Products obtained by conversion of glycolaldehyde derivatives with aminating agents and their conversion to ethyleneamines and ethanolamines

Abstract

A method for preparing ethyleneamines and ethanolamines, comprising the following steps: (i) converting an ethanolaldehyde derivative of formula (II) in a gas phase or a liquid phase, wherein R 2 , R 3 The same or different, is hydrogen, alkyl such as C 1‑6 Alkyl, or cycloalkyl such as C 3‑6 Cycloalkyl; and an aminating agent of formula (III), wherein R 1 is hydrogen (H), alkyl such as C 1‑6 Alkyl, or cycloalkyl such as C 3‑6 (ii) feeding the reaction product obtained in step (i) to a hydrogenation reactor, wherein the reaction product is converted with hydrogen in the presence of a hydrogenation catalyst.

Description

[0001] The present invention relates to a process for preparing ethyleneamines and ethanolamines by hydrogenating an intermediate formed by the conversion of an aminating agent and a glycolaldehyde derivative. The present invention further relates to novel triazinane derivatives, which are formed as intermediates by the conversion of an aminating agent and a glycolaldehyde derivative.

[0002] Glycolaldehyde is a useful raw material for the preparation of ethyleneamines and ethanolamines.

[0003] US 6,534,441 describes a process for the reductive amination of lower aliphatic paraffin derivatives using a nickel / rhenium catalyst. A possible starting material mentioned in the specification is ethanolaldehyde.

[0004] German patent application DE-A1-400591 describes a process for preparing amino alcohols by reacting hydroxycarbonyl compounds with hydrogen and an aminating agent at temperatures of 0-300° C. and pressures of 1-400 bar over a catalyst comprising 50-100% by weight of ruthenium. Glycolaldehyde is disclosed as a suitable hydroxycarbonyl compound for use in the process.

[0005] US 6,147,261 discloses the conversion of hydroxyalkanals to diamines in the presence of ammonia and hydrogen in the presence of a catalyst comprising nickel or cobalt. US 6,147,261 teaches that hydroxyalkanals are very reactive and tend to oligomerize and polymerize.

[0006] Although US Pat. No. 6,147,261, DE-A1-4400591 and US Pat. No. 6,534,441 mention the use of glycolaldehyde as a starting material in the reaction with an aminating agent, the specific reaction illustrated in the examples is not described.

[0007] CN107011194 discloses a method for converting glycolaldehyde using a noble metal catalyst containing a rare earth metal in the presence of hydrogen with different aminating agents such as ammonia, methylamine, ethylamine and butylamine.

[0008] WO2011 / 082994 discloses the conversion of glycolaldehyde with an aminating agent such as ammonia in the presence of hydrogen. Since glycolaldehyde tends to form oligomers, such as dimer 2,5-dihydroxy-1,4-dioxane, the six-membered ring compound formed has high thermodynamic stability, the conversion requires preactivation of the non-precious metal amination catalyst to achieve high conversion.

[0009] The effect of catalyst preactivation was subsequently confirmed by Liang et al. (Angew. Chem. 2017, 129, 3096-3100), who studied the conversion of ethanolaldehyde with ammonia in the presence of hydrogen and Ru catalyst.

[0010] Pelckmans et al. (ACS Catal. 2018, 8, 4201-4212) studied the reductive amination of various sugars with dimethylamine in the presence of hydrogen and different metal catalysts. The formation of glycolaldehyde as an intermediate during the reductive aminolysis of sugars was proposed. Therefore, the authors studied the reaction behavior of pure glycolaldehyde with dimethylamine and hydrogen on a nickel catalyst as a model reaction. High TMEDA and DMEOA conversions were obtained in MeOH solution.

[0011] WO 2011 / 082967 discloses the amination of glycolaldehyde with aminating agents MEA and DEA in the presence of hydrogen and an amination catalyst to produce alkanolamines.

[0012] The above application discloses the conversion of glycolaldehyde in the presence of a heterogeneous catalyst, ie an amination or hydrogenation catalyst.

[0013] US 4,677,213 discloses the reaction of glycolaldehyde with a primary amine as an aminating agent in the absence of a heterogeneous catalyst. At a temperature of 0-70° C., under an inert gas, 2,5-diamino-1,4-dioxane derivatives are obtained. US 4,677,213 discloses further conversion of dioxane derivatives with hydrocyanic acid to obtain amino acids.

[0014] The object of the present invention is to provide a process for preparing ethyleneamines and ethanolamines based on the glycolaldehyde used in the reaction with high yield. Another object is to obtain a high degree of conversion of glycolaldehyde and to obtain the desired ethyleneamines and ethanolamines with high selectivity. Another object is to provide a process for converting glycolaldehyde which does not require preactivation of the catalyst as described in WO2011 / 082994.

[0015] The purpose of the present invention is achieved as follows:

[0016] A method for preparing ethyleneamines and ethanolamines, comprising the following steps:

[0017] (i) converting the glycolaldehyde derivative of formula (II) in the gas phase or liquid phase:

[0018]

[0019] Where R 2 , R 3 The same or different, is hydrogen, alkyl such as C 1-6 Alkyl, or cycloalkyl such as C 3-6 Cycloalkyl; and

[0020] Aminating agent of formula (III):

[0021] R1-NH2 (III)

[0022] Where R1 is hydrogen (H), alkyl such as C 1-6 Alkyl, or cycloalkyl such as C 3-6 Cycloalkyl;

[0023] (ii) The reaction product obtained in step (i) is fed to a hydrogenation reactor, wherein the reaction product is converted with hydrogen in the presence of a hydrogenation catalyst.

[0024] Step (i):

[0025] In the process of the present invention, the glycolaldehyde derivative of formula (II) is converted with an aminating agent of formula (III).

[0026] In the glycolaldehyde derivative of formula (II), the group R 2 and R 3 Can be:

[0027] Hydrogen (H),

[0028] Alkyl groups, such as C 1-6 Alkyl, preferably C 1-4 alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl,

[0029] Cycloalkyl, such as C 3-6 The cycloalkyl group is preferably cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0030] In formula (II), the group R 2 and R 3 Can be the same or different.

[0031] Different groups R can be used 2 and R 3 A mixture of different ethanolaldehyde derivatives of formula (II).

[0032] Preferably, the glycolaldehyde derivative of formula (II) is glycolaldehyde, wherein R 2 and R 3 All are hydrogen groups (H).

[0033] Glycolaldehyde is commercially available and can be prepared, for example, by oxidation of ethylene glycol (see, for example, JP3246248 and JP3279342).

[0034] Glycolaldehyde is preferably synthesized by reaction of formaldehyde with carbon monoxide and hydrogen, as described, for example, in US2009012333, US2008081931, US2007249871, EP1697291, US4503260 and US4322568.

[0035] Glycolaldehyde can also be obtained from the pyrolysis of biomass such as sugar or wood, as disclosed in US 2004 / 0022912 or D. Mohan et al. ("Pyrolysis of Wood / Biomass for Bio-Oil", Energy Fuels 2006, 20, 3, 848-889) or CR Vitasari (Extraction of bio-based Glycolaldehyde from wood-derived pyrolysis oils Eindhoven: Technische Universiteit Eindhoven DOI: 10.6100 / IR738958).

[0036] In the aminating agent of formula (III), the group R 3 Can be:

[0037] Hydrogen (H),

[0038] Alkyl groups, such as C 1-6 Alkyl, preferably C 1-4 alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl,

[0039] Cycloalkyl, such as C 3-6 The cycloalkyl group is preferably cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0040] Preferably, the aminating agent of formula (III) is methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine and isobutylamine.

[0041] Most preferably, the aminating agent of formula (III) is ammonia.

[0042] It is also possible to use mixtures of aminating agents of the formula (III).

[0043] The aminating agent and the glycolaldehyde derivative may be provided to step (i) in gaseous or liquid form.

[0044] In a preferred embodiment, glycolaldehyde is provided to step (i) in liquid form.

[0045] Some glycolaldehyde derivatives of formula (II) are liquid at ambient temperature.

[0046] Glycolaldehyde itself has a melting point of about 96-97°C and a boiling point of about 131°C.

[0047] Due to the tendency of glycolaldehyde to form stable dimers in both solid and liquid phases, in a preferred embodiment the glycolaldehyde derivative is provided to step (i) in liquid form as a mixture in one or more solvents.

[0048] The solvent may be any solvent which is inert under the reaction conditions and has sufficient solubility for the reactants.

[0049] Preferably, the one or more solvents are selected from water, alcohols, acyclic or cyclic ethers, polyalkyl ethers and alkoxy polyalkyl ethers.

[0050] More preferably, the one or more solvents are selected from water, methanol, ethanol, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraglyme), dipropylene glycol dimethyl ether, bis(2-methoxyethyl) ether (diglyme) or other ethers of oligo- and poly-propylene oxides and oligo- and poly-ethylene oxides or mixed oligo- or poly-alkylene oxides.

[0051] Particular preference is given to water, THF, tetraglyme, dipropylene glycol dimethyl ether and diglyme.

[0052] Most preferably, a mixture of water and tetrahydrofuran is used as solvent, wherein the molar ratio of water to THF is from 1:1 to 20:1, more preferably from 4:1 to 15:1, most preferably from 5:1 to 10:1.

[0053] Even more preferably, a mixture of water and alkoxy polyalkyl ether is used as solvent, wherein the molar ratio of water to alkoxy polyalkyl ether is from 200:1 to 100:10, more preferably from 150:1 to 100:5, most preferably from 125:1 to 100:3. Preferably, the alkoxy polyalkyl ether is selected from dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.

[0054] Preferably, the concentration of the solution of the glycoaldehyde derivative of formula (II) is 1-95% by weight, preferably 10-85% by weight, more preferably 25-80% by weight, and most preferably 50-75% by weight, based on the weight of the glycoaldehyde derivative of formula (II) and the total weight of the solvent or solvents in which the glycoaldehyde derivative of formula (II) is dissolved.

[0055] In another preferred embodiment, the solution of the ethanolaldehyde derivative of formula (II) is directly obtained from the preparation method of the ethanolaldehyde derivative of formula (II). The solution can be obtained by cleaving an aqueous solution of an organic raw material at high temperature and condensing the gaseous effluent obtained from the cleavage reaction.

[0056] In a more preferred embodiment, the glycolaldehyde is obtained by pyrolysis of wood by (i) hydrothermal decomposition of sugars, such as the process disclosed in US 2004 / 0022912 (which is incorporated herein by reference), and (ii) condensing the gaseous effluent from the pyrolysis process or the process described by D. Mohan et al. ("Pyrolysis of Wood / Biomass for Bio-Oil", Energy Fuels 2006, 20, 3, 848-889) or CR Vitasari (Extraction of bio-based Glycolaldehyde from wood-derived pyrolysis oils Eindhoven: Technische Universiteit Eindhoven DOI: 10.6100 / IR738958), which are also incorporated herein by reference.

[0057] Preferably, the concentration of glycolaldehyde in the aqueous solution is 5-80% by weight, most preferably 10-70% by weight, and most preferably 25-60% by weight.

[0058] The aqueous solution obtained by these methods may contain other oxygen-containing compounds, such as formaldehyde, hydroxyacetone (acetol), dihydroxyacetone, glyoxal, methylglyoxal (methylglyoxal), acetic acid, levulinic acid, propionic acid, acrylic acid, glycolic acid, methanol, acetone and formic acid. Before the aqueous solution is provided to step (i), one or more of the above solvents may be added to the glycolaldehyde aqueous solution in the above amounts.

[0059] In a more preferred embodiment, the glycolaldehyde derivative is provided to step (i) in gaseous form.

[0060] In one embodiment, the glycolaldehyde derivative is provided in gaseous form by evaporating a liquid glycolaldehyde derivative in pure form.

[0061] In a more preferred embodiment, the glycolaldehyde derivative is provided in gaseous form by evaporating a solution of the glycolaldehyde derivative in one or more solvents. Evaporation from solution is particularly preferred for those glycolaldehyde derivatives that tend to form high boiling dimers and tend to oligomerize or polymerize when heated.

[0062] Suitable solvents that can provide the glycolaldehyde derivative in gaseous form are solvents that are inert under the reaction conditions and have sufficient solubility for the reactants.

[0063] Preferably, the one or more solvents are selected from water, alcohols, acyclic or cyclic ethers, polyalkyl ethers and alkoxy polyalkyl ethers.

[0064] More preferably, the one or more solvents are selected from water, methanol, ethanol, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraglyme), dipropylene glycol dimethyl ether or bis(2-methoxyethyl) ether (diglyme).

[0065] Most preferably, a mixture of water and tetrahydrofuran is used as solvent, wherein the molar ratio of water to THF is from 1:1 to 20:1, more preferably from 4:1 to 15:1, most preferably from 5:1 to 10:1.

[0066] Even more preferably, a mixture of water, THF and alkoxy polyalkyl ether is used as solvent, wherein the molar ratio of water to alkoxy polyalkyl ether is from 200:1 to 100:10, more preferably from 150:1 to 100:5, most preferably from 125:1 to 100:3, and the ratio of water to THF is within the above range. Preferably, the alkoxy polyalkyl ether is selected from dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.

[0067] Preferably, the concentration of the solution of the glycolaldehyde derivative of formula (II) from which the glycolaldehyde derivative is evaporated is 1-80% by weight, preferably 2.5-50% by weight, more preferably 5-30% by weight, most preferably 5-20% by weight, based on the weight of the glycolaldehyde derivative of formula (II) and the total weight of the solvent or solvents in which the glycolaldehyde derivative of formula (II) is dissolved. The concentration of the solution from which the glycolaldehyde derivative is evaporated is usually lower than the concentration of the solution used for the liquid phase reaction, because glycolaldehyde has a tendency to oligomerize and polymerize during the evaporation process.

[0068] The evaporation of the glycoaldehyde derivative of formula (II) or its respective solution can be carried out by operations known in the art, for example by heating the liquid to a temperature above the boiling point of the glycoaldehyde derivative of formula (II) and / or by reducing the pressure and / or by passing a gas stream through the liquid glycoaldehyde derivative of formula (II).

[0069] Preferably, the glycolaldehyde derivative of the formula (II) is transferred into the gas phase by evaporation with heating in a gas stream.

[0070] The gas is preferably hydrogen or an inert gas such as nitrogen or a rare gas such as He, Ne Ar, Kr or Xe.

[0071] Preferably, the gas is hydrogen, nitrogen or a mixture thereof.

[0072] Evaporators which can be used for evaporating the glycolaldehyde derivatives and their respective solutions are natural or forced circulation evaporators, falling film evaporators, rising film (or long tube vertical) evaporators, rising and falling film plate evaporators, multiple effect evaporators and stirred thin film evaporators. The evaporation can also be carried out by flash evaporation.

[0073] In another preferred embodiment, the glycoaldehyde derivative of the formula (II) in gaseous form is provided directly from the preparation process for preparing the glycoaldehyde derivative of the formula (II).

[0074] The gaseous stream can be obtained by cracking an aqueous solution of an organic raw material at high temperature.

[0075] In a more preferred embodiment, the glycolaldehyde solution is obtained by hydrothermal decomposition of sugars, such as the method disclosed in US 2004 / 0022912, which is incorporated herein by reference.

[0076] The advantage of using a stream directly from the preparation in which the glycolaldehyde derivative is already present in gaseous form is that the concentration of the glycolaldehyde derivative in the gaseous stream can be higher than in a stream in which the glycolaldehyde derivative is obtained in gaseous form by evaporation from a solution of the glycolaldehyde derivative.

[0077] Thus, in the preferred embodiment, the glycolaldehyde concentration in the gas stream is preferably 5-80 wt%, most preferably 10-70 wt%, most preferably 25-60 wt%.

[0078] The gas stream obtained by this process may comprise other oxygenates, for example formaldehyde, hydroxyacetone (acetol), dihydroxyacetone, glyoxal, methylglyoxal (methylglyoxal), acetic acid, levulinic acid, propionic acid, acrylic acid, glycolic acid, methanol, acetone and formic acid.

[0079] The aminating agent of formula (III) can also be provided to step (i) in gaseous or liquid form.

[0080] If the aminating agent is used in its liquid form, it is preferably used in its pure form.

[0081] The aminating agent may also be provided in the form of a solution thereof in one or more solvents. Preferably, the one or more solvents are the same as the solvent used to prepare the glycolaldehyde derivative solution. More preferably, an aqueous solution of the aminating agent is provided to step (i).

[0082] The concentration of the aminating agent in the solution is preferably 5-75% by weight, more preferably 10-60% by weight, more preferably 15-35% by weight, based on the total weight of the aminating agent and the sum of all solvents used for the solution.

[0083] The aminating agent may also be provided in gaseous form.

[0084] Some preferred aminating agents, such as ammonia, methylamine, and ethylamine, exist in gaseous form under ambient conditions.

[0085] Alternatively, the aminating agent can be transferred into the gas phase by evaporating the aminating agent in pure form or by evaporating a solution of the aminating agent as described above.

[0086] The molar ratio of the glycolaldehyde derivative of formula (II) to the aminating agent is preferably 1:1 to 100:1, more preferably 1:1 to 25:1, most preferably 1:1 to 15:1.

[0087] The conversion of the glycolaldehyde derivative and the aminating agent is preferably carried out under the following conditions: the hydrogenation or reductive amination of the glycolaldehyde derivative of formula (II), the aminating agent of formula (III) and any reaction products of the aminating agent and the glycolaldehyde derivative, in particular any triazine derivative of formula (I) and any diaminodioxane derivative of formula (IV) is substantially prevented or inhibited. In particular, the conditions include the absence of a hydrogenation catalyst and / or hydrogen in step (i). If hydrogen is present in step (i), step (i) is preferably carried out in the absence of a hydrogenation catalyst. If a hydrogenation catalyst is present in step (i), step (i) is preferably carried out in the absence of hydrogen. If hydrogen and a hydrogenation catalyst are present in step (i), the reaction conditions—in particular the temperature—are selected within a range that effectively inhibits hydrogenation, such as ambient temperature. If only a small amount of ethyleneamines such as ethylenediamine and alkanolamines such as monoethanolamine and diethanolamine are formed in step (i), hydrogenation and reductive amination are substantially prevented.

[0088] The conversion is preferably carried out under conditions that substantially prevent oxidation of the glycolaldehyde derivative. Therefore, the reaction is preferably carried out under inert conditions, preferably in a sealed system, or more preferably in an inert gas stream such as hydrogen, nitrogen or a rare gas such as He, Ne, Ar, Kr or Xe or a mixture thereof.

[0089] The conversion of the glycolaldehyde derivative and the aminating agent can be carried out in the liquid phase.

[0090] The conversion of the glycolaldehyde derivative and the aminating agent can be carried out continuously, batchwise or semi-continuously.

[0091] The conversion can be carried out in one or a series of reactors suitable for liquid phase reactions.

[0092] Preference is given to tubular reactors, reactors with external or internal recirculation, plug flow reactors, spray reactors, reaction columns and stirred tank reactors.

[0093] In a particularly preferred embodiment, the conversion is carried out in a tubular reactor.

[0094] In a further particularly preferred embodiment, the conversion is carried out in a stirred tank reactor.

[0095] The reactants may be mixed prior to entering the reactor (premixed) or they may be mixed inside the reactor.

[0096] Mixing can be performed by feeding the feed streams into a suitable reactor or into a common pipe leading to a suitable reactor.

[0097] Mixing can be facilitated through the use of conventional equipment such as pipes, nozzles, valves, static mixers, agitators, stirrers, flow meters, pumps, carrier gases, and the like.

[0098] The conversion of the glycolaldehyde derivative and the aminating agent in the liquid phase is preferably carried out at -25 to 150°C, more preferably -10 to 100°C, most preferably 0-75°C.

[0099] The conversion in the liquid phase is preferably carried out at a pressure of 0.5 to 100 bar, more preferably 0.8 to 50 bar, most preferably 1 to 20 bar.

[0100] Most preferably, the conversion in the liquid phase is carried out at a pressure of about 1 bar and at ambient temperature, for example at a temperature of 0-30°C.

[0101] In a preferred embodiment, the conversion of the glycolaldehyde derivative and the aminating agent is carried out in the gas phase.

[0102] The conversion of the glycolaldehyde derivative and the aminating agent can be carried out continuously, batchwise or semi-continuously.

[0103] The conversion can be carried out in one or a series of reactors suitable for gas phase reactions.

[0104] Preference is given to tubular reactors, reaction chambers or reactors with external or internal recirculation. In a particularly preferred embodiment, the conversion is carried out in a tubular reactor or reaction chamber.

[0105] The gaseous reactants may be mixed prior to entering the reactor (premixed), or they may be mixed inside the reactor.

[0106] The mixing can be carried out by feeding the gaseous feed streams into a suitable reactor or into a common pipe leading to a suitable reactor.

[0107] Mixing in the gas phase can be facilitated by using conventional equipment such as pipes, nozzles, valves, static mixers, flow meters, pumps, carrier gases, and the like.

[0108] The conversion in the gas phase is preferably carried out at 50-300°C, more preferably 60-250°C, most preferably 80-200°C.

[0109] The conversion in the gas phase is preferably carried out at a pressure of 0.1 to 200 bar, more preferably 0.5 to 100 bar, more preferably 1 to 30 bar, most preferably 1 to 20 bar.

[0110] The conversion of the glycolaldehyde derivative of formula (II) and the aminating agent of formula (III) can produce at least two different types of reaction products.

[0111] US 4,677,213 discloses that in step (i) the liquid phase conversion of a glycolaldehyde derivative and an aminating agent produces a reaction product identified as a diaminodioxane derivative of formula (IV):

[0112]

[0113] The group R 1 , R 2 and R 3 have the meanings given to them above.

[0114] In formula (I), each R 1 , each R 2 and each R 3 The groups may be different. This may be the case if a mixture of different glycolaldehyde derivatives of the formula (II) and a mixture of different aminating agents of the formula (III) are used as starting materials.

[0115] However, more preferably, each R 1 , each R 2 and each R 3 same.

[0116] Most preferably, each R 1 , each R 2 and each R 3 For hydrogen.

[0117] Surprisingly, it has been found that the conversion of a glycolaldehyde derivative of formula (II) and an aminating agent of formula (III) in the gas phase gives rise to a triazine derivative of formula (I):

[0118]

[0119] The group R 1 , R 2 and R 3 have the meanings given to them above.

[0120] Therefore, the present invention also relates to triazine derivatives of the formula (I).

[0121] In formula (I), each R 1 , each R 2 and each R 3 The groups may be different. This may be the case if a mixture of different glycolaldehyde derivatives of the formula (II) and a mixture of different aminating agents of the formula (III) are used as starting materials.

[0122] However, more preferably, each R 1 , each R 2 and each R 3 same.

[0123] Most preferably, each R 1 , each R 2 and each R 3 For hydrogen.

[0124] The compound of formula (V) is obtained by the reaction of ethanolaldehyde with ammonia in the gas phase:

[0125]

[0126] It cannot be excluded that the liquid or gas phase conversion of the glycolaldehyde derivative of formula (II) and the aminating agent of formula (III) may lead to other structures besides the above-mentioned diaminodioxane or triazine. Therefore, the reaction product of step (i) should not be limited to the specific structures disclosed above.

[0127] The reaction products obtained by the conversion of the glycolaldehyde derivative of the formula (II) and the aminating agent of the formula (III) in a gas phase reaction are generally high-boiling products which tend to desublimate or condense from the gas phase in solid or liquid form.

[0128] The separation of solid or liquid from the gas phase can be carried out using customary apparatus, such as inertial separators (cyclones, settling chambers, vortex chambers) or wet separators using a scrubbing liquid (Venturi scrubbers, jet scrubbers, scrubber towers).

[0129] Usable washing liquid is a liquid in which the reaction product of the glycolaldehyde derivative and the aminating agent has sufficient solubility.

[0130] Preferably, the washing liquid is selected from water, alcohols, acyclic or cyclic ethers, polyalkyl ethers and alkoxy polyethers.

[0131] More preferably, the one or more washing liquids are selected from water, methanol, ethanol, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraglyme), dipropylene glycol dimethyl ether or bis(2-methoxyethyl) ether (diglyme).

[0132] Preferably, the separation of the reaction products from the gas phase is carried out by condensation or desublimation of the reaction products. Preferably, the condensation or desublimation is carried out by feeding the gas stream into a heat exchanger.

[0133] The heat exchanger can be a shell and tube heat exchanger or a plate heat exchanger, preferably a heat exchanger.

[0134] The heat exchanger used for condensation or desublimation is preferably integrated into the process as a bypass and can therefore be easily disconnected, cleaned and integrated again while the process is running.

[0135] The cleaning on the side of the heat exchanger facing the process stream is usually carried out with a washing liquid, which strips off the adhering by-products to achieve a cleaning effect. The by-products are preferably completely or partially dissolved and removed from the heat exchanger as a solution or slurry. The cleaning speed by dissolving and discharging the products is increased by increasing the flow rate of the washing liquid during the cleaning process or by washing with heated washing liquid to increase the solubility of the reaction products in the washing liquid.

[0136] In a preferred embodiment, the conversion of the glycolaldehyde derivative and the aminating agent in step (i) is carried out in the presence of one or more washing liquids. The washing liquid is usually evaporated together with the aminating agent or the glycolaldehyde derivative and provided to step (i) in gaseous form. After the conversion of the glycolaldehyde derivative and the aminating agent in step (i), the washing liquid is also condensed in the heat exchanger. The condensation of the washing liquid on the heat exchanger has the effect that any desublimated or condensed reaction products are inherently washed out of the heat exchanger.

[0137] Depending on the reaction conditions in step (i) and the solvent present during step (i), the reaction product obtained in the liquid phase reaction may be obtained as a solution in the one or more solvents present during step (i), or the reaction product obtained in the liquid phase reaction may at least partially precipitate from the liquid phase.

[0138] Separation of solids from the liquid phase can be carried out using conventional methods, such as filtering, particularly cross-flow filtration, sedimentation or centrifugation. Before liquid-solid separation, the solution can be concentrated by evaporating at least a portion of the one or more solvents present during the reaction mixture or by cooling the solution. Alternatively, a solvent as a reaction product precipitation agent can be added to promote liquid-solid separation. Preferably, the precipitation agent is a non-polar solvent, such as an aliphatic hydrocarbon or an aromatic hydrocarbon, such as hexane, heptane, octane, cyclohexane, toluene or xylene.

[0139] Thus, the reaction product from the conversion of glycolaldehyde derivative and aminating agent in the gas phase or liquid phase can be obtained in solid form or as a dispersion or solution in the one or more solvents present during the conversion and / or the washing liquid used during the workup.

[0140] If the reaction product is obtained in step (i) as a solution or dispersion of the reaction product in one or more solvents, the dispersion or solution can be fed directly to the hydrogenation step (ii).

[0141] In a preferred embodiment, the solution or dispersion obtained from step (i) can be concentrated by evaporating at least a portion of the solvent contained in the solution to obtain a concentrated solution, a slurry or even a resinous solid. The advantage of this embodiment is that the solvent with a lower hydrogen solubility can be at least partially removed and replaced with a solvent with a higher hydrogen solubility.

[0142] If the reaction product is obtained in solid form, it is preferred to dissolve the reaction product in one or more solvents before feeding it to step (ii).

[0143] In another preferred embodiment,

[0144] (i) a solution or dispersion of the reaction product, or

[0145] (ii) isolated reaction products, or

[0146] (iii) the concentrated solution, slurry or resinous solid of the reaction product obtained after the concentration step is mixed with one or more solvents.

[0147] Preferably, the one or more solvents are selected from water, alcohols, acyclic or cyclic ethers, polyalkyl ethers and alkoxy polyalkyl ethers.

[0148] More preferably, the one or more solvents are selected from water, methanol, ethanol, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraglyme), dipropylene glycol dimethyl ether or bis(2-methoxyethyl) ether (diglyme).

[0149] More preferably, the one or more solvents added have a higher hydrogen solubility than the solvent removed in the preceding concentration step.

[0150] Most preferably, the water may be partially removed and replaced with methanol, thereby obtaining a mixture of the reaction product in water and methanol.

[0151] It has been found that the reaction products formed during step (i), in particular the triazine derivatives of the formula (I) and / or the diaminodioxane derivatives of the formula (iv), can be used as intermediates for the preparation of ethyleneamines and ethanolamines.

[0152] Step (ii):

[0153] According to the present invention, the reaction product of the aminating agent and the glycolaldehyde derivative obtained in step (i) is fed to a hydrogenation reactor, wherein the reaction product of step (i) is converted with hydrogen in the presence of a hydrogenation catalyst.

[0154] The reaction product obtained from step (i) comprises a diaminodioxane derivative of formula (IV) and a triazine derivative of formula (I). The reaction product obtained in step (i) may also comprise other adducts of an aminating agent and a glycolaldehyde derivative having a structure different from that of a triazine or diaminodioxane derivative.

[0155] In a preferred embodiment, the reaction product obtained in step (i) comprises 75-100% by weight, more preferably 80-100% by weight, most preferably 90-100% by weight of the triazine derivative of formula (I).

[0156] In another preferred embodiment, the reaction product obtained in step (i) comprises 75-100% by weight, more preferably 80-100% by weight, most preferably 90-100% by weight of the diaminodioxane derivative of formula (IV).

[0157] In another preferred embodiment, the reaction product obtained in step (i) comprises 75-100% by weight, more preferably 80-100% by weight, most preferably 90-100% by weight of the diaminodioxane derivative of formula (IV) and the triazine derivative of formula (I).

[0158] The present invention therefore also relates to a process for preparing ethyleneamines and ethanolamines by converting triazine derivatives of the formula (I) and / or diaminodioxane derivatives of the formula (IV) with hydrogen in the presence of a hydrogenation catalyst in a hydrogenation reactor.

[0159] Preferably, the reaction product obtained in step (i) is fed to step (ii) in the form of a solution thereof in one or more solvents.

[0160] Preferably, the one or more solvents is water,

[0161] ether, preferably methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran (THF), and

[0162] Alcohols, preferably methanol, ethanol and isopropanol.

[0163] Useful solvents also include suitable mixtures of the abovementioned solvents.

[0164] Particularly preferred solvents are methanol, THF, dioxane, glymes and water.

[0165] Particularly preferred solvents also include the reaction products of step (ii), such as monoethanolamine (MEOA), diethanolamine (DEOA), triethanolamine (TEOA) and ethylenediamine (EDA).

[0166] The concentration of the reaction product fed to step (ii) in the one or more solvents is preferably 1-100 g reaction product / 100 g solvent, more preferably 5-75 g reaction product / 100 g solvent, most preferably 10-50 g reaction product / 100 g solvent.

[0167] The hydrogenation step (ii) is carried out in the presence of hydrogen.

[0168] Hydrogen is usually used in technical purity. Hydrogen can also be used in the form of a hydrogen-containing gas, i.e. with the addition of other inert gases, such as nitrogen, helium, neon, argon or carbon dioxide. For example, in step (ii) hydrogen with a hydrogen content of more than 99% by weight, preferably more than 99.9% by weight, more preferably more than 99.99% by weight, and in particular more than 99.999% by weight can be used.

[0169] The hydrogen partial pressure in step (ii) is preferably 2.5-200 bar, more preferably 5-150 bar, even more preferably 10-100 bar, most preferably 20-50 bar.

[0170] In a particularly preferred embodiment, the hydrogenation step (ii) is carried out in the presence of an acid. The presence of an acid increases the yield of desired products such as ethyleneamines and alkanolamines.

[0171] The acid may be any organic or inorganic acid.

[0172] Organic carboxylic acids are preferred.

[0173] Non-limiting examples of the organic carboxylic acid are:

[0174] Saturated aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, ethylbutyric acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, etc.,

[0175] Unsaturated aliphatic monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, decenoic acid, palmitic acid, oleic acid, linoleic acid, etc.,

[0176] Saturated aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.,

[0177] Unsaturated aliphatic dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc.,

[0178] Aryl carboxylic acids, such as benzoic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, pyromellitic acid, toluic acid, and acid esters of polycarboxylic acids such as alkyl phthalate, etc.

[0179] Hydroxycarboxylic acids, such as glycolic acid, hydroxypropionic acid, ethyl lactic acid, hydroxybutyric acid, α-hydroxyisobutyric acid, hydroxycaproic acid, hydroxystearic acid, tartaric acid, malic acid, hydroxybenzoic acid, etc.,

[0180] Keto acids, for example pyruvic acid, oxaloacetic acid, levulinic acid.

[0181] Preferred acids from the above group include:

[0182] Monocarboxylic acids containing 1 to 8 carbon atoms, in particular formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid,

[0183] dicarboxylic acids containing 2 to 8 carbon atoms, in particular oxalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,

[0184] Hydroxycarboxylic acids of 2 to 8 carbon atoms, in particular glycolic acid, lactic acid, citric acid and mandelic acid.

[0185] More preferably, the one or more organic carboxylic acids are selected from the group consisting of formic acid, acetic acid, lactic acid, glycolic acid, levulinic acid, acrylic acid and pyruvic acid.

[0186] The concentration of the acid present in hydrogenation step (ii) is preferably 0.1-25 wt%, more preferably 0.5-20 wt%, most preferably 1-10 wt%, based on the total weight of the feed stream to hydrogenation step (ii).

[0187] In another preferred embodiment, the hydrogenation step (ii) is carried out in the presence of ammonia.

[0188] Ammonia may already be present in the effluent stream from step (i).

[0189] Alternatively, additional ammonia may be added to step (ii).

[0190] Preferably, the amount of ammonia present in the hydrogenation step (ii) is from 1 to 50% by weight, preferably from 5 to 40% by weight, more preferably from 10 to 30% by weight, based on the total weight of the feed stream to the hydrogenation step.

[0191] The hydrogenation step (ii) is carried out in the presence of a hydrogenation catalyst.

[0192] The hydrogenation catalyst may in principle comprise nickel, cobalt, iron, copper, chromium, manganese, copper, molybdenum, tungsten and / or other metals of Group 8 and / or 9 and / or 10 and / or 11 of the Periodic Table of the Elements.

[0193] Preference is given to using a hydrogenation catalyst which comprises at least one metal selected from the group consisting of Cu, Co, Ni, Pd, Pt, Ru, Rh, Ag, Au, Re and Ir.

[0194] More preferably, a hydrogenation catalyst comprising at least one metal selected from the group consisting of Cu, Co, Ni, Pd, Pt and Ru is used.

[0195] The abovementioned catalysts can be doped in a customary manner with promoters, for example with chromium, iron, cobalt, manganese, molybdenum, titanium, tin, metals of the alkali metal group, metals of the alkaline earth metal group and / or phosphorus.

[0196] The hydrogenation catalyst may be a supported or unsupported catalyst.

[0197] Suitable support materials are carbon compounds, for example graphite, carbon black and / or activated carbon, aluminum oxide (gamma, delta, theta, alpha, kappa, chi or mixtures thereof), silicon dioxide, zirconium dioxide, zeolites, aluminosilicates or mixtures thereof.

[0198] In a preferred embodiment of the present invention, a Raney-type hydrogenation catalyst is used.

[0199] As the Raney catalyst, it is preferred to use a Raney cobalt catalyst, a Raney nickel catalyst and / or a Raney copper catalyst. A Raney cobalt catalyst is particularly preferred.

[0200] In another preferred embodiment of the present invention, the hydrogenation catalyst is prepared by reducing a catalyst precursor in which the above-mentioned metals are present in the form of oxygen-containing compounds, such as their oxides, carbonates or bicarbonates.

[0201] The catalyst precursor can be prepared by known methods, for example by precipitation, application by precipitation or impregnation.

[0202] In a preferred embodiment, catalyst precursors which have been prepared by impregnation of a support material are used in the process according to the invention (impregnated catalyst precursors).

[0203] The support material used in the impregnation can be used, for example, in the form of powders or shaped bodies, such as extrudates, tablets, spheres or rings. Support materials suitable for fluidized bed reactors are preferably obtained by spray drying.

[0204] Useful support materials include, for example, carbon such as graphite, carbon black and / or activated carbon, aluminum oxide (gamma, delta, theta, alpha, kappa, chi or mixtures thereof), silicon dioxide, zirconium dioxide, zeolites, aluminosilicates or mixtures thereof.

[0205] The above-mentioned support materials can be impregnated by conventional methods (ABStiles, Catalyst Manufacture-Laboratoryand Commercial Preparations, Marcel Dekker, New York, 1983), for example by applying a metal salt solution in one or more impregnation steps. Useful metal salts generally include water-soluble metal salts, such as nitrates, acetates or chlorides of the corresponding catalytically active components or doping elements, such as cobalt nitrate or cobalt chloride. Subsequently, the impregnated support material is usually dried and optionally calcined.

[0206] The impregnation can also be carried out by the so-called "incipient wetness method", in which the support material is wetted with the impregnation solution until maximum saturation, depending on the water absorption capacity of the support material. However, the impregnation can also be carried out in the supernatant.

[0207] In the case of a multi-step impregnation process, drying and, if appropriate, calcination between the individual impregnation steps is appropriate.Multi-step impregnation can be used advantageously when the support material is contacted with relatively large amounts of metal salt.

[0208] To apply a plurality of metal components to the support material, the impregnation can be carried out simultaneously with all metal salts or in any desired sequence of the individual metal salts.

[0209] In another preferred embodiment, the catalyst precursor is prepared by coprecipitation of all its components. To this end, usually, soluble compounds of the corresponding active components and doping elements and optionally soluble compounds of the support material are mixed with a precipitant in a liquid while heating and stirring until precipitation is complete.

[0210] The liquid used is usually water.

[0211] Useful soluble compounds of the active ingredients generally include the corresponding metal salts, for example nitrates, sulfates, acetates or chlorides of the abovementioned metals.

[0212] The soluble compounds of the support materials used are generally water-soluble compounds of Ti, Al, Zr, Si, etc., for example water-soluble nitrates, sulfates, acetates or chlorides of these elements.

[0213] The soluble compounds of the doping elements used are generally water-soluble compounds of the doping elements, for example water-soluble nitrates, sulfates, acetates or chlorides of these elements.

[0214] The catalyst precursor can also be prepared by precipitation application.

[0215] Application by precipitation is understood to mean a preparation process in which a sparingly soluble or insoluble support material is suspended in a liquid, to which a soluble compound of an appropriate metal oxide, for example a soluble metal salt, is then added and which is then precipitated onto the suspended support by adding a precipitant (described, for example, in EP-A2-1106600, page 4 and ABStiles, Catalyst Manufacture, Marcel Dekker, Inc., 1983, page 15).

[0216] Useful sparingly soluble or insoluble support materials include, for example, carbon compounds such as graphite, carbon black and / or activated carbon, aluminum oxide (gamma, delta, theta, alpha, kappa, chi or mixtures thereof), silicon dioxide, zirconium dioxide, zeolites, aluminosilicates or mixtures thereof.

[0217] The support material is usually in the form of a powder or chips.

[0218] The liquid used in which the carrier material is suspended is generally water.

[0219] Useful soluble compounds include soluble compounds of the above-mentioned active components or doping elements.

[0220] Typically, in a precipitation reaction, a soluble compound is precipitated as a sparingly soluble or insoluble basic salt by adding a precipitant.

[0221] The precipitating agent used is preferably a base, especially an inorganic base, such as an alkali metal base. Examples of precipitating agents are sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide.

[0222] The precipitants used may also be ammonium salts, for example ammonium halides, ammonium carbonate, ammonium hydroxide or ammonium carboxylates.

[0223] The precipitation reaction can be carried out, for example, at a temperature of 20-100°C, preferably 30-90°C, especially 50-70°C.

[0224] The precipitate formed in the precipitation reaction is generally chemically inhomogeneous and generally comprises a mixture of oxides, hydrated oxides, hydroxides, carbonates and / or bicarbonates of the metals used. It has been found that the filterability of the precipitate is favoured when the precipitate is aged, i.e. when, after precipitation, the precipitate is left alone for a certain period of time, if appropriate under hot conditions or with air passing through it.

[0225] The precipitates obtained by these precipitation methods are usually processed by washing, drying, calcining and conditioning them.

[0226] After washing, the precipitate is generally dried at 80-200° C., preferably 100-150° C., and then calcined.

[0227] Calcination is usually carried out at a temperature of 300-800°C, preferably 350-600°C, especially 450-550°C.

[0228] After calcination, the pulverulent catalyst precursor obtained by precipitation reaction is generally conditioned.

[0229] Adjustment can be carried out, for example, by adjusting the precipitated catalyst to a specific particle size by grinding.

[0230] After grinding, the catalyst precursor obtained by precipitation reaction can be mixed with shaping aids such as graphite or stearic acid and processed further to give shaped bodies.

[0231] Commonly used shaping methods are described, for example, in Ullmann [Ullmann's Encyclopaedia Electronic Release 2000, chapter: "Catalysis and Catalysts", pages 28-32] and Ertl et al. [Ertl, Weitkamp, ​​Handbook of Heterogeneous Catalysis, VCH Weinheim, 1997, pp. 98 ff.].

[0232] As described in the cited references, the shaping process can provide a shaped body of any three-dimensional shape, such as round, angular, elongated, etc., such as in the form of extrudates, tablets, granules, balls, cylinders or granules. Common shaping processes are, for example, extrusion, tableting, i.e. mechanical pressing, or granulation, i.e. compaction by circular and / or rotary motion.

[0233] After conditioning or shaping, a heat treatment is usually carried out. The temperature of the heat treatment usually corresponds to the calcination temperature.

[0234] The catalyst precursor obtained by the precipitation reaction comprises the catalytically active components in the form of a mixture of their oxygen compounds, ie in particular oxides, mixed oxides and / or hydroxides. The catalyst precursor prepared in this way can be stored as such.

[0235] The hydrogenation catalyst used in the process of the invention is obtained by reducing a catalyst precursor which has been prepared by impregnation or precipitation as described above after calcination or conditioning.

[0236] The reduction of the dry, usually pulverulent catalyst precursor can be carried out at elevated temperature in mobile or stationary reduction furnaces.

[0237] The reducing agent used is generally hydrogen or a gas containing hydrogen.

[0238] The hydrogen is usually used in technical purity. The hydrogen can also be used in the form of a hydrogen-containing gas, i.e. mixed with other inert gases such as nitrogen, helium, neon, argon or carbon dioxide. The hydrogen stream can also be circulated as cycle gas to the reduction reaction, optionally mixed with fresh hydrogen and optionally after removal of water by condensation.

[0239] The catalyst precursor is preferably reduced in a reactor in which the shaped catalyst bodies are arranged in the form of a fixed bed. The catalyst precursor is more preferably reduced in the same reactor in which step (ii) is carried out.

[0240] Furthermore, the catalyst precursor can be reduced in a fluidized bed in a fluidized bed reactor.

[0241] The catalyst precursor is generally reduced at a reduction temperature of 50-600°C, especially 100-500°C, more preferably 150-450°C.

[0242] The hydrogen partial pressure is generally in the range from 1 to 300 bar, in particular from 1 to 200 bar, more preferably from 1 to 100 bar, the pressure figures here and hereinafter being based on the absolute measured pressure.

[0243] The reduction time is preferably 1 to 20 hours, more preferably 5 to 15 hours.

[0244] During the reduction, a solvent may be provided to remove the reaction water formed and / or in order, for example, to be able to heat the reactor faster and / or to be able to remove heat better during the reduction. In this case, the solvent may also be provided in supercritical form.

[0245] Suitable solvents used may be the above-mentioned solvents. Preferred solvents are water; ethers, such as methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran. Particularly preferred are water or tetrahydrofuran. Suitable solvents also include suitable mixtures.

[0246] The catalyst precursor can also be reduced in suspension, for example in a stirred autoclave. The temperature is generally from 50 to 300°C, in particular from 100 to 250°C, more preferably from 120 to 200°C.

[0247] The suspension reduction is usually carried out at a hydrogen partial pressure of 1 to 300 bar, preferably 10 to 250 bar, more preferably 30 to 200 bar. Usable solvents include the above-mentioned solvents.

[0248] The suspension reduction time is preferably 5-20 hours, more preferably 8-15 hours.

[0249] After reduction, the catalyst can be handled under inert conditions. The catalyst can preferably be handled and stored under an inert gas such as nitrogen, or under an inert liquid such as an alcohol, water or the product of the specific reaction in which the catalyst is used. If appropriate, the inert liquid must be removed from the catalyst before the actual reaction begins.

[0250] Storage of the catalyst under inert substances makes handling and storage of the catalyst uncomplicated and safe.

[0251] After reduction, the catalyst can also be contacted with an oxygen-containing gas stream such as air or a mixture of air and nitrogen. This provides a passivated catalyst. The passivated catalyst generally has a protective oxide layer. The protective oxide layer simplifies the handling and storage of the catalyst, so that, for example, the installation of the passivated catalyst in the reactor is simplified.

[0252] After passivation, the catalyst is usually activated. The catalyst can be activated by reducing the passivated catalyst. The passivated catalyst can be reduced by treating the passivated catalyst with hydrogen or a gas containing hydrogen as described above. The reduction conditions usually correspond to the reduction conditions used in the reduction of the catalyst precursor. Activation usually eliminates the protective passivation layer.

[0253] The activated catalyst must be handled under inert conditions during and after its activation reduction.

[0254] The activated catalyst is preferably handled and stored under an inert gas such as nitrogen, or under an inert liquid such as an alcohol, water or the product of the specific reaction in which the catalyst is used. If appropriate, the activated catalyst must then be freed of the inert liquid before the actual reaction begins.

[0255] Activation of the catalyst can also be carried out in situ during the hydrogenation step (ii).

[0256] In a preferred embodiment, the reaction product of step (i) is contacted with a reduced or activated hydrogenation catalyst.

[0257] Step (ii) is carried out in a hydrogenation reactor.

[0258] The process of the present invention can be carried out continuously, batchwise or semi-continuously.

[0259] Typical reactors are, for example, high-pressure stirred tank reactors, autoclaves, fixed bed reactors, fluidized bed reactors, moving beds, circulating fluidized beds, salt bath reactors, plate heat exchangers as reactors, staged reactors with a plurality of stages with or without heat exchange and with substreams taken off / supplying between the plates, in possible embodiments, the staged reactors can be radial flow reactors or axial flow reactors, continuous stirred tanks, bubble reactors, etc., the reactor used in each case being suitable for the desired reaction conditions (e.g. temperature, pressure and residence time).

[0260] The process of the invention is preferably carried out in a high-pressure stirred tank reactor, a fixed bed reactor or a fluidized bed reactor.

[0261] In a particularly preferred embodiment, the process according to the invention is carried out in one or more fixed bed reactors.

[0262] In a further particularly preferred embodiment, the reaction product from step (i) is hydrogenated in a high-pressure stirred tank reactor.

[0263] The hydrogenation is generally carried out at a pressure of 1 to 500 bar, preferably 10 to 350 bar, more preferably 50 to 300 bar, most preferably 80 to 220 bar. The pressure is generally maintained or controlled by metering in hydrogen.

[0264] The hydrogenation is usually carried out at a temperature of 15-350°C, preferably 50-250°C, more preferably 80-220°C.

[0265] In the case of a batch process, the residence time in the hydrogenation step is generally from 15 minutes to 72 hours, preferably from 60 minutes to 24 hours, more preferably from 2 to 10 hours.

[0266] In the case of a preferred continuous process, the hourly space velocity of the catalyst is generally from 0.01 kg of reaction product obtained in step (i) / kg catalyst / hour to 3.0 kg of reaction product obtained in step (i) / kg catalyst / hour, preferably from 0.05 kg of reaction product obtained in step (i) / kg catalyst / hour to 2.0 kg of reaction product obtained in step (i) / kg catalyst / hour, more preferably from 0.1 kg of reaction product obtained in step (i) / kg catalyst / hour to 1.5 kg of reaction product obtained in step (i) / kg catalyst / hour.

[0267] The effluent from the hydrogenation step comprises unreacted products, hydrogen, solvent, ethyleneamines and ethanolamines.

[0268] The effluent may optionally also comprise acid and / or ammonia.

[0269] Preferably, the ethyleneamines produced in the hydrogenation step (ii) are ethylenediamine (EDA), monoethanolamine (MEOA), diethanolamine (DEOA).

[0270] Higher ethyleneamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), piperazine (PIP) and aminoethylethanolamine (AEEA) may also be formed in smaller amounts.

[0271] The effluent of the hydrogenation step may be subjected to one or more post-treatment steps, such as removal of hydrogen, removal of ammonia, removal of solvents and distillation, to obtain the corresponding ethyleneamines and ethanolamines in purified form. The distillation may be carried out as a sequence of distillation steps using a conventional distillation column or a dividing wall column. The distillation post-treatment of ethyleneamines is well known in the prior art and may be found in more detail in Process Economic Program Report, Issue 138, "Alkyl Amines," published by SRI International, Menlo Park, California, March 1981.

[0272] If an acid is present, an alkaline material may be added to the effluent prior to distillation in an amount sufficient to convert the acid to a high boiling salt.

[0273] The invention has the advantage that it is possible to develop a method for converting glycolaldehyde, which can achieve high conversion of glycolaldehyde and the formation of products, especially MEOA, DEOA and / or EDA, with high yield and selectivity. In addition, the formation of undesirable piperazine by-products is reduced. In addition, a highly purified conversion product is obtained. These objects are achieved under the following premise: first, glycolaldehyde is converted into a useful intermediate, such as a triazine derivative of formula (I) or a diaminodioxane derivative of formula (IV) with ammonia. Obviously, these intermediates constitute the stable form of glycolaldehyde and show a reduced tendency to participate in undesirable side reactions such as oligomerization or polymerization. The intermediate can be hydrogenated in the presence of hydrogen and a hydrogenation catalyst in a second step to provide required ethyleneamines and ethanolamines in high yield.

[0274] The method of the present invention will be described in detail with reference to the following examples. Example:

[0275] Example 1: Conversion of glycolaldehyde and ammonia in the gas phase (step (i)):

[0276] Glycolaldehyde was provided by evaporating an aqueous solution of glycolaldehyde dimer in THF (7.5 wt % glycolaldehyde dimer, 11.5 wt % THF, 80 wt % water and 1 wt % tetraglyme) by heating the solution to 160° C. in a tubular evaporator containing Raschig rings. The gaseous feed was fed into an unheated reaction chamber operated at ambient pressure.

[0277] Gaseous ammonia at room temperature was also fed into the reaction chamber through a separate inlet.

[0278] Colorless crystals were observed to condense in the cooler parts of the reaction chamber.

[0279] The crystals were analyzed by gas chromatography and obvious peaks were obtained. 1 H-NMR and 13 C-NMR confirmed that the crystals have the following structure:

[0280]

[0281] 1 H-NMR (500MHz, D2O): 3.65 (d, 6H), 3.86 (t, 3H) ppm.

[0282] 13 C-NMR (125MHz, D2O): 64.3, 69.7ppm.

[0283] At the cooler at the bottom of the reaction chamber, the yellow-brown clear solution condenses from the gas phase. The product solution is discharged from the bottom of the reaction chamber through a valve.

[0284] The product solution was analyzed by GC, and a distinct product peak was obtained, which was identical to the peak obtained by GC on the crystals. Other substances in the product solution were identified as the solvent (THF, water, tetraglyme) from which glycolaldehyde was evaporated and excess ammonia.

[0285] The total yield of the conversion products of glycolaldehyde and ammonia (including triazine) was about 73%.

[0286] Example 2: Hydrogenation of the reaction product obtained in Example 1 (step (ii)):

[0287] 35 g of the product solution obtained from Example 1 were transferred into the autoclave.

[0288] The autoclave was pressurized to 20 bar and heated to 80°C.

[0289] The autoclave was pressurized with hydrogen at 80°C to a pressure of 100 bar.

[0290] The hydrogenation was carried out in the presence of 0.5 g of Raney cobalt catalyst.

[0291] After a reaction time of 12 hours, the autoclave was depressurized and cooled to ambient temperature.

[0292] The composition of the product solution was analyzed by gas chromatography.

[0293] The following composition was obtained (in area percentage):

[0294] EDA: 10%

[0295] MEOA: 36%

[0296] DEOA: 8%

[0297] MEG (monoethylene glycol): 3%

[0298] Example 3: Hydrogenation of the reaction product obtained in Example 1 (step (ii)):

[0299] Example 3 is identical to Example 2, except that a further 10 g of ammonia are added to the autoclave at 20°C and the solution is stirred at 80°C for 1 hour before the autoclave is pressurized to 100 bar with hydrogen.

[0300] The composition of the product solution was analyzed by gas chromatography.

[0301] The following composition was obtained (in area percentage):

[0302] EDA: 6%

[0303] MEOA: 38%

[0304] DEOA: 5%

[0305] MEG (monoethylene glycol): 1%

[0306] Example 4: Conversion of glycolaldehyde and ammonia in liquid phase (step (i)):

[0307] 10 g of glycolaldehyde dimer and 11.32 g of ammonia in the form of aqueous ammonia solution (25 wt %) were mixed in a reaction flask.

[0308] The reaction mixture was subjected to an evaporation step in a rotary evaporator to obtain a light brown solid residue which was separated off, washed with cold water and dried again.

[0309] Example 5: Hydrogenation of the reaction product obtained in Example 4 (step (ii)):

[0310] The solid residue obtained in Example 4 was dissolved in 50 ml of methanol.

[0311] The solution was transferred into an autoclave.

[0312] The autoclave was pressurized to 20 bar and heated to 80°C.

[0313] The autoclave was pressurized with hydrogen at 80°C to a pressure of 100 bar.

[0314] The hydrogenation was carried out in the presence of 0.5 g of Raney cobalt catalyst.

[0315] The composition of the product solution was analyzed by gas chromatography.

[0316] The following composition was obtained (in area percentage):

[0317] EDA: 4%

[0318] MEOA: 0%

[0319] DEOA: 21%

[0320] MEG (monoethylene glycol): 29%

[0321] Example 6: Hydrogenation of the reaction product obtained in Example 4 (step (ii)):

[0322] Example 6 was identical to Example 5, except that a further 15 g of ammonia were added to the autoclave at 20°C and the solution was stirred at 80°C for 1 hour before the autoclave was pressurized to 100 bar with hydrogen.

[0323] The composition of the product solution was analyzed by gas chromatography.

[0324] The following composition was obtained (in area percentage):

[0325] EDA: 6%

[0326] MEOA: 60%

[0327] DEOA: 3%

[0328] MEG (monoethylene glycol): 0%

[0329] Example 7: Conversion of ethanolaldehyde and ammonia in liquid phase (step (i)):

[0330] Glycolaldehyde was converted with aqueous ammonia as described in Example 1 of US Pat. No. 4,667,213.

[0331] A white crystalline precipitate was obtained which was washed with cold water and dried.

[0332] Example 8: Hydrogenation of the reaction product obtained in Example 7 (step (ii)):

[0333] 5 g of the precipitate from Example 7 were dissolved in 60 ml of methanol.

[0334] The solution was then transferred into an autoclave and pressurized with hydrogen to a pressure of 20 bar at 20°C.

[0335] The autoclave was heated to 100°C.

[0336] The autoclave was pressurized with hydrogen at 100°C to a pressure of 100 bar.

[0337] The hydrogenation was carried out in the presence of 1 g of Raney cobalt catalyst.

[0338] After a reaction time of 21 hours, the autoclave was depressurized and cooled to ambient temperature.

[0339] The composition of the product solution was analyzed by gas chromatography.

[0340] The following composition was obtained (in area percentage):

[0341] EDA: 0%

[0342] MEOA: 25%

[0343] DEOA: 51%

[0344] MEG (monoethylene glycol): 3%

[0345] Example 9: Hydrogenation of the reaction product obtained in Example 7 (step (ii)):

[0346] Example 9 was the same as Example 8, except that an additional 14 g of ammonia was added to the autoclave.

[0347] The composition of the product solution was analyzed by gas chromatography.

[0348] The following composition was obtained (in area percentage):

[0349] EDA: 1%

[0350] MEOA: 76%

[0351] DEOA: 2%

[0352] MEG (monoethylene glycol): 0%

[0353] Example 10: Hydrogenation of the reaction product obtained in Example 7 (step (ii)):

[0354] Example 10 is the same as Example 9, except that only 2.7 g of the precipitate of Example 7 is dissolved in 60 ml of methanol and 7.6 g of ammonia is added to the autoclave. In addition, the hydrogenation catalyst is a mixture of 0.5 g of Raney cobalt catalyst and 1 g of a catalyst consisting of TiO2.

[0355] The composition of the product solution was analyzed by gas chromatography.

[0356] The following composition was obtained (in area percentage):

[0357] EDA: 0%

[0358] MEOA: 59%

[0359] DEOA: 1%

[0360] MEG (monoethylene glycol): 0%

[0361] Example 11: Hydrogenation of the reaction product obtained in Example 7 in the presence of an acid (step (ii)):

[0362] Example 11 was the same as Example 9, except that an additional 0.34 g of acetic acid was added to the autoclave.

[0363] The composition of the product solution was analyzed by gas chromatography.

[0364] The following composition was obtained (in area percentage):

[0365] EDA: 0%

[0366] MEOA: 82%

[0367] DEOA: 6%

[0368] MEG (monoethylene glycol): 0%.

Claims

1. A method for preparing ethyleneamines and ethanolamines, comprising the following steps: (i) converting the glycolaldehyde derivative of formula (II) in the gas phase or liquid phase: Where R 2 , R 3 same or different, hydrogen or C 1-6 Alkyl; and Aminating agent of formula (III): R1-NH2(II) Where R 1 is hydrogen or C 1-6 alkyl; (ii) feeding the reaction product obtained in step (i) to a hydrogenation reactor, wherein the reaction product is converted with hydrogen in the presence of a hydrogenation catalyst; wherein the hydrogenation catalyst is a Raney-type catalyst, or A catalyst obtained by reduction of a metal oxide precursor, and the hydrogenation catalyst comprises at least one metal selected from the group consisting of Cu, Co, Ni, Pd, Pt, Ru, Rh, Ag, Au, Re and Ir; Before the reaction product is fed to step (ii), the reaction product obtained in step (i) is separated from the gas phase or liquid phase, or the solution or dispersion obtained in step (i) is concentrated by evaporating at least a portion of the solvent contained in the solution or dispersion.

2. The method according to claim 1, wherein the glycolaldehyde derivative of formula (II) is glycolaldehyde, and the aminating agent of formula (III) is ammonia.

3. The method according to claim 1, wherein the molar ratio of the aminating agent to the glycolaldehyde derivative is 1:1 to 100:

1.

4. The method according to claim 2, wherein the molar ratio of the aminating agent to the glycolaldehyde derivative is 1:1 to 100:

1.

5. The process according to any one of claims 1 to 4, wherein step (i) is carried out under conditions where hydrogenation or reductive amination of the glycolaldehyde derivative, the aminating agent and their reaction products is hindered.

6. The method according to any one of claims 1 to 4, wherein the glycolaldehyde derivative of formula (II) is provided to step (ii) in gaseous or liquid form and is obtained by hydrothermal decomposition of sugar or pyrolysis of wood.

7. The method according to claim 5, wherein the glycolaldehyde derivative of formula (II) is provided to step (ii) in gaseous or liquid form and is obtained by hydrothermal decomposition of sugar or pyrolysis of wood.

8. The process according to any one of claims 1 to 4, wherein the glycolaldehyde derivative of formula (II) and the aminating agent of formula (III) are provided in gaseous form, and step (i) is carried out in the gas phase.

9. The process according to claim 5, wherein the glycolaldehyde derivative of formula (II) and the aminating agent of formula (III) are provided in gaseous form, and step (i) is carried out in gas phase.

10. The process according to claim 6, wherein the glycolaldehyde derivative of formula (II) and the aminating agent of formula (III) are provided in gaseous form, and step (i) is carried out in a gas phase.

11. The process according to any one of claims 1 to 4, wherein step (ii) is carried out in the presence of ammonia.

12. The process according to claim 5, wherein step (ii) is carried out in the presence of ammonia.

13. The process according to claim 6, wherein step (ii) is carried out in the presence of ammonia.

14. The process according to claim 8, wherein step (ii) is performed in the presence of ammonia.

15. The process according to any one of claims 1 to 4, wherein step (ii) is carried out in the presence of one or more acids, wherein the acid is an organic carboxylic acid.

16. The process of claim 5, wherein step (ii) is performed in the presence of one or more acids, wherein the acid is an organic carboxylic acid.

17. The process of claim 6, wherein step (ii) is performed in the presence of one or more acids, wherein the acid is an organic carboxylic acid.

18. The process of claim 8, wherein step (ii) is performed in the presence of one or more acids, wherein the acid is an organic carboxylic acid.

19. The process of claim 11, wherein step (ii) is performed in the presence of one or more acids, wherein the acid is an organic carboxylic acid.

20. The method according to any one of claims 1 to 4, wherein step (i) or step (ii) is performed in the presence of one or more solvents.

21. The method of claim 5, wherein step (i) or step (ii) is performed in the presence of one or more solvents.

22. The method of claim 6, wherein step (i) or step (ii) is performed in the presence of one or more solvents.

23. The method of claim 8, wherein step (i) or step (ii) is performed in the presence of one or more solvents.

24. The method of claim 11, wherein step (i) or step (ii) is performed in the presence of one or more solvents.

25. The method of claim 15, wherein step (i) or step (ii) is performed in the presence of one or more solvents.

26. The method of claim 20, wherein the one or more solvents are selected from water, methanol, ethanol, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, tetrahydrofuran, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, bis(2-methoxyethyl) ether, and polyethylene oxide dimethyl ether.

27. The method according to any one of claims 1 to 4, wherein the reaction product of step (i) is: Triazine derivatives of formula I: Where R 1 , R 2 , R 3 same or different, hydrogen or C 1-6 Alkyl; or Diaminodioxane derivative formula (IV): Where R 1 , R 2 , R 3 same or different, hydrogen or C 1-6 alkyl.

28. Triazine derivatives of formula I: Where R 1 , R 2 , R 3 same or different, hydrogen or C 1-6 alkyl.

29. A process for preparing ethyleneamines and ethanolamines by converting a triazine derivative of formula (I) and / or a diaminodioxane derivative of formula (IV) with hydrogen in the presence of a hydrogenation catalyst in a hydrogenation reactor: Triazine derivatives of formula I: Where R 1 , R 2 , R 3 same or different, hydrogen or C 1-6 alkyl; Diaminodioxane derivative formula (IV): Where R 1 , R 2 , R 3 same or different, hydrogen or C 1-6 alkyl, The hydrogenation catalyst is a Raney-type catalyst, or a catalyst obtained by reduction of a metal oxide precursor, and the hydrogenation catalyst comprises at least one metal selected from the group consisting of Cu, Co, Ni, Pd, Pt, Ru, Rh, Ag, Au, Re and Ir.

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