Process for hydrogenating aromatic nitro compounds

Abstract

The present invention relates to a method for preparing an aromatic amine by hydrogenating an aromatic nitro compound, comprising the following steps: (I) preparing a copper tetramine salt-based impregnated catalyst containing a metal or metal oxide on a support, particularly an impregnated catalyst obtained by the incipient wetness method, as a hydrogenation catalyst, in which at least metallic copper or copper oxide (particularly CuO) is present, the molar fraction of Cu relative to all metals present being in the range of 0.75 to 1, and the support comprising a silicon dioxide or silicon carbide compact; (II) optionally activating the hydrogenation catalyst by treating with hydrogen in the absence of the aromatic nitro compound; and (III) optionally reacting the aromatic nitro compound with hydrogen in the presence of the activated hydrogenation catalyst to obtain an aromatic amine.

Description

[Technical field]

[0001] The present invention relates to a process for preparing an aromatic amine by hydrogenating an aromatic nitro compound, comprising the steps of: (I) providing as a hydrogenation catalyst a tetraammine copper-based impregnated catalyst comprising a metal or a metal oxide on a support, in particular an impregnated catalyst obtained by the incipient wetness method, in which at least metallic copper or copper oxide (in particular CuO) is present, the molar ratio of Cu to all metals present being in the range of 0.75 to 1, and the support comprising a shaped silicon dioxide body or a shaped silicon carbide body; (II) optionally activating the hydrogenation catalyst by treating with hydrogen in the absence of the aromatic nitro compound; and (III) optionally reacting the aromatic nitro compound with hydrogen in the presence of the activated hydrogenation catalyst to obtain the aromatic amine. [Background technology]

[0002] The hydrogenation of nitroaromatic compounds to the corresponding aromatic amines with hydrogen has been known for a long time and is of great industrial importance. A typical example is the hydrogenation of nitrobenzene to aniline. Most of the aniline produced worldwide is used in the production of diphenylmethane-based di- and polyamines (MDA), which are intermediates in the production of the important diphenylmethane-based di- and polyisocyanates (MDI).

[0003] The hydrogenation can be carried out in the liquid or gas phase, under isothermal or adiabatic conditions. A combination of isothermal and adiabatic reaction regimes is also known. A range of catalysts have been described for this purpose in the literature. Particular mention should be made here of palladium and copper-based catalytic systems.

[0004] For example, the use of palladium-based catalysts on ceramic supports is known. US Pat. No. 5,399,433 describes a process for reducing nitro compounds in the presence of a palladium-containing ternary supported catalyst in a cooled tubular reactor. In a preferred embodiment, the catalyst is 1 L of α-Al 2 O3 The catalyst contains 1-20 g of palladium, 1-20 g of vanadium and 1-20 g of lead per 1000 g of catalyst. Similar catalysts, but additionally doped with Mo, Re or W, are also described in Patent Document 2. Patent Document 3 discloses that it is advantageous to additionally dope such ternary supported catalysts with sulfur or phosphorus-containing, preferably phosphorus-containing compounds (e.g. phosphorus oxyacids or their alkali metal salts, such as, in particular, sodium dihydrogen phosphate, sodium phosphate or potassium phosphate, or sodium hypophosphite, etc.). Patent Document 4 describes the beneficial effect of potassium doping of the catalyst on the phenolic content of the aniline formed.

[0005] The use of copper-based catalysts, especially for the hydrogenation of nitrobenzene, has been known for some time (see US Pat. No. 5,399,623 and US Pat. No. 5,499,633). The support used for the catalytically active material was pumice, a natural stone containing silicates and sodium as main components.

[0006] The use of copper catalysts on silicon dioxide supports for the hydrogenation of nitrobenzene to aniline has likewise been known for a long time (for example US Pat. No. 5,399,623 or US Pat. No. 5,499,639 from the 1950s). In both patents the use of copper-ammine complexes as catalyst precursor compounds is described. For the preparation of the catalyst, a hydrogel is precipitated by acidifying a sodium silicate solution, which is mixed with the copper-ammine complex after filtration and washing. The hydrogel thus treated is filtered off, washed, dried and calcined in a reducing atmosphere. Although the treatment of the hydrogel with the copper-ammine complex is described as impregnation, the described procedure is closer to a simple deposition of copper particles on the hydrogel, due to the fine nature of the support (which, being in the form of a freshly precipitated hydrogel, does not have any pores that could incorporate the copper particles).

[0007] A tried and tested and commonly used method for preparing hydrogenation catalysts is impregnation with a metal salt solution, the support used having pores that absorb the metal salt solution. For this purpose, the support is either wetted with the metal salt solution up to maximum saturation of its water absorption capacity (called the "incipient wetness" method) or treated in the supernatant. Impregnation methods are described for example in the patent applications US Pat. No. 5,399,410, US Pat. No. 5,499,420, US Pat. No. 5,523,633, US Pat. No. 5,523,665, and US Pat. No. 5,523,671, which are discussed below.

[0008] Patent Document 9 discloses a SiO 2 A method for preparing aromatic amines, particularly anilines, using a copper-containing catalyst on a support is described. The method is carried out on SiO 2 is particularly characterized in that it is produced by wet grinding followed by spray drying. The wet grinding process results in silicon dioxide particles with dimensions of the order of micrometers, in particular with diameters in the range of 1 μm to 35 μm. Such small catalyst diameters are also required for the described method, since the catalysts thus produced are used in the form of fluidized bed catalysts, which cannot even be carried out with macroscopic shaped bodies with sizes in the millimeter range. For the application of catalytically active metals, impregnation from the supernatant with an ammoniacal carbonate solution is described, for example.

[0009] US Pat. No. 5,399,633 describes a method for preparing aromatic amines by hydrogenating the corresponding nitroaromatic compounds in the gas phase over a fixed bed catalyst. The catalyst contains a hydrogenation active metal on a support which can be prepared by impregnation. The hydrogenation catalyst used is in particular α-Al 2 O 3 α-Al, preferably precipitated in the form of a shell, containing 1 g to 100 g of Pd per 100 g of Pd. 2 O 3 Above all, catalysts containing palladium, which may additionally contain vanadium and lead, are mentioned. Catalysts based on ammine complexes are not mentioned.

[0010] Patent document 11 relates to an improvement of copper chromite catalysts used in the hydrogenation of ketones, carboxylic esters and nitro compounds. For this purpose, a method for preparing a copper chromite catalyst applied to a support is proposed, which is particularly characterized in that basic ammonium-copper(II) chromate is formed in the pores of an inorganic oxide support material by reaction of precursors of basic ammonium-copper(II) chromate which react with each other, and then the support material is heated to a temperature of about 250°C to 500°C for about 0.1 to 20 hours, in order to convert basic ammonium-copper(II) chromate into copper chromite. According to patent document 11, copper chromite is a compound of the formula "xCuO,Cr 2 O 3 ". It is immediately apparent to those skilled in the art that this is merely a description of the stoichiometric ratio and does not provide any information regarding the actual structure of the catalyst. No catalysts with a molar ratio of Cu of 75 mol % or more are disclosed.

[0011] US Pat. No. 5,399,633 relates to the preparation of alcohols by catalytic hydrogenation of the corresponding carbonyl compounds in the liquid phase at high temperature and pressure. For this purpose, SiO 2 Copper catalysts are described which are obtained by impregnating the containing support material with various thermally "easily" (i.e. below 350°C) decomposable copper salts such as copper nitrate, copper carbonate, copper formate, copper oxalate and their readily water-soluble amine (ammine) complexes.

[0012] Patent document 13 also relates to the preparation of alcohols by hydrogenation of carbonyl compounds. The hydrogenation catalyst used consists of a support material and at least one hydrogenation active metal, the support material being based on titanium dioxide, zirconium dioxide, aluminum oxide, silicon oxide or mixed oxides thereof, the hydrogenation active metal containing at least one element from the group copper, cobalt, nickel, chromium, and the support material further containing the element barium. One example described is the preparation of a copper-containing impregnated catalyst on aluminum oxide using an approximately 14% solution of copper tetraammine carbonate.

[0013] Catalytic alloys, such as known Raney catalysts, are quite different from impregnated catalysts. Patent document 14 discloses a shaped activated fixed bed metal catalyst having a pore volume of 0.05 ml / g to 1 ml / g and an outer activation shell consisting of a sintered fine catalytic alloy and, optionally, a promoter, the catalytic alloy containing metallic phase regions resulting from the preparation of the alloy, the largest phase in terms of volume being 0.5 μm -1 It has a specific interface density of greater than .

[0014] Patent document 15 relates to a catalyst for the hydrogenation of acetophenone to methylbenzyl alcohol. The catalyst is prepared by impregnation, understood in particular to mean spraying, of a silicon dioxide support with a solution of tetraammine copper carbonate and a solution of ammonium chromate, or a mixture thereof, followed by drying.

[0015] Patent document 16 relates to the regeneration of copper-, chromium- and / or nickel-containing hydrogenation catalysts used for the preparation of higher alcohols, in particular alcohols having 8 to 13 carbon atoms, by catalytic hydroformylation of olefins having one less carbon atom (also known as the Oxo process), followed by hydrogenation of the aldehydes formed.

[0016] No. 5,399,633 relates to the dehydrogenation of alcohols to aldehydes and ketones using a catalyst containing reduced copper oxide and small amounts of non-reduced copper oxide as well as "alkali metal oxides." The catalyst is prepared by heating a tetraammine copper complex followed by heating under hydrogen.

[0017] Patent Document 18 relates to a chromium- and nickel-free catalyst for the heterogeneous hydrogenation of oxo-process aldehydes. The catalyst contains only copper, but the support material used is silicon dioxide, and the Cu and SiO in the active catalyst are 2 It is necessary to precisely limit the content of to within a very narrow range.

[0018] Copper compounds are used as catalysts for a variety of different reactions, as well as in many other fields, for example as fungicides (see, for example, US Pat. No. 5,399,633).

[0019] The study of copper catalysts for various applications has also been covered in various articles in non-patent literature, such as Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3 and Non-Patent Document 4.

[0020] In addition to the use of palladium or copper based catalysts, the use of catalysts containing both metals is also known, an example of which is described in Patent Document 20. Patent Document 20 describes a catalyst for the treatment of automobile exhaust gases, which contains 0.5% to 25% copper and 0.01% to 3% palladium. [Prior art documents] [Patent documents]

[0021] [Patent Document 1] German Patent Application Publication No. 2849002 [Patent Document 2] German Patent Application Publication No. 19715746 [Patent Document 3] European Patent Application Publication No. 1882681 [Patent Document 4] International Publication No. 2013 / 030221 [Patent Document 5] U.S. Patent No. 1,207,802 [Patent Document 6] U.S. Patent No. 3,136,818 [Patent Document 7] British Patent No. 823,026 [Patent Document 8] U.S. Patent No. 2,891,094 [Patent Document 9] International Publication No. 2010 / 130604 [Patent Document 10] European Patent Application Publication No. 0696573 [Patent Document 11] German patent no. 2311114 [Patent Document 12] International Publication No. 95 / 32171 [Patent Document 13] International Publication No. 2009 / 027135 [Patent Document 14] WO 98 / 53910 [Patent Document 15] DE 3933661 [Patent Document 16] German Patent Application Publication No. 102010029924 [Patent Document 17] British Patent No. 825,602 [Patent Document 18] European Patent Application Publication No. 3320969 [Patent Document 19] U.S. Patent No. 3,900,504 [Patent Document 20] British Patent No. 961,394 [Non-patent literature]

[0022] [Non-Patent Document 1] Chem. Lett. 1980, 1197-1200 [Non-Patent Document 2] Appl. Catal. 1982, 3, 381-388 [Non-Patent Document 3] Appl. Catal. 1987, 31, 309-321 [Non-Patent Document 4] Procedia Engineering 2013, 51, 467-472 Summary of the Invention [Problem to be solved by the invention]

[0023] The prior art catalysts described for the hydrogenation of nitroaromatics, in particular nitrobenzene, are in principle suitable for this purpose, but there is still room for improvement with regard to selectivity and long-term stability. The emphasis here has been placed on copper-based catalysts, which are cheaper compared to the known palladium-based catalysts. [Means for solving the problem]

[0024] In view of the above, the present invention provides (I) providing as a hydrogenation catalyst an impregnated catalyst based on a tetraammine copper salt comprising a metal or metal oxide on a support, in particular an impregnated catalyst obtained (preferably prepared) by the incipient wetness method, in which at least metallic copper or copper oxide (particularly CuO) is present, the molar ratio of Cu to all metals present being in the range of 0.75 to 1, preferably 0.90 to 1, and the support comprising a shaped silicon dioxide body or a shaped silicon carbide body; (II) optionally (and preferably) activating the hydrogenation catalyst by treatment with hydrogen in the absence of an aromatic nitro compound; (III) reacting the aromatic nitro compound with hydrogen in the presence of an optionally activated hydrogenation catalyst to obtain an aromatic amine; The present invention relates to a process for the preparation of aromatic amines, particularly anilines, by hydrogenating aromatic nitro compounds, particularly nitrobenzene, comprising:

[0025] In the terminology of the present invention, a tetraammine copper salt-based impregnated catalyst containing a metal or metal oxide on a support is a catalyst in which the support is impregnated with a tetraammine copper salt (i.e., Cu II Tetraammine complex of [Cu II (NH 3 ) 4 ] 2+ is understood to mean a catalyst obtained by impregnation with an aqueous, in particular ammoniacal solution of a tetraammine copper salt (a salt containing as a cation) followed by drying and calcination (preferably in an oxygen-containing atmosphere). The support is impregnated by mixing with the aqueous, in particular ammoniacal solution of a tetraammine copper salt (by throwing the support into the tetraammine copper salt solution or by pouring the solution onto the support). The nature of the support and the amount of the aqueous, in particular ammoniacal solution of the tetraammine copper salt are There is more tetraammine copper salt solution than the pores of the support (see also the section on shaped bodies below) can accommodate (i.e., impregnation into the supernatant); Or they are adapted to each other here so that there is at most exactly as much tetraammine copper salt solution as the pores of the support can accommodate (preferably somewhat less, in particular 2% to 5% less) (i.e. the incipient wetness method, which is the preferred method).

[0026] With regard to the impregnation of such supports, it should be noted that in the terminology of the present invention, the term impregnation is limited to such impregnation and does not refer generically to virtually any type of application of hydrogenation active materials on supports, as is the case, for example, in various technical literature.

[0027] The impregnated catalyst is therefore in particular one that is obtained (preferably actually produced) by the incipient wetness method mentioned. In other words, in the process of producing the impregnated catalyst, it is preferred to impregnate the support with an aqueous, in particular ammoniacal solution of a tetraammine copper salt, so that the maximum absorption of the support, determined by the degree of saturation with water, is not exceeded, preferably not more than 5%, more preferably at least 2% below this. Means for determining the maximum absorption of the support, determined by the degree of saturation with water, are known in the art. The method described in the beginning of the examples, under the heading "Determination of the maximum absorption of the support", is of crucial importance for the purposes of the present invention.

[0028] According to the invention, the support comprises a shaped silicon dioxide or silicon carbide body, shaped body in this context is understood to mean that the support is in the form of discrete (i.e. visible to the naked eye) particles, in particular having an average diameter in the range of 1.0 mm to 15 mm, preferably in the range of 4.0 mm to 10 mm. Examples include in particular shaped cylinders and shaped spheres, in the case of shaped cylinders the diameter of the base is considered as the diameter in this context, the length of the shaped cylinder is always greater than the diameter. In the case of shaped cylinders, the individual cylinders can also be combined to form an aggregate comprising several cylinders, in particular to obtain a trilobe (an aggregate formed of three cylinders connected to each other in the longitudinal direction). In the case of such an aggregate of cylinders, the diameter is considered as the diameter of the theoretical circle surrounding the base of the interconnected cylinders.

[0029] Such shaped bodies are distinct from both amorphous structures (such as dust or hydrogels) and monolithic structures. Molded silicon dioxide or silicon carbide bodies have pores that are permeated with an aqueous solution of tetraammine copper salt. Silicon dioxide (SiO 2 ) is commonly referred to as silica in the English literature.

[0030] The molar ratio of Cu to all metals present (i.e., x(Cu)) is in each case based on the metals themselves, i.e., x(Cu) = moles of Cu / sum of moles of all metals present. The proportions by mass of the metals present on the catalyst are known from the preparation, from which the mole fraction of copper, x(Cu), can be easily calculated. If no other metals are present besides copper (which is preferred), then x(Cu) is 1.

[0031] First, a summary of various possible embodiments of the present invention is provided below, however, this list of embodiments should not be considered exhaustive.

[0032] In a first embodiment of the present invention, which can be combined with all other embodiments, step (II) is carried out, and the treatment with hydrogen is accomplished at a temperature in the range of 180°C to 240°C.

[0033] In a second embodiment of the present invention, which can be combined with all other embodiments, step (III) comprises: Adiabatically at a temperature in the range of 160°C to 500°C, preferably 180°C to 450°C, more preferably 200°C to 400°C, or The reaction is carried out isothermally at a temperature in the range of 180°C to 550°C, preferably 200°C to 500°C, and more preferably 220°C to 450°C.

[0034] In a third embodiment of the invention, which can be combined with all other, especially with the second, embodiment, step (III) comprises: Adiabatically at a molar ratio of hydrogen to nitro groups in the range of 10 to 200, preferably 20 to 150, more preferably 60 to 120, or The reaction is carried out isothermally at a molar ratio of hydrogen to nitro group in the range of 3 to 100, preferably 6 to 60, and more preferably 10 to 30.

[0035] In a fourth embodiment of the present invention which can be combined with all other embodiments, the mass ratio of the copper compound calculated as metallic Cu in the hydrogenation catalyst prepared in (I) is in the range of 3% to 35%, preferably 7% to 30%, more preferably 11% to 25% relative to the total mass of the catalyst.

[0036] In a fifth embodiment of the present invention, which can be combined with all other embodiments as long as it contains a shaped silicon dioxide body as a support, the support comprising the shaped silicon dioxide body is 100 mm 2 / g~350m 2 / g, preferably 100m 2 / g~300m 2 / g range, 0.3 cm 3 / g~1.5cm 3 / g range, preferably 0.3 cm 3 / g~1.4cm 3 / g and a side crushing strength in the range of 40N to 500N, preferably in the range of 40N to 350N.

[0037] In a sixth embodiment of the invention, which can be combined with all other embodiments, the hydrogenation catalyst used is an impregnated catalyst based on tetraammine copper carbonate.

[0038] In a seventh embodiment of the present invention, which is a specific configuration of the sixth embodiment, the hydrogenation catalyst used is a tetraammine copper carbonate / ammonium carbonate based impregnated catalyst or a tetraammine copper carbonate / ammonium acetate based impregnated catalyst, preferably a tetraammine copper carbonate / ammonium carbonate based impregnated catalyst.

[0039] In an eighth embodiment of the present invention, which can be combined with all other embodiments, step (I) comprises: (a) dissolving a copper salt in ammonia water to obtain an alkaline ammoniacal copper salt solution; (b) impregnating a support with the alkaline ammoniacal copper salt solution obtained in (a), followed by drying the impregnated support thus obtained to obtain a catalyst precursor; (c) calcining the catalyst precursor obtained in (c) to form a tetraammine copper-based impregnated catalyst; Includes.

[0040] In a ninth embodiment of the present invention which is a specific configuration of the eighth embodiment, the copper salt comprises basic copper carbonate.

[0041] In a tenth embodiment of the present invention, which is a specific configuration of the eighth and ninth embodiments, ammonium carbonate is also dissolved in the ammonia water in addition to the copper salt in step (I)(a).

[0042] In an eleventh embodiment of the present invention, which is a specific configuration of the eighth to tenth embodiments, the dissolution in step (I)(a) is carried out at a temperature in the range of 0.0°C to 10.0°C, preferably 1.0°C to 5.0°C.

[0043] In the twelfth embodiment of the present invention, which is a specific configuration of the eighth to eleventh embodiments, the drying in step (I)(b) is carried out at a temperature in the range of 80°C to 150°C, preferably in the range of 90°C to 130°C, and more preferably in the range of 100°C to 120°C.

[0044] In a thirteenth embodiment of the present invention, which is a specific configuration of the eighth to twelfth embodiments, the firing in step (I)(c) is carried out at a temperature in the range of 300°C to 600°C, preferably in the range of 350°C to 550°C, and more preferably in the range of 400°C to 500°C.

[0045] In the 14th embodiment of the present invention, which is a specific configuration of the 8th to 13th embodiments, the alkaline ammoniacal copper salt solution used for impregnation has a pH (20° C.) in the range of 7.0 to 14, preferably 8.0 to 12, and more preferably 9.0 to 11.

[0046] In a fifteenth embodiment of the invention which can be combined with all other embodiments, the shaped silicon dioxide or shaped silicon carbide body has an average diameter in the range of 1.0 mm to 15 mm, preferably in the range of 4.0 mm to 10.0 mm.

[0047] In a sixteenth embodiment of the present invention, which can be combined with all others, in particular the fifteenth embodiment, insofar as it comprises a shaped silicon dioxide body as a support, the shaped silicon dioxide body is (i) precipitating silicon dioxide from a silicate solution and isolating the precipitated silicon dioxide; (ii) drying the silicon dioxide; (iii) processing the dried silicon dioxide to obtain a shaped body; (iv) sintering the molded body at a temperature preferably in the range of 500°C to 1000°C; is obtained by

[0048] In a seventeenth embodiment of the present invention, which can be combined with all other embodiments, a compound of the formula: [ka] wherein R1 and R2 are independently hydrogen, methyl or ethyl, and R2 further comprises NO 2 The aromatic nitro compound (which may be

[0049] In an eighteenth embodiment of the present invention, which can be combined with all other embodiments, nitrobenzene is hydrogenated to aniline.

[0050] In a nineteenth embodiment of the present invention, which can be combined with all embodiments including step (b), in step (b), the support is impregnated with the ammoniacal copper salt solution obtained in (a) so as not to exceed the maximum absorption rate of the support determined by the degree of saturation with water (i.e. the incipient wetness method).

[0051] In a twentieth embodiment of the invention, which is a specific configuration of the nineteenth embodiment, the absorption is 5% or less below the maximum absorption of the support.

[0052] In a twenty-first embodiment of the invention, which is a specific configuration of the eighteenth and nineteenth embodiments, the absorption is at least 2% below the maximum absorption of the support.

[0053] In a twenty-second embodiment of the present invention, which can be combined with all other embodiments, the optionally activated hydrogenation catalyst is arranged in a fixed catalyst bed in step (III).

[0054] The above briefly outlined embodiments and possible further configurations of the invention are explained in detail below. The various embodiments can be combined with one another as desired, unless the context makes clear to the skilled person the contrary. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0055] Preparation of catalyst for hydrogenation Step (I) of the process of the present invention involves preparing a tetraammine copper salt-based impregnated catalyst comprising CuO on a shaped silicon dioxide body as a support. Such catalysts are stable to storage and transportation, so that the preparation of the catalyst can be completely decoupled from the actual hydrogenation, e.g. accomplished at a different site.

[0056] Fabrication of the support Molded silicon dioxide bodies suitable as supports can be produced by methods known to those skilled in the art and are commercially available.

[0057] The shaped silicon dioxide body is preferably obtained by precipitating fine silicon dioxide from an aqueous silicate solution (gel production). The precipitated fine silicon dioxide is isolated and dried to obtain silicon dioxide powder. To produce a shaped silicon dioxide body from the silicon dioxide powder, the silicon dioxide powder is further processed into a shaped body in a manner known to those skilled in the art, preferably by extrusion or granulation. The shaped body can be obtained in different three-dimensional forms, for example as a cylinder (including a collection of cylinders such as the above-mentioned trilobes) or a sphere. The presence of any slight deviation from the ideal cylindrical or spherical shape does not of course depart from the scope of the present invention.

[0058] Molded silicon carbide bodies suitable as supports can be produced by methods known to those skilled in the art and are commercially available, and may vary in the purity of the material. Particularly suitable is β-silicon carbide in mesoporous form (i.e., with pore sizes ranging from 2 nm to 50 nm). The definition of "mesoporous" used in the context of the present invention follows the corresponding IUPAC recommendations (see Pure & Appl. Chem., 1994, 66, 1739-1758).

[0059] Processing to obtain shaped silicon dioxide or silicon carbide bodies is preferably followed by a calcination step, preferably at a temperature in the range of 300° C. to 1000° C. Calcination can be carried out in an oxygen-containing atmosphere (particularly air), a hydrogen atmosphere or an inert atmosphere (particularly nitrogen or a rare gas atmosphere). Calcination in an oxygen-containing atmosphere is preferred.

[0060] The bodies in the form of cylinders (after sintering, if performed) preferably have an average length in the range of 3.0 mm to 18 mm, preferably in the range of 6.0 mm to 14 mm, and an average diameter in the range of 1.0 mm to 15 mm, preferably in the range of 4.0 mm to 10 mm. This can be achieved by establishing suitable conditions during extrusion and verified by simple measurements (for example with a caliper gauge).

[0061] Preferably, the spherical molded bodies (after sintering, if performed) have an average particle size (i.e., average size of the molded bodies = average diameter) x in the range of 1.0 mm to 15 mm, more preferably in the range of 4.0 mm to 10.0 mm. 50,3 This can be achieved by establishing suitable conditions during granulation and / or by sieving. The actual presence of the desired average particle size can be verified by particle size analysis. In the context of the present invention, a crucial test in this respect is sieve analysis. The average particle size as used herein is a mass-based value ("x 50,3 "). The procedure for determining the average particle size is to first subject a representative sample of the particles (i.e., compacts) to a sieve analysis and evaluate the results on a mass basis. The sieve analysis is accomplished using a vibrating sieving machine (e.g., Retsch AS 200 digit model), in which analytical sieves are stacked from smallest mesh size to large to form a sieve set. The choice of analytical sieves (diameter and mesh size) depends primarily on the amount of material to be sieved and the expected particle size distribution (preliminary tests may be necessary). The number of sieves and the gradations of nominal opening width should be selected so that the entire particle spectrum of the sample is resolved if possible. When performing the sieve analysis, it is necessary to ensure that the maximum passage of the material to be sieved (optimum quality of sieving) is achieved. If necessary (e.g., when using new particles that have not yet been operated), suitable sieving times and amplitudes should be experimentally confirmed in preliminary tests. A first indication of the amplitude is found from the observation of the motion of the material to be sieved. The movement should not be too weak or too strong. The optimum sieving time is obtained when the mass of the material passing through the sieve within one minute changes by less than 0.1% of the applied amount (DIN 66165, April 1987 edition). The skilled person is familiar with the method, which is only briefly outlined here. The result of the sieve analysis is the particle size distribution of the particles analyzed. The result is the mass ratio of the individual fractions of the bar graph ("p 3 " ) and cumulative percentage curves ("Q 3 Preferably, the median particle size is presented graphically by plotting the median particle size (x) against the nominal sieve opening width (x). 50,3(i.e., 50% by weight of the particles are smaller than the corresponding value x) can be readily calculated manually or, preferably, using a computerized evaluation program.

[0062] The support containing the shaped silicon dioxide body (after calcination, if performed) is 100 mm 2 / g~350m 2 / g, more preferably in the range of 100m 2 / g~300m 2 / g (determined according to FM Nelsen and FT Eggertsen, Analyt. Chem. 1958, 30, 1387-1392), 3 / g~1.4cm 3 / g range, preferably 0.3 cm 3 / g~1.4cm 3 / g and a lateral crushing strength (determined according to DIN 50 106, November 2016 edition; this method described for metallic materials is also suitable for supports in the context of the present invention) in the range of 40N to 500N, preferably in the range of 40N to 350N. For supports comprising mesoporous shaped β-silicon carbide bodies usable according to the present invention, comparable values ​​apply, with the exception of the BET surface area, which here is usually lower and preferably 20 m 2 / g~30m 2 / g range.

[0063] Preparation of tetraammine copper salt solutions Methods for preparing tetraammine copper salts are in principle known in the prior art. A preferred procedure is outlined below.

[0064] The starting copper salt used is preferably basic copper carbonate. However, other copper salts such as copper hydroxide and copper acetate can also be used. It is also possible to use a mixture of copper salts. The copper salt is dissolved in aqueous ammonia to obtain an ammoniacal copper salt solution. The aqueous ammonia preferably has a mass ratio of ammonia in the range of 15% to 30%, more preferably in the range of 20% to 30%, and most preferably in the range of 25% to 30%.

[0065] It is desirable to stabilize the tetraammine copper complex by maintaining the pH (20°C) in the range of 7.0 to 14, preferably in the range of 8.0 to 12, more preferably in the range of 9.0 to 11. It is therefore preferable to add part of the ammonia required for complex formation in the form of ammonium carbonate or ammonium acetate, preferably ammonium carbonate, thereby suppressing the increase in pH (buffering). It is preferable to add a sufficient amount of ammonium carbonate or ammonium acetate to achieve the desired pH after addition of the copper salt and complex formation. The pH can then be increased after mixing by the addition of aqueous ammonia. The solution of the tetraammine copper salt is prepared at low temperature to prevent outgassing of ammonia. Temperatures in the range of 0.0°C to 10.0°C, preferably in the range of 1.0°C to 5.0°C, have been found to be useful.

[0066] More preferably, the procedure is as follows: The copper salt, ammonium carbonate and 80% of the calculated ammonia solution are initially mixed at 5.0° C. With stirring, further ammonia solution (cooled to 5.0° C.) is added until a pH of 9.2 (Hartinger, Handbuch Abwasser und Recyclingtechnik [Handbook of Wastewater and Recycling Technology]; Figure 2.25; p. 85; 2017; see also Guenter Dietrich) is achieved.

[0067] Preparation of the catalyst from the support and a solution of tetraammine copper salt The impregnation of the support required as a first step can in principle be achieved by known methods. Both the incipient wetness method and impregnation in the supernatant liquid described above can be used. It is preferable to use the incipient wetness method, in particular in the variant in which the support is treated in the impregnation step (i.e. in the case of multiple impregnation steps, in each of the impregnation steps) with only a quantity of impregnation solution that is slightly (for example 2% to 5%) below the maximum absorption of the support determined above (see the Examples section for the determination of the maximum absorption). Impregnation in multiple steps is also possible if it is aimed at achieving a particularly high copper content. However, it is preferable to carry out not more than two impregnation steps. Impregnation is followed by drying (in particular at temperatures in the range of 80°C to 150°C, preferably in the range of 90°C to 130°C, more preferably in the range of 100°C to 120°C). This gives a precursor of the hydrogenation catalyst.

[0068] This precursor is used to obtain, by calcination, a tetraammine copper-based impregnated catalyst on a support comprising a shaped silicon dioxide body or a shaped silicon carbide body. Calcination is effected in particular at temperatures in the range of 300°C to 600°C, preferably in the range of 350°C to 550°C, more preferably in the range of 400°C to 500°C. Calcination can be carried out in an oxygen-containing atmosphere (in particular air), in a hydrogen atmosphere or in an inert atmosphere (in particular nitrogen or a rare gas atmosphere). Calcination in an oxygen-containing atmosphere is preferred. The calcination conditions determine the form in which the copper is present on the catalyst. In the case of calcination under oxidizing conditions, the copper becomes mainly completely oxidized, in particular CuO, and in the case of calcination under reducing conditions, the copper becomes mainly completely metallic.

[0069] The number of impregnation steps and the concentration of the tetraammine copper salt solution are preferably adapted to each other so that the hydrogenation catalyst after calcination has a mass ratio of copper compounds (present as a whole in the hydrogenation catalyst), calculated as metallic Cu, in the range of 3% to 35%, preferably 7% to 30%, more preferably 11% to 25%, based on the total mass of the hydrogenation catalyst.

[0070] Hydrogenation Procedure Nitroaromatic Compounds The process of the present invention is in principle suitable for the hydrogenation of all industrially relevant nitroaromatic compounds to the corresponding aromatic amines, more preferably of the formula: [ka] wherein R1 and R2 are independently hydrogen, methyl or ethyl, and R2 further comprises NO 2 The hydrogenation of nitrobenzene (R1=R2=H) to aniline is particularly preferred.

[0071] Catalyst activation (optionally as a separate step) Before the actual hydrogenation begins, the hydrogenation catalyst is preferably converted into its "active form" by reduction with hydrogen, in particular at temperatures in the range of 180°C to 240°C (activation of the catalyst; step (II) of the method of the invention). Activation is not absolutely necessary as a separate step upstream of the actual hydrogenation, since the catalyst is also exposed to reducing conditions in the actual hydrogenation. However, carrying out an upstream step (II) improves the instantaneous selectivity at the start of the hydrogenation. Activation is preferably carried out after inertization of the reactor with an inert gas, in particular nitrogen, at 1.0 bar. (絶対) ~3.0 bar (絶対) in the range of, for example, 1.5 bar (絶対) The activation is carried out with a hydrogen flow at a pressure of 0.1 MPa and the increase in temperature on the catalyst due to activation does not exceed 30° C. with the stepwise addition of hydrogen. The activation is carried out until no exothermic reaction is observed after the addition of 100% of the hydrogen. This step is preferably carried out directly in the reactor in which the actual hydrogenation is envisaged (see below).

[0072] Hydrogenation Step (III) of the process of the invention, the reaction of an aromatic nitro compound with hydrogen, preferably in the presence of an activated hydrogenation catalyst, to give an aromatic amine (i.e., hydrogenation), can in principle be effected as known from the prior art.

[0073] The hydrogenation is carried out in an apparatus designed for this purpose, a hydrogenation reactor or reactor for short. Suitable reactors are well known to those skilled in the art.

[0074] The hydrogenation of aromatic nitro compounds is preferably carried out continuously. When hydrogen is used in superstoichiometric amounts, it is preferred to recycle the unconverted hydrogen to the reaction. The reaction can be carried out in the liquid and gas phase. It is preferred to carry out the reaction in the gas phase.

[0075] The hydrogenation can be carried out adiabatically or isothermally. In the case of an adiabatic mode of operation, no special heat supply or removal takes place. Thus, apart from unavoidable heat losses, which are preferably minimized by the insulation of the reactor, the enthalpy of the reaction is quantitatively reflected in the temperature difference between the reaction mixture and the product mixture (adiabatic temperature jump). On the other hand, in an isothermal mode of operation, apart from unavoidable local "hot spots", the temperature is kept constant by external indirect cooling. Possible reaction regimes, which can also be used in the process of the invention, are described in EP-A-0 944 578 (isothermal mode of operation) and in EP-A-0 696 574, EP-A-1 062 103 and EP-A-1 099 141 (adiabatic mode of operation). It is particularly preferred to observe the following conditions, which have been found to be particularly useful for reactions in the gas phase: step (III) is carried out in a 200-2500 sulphuric acid solution, preferably ... Adiabatically at a temperature in the range of 160°C to 500°C, preferably 180°C to 450°C, more preferably 200°C to 400°C, or The reaction is carried out isothermally at a temperature in the range of 180°C to 550°C, preferably 200°C to 500°C, and more preferably 220°C to 450°C.

[0076] It is clear that the molar ratio of hydrogen to nitro groups must be at least stoichiometric, i.e. at least 3 (i.e. 3:1), in order to achieve complete conversion of the nitroaromatic compounds. However, it has been found to be useful to use hydrogen in a superstoichiometric amount, generally in adiabatic mode, chosen in particular to be in high excess over stoichiometry, so that a considerable heat of reaction is absorbed by this excess hydrogen. The invention therefore particularly relates to a process (III) comprising: Adiabatically at a molar ratio of hydrogen to nitro groups in the range of 10 to 200, preferably 20 to 150, more preferably 60 to 120, or The present invention also relates to a method which is carried out isothermally at a molar ratio of hydrogen to nitro group in the range of 3-100, preferably 6-60, and more preferably 10-30.

[0077] Preferred reactors for isothermally operated reactors are thermostatic tubular reactors or shell-and-tube reactors. Suitable embodiments of such reactors are described, for example, in DE-A-2201528, DE-A-2207166, DE-A-19806810, EP-A-1439901, EP-A-1569745, EP-A-1590076, EP-A-1587612, EP-A-1586370, EP-A-1627678 or DE-A-202006014116.

[0078] Preferred reactors for adiabatically operated reactors are those described in DE 10 2006 035 203 A1, paragraphs

[0030] to

[0033] .

[0079] Regardless of the operating mode (isothermal or adiabatic), it is preferred to arrange the hydrogenation catalyst in a fixed catalyst bed in step (III). That is, the shaped bodies are in a fixed position in the reactor used, for example in a thermostatic reactor tube (isothermally operated tubular reactors and shell-and-tube reactors) or on a support grid, in particular between two support grids (adiabatically operated reactors with a catalyst bed). At the other end of the spectrum from such fixed bed reactors are fluidized bed reactors (used, for example, in US Pat. No. 5,399,363), which put very fine catalyst particles (average size in the micrometer range) into a swirling motion.

[0080] The present invention will be explained in detail below using examples. EXAMPLES

[0081] General method Determination of maximum absorption of the support The maximum absorption rate is determined by weighing the shaped bodies before and after water absorption as described below. For this purpose, the support material is weighed and poured with demineralized water in a container that allows visual observation (for example a glass beaker) and left to stand (without moving the container) until no more air bubbles rise. The supernatant water is decanted and the surface of the moist shaped body is dried. This is done by absorbing the water adhering to the surface with filter paper, which can be done by rolling it on the filter paper or by tapping it with filter paper, depending on the shape of the shaped body. This drying step removes the water adhering to the surface but not the water absorbed in the pores of the support. The content is weighed and the starting weight is subtracted to obtain the water absorption in grams that corresponds to the maximum absorption rate of the shaped body used.

[0082] In all catalyst preparations, the amount of metal salt solution used for impregnation was adjusted to be 2% below the maximum absorption (incipient wetness method).

[0083] Starting materials Poletto Aldo's Cu(NO) has a density of 1.48 g / ml at 20°C, a Cu content of (14.5±0.5) mass%, and a pH of 3.5±0.5 (measured at room temperature between 20°C and 25°C).3 ) 2 solution Molded silicon dioxide body with a cylinder of 3 mm x 5 mm, absorption rate of 1.13 ml / g, and bulk density of 417 g / l

[0084] Example 1: Preparation of copper nitrate-based impregnated catalyst as a comparative catalyst 100 ml of silicon dioxide support was placed in a Cu(NO 3 ) 2 The catalyst was impregnated with the solution. It was necessary to stir the mixture until the liquid was completely absorbed by the support material. The impregnated body was dried to a constant mass at 120°C and then calcined at 450°C for 4 hours in an air atmosphere. The catalyst had a mass ratio of copper compounds calculated as metallic copper of about 24.0%.

[0085] Example 2: Hydrogenation of nitrobenzene using the catalyst of Example 1 (comparison) The catalyst of Example 1 was transferred in the oxidized state to a fixed bed reactor and nitrogen was passed through until the residual oxygen was driven off. The temperature was adjusted to a value in the range of 200°C to 240°C and activation was started by metering hydrogen. The exothermic reaction should be kept as low as possible. At the end of activation, excess hydrogen was removed by passing nitrogen through the catalyst. For the reaction, nitrobenzene (NB) was metered into the activated catalyst, the amount of nitrobenzene being continuously increased until 0.9 g. NB / ml cat The target input was adjusted to 100 / hr. The molar ratio of hydrogen to nitrobenzene was 10:1. The reaction was carried out polytropically, and the heat evolved during the reaction was removed by a heat transfer medium. In both cases, hydrogenation was carried out until breakthrough of nitrobenzene was observed.

[0086] The catalyst described in Example 1 exhibited a life span of 60 hours and an average aniline selectivity of 99.2%.

[0087] Example 3: Preparation of tetraamminecopper-based impregnated catalyst as hydrogenation catalyst for the process of the present invention Composition used for the solution with pH=9.2±1.0 and Cu mass ratio of (12.7±0.5)%: Ammonium carbonate 65.785g Basic copper carbonate 74.6g Ammonia 81.7g 100g demineralized water

[0088] First, the starting materials were cooled in a refrigerator to below 5° C. Water and ammonia were mixed in a sealable container. The solids were weighed in bulk onto a dish and quickly added to the cold ammonia solution, covered and mixed until the salts were dissolved.

[0089] 100 ml of the silicon dioxide support was impregnated with the amount of the tetraammine copper carbonate solution thus prepared, corresponding to the absorption rate of the support. The mixture had to be stirred until the liquid was completely absorbed by the support material. The impregnated shaped body was dried to constant weight at 120°C and then calcined at 450°C for 4 hours. The catalyst had a mass ratio of copper compounds, calculated as metallic copper, of about 14.8%.

[0090] Example 4: Hydrogenation of nitrobenzene using the catalyst of Example 3 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 295 hours and the average aniline selectivity was 99.6%.

[0091] Example 5: Preparation of tetraammine copper-based impregnated catalyst as hydrogenation catalyst for the process of the present invention at pH=10 Starting from Example 3, a catalyst was prepared at pH=10. The following amounts were used: Ammonium carbonate: 15.8g Basic copper carbonate: 18.18g Ammonia: 32.60g Demineralized water: 33.42g

[0092] First, the starting materials were cooled in a refrigerator to below 5° C. Water and ammonia were mixed in a sealable container. The solids were weighed in bulk onto a dish and quickly added to the cold ammonia solution, covered and mixed until the salts were dissolved.

[0093] 100 ml of the silicon dioxide support was impregnated with the amount of the thus prepared tetraammine copper carbonate solution corresponding to the absorption rate of the support. The mixture had to be stirred until the liquid was completely absorbed by the support material. The impregnated bodies were dried at 120°C to constant weight and then calcined at 450°C for 4 hours. The catalyst had a mass ratio of Cu of about 12.4%.

[0094] Example 6: Hydrogenation of nitrobenzene using the catalyst of Example 5 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 240 hours and the average aniline selectivity was 99.6%.

[0095] Example 7: Preparation of tetraammine copper-based impregnated catalyst as hydrogenation catalyst for the process of the present invention at pH 10 including "aging" The catalyst was prepared similarly to Example 5, except that in the impregnation process, the catalyst was allowed to stand wet for one week before drying.

[0096] Example 8: Hydrogenation of nitrobenzene using the catalyst of Example 7 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 240 hours and the average aniline selectivity was 99.5%.

[0097] Example 9: Preparation of tetraamminecopper-based impregnated catalyst as hydrogenation catalyst for the process of the present invention at pH 10 with multiple impregnations The procedure was the same as in Example 5, except that a higher copper content was achieved by double impregnation. The mass ratio of copper compounds calculated as metallic copper after calcination was about 22%.

[0098] Example 10: Hydrogenation of nitrobenzene using the catalyst of Example 9 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 360 hours and the average aniline selectivity was 99.6%.

[0099] Example 11: Preparation of tetraamminecopper-based impregnated catalysts as hydrogenation catalysts for the process of the present invention at pH 9.2 with multiple impregnations at lower metal concentrations The procedure was the same as in Example 5, except that the impregnation solution had a lower metal content and double impregnation was performed. The mass ratio of copper compounds calculated as metallic copper after calcination was about 15.3%.

[0100] Example 12: Hydrogenation of nitrobenzene using the catalyst of Example 11 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 290 hours and the average aniline selectivity was 99.6%.

[0101] Example 13: Preparation of tetraammine copper based impregnated catalyst as hydrogenation catalyst for the process of the invention at pH 9.2 on an alternative silica support The procedure is 80m 2 The same as in Example 3, except that an alternative silica support material with a lower specific surface area of ​​1.0 μg / g was used. The mass ratio of copper compounds calculated as metallic copper after calcination was about 12.9%.

[0102] Example 14: Hydrogenation of nitrobenzene using the catalyst of Example 13 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 260 hours and the average aniline selectivity was 99.5%.

[0103] Example 15: Preparation of tetraamminecopper-based impregnated catalysts as hydrogenation catalysts for the process of the invention at pH 10 on "trilobe" molded bodies The procedure was the same as in Example 5, except that the support material used was a silica-based trilobe molded body. The mass ratio of copper compounds calculated as metallic copper after calcination was about 11.6%.

[0104] Example 16: Hydrogenation of nitrobenzene using the catalyst of Example 15 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 240 hours and the average aniline selectivity was 99.7%.

[0105] Example 17: Preparation of tetraammine copper-based impregnated catalyst as hydrogenation catalyst for the process of the invention at pH 10 with multiple impregnations on "trilobe" molded bodies The procedure was the same as in Example 5, except that the support material used was a silica-based trilobe molded body and multiple impregnation was performed. The mass ratio of copper compounds calculated as metallic copper after calcination was about 19.6%.

[0106] Example 18: Hydrogenation of nitrobenzene using the catalyst of Example 17 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 300 hours, and the average aniline selectivity was 99.7%.

[0107] Example 19: Preparation of tetraammine copper-based impregnated catalyst as hydrogenation catalyst for the process of the invention at pH 10 with multiple impregnations on a silicon carbide support of relatively low purity (about 99.5% SiC) The procedure was the same as in Example 5, except that the support material used was a silicon carbide support (about 99.5% SiC) and multiple impregnation was performed. The mass ratio of copper compounds calculated as metallic copper after calcination was about 10.3%.

[0108] Example 20: Hydrogenation of nitrobenzene using the catalyst of Example 19 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 290 hours and the average aniline selectivity was 99.8%.

[0109] Example 21: Preparation of tetraammine copper based impregnated catalyst as hydrogenation catalyst for the process of the invention at pH 10 with multiple impregnations on silicon carbide supports of high purity (>99.85% SiC) compared to Example 19 The procedure was the same as in Example 5, except that the support material used was a silicon carbide support (>99.85% SiC) and multiple impregnation was performed. The mass ratio of copper compounds calculated as metallic copper after calcination was about 10.1%.

[0110] Example 22: Hydrogenation of nitrobenzene using the catalyst of Example 21 (invention) Except for the catalyst, the experiment was carried out in the same manner as in Example 2. The lifetime was 240 hours and the average aniline selectivity was 99.8%.

Claims

1. (I) providing a tetraammine copper salt-based impregnated catalyst as a hydrogenation catalyst, the catalyst comprising a metal or metal oxide on a support, the support comprising a shaped silicon dioxide body or a shaped silicon carbide body; provided that at least metallic copper or copper oxide is present in the impregnated catalyst, and the molar ratio of Cu to all metals present is in the range of 0.75 to 1; (II) optionally activating the hydrogenation catalyst by treatment with hydrogen in the absence of an aromatic nitro compound; (III) reacting an aromatic nitro compound with hydrogen in the presence of the optionally activated hydrogenation catalyst to obtain an aromatic amine; 2. A process for preparing an aromatic amine by hydrogenating an aromatic nitro compound, comprising:

2. 2. The method of claim 1, wherein step (II) is carried out and the treatment with hydrogen is accomplished at a temperature in the range of 180°C to 240°C.

3. Step (III) Adiabatically at temperatures in the range of 160°C to 500°C, or 3. The process according to claim 1 or 2, which is carried out isothermally at a temperature in the range of 180°C to 550°C.

4. Step (III) Adiabatically with a molar ratio of hydrogen to nitro groups in the range of 10 to 200, or 4. The process according to any one of claims 1 to 3, carried out isothermally with a molar ratio of hydrogen to nitro groups ranging from 3 to 100.

5. The method according to any one of claims 1 to 4, wherein the mass ratio of the copper compound calculated as metallic Cu in the hydrogenation catalyst prepared in (I) is in the range of 3% to 35% relative to the total mass thereof.

6. The process according to any one of claims 1 to 5, wherein the hydrogenation catalyst used is an impregnated catalyst based on tetraammine copper carbonate.

7. 7. The process according to claim 6, wherein the hydrogenation catalyst used is a copper tetraammine carbonate / ammonium carbonate based impregnated catalyst or a copper tetraammine carbonate / ammonium acetate based impregnated catalyst.

8. 8. The method according to any one of claims 1 to 7, wherein the impregnated catalyst is obtained by a process of impregnating the support with an aqueous solution of a tetraammine copper salt by an incipient wetness method, so as not to exceed the maximum absorption rate of the support, determined by the degree of saturation with water.

9. Step (I) comprises: (a) dissolving a copper salt in ammonia water to obtain an ammoniacal copper salt solution; (b) impregnating said support with the ammoniacal copper salt solution obtained in (a) and subsequently drying the impregnated support thus obtained to obtain a catalyst precursor; (c) calcining the catalyst precursor obtained in (c) to form a tetraammine copper based impregnated catalyst; The method according to any one of claims 1 to 8, comprising:

10. 10. The method of claim 9, wherein the ammoniacal copper salt solution used for impregnation has a pH (at 20° C.) in the range of 7.0 to 14.

11. formula: 【Chemistry 1】 wherein R1 and R2 are independently hydrogen, methyl or ethyl, and R2 further comprises NO ２ The process according to any one of claims 1 to 10, wherein an aromatic nitro compound, which may be

12. 11. The method according to claim 9 or 10, wherein the support in step (b) is impregnated with the ammoniacal copper salt solution obtained in (a) by the incipient wetness method so as not to exceed the maximum absorption rate of the support, determined by the degree of saturation with water.

13. The method of claim 12, wherein the absorption is no more than 5% below the maximum absorption of the support.

14. 14. The method of claim 12 or 13, wherein the absorption is at least 2% below the maximum absorption rate.

15. The process according to any one of claims 1 to 14, wherein the optionally activated hydrogenation catalyst in step (III) is disposed in a fixed catalyst bed.

Images