EP1483230A1 - Procede de production d'ethyldimethylamine et de triethylamine - Google Patents

Procede de production d'ethyldimethylamine et de triethylamine

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Publication number
EP1483230A1
EP1483230A1 EP03711916A EP03711916A EP1483230A1 EP 1483230 A1 EP1483230 A1 EP 1483230A1 EP 03711916 A EP03711916 A EP 03711916A EP 03711916 A EP03711916 A EP 03711916A EP 1483230 A1 EP1483230 A1 EP 1483230A1
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European Patent Office
Prior art keywords
catalyst
weight
diethylamine
triethylamine
reaction
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EP03711916A
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German (de)
English (en)
Inventor
Ralf Böhling
Ulrich Steinbrenner
Frank Funke
Günter Müller
Günter Gaus
Christoph Benisch
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BASF SE
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BASF SE
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Publication of EP1483230A1 publication Critical patent/EP1483230A1/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
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes

Definitions

  • the present application relates to a process for the preparation of ethyldimethylamine and triethylamine.
  • Triethylamine is used as a raw material for the production of surfactants, textile and flotation aids, bactericides, corrosion and foam inhibitors, additives for pharmaceuticals and as antioxidants for fats and oils.
  • the amine mentioned can be prepared by the hydrogenation of corresponding nitriles or nitro compounds, by the reductive amination of corresponding aldehydes and ketones and by the amination of corresponding alcohols. In particular, it is produced on an industrial scale by the amination of the corresponding alcohol or the corresponding carbonyl compound over metal catalysts, which are optionally supported, under hydrogenating conditions.
  • Ethyldimethylamine is also an important large-scale product. It is mainly used in the foundry industry, in the so-called cold box ner driving. Small amounts are used in the pharmaceutical industry.
  • aldehydes, ketones and nitriles and also of alcohols, in this case ethanol as the starting material for the production of alkylamines is in principle uneconomical compared to the use of the corresponding olefin, i.e. ethene, due to the prices of the starting materials.
  • US-A-4,336,162 and US-A-4,302,603 describe an approach to this problem by switching to the Rb and Cs amides or by using a eutectic of NaNH 2 and KNH 2 .
  • the technical implementation is forbidden because of the extremely high catalyst price
  • the space-time yields of the desired alkylamines are still too small.
  • the object of the present invention is to provide a process with which ethyldimethylamine and trimethylamine can be produced in one process, the desired amounts of ethyldimethylamine and triethylamine being able to be controlled.
  • the inventive method allows the production of ethyldimethylamine and triethylamine in a process in which a co-production of ethyldimethylamine and triethylamine is carried out, it being possible to produce these amines in a single process using simple process steps. Since ethyldimethylamine and triethylamine can easily be separated from one another and from diethylamine or a diethylamine / dimethylamine mixture by distillation, the process according to the invention is advantageous over the separate production of the two amines. Diethylamine and dimethylamine are used as starting materials for the reaction.
  • ethylene is reacted with diethylamine and dimethylamine under hydroaminating conditions.
  • the addition of ethylene to the respective amine produces triethylamine and ethyldimethylamine.
  • the relative amount of ethylene (partial pressure) and the amount of amines allow the distribution of the resulting products to be controlled.
  • Dimethylamine reacts with ethylene to a more stable product than diethylamine.
  • the amount of dimethylamine present then completely or almost completely reacts with ethylene before triethylamine is formed.
  • the product composition of the mixture obtained can thus be controlled in a simple manner via the composition of the starting material mixture, a deficit in ethylene causing an incomplete conversion of diethylamine.
  • the process according to the invention is intended to produce product mixtures which, in addition to the products ethyldimethylamine and triethylamine and any by-products which may be present, no longer contain diethylamine, an excess of ethylene is used in the hydroamination reaction. If a certain proportion of diethylamine is to be retained, a substoichiometric amount of ethylene is used.
  • the hydroamination according to the present invention is carried out in such a way that the amine from which the preferred alkylamine is produced is used in excess over the other starting material.
  • the starting materials diethylamine and dimethylamine are preferably used in a ratio of (8 to 15): 1, in particular in a ratio of 10: 1, so that triethylamine and ethyldimethylamine are also obtained in such a ratio , This usually corresponds to market demand.
  • the ratios of diethylamine and diethylamine to be used can, however, be flexibly adapted to the needs of the respective products, which is a further advantage of the process according to the invention.
  • a significant excess of ethylene is preferably also added.
  • the hydroamination according to the invention using diethylamine and dimethylamine is preferably carried out in one reaction step, the product distribution being set as set out above using the starting materials.
  • the hydroamination according to the invention is carried out using an alkali metal hydride or amides of the alkali metals as a catalyst.
  • the hydrides and amides which can be used are salts of Li, Na, K, Rb or Cs, preferably of Li, Na or K, in particular of Na.
  • the most preferred hydride is NaH.
  • the amides used according to the invention are diethylamide, dimethylamide and or ethylmethylamide. Diethylamide or dimethylamide or a mixture of the two is preferably used in any desired ratio. Na-diethylamide, Na-dimethylamide or mixtures thereof are particularly preferred.
  • the metal amides can be used as such, for example in the form of a solution, in the reaction according to the invention, it being possible for the metal amides to come from any source.
  • the metal amide is used from the corresponding amine, ie dimethylamine, before use in the reaction
  • the preparation of the amide is carried out either by reacting one
  • Alkali metal with the corresponding amine in the presence of an unsaturated compound such as butadiene, isoprene, naphthalene, pyridine or styrene as an electron transfer, by reacting a metal amide or hydride with the corresponding amine or reacting an organometallic compound, for example n-BuLi, MeLi, PhNa, Et 2 Mg or EttZr, with the corresponding amine.
  • an unsaturated compound such as butadiene, isoprene, naphthalene, pyridine or styrene
  • an organometallic compound for example n-BuLi, MeLi, PhNa, Et 2 Mg or EttZr
  • alkali metal In the production from amine and alkali metal, generally technical quality alkali metal is used which is contaminated by up to 10% by weight of oxides, hydroxides, calcium and the other alkali metals. Other elements can be present in traces (> 1% by weight), but these generally do not interfere even at higher concentrations. It is of course also possible to use pre-cleaned alkali metal which does not contain the impurities mentioned or only in traces. However, technical alkali metal is generally preferred for reasons of cost. All alkali metals can be used, preferably Li, Na or K are used, more preferred are Na or K, especially Na. If appropriate, mixtures of the alkali metals can also be used.
  • the alkali metal is dispersed in a suitable inert solvent before the addition of the amine.
  • Saturated hydrocarbons are preferably used as inert solvents, preferably low-boiling paraffins, such as n-butane, i-butane, pentanes and hexanes, cyclohexane and mixtures thereof, or high-boiling paraffins which may contain branched and saturated cycloparaffins, for example white oil.
  • the solvents mentioned are generally of technical origin and can also contain acidic impurities such as water, aldehydes, ketones, amides, nitriles or alcohols in small amounts.
  • the dispersion can be carried out above the melting temperature of the alkali metal using, for example, a suitable stirrer, a nozzle, a reaction mixing pump or a pump and a static mixer.
  • the alkali metal can also be injected into cold solvent or sprayed onto cold solvent from the gas phase. Spraying in cold gas with subsequent redispersion is also possible.
  • the alkali metal is generally introduced in the form of fine particles.
  • these particles preferably have a size distribution such that 50% by weight of the particles have a size of ⁇ 1000 ⁇ m, more preferably ⁇ 300 ⁇ m, in particular ⁇ 100 ⁇ m.
  • the alkali metal is dispersed in a paraffin and at least a large part of this paraffin is decanted off before the alkali metal is used in the reaction and replaced by trialkylamine and / or dialkylamine.
  • An electron transfer agent in particular 1,3-butadiene, is then metered in either alone or in a mixture with the educt dialkylamine. Alternatively, a simultaneous addition of the electron carrier and the dialkylamine is also possible.
  • Salt formation to the amide thus takes place in the presence of a suitable unsaturated compound, for example butadiene, isoprene, naphthalene, pyridine or styrene.
  • a suitable unsaturated compound for example butadiene, isoprene, naphthalene, pyridine or styrene.
  • butadiene or isoprene are used as the unsaturated compound, particularly preferably 1,3-butadiene.
  • the amide catalyst from elemental metal, preferably Na, a temperature of 0 to 150 ° C, preferably 20 to 90 ° C, in particular 30 to 70 ° C and a pressure of 1 to 200 bar, preferably 1 to 100 bar, in particular 3 to 50 bar.
  • the amide preparation can be carried out batchwise, semi-continuously or continuously.
  • the catalyst systems described above which are suitable for carrying out the reaction according to the invention can be used in solution, as a suspension or applied to a support.
  • Ethylene implemented. This creates a mixture of ethyldimethylamine and triethylamine.
  • the relative amount of the organylamines formed can be controlled by the amount of starting material.
  • ethene is hydroaminated with diethylamine and dimethylamine in the presence of catalytic amounts of an alkali metal diethyl or dimethyl amide or a mixture thereof or an alkali metal hydride.
  • the streams fed to the reactor contain 0 to 1% by weight, preferably ⁇ 0.1% by weight ammonia, 0 to 5% by weight, preferably ⁇ 1% by weight monoethylamine and monomethylamine, 20 to 80% by weight.
  • % preferably 40 to 70% by weight, (diethylamine + dimethylamine), 0 to 50% by weight, preferably ⁇ 40% by weight triethylamine, 5 to 50% by weight, preferably 10 to 30% by weight ethylene , 0.01 to 20% by weight, preferably 0.1 to 2% by weight of the catalyst and 0 to 20% by weight of a solvent for the catalyst.
  • the reaction can be carried out in various reactors e.g. B. in a bubble column (preferably cascaded), a stirred tank, a jet loop reactor or a reactor cascade.
  • the reaction is carried out at 40 to 150 ° C and 1 to 100 bar, in particular at 70 to 120 ° C and 5 to 40 bar.
  • the catalyst is preferably in homogeneous solution in the liquid phase. In principle, if the solubility of the catalyst is exceeded, the reactor can also be operated in the suspension mode.
  • the reaction discharge is worked up using the methods known to the person skilled in the art, preferably by distillation, in such a way that the low boilers (ethene, dimethylamine), the high boilers (catalyst, triethylamine) and diethylamine are separated off from the reaction discharge and returned to the reactor.
  • the products obtained as medium boilers triethylamine, ethyldimethylamine are separated and removed from the process.
  • the addition products formed are preferably distilled off directly from the reactor.
  • the catalyst can remain in the reactor and can thus be used for further reactions.
  • the adducts formed can be removed from the reaction mixture, for example by stripping with unreacted ethene.
  • the reaction mixture is preferably fed to flash evaporation or directly to a distillation.
  • the catalyst which is preferably dissolved in a high-boiling solvent (> 50% by weight) or in trialkylamine (> 50% by weight) and is obtained at the bottom of the column or in the liquid phase of the flash, is in a preferred embodiment in returned the reactor.
  • a partial stream is disposed of for high boiler and catalyst exclusion.
  • a filtration can be used for catalyst recovery or retention.
  • the low and medium boilers are worked up in a manner known to the person skilled in the art suitable distillation sequence, with ethene, dimethylamine and diethylamine being returned to the reactor.
  • Parts of the ethene dissolved in the reaction discharge can preferably first be separated from the reaction discharge in a flash evaporation and returned directly to the reactor via a compression. The remaining reaction discharge is carried out as described above.
  • inert alkylamines or saturated hydrocarbons can be present in the reactor. However, since they make it difficult to separate the product mixture by distillation, the presence of these compounds is not preferred.
  • the preparation of the amide and the hydroamination are carried out in a single process step.
  • one of the amines to be alkylated, or a mixture of these amines in the desired ratio is advantageously first reacted with the amount of Na required to form the necessary amount of amide in the presence of an electron-transferring compound, preferably butadiene.
  • an electron-transferring compound preferably butadiene.
  • the formation of the amide occurs spontaneously due to the presence of the electron carrier.
  • the excess of the amine or amines, which is not reacted with the Na to the amide reacts with ethylene to the desired product.
  • the amount of Na used in the production of the amide is chosen so that a molar ratio of Na to the total amount of ethylene is from 1: 5 to 500, preferably from 1:10 to 1: 200, in particular from 1:50 to 1: 150 is present.
  • amide preparation and the hydroamination are carried out as described above, this takes place at temperatures from 0 to 150 ° C., preferably 20 to 90 ° C., in particular 30 to 70 ° C., and pressures from 1 to 200 bar, preferably 1 to 100 bar , in particular 3 to 50 bar.
  • the main product desired will be triethylamine.
  • an excess of diethylamine, based on dimethylamine is used.
  • the excess of dietliylamine and possibly also the amount of ethylene is preferably adjusted so that triethylamine is formed in an 8- to 15-fold excess, in particular in a 10-fold excess, over dimethylethylamine.
  • the hydroamination of ethylene described above is carried out at temperatures from 30 to 180 ° C., preferably 50 to 100 ° C. and pressures from 1 to 200 bar, preferably 20 to 200 bar, in particular 30 to 50 bar.
  • reaction of the olefin with the amine is carried out in the presence of the amide in a manner known to the person skilled in the art.
  • the description of preferred implementation variants can be found in GP Pez et al., Pure and Applied Chemistry 57 (1985), pages 1917-26, RD Closson et al., J. Org. Chem. 22 (1957), pages 646-9, US 2,501,556, D. Steinborn et al., Z. Chem. 29 (1989), pages 333 -4, D. Steinborn et al., Z. Chem. 26 (1986), pages 349 -59 and H. Lehmkuhl et al ., J. Organomet. Chem.
  • reaction of the olefin with the amine in the presence of the metal alkyl amide can also be carried out in the presence of smaller amounts of ammonia, generally ⁇ 1 mol%, based on the amines used, as described, for example, in DE-A 21 17 970.
  • the metal alkyl amide can be converted into metal hydride during the reaction by ⁇ -elimination or the action of H 2 as described in DE-A 26 13 113, an imine being formed in the case of ⁇ -elimination.
  • This hydride can under the action of a primary or secondary amine according to DE-A 26 13 113, CA Brown, J. Am. Chem. Soc. 95 (3) (1973), 982ff or CA Brown, Synthesis (1978), 754ff, are converted back into metal alkyl amide and H 2 , so that the metal hydride can be regarded as a kind of "resting form" of the metal alkyl amide.
  • it is therefore equivalent to the metal alkyl amide.
  • a cocatalyst which has an acidity of ⁇ 35 on the McEven-Streitwieser-Appleguest-Dessy scale, preferably from 20 to 35, particularly preferably from 25 to 35, very particularly preferably from 30 to 35 , having.
  • the scale from McEven-Streitwieser-Appleguest-Dessy is in DJ. Cram, Fundamentals of Carbanion Chemistry 1965, Acad. Press, NY, Chapter 1 released.
  • Unsaturated nitrogen compounds are preferably used as cocatalysts. These can be imine or tautomeric enamine compounds. These can be cyclic or open chain.
  • Open-chain nitrogen compounds used with preference are selected from open-chain imine or the tautomeric enamine compounds of the general formula (I) or (Ia)
  • radicals R 1 to R 6 independently of one another denote hydrogen or alkyl radicals which can be branched or unbranched and / or can be interrupted by one or more nitrogen atoms.
  • R 1 to R 6 are preferably C 1 -C 2 -alkyl radicals, particularly preferably C 1 -C 6 -alkyl radicals.
  • Suitable alkyl radicals are, for example, methyl, ethyl, n- or isopropyl, n- or iso- or tert-butyl.
  • R 1 to R 6 can also be, independently of one another, cycloalkyl radicals which can be substituted by the above-mentioned functional groups or by alkyl, alkenyl or alkynyl groups and / or interrupted by one or more nitrogen atoms.
  • Cycloalkyl radicals which are preferably used have 3 to 12 carbon atoms - optionally partially replaced by nitrogen atoms - in their ring, particularly preferably 5 or 6 carbon atoms.
  • the cycloalkyl radicals are very particularly preferably unsubstituted.
  • Particularly suitable cycloalkyl radicals are, for example, cyclopentyl and cyclohexyl.
  • radicals R to R are, independently of one another, alkenyl radicals or alkynyl radicals which have one or more multiple bonds, preferably 1 to 4 multiple bonds.
  • the alkenyl or alkynyl radicals can be substituted in accordance with the alkyl radicals or interrupted by one or more nitrogen atoms.
  • radicals R 1 to R 6 together form a ring which in turn can be substituted by alkyl, alkenyl or alkynyl groups.
  • the radicals R to R are particularly preferably independently of one another hydrogen, methyl or ethyl, the radicals R 1 to R 6 being very particularly preferably each hydrogen.
  • Cyclic enamines which are preferably used have a C to C 8 carbon junction, particularly preferably a C to C 8 carbon junction. This carbon ring is at least monounsaturated and carries at least one amino group which has at least one hydrogen atom. Depending on the ring size, the carbon ring can also carry two or more double bonds. Cyclic enamines which are not further conjugated are preferably used. The carbon ring can be substituted by one or - depending on the ring size - several residues in addition to the amino group.
  • Suitable radicals correspond to those already mentioned above for R 1 to R 6 , with the exception of hydrogen (in the context of the substitution of this carbon ring with radicals, a substitution with hydrogen is not regarded as a radical).
  • Preferred radicals are alkyl radicals which can be branched or unbranched and have 1 to 6, particularly preferably 1 to 4, carbon atoms. The number of residues depends on the ring size, with no to 3 residues being preferred and the carbon ring particularly preferably carrying no or, very particularly preferably, no residue.
  • Suitable cyclic unsaturated nitrogen compounds are for example:
  • R 7 to R 12 are hydrogen or one of the radicals mentioned for R 1 to R 6 .
  • R 7 to R 12 are preferably hydrogen, methyl or ethyl radicals, very particularly preferably hydrogen or ethyl radicals.
  • the number of radicals R ' is preferably 0 to 3, particularly preferably 0 to 1, very particularly preferably 0, that is to say all carbon atoms of the carbon ring are substituted with hydrogen, with the exception of one carbon atom which bears the amino group.
  • Suitable alkyl radicals are, for example, methyl, ethyl, n- or isopropyl, n- or iso- or tert-butyl.
  • the radicals R ' can also be, independently of one another, cycloalkyl radicals which can be substituted by the functional groups mentioned above or by alkyl, alkenyl or alkynyl groups and / or interrupted by one or more nitrogen atoms.
  • Cycloalkyl radicals which are preferably used have 3 to 12 carbon atoms - optionally partially replaced by nitrogen atoms - in their ring, particularly preferably 5 or 6 carbon atoms.
  • the cycloalkyl radicals are very particularly preferably unsubstituted.
  • Particularly suitable cycloalkyl radicals are, for example, cyclopentyl and cyclohexyl.
  • radicals R 'to be, independently of one another, alkenyl radicals or alkynyl radicals which have one or more multiple bonds, preferably 1 to 4 multiple bonds.
  • the alkenyl or alkynyl radicals can be substituted in accordance with the alkyl radicals or interrupted by one or more nitrogen atoms.
  • radicals R ' are particularly preferably independently of one another methyl, ethyl or n- or isopropyl. From the listed compounds, no further conjugated enamines are selected from
  • N-heterocyclic compounds in the form of imines or enamines are cyclic compounds with a total of 3 to 20 atoms, preferably 5 to 12 atoms, particularly preferably 5 to 7 atoms.
  • the N-heterocyclic compound can contain further heteroatoms, preferably nitrogen atoms. The number of further heteroatoms depends on the ring size.
  • the N-heterocyclic compounds preferably contain from one ring size of 5 atoms no to 2 further heteroatoms, particularly preferably no or 1 further heteroatom.
  • the carbon atoms of the N-heterocyclic compound can carry further radicals.
  • Suitable radicals are the same as those already listed as radicals R 'of the carbon rings of the cyclic enamines mentioned above.
  • N-heterocyclic compounds which, in addition to the N atom, contain further heteroatoms, preferably nitrogen atoms, in addition to the carbon atoms, the heteroatoms, apart from one nitrogen atom, can also carry further radicals R '.
  • the N-heterocyclic compounds can have further double bonds which can be conjugated or non-conjugated to the imine or enamine double bond. N-heterocyclic compounds which have no conjugated double bonds are preferably used.
  • Suitable N-heterocyclic compounds are, for example:
  • R ' has the same meaning as the radical R' mentioned in connection with the preferred cyclic enamines.
  • R ' is preferably 0 to the number of ring atoms minus 1, particularly preferably all ring atoms of the N-heterocyclic compounds carry hydrogen atoms or a radical R, where at least one nitrogen atom of the N-heterocyclic ring carries a hydrogen atom.
  • N-heterocyclic compounds which have no conjugated double bonds are selected from
  • the cocatalyst is particularly preferably an imine or tautomeric enamine compound which is formed during the dehydrogenation of the reactant and / or product amines or a decay or secondary product of the corresponding imine or tautomeric enamine compound.
  • the cocatalyst is very particularly preferably an imine or tautomeric enamine compound which is formed during the dehydrogenation of the eductamine or a decomposition or secondary product of the imine or tautomeric enamine compound.
  • the cocatalyst is formed by reacting the hydride used as the catalyst or the metal used to prepare the catalyst with the mono- or dialkylamine (or optionally mono- or diarylamine or alkylarylamine) selected as the starting material before the reaction with the alkene. reacted and the hydrogen formed is removed from the reaction mixture.
  • the mixture is preferably distilled and then separated into a gas phase, a low boiler fraction containing the starting material and the cocatalyst and a bottom fraction containing the hydride or the metal. The low boiler fraction is then added to the bottom fraction, the procedure described is optionally repeated and the hydroamination is started by adding alkene and optionally further eductamine.
  • the cocatalyst is formed during the reaction by reacting diethylamine with ethylene in the presence of a metal hydride or metal as catalyst, the reaction mixture obtained preferably being separated by distillation into a gas phase (a) which contains hydrogen and unreacted ethylene, a low boiler fraction ( b) which contains unreacted starting amine and the cocatalyst, a middle boiler fraction (c), which contains product amine, and a bottom action (d), which contains the catalyst.
  • Fraction (b) is supplemented with fresh starting material and ethylene and returned to the bottom fraction which contains the catalyst. It is also possible to isolate the unreacted ethylene from the gas phase (a) and together with the low boiler fraction (b) to the bottom fraction
  • the process according to the invention is carried out in such a way that hydrogen formed during the reaction is removed from the reaction mixture. This can preferably be done by distillation or stripping. It must be taken into account here that the remaining substances separated off during the distillation are returned in whole or in part to the process.
  • the resulting enamine / imine has sufficient acidity, which is sufficient to enable protonation of the sodium hydride or oxidation of the metal to a high degree.
  • the imine can also be prepared by dehydrogenating the eductamine in the presence of a hydrogenation / dehydrogenation catalyst, which is shown below:
  • All conventional hydrogenation-Z-dehydrogenation catalysts are suitable as hydrogenation-Z-dehydrogenation catalysts.
  • Transition metal catalysts in the form of unsupported or supported catalysts are generally used. Preferred transition metals are selected from groups VHIb and Ib of the Periodic Table of the Elements. Fe, Ru, Co, Ni, Pd, Pt and Cu or alloys of these metals are particularly preferred. Suitable carrier materials are, for example, carbon, SiO 2 , Al 2 O, ZrO and TiO 2 .
  • the hydrogenation / dehydrogenation catalysts can contain promoters / modifiers selected from Sn, Sb, alkali metals, alkaline earth metals, Bi and Pb.
  • Suitable hydrogenation / dehydrogenation catalysts are, for example, Raney-Ni, Raney-Cu, Raney-Co, Pd / ⁇ -Al 2 O 3 , Pt / carbon, Ru / SiO 2 , Pd / Sn / Cs / ⁇ -Al 2 O 3 .
  • compositions of suitable hydrogenation-Z-dehydrogenation catalysts are known to the person skilled in the art.
  • the hydrogenation / dehydrogenation catalysts are used in one reactor together with the metal hydride or metal amide used as catalyst.
  • the hydrogen is removed from the system during the reactions described above in order to shift the equilibrium further in the direction of the desired cocatalysts.
  • the present application thus also relates to a process according to the invention for the preparation of alkylamines (product amines) by reacting ethylene with diethylamine and dimethylamine in the presence of a metal hydride or metal amide as catalyst, the reaction taking place in the presence of a cocatalyst.
  • the cocatalyst is formed in situ before the diethylamine is reacted with the ethylene (hydroamination) or during the reaction of the diethylamine with the ethylene.
  • complexing agents can be present as solvents both in the preparation of the catalyst and in the reaction.
  • amines with several amine N atoms per molecule such as. B. N.NjN'jN'-tetaethylethylenediamine, N-permethylated or N-perethylated triethylene tetramine to N-permethylated or N-perethylated polyimine with molecular weights up to 500,000 daltons, ethers and polyethers, such as. b. Diglyme, triglyme and the corresponding homologues, end-capped polyols - e.g. B. PEG, PPG, poly-THF, and complexing agents with amine N and ethereal O atoms in the molecule, such as. B. 3-methoxyethylamine, 3- (2-methoxyethoxy) propylamine or N, N, N ', N'-tetramethyl-diaminodiethyl ether, the reaction mixture.
  • the catalyst can be used as a solution, as a suspension or supported on a typical catalyst support such as. B. SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , activated carbon, MgO, MgAl 2 O 4 are present.
  • the catalyst is preferably present as a solution or suspension, particularly preferably as a solution.
  • the hydroamination of ethylene can be carried out batchwise (adding the olefin to the catalyst and amine), semi-continuously (adding the olefin to the reaction mixture) or continuously (adding all components).
  • a molar ratio of ethylene: secondary amine of 3: 1 to 1:10 is preferred in each case, and 1: 1 to 1: 2 is particularly preferred.
  • the catalyst is separated from the reaction mixture. This is done by the usual methods, for example Distillation under reduced or normal pressure, filtration, membrane filtration, sedimentation, washing with water, preferably acids, salt solutions or alcohol.
  • Non-protolyzed catalyst metal alkyl amide or metal hydride
  • by-products for example trimethylamine or diethylmethylamine
  • transalkylation reactions in addition to the desired products.
  • This by-product formation can be suppressed by a suitable reaction procedure, a suitable choice of the catalyst or its amount and further measures known to the person skilled in the art.
  • the reaction is preferably carried out in such a way that 0.5% by weight, preferably ⁇ 0.3% by weight, in particular ⁇ 0.1% by weight, of by-products are formed by transalkylation.
  • the amine mixtures obtained after the removal of the catalyst are separated and part of the triethylamine is isomerized with the addition of ammonia. After any further separation, the diethylamine formed is then recycled as a starting material.
  • the inventive method can be designed flexibly and the product range
  • transalkylation which is carried out under conditions known to the person skilled in the art, thus provides an eductamine for the hydroamination.
  • the isomerization / hydrogenation stage can optionally be designed as a reactive distillation.
  • the described reaction of the transalkylation of the amines is carried out at temperatures from 80 to 400 ° C. 30
  • amine exchange ammum alkylation
  • Suitable dehydration catalysts as transalkylation catalysts are e.g. B. disclosed in the application DE 101 55 524.5 of the applicant dated November 12, 2001.
  • the transalkylation catalysts disclosed in this application are an integral part of the present invention and are incorporated by reference.
  • the pressure is generally from 1 to 70 bar.
  • the pressure is generally 70 to 250 bar.
  • the temperature is generally 80 to 400 ° C., in particular between 100 and 350 ° C., preferably between 120 and 250 ° C., very particularly preferably between 150 and 230 ° C.
  • the loading of the catalyst with the starting material can be between 0.05 and 2 kg of starting material per liter of catalyst and per hour (kg / l * h), preferably between 0.1 and 1 kg / l * h, particularly preferably between 0.2 and 0.6 kg / l * h.
  • the molar ratio of the amines obtained to one another can vary widely depending on the desired product mix.
  • the discharge can be distilled off and diethylamine returned or triethylamine removed as product. Any monoethylamine that may be formed is removed from the reaction cycle. Ammonia can be recycled to the transalkylation.
  • Triethylamine synthesis 40 bar, 70 ° C, catalyzed with 60 mmol sodium diethylamide

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'éthyldiméthylamine et de triéthylamine comprenant les étapes consistant à : (i) faire réagir un mélange constitué de diéthylamine et de diméthylamine avec de l'éthylène en présence d'un catalyseur issu du groupe des diméthylamides de métaux alcalins, des diéthylamides de métaux alcalins et des hydrures de métaux alcalins ; (ii) retirer le catalyseur ; (iii) séparer le mélange résultant par distillation de façon à obtenir de la triéthylamine et de l'éthyldiméthylamine et éventuellement de la diéthylamine et de la diméthylamine ; (iv) éventuellement réintroduire le catalyseur ainsi que les amines de type éduit dans la réaction. Le procédé selon l'invention permet la production jumelée d'éthyldiméthylamine et de diéthylamine au moyen d'un processus simple.
EP03711916A 2002-03-04 2003-03-03 Procede de production d'ethyldimethylamine et de triethylamine Withdrawn EP1483230A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10209528A DE10209528A1 (de) 2002-03-04 2002-03-04 Verfahren zur Herstellung von Ethyldimethylamin und Triethylamin
DE10209528 2002-03-04
PCT/EP2003/002167 WO2003074468A1 (fr) 2002-03-04 2003-03-03 Procede de production d'ethyldimethylamine et de triethylamine

Publications (1)

Publication Number Publication Date
EP1483230A1 true EP1483230A1 (fr) 2004-12-08

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EP03711916A Withdrawn EP1483230A1 (fr) 2002-03-04 2003-03-03 Procede de production d'ethyldimethylamine et de triethylamine

Country Status (15)

Country Link
US (1) US7253322B2 (fr)
EP (1) EP1483230A1 (fr)
JP (1) JP4201715B2 (fr)
KR (1) KR20040095260A (fr)
CN (1) CN1308285C (fr)
AU (1) AU2003218681A1 (fr)
BR (1) BR0308205A (fr)
CA (1) CA2478189A1 (fr)
DE (1) DE10209528A1 (fr)
EA (1) EA009067B1 (fr)
MX (1) MXPA04008531A (fr)
MY (1) MY135723A (fr)
UA (1) UA79271C2 (fr)
WO (1) WO2003074468A1 (fr)
ZA (1) ZA200407045B (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008006750A1 (fr) * 2006-07-14 2008-01-17 Basf Se Procédé de production d'une amine
JP5942857B2 (ja) * 2011-02-01 2016-06-29 三菱瓦斯化学株式会社 アミノ化合物の製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2501556A (en) * 1949-12-16 1950-03-21 Du Pont Alkali metals and their hydrides as catalysts in amine condensation
US2750417A (en) 1953-04-14 1956-06-12 Ethyl Corp Amine alkylation
FR2088610A5 (fr) * 1970-04-17 1972-01-07 Commissariat Energie Atomique
CA1176661A (fr) * 1980-04-28 1984-10-23 David M. Gardner Reparation d'amines a partir d'olefines par recours a des catalyseurs faits de certains metaux de transition
US4336162A (en) 1980-12-18 1982-06-22 Allied Corporation Alkali metal amide catalyst
US4302603A (en) 1980-12-18 1981-11-24 Allied Chemical Corporation Producing alkylamines from olefins with alkali metal amide catalyst
DE10030619A1 (de) * 2000-06-28 2002-01-10 Basf Ag Verfahren zur Herstellung von Alkylaminen

Non-Patent Citations (1)

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Title
See references of WO03074468A1 *

Also Published As

Publication number Publication date
ZA200407045B (en) 2005-09-12
DE10209528A1 (de) 2003-09-18
WO2003074468A1 (fr) 2003-09-12
EA200401151A1 (ru) 2005-04-28
UA79271C2 (en) 2007-06-11
JP2005526743A (ja) 2005-09-08
BR0308205A (pt) 2005-04-26
AU2003218681A1 (en) 2003-09-16
CA2478189A1 (fr) 2003-09-12
MXPA04008531A (es) 2004-12-06
CN1649825A (zh) 2005-08-03
CN1308285C (zh) 2007-04-04
MY135723A (en) 2008-06-30
KR20040095260A (ko) 2004-11-12
US20050154235A1 (en) 2005-07-14
JP4201715B2 (ja) 2008-12-24
EA009067B1 (ru) 2007-10-26
US7253322B2 (en) 2007-08-07

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