EP2739594A1 - Procédé de métathèse des oléfines utilisant un catalyseur a base d'un matériau sphérique comprenant des particules métalliques oxydes piégées dans une matrice mésostructurée - Google Patents
Procédé de métathèse des oléfines utilisant un catalyseur a base d'un matériau sphérique comprenant des particules métalliques oxydes piégées dans une matrice mésostructuréeInfo
- Publication number
- EP2739594A1 EP2739594A1 EP12748729.6A EP12748729A EP2739594A1 EP 2739594 A1 EP2739594 A1 EP 2739594A1 EP 12748729 A EP12748729 A EP 12748729A EP 2739594 A1 EP2739594 A1 EP 2739594A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- oxide
- metal particles
- mixture
- precursors
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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Classifications
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- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Definitions
- the present invention relates to a process for the metathesis of olefins, which is a catalytic reaction for the conversion of olefins by exchanging the alkylidene groups of the starting olefins.
- the present invention relates to a process for metathesis of olefins using a catalyst based on a spherical material comprising metal oxide particles trapped in a mesostructured matrix.
- Metathesis of olefins or redistribution reaction of alkylidene groups with each other is a crucial reaction in various fields of chemistry.
- this reaction catalyzed by organometallic complexes, is used to obtain various molecules with high added value (drugs, etc.).
- the metathesis of olefins is of great practical interest, for example for the rebalancing between them light olefins from steam cracking, such as ethylene, propylene and butenes.
- catalysts are likely to be used in the metathesis reaction: either homogeneous catalysts, when their constituent elements are all soluble in the reaction medium, or heterogeneous catalysts, when at least one of the elements is insoluble in said medium.
- heterogeneous catalysts For the metathesis of light olefins, robust and inexpensive heterogeneous catalysts are used.
- a known commercial solution is the technology offered by Lummus Technology Company, based on the use of a tungsten oxide catalyst deposited on a silicic carrier W0 3 / SiO 2 described in JC Mol, J. Mol. Catal. A, 2004, 213, 1, 39; RJ Gartside; and the patent CA 2733890.
- Said heterogeneous catalysts known to those skilled in the art work at relatively high temperature, generally at a temperature above 200 ° C and are only moderately active.
- the rhenium oxide metathesis catalysts Re 2 0 7 described in the publication M. Stoyanova et al., Appl. Catal. A, 2008, 340, 2, 242 are known to those skilled in the art as being more active but they are also more expensive and unstable because they deactivate quickly.
- Molybdenum oxide catalysts described in DP Debecker et al., J. Catal., 2011, 277, 2, 154.
- Molybdenum (Mo) is much cheaper than the Rhenium (Re) and its stability and activity are intermediate to those of Rhenium (Re) and tungsten (W).
- the preparation of catalysts based on molybdenum oxides (MoO 3 ) is conventionally carried out by impregnation with an aqueous solution of a molybdenum salt such as, for example, ammonium heptamolybdate on a support such as for example a silica an alumina or a porous silica-alumina as described in DP Debecker et al., Catal. Today, 2011, 169, 1, 60 and J. Handzlik ef al., Appl. Catal. A, 2004, 273, 1-2, 99.
- the difficulty is to ensure that the molybdenum deposition is dispersed and up to the interior of the porosity of the support.
- the deposit is inhomogeneous, concentrated on the outer surface of the porous particles constituting the support and leads to the formation of inactive molybdenum oxide crystals.
- the abundant formation of aluminum molybdate (Al 2 (MoO 4 ) 3 ) following the wet impregnation step also limits the activity of the catalysts (X. Li ef a /, J Mol Catal A, 2006, 250, 1-2, 94).
- One way of circumventing the formation of the aforementioned inactive species during wet impregnation is to use other molybdenum precursors.
- the wet impregnation stage can be improved and better performance can be achieved (DP Debecker et al., J. Mol Catal, A, 2011, 340, 65-76).
- the impregnation remains a two-step process, requiring the prior preparation of a suitable support.
- Pyrolysis of aerosol spray is a one-step method, which produces active catalysts composed of silica-alumina nanoparticles decorated with molybdenum oxide (DP Debecker et al., J. Catal., 2011, 277.2, 154).
- the surface area of these non-porous solids remains relatively low, which limits the amount of MoO 3 that can be dispersed.
- the non-hydrolytic "sol-gel" method also makes it possible to obtain mixed oxides of molybdenum, silica and alumina in one step according to the publication DP Debecker et al., Chem. Mater., 2009, 21, 13, 2817.
- Obtaining a high performance metathesis catalyst therefore depends on the ability to obtain a material having a relatively high specific surface area, and a good dispersion of molybdenum so that the molybdenum is accessible on the surface of the support.
- the Applicant has sought to develop novel catalysts for the metathesis reaction of olefins by using the latter aerosol process.
- An object of the present invention is to provide a process for metathesis of olefins using a catalyst comprising at least one spherical inorganic material comprising metal particles oxide trapped in a mesostructured matrix, said spherical inorganic material being obtained by the particular synthetic technique called " aerosol".
- An advantage of using such a catalyst for the metathesis of olefins is to allow to obtain an increased catalytic activity compared with the use of conventional heterogeneous catalysts of the prior art.
- the present invention relates to a process for metathesis of olefins comprising bringing said olefins into contact with a catalyst that has been activated beforehand by heating at a temperature of between 100 and 1000 ° C. under a non-reducing gas atmosphere, said catalyst comprising at least one spherical inorganic material. comprising metal particles oxide trapped in a mesostructured matrix, said spherical inorganic material being obtained by the particular synthesis technique called "aerosol".
- the subject of the present invention is a process for metathesis of olefins comprising contacting said olefins with a catalyst previously activated by heating at a temperature of between 100 and 1000 ° C. under a non-reducing gas atmosphere, said catalyst comprising at least at least one inorganic material consisting of at least two elementary spherical particles, each of said elementary spherical particles comprising oxide metal particles having a size of at most 300 nm and containing at least one metal chosen from tungsten, molybdenum, rhenium, cobalt, tin, ruthenium, iron and titanium, said metal oxide particles being present in a mesostructured matrix based on an oxide of at least one Y element chosen from silicon, aluminum, titanium, tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, anganese, hafnium, niobium, tantalum, yttrium, cerium, ga
- the present invention therefore relates to a process for metathesis of olefins using said catalyst, in particular for the following non-limitatively enumerated reactions: ring closure by metathesis, metathesis polymerization of acyclic dienes, metathesis ring opening polymerization, metathesis of acyclic olefins, cross metathesis of cyclic and acyclic olefins and metathesis of functionalized olefins.
- the catalyst used in the olefin metathesis process comprises at least one inorganic material consisting of at least two elementary spherical particles, each of said elementary spherical particles comprising oxide metal particles having a size of at most 300 nm and containing at least one metal selected from tungsten, molybdenum, rhenium, cobalt, tin, ruthenium, iron and titanium alone or as a mixture, said metal oxide particles being present within a mesostructured matrix oxide-based material of at least one Y element selected from silicon, aluminum, titanium, tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese, hafnium, niobium, tantalum, yttrium, cerium, gadolinium, europium and neodymium and the mixture of at least two of these elements, said mesostructured matrix having a pore size of between 1.5 and 50 nm and having
- the element Y present in oxide form in the mesostructured matrix included in each of said spherical particles of said inorganic material used according to the invention is chosen from silicon, aluminum, titanium, tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese, Phafnium, niobium, tantalum, yttrium, cerium, gadolinium, europium and neodymium and the mixture of at least two of these elements.
- said element Y present in oxide form is chosen from silicon, aluminum, titanium, zirconium, gallium, germanium and cerium and the mixture of at least two of these elements.
- said element Y present in oxide form is chosen from silicon and aluminum and the mixture of these elements.
- said mesostructured matrix is preferably composed of aluminum oxide, silicon oxide or else a mixture of silicon oxide and aluminum oxide (aluminosilicate), and the combined Si / Al molar ratio is between 0.001 and 1000, preferably between 0.001 and 0.2 or between 3.5 and 1000 and very preferably between 0.03 and 0.1 or between 8 and 25.
- Said oxide-based matrix of at least said element Y is mesostructured: it has an organized porosity at the mesopore scale of each of the particles of the inorganic material used according to the invention, that is to say a pore-scale organized porosity having a uniform diameter of between 1.5 and 50 nm, preferably between 1.5 and 30 nm, and even more preferably between 2 and 20 nm and distributed s in a homogeneous and regular manner in each of said particles (mesostructuration of the matrix).
- the material located between the mesopores of the mesostructured matrix is amorphous and forms walls, or walls, whose thickness is between 1 and 30 nm and preferably between 1 and 10 nm.
- the thickness of the walls corresponds to the distance separating a first mesopore from a second mesopore, the second mesopore being the pore closest to the first mesopore.
- the organization of the mesoporosity described above leads to a structuring of said matrix, which may be hexagonal, vermicular or cubic and preferably vermicular.
- porosity of a microporous nature may also result from the interlaying of the surfactant, used during the preparation of the material used according to the invention, with the inorganic wall at the level of the organic-inorganic interface developed during the mesostructuration of the inorganic component of said material according to the invention.
- the material used according to the invention also has an interparticle textural macroporosity.
- the mesostructured matrix included in each of said elementary spherical particles of the material used according to the invention comprises oxide metal particles having a size of at most 300 nm, said metal oxide particles containing at least one metal chosen from tungsten, molybdenum, rhenium, cobalt, tin, ruthenium, iron and titanium alone or in mixture, and preferably containing at least one metal selected from tungsten, molybdenum, rhenium alone or in mixture.
- said metal oxide particles contain molybdenum alone.
- the said metal oxide particles contain at least one metal chosen from molybdenum, tungsten, rhenium, cobalt, tin, ruthenium, iron and titanium, taken alone or as a mixture, the said metals advantageously being found in an environment oxygen.
- said metal oxide particles are present within said mesostructured matrix. More specifically, said metal oxide particles are trapped in said mesostructured matrix. Said oxides metal particles are advantageously homogeneously and uniformly trapped in said mesostructured matrix included in each of said elementary spherical particles of the material used according to the invention.
- said metal oxide particles have a size of at most 300 nm, preferably at most 50 nm and even more preferably at most 3 nm.
- the size of said metal oxide particles is advantageously measured by transmission electron microscopy (TEM), when this is greater than 1 nm.
- TEM transmission electron microscopy
- the absence of detection of MET metal particles therefore means that said metal oxide particles have a size of less than 1 nm.
- Said metal oxide particles advantageously represent from 1 to 50% by weight, preferably from 2 to 45% by weight, preferably from 2 to 40% by weight and even more preferably from 2 to 25% by weight of the material used according to the invention. .
- the inorganic material used according to the invention comprises a mass content of element (s) molybdenum, tungsten, rhenium, cobalt, tin, ruthenium, iron, titanium, taken alone or in a mixture of between 1 and 40%, expressed in% by weight of oxide with respect to the mass of final material in oxide form, preferably between 2 and 35% by weight, preferably between 2 and 30% and even more preferably between 2 and 20%.
- element (s) molybdenum, tungsten, rhenium, cobalt, tin, ruthenium, iron, titanium taken alone or in a mixture of between 1 and 40%, expressed in% by weight of oxide with respect to the mass of final material in oxide form, preferably between 2 and 35% by weight, preferably between 2 and 30% and even more preferably between 2 and 20%.
- Said metal oxide particles are advantageously prepared according to protocols known to those skilled in the art described hereinafter in the disclosure of the invention.
- Said metal oxide particles may advantageously be preformed and used as such in the method of preparation of the inorganic material described below, or prepared in step a) of said process for preparing the inorganic material, using precursors of said metal oxide particles described. hereinafter in the description of the invention.
- said metal oxide particles are obtained from precursors of said metal oxide particles.
- (S) precursor (s) of said metal oxide particles are (a) preferably selected t (s) among the polyoxometalates of formula (X x M m O y H h) q ', and the monometallic precursors.
- said polyoxometalates of formula (X x M m O y H h) q ", especially isopolyanions and heteropolyanions and monometallic precursors are described below in the present description.
- said precursors of said metal particles oxides are selected from the polyoxometalates of formula (X "M m O y H h) q" and preferably from isopolyanions and heteropolyanions.
- said metal precursors represented by formula (xxiii m O y h h) q "(I) where h is hydrogen, O is an oxygen atom, X is an element selected from rhenium, phosphorous, silicon, boron, nickel, tin, ruthenium, iron, titanium and cobalt and M is one or more elements selected from molybdenum, tungsten, rhenium, cobalt, tin, ruthenium, iron, titanium, x being 0, 1, 2 or 4, m being 5, 6, 7, 8, 9, 10, 11, 12 and 18, y being between 17 and 72, h being between 0 and 12 and q being between 1 and 20, y, h and q being integers
- said precursors of said metal oxide particles in the form of polyoxometalates of formula (I) are preferably chosen from isopolyanions and heteropolyanions (denoted HPA).
- said precursors of formula (I) are heteropolyanions.
- Said precursors of formula (I), preferably in the form of heteroplyanions, are salts carrying a negative charge q compensated by positively charged counterions of identical or different nature.
- Counterions are advantageously provided by metal cations, in particular Group VIII metal cations such as Co 2+ , Ni 2+ , H + protons and / or NH + ammonium cations.
- metal cations in particular Group VIII metal cations such as Co 2+ , Ni 2+ , H + protons and / or NH + ammonium cations.
- heteropoly acid When all the counterions are H + protons, it is commonly called heteropoly acid to designate the form in which are found said precursors of formula (I).
- Such a heteropoly acid is, for example, phosphomolybdic acid (3H + , ⁇ 2 ⁇ 40 3 " ) or else phosphotungstite acid (3H + , PW 12 O 40 3" ).
- the isopolyanions and heteropolyanions used as metal precursors of said metal oxide particles are fully described in the book Heteropoly and Isopoly Oxometalates, Pope, Ed Springer-Verlag, 1983.
- the element M is one or more elements chosen advantageously from molybdenum, tungsten, rhenium, cobalt, ruthenium, tin, iron, titanium (Heteropoly and Isopoly Oxometalates, Pope, Ed Springer-Verlag, 1983, Chapter 4, Table 4.1).
- the element M is chosen from molybdenum and tungsten, alone or as a mixture.
- the m atoms M present in the general formula (I) are all exclusively either Mo or W atoms or a mixture of Mo and W atoms, either a mixture of Mo and Co atoms, or a mixture of Mo and Re atoms, or a mixture of W and Re atoms, or a mixture of Mo and w.
- the index m is equal to 5, 6, 7, 8, 9, 10, 11, 12 and 18. Even more preferably, m is equal to 6, 7 and 12.
- the value of m is preferably 7.
- the value of m is preferably equal to 12.
- O denotes the oxygen element with 17 ⁇ y ⁇ 48.
- the element M is a metal atom advantageously systematically in octahedral coordination in the structure of the heteropolyanion.
- the element M is one or more elements advantageously chosen from molybdenum, tungsten, cobalt, rhenium, tin, ruthenium, iron and titanium. More preferably, the element M is one or more elements chosen from molybdenum and tungsten.
- the m atoms M present in the general formula (I) are all exclusively either Mo atoms or W atoms, or a mixture of Mo and W atoms, or a mixture of atoms of Mo and Co, a mixture of Mo and Re atoms, a mixture of W and Re atoms.
- the index m is equal to 5, 6, 7, 8, 9, 10, 11, 12 and 18 and preferably equal to 5, 6, 9, 10, 11, 12, 18.
- O denotes the oxygen element with between 17 and 72, preferably between 23 and 42
- Such heteropolyanions are known as Anderson heteropolyanions (Nature, 1937, 150, 850).
- the heteropolyanion CoMo 6 0 24 H 6 3 " is a good example of a heteropolyanion of Anderson, Co being the heteroelement X of the HPA structure
- it is preferably dimeric.
- a mixture of the two monomeric and dimeric forms of said HPA can also be used.
- Anderson used to obtain the material used according to the invention is a dimeric HPA containing cobalt and molybdenum within its structure and the counterion of the HPA salt can be cobalt Co " 3 [Co l " 2 Mo 1 o0 38 H4].
- Heteropolyanions of formula XM 12 04oH h q are heteropolyanion having a Keggin structure and the heteropoly anions of the formula XM ⁇ C ⁇ l" are heteropolyanion having a lacunary Keggin structure.
- the heteropolyanions of Keggin structure are obtained, for variable pH ranges, according to the pathways described in the publication by A. Griboval, P. Blanchard, E. Payen, M. Fournier, JL Dubois, Chem. Lett., 1997, 12, 1259.
- Keggin structure heteropolyanions are also known in substituted forms in which a metal element, preferentially cobalt or rhenium, is substituted for the metal M present in the formula XM 12 O 4 O H h q ": such substituted Keggin species are, for example heteropolyanion PCoMonCvwH 6" (one Mo atom substituted with a Co atom) and PWniReNJJOs “(C. Dablemont et al, Chemistry, 2006, 12, 36, 9150.
- the PC0M0HO40H 6 " species is for example prepared according to the protocol described in the publication by LGA van de Water et al. J. Phys. Chem. B, 2005, 109, 14513.
- Other substituted species of Keggin heteropolyanions are the species PM03W9O40 3 " , PMo 6 W 6 O 40 3" , PM09W3O40 3 " .
- a precursor of said preferred metal oxide particles is Keggin heteropolyanion of the formula H 3 PMo 12 O 40 .
- Such heteropolyanions are so-called heteropolyanions of Strandberg. The preparation of Strandberg HPAs is described in the WC article. Cheng et al. J. Catal., 1988, 109, 163.
- the metal precursors of said metal oxide particles used to obtain the material used according to the invention are in the form of heteropolyanions chosen from the first, second and / or third category described above.
- said precursors may be a mixture of HPA of different formulas belonging to the same category or a mixture of HPA belonging to different categories.
- the isopolyanions or heteropolyanions as described above in the present description are prepared according to synthetic methods known to those skilled in the art or commercially available.
- the potential acidification of the reaction medium can lead to generating ⁇ -metatungstate, 12 times condensed: 12 W0 4 2 " + 18 H + ⁇ H 2 W 12 O 40 6 " + 8 H 2 0.
- isopolyanion species in particular the species Mo 7 0 24 6" and H 2 W 12 O 40 6 " are advantageously used as precursors for the metal oxide particles in the preparation process used according to the invention.
- the preparation of isopolyanions is amply described in Heteropoly and Isopoly Oxometallates, Pope, Ed Springer-Verlag, 1983 (Chapter II, pages 15 and 16).
- said precursors of said metal oxide particles are chosen from monometallic precursors.
- said monometallic precursors are based on molybdenum, tungsten, rhenium, cobalt, tin, ruthenium, iron, titanium, and preferably based on tungsten, molybdenum and rhenium, and very preferably, said monometallic precursors are based on molybdenum. It is also possible to use at least two monometallic precursors, each of said precursors being based on a different metal chosen from molybdenum, tungsten, rhenium, cobalt, tin, ruthenium, iron and titanium. .
- said elementary spherical particles constituting the material used according to the invention have a maximum diameter equal to 200 ⁇ , preferably less than 100 ⁇ , advantageously varying from 30 nm to 50 ⁇ , very advantageously from 50 nm to 30 ⁇ m. ⁇ and even more advantageously from 50 nm to 10 ⁇ m. More specifically, they are present in the material used according to the invention in the form of powder, beads, pellets, granules, or extrudates (hollow or non-hollow cylinders, multilobed cylinders with 2, 3, 4 or 5 lobes for example, twisted cylinders) or rings.
- the inorganic material contained in the catalyst used in the process according to the invention advantageously has a specific surface area of between 50 and 1100 m 2 / g and very advantageously between 50 and 600 m 2 / g and even more advantageously between 50 and 500 m 2 / g.
- the inorganic material contained in the catalyst used in the process according to the invention is advantageously prepared according to the method of preparation described below.
- the method comprises at least the following steps:
- step d) of removing at least said surfactant preferably by heat treatment allows the transformation of at least said metal precursor in said metal oxide particles constituting the inorganic material of the catalyst used in the process according to the invention
- an inorganic material is obtained which is then optionally shaped to be used as a catalyst in the process according to the invention, said inorganic material comprising metal oxide particles trapped within each of the mesostructured matrices. present in each of the elementary spherical particles constituting said inorganic material.
- the surfactant used for the preparation of the mixture according to step a) of said preparation process is an ionic or nonionic surfactant or a mixture of both.
- the ionic surfactant is chosen from phosphonium and ammonium ions and very preferably from quaternary ammonium salts such as cetyltrimethylammonium bromide (CTAB).
- CTAB cetyltrimethylammonium bromide
- the nonionic surfactant may be any copolymer having at least two parts of different polarities conferring properties of amphiphilic macromolecules.
- biological polymers such as polyamino acids (poly-lysine, alginates, etc.), dendrimers, polymers consisting of poly (alkylene oxide) chains.
- any copolymer of an amphiphilic nature known to those skilled in the art may be used (S. Forster, M. Antion
- a block copolymer consisting of poly (alkylene oxide) chains is used.
- Said block copolymer is preferably a block copolymer having two, three or four blocks, each block consisting of a poly (alkylene oxide) chain.
- one of the blocks consists of a poly (alkylene oxide) chain of hydrophilic nature and the other block consists of a poly (alkylene oxide) chain of a nature hydrophobic.
- the blocks For a copolymer with three blocks, at least one of the blocks consists of a chain of poly (alkylene oxide) hydrophilic nature while at least one of the other blocks consists of a poly ( alkylene oxide) of hydrophobic nature.
- the hydrophilic poly (alkylene oxide) chains are poly (ethylene oxide) chains denoted by (PEO) w and (PEO) 2 and the poly (alkylene oxide) chains of hydrophobic nature are poly (propylene oxide) chains denoted by (PPO) y , poly (butylene oxide) chains, or mixed chains in which each chain is a mixture of several alkylene oxide monomers.
- a compound of formula (PEO) w - (PPO) y - (PEO) z where w is between 5 and 300 and y is between 33 and 300 and z is from 5 to 300.
- the values of w and z are the same.
- nonionic surfactants known as Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide), Brij (Aldrich) are useful as nonionic surfactants.
- Pluronic BASF
- Tetronic BASF
- Triton Sigma
- Tergitol Union Carbide
- Brij Brij
- two of the blocks consist of a chain of poly (alkylene oxide) hydrophilic nature and the other two blocks consist of a chain of poly (oxides) of alkylene hydrophobic nature.
- an ionic surfactant such as CTAB
- a nonionic surfactant such as P123 or F127 is used.
- the precursor (s) of at least said element Y may be any compound comprising the element Y and capable of releasing this element in solution, for example in aqueous-organic solution, preferably in aqueous-organic solution. acid, in reactive form.
- Y is selected from the group consisting of silicon, aluminum, titanium, zirconium, gallium, germanium and cerium and the mixture of at least two of these elements
- the precursor (s) of at least said Y element considered may still be oxide (s) or hydroxide (s) of said element Y.
- the precursor of the element Y considered employed can also be of the form YOZ 2 , Z being a monovalent anion such as a halogen or the N0 3 group.
- said element (s) Y is (are) chosen from the group consisting of silicon, aluminum, titanium, zirconium, gallium, germanium and cerium and the mixture of at least two of these elements.
- the silicic and / or aluminum precursors used in step a) of the preparation process used according to the invention are precursors of inorganic oxides well known to those skilled in the art.
- a preferred silicic precursor is tetraethylorthosilicate (TEOS).
- TEOS tetraethylorthosilicate
- the aluminum precursor is advantageously an inorganic aluminum salt of formula AIZ 3 , Z being a halogen or the N0 3 group.
- Z is chlorine.
- the aluminum precursor may also be an aluminum oxide or hydroxide.
- Said surfactant and at least said precursor of at least one element Y used in the mixture of said step a) may advantageously be independently of one another in solution prior to step a), said solutions being then mixed in said step a).
- step a) is introduced into said mixture of either metal oxide particles or at least one precursor of said metal oxide particles.
- said mixture in solution of step a) can advantageously be produced according to a first embodiment described below.
- the precursor (s) of said metal oxide particles is dissolved or formed in solution prior to said step a).
- said solution is then introduced into the mixture of said step a).
- the solvent used for the dissolution or for the solution formation of the precursor (s) is aqueous and the solution obtained after solution or solution formation of the precursor (s) ), prior to step a), containing said precursors, is clear and of neutral, basic or acidic pH, preferably acidic.
- said precursors of the metal oxide particles are polyoxometalates of formula (I) and of preferably, heteropolyanions
- said precursors are either prepared from the precursors necessary for obtaining them, which are put in solution prior to the implementation of said step a), in a preferably aqueous solvent so as to form a clear solution and of neutral or acidic pH, preferably acid, before being introduced into said mixture according to step a), or dissolved in a preferably aqueous solvent before being introduced into said mixture according to said step a).
- the precursors of the metal oxide particles are polyoxometallates of formula (I) and preferably heteropolyanions and are prepared from the precursors necessary for obtaining them, which are put in solution prior to the implementation of said step a)
- at least one complexing agent to the solution in order to facilitate obtaining, during step a), an atomizable mixture with a view to carrying out said step b) of said method of preparation.
- Said complexing agent may advantageously be any compound known to those skilled in the art for its possible complexation with precursors of the heteropolyanion type.
- said complexing agent is urea, thiourea or acetylacetonate.
- step a) In the case where, in said mixture of step a), oxidic metal particles are introduced, said mixture in solution of step a) may advantageously be produced according to a second embodiment described below.
- a colloidal solution of said metal oxide particles is prepared via operating protocols that are well known to those skilled in the art, prior to said step a), said colloidal solution in which are dispersed the metal oxide particles being then introduced into the mixture according to said step a).
- the metal oxide particles, dispersed in colloidal solution may be obtained by a first method consisting of a hydroxylation step of a metal cation derived from the salt of said metal M, M being advantageously chosen from molybdenum, tungsten, rhenium, cobalt, tin, ruthenium, iron, titanium, by acid-base reaction (addition of an acid or a base) or by reaction of thermohydrolysis followed by a condensation step involving reactions olation or oxidation leading to said metal oxide particles.
- a third method for obtaining metal oxide particles dispersed in colloidal solution consists of using non-hydrolytic processes generally at low temperature, the systems studied being constituted by a precursor such as for example a salt or an alkoxide in a solvent.
- organic such as, for example, benzyl alcohol (M. Niederberger, MH Bard, GD Stucky, J. Am Chem Soc, 2002, 124, 46, 13642, PH Mutin and A. Vioux, Chem Mater, 2009, 21, 4, 582).
- said mixture in solution of step a) may advantageously be produced according to a third embodiment of embodiment described below.
- said metal oxide particles and / or at least one precursor of said metal oxide particles or a precursor of a polyoxometallate precursor of formula (I) containing at least one metal selected from molybdenum, tungsten, rhenium, cobalt, tin, ruthenium, iron, titanium alone or as a mixture, in isolated form in the mixing solution of step a) the method of said preparation process.
- the said metal oxide particles and at least one precursor of the said metal oxide particles used in step a) of the said preparation method may also be commercial.
- the catalyst used in the process according to the invention may advantageously be acidic, neutral or basic.
- said solution is acidic and has a maximum pH equal to 3, preferably between 0 and 2.
- the acids optionally used to obtain an acid solution are, in a non-exhaustive manner, hydrochloric acid, sulfuric acid and nitric acid.
- Said solution according to said step a) may be aqueous or may be a water-organic solvent mixture, the organic solvent preferably being a polar solvent miscible with water, especially an alcohol, preferably ethanol.
- Said solution according to said step a) of the preparation process used according to the invention can also be substantially organic, preferably substantially alcoholic, the quantity of water being such that the hydrolysis of the inorganic precursors is ensured (stoichiometric amount).
- said solution according to said step a) of the preparation process used according to the invention in which at least one surfactant, at least one precursor of at least one Y element, said metal oxide particles and / or at least one precursor of said metal oxide particles is an aquo-organic acid mixture, very preferably an acid-alcohol water mixture.
- the initial concentration of surfactant introduced into the mixture according to said step a) of said process for preparing the catalyst used in the process according to the invention is defined by c 0 and c 0 is defined with respect to the critical micelle concentration (c mc ) well known to those skilled in the art.
- the c mc is the limit concentration beyond which occurs the phenomenon of self-assembly of the molecules of the surfactant in the solution.
- the concentration c 0 may be less than, equal to or greater than the c mc , preferably it is less than c mc .
- the concentration c 0 is less than the c mc and said solution referred to in step a) of said preparation process used according to the invention is an acidic water mixture -alcohol.
- the solution referred to in step a) of the preparation process used according to the invention is a water-organic solvent mixture, preferably acidic
- it is preferred during said step a) of the preparation process used according to the invention that the surfactant concentration at the origin of the mesostructuration of the matrix is less than the critical micellar concentration, so that the evaporation of said aqueous-organic solution, preferably acidic, during step b) of method of preparation used according to the invention by the aerosol technique induces a phenomenon of micellization or self-assembly leading to the mesostructuration of the matrix of the material used according to the invention around said metal oxide particles and / or from at least one precursor of said metal oxide particles.
- the mesostructuration of the matrix of the material and prepared according to the process described above is consecutive to a progressive concentration, within each droplet, of at least the precursor of said element Y and the surfactant, until a concentration of surfactant c> c mc resulting from evaporation of the aqueous-organic solution, preferably acidic.
- the increase in the combined concentration of at least one precursor of said hydrolysed Y element and the surfactant causes the precipitation of at least said hydrolyzed precursor of said element Y around the self-organized surfactant and consequently the structuring of the matrix of the material used according to the invention.
- the interactions of the inorganic species with each other, organic / inorganic phases and organic species with each other lead, through a cooperative self-assembly mechanism, to the condensation of at least said precursor of said hydrolysed Y element around the self-organized surfactant.
- said metal oxide particles and / or at least one precursor of said metal oxide particles are trapped in said oxide-based mesostructured matrix of at least said element Y included in each of elementary spherical particles constituting the material used according to the invention.
- the aerosol technique is particularly advantageous for the implementation of said step b) of said process for preparing the catalyst used in the process according to the invention so as to constrain the reagents present in the initial solution to interact with each other, no loss of material except for the solvents, that is to say the solution, preferably the aqueous solution, preferably acidic, and optionally added with a polar solvent, not being possible, all of the said element (s) Y, said metal oxide particles and / or at least one precursor of said metal oxide particles, initially present being thus perfectly preserved throughout the process of preparation used according to the invention instead of being potentially eliminated during the filtration and washing steps encountered in conventional synthesis processes known to those skilled in the art.
- the step of atomizing the solution according to said step b) of said process for preparing the catalyst used in the process according to the invention produces spherical droplets.
- the size distribution of these droplets is lognormal.
- the aerosol generator used in the context of the present invention is a commercial apparatus of model 9306 A provided by TSI having a 6-jet atomizer.
- the atomization of the solution is carried out in a chamber in which a carrier gas is sent, preferably a 0 2 / N 2 mixture (dry air), at a pressure P equal to 1.5 bar.
- the diameter of the droplets varies depending on the aerosol apparatus employed. In general, the droplet diameter is between 90 nm and 600 ⁇ .
- step c) of said preparation process said droplets are dried.
- This drying is carried out by transporting said droplets by the carrier gas, preferably the 0 2 / N 2 mixture, in PVC tubes, which leads to the progressive evaporation of the solution, for example from the aquo-organic acid solution. obtained during said step a) and thus to obtain spherical elementary particles.
- This drying is perfect by a passage of said particles in a furnace whose temperature can be adjusted, the usual range of temperature ranging from 50 to 600 ° C and preferably from 80 to 500 ° C, the residence time of these particles in the oven being of the order of the second.
- the particles are then harvested on a filter.
- a pump placed at the end of the circuit promotes the routing of species in the aerosol experimental device.
- step d) of said preparation process the removal of the surfactant introduced in said step a) of said preparation process is advantageously carried out by heat treatment and preferably by calcination in air (optionally enriched in O 2). ) in a temperature range of 300 to 1000 ° C and preferably in a range of 500 to 600 ° C for a period of 1 to 24 hours and preferably for a period of 3 to 15 hours.
- Said step d) also allows the transformation of at least one precursor into said metallic oxide particles constituting the inorganic material of the catalyst used in the process according to the invention.
- the mesostructured inorganic material of the catalyst used in the process according to the invention thus obtained and consisting of elementary spherical particles comprising metal oxide particles trapped in a mesostructured matrix based on oxide of at least one element Y, can be shaped in the form of pelletized, crushed, sieved powder, balls, pellets, granules, or extrudates (hollow or non-hollow cylinders, multilobed rolls with 2, 3, 4 or 5 lobes, for example, twisted rolls), or rings, etc., these shaping operations being performed by conventional techniques known to those skilled in the art.
- said mesostructured inorganic material is obtained in the form of a powder, which consists of elementary spherical particles having a maximum diameter of 200 ⁇ .
- said mesostructured inorganic material is obtained in powder form, it can be used directly as a catalyst in the process according to the invention without prior shaping step.
- the shaping operation of said inorganic material comprises mixing said mesostructured material with at least one porous oxide material having the role of binder.
- 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, boron 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.
- the catalyst comprising at least one spherical inorganic material comprising oxide metal particles trapped in a mesostructured matrix used according to the invention is obtained.
- the material used according to the invention is characterized by several analysis techniques and in particular by X-ray diffraction at low angles (low-angle XRD), X-ray diffraction at high angles (XRD), by nitrogen volumetry. (BET), by transmission electron microscopy (TEM) optionally coupled to X analysis, scanning electron microscopy (SEM), X-ray fluorescence (FX), nuclear paramagnetic resonance (NMR), X-ray scattering to small angles (SAXS).
- TEM transmission electron microscopy
- SEM scanning electron microscopy
- FX X-ray fluorescence
- NMR nuclear paramagnetic resonance
- SAXS X-ray scattering to small angles
- the technique of low-angle X-ray diffraction makes it possible to characterize the periodicity at the nanoscale generated by the organized mesoporosity of the mesostructured matrix of the material used according to FIG. 'invention.
- the X-ray analysis is carried out on powder with a diffractometer operating in reflection and equipped with a rear monochromator using copper radiation (wavelength of 1.5406 A).
- the X-ray diffraction technique at large angles makes it possible to characterize a crystalline solid defined by the repetition of a unitary unit or unit cell at the molecular scale. It follows the same physical principle as that governing the low-angle X-ray diffraction technique.
- the DRX technique at large angles is therefore used to analyze the materials used according to the invention because it is particularly suitable for the structural characterization of the crystallizable metal oxide particles present in each of the elementary spherical particles constituting the material used according to the invention. .
- the nitrogen volumetry corresponding to the physical adsorption of nitrogen molecules in the porosity of the material via a progressive increase in the pressure at constant temperature gives information on the particular textural characteristics (pore diameter, pore volume, specific surface area) of the material. material used according to the invention. In particular, it provides access to the specific surface and the mesoporous distribution of the material.
- specific surface is meant the BET specific surface area (S BET in m 2 / g) determined by nitrogen adsorption in accordance with the ASTM D 3663-78 standard established from the BRUNAUER-EMMETT-TELLER method described in the periodical " The Journal of American Society, 1938, 60, 309.
- the representative porous distribution of a mesopore population centered in a range of 2 to 50 nm is determined by the Barrett-Joyner-Halenda model (BJH).
- BJH Barrett-Joyner-Halenda model
- the nitrogen adsorption-desorption isotherm according to the BJH model thus obtained is described in the periodical "The Journal of the American Society", 1951, 73, 373, written by EP Barrett, LG Joyner and PP Halenda.
- the diameter of the mesospores ⁇ of the mesostructured matrix corresponds to the value of the maximum diameter read on the pore size distribution curve obtained from the adsorption branch of the nitrogen isotherm.
- the shape of the nitrogen adsorption isotherm and the hysteresis loop can provide information on the nature of the mesoporosity of the material used according to the invention.
- Said mesh parameter a is connected to the distance d of correlation between pores by a geometric factor characteristic of the geometry of the phase.
- TEM transmission electron microscopy
- the TEM photos are made from microtome sections of the sample in order to visualize a section of an elementary spherical particle of the material used according to the invention.
- the analysis of the image also makes it possible to access the parameters d, ⁇ and e, characteristics of the mesostructured matrix defined above.
- the morphology and size distribution of the elementary particles were established by scanning electron microscopy (SEM) photo analysis.
- the metal oxide particles as described below in the present description are in particular characterized by Raman spectroscopy.
- Raman spectra were obtained with a dispersive Raman spectrometer equipped with a 532 nm exciter wavelength laser. The laser beam is focused on the sample using a microscope equipped with a ⁇ 50 long working distance lens. The laser power at the sample level is of the order of 1 mW.
- the Raman signal emitted by the sample is collected by the same objective and is dispersed using a 1800 rpm network and then collected by a CCD (Charge Coupled Device).
- the spectral resolution obtained is of the order of 2 cm -1 .
- the recorded spectral zone is between 300 and 1500 cm -1 .
- Nuclear magnetic resonance spectroscopy is also advantageously used to characterize the material used according to the invention. These include the 31 P, 27 AI and 29 Si NMR analyzes recorded on 300 or 400 MHz spectrometers. Nuclear magnetic resonance spectroscopy (NMR), in particular the 95 M and 183 W NMR, is also advantageously used to characterize the metal oxide particles described below in the present description.
- the present invention relates to a process for metathesis of olefins comprising bringing said olefins into contact with said catalyst which has been previously activated by heating at a temperature of between 100 and 1000 ° C. under a non-reducing gas atmosphere, in particular for the following reactions listed below. not limited to: ring closure by metathesis, metathesis polymerization of acyclic dienes, metathesis ring opening polymerization, metathesis of acyclic olefins, cross metathesis of cyclic and acyclic olefins and metathesis of functionalized olefins .
- the olefins used in the metathesis process according to the invention are advantageously chosen from monoolefins with 2 to 30 carbon atoms, preferably from 2 to 25 carbon atoms and even more preferably from 2 to 18 carbon atoms. , such as for example ethylene, propylene, butenes, pentenes, cycloolefins having 3 to 20 carbon atoms, such as for example cyclopentene, cyclooctene, norbornene, polyolefins having from 4 to 30 atoms carbon, such as, for example, 1,4-hexadiene, 1,7-octadiene, and cyclopolyolefins having from 5 to 30 carbon atoms, such as, for example, 1,5-cyclooctadiene, norbornadiene, dicyclopentadiene, said olefins being taken alone or as a mixture, said linear or cyclic monoolefins, polyolefins, being
- the olefins used in the metathesis process according to the invention are advantageously chosen from ethylene and butenes, taken alone or as a mixture, functionalized or otherwise, and preferably a mixture of ethylene and butenes, functionalized or no.
- the olefin metathesis process according to the invention consists in bringing olefins, advantageously in the liquid or gaseous state, into contact with a solid catalyst as described in the invention.
- the process consists of:
- said catalyst is activated beforehand by heating at a temperature of between 100 and 1000 ° C. and preferably between 300 and 600 ° C. under a non-reducing gas atmosphere advantageously chosen from oxygen and synthetic air. , nitrogen, argon, helium and oxygen diluted with nitrogen, and preferably under nitrogen, preferably under static or dynamic conditions, and preferably under a slight gas stream.
- the moisture content of the gas stream is preferably kept below 200 ppm (parts per million).
- the duration of this activation treatment is preferably between ten minutes and ten hours or more.
- the active catalyst thus obtained is cooled under an atmosphere, preferably anhydrous. It is advantageously possible to purge with nitrogen, if necessary, before contact with the hydrocarbon feedstock.
- the activation of said catalyst can advantageously be carried out either directly inside the reactor or outside the reactor before transferring the catalyst to the reactor.
- the metathesis process according to the invention is advantageously carried out by contacting the olefins with said catalyst in the liquid phase or in the gas phase independently of the structure and molecular weight of the olefins.
- the metathesis process according to the invention can advantageously be carried out in a stirred reactor, or by passing the olefin reactant (s) through a fixed, mobile or fluidized bed of said catalyst.
- the metathesis process according to the invention preferably operates at a temperature of between -20 and 200 ° C., preferably between 20 and 140 ° C., under varying pressure conditions depending on whether it is desired to conduct the reaction in phase. gaseous or in the liquid phase.
- the pressure must be sufficient so that the reactants and the optional solvent are maintained at least predominantly (more than 50%) in the liquid phase (or in the condensed phase).
- the catalyst can then advantageously be used either in the olefin (or olefins) pure (s) or in the presence of a solvent consisting of an aliphatic hydrocarbon, cycloaliphatic or aromatic, a halogenated hydrocarbon or a nitro derivative.
- a hydrocarbon or a halogenated hydrocarbon is preferably used.
- aqueous solution containing 0.41 g of H 3 PMo 12 04O and 15 g of deionized water is prepared with stirring at room temperature. 1. 09 g of aluminum trichloride are mixed with 19.3 g of deionized water and 7.00 mg of HCl. After stirring for 5 minutes at room temperature, 11.2 g of TEOS are added. The solution is allowed to hydrolyze for 16 h with stirring at room temperature (solution of the precursors of the matrix). Another solution is prepared by mixing 3.56 g of P123 in 35.9 g of deionized water, 13.1 mg of HCl and 8.48 g of ethanol.
- the 31 P NMR spectrum of the material reveals, at this stage, the presence of Keggin H 3 PMo 12 O 4 with a unique peak characteristic of this heteropolyanion at -3.8 ppm.
- the solid is characterized by low angle XRD, nitrogen volumetric, TEM and FX.
- the TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. In addition, this analysis does not detect the presence of any metal oxide particles, meaning that said particles have a size less than 1 nm.
- An EDX analysis coupled with the MET confirms the presence of metal.
- the Si / Al molar ratio obtained by FX is 12.
- An SEM image of the spherical elementary particles of the final material thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 nm to 30 ⁇ , the size distribution of these particles being particles being centered around 15 ⁇ m.
- the Raman spectrum of the final material reveals the presence of polymolybdate species, interacting with the matrix, with bands characteristic of these species at 950 cm -1 .
- An aqueous solution containing 0.29 g of MOCI 5 and 15.0 g of deionized water is prepared with stirring at room temperature.
- 0.69 g of aluminum trichloride is mixed with 12.1 g of deionized water and 4.40 mg of HCl.
- 7, 16 g of TEOS are added.
- the solution is allowed to hydrolyze for 16 hours with stirring at room temperature (solution of precursors of the matrix).
- Another solution is prepared by mixing 2.41 g of F127 in 22.4 g of deionized water, 8.20 mg of HCl and 5.29 g of ethanol.
- the organic aquo solution of F127 is then added to the precursor solution of the matrix.
- the solution containing MoCI 5 is added dropwise to the solution of the precursors of the matrix.
- the droplets are dried according to the protocol described in the disclosure of the invention above.
- the temperature of the drying oven is set at 350 ° C.
- the solid is characterized by low angle XRD, nitrogen volumetric, TEM and FX.
- the TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure.
- this analysis does not detect the presence of any metal oxide particles, meaning that said particles have a size less than 1 nm.
- the Si / Al molar ratio obtained by FX is 12.
- An SEM image of the spherical elementary particles of the final material thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 nm to 30 ⁇ m, the size distribution of these particles being particles being centered around 15 ⁇ .
- the Raman spectrum of the final material reveals the presence of polymolybdate species, interacting with the matrix, with bands characteristic of these species at 950 cm -1 .
- An aqueous solution containing 0.41 g of H3PMO12O40 (commercial) and 15.0 g of deionized water is prepared with stirring at room temperature. 1. 09 g of aluminum trichloride are mixed with 19.3 g of deionized water and 7.00 mg of HCl. After stirring for 5 minutes at room temperature, 1.2 g of TEOS are added. The solution is allowed to hydrolyze for 16 h with stirring at room temperature (solution of the precursors of the matrix). Another solution is prepared by mixing 3.56 g of Brij58 in 35.9 g of deionized water, 13.1 mg of HCl and 8.48 g of ethanol. The aquo-organic solution of Brij58 is then added to the solution of the precursors of the matrix.
- the solution containing the H3PMo 2 0 4 o is added dropwise to the solution of precursors of the matrix.
- the droplets are dried according to the protocol described in the disclosure of the invention above.
- the temperature of the drying oven is set at 350 ° C.
- the 31 P NMR spectrum of the material reveals, at this stage, the presence of ⁇ Keggin H 3 PMo 12 04o with a single peak characteristic of this heteropolyanion at -3.8 ppm.
- the solid is characterized by low angle XRD, nitrogen volumetric, TEM and FX.
- the TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure with a pore size of 2 nm. In addition, this analysis does not detect the presence of any metal oxide particles, meaning that said particles have a size less than 1 nm.
- An EDX analysis coupled with the MET confirms the presence of metal.
- the Si / Al molar ratio obtained by FX is 12.
- An SEM image of the spherical elementary particles of the final material thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 nm to 30 ⁇ m, the size distribution of these particles. particles being centered around 15 ⁇
- the Raman spectrum of the final material reveals the presence of polymolybdate species, interacting with the matrix, with bands characteristic of these species at 950 cm -1 .
- a suspension composed of 0.44 g of Mo (CO) 6 , 16.8 ml of phenoxybenzene and 0.84 ml of oleic acid is slowly heated from room temperature to 310 ° C under an inert atmosphere for 25 min.
- Oxygen gas is introduced by bubbling (flow rate: 200 ml / min) into the solution at 310 ° C for 30 min.
- 20 g of ethanol are added to the solution (protocol adapted from Park et al., Materials Mater 2007, 19, 2706).
- 0.68 g of aluminum trichloride are mixed with 12.1 g of deionized water and 4.40 mg of HCl. After stirring for 5 minutes at room temperature, 7.02 g of TEOS are added.
- the solution is allowed to hydrolyze for 16 h with stirring at room temperature (solution of the precursors of the matrix).
- Another solution is prepared by mixing 2.22 g of P123 in 22.4 g of deionized water, 8.20 mg of HCl and 15.32 g of ethanol.
- the aquo-organic solution of P123 is then added to the solution of the precursors of the matrix.
- the colloidal solution of MoO 3 nanoparticles is added dropwise.
- the droplets are dried according to the protocol described in the disclosure of the invention above.
- the temperature of the drying oven is set at 350 ° C.
- the solid is characterized by low angle XRD, nitrogen volumetric, TEM and FX.
- the TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. In addition, this analysis makes it possible to detect the presence of metal oxide particles of MoO 3 with an average size of 2.5 nm.
- the Si / Al molar ratio obtained by FX is 12.
- An SEM image of the spherical elementary particles of the final material thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 nm to 30 ⁇ m, the size distribution of these particles being particles being centered around 15 ⁇ m.
- An aqueous solution containing 0.29 g of MoCl 5 and 15.0 g of deionized water is prepared with stirring at room temperature. 1. 09 g of aluminum trichloride are mixed with 19.3 g of deionized water and 7.00 mg of HCl. After stirring for 5 minutes at room temperature, 11.2 g of TEOS are added. The solution is allowed to hydrolyze for 16 h with stirring at room temperature (solution of the precursors of the matrix). Another solution is prepared by mixing 3.56 g of Brij58 in 35.9 g of deionized water, 13.1 mg of HCl and 8.48 g of ethanol. The aquo-organic solution of P123 is then added to the solution of the precursors of the matrix.
- the solution containing H 3 PMo 12 O 4 O is added dropwise to the solution of the precursors of the matrix.
- the droplets are dried according to the protocol described in the disclosure of the invention above.
- the temperature of the drying oven is set at 450 ° C.
- the solid is characterized by low angle XRD, nitrogen volumetric, TEM and FX.
- the TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure with a pore size of 2 nm. In addition, this analysis does not detect the presence of any oxide metal particles, meaning that said particles have a size less than 1 nm.
- the Si / Ai molar ratio obtained by FX is 12.
- An SEM image of the spherical elementary particles of the final material thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 nm to 30 ⁇ - ⁇ , the size distribution of these particles being centered around 15 ⁇ .
- the Raman spectrum of the final material reveals the presence of polymolybdate species, interacting with the matrix, with bands characteristic of these species at 950 cm -1 .
- the catalyst is characterized by nitrogen volumetry, wide angle XRD, TEM and NMR. After impregnation, the surface area and the pore volume drop to 400 m 2 / g and 0.56 ml / g respectively, but the average pore diameter is not affected. Part of the molybdenum oxide deposit is located outside the support particles. X-ray diffraction at large angles demonstrates the presence of Mo oxide crystals. Their presence outside the support particles is confirmed by TEM observation. NMR 27 AI reveals the abundant presence of Al 2 (MoO 4 ) 3 .
- the catalyst is characterized by nitrogen volumetry, wide angle XRD, TEM and NMR. After impregnation, the specific surface area and the pore volume drop to 400 m 2 / g and 0.56 ml / g respectively, but the average pore diameter is not affected. Part of the molybdenum oxide deposit is located outside the support particles. X-ray diffraction at large angles demonstrates the presence of Mo oxide crystals. Their presence outside the support particles is confirmed by TEM observation. NMR 27 Al reveals the abundant presence of Al 2 (MoO 4 ) 3 .
- EXAMPLE 8 Catalytic Metatesis Reaction of Butene and Ethylene Using Catalysts A to G
- Materials A to G are obtained in powder form and are shaped by pelletizing and crushing the synthesized powder to be used as catalyst A to G in the process of metathesis of olefins according to the invention.
- the catalysts A to G used are pressed, milled and sieved in the 200-315 micron size fraction and introduced (200 mg) into a quartz reactor of 5 mm inner diameter. They are activated under nitrogen (20 ml / min) at 550 ° C for 2 hours. Always under nitrogen flow, they are cooled to the reaction temperature, ie 40 ° C.
- Ethylene and 2-butenes are converted to propene via the metathesis reaction with a selectivity of the order of 99%. Only traces of secondary products of metathesis (-butene, pentenes, hexenes) or isomerization (iso-butene) are detected. Specific activity is defined as the number of moles of propene produced per g of catalyst per hour. The number of moles of propene produced per g of catalyst per hour is measured conventionally by gas chromatography. Activity is measured for one hour. The results are given for the reaction time 14 minutes (Table 1).
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FR1102221A FR2977890B1 (fr) | 2011-07-15 | 2011-07-15 | Procede de metathese des olefines utilisant un catalyseur a base d'un materiau spherique comprenant des particules metalliques oxydes piegees dans une matrice mesostructuree |
PCT/FR2012/000285 WO2013011209A1 (fr) | 2011-07-15 | 2012-07-11 | Procédé de métathèse des oléfines utilisant un catalyseur a base d'un matériau sphérique comprenant des particules métalliques oxydes piégées dans une matrice mésostructurée |
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FR3007029B1 (fr) * | 2013-06-17 | 2015-07-24 | IFP Energies Nouvelles | Procede de metathese des olefines utilisant un catalyseur a base d'un materiau spherique a porosite hierarchisee comprenant des particules metalliques oxydes piegees dans une matrice comprenant de l'oxyde de silicium |
CN104557399B (zh) * | 2013-10-28 | 2017-07-14 | 中国石油化工股份有限公司 | 戊烯与乙烯歧化制丙烯的方法 |
CN104557398B (zh) * | 2013-10-28 | 2017-08-11 | 中国石油化工股份有限公司 | 碳五生产丙烯的方法 |
EP3069788A1 (fr) * | 2015-03-20 | 2016-09-21 | Terramark Markencreation GmbH | Système catalyseur pour la métathèse d'oléfines |
FR3039544B1 (fr) * | 2015-07-31 | 2020-02-28 | IFP Energies Nouvelles | Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs |
FR3039545B1 (fr) * | 2015-07-31 | 2020-02-28 | IFP Energies Nouvelles | Procede de metathese des olefines utilisant un catalyseur contenant de l'aluminium et du molybdene |
FR3039543B1 (fr) * | 2015-07-31 | 2019-04-12 | IFP Energies Nouvelles | Procede de metathese des olefines utilisant un catalyseur contenant de l'aluminium et du molybdene incorpores au moyen d'au moins deux precurseurs |
FR3039546B1 (fr) * | 2015-07-31 | 2017-08-11 | Ifp Energies Now | Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene |
US10125062B2 (en) * | 2015-11-06 | 2018-11-13 | Lyondell Chemical Technology, L.P. | Propylene production processes and catalyst systems for use therein |
FR3044005B1 (fr) | 2015-11-23 | 2017-12-15 | Ifp Energies Now | Procede de synthese d'hydrocarbures a partir de gaz de synthese en presence d'un catalyseur a base de cobalt piege dans une matrice oxyde mesoporeuse et obtenu a partir d'au moins un precurseur monomerique |
SG11202002857UA (en) * | 2017-10-24 | 2020-05-28 | Saudi Arabian Oil Co | Methods of making spray-dried metathesis catalysts and uses thereof |
WO2019131890A1 (fr) * | 2017-12-27 | 2019-07-04 | 積水化学工業株式会社 | Catalyseur ainsi que procédé de fabrication de celui-ci, et procédé de fabrication de composé diène mettant en oeuvre ledit catalyseur |
US10981151B2 (en) * | 2018-06-29 | 2021-04-20 | Uop Llc | Poorly crystalline transition metal molybdotungstate |
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DE19805716A1 (de) | 1998-02-12 | 1999-08-19 | Basf Ag | Verfahren zur Herstellung von Propen und gegebenenfalls 1-Buten |
FR2843050B1 (fr) * | 2002-08-01 | 2005-04-15 | Inst Francais Du Petrole | Catalyseur a base de metaux du groupe vi et du groupe viii presents au moins en partie sous la forme d'heteropolyanions dans le precurseur oxyde |
US7214841B2 (en) | 2003-07-15 | 2007-05-08 | Abb Lummus Global Inc. | Processing C4 olefin streams for the maximum production of propylene |
US7220886B2 (en) * | 2004-10-27 | 2007-05-22 | Catalytic Distillation Technologies | Olefin metathesis |
FR2880018B1 (fr) | 2004-12-27 | 2007-02-23 | Inst Francais Du Petrole | Production de propylene mettant en oeuvre la dimerisation de l'ethylene en butene-1, l'hydro-isomerisation en butene-2 et la metathese par l'ethylene |
FR2886636B1 (fr) | 2005-06-02 | 2007-08-03 | Inst Francais Du Petrole | Materiau inorganique presentant des nanoparticules metalliques piegees dans une matrice mesostructuree |
FR2904243B1 (fr) * | 2006-07-31 | 2008-10-31 | Inst Francais Du Petrole | Catalyseur a base d'un support hybride organique - inorganique et son utilisation en hydroraffinage et hydroconversion |
DE102006039904A1 (de) | 2006-08-25 | 2008-02-28 | Linde Ag | Verfahren zur Propenerzeugung in einer Anlage zur Dampfspaltung von Olefinen |
FR2929264B1 (fr) * | 2008-03-31 | 2010-03-19 | Inst Francais Du Petrole | Materiau inorganique forme de particules spheriques de taille specifique et presentant des nanoparticules metalliques piegees dans une matrice mesostructuree |
FR2931705B1 (fr) * | 2008-05-28 | 2010-09-03 | Inst Francais Du Petrole | Catalyseur a base d'un materiau amorphe comprenant du silicium a porosite hierarchisee et organisee et procede ameliore de traitement de charges hydrocarbonees |
TWI388544B (zh) | 2008-08-12 | 2013-03-11 | Lummus Technology Inc | 經整合之丙烯生產技術 |
US8704028B2 (en) * | 2010-03-30 | 2014-04-22 | Uop Llc | Conversion of acyclic symmetrical olefins to higher and lower carbon number olefin products |
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2011
- 2011-07-15 FR FR1102221A patent/FR2977890B1/fr not_active Expired - Fee Related
-
2012
- 2012-07-11 CA CA2840530A patent/CA2840530A1/fr not_active Abandoned
- 2012-07-11 US US14/232,313 patent/US20140179973A1/en not_active Abandoned
- 2012-07-11 WO PCT/FR2012/000285 patent/WO2013011209A1/fr active Application Filing
- 2012-07-11 CN CN201280035137.XA patent/CN103857647B/zh not_active Expired - Fee Related
- 2012-07-11 EP EP12748729.6A patent/EP2739594A1/fr not_active Withdrawn
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See references of WO2013011209A1 * |
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FR2977890B1 (fr) | 2013-07-19 |
US20140179973A1 (en) | 2014-06-26 |
CN103857647A (zh) | 2014-06-11 |
WO2013011209A1 (fr) | 2013-01-24 |
FR2977890A1 (fr) | 2013-01-18 |
CA2840530A1 (fr) | 2013-01-24 |
CN103857647B (zh) | 2015-09-23 |
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