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    • 专利摘要:
    The invention relates to a method for metathesis of olefins implemented with a catalyst comprising a mesoporous matrix and at least the molybdenum and aluminum elements, said elements being incorporated in said matrix by means of at least two precursors of which at least one precursor contains molybdenum and at least one precursor contains aluminum.
    公开号:FR3039543A1
    申请号:FR1557367
    申请日:2015-07-31
    公开日:2017-02-03
    发明作者:Audrey Bonduelle；Alexandra Chaumonnot；Damien Delcroix；Christophe Vallee
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    The present invention relates to a method for metathesis of olefins using a catalyst prepared from at least two precursors of which at least one precursor contains molybdenum and at least one precursor contains aluminum.
    Prior art
    The metathesis of olefins is an important reaction in various fields of chemistry. In organic synthesis, this reaction, catalyzed by organometallic complexes, is used to obtain various molecules with high added value. In petrochemicals, the metathesis of olefins is of great practical interest, particularly for the rebalancing of light olefins from steam cracking, such as ethylene, propylene and butenes. In particular, the cross metathesis of ethylene with butene-2 to give propylene is a reaction of interest given the increasing demand for propylene on the market.
    Different types of catalysts are likely to be used in the metathesis reaction. It is possible to use homogeneous catalysts, the constituent elements of which are all soluble in the reaction medium, or else heterogeneous catalysts insoluble in the reaction medium.
    The metathesis of light olefins uses heterogeneous catalysts. A known solution is the technology described in US Pat. No. 8,586,813, which uses a catalyst based on tungsten oxide deposited on a silicic support WCySiO 2. However, tungsten-based heterogeneous catalysts operate at a relatively high temperature, generally at a temperature above 300 ° C and are only moderately active.
    It is moreover known that rhenium oxide-based metathesis catalysts Re207 such as those described in the publication by Chauvin et al. Journal of Molecular Catalysis 1991, 65, 39 show good activity at temperatures near ambient temperature. Other catalysts based on molybdenum oxide such as those described in DP Debecker et al., J. Catal., 2011, 277, 2, 154 and GB 1,164,687 and GB 1,117,968 owned by Shell company were also developed. The Shell method uses, for example, catalysts based on molybdenum oxides and cobalt deposited on an aluminomeric support C0M0O4 / Al2O3 and doped with phosphorus, as described in US Patent 4,754,099.
    An interest of molybdenum (Mo) is that it is cheaper than rhenium (Re). In addition, its stability and activity are intermediate between those of rhenium (Re) and tungsten (W). In particular, molybdenum can be active from room temperature.
    The preparation of catalysts based on molybdenum oxides (M0O3) is conventionally carried out by impregnation with an aqueous solution of a molybdenum salt or a heteropolyanion containing molybdenum such as, for example, isopolyanion ammonium heptamolybdate on a support such as silica, alumina or a porous aluminosilicate. Catalysts prepared from ammonium heptamolybdate precursors, however, lack activity and stability. Catalysts based on other heteropolyanions, such as H3PM012O40, have been prepared and can significantly increase the activity, but still need to be improved.
    There is therefore still a need to develop new catalysts with improved performances in terms of activity and selectivity for the metathesis reaction of olefins and more particularly for the metathesis between ethylene and butene-2 for the production of propylene .
    The applicant, in his research to improve the performance of heterogeneous olefin metathesis catalysts, has developed novel catalysts for the metathesis reaction of olefins. These catalysts are prepared from a mesoporous matrix and at least two precursors of which at least one precursor contains molybdenum and at least one precursor contains aluminum. It has been unexpectedly found that the use of these types of precursors for the preparation of the catalyst according to the invention improves the activity and stability of the heterogeneous catalyst obtained for the metathesis reaction of olefins, compared with catalysts prepared by means of other precursors of the prior art. The conversion of olefins is improved. The stability of the catalyst is also improved.
    An object of the present invention is to provide a process for metathesis of olefins using a catalyst having improved performance in terms of activity and selectivity with respect to the use of heterogeneous catalysts of the prior art.
    The catalysts according to the invention have the advantage of being able to operate on longer cycle times before regeneration, which has a strong economic impact on the operating costs of the process according to the invention.
    Object of the invention
    The present invention relates to a process for metathesis of olefins carried out by contacting the olefins with a catalyst comprising a mesoporous matrix and at least the molybdenum and aluminum elements, said elements being incorporated in said matrix by means of at least two precursors of which at least at least one precursor contains molybdenum and at least one precursor contains aluminum.
    Precursor containing molybdenum
    Advantageously, the precursor containing molybdenum according to the present invention is a coordination complex precursor based on molybdenum and / or polyoxometalate type based on molybdenum and / or (thio) molybdate type.
    When the precursor containing molybdenum according to the present invention is a molybdenum-based coordination complex precursor, it advantageously corresponds to formula (I)
    Mom (= Y) n (n) n> (X) 0 (= CR2) r (I) in which, the groups Y, which are identical to or different from one another, can be chosen from O, S and NR; X groups, which are identical to or different from one another, may be chosen from halides, such as F, Cl, Br, I, chlorate, bromate, iodate, nitrate, sulphate or hydrogen sulphate, alkyl sulphate, thiosulphate, carbonate or hydrogencarbonate, phosphate or hydrogen phosphate, or dihydrogenophosphate, substituted or unsubstituted alkyl, cycloalkyl or aryl groups, substituted or unsubstituted cyclopentadienyls, alkoxy, aryloxy, siloxy, amide, hydrido, nitro, carboxylate, acetylacetonate, sulfonate, β-diketiminate, iminopyrride, amidinate, borate, cyanide groups , cyanate, thiocyanate or NR2-CS2 ', - the groups R and R', which are identical to or different from one another, can be chosen from alkyl and aryl groups, preferably comprising from 1 to 10 carbon atoms, the alkoxy and aryloxy groups; , - m es t equal to 1 or 2, - n is between 0 and 4, - n 'is between 0 and 2, - 0 is between 0 and 10, - r is between 0 and 2, - n + n' + o + r is greater than or equal to 1, preferably greater than or equal to 2.
    According to the invention, the molybdenum-based coordination complex precursor may also contain in its coordination sphere one or more L-type ligands, optionally polydentate. The ligand type L may be chosen from carbon compounds, such as carbon monoxide, alkenes, alkynes, phosphorus compounds such as phosphines, phosphinites, phosphonites, phosphites, oxygenates such as water, ethers, nitrogen compounds such as amines, aromatic nitrogen compounds such as pyridine and / or phenanthroline, and / or sulfur compounds such as thioethers.
    The molybdenum-based coordination complex precursor of formula (I) is incorporated by its chemical nature in neutral form.
    The molybdenum-based coordination complex precursor may, for example, be chosen from the following compounds: MoCl.sub.5, MoOC.sub.4, MoSCl.sub.4, Mo (C.sub.5H.sub.5) Cl.sub.4, Mo (SO.sub.4) .sub.3, Mo.sub.2 (C.sub.5H.sub.5) .sub.2 (CO) .sub.6, Mo (= CH-C (me) 2 Ph) (= N-
    Ph (iPr) 2) (OSO 2 CF 3) 2 (CH 3 O (CH 2) 20 CH 3), MoO 2 (acetylacetonate) 2, Μ o (= O) (O 8) 3, Mo (N N) (OSi Ph 3) 3 (C 6 H 5 N), Mo [OOCCH (C2H5) C4H9] 4, Mo [OOCC7H15] 2, molybdenum naphthenate, Mo (CO) 6, etc.
    When the molybdenum-containing precursor according to the present invention is a polyoxometalate precursor based on molybdenum, it advantageously corresponds to the formula (II) (XxMomMbOyHh) q'.nH20 (II) in which, • x is greater than or equal to 0, • m is greater than or equal to 2, • b is greater than or equal to 0, • y is greater than or equal to 7, • h is 0 to 12, • q is 1 to 20, • n is between 0 and 200, • x, m, b, y, h, n and q being integers, X being a member selected from phosphorus, silicon and boron, M being a metallic element selected from aluminum , zinc, nickel, cobalt, tungsten, vanadium, niobium, tantalum, iron and copper, preferably M is a metal element selected from aluminum, cobalt and tungsten, more preferably preferred among aluminum and cobalt and even more preferably, the metal element M is cobalt.
    The molybdenum-based polyoxometalate precursor of formula (II) can be incorporated into the mesoporous matrix in salt form or in acid form. In the case where the molybdenum-based polyoxometalate precursor of formula (II) is incorporated in acid form, the charge q 'is compensated by H + protons. When the molybdenum-based polyoxometalate precursor of formula (II) is introduced in salt form, the counterions of the salt of the polyoxometalate are chosen from all the cations known to those skilled in the art. Examples that may be mentioned include proton, ammoniums, phosphoniums, alkalis, alkaline earths, transition elements, and the like. The molybdenum-based polyoxometalate salt may comprise a mixture of the same cation or different cations.
    The polyoxometallate precursor is preferentially chosen from molybdenum-based isopolyanions and molybdenum-based heteropolyanions.
    The isopolyanion precursors based on molybdenum according to the invention correspond to the precursor according to the formula (II) (XxMomMbOyHh) q'.nH20 (II) in which the index x of the element X is equal to 0, all things being equal in addition to the definition of indices and elements according to the invention. The isopolyanion precursors based on molybdenum according to the invention may be chosen for example from Mo.sub.2 O.sub.7, Mo.sub.7.sub.2 O.sub.6 '.
    The polyoxometallate precursor is preferentially chosen from isopolyanions and heteropolyanions. When using isopolyanions, the element X in the formula (II) above is absent and x = 0. The precursors of the isopolyanion type can be chosen from Mo.sub.2 O.sub.7, Mo.sub.7.sub.7 O.sub.6.
    The molybdenum-based polyoxometalate precursor according to the invention may contain one or more metal elements M chosen from aluminum, zinc, nickel, cobalt, tungsten, vanadium, niobium and tantalum. , iron and copper, in substitution for one or more molybdenum atoms contained in said polyoxometalate precursor of formulas described above. Preferably, the metal element M is chosen from aluminum, cobalt and tungsten, more preferably from aluminum and cobalt and even more preferably, the metal element M is cobalt.
    When the polyoxometallate precursor used in the preparation of the catalyst used in the metathesis process according to the invention does not contain a metal element M other than molybdenum, it is advantageously chosen from the group formed by a Strandberg heteropolyanion of Formula X2Mo5023H2 nH20, an Anderson heteropolyanion of formula XMo6C> 24Hhq nH20, the Keggin heteropolyanion of formula XMol2C> 4oHhq nH20, a lacunar Keggin heteropolyanion of formula XMo1O39Hhq ', nH20, a lacunary Keggin heteropolyanion of formula ## STR2 ## a heteropolyanion of Dawson of formula X2Moi8062Hhq nH20, a Preysler heteropolyanion of formula X5Mo3oOnoHhq nH20 with X, h and q having the above definitions according to the invention.
    When the molybdenum-based polyoxometalate precursor used in the preparation of the catalyst used in the metathesis process according to the invention contains a metal element M other than molybdenum, preferably M being cobalt, it is advantageously chosen from the group formed by a Strandberg heteropolyanion of formula X2Mo4CoC> 23Hhq ', nH20, an Anderson heteropolyanion of formula XMo5CoO24Hhq', nH20, a Keggin heteropolyanion of formula XMonCoO4oHhq ', nH20, a lacunar Keggin heteropolyanion of formula XMoioCo039Hhq nH20 , a lacunar Keggin heteropolyanion of formula XMo8CoC> 34Hhq nH20, a Dawson heteropolyanion of formula X2Moi7CoO62Hhq nH20, a Preysler heteropolyanion of formula X5Mo29CoOi10Hhq ', nH20 with X, h and q having the abovementioned definitions according to the invention, the preparation is precisely described in application FR 2.764.211.
    When the precursor containing molybdenum according to the present invention is a precursor of (thio) molybdate type, it advantageously corresponds to formula (III)
    Cc (MoY4) z (NI) in which - C represents an organic or inorganic cation chosen from among all the cations known to those skilled in the art. Examples that may be mentioned include protons, ammoniums, phosphoniums, alkalis, alkaline earths, transition elements; groups Y, which are identical to or different from one another, may be chosen between O and S; c is between 1 and 4, - z is between 1 and 10.
    The precursor of the type (thio) molybdate containing molybdenum may for example be selected from the following compounds: (NH4) 2MoS4, (NEt4) 2MoS4, Na2MoO4, (NH4) 2MoO4, Fe2 (MoO4) 3.
    One or more precursors of the type corresponding to formula (I), (II) and / or (III) can be used in the process according to the invention.
    Precursor containing aluminum
    Advantageously, the aluminum-containing precursor according to the present invention is a precursor chosen from any source of aluminum and advantageously chosen from aluminum-based coordination complex precursors and / or aluminum-salt precursors. and / or aluminum-based heteropolyanion salt precursors and / or any colloidal solution of alumina.
    When the aluminum-based precursor according to the present invention is an aluminum-based coordination complex precursor, it advantageously corresponds to formula (IV)
    AlnRm. χΗ20 (IV) in which, n is between 1 and 3, m is between 1 and 3, x is between 0 and 200, the groups R which are identical to or different from one another may be chosen from hydrogen, halides, such as F, Cl, Br, I, chlorate, bromate, iodate, nitrate, sulfate or hydrogen sulphate, alkyl sulphate, thiosulphate, carbonate or hydrogencarbonate, phosphate or hydrogen phosphate or dihydrogen phosphate, alkyl, alkenyl, alkynyl, cycloalkyl groups or substituted or unsubstituted aryls, substituted or unsubstituted cyclopentadienyls, hydroxy, alkoxy, aryloxy, carboxylate, nitrate, acetylacetonate, sulfonate, perchlorate groups.
    According to the invention, the aluminum-based coordination complex precursor may also contain in its coordination sphere one or more L-type ligands, optionally polydentate. The ligand type L may be chosen from carbon compounds, such as carbon monoxide, alkenes, alkynes, phosphorus compounds such as phosphines, phosphinites, phosphonites, phosphites, oxygenates such as water, ethers, nitrogen compounds such as amines, aromatic nitrogen compounds such as pyridine and / or phenanthroline, cyclohexane-diamino-A /, V'-bis (alkyl) salicylidene saline and salane ligands; and / or sulfur compounds such as thioethers.
    The aluminum coordination complex type precursor of formula (IV) is incorporated by its chemical nature in neutral form.
    The aluminum coordination complex type precursor may, for example, be chosen from the following compounds: AlCl 3, Al (ClO 4) 3. 9H20, Al (acetylacetonate) 3, Al (CF3COCHCOCF3) 3, Al [OCH (CH3) 2] 3, Al2 (SO4) 3. 18H20, Al [OOCCH (C 2 H 5) C 4 H 9] 2, (C 2 H 5) 2 AlCl, Al (CH 3) 3.
    When the precursor containing aluminum according to the present invention is an aluminum salt precursor, it advantageously corresponds to formula (V) in which,
    • n is between 1 and 3, • m is between 1 and 3, • x is between 0 and 200, • the groups R which are identical to or different from one another may be chosen from hydrogen, the oxo group, halides, such as F, Cl, Br, I, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl or aryl groups, substituted or unsubstituted cyclopentadienyls, hydroxy, alkoxy, aryloxy, carboxylate, sulphonate, nitrate, acetylacetonate, perchlorate groups • C is selected from hydrogen, alkali, alkaline earth, transition metals, poor metals and rare earths, ammonium cations and phosphoniums.
    The aluminum salt precursor containing aluminum can for example be chosen from the following compounds: [AlO 2] '[Na] +, [AlCl 4]' [Cs] +, [Al (SO 4) 2] [ NH4] +, [AIH4] '[Li] +, etc.
    When the precursor containing aluminum according to the present invention is an aluminum-based heteropolyanion salt precursor, it advantageously corresponds to the formula (VI) (AlaM1mM2bXxOyHh) q- (Cr +) c. ηΗ20 (VI) wherein, • a is greater than or equal to 0, • m is greater than or equal to 1, • b is greater than or equal to 0, • x is greater than or equal to 0, • y is greater than or equal to 10, • h is between 0 and 12,
    Q is 0 to 20, r is 0 to 20, c is 0 to 20, n is 0 to 200, x, m, y, h, n and q are integers, X being a member chosen from phosphorus, silicon and boron, M1 and M2, identical or different from each other, being metal elements chosen from aluminum, zinc, nickel, cobalt, molybdenum, tungsten, vanadium, niobium, tantalum, iron and copper, • C represents one or more atoms, identical or different, hydrated or not, chosen from the elements of the periodic table which may exist in cationic form, such as hydrogen, the alkaline, alkaline-earth, transition metal, poor metals and rare earth elements, in hydrated or non-hydrated forms, chosen from organic oxygenated and / or nitrogen and / or phosphorus-containing cations, such as ammonium and phosphoniums.
    According to the invention, the aluminum-based heteropolyanion salt precursor can be stabilized by one or more additional organic species selected from oxygenated and / or nitrogenous organic molecules, such as histidine, piperazine, choline, urea, phenanthroline copper complexes, acetate ion, acetic acid, alone or as a mixture.
    The precursor of the aluminum-based heteropolyanion salt type can for example be chosen from the following compounds: [Al (OH) 6 MoOO 8] 3 '[(C 6 H 10 N 3 O 2) 2 Na (H 2 O) 2] 3+, 6H 2 O (C 6 H 10 N 3 O 2 = histidinium ), [Al (OH) 6Mo6O18] 3 '{Na [Me3N (CH2) 20H] 2} 3 + 4NH2CONH2, 2H20, [Al (OH) 6MO6O18] 3' - (H3O +) [Cu (C6NO2H4) (phenantroline) ( H2O)] + 2, 5H2O, [ΑΙ (ΟΗ) 6Μθ6θ18] 3 · [ΑΙ (Η2θ) 6] 3+, 10H2O, [Al (OH) 6Mo6018] 3 [(NH4) +] 3, 7H2O.
    One or more precursors of coordination complex type, corresponding to the formulas (IV), (V) and / or (VI) can be used (s).
    The mesoporous matrix according to the invention is advantageously an oxide-based matrix of at least one element X chosen from silicon, aluminum, titanium, zirconium, magnesium, lanthanum, cerium and their mixtures. Preferably, the element X is silicon or a mixture of aluminum and silicon. Even more preferably, the element X is silicon.
    Said so-called mesoporous oxide-based matrix is understood according to the present invention as a matrix comprising pores ranging in size from 2 to 50 nm according to the IUPAC classification (KSW Sing, DH Everett, WRA Haul, L. Moscow, J. Pierotti, J. Rouquerol, T. Siemieniewska, Pure Appl Chem 1985, 57, 603), and / or a mesoporous mesostructured matrix, that is to say having mesopores of uniform size and distributed over periodically in said matrix and / or a matrix with hierarchical porosity, that is to say comprising micropores and / or macropores additional to the mesopores.
    The preformed mesoporous matrix may be commercial or well synthesized according to the methods known to those skilled in the art, in particular by using the "traditional" inorganic synthesis methods: precipitation / gelling from salts under mild conditions of temperature and humidity. pressure; or "modern" metallo-organic: precipitation / gelling from alkoxides under mild conditions of temperature and pressure. In the rest of the text and for the sake of simplification, these methods are simply called "sol-gel". It is also possible to use "sol-gel" methods combined with the use of specific synthesis methods such as atomization (spray-drying according to the English terminology), dip coating (dip-coating according to Anglo-Saxon terminology), or other.
    The preformed mesoporous matrix may be in powder form or shaped, for example in the form of pelletized, crushed, sieved powder, granules, tablets, balls, wheels, spheres or extrusions (hollow cylinders or no, multilobed cylinders with 2, 3, 4 or 5 lobes for example, twisted cylinders), or rings, etc. Preferably, a mesoporous matrix based on silicon oxide having a specific surface area of 50 to 1200 m 2 / g, and preferably of 150 m 2 / g to 1200 m 2 / g, and a pore volume of at least 0, are used. , 1 ml / g, and preferably a pore volume of between 0.2 and 1.2 ml / g according to the BET method.
    The catalyst used according to the invention comprises a mass content of molybdenum element provided by the precursor of formula (I) and / or (II) and / or (III) according to the invention of between 1 and 40%, preferably between 2 and and 30%, preferably between 2 and 20%, expressed as a weight percent of molybdenum relative to the mass of the mesoporous matrix.
    The catalyst used according to the invention comprises a mass content of aluminum element provided by the precursor of formula (IV), (V) and (VI) according to the invention of between 0.01 and 50%, preferably between 0.02 and and 35%, preferably between 0.02 and 25% expressed as a weight percentage of aluminum element relative to the mass of the mesoporous matrix.
    The catalyst according to the invention can be prepared according to methods known to those skilled in the art.
    The deposition of at least one precursor containing molybdenum and at least one precursor containing aluminum on the mesoporous matrix can be done before, during or after forming the mesoporous matrix.
    The deposition of the precursors according to the invention on the mesoporous matrix can be done by the so-called methods of dry impregnation, excess impregnation, CVD (Chemical vapor deposition according to the English terminology), CLD (Chemical liquid deposition according to Anglo-Saxon terminology), etc. described for example in "Catalysis by transition metal sulphides, from molecular theory to industrial application, Ed Herve Toulhouat and Pascal Raybaud, p137".
    For a deposit of the precursors according to the invention on the surface of the preformed mesoporous matrix, the so-called dry and excess impregnation methods are preferred.
    With regard to dry impregnation, no particular limitation exists as to the number of times that said dry impregnation step is repeated. The different steps can be carried out without solvent or with the aid of one or more solvents or mixture of solvents in which the precursors according to the invention are soluble. These solvents may be polar / protic such as water, methanol or ethanol, polar / aprotic such as toluene or xylene or apolar / aprotic such as hexane. The acid-baseicity of the solutions can also be adapted to improve the solubility of the species. Similarly, each of the precursors according to the invention can be impregnated alone or co-impregnated with at least one of the other precursors, the only limitation being the joint presence of at least one precursor containing molybdenum and at least one a precursor containing aluminum at the end of the process for preparing the catalyst according to the invention.
    In a preferred variant, the catalyst may be prepared by dry impregnation according to the process comprising the following steps: a) solubilization of the molybdenum-containing precursor of formula (I), (II) and / or (III) and of the precursor containing aluminum of formula (IV), (V) and / or (VI) in a volume of solution, preferably aqueous, corresponding to the pore volume of a mesoporous matrix based on preformed oxide, b) impregnation of the matrix mesoporous oxide-based preformed with the solution obtained in step a), optional maturation of the solid thus obtained, c) optional step of drying, calcination and / or steam treatment of the solid obtained at the end of step b), at a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range from 50 ° C to 1000 ° C, d) thermal activation step of solid obtained at the end of step c), at a higher pressure less than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range of 100 ° C to 1000 ° C.
    In another variant, the catalyst may be prepared by dry impregnation according to the process comprising the following steps: a ') solubilization of the molybdenum-containing precursor of formula (I), (II) and / or (III) in a volume of solution, preferably aqueous, corresponding to the pore volume of a preformed oxide-based mesoporous matrix, b ') impregnation of the preformed oxide-based mesoporous matrix with the solution obtained in step a), optional maturation of the solid so obtained, c ') drying step for discharging the impregnating solvent of the solution a'), solubilization of the precursor containing aluminum of formula (IV), (V) and / or (VI ) in a volume of solution, preferably aqueous, corresponding to the pore volume of the solid obtained in step c '), e') impregnation of the solid obtained in step c ') with the solution obtained in step d' ), possible maturation of the solid thus obtained f) optional step of drying, calcining and / or steam treatment of the solid obtained at the end of step e '), at a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range from 50 ° C. to 1000 ° C., g ') step of thermal activation of the solid obtained at the end of step f'), at a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range of 100 ° C to 1000 ° C.
    The steps a ') and d') can be reversed, that is to say, that one can first impregnate the precursor containing aluminum and then the precursor containing the Mo.
    The maturation optionally used in steps b), b ') and e') is carried out in a controlled atmosphere and at a temperature so as to promote the dispersion of said precursor (s) on the all of the surface of the mesoporous matrix based on preformed oxide. Advantageously, the maturation is carried out at a temperature of between 20 and 120 ° C. and a pressure of between 0.01 and 1 MPa.
    Steps c) and / or d) or steps c ') and / or f) and / or g') can be carried out under an oxidizing, reducing or neutral atmosphere.
    Preferably, the drying steps c) and f ') are carried out in a temperature range from 20 ° C to 200 ° C, preferably from 50 ° C to 150 ° C and preferably from 100 ° C to 130 ° C for a period less than 72 h and preferably less than 24 h.
    Preferably, the thermal activation steps d) and g ') are carried out under a neutral atmosphere at atmospheric pressure in a temperature range from 200 ° C to 800 ° C, preferably from 350 ° C to 650 ° C. Preferably, the neutral atmosphere is nitrogen in a flow rate range from 0.01 to 20 Nl / h per gram of solid obtained after steps c) and f), preferably from 0.1 to 10 Nl / h per gram of solid obtained at the end of steps c) and f).
    In the case of the excess impregnation, the catalyst may be prepared by excess impregnation according to the process comprising the following steps: a) solubilization of the molybdenum-containing precursor of formula (I), (II) and / or (III) and aluminum-containing precursor of formula (IV), (V) and / or (VI) in a volume of solution, preferably aqueous, corresponding to between 1.5 and 20 times the pore volume of the mesoporous matrix at preformed oxide base, b ") impregnation of the mesoporous matrix based on preformed oxide, with the solution obtained in step a"), filtration and recovery of the solid, optional maturation of the solid thus obtained, c ") stage optional drying, calcining and / or steam treatment of the solid obtained at the end of step b ") at a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range from 50 ° C to 1000 ° C, d ") step d thermal activation of the solid obtained after step c ") at a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range from 100 ° C to 1000 ° vs.
    The maturation optionally implemented in step b ") is carried out in a controlled atmosphere and temperature so as to promote the dispersion of said precursor over the entire surface of the mesoporous matrix based on preformed oxide. Advantageously, the maturation is carried out at a temperature between 20 and 120 ° C and a pressure between 0P1 and 1 MPa.
    Preferably, the solubilization of the precursor containing molybdenum and the precursor containing aluminum, of formula (I), (II) and / or (III) and of formula (IV), (V) and / or (VI) in step a ") is carried out in a volume of solution corresponding to between 2 and 10 times the pore volume of the preformed oxide-based mesoporous matrix.
    Steps c ") and / or d") can be carried out under an oxidizing, reducing or neutral atmosphere.
    Preferably, the optional c ") drying step is carried out in a temperature range of 20 ° C to 200 ° C, preferably 50 ° C to 150 ° C and preferably 100 ° C to 130 ° C during a period of less than 72 hours and preferably less than 24 hours.
    Preferably, the thermal activation step d) is carried out under a neutral atmosphere at atmospheric pressure in a temperature range from 200 ° C. to 800 ° C., preferably from 350 ° C. to 650 ° C. Preferably, the neutral atmosphere is nitrogen in a flow rate range from 0.01 to 10 Nl / h per gram of solid obtained after step c "), preferably from 0.1 to 5 Nl / h per gram of solid obtained at the end of step c ").
    Organic compounds, called organic additives, can also be used in the preparation of the catalyst according to the invention. At least one organic additive may be introduced by impregnation onto the mesoporous matrix before the step of impregnating the precursors, by co-impregnation with the precursors or post-impregnation after impregnation of the precursors.
    The organic compounds or additives used are chosen from chelating agents, non-chelating agents, reducing agents and additives known to those skilled in the art.
    Said organic compounds or additives are advantageously chosen from optionally etherified mono-, di- or polyalcohols, carboxylic acids (citric acid, acetic acid, etc.), sugars, non-cyclic mono, di or polysaccharides such as glucose, fructose, maltose, lactose or sucrose, cyclic or non-cyclic esters, cyclic or non-cyclic ethers, ketones, compounds combining several of these functions (ketones, carboxylic acids, ethers, esters, alcohols, amines, etc.). ), crown ethers, cyclodextrins and compounds containing at least sulfur, or phosphorus or nitrogen such as nitriloacetic acid, ethylenediaminetetraacetic acid, or diethylenetriamine, amino acids and zwitterionic compounds, taken alone or in mixture.
    The impregnating solvent is preferably water but any solvent known to those skilled in the art can be used.
    One or more other metallic elements can also be used in the composition of the catalyst used in the process according to the invention. This metal element may be selected from zinc, nickel, cobalt, tungsten, vanadium, niobium, tantalum, iron and copper. This metal element is introduced at a content of between 0.01 and 10%, and preferably between 0.02 and 5% expressed in% by weight of metal relative to the mass of the mesoporous matrix based on oxide.
    This metal element may be provided by a compound chosen from salts and / or oxides of zinc, nickel, cobalt, tungsten, vanadium, niobium, tantalum, iron and copper, preferably salts and / or oxides of zinc, nickel, cobalt, tungsten. Preferably, the compound is a salt, a carboxylate, an alkoxide or a cobalt oxide. Preferably, the compound is Co (NO 3) 2 or CoO. Most preferably, the compound is Co (NC 3) 2 ·
    This compound may be introduced by impregnation onto the mesoporous matrix before impregnating the molybdenum-containing precursor of formula (I), (II) and / or (III) and the precursor containing aluminum of formula (IV), ( V) and / or (VI) co-impregnating with said precursors or post-impregnation after impregnation of said precursors.
    In the case where the catalyst used in the process according to the invention is obtained in powder form at the end of the various preparation processes described above, the latter can be shaped according to the methods well known to humans. of career. Thus, it may be in the form of pelletized, crushed, sieved powder, granules, tablets, balls, wheels, spheres or extrudates (hollow or non-hollow cylinders, multilobed cylinders with 2, 3, 4 or 5 lobes for example, twisted rolls), or rings, etc. Preferably, said catalyst is in the form of extrudates.
    During said shaping operation, the catalyst used in the process according to the invention may optionally be mixed with at least one porous oxide material having the role of binder so as to generate the physical properties of the catalyst which are suitable for the process according to the invention. invention (mechanical strength, attrition resistance, etc.).
    Said porous oxide material is preferably a porous oxide material chosen from the group formed by alumina, silica, silica-alumina, magnesia, clays, titanium oxide, zirconium oxide, lanthanum, cerium oxide, aluminum phosphates and a mixture of at least two of the oxides mentioned above. Said porous oxide material may also be chosen from mixtures of alumina-boron oxide, alumina-titanium oxide, alumina-zirconia and titanium-zirconia oxide. Aluminates, for example aluminates of magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper and zinc, as well as mixed aluminates, for example those containing at least two of the metals mentioned above, are advantageously used as porous oxide material. It is also possible to use titanates, for example titanates of zinc, nickel or cobalt. It is also advantageous to use mixtures of alumina and silica and mixtures of alumina with other compounds such as group VIB elements, phosphorus, fluorine or boron. It is still possible to use simple, synthetic or natural clays of 2: 1 dioctahedral phyllosilicate or 3: 1 trioctahedral phyllosilicate such as kaolinite, antigorite, chrysotile, montmorillonite, beidellite, vermiculite, talc. , hectorite, saponite, laponite. These clays can be optionally delaminated. It is also advantageous to use mixtures of alumina and clay and mixtures of silica-alumina and clay. The various mixtures using at least two of the compounds mentioned above are also suitable for acting as binder. Optionally, at least one organic adjuvant is also mixed during said shaping step. The presence of said organic adjuvant facilitates extrusion shaping. Said organic adjuvant may advantageously be chosen from polyvinylpyrrolidones, cellulosic polymers and their derivatives, preferably chosen from cellulose ethers such as, for example, Methocel, marketed by Dow Chemical, polyvinyl alcohols, polyethylene glycols, polyacrylamides. polysaccharides, natural polymers and their derivatives, such as, for example, alginates, polyesters, aromatic polyamides and polyamides, polyethers, poly (aryl ethers), polyurethanes, polysulfones such as polyether sulfonates, heterocyclic polymers, preferably chosen from polyimides, polyether imides, polyesters imides, polyamide imides, and polybenzimidazole.
    The proportion of said organic adjuvant is advantageously between 0 and 20% by weight, preferably between 0 and 10% by weight and preferably between 0 and 7% by weight, relative to the total mass of the mesoporous shaped matrix. . Metathesis reaction
    The olefin metathesis process carried out by contacting the olefins with the catalyst defined above is advantageously carried out at a temperature of between 0 and 500 ° C., preferably between 0 and 400 ° C., more preferably between At 20 and 350 ° C and more preferably at 30 to 350 ° C.
    The metathesis reaction of the olefins can be carried out in the gas phase or in the liquid phase. The reaction may be carried out batchwise, in a stirred reactor, or continuously, passing the olefinic reactant (s) through a fixed bed, moving bed, or fluidized bed of the catalyst.
    The pressure at which the process according to the invention is carried out is not critical. However, for liquid phase operation, it is advantageous to maintain a pressure at least equal to the vapor pressure of the reaction mixture at the reaction temperature.
    The reaction is preferably carried out in the absence of solvents. However, the reaction can be carried out in the presence of a solvent such as a hydrocarbon, or a halogenated, aliphatic, cyclanic or aromatic hydrocarbon.
    The olefins capable of reacting in metathesis in the process according to the invention may be linear olefins corresponding to the general formula R 1 R 2 C = CR 3 R 4, where R 1, R 2, R 3 and R 4, which are identical or different, are hydrogen or a hydrocarbyl radical of 1 to 20 carbon atoms, or olefins of cyclic structure, the ring having from 3 to 20 carbon atoms.
    It is possible either to react an olefin on itself or to react several olefins together in a mixture. The process according to the invention is in particular the cross-metathesis reaction of ethylene with butene-2 to give propylene, or the reverse conversion reaction of propylene to a mixture of ethylene and butene-2. Other olefins capable of reacting in metathesis are the linear or cyclic monoolefins or polyolefins carrying functional groups such as, for example, halogens or ester groups. The process can also carry out, in co-metathesis, a mixture of the preceding olefins.
    In the case of the propylene production by metathesis between ethylene and butene-2, butene-2 may preferably come from a dimerization reaction of ethylene in the presence of a homogeneous or heterogeneous catalyst known to the art. 'Man of the trade. For example, butene-2 can come from a dimerization of ethylene in the presence of a nickel complex of the NiCl 2 (PBu 3) 2 type producing a mixture of butene-1 and butene-2 by homogeneous catalysis. For example, butene-2 can come from a dimerization of ethylene in the presence of a nickel-based heterogeneous catalyst of N1SO4 / Al2O3 type producing a mixture of butene-1 and butene-2 by heterogeneous catalysis.
    In the case of propylene production by metathesis between ethylene and a mixture of butene-2 and butene-1, an isomerization catalyst of butene-1 to butene-2 is preferably used to maximize the yield of propylene . For example, an MgO or K20 type oxide catalyst can be used to isomerize butene-1 to butene-2. Ethylene can advantageously be obtained by dehydration of ethanol biosourced by any dehydration method known to those skilled in the art to allow the production of biobased propylene.
    EXAMPLES
    In the examples, the heteropolyanion-containing molybdenum precursor PM012O40H3 and the coordination complex type aluminum-containing precursors AI2 (SC> 4) 3 are commercially available.
    Example 1A (not in accordance with the invention): preparation of 6.7% Mo / SiC> 9 by dry impregnation of a solution of ΡΜθΐ9θ4η3 ~ .3Η + .30Η9θ 1.5 g of ΡΜθΐ2θ4ο3 '· 3Η + .30Η20 are dissolved at 60 ° C in 11.7 ml of distilled water At complete dissolution, a silica (SBet = 462 m 2 / g, Vp = 0.75 ml / g) is impregnated with this solution. The solid obtained is matured for 24 hours at 25 ° C. under air. The resulting solid is oven-dried at 120 ° C for 24 h and then activated under nitrogen at 550 ° C for 2 h.
    Example 1B (in accordance with the invention): preparation of 6.4% Mo + 1% Al / SiO.sub.9 by dry impregnation of a solution of PMoi9Q4n3 ~ .3H + .301-bO and Alp (SCM3.18HpO 1.5 g of ΡΜθι204ο3 ' · 3Η + .30Η20 and 1.83 g of Al 2 (SO 4) 3 · 18H 2 O are dissolved at 60 ° C. in 11.7 ml of distilled water, with complete dissolution a silica (Sbet = 462 m 2 / g, Vp = 0). 75 ml / g) is impregnated with this solution The solid obtained is matured for 24 hours at 25 ° C. in air The resulting solid is dried in an oven at 120 ° C. for 24 h and then activated under nitrogen at 550 ° C. C for 2 h.
    Example 2: Metathesis of propylene to ethylene and butene-2 2 g of catalyst prepared in Example 1A and 1B are mixed at a height of 50% by weight with silicon carbide (SiC) in a double-jacketed fixed bed reactor. The coolant of the jacket is heated to 70 ° C. Pure propylene is fed by a Gilson pump to the reactor and the pressure is set at 4.5 MPa. The productivity of the catalysts expressed in millimoles of propylene consumed per gram of catalyst per hour is quantified as a function of the time noted t (in hours noted h) in FIG. 1. The activity of the catalyst 1B according to the invention prepared by impregnation a precursor containing molybdenum and an aluminum-containing precursor is greater than the activity of catalyst 1A not in accordance with the invention and prepared by impregnation of a single precursor containing molybdenum.
    The stability of the catalyst 1B according to the invention is better than the stability of the catalyst 1A not according to the invention.
    权利要求:
    Claims (19)
    [1" id="c-fr-0001]
    1. Process for metathesis of olefins carried out by contacting the olefins with a catalyst comprising a mesoporous matrix and at least the molybdenum and aluminum elements, said elements being incorporated in said matrix by means of at least two precursors including at least one precursor contains molybdenum and at least one precursor contains aluminum.
    [2" id="c-fr-0002]
    2. Method according to claim 1 wherein the precursor containing molybdenum is a coordination complex precursor based on molybdenum and / or polyoxometalate type based on molybdenum and / or (thio) molybdate type.
    [3" id="c-fr-0003]
    3. A process according to claim 1 or 2 wherein the molybdenum coordination complex type molybdenum precursor has the formula (I) Mom (= Y) n (n) n> (X) 0 (= CR2) r (I) in which the groups Y, which are identical to or different from each other, are chosen from O, S and NR ', the groups X, which are identical to or different from one another, are chosen from halides, such as F Cl, Br, I, chlorate, bromate, iodate, nitrate, sulfate or hydrogen sulphate, alkyl sulphate, thiosulfate, carbonate or hydrogen carbonate, phosphate or hydrogen phosphate or dihydrogen phosphate, substituted or unsubstituted substituted alkyl, cycloalkyl or aryl groups, substituted or unsubstituted cyclopentadienyls, the alkoxy, aryloxy, siloxy, amide, hydrido, nitro, carboxylate, acetylacetonate, sulphonate, β-diketiminate, iminopyrride, amidinate, borate, cyanide, cyanate, thiocyanate or NR2-CS2 'groups, the identical R and R' groups, or different from each other, are chosen from among the alkyl and aryl groups, preferably comprising from 1 to 10 carbon atoms, the alkoxy and aryloxy groups, m is equal to 1 or 2, n is between 0 and 4, n is between 0 and 4; and 2, - o is 0 to 10, - r is 0 to 2, - n + n '+ o + r is greater than or equal to 1.
    [4" id="c-fr-0004]
    4. Process according to claim 1 or 2, in which the precursor containing molybdenum-based polyoxometalate molybdenum corresponds to the formula (II) (XxMomMbOyHh) q'.nH20 (II) in which, • x is greater than or equal to 0, • m is greater than or equal to 2, • b is greater than or equal to 0, • y is greater than or equal to 7, • h is 0 to 12, • q is 1 to 20, • n is between 0 and 200, • x, m, b, y, h, n and q being integers, X being a member selected from phosphorus, silicon and boron, M being a metallic element selected from aluminum , zinc, nickel, cobalt, tungsten, vanadium, niobium, tantalum, iron and copper.
    [5" id="c-fr-0005]
    5. Process according to claim 4, in which the molybdenum-based polyoxometalate precursor is a molybdenum-based isopolyanion in which the index x of the element X is equal to 0.
    [6" id="c-fr-0006]
    The process according to claim 4 wherein the molybdenum-based polyoxometalate precursor is a heteropolyanion selected from the group consisting of Strandberg heteropolyanion of formula X2Mo5C> 23Hhq nH20, Anderson heteropolyanion of formula XMo6C> ## STR5 ## wherein Keggin heteropolyanion of the formula ## STR1 ## is a lacunar Keggin heteropolyanion of the formula ## STR5 ## wherein the lacunar Keggin heteropolyanion of the formula ## STR1 ## Preyssler heteropolyanion of the formula X5Mo3oOi10Hhq ', nH20 with X, h and q having the definitions of claim 4.
    [7" id="c-fr-0007]
    The process of claim 4 wherein the molybdenum-based polyoxometalate precursor is a heteropolyanion selected from the group consisting of Strandberg heteropolyanion of formula X2Mo4CoO23Hhq ', nH20, Anderson heteropolyanion of formula XMo5CoO24Hhq', nH20, the Keggin heteropolyanion of formula XMonCoO4oHhq nH20, a lacunar Keggin heteropolyanion of formula XMo0CoC> 39Hhq nH20, the lacunar Keggin heteropolyanion of formula XMo8CoO34Hhq nH20, the Dawson heteropolyanion of formula X2Moi7Co062Hhq ', nH20, Preyssler heteropolyanion of formula X5Mo29CoOnoHhq nH20 with X, h and q having the definitions of claim 4.
    [8" id="c-fr-0008]
    8. Process according to claim 1 or 2 wherein the precursor containing molybdenum (thio) molybdate type corresponds to the formula (III) Cc (MoY4) z (IN) in which - C represents an organic or inorganic cation, such as that the protons, the ammoniums, the phosphoniums, the alkalis, the alkaline-earths, the transition elements, the groups Y, identical or different from each other, can be chosen between O and S, - c is between 1 and 4; z is between 1 and 10.
    [9" id="c-fr-0009]
    9. Process according to claim 1, in which the precursor containing aluminum is chosen from aluminum-based coordination complex precursors and / or aluminum salt precursors and / or salt-type precursors. aluminum-based heteropolyanion and / or any colloidal solution of alumina.
    [10" id="c-fr-0010]
    The process according to claim 1 or 9 wherein the aluminum coordination complex-type precursor of the coordination complex type has the formula (IV) AlnRm. xH 2 O (IV) in which, n is between 1 and 3, m is between 1 and 3, x is between 0 and 200, the groups R which are identical to or different from one another are chosen from hydrogen. , halides, such as F, Cl, Br, I, chlorate, bromate, iodate, nitrate, sulfate or hydrogen sulphate, alkyl sulphate, thiosulfate, carbonate or hydrogen carbonate, phosphate or hydrogen phosphate or dihydrogen phosphate, alkyl, alkenyl, alkynyl, cycloalkyl or substituted or unsubstituted aryls, substituted or unsubstituted cyclopentadienyls, hydroxy, alkoxy, aryloxy, carboxylate, nitrate, acetylacetonate, sulfonate, perchlorate groups.
    [11" id="c-fr-0011]
    11. The method of claim 1 or 9 wherein the precursor containing aluminum aluminum salt type corresponds to the formula (V) [AlnRm] '[C] +. nH20 (V) in which, n is between 1 and 3, m is between 1 and 3, x is between 0 and 200, the groups R which are identical to or different from one another may be chosen from hydrogen, the oxo group, halides, such as F, Cl, Br, I, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl or aryl groups, substituted or unsubstituted cyclopentadienyls, hydroxy, alkoxy, aryloxy, carboxylate groups, sulfonate, nitrate, acetylacetonate, perchlorate, • C is selected from hydrogen, alkali, alkaline earth, transition metals, poor metals and rare earths, ammonium cations and phosphoniums.
    [12" id="c-fr-0012]
    The process of claim 1 or 9 wherein the aluminum-containing heteropolyanion salt-type precursor is of the formula (VI) (AlaM1mM2bXxOyHh) q- (Cr +) c. ηΗ20 (VI) wherein, • a is greater than or equal to 0, • m is greater than or equal to 1, • b is greater than or equal to 0, • x is greater than or equal to 0, • y is greater than or equal to 10, • h is 0 to 12, • q is 0 to 20, • r is 0 to 20, • c is 0 to 20, • n is 0 to 200, • x m, y, h, n and q being integers, X being a member chosen from phosphorus, silicon and boron, M1 and M2, which are identical to or different from each other, being metallic elements chosen from aluminum, zinc, nickel, cobalt, molybdenum, tungsten, vanadium, niobium, tantalum, iron and copper, • C represents one or more atoms, identical or different, hydrated or not, selected from the elements of the periodic classification may exist in cationic form, such as hydrogen, alkaline, alkaline earth, transit metal ion, poor metals and rare earths, in hydrated or non-hydrated forms, chosen from organic oxygenated and / or nitrogen and / or phosphorus-containing cations, such as ammoniums and phosphoniums.
    [13" id="c-fr-0013]
    13. Method according to one of the preceding claims wherein the mesoporous matrix is an oxide-based matrix of at least one element X selected from silicon, aluminum, titanium, zirconium, magnesium, lanthanum. , cerium and their mixtures.
    [14" id="c-fr-0014]
    14. Method according to one of the preceding claims wherein the catalyst is prepared by dry impregnation according to the process comprising the following steps: a) solubilization of the precursor containing molybdenum and the precursor containing aluminum in a volume of corresponding solution to the pore volume of a mesoporous matrix based on preformed oxide, b) impregnation of the preformed oxide-based mesoporous matrix with the solution obtained in step a), optional maturation of the solid thus obtained, c) optional step drying, calcining and / or steam treatment of the solid obtained after step b), at a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range from 50 ° C to 1000 ° C, d) thermal activation step of the solid obtained at the end of step c) at a pressure greater than or equal to 0.1 MPa or less than or equal to0.1 MPa, in a temperature range of 100 ° C to 1000 ° C.
    [15" id="c-fr-0015]
    15. Method according to one of claims 1 to 13 wherein the catalyst is prepared by dry impregnation according to the process comprising the following steps: a ') solubilization of the precursor containing molybdenum in a volume of solution corresponding to the pore volume of a mesoporous matrix based on preformed oxide, b ') impregnating the preformed oxide-based mesoporous matrix with the solution obtained in step a), optionally maturing the solid thus obtained, c') drying step intended for evacuating the impregnating solvent from solution a '), solubilizing the precursor containing aluminum in a volume of solution corresponding to the pore volume of the solid obtained in step c'), e ') impregnating the solid obtained in step c ') with the solution obtained in step d), optionally maturation of the solid thus obtained, f) optional step of drying, calcination and / or treatment with v solids solid obtained after step e '), at a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range from 50 ° C to 1000 ° C, g ') step of thermal activation of the solid obtained at the end of step f'), at a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a range of temperature ranging from 100 ° C to 1000 ° C.
    [16" id="c-fr-0016]
    16. Method according to one of claims 1 to 13 wherein the catalyst is prepared by excess impregnation according to the process comprising the following steps: a ") solubilization of the precursor containing molybdenum and the precursor containing aluminum in a volume of solution, preferably aqueous, corresponding to between 1.5 and 20 times the pore volume of the preformed oxide-based mesoporous matrix, b ") impregnation of the preformed oxide-based mesoporous matrix with the solution obtained at step a "), filtration and recovery of the solid, optional maturation of the solid thus obtained, c") optional step of drying, calcination and / or steam treatment of the solid obtained at the end of step b ") At a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range from 50 ° C to 1000 ° C, d") thermal activation step of the solid obtained at the from step c ") at a pressure greater than or equal to 0.1 MPa or less than or equal to 0.1 MPa, in a temperature range of 100 ° C to 1000 ° C.
    [17" id="c-fr-0017]
    17. Method according to one of the preceding claims wherein the metathesis reaction is carried out at a temperature between 0 and 500 ° C.
    [18" id="c-fr-0018]
    18. The method of claim 17 wherein the olefins are linear olefins having the general formula R1R2C = CR3R4, where R1, R2, R3 and R4, identical or different, are hydrogen or a hydrocarbyl radical of 1 to 20 atoms of carbon, or olefins of cyclic structure, the ring having from 3 to 20 carbon atoms.
    [19" id="c-fr-0019]
    19. Method according to one of the preceding claims wherein the metathesis reaction is the cross metathesis reaction of ethylene with butene-2, or the reverse reaction of conversion of propylene to a mixture of ethylene and butene. -2.
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    引用文献:
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    FR3007029A1|2013-06-17|2014-12-19|IFP Energies Nouvelles|METHOD OF OLEFIN METATHESIS USING A CATALYST BASED ON HIERARCHISED POROSITY SPHERICAL MATERIAL COMPRISING OXIDE METALLIC PARTICLES PITCHED IN A MATRIX COMPRISING SILICON OXIDE|
    FR2826880B1|2001-07-04|2004-06-18|Inst Francais Du Petrole|IMPROVED CATALYST COMPOSITION FOR OLEFIN METATHESIS|US10550048B2|2017-01-20|2020-02-04|Saudi Arabian Oil Company|Multiple-stage catalyst system for self-metathesis with controlled isomerization and cracking|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1557367A|FR3039543B1|2015-07-31|2015-07-31|OLEFIN METATHESIS METHOD USING A CATALYST CONTAINING ALUMINUM AND MOLYBDENUM INCORPORATED BY MEANS OF AT LEAST TWO PRECURSORS|
    FR1557367|2015-07-31|FR1557367A| FR3039543B1|2015-07-31|2015-07-31|OLEFIN METATHESIS METHOD USING A CATALYST CONTAINING ALUMINUM AND MOLYBDENUM INCORPORATED BY MEANS OF AT LEAST TWO PRECURSORS|
    US15/749,368| US10322984B2|2015-07-31|2016-07-26|Olefin metathesis method using a catalyst containing aluminium and molybdenum incorporated by means of at least two precursors|
    CN201680044741.7A| CN108137440A|2015-07-31|2016-07-26|Use the olefin metathesis method containing the aluminium being incorporated to by least two precursors and the catalyst of molybdenum|
    PCT/EP2016/067829| WO2017021232A1|2015-07-31|2016-07-26|Olefin metathesis method using a catalyst containing aluminium and molybdenum incorporated by means of at least two precursors|
    TW105124185A| TW201713609A|2015-07-31|2016-07-29|Process for the metathesis of olefins using a catalyst containing aluminium and molybdenum incorporated by means of at least two precursors|
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