Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
  • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
  • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
  • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
  • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • 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

Definitions

• the present invention relates to a process for the preparation of a mono-N-alkyl-piperazine of the formula I.
• R 1 is d- to Cs-alkyl or 2- (2-hydroxy-ethoxy) -ethyl, by reacting diethanolamine (DEOA) of the formula II
• the process products find inter alia. Use as intermediates in the preparation of fuel additives (US 3,275,554 A, DE 21 25 039 A and DE 36 1 1 230 A), surfactants, pharmaceutical and plant protection agents, hardeners for epoxy resins, catalysts for polyurethanes, intermediates for the preparation of quaternary ammonium compounds, plasticizers, Corrosion inhibitors, synthetic resins, ion exchangers, textile auxiliaries, dyes, vulcanization accelerators and / or emulsifiers.
• WO 201 1/067199 A1 (BASF SE) relates to certain aluminum oxide, copper, nickel, cobalt and tin-containing catalysts and their use in processes for the preparation of an amine from a primary or secondary alcohol, aldehyde and / or ketone.
• the preparation of N-methyl-piperazine from DEOA and monomethylamine is generally mentioned on page 25, lines 20-21.
• WO 201 1/157710 A1 BASF SE describes the preparation of certain cyclic tertiary methylamines, wherein an amino alcohol from the group 1, 4-aminobutanol, 1, 5-aminopentanol, aminodiglycol (ADG) or aminoethyl ethanolamine, with methanol at elevated temperature in the presence of a copper-containing heterogeneous catalyst in the liquid phase.
• ADG aminodiglycol
• ADG aminoethyl ethanolamine
• WO 2012/049101 A1 (BASF SE) relates to a process for preparing certain cyclic tertiary amines by reacting an amino alcohol from the group 1, 4-aminobutanol, 1, 5-aminopentanol, aminodiglycol (ADG) or aminoethyl-ethanolamine, with a particular primary or secondary alcohol at elevated temperature in the presence of a copper-containing heterogeneous catalyst in the liquid phase.
• CN 102 101 847 A Zhangjiagang Tianyou New Materials Techn. Co., Ltd. describes a two-step synthesis of N-methyl-N- (2-chloroethyl) -piperazine from aminodiglycol (ADG) via N-methyl-piperazine as an intermediate.
• CN 102 304 101 A (Shaoxing Xingxin Chem. Co., Ltd.) relates to the simultaneous production of piperazine and N-alkylpiperazines by reacting N-hydroxyethyl-1, 2-ethanediamine with primary C-7 alcohols in the presence of metallic catalysts
• EP 446 783 A2 (BASF AG) relates inter alia. the preparation of N-aryl-substituted piperazines by amination of corresponding N, N-di- (2-hydroxyalkyl) -N-aryl-amines.
• EP 235 651 A1 (BASF AG) teaches a process for the preparation of N-methyl-piperazine from DE-OA and methylamine in the presence of metal-containing supported catalysts, in particular Cu-containing catalysts.
• WO 04/085356 A1 and WO 2010/1 15759 A2 (both BASF AG) describe the use of certain Al 2 O 3 / Cu / lanthanum oxide catalysts for the hydrogenation of certain carbonyl compounds. It was an object of the present invention to improve the economy of previous processes for the preparation of mono-N-alkyl-piperazines of the formula I and to remedy a disadvantage or several disadvantages of the prior art. It should be found conditions which are technically easy to prepare and which allow the process with high conversion, high yield, space-time yields (RZA), selectivity coupled with high mechanical stability of the catalyst molding and lower .
• RZA space-time yields
• the oxide material is obtainable by simultaneously or sequentially precipitating the component copper oxide, the component alumina and the component lanthanum oxide and then drying and calcining
• the catalyst molding is calcined again.
• the radical R 1 is 2- (2-hydroxyethoxy) ethyl or C 1-5 -alkyl, preferably C 1-3 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, more preferably methyl, ethyl and 2- (2-hydroxy ethoxy) -ethyl.
• the primary amine III is particularly preferably monomethylamine, monoethylamine or 1-amino-2- (2-hydroxyethoxy) ethane (aminodiglycol, ADG).
• catalyst body particles are used, which are characterized in that the oxidic material
• alumina at a level in the range of 15 to 35% by weight, preferably 20 to ⁇ 30% by weight, and
• the process can be carried out continuously or batchwise. Preferred is a continuous driving style.
• the starting materials (DEOA, the primary amine III) are evaporated in a circulating gas stream and fed into the reactor in gaseous form.
• the educts (DEOA, the primary amine III) can also be evaporated as aqueous solutions and passed with the circulating gas stream on the catalyst bed.
• Preferred reactors are tubular reactors. Examples of suitable reactors with recycle gas stream can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. B 4, pages 199-238, "Fixed-Bed Reactors".
• the reaction is advantageously carried out in a tube bundle reactor or in a monostane system.
• a tube bundle reactor or in a monostane system.
• a Monostrangstrom the tubular reactor in which the reaction takes place from a
• the cycle gas preferably contains at least 10, especially 50 to 100, especially 80 to 100,% by volume of hydrogen (H 2 ).
• the shaped catalyst bodies are used as full, impregnating, shelling or precipitation catalysts.
• the catalyst for the amination used in the process according to the invention is characterized in that the component copper oxide, the component aluminum oxide and the component lanthanum oxide, preferably with a soda solution, are precipitated simultaneously or successively, subsequently dried, calcined, deformed, eg tabletted, and calcined again.
• Copper oxide means CuO, CU2O or a mixture of both oxides.
• copper (I) oxide is calculated as copper (II) oxide.
• Alumina Al2O3 and lanthanum oxide means La2Ü3.
• precipitation method is considered:
• a copper salt solution, an aluminum salt solution and a solution of a salt of lanthanum or a solution containing copper, aluminum and lanthanum salt are simultaneously precipitated with a soda solution.
• a copper salt solution and, separately, a solution of a salt of lanthanum or a solution containing copper salt and a salt of lanthanum on a prefabricated alumina support.
• This is in a particularly preferred embodiment as a powder in an aqueous suspension.
• the carrier material may, however, be e.g. also present as balls, strands, chippings or tablets.
• a copper salt solution and a solution of a salt of lanthanum or a solution containing copper salt and a salt of lanthanum, preferably with soda solution, precipitated As a template, an aqueous suspension of the support material alumina is used.
• Precipitated precipitates resulting from A) or B) are separated in a conventional manner, e.g. filtered, and preferably washed alkali-free, as described for example in DE 198 09 418 A1 (BASF AG).
• these are dried at elevated temperature, especially at temperatures of 50 to 150 ° C, preferably at 1 10 to 130 ° C (eg over a period of 5 up to 30 hours, preferably 10 to 20 hours) and subsequently, preferably, for example over a period of 0.5 to 6 hours, especially 1 to 3 hours, at generally 200 to 700 ° C, especially at 400 to 650 ° C, calcined.
• solvents (preferably water) used in the precipitation can be soluble Cu (I) and / or Cu (II) salts, for example nitrates, carbonates, acetates, oxalates or ammonium complexes, as well as analogous aluminum salts and salts of lanthanum.
• Particular preference is given to using copper (II) nitrate as the copper salt.
• the lanthanum salt used is preferably lanthanum nitrate.
• the aluminum salt used is preferably aluminum nitrate.
• the composition of the oxide material is preferably such that the proportion of copper oxide in the range of 50 to 80 wt .-%, particularly 55 to 75 wt .-%, each calculated as CuO, the proportion of lanthanum oxide in the range of 2 to 20 Wt .-%, especially 3 to 15 Wt .-%, and the proportion of aluminum oxide in the range 15 to 35 wt .-%, particularly 20 to 30 wt .-%, for all components in each case based on the total weight of the sum of the above-mentioned oxidic constituents, these three Oxides together represent at least 80 wt .-%, particularly at least 95 wt .-%, of the oxidic material after calcination, wherein optionally added cement, for example alumina cement, is not attributed to the oxidic material in the above sense.
• optionally added cement for example alumina cement
• the present invention therefore relates to a method as described above, which is characterized in that the oxidic material
• alumina at a level in the range of 15 to 35% by weight, preferably 20 to ⁇ 30% by weight, and
• the catalysts used in the process according to the invention are also distinguished by the fact that the addition of the lanthanum salt in the precipitation leads to a high stability of the finally resulting molded body used as catalyst.
• the oxidic material is / are then added (step ii) powdered copper and / or copper flakes and optionally graphite. Preference is given to adding powdered copper and graphite.
• the addition of graphite can also be carried out before the copper addition, in which case preferably precompacting is carried out first.
• the powdered copper used is preferably one which has a particle diameter in the range from 1 to 700 ⁇ m, preferably in the range from 5 to 500 ⁇ m. Particular preference is given to using a pulverulent copper in which the sieve analysis gives a proportion of particles> 500 ⁇ m of ⁇ 6%, in particular a fraction of particles> 350 ⁇ m of ⁇ 5%.
• the grain morphology is preferably spherical.
• the copper sheets used are preferably those which have a D 50 value in the range from 5 to 40 ⁇ m, in particular in the range from 10 to 35 ⁇ m (', D 50 value' means 50% of the particles are smaller than the specified value).
• the sieve analysis gives a proportion of particles> 45 ⁇ of ⁇ 6%, especially ⁇ 2%.
• the copper flakes preferably have a lamellar flake structure.
• powdered copper and / or copper flakes are taken together in amounts ranging from 0.5 to 40 wt .-%, preferably in the range of 2 to 20 wt .-%, particularly preferably in the range of 3 to 10 wt .-%, respectively based on the total weight of the oxidic material after calicination.
• the oxidic material in a proportion of at most 10 wt .-%, preferably at most 5 wt .-%, based on the total weight of the oxidic material after calcination, at least one further component selected from the group consisting of Oxides of the elements Re, Fe, Ru, Co, Rh, Ir, Ni, Pd and Pt.
• the shaped catalyst body contains no oxygen-containing compounds of silicon, zirconium and / or chromium.
• the shaped catalyst body contains no oxygen-containing compounds of titanium.
• step iii the mixture resulting from step ii is shaped into a shaped article and then calcined.
• graphite is added to the mixture prior to molding to form the body.
• so much graphite is added that the deformation can be better performed to form a molded body.
• the sum of the proportions of oxidic material, metallic copper powder and / or copper flakes and possibly graphite preferably gives at least 95 wt .-%, particularly at least 98 wt .-%, of the catalyst molding.
• the deformation in step iii preferably leads to tablets, rings, ring tablets, extrudates, honeycomb bodies or similar shaped bodies. All methods known from the prior art are suitable for this purpose. Moldings obtained after the deformation are calcined again, at least once. The calcination is preferably carried out over a period of generally 0.5 to 10 hours (h), especially 0.5 to 2.5 hours.
• the temperature in this at least one calcination step is generally in the range of 200 to 600 ° C, preferably in the range of 250 to 500 ° C, and more preferably in the range of 270 to 400 ° C.
• the molded body obtained can also be treated with boiling water and / or steam before it is used for the amination.
• the shaped body When used as a catalyst in the oxidic form, the shaped body before charging with the educts with reducing gases, for example hydrogen, preferably hydrogen / inert gas mixtures, in particular hydrogen / nitrogen mixtures, at elevated temperatures, e.g. in the range of 100 to 500 ° C, preferably in the range of 150 to 350 ° C and in particular in the range of 180 to 200 ° C, prereduced. Preference is given to using a gas mixture having a hydrogen content in the range from 1 to 100% by volume, particularly preferably in the range from 1 to 50% by volume.
• the shaped body is activated prior to use as a catalyst in a conventional manner by treatment with reducing media. The activation takes place either in advance in a reduction furnace or after installation in the reactor. If the reactor was previously activated in the reduction furnace, it is installed in the reactor and charged directly under hydrogen pressure with the starting materials.
• gases for example hydrogen, preferably hydrogen / inert gas mixtures, in particular hydrogen / nitrogen mixtures
• the inventive method is preferably carried out continuously, wherein the catalyst is preferably arranged as a fixed bed in the reactor. Both an inflow of the fixed catalyst bed from above and from below is possible.
• the primary amine III is preferably in the molar amount of 0.5 to 20 times, more preferably in the molar amount of 2 to 17 times, particularly in the molar amount of 5 to 15 times, especially in the 6 to 15 molar amount 14-fold molar amount, further particularly in the 7- to 13-fold molar amount, especially in the 8 to 12-fold molar amount, more particularly in the 8 to 10-fold molar amount, in each case based on the used DEOA.
• the primary amine is particularly preferred in the 0.5 to 2-fold, in particular in the 0.6 to 1, 2-fold, molar amount, in each case based on the used DEOA.
• the primary amine III is particularly preferred in the case of monomethylamine (MMA) as the primary amine III, the primary amine in the 4- to 13-fold, in particular in the 5- to 12-fold molar amount, in each case based on the DEOA used.
• the primary amine in the 2- to 10-fold is particularly preferred in the case of monoethylamine (MEA) as the primary amine III, the primary amine in the 2- to 10-fold, in particular in the 3- to 9-fold molar amount, in each case based on the DEOA used.
• the primary amine III can be used as an aqueous solution, especially as a 30 to 95 wt .-% aqueous solution, for. As well as 65 to 90 wt .-% aqueous solution can be used.
• Monomethylamine and monoethylamine are preferably also used without further solvent (compressed gas, purity especially 95 to 100 wt .-% strength).
• the starting material DEOA is preferably used as an aqueous solution, in particular as a 75 to 95% strength by weight aqueous solution, for example as an 80 to 85% strength by weight aqueous solution.
• Catalyst volume data always refer to the bulk volume.
• the amination of the primary alcohol groups of the starting material DEOA is carried out in the liquid phase.
• the fixed bed process is in the liquid phase.
• the educts (DEOA, primary amine III) including hydrogen are first passed at a temperature in the range from 80 to 160.degree. C., preferably 100 to 140.degree. C., more preferably 110 to 130.degree. C., over the catalyst and then, e.g. after 1 to 240 minutes, preferably 5 to 120 minutes, particularly preferably 10 to 90 minutes, more preferably 20 to 60 minutes, the temperature is increased to 180 to 240 ° C, especially 180 to 235 ° C, preferably 185 to 230 ° C, in particular 190 to 225 ° C.
• a procedure for starting up at lower temperatures is upstream.
• the reaction product resulting from the start-up procedure can be discarded or returned to the conversion.
• the reactants are passed, preferably simultaneously, in the liquid phase at pressures of 15.0 to 25.0 MPa (150 to 250 bar), preferably 15.5 to 23.0 MPa , More preferably 16.0 to 22.0 MPa, more preferably 16.5 to 21, 5 MPa, more preferably 17.0 to 21, 0 MPa, and temperatures of generally 180 to 240 ° C, especially 180 to 235 ° C, preferably 185 to 230 ° C, in particular 190 to 225 ° C, including hydrogen over the catalyst, which is usually located in a preferably heated from outside fixed bed reactor. It is both a trickle way and a sumping possible.
• the catalyst loading is generally in the range of 0.2 to 0.8, preferably 0.3 to 0.7, more preferably 0.4 to 0.6, more preferably 0.4 to 0.5, kg of DEOA per liter of catalyst
• reaction volume (Bulk volume) and hour (DEOA calculated as 100%).
• dilution of the reactants with a suitable solvent such as water, tetrahydrofuran, dioxane, N- Methylpyrrolidone or ethylene glycol dimethyl ether, take place.
• a suitable solvent such as water, tetrahydrofuran, dioxane, N- Methylpyrrolidone or ethylene glycol dimethyl ether
• the reaction is preferably carried out at a catalyst loading in the range of 100 to 1500 standard liters of hydrogen / (cat ⁇ hr), especially a catalyst loading in the range of 400 to 1400 standard liters of hydrogen / (1 Ka ⁇ t ⁇ h).
• the catalyst is arranged as a fixed bed, it may be advantageous for the selectivity of the reaction to mix the shaped catalyst bodies in the reactor with inert fillers, so to say to "dilute" them.
• the proportion of fillers in such catalyst preparations may be 20 to 80, especially 30 to 60 and especially 40 to 50 parts by volume.
• reaction water formed in the course of the reaction in each case one mole per mole of reacted alcohol group
• the reaction water formed in the course of the reaction generally does not interfere with the degree of conversion, the rate of reaction, the selectivity and the catalyst lifetime and is therefore expediently removed from the reaction product only during the work-up of the reaction product , z. B. distillative.
• the excess hydrogen and the excess amination agent present, if any, are removed from the reaction effluent and the reaction crude product obtained is purified, for. B. by a fractional rectification. Suitable work-up procedures are for. In EP 1 312 600 A and EP 1 312 599 A (both BASF AG). The excess primary amine and the hydrogen are advantageously returned to the reaction zone. The same applies to the possibly not fully implemented DEOA.
• a workup of the product of the reaction is preferably configured as follows:
• R 1 C 1 to C 12 -alkyl, detached overhead
• step iv from the bottom of step iv optionally present unreacted DEOA (II) and / or optionally present Alkylaminoethylethanolamin as a byproduct with the formula IV is removed overhead and recycled to the reaction.
• step i separated primary amine III having a purity of 90 to 99.9 wt .-%, especially 95 to 99.9 wt .-% is preferably recycled to the reaction, wherein more preferably a portion of the separated amine III , Particularly 1 to 30 wt .-% of the separated amine III, more particularly 2 to 25 wt .-% of the separated amine III, is discharged.
• the resulting compactate was coated with 5% by weight of Cu flakes having a D 50 value in the range from 5 to 40 ⁇ m (obtainable, for example, from Schlenk Metallpulver GmbH & Co. KG, D-91 154 Roth-Barnsdorf). , and then mixed with 2 wt .-% graphite and pressed into tablets of 3 mm diameter and 3 mm in height. The tablets were finally calcined for 2 hours at 350 ° C.
• the catalyst thus prepared had the chemical composition of 61, 5 wt .-% CuO / 28.5 wt .-% Al 2 0 3 / 5.0 wt .-% La 2 0 3/5 wt .-% Cu, (graphite content eliminated).
• a heated tubular reactor with 14 mm inner diameter, a centrally mounted thermocouple and a total volume of 1000 ml was filled in the lower part with a layer of glass beads (250 ml), over this filled with 500 ml of the catalyst A and finally the remaining part with glass beads.
• the reactor was maintained at a temperature of about 185 to 220 ° C and a total pressure of 200 bar.
• the reaction temperature was chosen so that a DEOA conversion of> 90% was achieved.
• the mixture leaving the reactor was cooled and vented to atmospheric pressure.
• samples were taken from the reaction mixture and analyzed by gas chromatography.
• a 30 m long GC column "RTX-5 Amines” was used, with a temperature program: 70 ° C / 5 min, heat to 280 ° C at a rate of 5 ° C / min, at 280 ° C / 10 minutes.
• NMePIP monomethylpiperazine (N-methyl-PIP)
• a 30 m long GC column "RTX-5 Amines” was used, with a temperature program: 70 ° C / 5 min, heat to 280 ° C at a rate of 5 ° C / min, at 280 ° C / 10 minutes.
• NEtPIP monoethylpiperazine (N-ethyl-PIP)
• a batch reactor with stirrer, a thermocouple and a total volume of 300 ml was filled with 7.5 g of activated catalyst.
• the starting material mixture of DEOA and ADG was initially charged and the reactor was heated to 180.degree. The entire reaction mixture was then charged with 200 bar of hydrogen. At various times, samples were taken from the reaction mixture and analyzed by gas chromatography.
• a 30 m long GC column "RTX-5 Amines” was used, with a temperature program: 70 ° C / 5 min, heat to 280 ° C at a rate of 5 ° C / min, at 280 ° C / 10 minutes.
• ADG DEOA DEOA ADG OEtPIP HEOEtPIP mol / mol ref. DEOA bez.
• the work-up may preferably be carried out by the following five steps (in this case using the example of a reaction of DEOA with monomethylamine or monoethylamine):

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