Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
• • 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
  • B01J23/76—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
  • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/889—Manganese, technetium or rhenium
  • B01J23/8892—Manganese
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
  • C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with 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
  • 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
  • B01J35/55—Cylinders or rings

Definitions

• the present invention relates to a process for the synthesis of secondary and/or tertiary amines by reaction in the gas phase of a primary or secondary alcohol and/or of a ketone with ammonia or a primary or secondary amine, in the presence of a catalyst comprising copper as the catalytically active metal, doped with manganese.
• the present invention also relates to the use of such a catalyst for the synthesis of secondary and/or tertiary amines.
• Amines and in particular alkylamines, are organic compounds with a wide variety of industrial applications. These compounds are used in particular as neutralizing agents, corrosion inhibitors, polymerization and/or crosslinking catalysts, and especially as synthesis intermediates in pharmacy, agrochemistry, electronics and in detergents.
• Examples of such compounds include:
• DIPA diisopropylamine
• Hünig base N-ethyldiisopropylamine
• DIPA also provides access to diisopropylaminosilane (DIPAS) and other volatile aminosilane derivatives, precursors of choice for the controlled deposition of silicon oxide or silicon nitride films in the manufacture of semiconductor devices;
• EMA N-ethylmethylamine
• DMEA N,N-dimethylethylamine
• DMIPA N,N-dimethylisopropylamine
• DIPA diisopropylamine
• MIPA monoisopropylamine
• This synthesis is usually carried out continuously via gas-phase or liquid-phase processes which lead to the majority or even almost exclusive production of MIPA, the main worldwide application of which remains glyphosate salt.
• ketones especially acetone
• alcohols especially isopropanol
• a high temperature and/or a large excess of nitrogenous reagent can be responsible for the formation of undesirable amino impurities.
• impurities formed we can note those resulting from secondary reactions of transamination or disproportionation which give rise to the formation of undesired amines.
• MIBK methyl isobutyl ketone
• DMBIPA N-(1,3-dimethylbutyl)isopropylamine
• DMA dimethylamine
• MMA monomethylamine
• MMA can also react with alcohol or ketone to form secondary amines that are difficult to separate from the desired amines.
• MMA for the manufacture of secondary amines of the alkylmethylamine type such as N-ethylmethylamine (EMA) or N-isopropylmethylamine
• EMA N-ethylmethylamine
• DMA dimethylamine
• ammonia depending on the reaction: r . , H 3 C
• DMA In the case of the manufacture of EMA from ethanol, the by-produced DMA can then react with the ethanol to form DMEA with a boiling point very close to that of EMA (36.5 vs 32.6°C) thus making the purification of EMA very complex to achieve the required specifications, especially for electronics applications.
• Ammonia can also react with ethanol to lead to the underproduction of mono-, di- and/or tri-ethylamines.
• the object of the present invention is to provide a process for the synthesis of secondary and/or tertiary amines that is simple and industrially viable.
• the present invention also aims to provide a process for the synthesis of secondary and/or tertiary amines in the gas phase that is easy to implement.
• Another object of the present invention is to provide a selective process for the synthesis of secondary or tertiary amines, preferably secondary amines.
• the object of the present invention is to provide an amination catalyst which makes it possible to obtain a satisfactory, or even high, selectivity for secondary or tertiary amines.
• the aim of the present invention is to provide an amination catalyst which limits, or even avoids, the transamination or disproportionation reactions of amines and thus the formation of amine impurities.
• the present invention meets all or part of the above objectives.
• the present inventor has discovered a new process for the preparation of amines using a catalyst making it possible to obtain satisfactory conversion and/or selectivity (s) or even high (s) or improved (s) in secondary and/or tertiary amines.
• the new catalyst limits or even avoids the formation of amine impurities, in particular those formed by transamination or disproportionation of amines.
• the reaction thus catalyzed is improved and easy to implement.
• the secondary and/or tertiary amines formed according to the invention can be purified more easily.
• the present inventor has also surprisingly discovered a process for the synthesis of highly selective secondary amines, in particular when the catalyst according to the invention is used and the primary and/or tertiary amines co-produced are recycled at the level of the amination step. Such a process makes it possible in particular to achieve a selectivity for secondary amines greater than 90%.
• the process according to the invention allows the selective synthesis of secondary amines directly from alcohol and/or ketone and ammonia.
• the present invention relates to a process for preparing secondary and/or tertiary amines comprising an amination step, said amination step being carried out by reacting a primary or secondary alcohol and/or a ketone with ammonia or a primary or secondary amine, in the gas phase and in the presence of a catalyst and hydrogen; said catalyst comprising copper doped (or promoted) with manganese, and the amount of manganese being between 1% and 10% by weight, relative to the total weight of the catalyst.
• the present invention also relates to the use of a catalyst comprising copper doped with manganese, the manganese being present in an amount of between 1% and 10% by weight relative to the total weight of the catalyst, for the preparation of secondary and/or tertiary amines.
• the term “catalyst” is understood to mean the catalytic composition comprising the active metals and the dopants (in particular copper and manganese, whatever their form, oxidized or not) as well as the support and any additives.
• the percentages by weight mentioned below correspond to the catalyst before preactivation or optional activation.
• copper is the active metal and that manganese is a dopant.
• dopant (also called “promoter”) is understood to mean a chemical substance or a composition of chemical substances capable of modifying, in particular improving, the catalytic activity of a catalyst.
• dopant means a chemical substance or a composition of chemical substances making it possible to improve the conversion and/or the selectivity of the catalyzed reaction compared to the catalyst without dopant.
• nitrogenous reagent means ammonia, primary or secondary amines used as reagents in the amination reaction as according to the invention.
• “Selectivity” means SA OR the selectivity for the amine (A) produced with respect to the reactants converted, calculated according to the following equation:
• SA 100 x (Zreagent / Zamine) x (number of moles of desired amine formed / number of moles of reactant converted), with Zamine being the stoichiometric coefficient of the amine and Zreagent being the stoichiometric coefficient of the reactant.
• the reactant used for the above calculation is the limiting reactant.
• the process according to the invention makes it possible to obtain a selectivity for secondary amines greater than or equal to 50%, for example between 50% and 90%, preferably between 70% and 90%.
• the process according to the invention makes it possible to obtain a selectivity for tertiary amines of between 90% and 100%, preferably between 90% and 99%.
• amino impurity is understood in particular to mean any undesired primary, secondary or tertiary amine and obtained following a parasitic transamination or disproportionation reaction or following self-condensation of the ketone. It is sought in particular to limit, or even to avoid, the formation of these impurities.
• the catalyst according to the invention comprises copper doped with manganese, the amount of manganese being between 1% and 10% by weight, relative to the total weight of the catalyst.
• the amount of copper in the catalyst is less than or equal to 60% by weight, relative to the total weight of the catalyst.
• the amount of copper is between 15% and 60% by weight, relative to the total weight of the catalyst.
• the amount of copper is in particular between 20% and 60% by weight, preferably between 35% and 50% by weight, more preferably between 40% and 50% by weight, for example between 44% and 48% by weight, by relative to the total weight of the catalyst.
• the copper may be present in the form of copper oxide(s), preferably in the CuO form.
• the amount of manganese is between 4% and 10% by weight, more preferably between 4% and 8% by weight, relative to the total weight of the catalyst.
• the manganese can be present in the form of oxide(s), preferably in the form of manganese dioxide (MnO 2 ) or Mn 3 O 4 .
• the catalyst may also comprise a support chosen from the group consisting of: alumina (Al 2 O 3 ), silica (SiO 2 ), titanium dioxide, zirconia, as well as mixtures of two or more of them, preferably alumina and/or silica.
• the catalyst comprises:
• said catalyst comprises copper in CuO form and manganese in MnO 2 form and/or in Mn 3 O 4 form. Copper and manganese are in particular present in the form of oxide(s) before activation of the catalyst.
• said catalyst consists essentially, or even consists, of copper in oxidized form, of manganese in oxidized form, of a support such as alumina or silica and of optional additives.
• the catalyst comprises:
• manganese oxides (expressed as MnO 2 ), relative to the total weight of the catalyst.
• the catalyst does not comprise any active metal other than copper (ie whether in elemental form or in the form of an organic or inorganic compound, for example a metal oxide).
• the catalyst does not comprise any dopant other than manganese (ie whether in the elementary form or in the form of a compound organic or inorganic, for example a metal oxide).
• said catalyst does not include chromium and/or nickel.
• the catalyst does not comprise a rare earth.
• Rare earth means scandium, yttrium and lanthanides such as lanthanum, cerium, praseodymium, neodymium and dysprosium.
• the catalyst does not include cerium.
• the catalyst does not include an element from groups 8, 9 and 10 of the periodic table (formerly group VIII).
• the catalyst does not include platinum, palladium, ruthenium or rhodium. More particularly, the catalyst according to the invention does not comprise any rare earth or element from groups 8, 9 and 10 of the periodic table.
• other metal compounds can be included in the catalyst.
• such compounds mention may be made of molybdenum, tungsten, chromium, vanadium and magnesium. They can be in oxidized form, for example in MoO 2 , WO 2 , Cr 2 O 3 , V 2 O 5 and MgO form.
• the catalyst can also comprise other additives such as stabilizers and/or shaping aids such as graphite, which are customary in the field of catalysts. Generally, these compounds are included in an amount of between 1% and 15% by weight, relative to the total weight of the catalyst.
• the catalyst is preferably used in the form of pellets with a diameter of between 3 and 6 mm and a length of between 3 and 6 mm.
• HySat® 200 tab 4.8X4.8 catalyst from Clariant®.
• the process according to the invention makes it possible in particular to form secondary and/or tertiary alkylamines.
• the amine formed is of the following general formula (A):
• Ri represents a linear, branched or cyclic alkyl radical, comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 4 carbon atoms optionally substituted (preferably by an aryl radical such than phenyl);
• R 2 is chosen from the hydrogen atom and a linear, branched or cyclic alkyl radical, comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 4 carbon atoms optionally substituted (preferably by an aryl radical such as a phenyl); or
• Ri and R 2 form together and with the nitrogen atom which carries them, a cyclic radical, saturated or partially or totally unsaturated, optionally substituted and which may comprise one or more heteroatoms chosen from oxygen and nitrogen; said cycle possibly comprising a number of vertices comprised between 3 and 9, preferably 5 or 6 vertices;
• R 3 represents a linear, branched or cyclic hydrocarbon chain, aromatic or not, comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 4 carbon atoms and optionally substituted (by preferably by an aryl radical such as a phenyl);
• R 4 is chosen from the hydrogen atom and a linear, branched or cyclic hydrocarbon chain, aromatic or not, comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 4 carbon atoms and optionally substituted (preferably by an aryl radical such as a phenyl); or
• R 3 and R 4 form together and with the carbon atom which carries them, a cyclic radical, saturated or partially unsaturated, optionally substituted and which may comprise one or more heteroatoms chosen from oxygen and nitrogen; said cycle comprising a number of vertices comprised between 3 and 9, preferably 5 or 6 vertices.
• Ri and/or R 2 when they are represented by an alkyl radical as defined above may be substituted by one or more aryl group(s) containing between 6 and 10 carbon atoms, preferably a phenyl.
• R 3 and/or R 4 when they are represented by an alkyl radical as defined above may be substituted by one or more aryl group(s) containing between 6 and 10 carbon atoms, of preferably a phenyl.
• R 3 and R 4 when they form together and with the carbon atom which carries them, a cyclic radical, saturated or partially unsaturated, can be substituted by one or more group(s) alkyl(s) comprising between 1 and 10 atoms carbon, preferably by one or more methyl group(s).
• Ri represents a linear or branched alkyl radical, comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 4 carbon atoms;
• R 2 is chosen from the hydrogen atom and a linear or branched alkyl radical, comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 4 carbon atoms;
• R 3 represents a linear or branched alkyl radical, comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 4 carbon atoms;
• R 4 is chosen from the hydrogen atom and a linear or branched alkyl radical, comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 4 carbon atoms.
• R 2 and/or R 4 is a hydrogen atom.
• the amine formed is chosen from the group consisting of: diisopropylamine (DIPA), di-n-propylamine (DPA), N-ethylmethylamine (EMA), N-isopropylmethylamine, N-ethylpropylamine, N-ethylisopropylamine, N-ethylbutylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-ethylbenzylamine, N,N-dimethylethylamine (DMEA), N,N-dimethylisopropylamine (DMIPA), (N,N- dimethylpropylamine (DMPA), N,N-dimethylbutylamine, N,N-diethylmethylamine (DEMA), triethylamine (TEA) and di-sec-butylamine (DB2A).
• DIPA diisopropylamine
• DPA di-n-propylamine
• EMA
• the amine formed is chosen from the group consisting of DIPA, DMEA, DMIPA and EMA; even more preferentially DIPA and EMA.
• Said amination step may in particular correspond to one or more of the following reactions:
• secondary and/or tertiary amines preferably secondary amines.
• an alcohol of formula (I) and/or a ketone of formula (II) is used with ammonia or an amine of formula (III): in which Ri, R 2 , R3 and R 4 are as defined previously, with R 4 different from the hydrogen atom for the ketone of formula (II).
• alcohols of formula (I) mention may be made of the following: ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, n-pentanol, n-hexanol, methyl isobutyl carbinol, n-heptanol, 2 -ethylhexanol, n-octanol, diisobutylcarbinol, cyclohexanol, benzyl alcohol, 2-phenylethanol and 3,3,5-trimethylcyclohexanol.
• ketones of formula (II) mention may be made of the following: acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone (MIBK), diisobutyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, acetophenone, isophorone and 3,3,5 -trimethylcyclohexanone.
• MEK methyl ethyl ketone
• MIBK methyl isobutyl ketone
• MIBK methyl isobutyl ketone
• the preferred amine reactants of formula (III) are the following: methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butylamine, isobutylamine, 2-butylamine, pyrrolidine, piperidine, morpholine, cyclohexylamine, benzylamine and 2-phenylethylamine.
• DIPA diisopropylamine
• DPA di-n-propylamine
• EMA N-ethylmethylamine
• MMA monomethylamine
• DMEA N,N-dimethylethylamine
• DMA dimethylamine
• DMIPA N,N-dimethylisopropylamine
• DMPA N,N-dimethylpropylamine
• the amination step according to the invention makes it possible to form secondary and/or tertiary amines (and water) in the gas phase and in the presence of hydrogen. Said process can be carried out in batch or continuously, preferably continuously.
• gas phase or “gas phase”, it is meant in particular that the reactants (alcohol and/or ketone and nitrogenous reactant) are in the gaseous state, under the temperature and pressure conditions of said amination step.
• the gas phase reactor can be fed by first passing the reactants, which are liquid, through an evaporator (for example heated with steam or by any other known means). The temperature of the evaporator is set in such a way as to ensure the passage of the reactants from the liquid state to the gaseous state under the pressure conditions implemented. The gases formed can then be carried towards the inlet of the reactor, for example with the flow of hydrogen and, where appropriate, ammonia.
• the catalytic reaction can be carried out under hydrogen (H 2 ) pressure, preferably in excess.
• H 2 hydrogen
• the molar ratio of hydrogen to alcohol and/or ketone is between 0.5 and 20 mol/mol, preferably between 1 and 15 mol/mol and more preferably between 2 and 10 mol/mol.
• the amination reaction is carried out through one or more fixed bed(s) of catalyst such as according to the invention.
• the fixed bed(s) may comprise one or more layer(s) of catalyst according to the invention.
• the metal concentration for example in Cu and/or in Mn
• the number of layers which can vary depending on the length of the catalytic bed.
• the amination reaction can be carried out within one (or more) tubular or multitubular reactor(s), in series or in parallel.
• the amination reaction can be carried out under an absolute pressure in the reactor of less than or equal to 30 bars, preferably between 1 and 20 bars and more preferably between 2 and 10 bars.
• the amination reaction can be carried out at a temperature between 120°C and 220°C, preferably between 140°C and 200°C and more preferably between 150°C and 190°C.
• Maintaining the temperature of the reactor can be ensured by means of a heat transfer fluid which can be heated by steam, electrically or by any other known means and which can be cooled by means of a water and/or ethylene glycol refrigeration circuit. or any other known refrigerant.
• the heat transfer fluid may in particular comprise a mixture of molten nitrate salts (KNO 3 , NaNO 3 , LiNO 3 ).
• the amination reaction can be carried out with a molar ratio of alcohol and/or ketone to nitrogenous reagent of between 0.1 and 20 mol/mol, preferably between 0.5 and 10 mol/mol and more preferably between 1 and 5 mol. /mol.
• the mass flow rate of alcohol and/or ketone per unit volume of catalytic bed can be between 0.05 and 1.0 kg/L.h, preferably between 0.10 and 0.80 kg/L.h and more preferably between 0.15 and 0.60 kg/L.h.
• the preparation process according to the invention may also comprise the following steps: i) amination step as defined above; said step making it possible to obtain an outgoing stream G comprising a secondary and/or tertiary amine and water; ii) at least one flow separation step G, so as to obtain:
• a flux comprising the secondary amine and/or the tertiary amine optionally, a step for separating the stream comprising both a secondary amine and a tertiary amine, so as to obtain: a stream comprising the secondary amine; and a flux comprising the tertiary amine; and iv) optionally, recycling the stream comprising the tertiary amine, to step i).
• the secondary and/or tertiary amines can then be recovered and optionally purified.
• said method may comprise the following steps: a) amination step as defined above; said step making it possible to obtain an outgoing flow G in the gaseous state comprising a secondary and/or tertiary amine, water and unreacted hydrogen; b) condensation and separation of said stream G, so as to obtain:
• a stream K comprising water, and a stream L comprising the secondary amine and/or the tertiary amine; e) optionally, separation of the stream L when the latter comprises both a secondary amine and a tertiary amine, so as to obtain: a stream M comprising the secondary amine; and an N stream comprising the tertiary amine; and f) optionally, recycling of the flow N, in step a).
• Steps b) and d) may or may not be simultaneous.
• the gas stream G′′ may comprise traces of secondary and/or tertiary amines and possibly primary amines.
• ammonia When ammonia is used as a reactant and does not fully react, it can end up in the G” stream as well as in trace amounts in G’. In this case, an additional separation of the stream G' and/or G" can be carried out to recover the ammonia and recycle it to step a).
• the corresponding primary amine can also be formed as a by-product.
• This primary amine is found successively in the G, G' and L streams (and possibly in G” in trace amounts). It can be separated from the stream L at the end of separation step e) so as to obtain a stream P comprising it. Said stream P can be recycled to amination step a).
• the separation stages b), d) and e) can be carried out by any known means (for example by distillation or decantation) and preferably by distillation.
• the secondary and/or tertiary amines produced can then be purified if necessary.
• fractional distillation is used by means of a series of distillation columns operating continuously.
• said method may comprise the following steps: a) amination step as defined above; said step making it possible to obtain an outgoing flow G in the gaseous state comprising a secondary and/or tertiary amine, water and optionally the unreacted reactants as well as the alcohol resulting from the hydrogenation reaction of the ketone to alcohol; b) condensation and separation of said stream G, so as to obtain:
• liquid stream G' comprising a secondary and/or tertiary amine, water and possibly the unreacted reactants as well as the alcohol resulting from the hydrogenation reaction of the ketone to alcohol, and
• a hydrogen gas stream G comprising traces of secondary and/or tertiary amine, and possibly traces of unreacted reagents as well as traces of the alcohol resulting from the hydrogenation reaction of the ketone in alcohol; c) optionally, recycling of the flow G” to step a); d) separation of the flow G', so as to obtain:
• the catalyst can be activated before step a).
• the catalysts are generally loaded into the reactor in oxidized or pre-reduced form (that is to say that the metals, such as Or and Mn, are wholly or partly in the form of oxides).
• the catalyst is preferably activated beforehand.
• the activation takes place by reduction, preferably in the reactor in which the amination step will be carried out (in situ activation).
• the activation of the catalyst is carried out by conventional methods, well known to those skilled in the art. It makes it possible to obtain the active metal species for hydrogenation or dehydrogenation by reduction of the corresponding oxidized forms.
• the catalyst can be activated under a flow of hydrogen (H 2 ) at a temperature between 150°C and 400°C, for example between 2®° and 400°, preferably between 250°C and 350°C.
• the present invention also relates to the use of a catalyst as defined above, for a process for the preparation of secondary and/or tertiary amines as defined above, and in particular for the amination stage such as described above.
• the selectivities are calculated on the basis of the mass compositions of the crude mixtures leaving the reaction zone; compositions determined by gas chromatographic analyses.
• NL NormoLitre corresponds to a volume of 1 L under normal pressure (1.013 bar) and temperature (273 K) conditions.
• the tests are carried out in a vertical tubular reactor containing a catalytic bed with a volume of 7 L and a length of 2.8 m.
• the reactor is immersed in a bath of molten nitrate salts (KNO 3 , NaNO 3 , LiNO 3 ) electrically heated and cooled by circulating water through a cooling pin.
• KNO 3 , NaNO 3 , LiNO 3 molten nitrate salts
• the three-layer catalytic bed comprises a catalyst based on nickel in cylindrical pellets (4.8x4.8 mm) of the following composition by weight before activation:
• the single-layer catalytic bed comprises cylindrical pellets (4.8 ⁇ 4.8 mm) of a manganese-doped copper-based catalyst on an alumina (Al 2 O 3 ) support; copper and manganese being in oxidized form before activation.
• the copper concentration by weight of the catalyst is 46% (corresponding to 57.6% expressed as CuO) and the manganese concentration by weight is 6% (corresponding to 9.5% expressed as MnO 2 ) before activation.
• the reactor is then fed from the bottom upwards with a mixture of fresh acetone, recycled isopropanol, ammonia and hydrogen which has been evaporated beforehand and preheated through a steam exchanger.
• the reactor pressure is maintained at 4 bar absolute and the temperature at 150°C.
• Catalyst C1 makes it possible to obtain a much greater selectivity for diisopropylamine than the nickel catalyst and without secondary formation of ElPA, which is difficult to separate from DIPA by distillation. It is possible to directly achieve a DIPA selectivity close to 90% without recycling Ml PA.
• the catalytic bed is made of cylindrical pellets (6 ⁇ 5 mm) with a composition by weight before activation: 76% CuO, 3% MgO, 1.5% Cr 2 O 3 , on silica (SiO 2 ).
• the reactor is fed from the bottom upwards with a mixture of fresh acetone and/or fresh and/or recycled isopropanol, DMA and hydrogen previously evaporated and preheated through an electrically heated exchanger.
• the synthesis is carried out with a large molar excess of acetone and/or isopropanol relative to the DMA, under a pressure of 8 bars and at a temperature of 185°C.
• the selectivity for DMIPA relative to DMA is 8 to 9% lower than that obtained with catalyst C1. This may be due to a greater disproportionation of DMA into TMA and MMA; MMA then reacts with acetone to form methylisopropylamine (Me-IPA) and methyldiisopropylamine (Me-DIPA).
• Me-IPA methylisopropylamine
• Me-DIPA methyldiisopropylamine
• Example No. 3 Synthesis of ethylmethylamine (EMA - secondary amine) and/or diethylmethylamine (DEMA - tertiary amine) from ethanol and MMA, with or without DEMA recycling
• the synthesis is carried out with a molar excess of ethanol relative to the MMA, in the presence of hydrogen, under a pressure of 8 bars and at a temperature of 175°C and, if necessary, with a recycling of DEMA.
• the results at 512 h and 760 h of operation correspond to tests carried out with recycling of the DEMA recovered at the end of the reaction by distillation and reintroduced into the reactor. It can be seen that, depending on the flow rate of recycled tertiary amine (DEMA), the selectivity for secondary amine (EMA) with respect to MMA can become greater than 90%.
• DEMA recycled tertiary amine
• Example No. 4 Synthesis of the secondary amine ethylcropylamine (EPA) from ethanol and MEA
• the conversion of the MEA at the reactor outlet is 81% and the EPA is obtained with a selectivity of 92% with respect to the converted MEA.
• Example No. 5 Synthesis of the secondary amine di-n-tropylamine (PPA) from n-propanol and ammonia, with recycling of n-PA (n-propylamine) and TPA (tripropylamine)
• PPA secondary amine di-n-tropylamine
• Example No. 6 Synthesis of the tertiary amine dimethybropylamine (DMPA) from n-propanol and DMA
• Example No. 7 Synthesis of the tertiary amine dimeth ethylamine (DMEA) from ethanol and DMA - Alternating syntheses
• the implementation of the catalytic bed is done alternately in the production of DMEA and in the production of DMIPA in order to evaluate the stability of the catalyst after different production campaigns.
• the catalyst can be easily regenerated by an oxidation step followed by a new reduction with hydrogen without loss of performance.

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