WO2012143658A1 - Procede de preparation d'un element monolithique de catalyse comprenant un support fibreux et ledit element monolithique de catalyse - Google Patents
Procede de preparation d'un element monolithique de catalyse comprenant un support fibreux et ledit element monolithique de catalyse Download PDFInfo
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- WO2012143658A1 WO2012143658A1 PCT/FR2012/050829 FR2012050829W WO2012143658A1 WO 2012143658 A1 WO2012143658 A1 WO 2012143658A1 FR 2012050829 W FR2012050829 W FR 2012050829W WO 2012143658 A1 WO2012143658 A1 WO 2012143658A1
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- Prior art keywords
- function
- catalytic
- functions
- metal
- aromatic compound
- Prior art date
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- 239000011159 matrix material Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- DLOBKMWCBFOUHP-UHFFFAOYSA-N pyrene-1-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 DLOBKMWCBFOUHP-UHFFFAOYSA-N 0.000 claims description 6
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
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- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
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- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- MZMNEDXVUJLQAF-UHFFFAOYSA-N 1-o-tert-butyl 2-o-methyl 4-hydroxypyrrolidine-1,2-dicarboxylate Chemical compound COC(=O)C1CC(O)CN1C(=O)OC(C)(C)C MZMNEDXVUJLQAF-UHFFFAOYSA-N 0.000 claims description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 1
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- FQPSLZJDCXEWKE-UHFFFAOYSA-M sodium butanoate pyrene Chemical compound [Na+].CCCC([O-])=O.c1cc2ccc3cccc4ccc(c1)c2c34 FQPSLZJDCXEWKE-UHFFFAOYSA-M 0.000 description 4
- 238000006957 Michael reaction Methods 0.000 description 3
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- 230000009471 action Effects 0.000 description 3
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
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- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- TZNXEWGKCWPLQI-UHFFFAOYSA-N pyren-1-ylmethanamine Chemical compound C1=C2C(CN)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 TZNXEWGKCWPLQI-UHFFFAOYSA-N 0.000 description 1
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
Definitions
- the present invention is in the field of heterogeneous catalysis. More precisely, it aims:
- Such a monolithic (coherent) catalytic element that can be obtained by said method.
- the patent application WO 2003/048039 describes the application in catalysis of materials: C (carbon, in the form of beads, felts, extrudates, foams, monoliths, pellets, etc.) / NFC or NTC (carbon nanofibers or nanotubes of carbon, formed by vapor deposition).
- the catalysts deposited on the materials are metal catalysts, in particular based on noble metals. They are deposited in three stages: a) impregnation of the material (previously functionalized on the surface by an oxidation treatment) with a metal salt, b) calcination of the impregnated material for the conversion of the salt to oxide and c) reduction of said oxide to metal .
- the patent application WO 2004/025003 describes the enrichment of three-dimensional fiber structures in refractory fibers by carbon nanotubes (generated in situ by growth on said refractory fibers). Such enriched three-dimensional fiber structures constitute particularly advantageous preforms for producing thermostructural composite materials.
- the patent application FR 2 892 644 describes a packing macrostructure of a fluid exchange column based on a plurality of rows of bundles of tubes.
- the plurality of carbon or ceramic composite material tubes can be densified, stiffened, by carbon deposition within it (by chemical vapor deposition (CVD)).
- the surface of tubes made of carbon composite material of such a structure can be made hydrophilic by oxidation and it is then possible to attach to said surface a catalyst by a conventional method comprising the successive stages of impregnation by a solution containing the catalyst and drying.
- Such a document does not describe enrichment of the macrostructure by nanocarbon, or supply of catalyst via an organic compound.
- the inventors propose a process for the preparation of a monolithic (coherent) catalytic element comprising a fibrous support and a catalytic phase supported by said fibrous support (preparation process (of a heterogeneous catalyst) which constitutes the first object of the presently claimed invention); said catalytic phase, organic and / or inorganic, being dispersed homogeneously within said fibrous support and, when it contains at least one metallic element, containing it in the form of nanoparticles, having a small standard deviation particle size.
- the present invention therefore relates to a method for preparing a monolithic catalyst element comprising a fibrous support and a catalytic phase supported by said fibrous support.
- said method comprises:
- the grafting on said substrate by interaction ⁇ , of at least one aromatic compound containing in its chemical formula, on the one hand, at least one aromatic ring, advantageously at least two, very advantageously four, aromatic rings and the other on the one hand, at least one function chosen from acidic catalytic functions, basic catalytic functions, metal precursor functions, functions that can be converted into situ into metal precursor functions and their mixtures.
- the fibrous support of the catalytic element prepared according to the invention is therefore a porous coherent structure based on refractory fibers, enriched in nanocarbon; it consists more precisely of a substrate comprising a porous coherent structure based on refractory fibers and nanocarbon (generally a substrate consisting essentially, or exclusively exclusively, of a porous coherent structure based on refractory fibers and nanocarbon), said nanocarbon being supported by said porous coherent structure in the volume thereof (said nanocarbon being secured to said porous coherent structure).
- Said structure is coherent in that it is able to maintain its cohesion (its structural integrity) and its shape during manipulations. It is advantageously self-supporting.
- At least one aromatic compound (aromatic with one or more rings) is typically grafted, by interaction ⁇ , on said substrate (by interaction ⁇ between the delocalized ⁇ electron cloud of the nanocarbon and the ⁇ electrons of the aromatic compound in the presence of said nanocarbon).
- the grafting is generally obtained by adsorption in a solvent medium.
- Said at least one aromatic compound carries at least one catalytic function and / or at least one metal precursor function and / or at least one transformable function (after grafting within the nanocarbon-enriched fibrous structure) such a precursor metal function (in fact a function itself precursor of a metal precursor function).
- a precursor metal function in fact a function itself precursor of a metal precursor function.
- aromatic acid and / or basic in the case where said at least one aromatic compound contains at least one acidic catalytic function and / or at least one basic catalytic function and salt of ⁇ (poly) aromatic type - Me x + ⁇ or precursor of such a salt in the case where it contains, respectively, (at least) a metal precursor function (of metal) or an in situ transformable function in such a metal precursor function. It is understood that all the mixed variants are possible.
- Such a metal precursor function is a precursor function of an active catalytic function, based on the action of a metal (in the form of metal or metal oxide). It is actually a precursor of a metal, particles of a metal.
- the metal in question may consist of a noble metal or not. It is advantageously chosen from nickel, cobalt, iron, copper, manganese, gold, silver, platinum, palladium, iridium and rhodium. This list is not exhaustive. Incidentally note here that different metal precursor functions are quite likely to be grafted, in the context of the method of the invention, on the same support.
- Such a function that can be converted into a metal precursor function is, for example, an acid function (-COOH) or a function ligante (-COOX function, X being a cation that can be exchanged with a metal, for example an alkaline or alkaline earth salt cation).
- a transformable function is generally linked to an aromatic ring via a hydrocarbon chain.
- the grafting of at least one aromatic compound with metal precursor function (s) can therefore be a direct grafting of the pre-existing aromatic compound (such a compound with a (for example) metal precursor function has in particular been obtained prior to said grafting, ex-situ, from the corresponding aromatic compound carrying a ligating function reacted with a metal precursor
- the reaction (ion exchange): sodium pyrene butanoate + cobalt chloride (CoCl 2 .2H 2 O) generates, for example, an aromatic compound (complex) with 4 aromatic rings with a metal precursor function (Co) suitable for grafting by ⁇ interaction within the meaning of the invention) or grafting ("Indirect") of a first aromatic compound followed by an in situ transformation of said grafted aromatic compound.
- a two-step grafting comprises:
- the grafting can thus be implemented with at least one aromatic compound containing at least one acid function.
- said at least one acid function by reaction with a metal precursor, is converted directly into a metal precursor function or it is first transformed into a ligand function and then said ligating function is reacted with a metal precursor for obtaining the metal precursor function.
- said at least one acid function of the aromatic compound is converted into ligating function, before ex situ grafting).
- said ligating function is reacted with a metal precursor (thus, it is possible, for example according to this variant, a) sodium ⁇ -pyrene butanoate is then grafted by interaction ⁇ and then b) the cobalt chloride is reacted with the grafted sodium pyrene butanoate to generate the metal precursor function in situ (by ion exchange).
- Aromatic compounds are understood to mean, in a conventional manner, compounds which contain in their formula an aromatic ring (benzene compounds) and compounds which contain in their formula at least two aromatic rings, advantageously contiguous (for example, naphthenic, anthracene, pyrenic compounds ).
- the aromatic compounds in question advantageously contain in their formula at least two aromatic rings, very advantageously four aromatic cycles.
- the at least one aromatic compound grafted onto the substrate is preferably of the pyrenic type.
- the starting porous (fibrous) coherent structure can be a two- or three-dimensional structure (2D or 3D).
- a two-dimensional structure (2D) always has a certain thickness so that the nanocarbon can be stably fixed in its volume.
- Such a two-dimensional structure may in particular consist of a fabric.
- the starting porous coherent structure is a three-dimensional (3D) self-supporting structure.
- it consists of a flat 3D structure, such as in particular described in the patent application FR 2 584 106 or in a 3D structure of revolution such as in particular described in the patent application FR 2 557 550 or the patent application FR 2,584,107 or patent application FR 2 892 644.
- said porous coherent structure is a needled fibrous structure or a fibrous structure consolidated by a matrix. Needling and consolidation by a matrix of fibrous structures are techniques familiar to those skilled in the art. Such consolidation comprises the deposition, in a fibrous structure, of a material constituting a matrix. In order to obtain a porous coherent structure within the meaning of the invention, said material is deposited in an amount sufficient to confer on the fibrous structure its cohesion (ie so that said fibrous structure is sufficiently rigid to maintain its structural integrity and its shape during handling), but not excessive so that the consolidated fibrous structure has an accessible porosity in all its volume.
- the constituent material of the consolidation matrix may especially consist of resin coke or pyrocarbon.
- the porous coherent structure may consist of:
- a needled fibrous structure (of a stack of fibrous needled mats), or
- each of said tubes being made from refractory fibers (for example, carbon fibers) consolidated by a matrix (of pyrocarbon, for example); said tubes being arranged in four directions (such a structure particularly suitable for constituting a packing structure of a fluid exchange column as described in application FR 2 892 644).
- refractory fibers for example, carbon fibers
- matrix of pyrocarbon, for example
- Obtaining a porous coherent structure based on refractory fibers, in particular such a 2D or 3D structure, more particularly of such a 3D structure of one of the above types, does not pose particular difficulties to the skilled person (see in particular the teaching of the RF applications identified above).
- nanocarbon generally a suspension of nanocarbon into a liquid
- a resin coke the nanocarbon has generally been introduced resin-coated and the coke resulting from the pyrolysis of said resin solidarises said nanocarbon fibers
- a film of pyrocarbon generated in situ by CVI the nanocarbon has generally been introduced resin-coated and the coke resulting from the pyrolysis of said resin solidarises said nanocarbon fibers
- One or the other of these variants allows the stable bonding of nanocarbon to refractory fibers, stable bonding at the heart of the porous coherent structure.
- the nanocarbon is generally present in the form of nanotubes (CNTs, “nanotubes”) and / or nanofibers (NCFs, "herringbones”), as especially described in the publication of S.-H. Yoon et al., Carbon 43 (2005) 1828-1838, (see more particularly Figure 8, page 1836, of this publication). It is more generally present in the form of nanotubes or nanofibers. It is advantageously present in the form of nanofibers. Indeed, it is, on the one hand, easier to obtain nanofibers than nanotubes, in particular by nanocarbon growth in situ and, on the other hand, nanofibers offer more accessible graphene planes for interaction grafting. ⁇ of aromatic molecules.
- the nanocarbon is generally present in a proportion, by weight, of 2 to 200% of the mass of said fibrous structure.
- the refractory fibers As regards the nature of the refractory fibers, it is generally carbon fibers and / or ceramic fibers (for example carbides such as SiC, oxides such as Al 2 O 3 , SiO 2 , silico-aluminous (for example, Nextel® 610 from company 3)).
- the porous coherent structure is in fact advantageously a structure based on carbon fibers or ceramic fibers. It is very advantageously a structure based on carbon fibers (it can then have a 100% carbon substrate). Is the ⁇ interaction grafting of the process of the invention thus advantageously implemented on a substrate of the following type: porous coherent structure based on carbon fibers and nanocarbon (C / NC), very advantageously implemented on a substrate? of porous coherent structure based on carbon fibers / nanofibers of C (C / NFC) (see above).
- At least one aromatic ring advantageously at least two aromatic rings, very advantageously four aromatic rings; and -
- Said compound (catalyst per se or catalyst precursor) advantageously consists, as already indicated above, in a compound of the pyrenic type.
- Said compound may therefore contain in its formula at least one acidic catalytic function. This is advantageously chosen from carboxylic, sulphonic and boronic functions. Said compound may thus contain, in its formula, for example, one or more carboxylic functions, a carboxylic function and a sulphonic function, a single sulphonic function. All scenarios are possible.
- the at least one aromatic compound with an acid catalytic function is 1-pyrene sulfonic acid or 1-pyrene butyric acid.
- Said compound can therefore contain in its formula at least one basic catalytic function. This is advantageously chosen from amine, linear or branched functions, guanidine type functions and phosphazene type functions.
- Said compound may therefore contain in its formula at least one metal precursor function. It generally consists of a salt of ⁇ (poly) aromatic-Me x + ⁇ type, where Me represents a metal, advantageously chosen from nickel, cobalt, iron, copper, manganese, gold and silver. .
- Said salt is generally an ester and metal salt (obtained by ion exchange from the corresponding salt of ester and alkali or alkaline earth metal (see the above example of sodium pyrene butanoate)).
- the metal in question in the form of oxide or metal (see below), is ultimately the catalytic phase supported, uniformly distributed, the desired monolithic catalyst element.
- Said compound can therefore contain in its formula at least one transformable function in situ metal precursor function.
- a transformable function can notably consist of an acid function (-COOH) or a ligand function (-COOX, X being a cation capable of being exchanged with a metal, for example an alkaline or alkaline-earth salt cation).
- aromatic compounds each with at least one different catalytic or precursor or transformable function and / or with a different number and / or arrangement of aromatic rings
- the same aromatic compound may contain several functions selected from the four types of function specified above, the same type or not.
- an ⁇ -interaction is deposited on the substrate, an aromatic compound which contains at least one (generally a single) catalytic, acidic or basic function, or a aromatic compound which contains at least one (usually a single) metal precursor function (which is then converted to an active catalytic function, based on the action of a metal (in the metal state or at the state of oxide)) or an aromatic compound which contains at least one (generally a single) function convertible into at least one (generally a) metal precursor function (which is then successively converted into said at least one metal precursor function and then catalytic function active, based on the action of a metal (in the metal state or in the oxide state)).
- an aromatic compound which contains at least one (generally a single) catalytic, acidic or basic function or a aromatic compound which contains at least one (usually a single) metal precursor function (which is then converted to an active catalytic function, based on the action of a metal (in the metal state or at the state of oxide)) or an aromatic compound which contains at
- the desired monolithic catalytic element whose catalytic phase is metallic consisting of a metal or an oxide.
- Said catalytic phase - acidic, basic and / or metallic - is uniformly distributed in the volume of the substrate.
- It also comprises, as already mentioned above, the treatment of the substrate grafted with said at least one aromatic compound containing in its chemical formula at least one metal precursor function, for the purpose of transforming said at least one precursor function. metal into a catalytically active (metallic) function.
- the treatment may consist of a thermal activation.
- Such thermal activation generates particles based on the metal (metals) corresponding to said at least one metal precursor, mainly oxide particles of said metal (said metals).
- Such thermal activation may or may not, depending on its temperature of implementation, lead to a thermal decomposition of the aromatic compound present. It generally leads to an at least partial decomposition of said compound. It can be assumed that said at least one partially decomposed aromatic compound serves as an adhesive for the metal-based particles (s) generated in situ.
- the migration of the catalytic metal phase uniformly dispersed due to the original grafting of the process of the invention, is avoided and thereby the magnification of said particles generated in situ.
- the catalytic mineral phase thus obtained is very well distributed within the porous coherent structure based on refractory fibers, in the form of nanoparticles (having a particle size distribution with a small standard deviation).
- the oxide particles are then reduced to metal particles.
- the dispersions and sizes (sizes per se e distributions of said sizes) of said metal particles are, in the same way, particularly advantageous.
- the treatment may advantageously consist of a reduction in hydrogen.
- Such reduction under hydrogen generates particles based on the metal (metals) corresponding to said at least one metal precursor, mainly particles of said metal (said metals).
- the fate of the aromatic compound (s) which has (have) been used, as indicated above, of the catalytic phase dispersing agent, is related to the temperature of implementation of said reduction under hydrogen.
- said reduction under hydrogen is carried out under mild conditions (at a temperature of at most 500 ° C., generally between 350 and 500 ° C., so that the aromatic compound (s) introduced ( s) is (are) conserved (almost) intact, in which case the catalytic phase, evenly distributed, does not have the ability to migrate and grow (the size distribution of the nanoparticles obtained is very tight)
- mild conditions at a temperature of at most 500 ° C., generally between 350 and 500 ° C.
- the transformation treatment of the at least one metal precursor function into a catalytic function active is advantageously carried out at a temperature where the at least one aromatic compound is only partially or not pyrolyzed.
- a metal precursor within the substrate (generally by impregnation with a solution containing a salt) and transforming said metal precursor (s) into metal element (s) (s) ) (by thermal activation and / or reduction under H 2 ) for the in situ generation of a metallic catalytic phase (within said substrate); or deposit (directly) a metallic catalytic phase (within said substrate) by chemical vapor deposition (CVD) or plasma deposition,
- At least one aromatic compound containing in its chemical formula on the one hand, at least one aromatic ring, advantageously at least two, very advantageously four, aromatic rings and on the other hand, at least one function selected from acidic catalytic functions, basic catalytic functions and mixtures thereof.
- the procedure is therefore carried out in a conventional manner and then the process according to the invention for the introduction of catalytic function (s) acid (s) and / or or basic (s).
- catalytic function s
- acid s
- / or or basic s
- the method of the invention can be implemented in multiple variants to ensure a homogeneous distribution within a specific substrate - substrate comprising the porous coherent structure based on refractory fibers and the nanocarbon supported by said porous coherent structure in the volume thereof, in particular substrate of the type: refractory fibers / NC (nanocarbon) and more particularly substrate of the type: C / NC fibers (nanocarbon), C / NFC fibers (nanofibres) of carbon) - many types of catalysts: organic and / or inorganic.
- Their original structure thus comprises, on the one hand, the fibrous support - substrate comprising the porous coherent structure and the nanocarbon supported by said porous coherent structure in the volume thereof (fibrous structure based on nanocarbon-enriched refractory fibers) - and secondly, secured to said fibrous support, an original catalytic phase.
- the catalytic phase present is organic. It contains at least one aromatic compound containing in its chemical formula, on the one hand, at least one aromatic ring, advantageously at least two, very advantageously four, aromatic rings and, on the other hand, at least one function chosen from catalytic functions. acids and basic catalytic functions; said at least one aromatic compound being linked, by interaction ⁇ , to the fibrous support. It has been seen above that the said at least one aromatic compound is essentially linked, by ⁇ interaction, to the nanocarbon of the said fibrous support.
- the catalytic phase present is mineral. It contains nanoparticles of metal oxide and / or metal (the metal in question being advantageously chosen from nickel, cobalt, iron, copper, manganese, gold, silver, platinum, palladium, iridium and rhodium), secured to the fibrous support (mainly nanocarbon said fibrous support) via at least one aromatic compound, not, partially or almost completely pyrolyzed (preferably not or only partially pyrolyzed).
- the nanoparticles in question have a size (a mean diameter) of only a few nanometers (generally from 0.1 to 10 nm, more generally from 1 to 5 nm).
- the method of the invention for obtaining this mineral catalytic phase has left several signatures: the small particle size and the particle size distribution with a small standard deviation of said particles, the homogeneous dispersion of said particles in the fibrous structure and the presence more or less visible from the at least one aromatic compound.
- the monolithic catalyst elements of the invention with a catalytic mineral phase, can certainly be conveniently used for the implementation of multiple chemical reactions known to be catalyzed by such and / or such metal.
- the catalytic phase is mixed. It consists partly of an organic catalytic phase as specified above ("organic catalytic phase of the invention") and partly of a catalytic mineral phase, which may be a mineral catalytic phase "according to the invention (obtained via at least one organic compound) and / or a mineral catalytic phase of the prior art (see above).
- the (the) phase (s) catalytic (s) obtained (s) by the method of the invention - via grafting interaction ⁇ - is (are) uniformly distributed (s) within the substrate (very predominantly on the nanocarbon said substrate).
- FIG. 1 shows the yields obtained, after 2 hours of reaction, for a Micha ⁇ l reaction carried out in the presence of various catalytic elements, including the catalytic elements A, B and C of the invention (see Example A III. 2 below).
- FIGS. 2A and 2B show the yields obtained under the same conditions (for respectively the catalytic elements A and B of the invention) after n cycles of use (see Example A III.3 below).
- FIGS. 3A and 3B are scanning electron microscopy (SEM) pictures at different magnifications
- FIGS. 4A to 4D are transmission electron microscopy (TEM) pictures at different magnifications, of catalysis elements of the invention to catalyzed phase supported mineral; said supported mineral catalytic phase having been obtained, typically, via the grafting of an organic compound (see Example B III, below).
- SEM scanning electron microscopy
- TEM transmission electron microscopy
- the fibrous supports used are based on carbon fibers, in the form of 2D fabrics or arranged in volume in the form of self-supporting 3D structures (according to the application FR 2 892 644, the application FR 2 584 106 or the application FR 2 584 107), obtained by pyrolysis of rayon fibers (ex-RAY support) or polyacrylonitrile fibers (ex-PAN support).
- Said fibrous supports have been enriched with a carbon core (nanofiber type: NFC) (nanocarbon growth has been implemented by CVI (atmospheric pressure, temperature of 700 ° C., duration of 30 min, in the presence of Ni (catalyst) from a hydrogen / ethylene mixture)).
- Carbon nanofibers are present at about 7%, 30% or 20% by weight (NFC / C + NFC) in the fibrous supports used. More specifically, have been used:
- the aromatic compound in question is 1-pyrene sulfonic acid, of formula:
- Standard sulfonated charcoal and sulfonated silica reference elements were also prepared using, respectively:
- Vulcan XC 72 coal (said raw coal constitutes reference D '), treated with hot concentrated sulfuric acid for 4 hours. The catalyst is then washed (water then ethanol) and dried in an oven to give Vulcan XC 72-SO 3 H catalyst.
- the final concentration of -SO 3 H group is 0.8 mmol g -1 ,
- reaction generates the compound whose formula is given above. It is presently 3- (1-phenyl-2-nitroethyl) -1H-indole.
- the reaction of Michael allows, more generally, the preparation of indole derivatives alkylated in position 3 (according to the reaction scheme above). The said derivatives are of interest in the pharmaceutical field.
- FIGS. 2A and 2B are shown in FIGS. 2A and 2B appended, for respectively the catalytic elements of the invention A and B.
- substrate B shows better stability than substrate A.
- the inventors have tested, under the same conditions, the stability of the aromatic compound (1-pyrene sulfonic acid) perse and the yield of 83% at the first cycle drops to 35% at the second cycle) and that of a catalytic element consisting of said aromatic compound. fixed (under the conditions indicated above to obtain the catalyst elements of the invention) on Vulcan XC 72 coal (the yield of 75% in the first cycle is 68% in the second cycle and 53% in the third cycle).
- Pyrene butyric acid (100 mg, 3.5 ⁇ 10 -4 mmol) is suspended in distilled water (50 mL), followed by a solution of 0.05 mol L 1 NaOH (7 mL, 3 mL). May 10 "4 mmol) was added dropwise to form the sodium pyrene butanoate.
- CoCl 2 , 2H 2 O (57.7 mg, 3.5 ⁇ 10 -4 mmol), solubilized in water, is added dropwise A pinkish precipitate is formed The suspension is stirred for 30 min at room temperature then centrifuged (3500 rpm, 10 min) to remove the supernatant The pinkish solid is washed with distilled water (25 mL) and then with acetone (25 mL).
- the solid (aromatic compound (pyrenic type) within the meaning of the invention, the formula contains 4 aromatic rings and a metal precursor function) is dried in an oven at 70 ° C for 2 h, then at 90 ° C for 12 h.
- the fibrous support, C / NFC substrate (50 mg), is impregnated with the cobalt complex (10 mg, 1.8% by weight in Co) solubilized in a minimum of THF (volume ⁇ 1 mL).
- Said impregnated fibrous support is then dried in an oven for 12 hours.
- FIG. 3A Scanning electron micrographs at various magnifications of said catalyst element are shown in Figures 3A and 3B.
- FIG. 3A the carbon fibers of the fibrous structure are clearly visible.
- Figure 3B at higher magnification, we see the surface of a fiber enriched in carbon nanofibers.
- This method of impregnation of the cobalt complex is therefore very efficient in that it allows in particular a control of the distribution and the size of the cobalt oxide particles. It is advantageously substituted for conventional treatments of carbon nanotubes or C / C substrates requiring a preliminary stage of oxidation with acids: said conventional treatments generate larger particles.
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GB1318145.8A GB2507875A (en) | 2011-04-19 | 2012-04-16 | Process for preparing a monolithic catalysis element comprising a fibrous support and said monolithic catalysis element |
KR1020137030173A KR20140066975A (ko) | 2011-04-19 | 2012-04-16 | 섬유상 지지체를 포함하는 일체식 촉매 앨리먼트를 제조하기 위한 방법 및 상기 일체식 촉매 앨리먼트 |
CN201280019519.3A CN103492065A (zh) | 2011-04-19 | 2012-04-16 | 包含纤维载体的整体式催化元件的制备方法以及所述整体式催化元件 |
DE112012001773.0T DE112012001773T5 (de) | 2011-04-19 | 2012-04-16 | Verfahren zur Herstellung eines monolithischen Katalyseelements, umfassend einen faserigen Träger und das monolithische Katalyseelement |
US14/112,953 US20140287912A1 (en) | 2011-04-19 | 2012-04-16 | Process for Preparing a Monolithic Catalysis Element Comprising a Fibrous Support and Said Monolithic Catalysis Element |
JP2014505699A JP2014515702A (ja) | 2011-04-19 | 2012-04-16 | 繊維状支持体を含むモノリス触媒エレメントの製造方法、およびモノリス触媒エレメント |
Applications Claiming Priority (2)
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FR1153370A FR2974314B1 (fr) | 2011-04-19 | 2011-04-19 | Procede de preparation d'un element monolithique de catalyse comprenant un support fibreux et ledit element monolithique de catalyse |
FR1153370 | 2011-04-19 |
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WO2012143658A1 true WO2012143658A1 (fr) | 2012-10-26 |
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PCT/FR2012/050829 WO2012143658A1 (fr) | 2011-04-19 | 2012-04-16 | Procede de preparation d'un element monolithique de catalyse comprenant un support fibreux et ledit element monolithique de catalyse |
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US (1) | US20140287912A1 (fr) |
JP (1) | JP2014515702A (fr) |
KR (1) | KR20140066975A (fr) |
CN (1) | CN103492065A (fr) |
DE (1) | DE112012001773T5 (fr) |
FR (1) | FR2974314B1 (fr) |
GB (1) | GB2507875A (fr) |
WO (1) | WO2012143658A1 (fr) |
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KR101624389B1 (ko) * | 2013-12-24 | 2016-05-25 | 주식회사 포스코 | 비공유결합 개질된 탄소구조체 및 이를 포함하는 탄소구조체/고분자 복합체 |
FR3033268B1 (fr) * | 2015-03-05 | 2019-08-16 | IFP Energies Nouvelles | Catalyseur comprenant de l'or disperse de maniere homogene dans un support poreux |
WO2019073876A1 (fr) * | 2017-10-10 | 2019-04-18 | 日本電気株式会社 | Dispositif de séparation de nanocarbone et méthode de séparation de nanocarbone |
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FR2557550A1 (fr) | 1983-12-28 | 1985-07-05 | Europ Propulsion | Procede et appareillage pour la fabrication de structures tridimensionnelles de revolution |
FR2584106A1 (fr) | 1985-06-27 | 1987-01-02 | Europ Propulsion | Procede de fabrication de structures tridimensionnelles par aiguilletage de couches planes de materiau fibreux superposees et materiau fibreux utilise pour la mise en oeuvre du procede |
FR2584107A1 (fr) | 1985-06-27 | 1987-01-02 | Europ Propulsion | Procede de fabrication de structures de revolution tridimensionnelles par aiguilletage de couches de materiau fibreux et materiau utilise pour la mise en oeuvre du procede |
US6346136B1 (en) | 2000-03-31 | 2002-02-12 | Ping Chen | Process for forming metal nanoparticles and fibers |
WO2003048039A2 (fr) | 2001-11-23 | 2003-06-12 | Sicat | Composites a base de nanotubes ou nanofibres de carbone deposes sur un support active pour application en catalyse |
WO2004025003A2 (fr) | 2002-09-12 | 2004-03-25 | Snecma Propulsion Solide | Structure fibreuse tridimensionnelle en fibres refractaires, procede pour sa realisation et application aux materiaux composites thermostructuraux. |
WO2005009589A1 (fr) | 2003-07-18 | 2005-02-03 | Koslow Technologies Corporation | Nanofibres de carbone ou de carbone active |
FR2892644A1 (fr) | 2005-10-28 | 2007-05-04 | Snecma Propulsion Solide Sa | Structure de garnissage pour colonne d'echange de fluides |
WO2008011623A2 (fr) * | 2006-07-21 | 2008-01-24 | International Business Machines Corporation | Complexes de nanotubes de carbone et fullerènes dotés de clips moléculaires et leurs utilisations |
WO2009097669A1 (fr) | 2008-01-15 | 2009-08-13 | Universidade Federal De Minas Gerais-Ufmg | Procédé de synthèse de systèmes nanostructurés hybrides constitués par des nanotubes de carbone et des nanoparticules métalliques |
US20110129762A1 (en) * | 2009-11-30 | 2011-06-02 | Hyundai Motor Company | Method of increasing hydrophilic property of crystalline carbon using surface modifier and method of preparing platinum catalyst using the same |
-
2011
- 2011-04-19 FR FR1153370A patent/FR2974314B1/fr active Active
-
2012
- 2012-04-16 US US14/112,953 patent/US20140287912A1/en not_active Abandoned
- 2012-04-16 GB GB1318145.8A patent/GB2507875A/en not_active Withdrawn
- 2012-04-16 KR KR1020137030173A patent/KR20140066975A/ko not_active Application Discontinuation
- 2012-04-16 JP JP2014505699A patent/JP2014515702A/ja active Pending
- 2012-04-16 WO PCT/FR2012/050829 patent/WO2012143658A1/fr active Application Filing
- 2012-04-16 DE DE112012001773.0T patent/DE112012001773T5/de not_active Withdrawn
- 2012-04-16 CN CN201280019519.3A patent/CN103492065A/zh active Pending
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FR2557550A1 (fr) | 1983-12-28 | 1985-07-05 | Europ Propulsion | Procede et appareillage pour la fabrication de structures tridimensionnelles de revolution |
FR2584106A1 (fr) | 1985-06-27 | 1987-01-02 | Europ Propulsion | Procede de fabrication de structures tridimensionnelles par aiguilletage de couches planes de materiau fibreux superposees et materiau fibreux utilise pour la mise en oeuvre du procede |
FR2584107A1 (fr) | 1985-06-27 | 1987-01-02 | Europ Propulsion | Procede de fabrication de structures de revolution tridimensionnelles par aiguilletage de couches de materiau fibreux et materiau utilise pour la mise en oeuvre du procede |
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WO2003048039A2 (fr) | 2001-11-23 | 2003-06-12 | Sicat | Composites a base de nanotubes ou nanofibres de carbone deposes sur un support active pour application en catalyse |
WO2004025003A2 (fr) | 2002-09-12 | 2004-03-25 | Snecma Propulsion Solide | Structure fibreuse tridimensionnelle en fibres refractaires, procede pour sa realisation et application aux materiaux composites thermostructuraux. |
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FR2892644A1 (fr) | 2005-10-28 | 2007-05-04 | Snecma Propulsion Solide Sa | Structure de garnissage pour colonne d'echange de fluides |
WO2008011623A2 (fr) * | 2006-07-21 | 2008-01-24 | International Business Machines Corporation | Complexes de nanotubes de carbone et fullerènes dotés de clips moléculaires et leurs utilisations |
WO2009097669A1 (fr) | 2008-01-15 | 2009-08-13 | Universidade Federal De Minas Gerais-Ufmg | Procédé de synthèse de systèmes nanostructurés hybrides constitués par des nanotubes de carbone et des nanoparticules métalliques |
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Also Published As
Publication number | Publication date |
---|---|
DE112012001773T5 (de) | 2014-01-16 |
GB2507875A8 (en) | 2014-05-21 |
US20140287912A1 (en) | 2014-09-25 |
CN103492065A (zh) | 2014-01-01 |
KR20140066975A (ko) | 2014-06-03 |
FR2974314B1 (fr) | 2013-05-10 |
FR2974314A1 (fr) | 2012-10-26 |
GB201318145D0 (en) | 2013-11-27 |
GB2507875A (en) | 2014-05-14 |
JP2014515702A (ja) | 2014-07-03 |
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