WO2018141113A1 - Procédé de préparation d'amine par réaction d'amination directe - Google Patents

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

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WO2018141113A1
WO2018141113A1 PCT/CN2017/072998 CN2017072998W WO2018141113A1 WO 2018141113 A1 WO2018141113 A1 WO 2018141113A1 CN 2017072998 W CN2017072998 W CN 2017072998W WO 2018141113 A1 WO2018141113 A1 WO 2018141113A1
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process according
reactant
group
catalyst
metal oxide
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PCT/CN2017/072998
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Ajay TOMER
Marc Pera Titus
Anne PONCHEL
Zhen YAN
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Rhodia Operations
Le Centre National De La Recherche Scientifique
Université D'artois
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Priority to PCT/CN2017/072998 priority Critical patent/WO2018141113A1/fr
Publication of WO2018141113A1 publication Critical patent/WO2018141113A1/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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • This invention provides an effective process for converting alcohols to an amine.
  • This invention provides an effective process for converting alcohols to an amine, notably primary, with desired characteristics such as inexpensiveness, high selectivity and conversion.
  • the reaction is performed in the presence of a low loading transition metal catalyst, notably noble metal-free metal.
  • Heterogeneous catalyst used in direct amination reaction is very attractive technology nowadays for its ease of separation and recyclability.
  • Rare earth oxides such as cerium oxide is always used in the catalytic amination reactions.
  • WO15054828 A1 discloses cerium oxide is used as a support to noble metal in the direct amination reaction.
  • US2013178656 reports a process for preparing secondary amines by aminating excess primary or secondary alcohols with primary amines in the liquid phase in the presence of copper-comprising catalysts.
  • Said oxidic support could be aluminum oxides, silicon dioxide, titanium dioxides, zirconium dioxide, lanthanum oxide, molybdenum oxide, tungsten oxide or mixtures of these oxides. However, it only links to high copper loading alumina supporting catalyst.
  • Ken-ichi Shimizu et al. ACS Catalysis (2013) , 3 (1) , 112-117 reports a noble metal-free catalytic system for synthesis of primary amines from alcohols and NH 3 by Al 2 O 3 supported Ni catalysts.
  • Various Ni loadings were tested according to this paper (1-20%) and catalysts with 5wt%and 10 wt%are found to be optimal.
  • US4209424 teaches a catalyst for implementing a process for manufacturing amines from alcohols is composed of an active element in the transition metals family uniformly combined with a refractory porous structure with a specific surface of between 10 and 300m 2 /g and with a pore diameter less than 5000 A, wherein the transition metal content represents 30-70%of the total catalyst weight.
  • the catalyst and the process are specifically applicable to the ethanolamine-ammonia reaction with a view to producing ethylenediamine, piperazine, and useful byproducts and the conversion of reactant is not quite good.
  • the reaction is performed in the presence of a low loading transition metal catalyst, notably noble metal-free metal.
  • the present invention pertains to a process for preparing an amine, comprising reacting:
  • a catalyst comprising at least one transition metal chosen in the group consisting of Fe, Co, Ni, Cu, Zn and combinations thereof, and a support comprising at least one rare earth metal oxide M 1 and at least one metal oxide M 2 chosen in the group consisting of magnesia, alumina, silica, titanium oxide, zirconia and combinations thereof; wherein the loading of the transition metal is comprised from 0.10wt%to 5.00wt%with respect to total weight of the catalyst.
  • the invention also concerns a composition
  • a composition comprising:
  • a catalyst comprising at least one transition metal chosen in the group consisting of Fe, Co, Ni, Cu, Zn and combinations thereof, and a support comprising at least one rare earth metal oxide M 1 and at least one metal oxide M 2 chosen in the group consisting of magnesia, alumina, silica, titanium oxide, zirconia and combinations thereof; wherein the loading of the transition metal is comprised from 0.10wt%to 5.00wt%with respect to total weight of the catalyst.
  • 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) .
  • Lides refer to metals with atomic number 57 to 71.
  • rare earth metal As used herein, rare earth metal (REM) , as defined by IUPAC, is one of a set of seventeen chemical elements in the periodic table, specifically the fifteen lanthanides, as well as scandium and yttrium. Rare earth elements are cerium (Ce) , dysprosium (Dy) , erbium (Er) , europium (Eu) , gadolinium (Gd) , holmium (Ho) , lanthanum (La) , lutetium (Lu) , neodymium (Nd) , praseodymium (Pr) , promethium (Pm) , samarium (Sm) , scandium (Sc) , terbium (Tb) , thulium (Tm) , ytterbium (Yb) and yttrium (Y) .
  • Ce cerium
  • Dy dysprosium
  • Er erbium
  • Er europ
  • 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.
  • 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.
  • the present invention provides a process for preparing an amine, comprising reacting:
  • a catalyst comprising at least one transition metal chosen in the group consisting of Fe, Co, Ni, Cu, Zn and combinations thereof, and a support comprising at least one rare earth metal oxide M 1 and at least one metal oxide M 2 chosen in the group consisting of magnesia, alumina, silica, titanium oxide, zirconia and combinations thereof; wherein the loading of the transition metal is comprised from 0.10wt%to 5.00wt%with respect to total weight of the catalyst.
  • the transition metal of present invention is Ni.
  • the loading amount of metal on support of present invention could preferably be comprised from 0.50wt%to 4.50wt%with respect to total weight of catalyst and more preferably from 1.50wt%to 2.50wt%.
  • the rare earth metal oxide M 1 could be chosen in the group consisting of lanthanum oxide (La 2 O 3 ) , cerium oxide (CeO 2 ) , praseodymium oxide (Pr 6 O 11 ) , neodymium oxide (Nd 2 O 3 ) and samarium oxide (Sm 2 O 3 ) and more preferably cerium oxide (CeO 2 ) .
  • the support also comprises at least one metal oxide M 2 chosen in the group consisting of magnesia, alumina, silica, titanium oxide and zirconia.
  • the metal oxide could be alumina and more preferably ⁇ -Al 2 O 3 .
  • the weight ratio of metal oxide M 1 to metal oxide M 2 of present invention may be comprised from 0.05 to 0.50 and preferably from 0.10 to 0.30 and more preferably from 0.11 to 0.17.
  • the content of metal oxide M 1 and metal oxide M 2 in the support could be comprised from 80.00wt%to 100.00wt%with respect to total weight of support and preferably from 95.00wt%to 100.00wt%.
  • the support of present invention is composed of a mixture of metal oxide M 1 and metal oxide M 2 .
  • the mixture of metal oxide M 1 and metal oxide M 2 above mentioned could be prepared by all well-known ways, such as wet chemical method and precipitation method.
  • wet chemical method refers to impregnation of metal precursor on an oxide support in the excess of solvent thermally treated at a particular temperature. Typically, a known concentration of metal precursor solution is added to the support solution (thermally treated at a particular temperature) over a period of time and mixture is allowed to stir for another few hours at that temperature.
  • precipitation method refers to precipitating a known metal precursor or solutions over the oxide support in the presence of acid-base with a thermal treatment. Typically, first a known concentration of metal precursor is added to the support over a period of time followed by the addition of acid-base solution slowly to the solution and mixture is aged for few hours at that temperature.
  • Catalyst of present invention could be prepared by well-known ways, such as incipient wetness impregnation (IWI) method.
  • IWI incipient wetness impregnation
  • Incipient wetness impregnation also called capillary impregnation or dry impregnation
  • capillary 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.
  • the concentration profile of the impregnated compound depends on the mass transfer conditions within the pores during impregnation and drying.
  • the mixture of metal oxide M 1 and metal oxide M 2 comprised in support could be calcined before being prepared into catalyst.
  • the support comprising mixture of metal oxide M 1 and metal oxide M 2 prepared by wet chemical method could be directly prepared into catalyst by the way of incipient wetness impregnation (IWI) method.
  • IWI incipient wetness impregnation
  • the support comprising mixture of metal oxide M 1 and metal oxide M 2 prepared by precipitation method could be calcined at a temperature from 300°C to 800°C before being prepared into catalyst by the way of incipient wetness impregnation (IWI) method.
  • IWI incipient wetness impregnation
  • 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 /g to 150m 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.
  • the pore volume of catalyst may be comprised from 0.2cm 3 /g to 0.7cm 3 /g and preferably from 0.3cm 3 /g to 0.6cm 3 /g.
  • the total pore volume may be measured by N 2 adsorption at 77.4 K at a P/P 0 value of 0.99, where P is the N 2 pressure and P 0 is the saturation vapor pressure of N 2 .
  • 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 40%and preferably is comprised from40%to 95%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 percentage of supported catalyst may be comprised from 0.5%to 5%with respect to alcohol introduced.
  • 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 . 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°Cfor about 2 to 24 hours in the presence of oxygen.
  • the conversion of first reactant could reach at least 70%.
  • 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 chosen in the group consisting of Fe, Co, Ni, Cu, Zn and combinations thereof, and a support comprising at least one rare earth metal oxide M 1 and at least one metal oxide M 2 chosen in the group consisting of magnesia, alumina, silica, titanium oxide, zirconia and combinations thereof; wherein the loading of the transition metal is comprised from 0.10wt%to 5.00wt%with respect to total weight of the catalyst.
  • EXAMPLE 1 Cerium-aluminum mixed oxides prepared by wet chemical method (WI)
  • EXAMPLE 2 Cerium-aluminum mixed oxides prepared by precipitation method (PPT)
  • EXAMPLE 3 Cerium-titanium mixed oxides prepared by wet chemical method (WI)
  • Cerium-titanium mixed oxides was prepared by the same way as EXAMPLE 1. Titanium oxide was available from Evonik.
  • EXAMPLE 4 Cerium-zirconium mixed oxides prepared by wet chemical method (WI)
  • Cerium-zirconium mixed oxides was prepared by the same way as EXAMPLE 1. Zirconium oxide was available from Evonik.
  • Nickel was impregnated on prepared mixed oxides by Incipient Wetness Impregnation (IWI) method. 0.3032 g of nickel nitrate hexahydrate salt (Sigma Aldrich) was dissolved in 1.53 mL of distilled H 2 O to get an aqueous solution. 3 g mixed oxides of EXAMPLE 1 was directly impregnated with nickel nitrate solution and then calcined at 500°C for 6 hours in a muffle furnace.
  • IWI Incipient Wetness Impregnation
  • Nickel was impregnated on prepared mixed oxides by Incipient Wetness Impregnation (IWI) method.
  • IWI Incipient Wetness Impregnation
  • 0.3032 g of nickel nitrate hexahydrate salt (Sigma Aldrich) was dissolved in 1.53 mL of distilled H 2 O to get an aqueous solution.
  • 3 g mixed oxides of EXAMPLE 1 was first calcined at 500°C and then impregnated with nickel nitrate solution and further calcined at 500°C for 6 hours in a muffle furnace.
  • Nickel was impregnated on prepared mixed oxides by Incipient Wetness Impregnation (IWI) method. 0.3032 g of nickel nitrate hexahydrate salt (Sigma Aldrich) was dissolved in 1.53 mL of distilled H 2 O to get an aqueous solution. 3 g mixed oxides of EXAMPLE 2 was directly impregnated with nickel nitrate solution and then calcined at 500°C for 6 hours in a muffle furnace.
  • IWI Incipient Wetness Impregnation
  • Nickel was impregnated on prepared mixed oxides by Incipient Wetness Impregnation (IWI) method. 0.3032 g of nickel nitrate hexahydrate salt (Sigma Aldrich) was dissolved in 1.53 mL ofdistilled H 2 O to get an aqueous solution. 3 g mixed oxides of EXAMPLE 2 was first calcined at 500°C and then impregnated with nickel nitrate solution and further calcined at 500°C for 6 hours in a muffle furnace.
  • IWI Incipient Wetness Impregnation
  • Ni supported by cerium-titanium mixed oxides was prepared by the same way as EXAMPLE 5.
  • Solvay CeO 2 Actalys HSA5 was pre-calcined at 600°C and labelled as CeO 2 _600.
  • Ni supportedby CeO 2 _600 was prepared by the same way as EXAMPLE 5.
  • Ni supported by aluminum mixed oxide was prepared by the same way as EXAMPLE 5.
  • Ni supported by aluminum mixed oxide was prepared by the same way as EXAMPLE 5.
  • the catalytic tests were carried out in 30 mL stainless steel autoclaves geared with a pressure gauge a safety rupture disk.
  • the reactor was charged with 1.3 mmol 1-octanol, 3mL o-xylene as solvent and 65 mg catalyst of EXAMPLE 5 pre-reduced (ex-situ) under H 2 at 580°C for 30 minutes.
  • the reactor was sealed and evacuated by applying vacuum followed by charging NH 3 (7 bar) into the reactor.
  • the reactor was then placed on a hot plate equipped with a magnetic stirrer for 4 h at 180°C. After the reaction, the reactor was cooled down to room temperature and the mixture was analyzed on an Agilent 7890 GC equipped with a HP-5 capillary column with 5 wt%phenyl groups using biphenyl as the internal standard.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé efficace pour convertir des alcools en une amine, notamment primaire, avec des caractéristiques souhaitées tel qu'un faible coût, une grande sélectivité et une conversion élevée. Selon l'invention, la réaction est réalisée particulièrement, en présence d'un catalyseur de métal de transition à faible charge, notamment un métal sans métal noble.
PCT/CN2017/072998 2017-02-06 2017-02-06 Procédé de préparation d'amine par réaction d'amination directe WO2018141113A1 (fr)

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CN104039752A (zh) * 2012-01-11 2014-09-10 巴斯夫欧洲公司 在液相中制备仲胺的方法
CN104549314A (zh) * 2015-01-19 2015-04-29 南京大学连云港高新技术研究院 用于制备异丙胺的催化剂及其制备方法

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CN114539071A (zh) * 2022-03-09 2022-05-27 天津大学 一种正己醇胺化反应制正己胺的方法
CN114539071B (zh) * 2022-03-09 2024-05-03 天津大学 一种正己醇胺化反应制正己胺的方法

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