can be for example of formula (R'-C ^ where R 'represents an alkyl radical, linear or branched. By aralkylidyne radical is generally understood an aliphatic trivalent radical originating from the removal of three hydrogen atoms from the same carbon of an alkyl radical , alkenyl or alkynyl connected to an aromatic group.

More particularly, the hydrocarbon radical, R, can be chosen from the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neopentyl, allyl, neopentylidene, allylidene, neopentylidyne and neosilyl radicals.

The tungsten atom of the compound according to the invention can be complexed with one or more hydrocarbon ligands, in particular aromatic or carbonyl ligands.

The tungsten hydride grafted onto the support based on aluminum oxide can be represented diagrammatically by the following formula: ~ (Al- O) _x Hy \ /

W (2)

/ \ - (M- 0) _z R _w in which W, Al, O and H represent respectively tungsten, aluminum, oxygen and hydrogen atoms, M represents an atom of one or more elements d 'another oxide, as defined above, R represents a hydrocarbon radical, as defined above, and x, y, w and z are whole numbers whose sum (w + x + y + z) = 2 to 6, and with x = 1 to 3, y = 1 to 5, w = 0 to 4 and z = 0 to 2. In formula (2), the connections - (Al - O) and - (M - O) represent a or several single or multiple bonds connecting the aluminum atom and the M atom respectively to one of the atomic constituents of the support based on aluminum oxide, in particular to one of the oxygen atoms of this support.

The compound according to the invention generally exhibits, by infrared spectroscopy, one or more absorption bands specific for the bond (WH), bands whose frequency can vary according to the coordination sphere of tungsten and depend in particular on the number of bonds of tungsten with the support, with the hydrocarbon radicals R and with other hydrogen atoms. Thus, for example, at least two absorption bands were found at 1903 and 1804 cm ^" , specific bands in particular of the bond (WH) considered in particular in the environment of bonds (W-OA1) binding the same tungsten atom to an oxygen atom itself bound to an aluminum atom of an α-alumina. By way of comparison, tungsten hydride grafted under the same conditions on a silica support generally exhibits in infrared spectroscopy a at least of the two absorption bands at 1940 and 1960 cm ^"1 , bands which are different from the previous ones and which are in particular specific for the bond (WH) considered in particular in the environment of the bonds (W-OSi) binding the same tungsten atom to an oxygen atom itself linked to a silicon atom of the silica support.

Another way which can characterize the presence of a bond (W - H) in the compound according to the invention comes from a measurement by Nuclear Magnetic Resonance of the proton (H-solid NMR) under 500 MHz where the value of the chemical shift of tungsten hydride (δ _W - _H ) is equal to 10.6 ppm (parts per million).

The compound according to the invention may also comprise an aluminum hydride, in particular on the surface of the support and in particular in the vicinity of the grafted tungsten hydride. It is believed that an aluminum hydride can form by opening an aluminoxane bridge (of formula Al-O-Al) present in particular on the surface of the support and by reaction between a hydrogen atom of a grafted tungsten hydride. and the aluminoxane bridge thus opened. A simple test for characterizing the aluminum hydride present in the compound of the invention alongside a tungsten hydride comprises a deuteration reaction of said compound. The test can be carried out by bringing the compound according to the invention into contact with a deuterium atmosphere under an absolute pressure of 66.7 kPa, at a temperature chosen between 25 and 80 ° C., preferably equal to 60 ° C, for a period of 15 minutes. A selective deuteration reaction is thus carried out under these conditions: it makes it possible to substitute the hydrogen atoms by deuterium atoms in the bonds (WH) and thus to form new bonds (W- D) which in infrared spectroscopy present two absorption bands at 1293 and 1393 cm ^"1 , while leaving unchanged the hydrogen atoms in the bonds (Al-H) which can then be characterized in infrared spectroscopy by an absorption band at 1914 cm ^"1 .

The present invention also relates to a process for the preparation of the supported metal compound. The compound according to the invention which is essentially in the form of a tungsten hydride grafted on a support based on aluminum oxide, can be prepared by a process comprising the following steps:

(1) a step of dispersing and grafting an organometallic precursor ^' of tungsten (Pr) onto a support based on aluminum oxide, precursor in which the tungsten is in particular bonded or complexed to at least one hydrocarbon ligand, so as to form a tungsten hydrocarbon compound or complex grafted onto said support, then

(2) a step of hydrogenolysis of the grafted tungsten hydrocarbon compound or complex, resulting from the preceding step, so as to form a tungsten hydride grafted on said support.

The organometallic tungsten precursor, Pr, preferably comprises a tungsten atom linked or complexed with one or more hydrocarbon ligands. The atony of tungsten can in particular be linked to a carbon of the hydrocarbon ligand by single, double or triple (carbon-tungsten) bonds. The hydrocarbon ligands can be hydrocarbon radicals, identical or different, saturated or unsaturated, in particular aliphatic or alicyclic, preferably from Ci to C ₂ o, in particular from Ci to Cio, and can be chosen in particular from hydrocarbon radicals, R, described previously. The number of hydrocarbon ligands linked to the tungsten atom depends on the degree of oxidation of tungsten in the precursor Pr and may be at most equal to the degree of oxidation of tungsten in the precursor Pr, in particular be greater than 0 and at most equal to the maximum degree of oxidation of the tungsten and preferably have any value ranging from 2 to 6, in particular from 4 to 6.

The precursor Pr may include a tungsten atony, in particular complexed with one or more hydrocarbon ligands, the degree of oxidation of the tungsten being, in this case, equal to zero. The hydrocarbon ligand can be chosen from aromatic ligands or carbonyl ligands. Thus, the precursor Pr can be chosen from tungsten bis-arene and tungsten hexacarbonyl.

Prior to the first stage of dispersion and grafting, the support based on aluminum oxide can be subjected to a prior stage of calcination and / or dehydroxylation. The calcination of the support can be carried out so as to oxidize the carbon possibly present in the support and to eliminate it in the form of carbon dioxide. It can be carried out by subjecting the support to an oxidizing heat treatment, in particular under a stream of dry air, at a temperature below the sintering temperature of the support, for example at a temperature ranging from 100 to 1000 ° C., preferably from 200 to 800 ° C, for a sufficient time allowing the elimination of carbon dioxide and which can range from 0.1 to 48 hours, under a pressure lower, equal to or higher than atmospheric pressure.

The support can also be subjected to another prior step, called dehydroxylation. This step can be carried out so as to optionally remove the residual water from the support and part of the hydroxyl groups, to allow a residual amount of the hydroxyl groups to remain in particular on the surface of the support and to optionally form aluminoxane bridges (of formula Al-O -Al). The dehydroxylation can be carried out by subjecting the support to a heat treatment under an inert gas stream, for example under a stream of nitrogen, argon or helium, under a pressure preferably lower than atmospheric pressure, for example under an absolute pressure ranging from 10 ^"4 Pa to 10 ² kPa, preferably from 10 ^{" 2} Pa to 50 kPa, at a temperature below the sintering temperature of the support, for example at a temperature ranging from 100 to 1000 ° C, from preferably 200 to 800 ° C, and for a sufficient time permitting to leave an appropriate residual amount of hydroxyl and / or aluminoxane groups in the support and which can range from 0.1 to 48 hours. The dehydroxylation step can advantageously be carried out after the calcination step.

The dispersion and grafting step can be carried out by sublimation, by impregnation using a solvent, or by dry mixing. In the case of a sublimation step, the precursor Pr, which generally occurs in the solid state under normal conditions, is heated in particular under a pressure below atmospheric pressure and under temperature conditions ensuring its sublimation and its migration in the gaseous state on the support. The sublimation may be carried out at a temperature ranging from -30 to 200 ° C, and in particular an absolute pressure ranging from 10 ^{^"4-1} Pa. The grafting of the Pr precursor on the support can be monitored by infrared spectroscopy. The 'excess of precursor Pr which is not grafted on the support, can be eliminated by reverse sublimation.

The dispersion and grafting step can also be carried out by impregnation using a solvent. In this case, the precursor Pr can be dissolved in an organic solvent, polar or non-polar, for example pentane or ethyl ether. The impregnation can be carried out by bringing the support based on aluminum oxide into contact with the solution of the precursor Pr prepared previously. The impregnation can be carried out at a temperature ranging from -80 to 200 ° C., under an inert atmosphere, for example an atmosphere of nitrogen, argon or helium, and preferably with stirring. A suspension of a tungsten hydrocarbon compound or complex is thus obtained grafted onto the support. The excess of precursor Pr which has not been grafted onto the support can be eliminated by washing with an organic solvent, identical or different from that used during the impregnation.

The dispersion and grafting step can also be carried out by dry mixing, in particular by mechanical dry mixing, in the absence of liquid or of liquid solvent. In this case, the precursor Pr which is present in the form of a solid, is mixed with the support based on aluminum oxide, in the absence of liquid or of liquid solvent, in particular under mechanical stirring and under a inert atmosphere, for example an atmosphere of nitrogen, argon or helium, so as to form a mixture of two solids. During or after dry mixing, a heat treatment and / or a treatment can be carried out at a pressure below the pressure atmospheric, so as to migrate and react the precursor Pr with the support. The precursor which has not been grafted onto the support can be removed by reverse sublimation or by washing using an organic solvent.

The preparation of the compound according to the invention may comprise a second step called hydrogenolysis. It is a hydrogenolysis reaction of the tungsten hydrocarbon compound or complex grafted onto the support, as prepared in the previous step. The reaction is generally carried out so as to form a tungsten hydride grafted on the support. Hydrogenolysis is generally understood to mean a scission reaction of a molecule with fixation of hydrogen on the two split portions. In this case, the cleavage reaction takes place in particular between the tungsten atom grafted on the support and the carbon atom of the precursor Pr fixed or complexed with said tungsten atom. Hydrogenolysis can be carried out using hydrogen or a reducing agent, capable in particular of transforming the grafted tungsten hydrocarbon compound or complex into grafted tungsten hydride. Hydrogenolysis can be carried out by bringing the grafted tungsten hydrocarbon compound or complex into contact with hydrogen or the reducing agent. It can be carried out under a hydrogen atmosphere or an inert atmosphere when a reducing agent is used, under an absolute pressure ranging from 10 ^"2 to 10 MPa, at a temperature ranging from 20 to 500 ° C., for a duration ranging from 0.1 to 48 hours The present invention also relates to the use of the compound according to the invention in a process implementing cleavage and recombination reactions of hydrocarbon (s). of the compound according to the invention in a process for the manufacture of hydrocarbon (s) having a carbon skeleton modified by reaction of at least one aliphatic hydrocarbon with itself, or with at least one other aliphatic hydrocarbon, or also with at least an aromatic or cyclanic hydrocarbon substituted by at least one alkyl radical. In this process, an aliphatic hydrocarbon chosen from linear aliphatic hydrocarbons, in particular from C ₂ to C ₃₀ , preferably from C ₂ to C ₀ , and branched aliphatic hydrocarbons, in particular from C ₄ to C ₃₀ , preferably from C ₄ to C ₂₀ , or an aromatic hydrocarbon substituted by at least one alkyl radical chosen from the hydrocarbons substituted aromatics from C to C ₃₀ , preferably from C to C ₂₀ , with at least at least one linear or branched alkyl radical, in particular from Ci to C ₂₄ , preferably from Ci to Cι, or a cyclanic hydrocarbon substituted by at least one alkyl radical chosen from cyclanic hydrocarbons substituted from C ₄ to C ₃ o, preferably from C to C ₂ o, with at least one linear or branched alkyl radical, in particular from Ci to C ₂₇ , preferably from Ci to Cι ₇ . Such a method is in particular described in international patent application WO 98/02244. The process can be carried out at a temperature ranging from 20 to 600 ° C., preferably from 50 to 500 ° C., under an absolute pressure ranging from 0.1 to 100 MPa, preferably from 0.1 to 50 MPa. It can preferably be carried out in the presence of hydrogen or of an agent forming "in situ" of hydrogen, for example under a partial pressure of hydrogen ranging from 0.01 to 50 MPa, preferably from 0.1 to 20 MPa. The compound according to the invention acts in particular as a catalyst, in particular as a reaction catalyst for metathesis of hydrocarbon (s). It can be reactivated or regenerated by contacting with hydrogen or any agent forming “in situ” hydrogen, during or separately from the hydrocarbon (s) manufacturing process.

The compound according to the invention can in particular be used as a reaction catalyst for metathesis of hydrocarbon (s) and in particular of alkane (s). In a particularly remarkable way, it exhibits an extremely high catalytic activity in metathesis and / or homologation (or disproportionation) reactions of hydrocarbon (s), and a very high selectivity in the formation of normal hydrocarbons (c (that is to say straight chain) in comparison with the formation of branched chain hydrocarbons, in particular of hydrocarbons in "iso" form. The compound according to the invention exhibits in particular a particularly high catalytic activity in the reactions of metathesis and / or homologation (or disproportionation) of alkane (s) and simultaneously a high selectivity in n-alkanes in comparison with the iso- alkanes formed.

The compound according to the invention can also be used, in particular as a catalyst, in a process for the manufacture of hydrocarbon (s) by reaction of methane with at least one other aliphatic hydrocarbon, or with at least one aromatic or cyclanic hydrocarbon substituted with minus one alkyl radical. Such a method is described in international patent application WO 01/04077. The process includes in particular bringing methane into contact with at least one of the hydrocarbons mentioned above, in the presence of the metallic compound supported according to the invention. The reactions resulting from these contacts are generally metathesis reactions of hydrocarbons comprising cleavage and recombination reactions of hydrocarbons and simultaneously reactions of incorporation of methane into these hydrocarbons. These reactions are generally known as the "methane-olysis" reaction. In this process, methane can be used with at least one other aliphatic hydrocarbon chosen from linear aliphatic hydrocarbons, in particular from C ₂ to C ₃₀ , preferably from C ₃ to C ₂₀ , and branched aliphatic hydrocarbons, in particular from C to C ₃₀ , preferably from C ₄ to C ₂ o, or an aromatic hydrocarbon substituted by at least one alkyl radical chosen from aromatic hydrocarbons substituted from C ₇ to C ₃₀ , preferably from C to C ₂ o, with at least one linear or branched alkyl radical, in particular from Ci to C ₂₄ , preferably from Ci to Cu, or a cyclanic hydrocarbon substituted by at least one alkyl radical chosen from cyclanic hydrocarbons substituted from C to C ₃ o, preferably from C to C ₂ o, with at least one linear or branched alkyl radical, in particular from Ci to C ₂ , preferably from Ci to Cι ₇ . In this process, it is also possible to use a mixture of methane with one or more other aliphatic and / or cyclanic hydrocarbons, such as natural gas, liquefied petroleum gases or LPG (in English: "liquefied petroleum gas" or LPG), wet gas or wet natural gas (in English: "wet gas" or "wet natural gas", that is to say a mixture of methane with alkanes of C ₂ to C ₅ or C ₃ and / or C), natural gas liquids or LGN (in English: "natural-gas liquids" or NGL), or cuts of light hydrocarbons from Ci to C ₆ , or from Ci to C ₅ , or from Ci to C, or from Ci to C ₃ , or from Ci to C ₂ . The process can be carried out at a temperature ranging from 20 to 600 ° C, preferably from 50 to 500 ° C, in particular under a partial methane pressure ranging from

0.1 to 100 MPa, preferably 0.1 to 50 MPa, and optionally in the presence of hydrogen or of an agent forming "in situ" of hydrogen, for example under a partial pressure of hydrogen ranging from 0 , 01 to 50 MPa, preferably 0.1 to 20 MPa.

The compound according to the invention can also be used, in particular as a catalyst, in a process for the manufacture of alkane (s), in particular of ethane, by reaction of methane with itself. It is more precisely a process comprising bringing methane into contact with the compound according to the invention. This process is generally known as the methane to emanate conversion process. In this case, the methane conversion process is in particular a non-oxidizing conversion process, carried out in particular by catalytic coupling of methane in order to convert methane essentially into ethane, with in particular an extremely high ethane selectivity. The process can be carried out at a temperature ranging from 20 to 800 ° C, preferably from 50 to 600 ° C, under an absolute pressure ranging from 0.01 to 100 MPa, preferably from 0.1 to 50 MPa.

The compound according to the invention can also be used in a process for the manufacture of hydrocarbon (s) by cross-metathesis reaction between at least one initial hydrocarbon and said compound. Such a method is in particular described in international patent application WO 00/27781. The cross metathesis reaction is that in particular obtained by scission of the hydrocarbon radical or ligand linked or complexed with the tungsten hydride of the compound according to the invention and by recombination of said radical or ligand with at least one other radical originating from a scission of the initial hydrocarbon. In this process, one can use an initial hydrocarbon chosen from aliphatic hydrocarbons, linear or branched, in particular from C ₂ to C ₃₀ , preferably from C ₂ to C ₂₀ , and cyclanic hydrocarbons substituted with at least one alkyl radical, in particular from C ₄ to C ₃ o, preferably from C ₄ to C ₂₀ , the alkyl radical being linear or branched, in particular from C 1 to C ₂₇ , preferably from C ₁ to C ₁ . The compound according to the invention especially comprises at least one hydrocarbon radical R or a hydrocarbon ligand linked to tungsten hydride. The process can be carried out at a temperature ranging from 20 to 500 ° C, preferably from 50 to 400 ° C, under an absolute pressure ranging from 0.01 to 50 MPa, preferably from 0.1 to 20 MPa. The compound according to the invention can also be used, in particular as a catalyst, in a process for the manufacture of hydrocarbon (s) or oligomer (s) or of hydrocarbon polymer (s) with a carbon skeleton modified by reaction d 'an initial hydrocarbon polymer with hydrogen. Such a process is in particular described in European patent application EP 0 840 771. The initial hydrocarbon polymer can be a (co-) polymer of one or more olefinic or vinyl monomers, in particular a polyolefin such as a polyethylene, polypropylene, polybutene-1, a polyisobutene, a copolymer of ethylene with at least one C ₃ to C ₈ alpha olefin, a copolymer of propylene with at least one C ₄ to C ₈ alpha olefin, a copolymer of isobutene with butene- 1, or an aromatic polyvinyl such as a polystyrene or a polyalpha-methylstyrene. The hydrocarbon-based polymer can have a weight-average molecular mass, Mw, ranging from 10 ³ to 10 ⁷ , preferably from 10 ⁴ to 10. The process can be carried out by bringing the initial polymer into contact with the metallic compound supported according to the invention, in the presence of hydrogen and optionally a solvent medium, in particular capable of dissolving the initial polymer, or under temperature conditions making it possible to use the initial polymer in the molten state during contacting. The process can be carried out at a temperature ranging from 20 to 400 ° C, preferably from 50 to 300 ° C, under a partial pressure of hydrogen ranging from 0.001 to 20 MPa, preferably from 0.01 to 10 MPa, for a duration ranging in particular from 5 minutes to 100 hours, preferably from 10 minutes to 50 hours. The process can in particular be carried out under an increasing centrifugal force field, for example from 5 to 1000 times greater than the earth's gravitational force, in particular in a rotating disc reactor. In this case, the duration of the process can be from 1 second to 5 minutes, preferably from 2 seconds to 2 minutes.

The use of the compound according to the invention in one of the processes described above is particularly advantageous, since a considerable increase in the catalytic activity of this compound is generally observed in the cleavage and recombination reactions of carbon-carbon bonds , carbon-hydrogen and possibly tungsten-carbon, in particular in the metathesis reactions of hydrocarbon (s), in particular of alkane (s). Furthermore, the compound according to the invention exhibits in the metathesis reactions of alkane (s) an extremely high selectivity for n-alkanes, in comparison with the iso-alkanes formed.

The following examples illustrate the present invention.

Example 1: preparation of a tungsten hydride grafted onto an alumina. In a preliminary step, 530 mg of an α-alumina having an average size of 40 μm and a specific surface (BET) of 200 m ² / g, containing 90% by weight alumina and 9% by weight of water, and sold by Johnson Matthey (Great Britain), are subjected to a calcination treatment under a stream of dry air at 500 ° C for 15 hours, then to a treatment of dehydroxylation under an absolute pressure of 10 ^"2 Pa, at 500 ° C for 15 hours, so that the alumina thus calcined and dehydroxylated presents in infrared spectroscopy three absorption bands respectively at 3774, 3727 and 3683 cm ^{" 1} , characteristics in particular of residual bonding (AlO - H).

In a first step, 530 mg of the alumina prepared above is introduced into a glass reactor, under an argon atmosphere and at 25 ° C., then a solution of 6 ml of n-pentane containing 300 mg of tris ( neopentyl) neopentylidyne of tungsten, used as a precursor Pr and corresponding to the general formula:

W [- CH ₂ - C (CH ₃ ) ₃ ] ₃ [≡C - C (CH ₃ ) ₃ ] (3)

The mixture thus obtained is maintained at 25 ° C for 3 hours. At the end of this time, an organo-metallic tungsten compound grafted onto the alumina is obtained, the excess of precursor Pr which has not reacted, being removed by washing with n-pentane at 25 ° C. The organo-metallic tungsten compound thus grafted is dried under vacuum. It contains 1.5% by weight of tungsten and corresponds to the general formula:

(Al - 0) _x W [- CH ₂ - C (CH ₃ ) ₃ ] _y [= CH - C (CH ₃ )] (4) with x = 1 and y = 2.

In a second step, 40 mg of the organo-metallic grafted tungsten compound obtained above are isolated, which are subjected in a glass reactor to a hydrogenolysis treatment by contacting with hydrogen, under absolute hydrogen pressure. 73 kPa at 150 ° C for 15 hours. At the end of this time, the reactor is cooled to 25 ° C., a compound (W / Al-1) according to the invention is obtained and isolated under argon, which in particular comprises a tungsten hydride grafted on alumina. The compound (W / Al-1) contains 1.5% by weight of tungsten and has, by infrared spectroscopy, two absorption bands respectively at 1903 and 1804 cm ^"1 , characteristics of the bond (W -H), in particular grafted on alumina. Example 2: preparation of a tungsten hydride grafted onto an alumina.

The preliminary stages of calcination and dehydroxylation of alumina-o; are exactly identical to those of Example 1. In a first step, 53 mg of the alumina prepared above are isolated and they are introduced into a reactor at night temperature at 25 ° C. under an atmosphere of argon. Then, the precursor Pr of general formula (3) as used in Example 1 is introduced into the reactor. The reactor is then heated to 70 ° C. for 2 hours, so as to sublimate the precursor Pr on the alumina. and forming an organometallic tungsten compound grafted onto alumina. At the end of this time, the excess of unreacted Pr precursor is eliminated by reverse sublimation at 70 ° C. Then the reactor is cooled to

25 ° C and is isolated under argon an organometallic tungsten compound thus grafted which contains 3.7% by weight of tungsten and which corresponds to the general formula (4) above.

The second step is carried out exactly as in Example 1, except that the organometallic compound of tungsten grafted on the alumina used in the previous step is used. A compound (W / Al-2) according to the invention is thus obtained comprising a tungsten hydride grafted on alumina and containing 3.7% by weight of tungsten. It presents in infrared spectroscopy two absorption bands respectively at 1903 and 1804 cm ^"1 , characteristics of the bond (W - H) in particular grafted on alumina.

The compound (W / Al-2) is subjected to a selective deuteration test showing that it comprises a tungsten hydride and an aluminum hydride, both grafted onto alumina. A sample of the compound (W / Al-2) is placed in a venous reactor, then is brought into contact in this reactor with a deuterium atmosphere under an absolute pressure of 66.7 kPa, at a temperature of 60 ° C., for 15 minutes. At the end of this time, the reactor is cooled to 25 ° C. and the solid compound thus deuterated is isolated under argon, which exhibits, by infrared spectroscopy, an absorption band at 1914 cm ⁻¹ , characteristic of the bond (Al - H ) unchanged by the deuteration reaction carried out under these conditions. It is also observed that the absorption bands at 1903 and 1804 cm ^"1 characteristics of the bond (W - H) grafted on the alumina disappear in favor of the bands absorption respectively at 1293 and 1393 cm ^"1 , characteristics of the bond (W - D) grafted onto the alumina and formed by the deuteration reaction of the bonds (W - H).

Example 3: Preparation of a tungsten hydride grafted on an alumina.

The preliminary stages of calcination and dehydroxylation of alumina-ce are exactly identical to those of Example 1.

In a first step, 2 g of the alumina prepared above are isolated and they are introduced under an argon atmosphere into a glass reactor at 25 ° C. fitted with a magnetic stirring bar. Then, 305 mg of the precursor Pr of general formula (3) as used in Example 1 is introduced into the reactor. The reactor is heated to 66 ° C. and the mixture thus produced is stirred dry for 4 hours. At the end of this time, the reactor is cooled to 25 ° C., then the solid mixture is washed with n-pentane at 25 ° C. The solid compound thus washed is dried under vacuum, then is isolated under argon so as to obtain an organometallic compound of tungsten grafted on alumina containing 3.9% by weight of tungsten and which corresponds to the general formula (4) above.

The second step is carried out exactly as in Example 1, except that the organometallic compound of tungsten grafted on the alumina prepared previously is used. A compound (W / Al-3) according to the invention is thus obtained comprising a tungsten hydride grafted on alumina and containing 3.9% by weight of tungsten. It presents in infrared spectroscopy two absorption bands respectively at 1903 and 1804 cm ^"1 , characteristics of the bond (W - H) grafted on alumina. In addition, it presents in nuclear magnetic resonance (1 H-NMR solid ) at 500 MHz a value of the chemical shift of tungsten hydride (δw-n) equal to 10.6 ppm (parts per million). Example 4 (comparative): preparation of a tungsten hydride grafted onto a silica.

In a preliminary stage, 44 mg of a silica sold under the commercial reference "Aerosil 200" ® by Degussa (Germany), having a BET specific surface of 200 m ² / g, are subjected to a dehydroxylation treatment under absolute pressure of 10 ^"2 Pa, at 700 ° C, for 15 hours, so that the silica thus dehydroxylated has, by infrared spectroscopy, an absorption band at 3747 cm ^{" 1} , characteristic in particular of the residual bond (SiO - H) .

In a first step, 44 mg of the previously prepared silica are isolated, which are introduced into a glass reactor at 25 ° C. under an argon atmosphere. Then, the precursor Pr of general formula (3), as used in Example 1, is introduced into the reactor. The reactor is then heated to 70 ° C. for 2 hours, so as to sublimate the precursor Pr on silica. and forming an organometallic tungsten compound grafted onto the silica. At the end of this time, the excess of unreacted Pr precursor is eliminated by reverse sublimation at 70 ° C. Then, the reactor is cooled to 25 ° C. and the organometallic tungsten compound thus grafted onto silica is isolated under argon, which contains 5.5% by weight of tungsten and which corresponds to the general formula: (Si - 0) _x W [- CH ₂ - C (CH ₃ ) ₃ ] _y [≡C - C (CH ₃ )] (5) with x = 1 and y = 2. In a second step, the organometallic tungsten compound grafted onto the prepared silica in the previous step is subjected to a hydrogenolysis treatment by contacting with hydrogen under a pressure of 73 kPa, at 150 ° C, for 15 hours. At the end of this time, a compound (W / Si-1) is obtained and isolated under argon for comparison, comprising a tungsten hydride grafted on silica and containing 5.5% by weight of tungsten. It presents in infrared spectroscopy an absorption band at 1940 cm ^"1 , characteristic of the bond (W - H) in particular grafted on silica. Example 5 (comparative): preparation of a tantalum hydride grafted onto an alumina.

The procedure is exactly as in Example 2, except that in the first step 50 mg of the alumina prepared during the previous steps are isolated and that the tris is introduced into the reactor, in place of the precursor Pr (neopentyl) neopentylidene of tantalum, as a precursor Pr ', corresponding to the general formula:

Ta [- CH ₂ - C (CH ₃ ) ₃ ] ₃ [= CH - C (CH ₃ ) ₃ ] (6)

An organometallic tantalum compound grafted onto alumina is thus obtained, containing 5.6% by weight of tantalum.

The second step is carried out exactly as in Example 2, except that the organometallic tantalum compound grafted on the alumina used previously is used. A compound (Ta / Al-1) is thus obtained for comparison, comprising a tantalum hydride grafted onto alumina and containing 5.6% by weight of tantalum. It presents in infrared spectroscopy a band of absoiption at 1830 cm ^"1 , characteristic of the bond (Ta - H) grafted on alumina, next to another band at 1914 cm ^{" 1} , characteristic in particular of bond (Al - H).

Example 6 (comparative): preparation of a tantalum hydride grafted onto a silica.

The procedure is exactly as in Example 4, except that in the first step 50 mg of the silica prepared during the previous step are isolated and that is introduced into the reactor, in place of the precursor Pr, the tris (neopentyl) neopentylidene of tantalum as a precursor Pr ', corresponding to the general formula (6). An organometallic tantalum compound grafted onto the silica is thus obtained which contains 5.5% by weight of tantalum.

The second step is carried out exactly as in Example 4, except that the organometallic tantalum compound grafted on the silica prepared above is used. A compound (Ta / Si-1) is thus obtained for comparison, comprising a tantalum hydride grafted on the silica and containing 5.5% by weight of tantalum. He introduces in infrared spectroscopy an absorption band at 1830 cm ^"1 , characteristic of the bond (Ta - H) grafted on the silica.

Example 7: metathesis of propane. Supported metal compounds (W / Al-3), (W / Si-1), (Ta / Al-1) and

(Ta / Si-1) prepared respectively in Examples 3, 4, 5 and 6 are successively used in a propane metathesis reaction which can be represented by the following equation:

2 C ₃ H ₈ ^ C ₂ H ₆ + C ₄ H ₁₀ (7) Each propane metathesis reaction is carried out under the following conditions. The supported metal compound is prepared "in situ" in a reactor in veιτe as described above. The reactor is then placed under vacuum, then is filled with propane to a pressure of 76 kPa, and is heated to 150 ° C. We then observe the formation of a mixture essentially of ethane and n- and iso-butanes, and also in a smaller amount of methane, n- and iso-pentanes, and even C ₆ homologs in very large quantities. low.

For each of the tests carried out with the supported metal compounds, the cumulative number (NC) of moles of propane transformed over time per mole of tungsten or tantalum of the supported metal compound is measured and calculated after 120 hours. of reaction.

Furthermore, for each of these tests, the ratio of the selectivity (SnC ₄ ) of the reaction in n-butane formed to the selectivity (SiC) of the reaction in iso-butane formed after 120 hours is measured and calculated. The selectivities (SnC ₄ ) and (SiC) are calculated respectively according to the following equations: (8) SnC = (number of moles of n-butane formed) / (total number of moles of alkanes formed) and

(9) SiC ₄ = (number of moles of iso-butane formed) / (total number of moles of alkanes formed)

Table 1 brings together the results of the measurements and calculations cited above for each of the tests carried out in propane metathesis. Table 1

Analysis of the results in Table 1 shows that the metal compound supported according to the invention (W / Al-3) exhibits a mice catalytic activity in the propane metathesis reaction which is extremely high and much greater than the catalytic activities of the other compounds, with a selectivity ratio between n-butane and iso-butane formed which corresponds to a high level.

Example 8: "methane-olysis" of propane. Through a reactor with a capacity of 5 ml, heated to 250 ° C and containing

300 mg of the metallic compound supported according to the invention (W / Al-3) prepared in Example 3, a mixture comprising 800 moles of propane per 10 ⁶ moles is passed continuously at a flow rate of 1.5 ml / min of methane under a partial methane pressure of 5 MPa. The propane “methane-olysis” reaction can be written according to the following equation:

CH ₄ + C ₃ H ₈ - 2 C ₂ H ₆ (10)

We observe a formation of ethane over time.

Claims

1. Supported metal compound comprising a support based on aluminum oxide on which is grafted a tungsten hydride.

2. Compound according to claim 1, characterized in that the support is chosen from homogeneous supports in composition based on aluminum oxide and among heterogeneous supports based on aluminum oxide comprising oxide aluminum essentially on the surface of said supports.

3. Compound according to claim 1 or 2, characterized in that the support has a specific surface (BET) chosen from a range going from 0.1 to 1000 m / g, preferably from 0.5 to 800 m ² / g .

4. Compound according to any one of claims 1 to 3, characterized in that the support comprises aluminum oxide, mixed aluminum oxides or modified aluminum oxides, in particular modified by one or more elements of the

Groups 15 to 17 of the Periodic Table of the Elements.

5. Compound according to claim 4, characterized in that the support comprises aluminum oxide chosen from porous aluminas, non-porous aluminas and mesoporous aluminas.

6. Compound according to claim 5, characterized in that the porous alumina is chosen from alumina-γ, alumina-??, alumina-δ, alumina-fl, Talumine-K, l alumina-p and alumina-χ, preferably from alumina-γ and alumina-?].

7. Compound according to claim 6, characterized in that the porous alumina has a specific surface (BET) in a range from 100 to 1000 m ² / g, preferably from 300 to 1000 m ² / g, in particular from 300 at 800 m ² / g.

8. Compound according to claim 5, characterized in that the non-porous alumina is T alumina-ce.

9. Compound according to claim 8, characterized in that the non-porous alumina has a specific surface (BET) in a range from 0.1 to 300 m / g, preferably from 0.5 to 300 m ² / g, in particular from 0.5 to 250 m ² / g.

10. Compound according to claim 6 or 7, characterized in that the porous alumina comprises a mixture of one or more crystalline forms of the porous alumina with alumina, in particular in a weight proportion ranging from 20 to 80%.

11. Compound according to claim 4, characterized in that the mixed aluminum oxides are chosen from aluminum oxides combined with at least one other oxide in a proportion by weight preferably of 2 to less than 80%, in particular of 2 less than 50%, in particular 2 to less than 40%.

12. Compound according to claim 11, characterized in that the other oxide or oxides are oxides of the elements, M, chosen from the metals of Groups 1 to 13 and the elements of Group 14, with the exception of carbon, from the Table of the Periodic Classification of the Elements.

13. Compound according to claim 11, characterized in that the other oxide (s) are chosen from the oxides of alkali metals, alkaline earth metals, transition metals and elements of Groups 13 and 14, with the exception of carbon, from the Periodic Table of Elements.

14. Compound according to claim 4, characterized in that the modified aluminum oxides comprise one or more of the elements of Groups 16 or 17 of the Table of the Periodic Classification of the Elements, and preferably are chosen from the super-acids of alumina and sulphated, sulphurized, fluorinated and chlorinated aluminum oxides.

15. Compound according to any one of claims 1 to 14, characterized in that it is in the form of particles having an average size ranging from 10 nm to 5 mm, preferably from 20 nm to 4 mm.

16. Compound according to any one of claims 1 to 15, characterized in that the degree of oxidation of the tungsten has a value chosen from a range going from 2 to 6, preferably from 4 to 6.

17. Compound according to any one of claims 1 to 16, characterized in that the tungsten atom is linked to one or more hydrogen atoms and optionally to one or more hydrocarbon radicals, R.

18. Compound according to claim 17, characterized in that the hydrocarbon radicals R are hydrocarbon radicals, identical or different, saturated or unsaturated, comprising in particular from 1 to 20, in particular from 1 to 10 carbon atoms and optionally comprising silicon .

19. Compound according to any one of claims 1 to 18, characterized in that the tungsten atom is complexed by one or more hydrocarbon ligands, in particular aromatic ligands or carbonyl ligands.

20. Compound according to any one of claims 1 to 19, characterized in that it exhibits, by infrared spectroscopy, at least one of the two absorption bands at 1903 and 1804 cm ^"1 .

21. Compound according to any one of claims 1 to 20, characterized in that it presents in nuclear magnetic resonance of the proton ('H-NMR solid) under 500 MHz a value of the chemical shift of tungsten hydride (δw-u ) equal to 10.6 ppm.

22. Process for preparing the compound according to any one of claims 1 to 21, characterized in that it comprises (1) a step of dispersing and grafting an organometallic tungsten precursor, Pr, onto a support based aluminum oxide, precursor in which the tungsten is in particular bonded or complexed with at least one hydrocarbon ligand, so as to form a compound or hydrocarbon complex of tungsten grafted on said support, then (2) a step of hydrogenolysis of grafted tungsten hydrocarbon compound or complex, resulting from the previous step, so as to form a tungsten hydride grafted on said support.

23. The method of claim 22, characterized in that the support based on aluminum oxide is subjected to a prior step of calcination and / or dehydroxylation.

24. The method of claim 22 or 23, characterized in that the dispersion and grafting step is carried out by sublimation, by impregnation using a solvent, or by dry mixing.

25. Method according to any one of claims 22 to 24, characterized in that the hydrogenolysis step is carried out by bringing the tungsten hydrocarbon compound or complex grafted into contact with hydrogen or a reducing agent.

26. Use of the compound according to any one of claims 1 to 21 in a process implementing cleavage and recombination reactions of hydrocarbon (s).

27. Use of the compound according to any one of claims 1 to 21 as catalyst for the metathesis reaction of hydrocarbon (s), in particular of alkane (s).

28. Use of the compound according to any one of claims 1 to 21 in a process for the manufacture of hydrocarbon (s) having a carbon skeleton modified by reaction of at least one aliphatic hydrocarbon with itself, or with at least one other hydrocarbon aliphatic, or with at least one aromatic or cyclanic hydrocarbon substituted by at least one alkyl radical.

29. Use according to claim 28, characterized in that the aliphatic hydrocarbon is chosen from linear aliphatic hydrocarbons, in particular from C ₂ to C ₃₀ , and branched aliphatic hydrocarbons, in particular from C to C ₃₀ , the substituted aromatic hydrocarbon with at least one alkyl radical is chosen from the substituted aromatic hydrocarbons from C ₇ to C ₃₀ with at least one linear or branched alkyl radical, in particular from C 1 to C ₂₄ , and the cyclanic hydrocarbon substituted with at least one alkyl radical is chosen among the cyclanic hydrocarbons substituted from C to C ₃₀ with at least one linear or branched alkyl radical, in particular from C to C ₂₇ .

30. Use of the compound according to any one of claims 1 to 21 in a process for the manufacture of hydrocarbon (s) by reaction of methane with at least one other aliphatic hydrocarbon, or with at least one aromatic or cyclanic hydrocarbon substituted with at least one alkyl radical.

31. Use of the compound according to any one of claims 1 to 21 in a process for the manufacture of alkane (s), in particular ethane, by reaction of methane with itself.

32. Use of the compound according to any one of claims 1 to 21 in a process for the production of hydrocarbon (s) by cross-metathesis reaction between at least one initial hydrocarbon and said compound.

3. Use of the compound according to any one of claims 1 to 21 in a process for the manufacture of hydrocarbon (s) or oligomer (s) or of hydrocarbon polymer (s) with a carbon skeleton modified by reaction of a initial hydrocarbon polymer with hydrogen.