WO2018157395A1 - Procédé de préparation d'une amine par réaction d'amination directe - Google Patents

Procédé de préparation d'une amine par réaction d'amination directe Download PDF

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WO2018157395A1
WO2018157395A1 PCT/CN2017/075640 CN2017075640W WO2018157395A1 WO 2018157395 A1 WO2018157395 A1 WO 2018157395A1 CN 2017075640 W CN2017075640 W CN 2017075640W WO 2018157395 A1 WO2018157395 A1 WO 2018157395A1
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catalyst
process according
reactant
comprised
group
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PCT/CN2017/075640
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Ajay TOMER
Marc Pera Titus
Anne PONCHEL
Eric Monflier
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Rhodia Operations
Le Centre National De La Recherche Scientifique
Ecole Normale Superieure De Lyon
Universite Lille 1 - Sciences Et Technologies
Ecole Centrale De Lille
Universite D'artois
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Priority to PCT/CN2017/075640 priority Critical patent/WO2018157395A1/fr
Publication of WO2018157395A1 publication Critical patent/WO2018157395A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/755—Nickel
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt

Definitions

  • This invention provides a process for preparing an amine by direct amination of alcohols in the presence of CD assisted catalyst, notably permitting then to produce aliphatic amines by aliphatic alcohols.
  • Ken-ichi Shimizu et al. ACS Catalysis (2013) , 3 (1) , 112-117 reported a noble metal-free catalytic system for synthesis of primary amines from alcohols and NH 3 by Al 2 O 3 supported Ni catalysts.
  • Victor A. Bassili et. al Applied Catalysis, 65 (1990) 293-308 and Applied Catalysis, 70, (1991) 325-338 reported catalytic amination of 1-methoxypropano-2-ol over silica supported nickel.
  • Bimetallic catalysts have also been reported for amination of diols and aromatic alcohols.
  • Cyclodextrin (CD) are oligosaccharides composed of six, seven or eight glucose residues attached by ⁇ -1, 4-linkages in a cyclic array and have been found its applications in catalysis recently.
  • the present invention pertains to a process for preparing an amine, comprising reacting:
  • a catalyst comprising at least one transition metal, a support and at least one organic compound formed by at least one cyclic oligosaccharide.
  • the invention also concerns a composition
  • a composition comprising:
  • -a catalyst comprising at least one transition metal, a support and at least one organic compound formed by at least one cyclic oligosaccharide.
  • any particular upper concentration can be associated with any particular lower concentration.
  • metals of group IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB are often referred to as transition metals.
  • This group comprises the elements with atomic number 21 to 30 (Sc to Zn) , 39 to 48 (Y to Cd) , 72 to 80 (Hf to Hg) and 104 to 112 (Rf to Cn) .
  • hydrocarbon group refers to a group mainly consisting of carbon atoms and hydrogen atoms, which group may be saturated or unsaturated, linear, branched or cyclic, aliphatic or aromatic.
  • alkyl refers to a monovalent saturated aliphatic (i.e. non-aromatic) acyclic hydrocarbon group which may be linear or branched and does not comprise any carbon-to-carbon double bond or any carbon-to-carbon triple bond.
  • Representative saturated straight chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like; while saturated branched alkyls include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, and the like.
  • alkenyl refers to a monovalent unsaturated aliphatic acyclic hydrocarbon group which may be linear or branched and comprises at least one carbon-to-carbon double bond while it does not comprise any carbon-to-carbon triple bond.
  • Representative unsaturated straight chain alkenyls include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl and the like.
  • aryl refers to a monovalent aromatic hydrocarbon group, including bridged ring and/or fused ring systems, containing at least one aromatic ring. Examples of aryl groups include phenyl, naphthyl and the like.
  • arylalkyl or the term “aralkyl” refers to alkyl substituted with an aryl.
  • arylalkoxy refers to an alkoxy substituted with aryl.
  • cyclic group means a closed ring hydrocarbon group that is classified as an alicyclic group, aromatic group, or heterocyclic group.
  • alicyclic group means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.
  • cycloalkyl as used herein means cycloalkyl groups containing from 3 to 8 carbon atoms, such as for example cyclohexyl.
  • heterocyclic means heterocyclic groups containing up to 6 carbon atoms together with 1 or 2 heteroatoms which are usually selected from O, N and S, such as for example radicals of: oxirane, oxirene, oxetane, oxete, oxetium, oxalane (tetrahydrofurane) , oxole, furane, oxane, pyrane, dioxine, pyranium, oxepane, oxepine, oxocane, oxocinc groups, aziridine, azirine, azirene, azetidine, azetine, azete, azolidine, azoline, azole, azinane, tetrahydropyridine, tetrahydrotetrazine, dihydroazine, azine, azepane,
  • Heterocyclic may also mean a heterocyclic group fused with a benzene-ring wherein the fused rings contain carbon atoms together with 1 or 2 heteroatom’s which are selected from N, O and S.
  • an oligosaccharide is a saccharide polymer containing a small number (typically two to ten) of simple sugars (monosaccharides) .
  • cyclodextrins are a family of cyclic oligosaccharides composed of ⁇ - (1, 4) -bonded glucopyranose subunits. They are cage molecules.
  • the present invention provides a process for preparing an amine, comprising reacting:
  • a catalyst comprising at least one transition metal, a support and at least one organic compound formed by at least one cyclic oligosaccharide.
  • the transition metal of present invention may be metal element chosen in a group consisting elements of VIB, VIIB and VIIIB of the Periodic Table.
  • the transition metal could be chosen in the group consisting of Fe, Co, Ni, Cu, Pd, Pt, Ag, Ru and Rh and more preferably Ni, Pd, Pt, Ag, Ru and Rh and most preferably Ni or Pd.
  • the catalyst may be monometallic catalyst, which comprises one and only one transition metal. In another preferred embodiment, the catalyst may be bimetallic catalyst comprising two transition metals.
  • the loading amount of transition metal on support of present invention is not particularly limited and depends on the metal source.
  • the loading could preferably be comprised from 3.0wt%to 30.0wt%with respect to total weight of catalyst and more preferably from 5.0wt%to 20.0wt%and most preferably from 5.0wt%to 15.0wt%.
  • the Ni loading could preferably be comprised from 1.0wt%to 20.0wt%and Pd loading could preferably be comprised from 0.1wt%to 1.0wt%with respect to total weight of catalyst and more preferably Ni loading could be comprised from 2.0wt%to 10.0wt%and Pd loading could preferably be comprised from 0.2wt%to 0.6wt%.
  • the particle size of transition metal loaded on the support may be preferably comprised from 2nm to 10nm.
  • the support of catalyst is not particularly limited as long as its presence does not prevent interaction of metal and organic compound formed by at least one cyclic oligosaccharide.
  • the support could notably be metal oxides chosen in the group consisting of aluminum oxide (Al 2 O 3 ) , silicon dioxide (SiO 2 ) , titanium oxide (TiO 2 ) , zirconium dioxide (ZrO 2 ) , calcium oxide (CaO) , magnesium oxide (MgO) , lanthanum oxide (La 2 O 3 ) , niobium dioxide (NbO 2 ) , cerium oxide (CeO 2 ) and any combination thereof.
  • said support may comprise aluminum oxide in ⁇ , ⁇ , ⁇ or ⁇ crystallographic phase.
  • the support of catalyst could also be zeolites.
  • Zeolites are substances having a crystalline structure and a unique ability to change ions.
  • the support of catalyst could even be chosen Kieselguhr, clay or carbon.
  • the catalyst of present invention may have a specific surface area (S BET ) comprised from 100m 2 /g to 300m 2 /g and preferably from 120m 2 /gto 200m 2 /g.
  • S BET specific surface area
  • the specific surface area referred to in the present specification is measured according to the BET method utilizing absorption of nitrogen gas, which is the most standard method for measuring the specific surface area of powders.
  • specific surface area is understood to mean the BET specific surface area determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 laid down from the Brunauer-Emmett-Teller method described in the periodical “The Journal of the American Chemical Society, 60, 309 (1938) ” . Specific surface areas are expressed for a designated calcination temperature and time. For instance, the sample could be calcined for 12 hours at 100°C.
  • said organic compound is formed by at least one cyclic oligosaccharide.
  • said organic compound is formed by at least one cyclic oligosaccharide comprising at least 6 ⁇ - (1, 4) -bonded glucopyranose subunits.
  • a spatial representation of a glucopyranose subunit is given below:
  • Said organic compound is preferably chosen in the group consisting of cyclodextrins, substituted cyclodextrins, polymerized cyclodextrins and mixtures thereof.
  • preferred cyclodextrins are ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin respectively composed of 6, 7 and 8 ⁇ - (1, 4) -bonded glucopyranose subunits.
  • Developed representations of ⁇ - cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin are given below as formula (I) , (II) and (III) respectively.
  • ⁇ -cyclodextrin is used in present invention, composed of 7 ⁇ - (1, 4) -bonded glucopyranose subunits.
  • Cyclodextrins are commercially available compounds, such as cyclodextrins – ⁇ , ⁇ and ⁇ in standard technical grade under the product name available from WACKER.
  • the molar ratio of organic compound to transition metal of present invention may be comprised from 0.001: 1 to 1.000: 1 and preferably from 0.01: 1 to 0.50: 1 and most preferably from 0.05: 1 to 0.10: 1, notably 0.05: 1, 0.10: 1, 0.15: 1, 0.20: 1, 0.25: 1, 0.30: 1, 0.35: 1, 0.40: 1, 0.45: 1 and 0.50: 1, or any range comprised between these values.
  • organic compounds especially those chosen from cyclodextrins, substituted cyclodextrins or polymerized cyclodextrins could be directly introduced into reaction.
  • cyclodextrins, substituted cyclodextrins or polymerized cyclodextrins could be introduced in the form of supramolecular inclusion complex. It could be understood that owing to cyclodextrin compound’s hydrophobic internal cavity and hydrophilic external surface, these macromolecules are known to interact with a large variety of compounds (e.g., organic molecules, surfactants) , coordination complexes (e.g., ferrocene) and inorganic ions (e.g., iodide ions) in the form of host-guest complexes.
  • compounds e.g., organic molecules, surfactants
  • coordination complexes e.g., ferrocene
  • inorganic ions e.g., iodide ions
  • supramolecular inclusion complex are: cyclodextrin-pentanol, cyclodextrin-hexanol, cyclodextrin-heptanol, cyclodextrin-octanol, cyclodextrin-nonanol, cyclodextrin-decanol, cyclodextrin-benzoic acid and cyclodextrin-adamentanol.
  • said supramolecular inclusion complex could be formed by cyclodextrins and first reactant of present invention.
  • the catalyst ofpresent invention could be prepared by any method that is well known to the skilled person.
  • the monometallic catalyst of present invention could be prepared by wet impregnation (WI) .
  • wet impregnation refers to impregnation of metal precursor on an oxide support in the excess of solvent. Typically, a known concentration of metal precursor solution is added to the support solution over a period of time and mixture is allowed to stir for another few hours. For example, wet impregnation could be used to prepare the monometallic catalyst when ⁇ -cyclodextrin is employed.
  • the monometallic catalyst of present invention could be prepared by incipient wetness impregnation (IWI) .
  • IWI incipient wetness impregnation
  • capillary impregnation or dry impregnation is a commonly used technique for the synthesis of heterogeneous catalysts.
  • the active metal precursor is dissolved in an aqueous or organic solution.
  • the metal-containing solution is added to a catalyst support containing the same pore volume as the volume of the solution that was added. Solution added in excess of the support pore volume causes the solution transport to change from a capillary action process to a diffusion process, which is much slower.
  • the catalyst can then be dried and calcined to drive off the volatile components within the solution, depositing the metal on the catalyst surface.
  • the maximum loading is limited by the solubility of the precursor in the solution.
  • concentration profile of the impregnated compound depends on the mass transfer conditions within the pores during impregnation and drying. For example, incipient wetness impregnation could be used to prepare the monometallic catalyst when ⁇ -cyclodextrin or ⁇ -cyclodextrin is employed.
  • bimetallic catalyst could be prepared by co-impregnation method, in which all metal precursors are mixed together in a known amount of solvent (H 2 O) and then impregnated on the support followed by drying and calcining at particular temperature.
  • bimetallic catalyst could also be prepared by sequential impregnation method, in which a first metal is impregnated on the support by drying and calcining at particular temperature. Then a second metal is impregnated on prepared catalyst and further subjected to drying and calcination steps at particular temperature.
  • the sequence of adding raw materials to prepare the monometallic or bimetallic catalyst by above mentioned methods is not particularly limited.
  • the raw materials could be added in sequence or simultaneously.
  • the Ni-Pd bimetallic catalyst could be prepared by a co-impregnation method, in which Ni precursor, Pd precursor and Al 2 O 3 are added into CD aqueous solution in sequence. The mixture is stirred for sufficient time to get good mixing effect every time one raw material is added. The catalyst is then obtained after drying and calcination steps at particular temperature.
  • the Ni-Pd bimetallic catalyst could be prepared by a co-impregnation method, in which Al 2 O 3 , mixture of Ni and Pd precursor and are added into CD aqueous solution in sequence. The mixture is stirred for sufficient time to get good mixing effect every time one raw material is added. The catalyst is then obtained after drying and calcination steps at particular temperature.
  • This first reactant may notably be a compound of formula (I) :
  • -R 1 is a straight, branched or cyclic C 2 -C 30 hydrocarbon group
  • R 1 may represent straight, branched or cyclic C 2 -C 30 hydrocarbon group that can be an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group, eventually comprising one or several heteroatoms such as O, S, F, and N. More preferred groups for R 1 may be for example C 2 -C 12 straight aliphatic hydrocarbon group, benzyl, furfuryl, and tetrahydrofurfuryl.
  • the first reactant may comprise additional functionalities.
  • the additional functionalities may behave as electron donating or electron withdrawing groups as long as their presence does not prevent reaction with the amine to form the imine intermediate.
  • Preferred first reactant of the present invention is chosen in the group consisting of: n-ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol and n-decanol, furfuryl alcohol, 2, 5-furandimethanol, 2, 5-tetrahydrofuranedimethanol, benzyl alcohol, 1, 6-hexandiol and 1, 7-heptandiol.
  • the first reactant could be a primary alcohol, which is chosen in the group consisting of n-ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol and n-decanol, furfuryl alcohol and benzyl alcohol.
  • a primary alcohol which is chosen in the group consisting of n-ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol and n-decanol, furfuryl alcohol and benzyl alcohol.
  • This second reactant may notably be a compound of formula (II) :
  • R 2 is H or a straight, branched or cyclic hydrocarbon group.
  • R 2 may represent straight, branched or cyclic hydrocarbon group that can be an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group, eventually comprising one or several heteroatoms such as O, S, F, and N.
  • Preferred groups for R 2 may be for example: H, alkyl, phenyl, benzyl, cycloalkyl, and cycloalkene. More preferred groups for R 2 may be H or alkyl. More preferred groups for R 2 may be H or C 1 -C 5 alkyl.
  • the second reactant may comprise additional functionalities.
  • the additional functionalities may behave as electron donating or electron withdrawing groups as long as their presence does not prevent reaction with the amine to form the imine intermediate.
  • Preferred second reactant of the present invention such as compounds of formula (II) , is chosen in the group consisting of: NH 3 , methylamine, ethylamine, propylamine and aniline. NH 3 is more preferable among these compounds.
  • the amine produced by the method of present invention could be chosen in the group consisting of primary, secondary and tertiary amine.
  • the amine is a primary amine.
  • the so prepared amine is or includes a primary amine and the selectivity of the primary amine is of at least 50%and preferably is comprised from 40%to 90%and more preferably from 60%to 80%.
  • the amine produced by the method of the present invention may notably be a compound of formula (III) :
  • x and R 1 have the same meaning as above defined.
  • Preferred amine produced in present invention could be chosen in the group consisting of: n-ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, benzylamine, furan-2-ylmethanamine, (tetrahydrofuran-2, 5-diyl) dimethanamine, (furan-2, 5-diyl) dimethanamine, 1, 6-hexamethylenediamine, 1, 7-heptamethylenediamine, N-phenylbenzylamine and N, N-Dibenylaniline.
  • amine produced such as compounds of formula (III)
  • amine produced could be chosen in the group consisting of n-ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and benzylamine.
  • Preferred reactions of the present invention are the following:
  • the molar ratio of transition metal in catalyst to first reactant is not particularly limited and depends on the metal source.
  • the molar ratio of Ni to first reactant could be comprised from 0.01 to 0.20 and preferably from 0.05 to 0.15.
  • the molar ratio of Pd to first reactant could be comprised from 0.0005 to 0.005 and preferably from 0.001 to 0.003.
  • the method for forming an amine might be performed at a temperature and for a time sufficient for the primary amine, secondary amine or tertiary amine to be produced.
  • the reaction temperature may be comprised between-100°C and 280°C, preferably between 0°C and 250°C, more preferably between 150°C and 200°C.
  • the reaction may be carried out in liquid or gas phase. In liquid phase, the reaction may be performed in the absence or presence of a solvent.
  • the solvent is typically chosen based on its ability to dissolve the reactants.
  • the solvent may be protic, aprotic or a combination of protic and aprotic solvents.
  • Exemplary solvents include toluene, octane, xylene, benzene, n-butanol, and acetonitrile.
  • the solvent is a non-polar, aprotic solvent such as toluene. Solvents comprising hydroxyl functionalities or amine functionalities may be used as long as the solvent does not participate in the reaction in place of the reactant.
  • the reactants, with an optional solvent, and the catalyst are typically combined in a reaction vessel and stirred to constitute the reaction mixture.
  • the reaction mixture is typically maintained at the desired reaction temperature under stirring for a time sufficient to form the amines in the desired quantity and yield.
  • Hydrogen could be optionally introduced into the reaction medium in this invention.
  • NH 3 and H 2 might be mixed and introduced into reaction medium in one embodiment.
  • the reaction may be performed under a pressure comprised between 1 and 100 bars, preferably between 2 and 20 bars.
  • the reaction may be carried out in the presence of air but preferably with an inert atmosphere, such as N 2 , Ar, or CO 2 .
  • an inert atmosphere such as N 2 , Ar, or CO 2 .
  • those atmospheres may be introduced to the reaction mixture solely or in a form of mixture with NH 3 and/or H 2 .
  • the catalyst is typically removed from the reaction mixture using any solid/liquid separation technique such as filtration, centrifugation, and the like or a combination of separation methods.
  • the product may be isolated using standard isolation techniques, such as distillation.
  • the catalyst can be reused. If desired, the catalyst can be regenerated by washing with methanol, water or a combination of water and methanol and subjecting the washed catalyst to a temperature of about 100°C to about 500°C for about 2 to 24 hours in the presence of oxygen.
  • the conversion of first reactant could reach at least 50%.
  • the conversion of first reactant may be comprised from 70%to 100%and more preferably from 75%and 90%.
  • the invention also concerns a composition
  • a composition comprising:
  • -a catalyst comprising at least one transition metal, a support and at least one organic compound formed by at least one cyclic oligosaccharide.
  • Support ⁇ -Al 2 O 3 (Puralox SCCA 5/170, 154 m 2 g -1 ) was purchased from SASOL Germany and used without any pre-treatment.
  • Catalysts were synthesized by wet impregnation method.
  • Nickel (II) nitrate hexahydrate (1.303 g) was added to 250 mL of distilled H 2 O taken in 500 mL R.B. with magnetic stirrer.
  • 5 g of support ( ⁇ -Al 2 O 3 ) was added and solid suspension was further stirred for 2h. After this, water was slowly removed over rotary evaporator at 60°C until dryness. The recovered solid was dried overnight in an oven at 100°C and calcined at 400°C for 4h with heating rate of 2°C min -1 in air flow of 2L h -1 .
  • the obtained catalysts were denoted as 5Ni/Al 2 O 3 -WI.
  • Catalysts were synthesized by wet impregnation method.
  • This solution was kept under constant stirring for 2h at ambient temperature.
  • the support (5g) was then added to above solution and solid suspension was further stirred for another 2h. After this, water was slowly removed over rotary evaporator at 60°C until dryness.
  • the recovered solid was dried overnight in an oven at 100°C and calcined at 400°C for 4h with heating rate of 2°C min -1 in air flow of 2L h -1 .
  • This comparative example relates to amination of 1-octanol with ammonia (NH 3 ) by catalysts of EXAMPLE 1&2.
  • Amination of 1-octanol with ammonia (Atm. Pressure, 8bar) was carried out in 30 mL stainless steel reactor geared with pressure gauge and safety rupture disk.
  • reactor is charged with 1.3mmol 1-octanol soluble in 3mL o-xylene and pre-reduced catalyst (55 mg) .
  • the reactor is sealed and flushed with N 2 two times followed by introducing 7 bar NH 3 into the reactor.
  • the reactor is heated on hot plate equipped with magnetic stirring for 4h at 180°C.
  • reaction mixture is syringe filtered and analyzed on Agilent 7890 GC equipped with HP-5 capillary column with 5wt%phenyl group using biphenyl as an internal standard.
  • the monometallic assisted by cyclodextrin shows better catalytic performance than the one without cyclodextrin in amination of aliphatic alcohol with ammonia.
  • This example relates to recycle study of the 5Ni/Al 2 O 3 -WI of EXMAPLE 1 and 5Ni/Al 2 O 3 -CD 0.1 EXAMPLE 2, which was carried out as follows: after the first reaction, the reaction mixture is centrifuged and the catalysts is separated, dried in oven at 110°C and calcined at 400°C for 2 h.
  • the 5Ni-0.5Pd/Al 2 O 3 _M1 catalysts were synthesized by a direct co-impregnation method without CD.
  • a direct co-impregnation method without CD 1.310 g nickel (II) nitrate hexahydrate and 0.0661 g palladium nitrate dihydrate was dissolved in 250 mL distilled water and stirred for 5 min.
  • the ⁇ -Al 2 O 3 support (5 g) was then added and the solid suspension was stirred at room temperature for 2 h. The excess of water was slowly removed using a rotary evaporator at 60°C until dryness.
  • the recovered solid was dried overnight in an oven at 100°C and calcined at 400°C for 4 h using a heating rate of 2°C ⁇ min -1 under 2 L (STP) ⁇ h -1 airflow.
  • the catalysts 2Ni-0.2Pd/Al 2 O 3 _M1 and 5Ni-1.0Pd/Al 2 O 3 _M1 were synthesized by the same way.
  • the 5Ni-1.0Pd/Al 2 O 3 -CD 0.1 _M2 bimetallic catalysts were synthesized in the presence of ⁇ -CD as follows: 0.5109 g of ⁇ -CD (0.1 mol equiv with respect to Ni) was first added to 250 mL of distilled water and stirred for 5 min. An aqueous mixture of nickel (II) nitrate hexahydrate (1.310 g) and palladium nitrate dihydrate (0.132 g) was added to ⁇ -CD aqueous solution. This solution was kept under constant stirring at room temperature for 2 h. The support (5 g) was then added and the solid suspension was further stirred for another 2 h.
  • Method 3 consists of a modified version of Method 2.
  • 0.5109 g of ⁇ -CD 0.1 mol equiv with respect to Ni
  • 0.5109 g of ⁇ -CD 0.1 mol equiv with respect to Ni
  • 0.5109 g of ⁇ -CD 0.1 mol equiv with respect to Ni
  • 1.310 g of nickel nitrate hexahydrate was added and the solution was stirred for 2 h.
  • 0.0661 g palladium nitrate dihydrate was quickly introduced and the solution was stirred for 2 min immediately followed by the addition of ⁇ -Al 2 O 3 (5 g) .
  • the solid suspension was mixed at room temperature for another 2 h. Later on, water was slowly removed using a rotary evaporator at 60°C until dryness.
  • the recovered solid was dried overnight in an oven at 100°C and calcined at 400°C for 4 h using a heating rate of 2°C ⁇ min -1 under 2 L (STP) ⁇ h -1 air flow.
  • the catalyst synthesized by this method was denoted as 5Ni-0.5Pd/Al 2 O 3 -CD 0.1 _M3.
  • the ⁇ -CD (0.5109 g) was first added to 250 mL of distilled water and stirred for 5 min followed by ⁇ -Al 2 O 3 addition (5 g) .
  • the ⁇ -Al 2 O 3 / ⁇ -CD suspension was stirred for another 5 min and then the bimetallic solution (1.310 g Ni nitrate hexahydrate and 0.0661 g Pd nitrate dihydrate) was introduced.
  • the resulting suspension was stirred at room temperature for 2 h. After this period, water was slowly removed using a rotary evaporator at 60°C until dryness.
  • the recovered solid was dried overnight in an oven at 100°C and calcined at 400°C for 4 h using a heating rate of 2°C ⁇ min -1 under 2 L ⁇ h -1 airflow.
  • the catalyst synthesized by this method was denoted as 5Ni-0.5Pd/Al 2 O 3 -CD 0.1 _M4.2Ni-0.2Pd/Al 2 O 3 -CD 0.1 _M4 was synthesized by the same way.
  • the first part was devoted to the preparation of the monometallic 5Ni/Al 2 O 3 - ⁇ -CD 0.1 by wet impregnation as described in EXAMPLE 2.
  • the second part of the synthesis was performed by impregnating the palladium nitrate hexahydrate in water in the absence of ⁇ -CD as follows: 0.0661 g palladium nitrate dihydrate salt was added to 250 mL of distilled water and stirred for 5 min. After this, 5 g of the calcined catalyst synthesized in the first part (5Ni/Al 2 O 3 - ⁇ -CD 0.1 ) was introduced and the solid suspension was stirred for 2 h.
  • the remaining post treatment procedure was identical to that described in EXAMPLE 3 (water removal, drying and calcination at 400 °C under air) .
  • the catalyst synthesized by this method was denoted as 5Ni-0.5Pd/Al 2 O 3 -CD 0.1 _M5.
  • Method 6 also relies on a sequential impregnation method and is same as Method 5 of EXAMPLE 7 differing only in the second part of the catalyst synthesis, where palladium impregnation was carried out in the presence of ⁇ -CD (0.028g ⁇ -CD in 250 mL distilled water) .
  • ⁇ -CD 0.028g ⁇ -CD in 250 mL distilled water
  • ⁇ -CD was used twice, i.e. during Ni/Al 2 O 3 synthesis and during Pd impregnation over Ni/Al 2 O 3 .
  • the catalyst synthesized by this method was denoted as 5Ni-0.5Pd/Al 2 O 3 -CD 0.1 _M6.
  • This comparative example relates to amination of 1-octanol with ammonia (NH 3 ) by catalysts of EXAMPLE 3 to 8.
  • This comparative example is performed in the same way of COMPARATIVE EXAMPLE 1 differing only reaction temperature.
  • the monometallic assisted by cyclodextrin shows better catalytic performance than the one without cyclodextrin in amination of aliphatic alcohol with ammonia.

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Abstract

La présente invention concerne un procédé de préparation d'une amine par amination directe d'alcools en présence d'un catalyseur assisté par CD, permettant notamment de produire ensuite des amines aliphatiques par des alcools aliphatiques.
PCT/CN2017/075640 2017-03-03 2017-03-03 Procédé de préparation d'une amine par réaction d'amination directe WO2018157395A1 (fr)

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CN113877630A (zh) * 2021-10-11 2022-01-04 万华化学集团股份有限公司 一种制备双[（3-二甲基氨基）丙基]胺的催化剂及其应用

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EP0697395A2 (fr) * 1994-08-19 1996-02-21 Basf Aktiengesellschaft Procédé de préparation de diamines par amination catalytique d'amino alcools
EP0729785A1 (fr) * 1995-02-28 1996-09-04 Basf Aktiengesellschaft Catalyseurs d'animation d'alcools, de cétones et d'aldéhydes
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WO2012031884A1 (fr) * 2010-09-10 2012-03-15 Evonik Degussa Gmbh Procédé pour l'amination directe d'alcools secondaires avec de l'ammoniac en amines primaires
WO2012076560A1 (fr) * 2010-12-08 2012-06-14 Evonik Degussa Gmbh Procédé par catalyse homogène d'amination directe hautement sélective, d'alcools primaires avec l'ammoniac, pour donner des amines primaires, sous de hauts rapports volumiques entre la phase liquide et la phase gazeuse et/ou en présence de pressions élevées
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WO2016074121A1 (fr) * 2014-11-10 2016-05-19 Rhodia Operations Procédé de formation d'amine par réaction d'amination directe

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CN113877630A (zh) * 2021-10-11 2022-01-04 万华化学集团股份有限公司 一种制备双[（3-二甲基氨基）丙基]胺的催化剂及其应用

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