Process for preparing secondary and / or tertiary amines in the presence of manganese-doped copper catalyst - Patents.com

Abstract

The present invention relates to a process for making secondary and / or tertiary amines comprising an amination step, said amination step being carried out by gas phase reaction of a primary or secondary alcohol and / or ketone with ammonia or a primary or secondary amine in the presence of a catalyst, said catalyst comprising copper and doped with manganese, the amount of manganese being between 1% and 10% by weight relative to the total weight of the catalyst.

Description

[Technical field]

[0001] The present invention relates to a process for the synthesis of secondary and / or tertiary amines by gas phase reaction of primary or secondary alcohols and / or ketones with ammonia or primary or secondary amines in the presence of a catalyst comprising manganese doped copper as catalytically active metal.

[0002] The present invention also relates to the use of such a catalyst (cata) for the synthesis of secondary and / or tertiary amines. [Background technology]

[0003] Amines and, in particular, alkylamines, are organic compounds with very diverse industrial applications: they are used, in particular, as neutralizing agents, corrosion inhibitors, polymerization and / or crosslinking catalysts, and as synthetic intermediates in pharmaceuticals, agrochemicals, electronics and cleaning applications, among others.

[0004] Possible examples of such compounds include: - Diisopropylamine (DIPA) (a secondary amine) which is the main synthetic precursor to N-ethyldiisopropylamine (Hunig's base) used as an acid scavenger in the synthesis of pharmaceutical or agrochemical active ingredients (DIPA is also the access point for diisopropylaminosilane (DIPAS) and other volatile aminosilane derivatives, which are the precursors of choice for the controlled deposition of silicon oxide or nitride films in the fabrication of semiconductor devices); - zirconium compounds which are the volatile precursor of choice for the production of active pharmaceutical molecules intended to treat degenerative diseases of the nervous system, for example as tetrakis(ethylmethylamino)hafnium, N-ethylmethylamine (EMA), which is involved in the synthesis of metal salts or for the production of deposited metal films by CVD (chemical vapor deposition) or ALD (atomic layer deposition) in the fabrication of semiconductors; and - N,N-Dimethylethylamine (DMEA) and N,N-Dimethylisopropylamine (DMIPA), tertiary amines used as polymerization catalysts for polyurethane resins for the production of casting molds by the "cold box" method Examples include:

[0005] The preparation of secondary and / or tertiary amines by amination of alcohols and / or ketones with ammonia or primary or secondary amines in the presence of hydrogen and a hydrogenation / dehydrogenation catalyst is widely known (Amines, Aliphatic, sections 3.1 and 3.2, Ullmann's Encyclopedia of Industrial Chemistry, 2015, Wiley Online Library). The preparation proceeds in the liquid or gas phase depending on the nature of the starting materials and / or the type of catalyst.

[0006] One possible synthesis example is that of diisopropylamine (DIPA), which is conventionally obtained as a by-product in processes for producing monoisopropylamine (MIPA) by catalytic amination of acetone and / or isopropanol with ammonia.

[0007] The synthesis from acetone is carried out according to the following reaction scheme: [ka]

[0008] In the case of isopropanol, the reaction is similar after prior in situ dehydrogenation of isopropanol to acetone. [ka]

[0009] This synthesis is usually carried out continuously via gas or liquid phase processes and produces primarily or almost exclusively MIPA, whose primary use worldwide remains as a glyphosate salt.

[0010] To obtain DIPA selectively, DIPA can be produced directly from MIPA and acetone as starting reactants, or MIPA can be continuously disproportionated at high temperature through a fixed bed of catalyst or zeolite, usually according to the following scheme: [ka]

[0011] It is therefore clear that the most selective synthesis of DIPA, and secondary amines in general, requires either carrying out the amination of acetone (more generally an aldehyde or ketone) or isopropanol (more generally an alcohol) with a primary amine (MIPA in the case of DIPA) or carrying out a disproportionation of the latter compound. These two techniques therefore require the pre-production of a primary amine as the main product, which is then converted to a secondary amine.

[0012] There is therefore a need for a method for the synthesis of secondary amines, starting from ketones and / or alcohols and ammonia, in particular for the synthesis of secondary amines, to synthesize secondary and / or tertiary amines as main products (and not as by-products).

[0013] There is a need for a method for synthesizing secondary and / or tertiary amines that is easy to implement and industrially viable.

[0014] Moreover, ketones (especially acetone) are the preferred starting material when they are cheaper than the corresponding alcohols (especially isopropanol). However, the reductive amination of ketones with ammonia or primary or secondary amines is a much more exothermic process than the reductive amination of alcohols. If the amination reaction of ketones is carried out continuously with a fixed catalyst bed, this high level of heat of formation leads to a substantial increase in the temperature within the catalyst grains, which leads to secondary reactions, resulting in a decrease in selectivity, or the need to work with a lower volumetric flow rate (LHSV) of ketone per unit volume of catalyst, resulting in a decrease in productivity relative to the same process carried out starting from alcohols. This higher temperature can also have a negative impact on the aging of the catalyst and therefore on its lifespan.

[0015] Thus, high temperatures and / or a substantial excess of nitrogenous reactants can result in the formation of undesirable amine impurities, including those resulting from secondary reactions of transamination or disproportionation that result in the formation of unwanted amines.

[0016] For example, and not exhaustively, in the case of DIPA, decomposition of acetone to acetaldehyde results in the formation of, among others, monoethylamine (MEA) and N-ethylisopropylamine (EIPA) according to the following scheme: [ka] and / or [ka]

[0017] Furthermore, the concomitant self-condensation of acetone results in the formation of methyl isobutyl ketone (MIBK), which, upon reductive amination with ammonia and monoisopropylamine, leads to the secondary formation of 1,3-dimethylbutylamine (1,3-DMBA) and N-(1,3-dimethylbutyl)isopropylamine (DMBIPA), respectively.

[0018] Similarly, when dimethylamine (DMA) is used to prepare tertiary amines of the dimethylalkylamine type, such as DMEA, DMIPA, or DMPA, the DMA can be partially disproportionated to trimethylamine (TMA) and monomethylamine (MMA) according to the following reaction: [ka]

[0019] MMA can also react with alcohols or ketones to form secondary amines that are difficult to separate from the desired amine.

[0020] When MMA is used to prepare secondary amines of the alkylmethylamine type, such as N-ethylmethylamine (EMA) or N-isopropylmethylamine, the MMA can be partially disproportionated to dimethylamine (DMA) and ammonia according to the following reaction: [ka]

[0021] In the manufacture of EMA starting from ethanol, the by-product DMA can then react with ethanol to form DMEA, whose boiling point is very close to that of EMA (36.5°C versus 32.6°C), which makes it very complicated to purify EMA to meet the required specifications, especially for electronics applications. Ammonia can also react with ethanol to produce the by-products monoethylamine, diethylamine and / or triethylamine.

[0022] It is therefore clear that current amination reactions result in the formation of many amine impurities that make it particularly difficult to obtain good (let alone high) purity secondary and / or tertiary amines.

[0023] Thus, there is also a need for methods for synthesizing secondary and / or tertiary amines that are selective for the desired secondary or tertiary amine, and in particular that limit or prevent the formation of amine impurities. Summary of the Invention [Problem to be solved by the invention]

[0024] It is an object of the present invention to provide a simple, industrially viable method for the synthesis of secondary and / or tertiary amines.

[0025] Another object of the present invention is to provide a gas phase method for the synthesis of secondary and / or tertiary amines that is easy to implement.

[0026] It is a further object of the present invention to provide a selective method for the synthesis of secondary or tertiary amines, preferably secondary amines.

[0027] One object of the present invention is to provide an amination catalyst which makes it possible to obtain good or even higher selectivities towards secondary or tertiary amines.

[0028] It is an object of the present invention to provide an amination catalyst which limits or even prevents the transamination or disproportionation of amines, thereby limiting or even preventing the formation of amine impurities. [Means for solving the problem]

[0029] The present invention fulfills all or part of the above objectives.

[0030] The inventors have found a new method for making amines using a catalyst that allows obtaining good or even higher or improved conversion and / or selectivity towards secondary and / or tertiary amines. The new catalyst limits or even prevents the formation of amine impurities, especially those formed by transamination or disproportionation of amines. In this way, the catalyzed reactions are improved and easier to achieve. The secondary and / or tertiary amines formed according to the present invention can be more easily purified.

[0031] The inventors have also surprisingly found a process for the synthesis of secondary amines which is highly selective, especially when the catalyst according to the invention is used and the by-produced primary and / or tertiary amines are recycled to the amination step, such a process being in particular capable of obtaining a selectivity of more than 90% towards the secondary amines.

[0032] In particular, the method according to the invention allows the selective synthesis of secondary amines starting directly from alcohols and / or ketones and ammonia.

[0033] The present invention therefore relates to a method for making secondary and / or tertiary amines comprising an amination step, said amination step being carried out by gas phase reaction of a primary or secondary alcohol and / or a ketone with ammonia or a primary or secondary amine in the presence of a catalyst and hydrogen, wherein the catalyst comprises manganese doped (or promoted) copper and the amount of manganese is between 1% and 10% by weight based on the total weight of the catalyst.

[0034] The present invention also relates to the use of a catalyst comprising copper doped with manganese for making secondary and / or tertiary amines, wherein the manganese is present in an amount between 1% and 10% by weight relative to the total weight of the catalyst. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] definition According to the invention, "catalyst" refers to a catalyst composition comprising active metals and dopants (in particular copper and manganese in any form, oxidized or otherwise), and furthermore a support and any additives. The weight percentages below correspond to the catalyst before any preactivation or activation.

[0036] In the catalyst of the present invention, copper is understood to be the active metal and manganese is the dopant. "Dopant" (also known as "promoter") refers to a chemical or composition of chemicals capable of modifying, and in particular enhancing, the catalytic activity of a catalyst. For example, "dopant" refers to a chemical or composition of chemicals for enhancing the conversion and / or selectivity of a catalyzed reaction relative to a catalyst without the dopant.

[0037] "Nitrogenous reactant" refers to ammonia and / or primary or secondary amines used as reactants in an amination reaction as per the present invention.

[0038] The "selectivity" is calculated according to the following formula: A or the selectivity for the amine (A) formed relative to the reactants converted: S A = 100 x (Z reactant / Z amine) x (moles of target amine formed / moles of reactant converted) where Zamine is the stoichiometric coefficient of the amine and Zreactant is the stoichiometric coefficient of the reactant. The reactant used for the above calculation is preferably the limiting reactant.

[0039] In particular, the method according to the present invention allows obtaining a selectivity towards secondary amines of 50% or more, for example 50% to 90%, preferably 70% to 90%.

[0040] In particular, the process according to the invention makes it possible to obtain a selectivity towards tertiary amines of between 90% and 100%, preferably between 90% and 99%.

[0041] "Amine impurities" refers in particular to any unwanted primary, secondary or tertiary amines obtained after concomitant reactions of transamination or disproportionation or after self-condensation of ketones. In particular, the aim is to limit or even prevent the formation of these impurities.

[0042] Catalyst according to the present invention The catalyst according to the present invention comprises copper doped with manganese, the amount of manganese being 1% to 10% by weight relative to the total weight of the catalyst. The amount of copper in the catalyst is preferably 60% by weight or less relative to the total weight of the catalyst. In particular, the amount of copper is 15% to 60% by weight relative to the total weight of the catalyst. The amount of copper is in particular 20% to 60% by weight, preferably 35% to 50% by weight, more preferably 40% to 50% by weight, for example 44% to 48% by weight, relative to the total weight of the catalyst. The copper may be present in the form of one or more copper oxides, preferably in the form of CuO.

[0043] The amount of manganese is preferably between 4% and 10% by weight, more preferably between 4% and 8% by weight, based on the total weight of the catalyst. The manganese may be in the form of one or more oxides, preferably manganese dioxide (MnO 2 ) or Mn 3 O 4 It may exist in the form:

[0044] The catalyst is alumina (Al 2 O 3 ), silica (SiO 2 ), titanium dioxide, zirconia, and mixtures of two or more thereof, preferably alumina and / or silica.

[0045] In particular, the catalyst comprises: - 20% to 60% by weight, preferably 35% to 50%, for example 40% to 50% by weight of copper relative to the total weight of the catalyst, - from 1% to 10% by weight, preferably from 4% to 10%, for example from 4% to 8% by weight, of manganese relative to the total weight of the catalyst, and - Contains alumina.

[0046] The catalyst preferably comprises copper in the form of CuO, as well as MnO 2 and / or Mn 3 O 4 The copper and manganese are present, in particular in the form of one or more oxides, prior to activation of the catalyst. The catalyst preferably consists essentially of, or further consists of, copper in oxidized form, manganese in oxidized form, a support such as alumina or silica, and any additives.

[0047] More particularly, the catalyst comprises: - from 25% to 75% by weight, preferably from 40% to 65% by weight, of copper oxide (expressed as CuO) relative to the total weight of the catalyst, and - 1 wt% to 20 wt%, preferably 5 wt% to 15 wt%, of manganese oxide (MnO 2 (expressed as

[0048] The catalyst preferably does not contain any active metals other than the copper (i.e. whether in elemental form or in the form of an organic or inorganic compound, e.g. a metal oxide). The catalyst preferably does not contain any dopants other than the manganese (i.e. whether in elemental form or in the form of an organic or inorganic compound, e.g. a metal oxide). In particular, the catalyst does not contain chromium and / or nickel.

[0049] Preferably, the catalyst does not contain rare earth metals, by which is meant scandium, yttrium and the lanthanides such as lanthanum, cerium, praseodymium, neodymium, dysprosium, etc. More particularly, the catalyst does not contain cerium.

[0050] Preferably, the catalyst does not contain elements from groups 8, 9 and 10 (previously group VIII) of the periodic table. In particular, the catalyst does not contain platinum, palladium, ruthenium and rhodium. More particularly, the catalyst does not contain rare earth metals or elements from groups 8, 9 and 10 of the periodic table.

[0051] According to another embodiment, other metal compounds may be included in the catalyst. Possible non-limiting examples of such compounds include molybdenum, tungsten, chromium, vanadium and magnesium. They may be in the form of oxides, e.g., MoO 2 , WO 2 , Cr 2 O 3 , V 2 O 5 and MgO.

[0052] The catalyst may also contain other additives, such as stabilizers and / or forming aids, such as graphite, as are customary in the field of catalysis. These compounds are generally present in an amount ranging from 1% to 15% by weight relative to the total weight of the catalyst.

[0053] The catalyst is preferably used in the form of pellets having a diameter of 3 to 6 mm and a length of 3 to 6 mm.

[0054] One example that may be mentioned is the catalyst HySat® 200 tab 4.8×4.8 from Clariant®.

[0055] The method according to the present invention The process according to the invention allows in particular the formation of secondary and / or tertiary alkylamines. The amines formed are preferably of the following general formula (A): [ka]

[0056] R 1represents a straight chain alkyl radical, branched chain alkyl radical or cyclic alkyl radical containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms, optionally substituted (preferably by an aryl radical such as phenyl); R 2 is selected from a hydrogen atom and a linear, branched or cyclic alkyl radical containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms, optionally substituted (preferably by an aryl radical, such as phenyl); or R 1 and R 2 together and with the nitrogen atom which carries them, form a saturated or partially or fully unsaturated cyclic radical, which is optionally substituted and may contain one or more heteroatoms selected from oxygen and nitrogen; said cyclic moiety may contain a number of 3- to 9-membered rings, preferably 5- or 6-membered rings; R 3 represents an optionally substituted (preferably by an aryl radical, such as phenyl) linear, branched or cyclic aromatic or non-aromatic hydrocarbon chain containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms; R 4 is selected from hydrogen atoms and optionally substituted (preferably by an aryl radical, such as phenyl) linear, branched or cyclic aromatic or non-aromatic hydrocarbon chains containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms; or R 3 and R 4together and with the carbon atoms which carry them form a saturated or partially unsaturated cyclic radical, which is optionally substituted and may contain one or more heteroatoms selected from oxygen and nitrogen; said cyclic moieties contain many 3- to 9-membered rings, preferably 5- or 6-membered rings.

[0057] R 1 and / or R 2 When represented by an alkyl radical as defined above, it may be substituted by one or more aryl groups containing 6 to 10 carbon atoms, preferably phenyl.

[0058] R 3 and / or R 4 When represented by an alkyl radical as defined above, it may be substituted by one or more aryl groups containing 6 to 10 carbon atoms, preferably phenyl.

[0059] R 3 and R 4 may, when taken together and with the carbons which carry them, form a saturated or partially unsaturated cyclic radical, be substituted by one or more alkyl groups containing 1 to 10 carbon atoms, preferably by one or more methyl groups.

[0060] In particular, R 1 represents a linear or branched alkyl radical containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms; R 2 is selected from a hydrogen atom and a linear or branched alkyl radical containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms; R 3 represents a linear or branched alkyl radical containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms; and R 4is selected from a hydrogen atom and a linear or branched alkyl radical containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms.

[0061] R 2 and / or R 4 is preferably a hydrogen atom.

[0062] More specifically, the amine formed is: The compound is selected 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).

[0063] Even more particularly, the amine formed is selected from the group consisting of DIPA, DMEA, DMIPA and EMA, more preferably DIPA and EMA.

[0064] Said amination step may notably correspond to one or more of the following reactions: - reaction of ammonia with primary or secondary alcohols and / or ketones to form primary, secondary and tertiary amines, preferably mainly secondary amines; - reaction of primary amines with primary or secondary alcohols and / or ketones to form secondary and tertiary amines, preferably mainly secondary amines; or - Reaction of a secondary amine with a primary or secondary alcohol and / or a ketone to form a tertiary amine.

[0065] In particular, in the context of the present invention, it is desired to form secondary and / or tertiary amines, preferably secondary amines.

[0066] In particular, use is made of alcohols of formula (I) and / or ketones of formula (II) with ammonia or with amines of formula (III): [ka] JPEG2024546307000010.jpg3939 JPEG2024546307000011.jpg3437 Here, R 1 , R 2 , R 3 and R 4 is as defined above, R 4 is other than a hydrogen atom for the ketone of formula (II).

[0067] Alcohols of formula (I) include the following: ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, n-pentanol, n-hexanol, methylisobutylcarbinol, n-heptanol, 2-ethylhexanol, n-octanol, diisobutylcarbinol, cyclohexanol, benzyl alcohol, 2-phenylethanol, and 3,3,5-trimethylcyclohexanol.

[0068] Ketones of formula (II) include 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.

[0069] It is understood that under the operating conditions of the amination process, the alcohol undergoes dehydration to form a ketone, which then reacts with hydrogen and the nitrogenous reactant.

[0070] Besides ammonia, preferred amine reactants of formula (III) are: 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.

[0071] Examples of secondary or tertiary amines which may preferably be prepared in this way according to the method of the present invention include: - diisopropylamine (DIPA), starting from acetone and / or isopropanol and ammonia; - di-n-propylamine (DPA) starting from propanol and ammonia, - di-sec-butylamine starting from methyl ethyl ketone and / or 2-butanol and ammonia, - N-ethylmethylamine (EMA) starting from ethanol and monomethylamine (MMA); - N-isopropylmethylamine starting from acetone and / or isopropanol and MMA, - N-ethylpropylamine, starting from n-propanol and monoethylamine or from ethanol and n-propylamine; N-ethylisopropylamine, starting from ethanol and isopropylamine or starting from acetone and / or isopropanol and monoethylamine, - N-ethylbutylamine, starting from n-butanol and monoethylamine or from ethanol and n-butylamine; - N-methylcyclohexylamine starting from cyclohexanol and / or cyclohexanone and MMA, N-ethylcyclohexylamine, starting from cyclohexanol and / or cyclohexanone and monoethylamine or starting from ethanol and cyclohexylamine, - N-ethylbenzylamine, starting from benzyl alcohol and monoethylamine or from ethanol and benzylamine; - N,N-Dimethylethylamine (DMEA) starting from ethanol and dimethylamine (DMA), - N,N-Dimethylisopropylamine (DMIPA), starting from acetone and / or isopropanol and DMA; - N,N-Dimethylpropylamine (DMPA) starting from n-propanol and DMA, - N,N-dimethylbutylamine starting from n-butanol and DMA, - N,N-Diethylmethylamine (DEMA) which starts from ethanol and DMA.

[0072] The amination process according to the invention allows the formation of secondary and / or tertiary amines (and water) in the gas phase and in the presence of hydrogen. The process may be carried out batchwise or continuously, preferably continuously.

[0073] "Gas phase" or "gaseous phase" means in particular that the reactants (alcohol and / or ketone and nitrogenous reactant) are in the gaseous state under the temperature and pressure conditions of the amination step. The reactor may be supplied with a gaseous phase by passing the liquid reactants through an evaporator (heated, for example, by steam or by any other known means). The evaporator temperature is set so as to ensure that the reactants pass from the liquid to the gaseous state under the pressure conditions used. The gas formed may then be conveyed towards the inlet of the reactor, for example by a flow of hydrogen and, where appropriate, ammonia.

[0074] The catalytic reaction is preferably carried out under excess hydrogen pressure (H 2The molar ratio of hydrogen to alcohol and / or ketone is preferably from 0.5 to 20 mol / mol, more preferably from 1 to 15 mol / mol, more preferably from 2 to 10 mol / mol.

[0075] The amination reaction is preferably carried out through one or more fixed beds of a catalyst as in accordance with the present invention. The one or more fixed beds may comprise one or more layers of the catalyst as in accordance with the present invention. When a catalyst bed comprising multiple layers of catalyst is used, the concentration of metals (e.g. Cu and / or Mn) may increase from the inlet to the outlet of the reactor and the number of layers may vary depending on the length of the catalyst bed.

[0076] The amination reaction may be carried out in one (or more) tubular reactor or multi-tubular reactors, either in series or in parallel.

[0077] The amination reaction may be carried out under an absolute pressure in a reactor up to 30 bar, preferably between 1 and 20 bar, more preferably between 2 and 10 bar.

[0078] The amination reaction may be carried out at a temperature of from 120°C to 220°C, preferably from 140°C to 200°C, and more preferably from 150°C to 190°C.

[0079] The temperature of the reactor may be maintained by a heat transfer fluid, which may be heated with steam, electrically or by any other means, and cooled by a cooling circuit with water and / or ethylene glycol or any other known cooling fluid. The heat transfer fluid is in particular molten nitrates (KNO 3 , NaNO 3 , LiNO 3 ) may be included.

[0080] The amination reaction may be carried out at a molar ratio of alcohol and / or ketone to nitrogenous reactant of from 0.1 to 20 mol / mol, preferably from 0.5 to 10 mol / mol, and more preferentially from 1 to 5 mol / mol.

[0081] The mass flow rate (MVH) of the alcohol and / or ketone per unit volume of the catalyst bed may be from 0.05 to 1.0 kg / Lh, preferably from 0.10 to 0.80 kg / Lh, and more preferentially from 0.15 to 0.60 kg / Lh.

[0082] The method of the present invention comprises the following steps: i) an amination step as defined above, which produces a diversion stream G comprising secondary and / or tertiary amines and water; ii) separating said stream G; - Water-bearing streams, and - a stream comprising said secondary amine and / or said tertiary amine providing at least one of: iii) optionally separating said stream containing both secondary and tertiary amines, - a stream comprising said secondary amine; and - a stream comprising said tertiary amine providing iv) optionally recycling said stream comprising said tertiary amine to step i); may include: The secondary amine and / or the tertiary amine may then be recovered and, optionally, purified.

[0083] More particularly, the method comprises the steps of: a) an amination step as defined above, which produces a diversion stream G in the gaseous state comprising secondary and / or tertiary amines, water and unreacted hydrogen; b) collecting and separating said stream G; a liquid stream G' comprising secondary amines and / or tertiary amines and water, and - Gaseous hydrogen flow G” To provide; c) optionally recycling said stream G″ to step a); d) separating said stream G'; - a water-containing stream K, and - a stream L comprising said secondary amine and / or said tertiary amine To provide; e) optionally, when said stream L comprises both secondary and tertiary amines, separating said stream L, - a stream M comprising said secondary amine; and - the tertiary amine-containing stream N To provide f) optionally recycling said stream N to step a). may include: Steps b) and d) may or may not be simultaneous.

[0084] The gas stream G" may contain trace amounts of secondary and / or tertiary amines, and possibly trace amounts of primary amines.

[0085] If ammonia is used as reactant and does not react completely, it may be found in stream G" and also in trace form in G'. It is then possible to carry out an additional separation of stream G' and / or stream G" and to recover the ammonia and to recycle it to step a).

[0086] Furthermore, when ammonia is used as reactant, the corresponding primary amine may be formed as a by-product. This primary amine is found continuously in streams G, G' and L (and may be found in trace amounts in G"). The primary amine may be separated from stream L at the end of separation step e) to provide a stream P comprising the primary amine. The stream P may be recycled to the amination step a).

[0087] The separation steps b), d) and e) may be carried out by any known means (eg by distillation or settling), preferably by distillation.

[0088] The secondary amine and / or the tertiary amine produced may subsequently be purified, if necessary, by a series of distillation columns operating in succession, in particular by fractional distillation.

[0089] More particularly, the method comprises the steps of: a) an amination step as defined above, which produces a diversion stream G in the gaseous state comprising secondary and / or tertiary amines, water and possibly unreacted reactants, and alcohol resulting from the hydrogenation reaction of a ketone to an alcohol; b) collecting and separating said stream G; a liquid stream G' comprising secondary and / or tertiary amines, water and possibly unreacted reactants and alcohol resulting from the hydrogenation reaction of ketones to alcohols, and a gaseous hydrogen stream G” containing traces of secondary and / or tertiary amines, possibly traces of unreacted reactants and, furthermore, traces of alcohol resulting from the hydrogenation reaction of ketones to alcohols. To provide; c) optionally recycling said stream G″ to step a); d) separating said stream G'; a stream K comprising water and possibly unreacted reactants and alcohol resulting from the hydrogenation reaction of ketones to alcohols, and - a stream L comprising said secondary amine and / or said tertiary amine To provide; e) optionally, when said stream L comprises both secondary and tertiary amines, separating said stream L, - a stream M comprising said secondary amine; and - the tertiary amine-containing stream N To provide f) optionally recycling said stream N to step a). may include:

[0090] The stream K may be separated to provide a stream O comprising water and a stream T comprising the alcohol. The alcohol thus recovered may be recycled to step a).

[0091] Optional activation of the catalyst The catalyst may be activated before step a), since it is generally charged to the reactor in oxidized or pre-reduced form, meaning that metals such as Cu and Mn are completely or partially in the form of oxides. In this case, the catalyst is preferably pre-activated. The activation is preferably carried out by reduction in the reactor in which the amination step is carried out (in situ activation). The catalyst is activated by conventional methods well known to those skilled in the art, which yield metal species that are active for hydrogenation or dehydrogenation by reduction of the corresponding oxidized form. Thus, copper is reacted with copper in the following reaction: CuO+H 2 →Cu+H 2 Through O, Cu II state (in CuO) to Cu 0 Move to state.

[0092] Therefore, the catalyst is capable of reacting with hydrogen (H 2 ) may be activated in the flow.

[0093] Use according to the invention The present invention also relates to the use of a catalyst as defined above for a process for making a secondary amine and / or a tertiary amine as defined above, and in particular for an amination step as defined above. EXAMPLES

[0094] Abbreviations and Definitions: ACE: Acetone ISO: Isopropanol EtOH: Ethanol MIPA: Monoisopropylamine DIPA: Diisopropylamine EMA: N-ethylmethylamine DEMA: N,N-diethylmethylamine DMEA: N,N-Dimethylethylamine DMIPA: N,N-dimethylisopropylamine RM: Molar ratio MVH: Mass flow rate per hour of the feed per unit volume of catalyst (unit: kg / Lh) S A = selectivity for the amine (A) formed relative to the reactants converted The selectivity is calculated based on the mass composition of the crude mixture exiting the reaction zone, said composition being determined by gas chromatographic analysis. DC DMA = Degree of conversion of DMA used = Conversion of DMA NL: Standard liter, equivalent to a volume of 1 L under standard conditions of pressure (1.013 bar) and temperature (273 K).

[0095] Example 1: Synthesis of diisopropylamine (DIPA) - a secondary amine The tests are carried out in a vertical tubular reactor containing a catalyst bed of 7 L volume and 2.8 m length. Molten nitrate (KNO 3 , NaNO 3 , LiNO 3 The reactor is immersed in a bath of 10 ...

[0096] Nickel catalyst (comparison): A triple-layer catalyst bed comprising a nickel-based catalyst in the form of cylindrical pellets (4.8×4.8 mm) having the following composition by weight before activation: - Bottom layer (reactor inlet) = 0.33L: Al 2 O 3 5.3% Ni (in the form of Ni and NiO) and 2.5-5% graphite in the above, - Middle layer=0.33L: Al 2 O 3 20% Ni (in the form of Ni and NiO) and 2.5-5% graphite in the above, - Top layer (reactor outlet) = 0.33L: Al 2 O 3 43% Ni (in the form of Ni and NiO) and 10% graphite in the above.

[0097] Copper catalyst C1 of the present invention: The single-layer catalyst bed is made of an alumina support (Al 2 O 3 The catalyst comprises a cylindrical pellet (4.8×4.8 mm) of manganese-doped copper-based catalyst on a catalyst support (1000×1000 μm), the copper and the manganese being in oxidized form prior to activation.

[0098] Before activation, the catalyst had a copper concentration by weight of 46% (corresponding to 57.6% expressed as CuO) and a manganese concentration by weight of 6% (MnO 2 This corresponds to 9.5% expressed as

[0099] Activation of the nickel catalyst and catalyst C1: In a tubular reactor preheated to 240 °C at atmospheric pressure, H 2 50NL / Lh and N 2 Hydrogen and nitrogen flows are charged at a volumetric flow rate (HSV) per unit volume of the catalyst bed of 500 NL / Lh. As soon as the zone of maximum heat production, monitored by a multipoint temperature probe, passes through the entire catalyst bed (after about 8 hours), the introduction of nitrogen is stopped and the reactor temperature is increased to 280°C for the copper catalyst and 350°C for the nickel catalyst while introducing 100 NL / Lh of H. 2 Hydrogen injection will continue for 12 hours at HSV.

[0100] Amination step: The reactor is then fed from bottom to top with a mixture of fresh acetone, recycled isopropanol, ammonia and hydrogen, previously evaporated and preheated through a steam exchanger. The pressure in the reactor is maintained at 4 bar absolute and the temperature at 150°C.

[0101] The following table shows the properties of the catalyst bed, the proportion of recycled isopropanol, and the NH 3 and H 2 The results obtained according to the MVH and RM of [Table 1]

[0102] Catalyst C1 has a much higher selectivity for diisopropylamine than the nickel catalyst and does not produce the secondary product of EIPA, which is difficult to separate from DIPA by distillation. Close to 90% selectivity for DIPA can be directly obtained without recycling MIPA.

[0103] Example 2: Synthesis of Dimethylisopropylamine (DMIPA) - A Tertiary Amine These tests were carried out in a thermally controlled vertical tubular reactor of 1 L volume and 80 cm length containing a catalyst bed containing either catalyst C1 or catalyst C2.

[0104] Copper catalyst C1 (of the invention): as described in Example 1 Copper catalyst C2 (comparison): The catalyst bed is made of cylindrical pellets (6 × 5 mm) with the following composition by weight before activation: silica (SiO 2 ) on 76% CuO, 3% MgO, 1.5% Cr 2 O 3 .

[0105] Amination step: 250~350℃ 2After preactivation of the catalyst by reduction with 1,000 cc of 1,000 cc of DMA, the reactor is fed from bottom to top 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 operated under a pressure of 8 bar, at a temperature of 185° C. and with a large molar excess of acetone and / or isopropanol relative to the DMA.

[0106] The table below shows the results obtained according to the nature of the catalyst bed and the respective molar flow rates of ACE+ISO and DMA, with a conversion of DMA of more than 99% in each case. [Table 2]

[0107] The selectivity for DMIPA over DMA with catalyst C2 is 8-9% lower than that obtained with catalyst C1, which may be due to the greater disproportionation of the DMA to TMA and MMA, which subsequently reacts with acetone to form methylisopropylamine (Me-IPA) and methyldiisopropylamine (Me-DIPA).

[0108] Example 3: Synthesis of ethylmethylamine (EMA-secondary amine) and / or diethylmethylamine (DEMA-tertiary amine) from ethanol and MMA with and without recycling DEMA These tests were carried out in an apparatus identical to that of Example 2 with prereduced catalyst C1.

[0109] The synthesis is operated in the presence of hydrogen, at a pressure of 8 bar, at a temperature of 175° C., with a molar excess of ethanol relative to the MMA, where applicable, with a recycle of DEMA.

[0110] The table below shows the results obtained according to the EtOH / MMA molar ratio and the optional recycling of DEMA. [Table 3]

[0111] The results for 512 and 760 hours 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.

[0112] It is evident that the selectivity for the secondary amine (EMA) relative to MMA can exceed 90% depending on the flow rate of the recycled tertiary amine (DEMA).

[0113] Example 4: Synthesis of the secondary amine ethylpropylamine (EPA) from ethanol and MEA These tests were carried out in an apparatus identical to that of Example 2 with prereduced catalyst C1.

[0114] At a temperature of 170°C, H 2 (RM H 2 A continuous feed of 6 mol / h ethanol and 2 mol / h monoethylamine (MEA) is fed under a pressure of 4 bar in the presence of 1000 sulphuric acid (1000 sulphuric acid / EtOH=4). The conversion of MEA at the reactor outlet is 81% and EPA is obtained with a selectivity of 92% relative to the converted MEA.

[0115] Example 5: Synthesis of secondary amine di-n-propylamine (DPA) from n-propanol and ammonia by recycling n-PA (n-propylamine) and TPA (tripropylamine) These tests were carried out in an apparatus identical to that of Example 2 with prereduced catalyst C1.

[0116] At a temperature of 165°C, H 2 (RM H 2 8 mol / h n-propanol (MVH=0.48 kg / Lh) and 24 mol / h ammonia (RM PrOH / NH3 = 0.33) and by recycling 196 g / h of n-PA and 90 g / h of TPA, DPA is obtained with a selectivity of 92.5% for a conversion of n-propanol of 79.0%.

[0117] Example 6: Synthesis of the tertiary amine dimethylpropylamine (DMPA) from n-propanol and DMA At an absolute pressure of 8 bar, the reaction temperature T R These tests were carried out in an apparatus identical to that of Example 2 with the catalyst C1 previously reduced at .

[0118] The table below shows the results obtained according to the nature of the catalyst bed and the reaction conditions used. [Table 4]

[0119] Catalyst C1 gives very high selectivity to DMPA, greater than 98%, at a degree of conversion (DC) of DMA greater than 99%, with very low levels of amine impurities.

[0120] Example 7: Synthesis of the tertiary amine dimethylethylamine (DMEA) from ethanol and DMA - Alternating synthesis These tests were carried out in an apparatus similar to that of Example 1, but with a catalytic bed of catalyst C1 having a volume of 3.2 L and a length of 2.8 m, under the following reaction conditions: - Average molar flow rate of REN grade ethanol with 4.3% water: 0.435 kg / L cata h, which corresponds to an average MVH of 28.8 mol / h of ethanol. - DMA average molar flow rate: 0.135 kg / L cata h, and 6.6 mol / h, corresponding to an average MVH of DMA of 1.0 and an average EtOH / DMA molar ratio of 3. - average molar ratio H 2 / EtOH=8, - Reaction carried out at 8 bar absolute pressure.

[0121] To evaluate the stability of the catalyst after different production runs, the catalyst bed is operated alternately for the production of DMEA and for the production of DMIPA.

[0122] The table below shows the corresponding selectivity for DMA, just as the selectivity for the formation of DMEA is calculated below. [Table 5]

[0123] These results show the stability of the catalyst performance over time, despite the intermediate operation for DMIPA starting from acetone (a more exothermic reaction). Therefore, this catalyst can be advantageously used in a multipurpose production unit where different types of amines can be produced by successive operations.

[0124] It is also clear that, if necessary, the catalyst can be easily regenerated without loss of performance by a step of oxidation followed by a new reduction with hydrogen.

Claims

1. 1. A method for making secondary and / or tertiary amines, comprising an amination step, the amination step is carried out by a gas phase reaction of a primary or secondary alcohol and / or a ketone with ammonia or a primary or secondary amine in the presence of a catalyst and hydrogen; the catalyst comprises manganese-doped copper; and the amount of manganese is 1 wt. % to 10 wt. % based on the total weight of the catalyst; How to make it.

2. the amount of copper in the catalyst is 20% to 60% by weight, more preferably 35% to 50% by weight, based on the total weight of the catalyst; The method of claim 1 .

3. the amount of manganese is 4% to 10% by weight, preferably 4% to 8% by weight, based on the total weight of the catalyst; The method of claim 1 .

4. The catalyst is alumina (Al ２ O ３ ), silica (SiO ２ ), a support selected from the group consisting of titanium dioxide, zirconia, and mixtures of two or more thereof, preferably comprising alumina and / or silica; The method of claim 1 .

5. The amine formed is an amine of the following general formula (A): 【Chemistry 1】 During the ceremony: R １ represents an optionally substituted linear, branched or cyclic alkyl radical containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms; R ２ is selected from a hydrogen atom and an optionally substituted linear, branched or cyclic alkyl radical containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms; or R １ and R ２ together and with the nitrogen atom which carries them, form a saturated or partially or fully unsaturated cyclic radical, which is optionally substituted and which may contain one or more heteroatoms selected from oxygen and nitrogen; said cyclic moiety may contain a 3- to 9-membered ring, preferably a 5- or 6-membered ring; R ３ represents an optionally substituted linear, branched or cyclic aromatic or non-aromatic hydrocarbon chain containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms; R ４ is selected from hydrogen atoms and optionally substituted linear, branched or cyclic aromatic or non-aromatic hydrocarbon chains containing 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms; or R ３ and R ４ together and with the carbon atoms which carry them form a saturated or partially unsaturated cyclic radical, which is optionally substituted and may contain one or more heteroatoms selected from oxygen and nitrogen; said cyclic moiety comprises a 3- to 9-membered ring, preferably a 5- or 6-membered ring, The method of claim 1 .

6. the amine formed is selected 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); The method of claim 1 .

7. the amine formed is selected from the group consisting of DIPA, DMEA, DMIPA and EMA, more preferably DIPA and EMA; The method of claim 1 .

8. The catalyst is preferably hydrogen (H ２ ) in a stream of 150°C to 400°C, The method of claim 1 .

9. The following steps: i) an amination step as defined in any one of claims 1 to 8, which produces a diversion stream G comprising a secondary and / or tertiary amine and water; ii) separating said stream G; Water-containing streams, and at least one step of providing a stream comprising said secondary amine and / or said tertiary amine; iii) optionally separating said stream containing both secondary and tertiary amines, a stream comprising the secondary amine; and providing a stream comprising said tertiary amine; and iv) optionally recycling said stream comprising said tertiary amine to step i), The method according to any one of claims 1 to 8.

10. The following steps: a) an amination process as defined in any one of claims 1 to 8, which produces a deviation stream G in the gaseous state comprising secondary and / or tertiary amines, water and unreacted hydrogen; b) condensing and separating said stream G; a liquid stream G′ comprising a secondary amine and / or a tertiary amine and water, and providing a gaseous hydrogen stream G"; c) optionally recycling said stream G″ to step a); d) separating said stream G'; a water-containing stream K, and providing a stream L comprising said secondary amine and / or said tertiary amine; e) optionally, if said stream L comprises both secondary and tertiary amines, separating said stream L, a stream M comprising the secondary amine; and providing a stream N comprising said tertiary amine; and f) optionally recycling said stream N to step a), The method according to any one of claims 1 to 8.

11. If the reactant is ammonia, the stream G also contains primary amines as by-products, which are subsequently present in stream G′ and stream L and are separated into stream P at the end of separation step e), which can optionally be recycled to step a). The method of claim 10.

12. 1. Use of a catalyst comprising manganese-doped copper for making secondary amines and / or tertiary amines, wherein the manganese is present in an amount of 1% to 10% by weight based on the total weight of the catalyst. use.

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