Tableted copper-manganese-based catalyst with increased stability against acid exposure

Description

[0001] The present invention relates to an improved catalyst based on a tableted catalyst body comprising a material of the formula CuAl a Mn b Zn c O d with calcium aluminate as a binder for the hydrogenation of carbonyl groups in organic compounds, characterized in that the catalyst body comprises a weight fraction of calcium aluminate in an amount of 0.5 to 10.0 wt.%, based on the catalyst body, and the lateral compressive strength is 100-300 N, determined according to DIN EN 1094-5. The present invention also relates to the production of the catalyst and its use in the hydrogenation of carbonyl groups in organic compounds. Background of the invention

[0002] Catalytic processes for the hydrogenation of carbonyl groups in organic compounds such as esters, diesters, aldehydes, or ketones are of great industrial importance. They serve, among other things, to convert carboxylic acids or their esters, especially fatty acid esters, into the corresponding alcohols.

[0003] Suitable catalysts include systems based on copper in combination with other transition metals. These catalysts are typically available in the form of tablets, extrudates, or granules.

[0004] WO 2004 / 085356 describes the manufacture of a catalyst for the hydrogenation of carbonyl compounds, which, in addition to copper and aluminium, contains at least one oxide of lanthanum, tungsten, molybdenum, titanium or zirconium, and to which copper powder or flakes, cement powder or graphite are added.

[0005] US Patent 6,020,285 describes the production of a cobalt- or nickel-containing catalyst that also includes calcium aluminate with an Al / Ca ratio greater than 2.5. The catalyst is suitable for the decomposition of hypochlorite.

[0006] WO 98 / 11985 discloses catalysts containing cobalt or nickel, which also include calcium aluminate with an Al / Ca ratio greater than 4.0, as well as alumina and / or magnesia. The catalyst is suitable for the decomposition of oxidizing substances.

[0007] US Patent 7,084,312 describes the production of catalysts based on copper, zinc, and aluminum, for which an oxide mixture of copper, zinc, and aluminum is blended with metallic copper, a cement, or a mixture of both materials and formed into tablets. The catalyst is used for the hydrogenation of organic compounds containing carbonyl groups.

[0008] Yakerson et al. (Scientific Bases for the Preparation of Heterogeneous Catalysts, Preparation of Catalysts, p. 879 ff.) describe the preparation of cement-containing metal catalysts, such as nickel-, copper-, or zinc-containing catalysts. The corresponding metal hydroxocarbonates are used for this purpose.

[0009] DE 10 2005 032726 A1 discloses a catalyst and a process for the hydrogenation of an organic compound having at least one carbonyl group.

[0010] The starting materials for hydrogenation processes typically contain traces of acidic compounds. These include, for example, carboxylic acids, which are present as byproducts in esterification reactions. Under the reaction conditions of the hydrogenation reaction, these compounds attack the catalyst, leading to a reduction in mechanical stability and, in some cases, the leaching of catalytically active metals. These metals are carried out of the reaction reactor with the product stream and must be separated from it. Furthermore, as the catalytically active metals are leached out, the catalytic activity of the catalyst also decreases.

[0011] Such reactions use catalysts containing copper and chromium.

[0012] These typically exhibit increased stability against acid exposure. Due to stricter environmental regulations, the use of chromium-containing catalysts is subject to increasingly stringent requirements, creating a need to replace existing CuCr systems with environmentally friendly alternatives that nevertheless possess comparable catalytic and physical properties.

[0013] The object of the present invention was therefore to provide a catalyst for hydrogenation of carbonyl groups in organic compounds, which is characterized by improved mechanical stability and is less susceptible to the action of acidic compounds.

[0014] This problem is solved by the catalyst according to the invention. Description of the invention

[0015] The invention relates to a catalyst body in tablet form, comprising a material of the formula CuAl a Mn b Zn c O d and calcium aluminate as a binder in a weight fraction of 0.5 to 10.0%, based on the catalyst body, wherein the lateral compressive strength is 100-300 N, determined according to DIN EN 1094-5. a is between 0 and 2.5, b between 0.001 and 0.6, c between 0 and 2.5, and d is selected such that the total charge of the molecular formula is zero. In a particular embodiment, a is between 0.8 and 1.2, b between 0.05 and 0.3, c 0, and d is selected such that the total charge of the molecular formula is zero. In another preferred embodiment, a has the value 0, b is between 0.04 and 0.1, c is between 0.8 and 1.5, and d is chosen such that the total charge of the sum formula is zero.

[0016] The oxidation states of the elements are +2 for Cu, +3 for Al, and +2 for Zn. Depending on the amount of Mn, the oxidation state for Mn is +2, +3, or +4. Materials can also exist in which some Mn atoms have an oxidation state of +2 and others have an oxidation state of +3 or +4, resulting in an average oxidation state in the range of +2 to +4.

[0017] Calcium aluminate is a compound containing calcium and aluminum in the form of oxides and / or hydroxides. For example, it is a calcined calcium aluminate of the general formula CaO · Al₂O₃ or a chemically precipitated calcium aluminate of the general formula Ca₂O · Al₂ · (OH)₂. Depending on the treatment of the calcium aluminates, intermediate forms of these two formulas may also be present, which are likewise suitable as binders. In addition to these elements, other elements may be present in the calcium aluminate. In a preferred embodiment, the calcium aluminate contains further elements in a weight fraction of less than 5.0 wt.%, preferably less than 1.0 wt.%, and particularly preferably less than 0.1 wt.%, based on the weight of the calcium aluminate.

[0018] The catalyst body according to the invention is characterized in that it contains calcium aluminate as a binder material in a weight fraction of 0.5 to 10.0%, based on the catalyst body. Preferably, the fraction is 0.5 to 5.0%, more preferably 0.5% to less than 5.0%, and most preferably 0.5 to 3.0%, based on the catalyst body.

[0019] The atomic Ca / Al ratio of the calcium aluminate used in the present invention can vary and is preferably between 0.9 and 3.5, more preferably between 1.0 and 2.0.

[0020] Synthetically produced materials are suitable as calcium aluminates. However, naturally occurring calcium aluminates, such as katoite, can also be used.

[0021] The tablet-shaped catalyst body can be in various dimensions. The diameter of the tablets can be between 2 and 6 mm, and preferably between 2 and 4 mm. A diameter of 3 mm is particularly preferred. The height of the tablets can be between 2 and 6 mm, and preferably between 2 and 4 mm. A height of 3 mm is particularly preferred.

[0022] The calcium aluminate can be subjected to thermal treatment (calcination) before being used as a binder. This takes place at a temperature between 300 and 800 °C, preferably between 450 and 750 °C, and particularly preferably between 450 and 650 °C.

[0023] In one embodiment of the invention, the calcium aluminate particles have an average particle size with a d50 value in the range of 0.1 to 200 µm, preferably in the range of 5 to 50 µm, measured by laser sizing according to ISO 13302 / 2009. In another embodiment, the d90 value is in the range of 10 to 300 µm, preferably in the range of 20 to 100 µm.

[0024] The catalyst body according to the invention, comprising a material of the formula CuAl a Mn b Zn c O d and containing calcium aluminate as a binder material in a weight fraction of 0.5 to 10.0%, based on the catalyst body, is produced by the following steps according to the invention: a) Mixing a metal-containing mixture containing copper, manganese and at least one element selected from zinc and aluminum with calcium aluminate, a lubricant and water, b) Tableting the mixture according to step a) to obtain a tableted body, c) Thermal treatment of the tableted bodies at a temperature between 200 and 800 °C for a duration between 30 min and 4 h, wherein a is between 0 and 2.5, b is between 0.001 and 0.6 and c is between 0 and 2.5, and d is chosen such that the total charge of the molecular formula is zero.

[0025] In a particular embodiment, a is between 0.8 and 1.2, b is between 0.05 and 0.3, c is 0, and d is selected such that the total charge of the chemical formula is zero. In another preferred embodiment, a has the value 0, b is between 0.04 and 0.1, c is between 0.8 and 1.5, and d is selected such that the total charge of the chemical formula is zero.

[0026] In a preferred embodiment, the weight fraction of calcium aluminate is 0.5 to 5.0%, more preferably 0.5% to less than 5.0%, and most preferably 0.5 to 3.0%, based on the catalyst body.

[0027] The mixture used in step a) containing copper, manganese, and at least one element selected from zinc and aluminum can be chosen from the group of oxides, hydroxides, or carbonates. The oxides of the corresponding elements are particularly suitable. The elements can be present either as individual compounds, such as copper oxide and oxides of manganese, zinc, or aluminum, or as mixed compounds, such as mixed oxides of copper, manganese, and at least one element selected from zinc and aluminum.

[0028] The metal-containing mixture from step a) can be obtained by precipitation of the dissolved metal ions from aqueous solution. In principle, all compounds soluble in water, basic, or acidic aqueous solutions are suitable as starting materials. Nitrates, halides, oxides, sulfates, acetates, or formates are preferred.

[0029] The mixture obtained after step a) can optionally be subjected to an aging step. In this step, the mixture is left to stand for 5 minutes to 10 hours, preferably for 5 minutes to 3 hours, without the addition of any further components or the agitation of the mixture. The aging temperature typically corresponds to the ambient temperature of the mixture, but it can be controlled within a range of 0 °C to 90 °C.

[0030] The mixture obtained after step a), which may have been further aged, is then typically compacted and / or granulated without thermal treatment and subsequently subjected to tableting step b). Commercially available tableting machines are used, for example, the Pressima type from IMA Kilian. The mixture after step a) contains a lubricant. This lubricant is a compound that enhances the tableting properties of the mixture. Suitable lubricants are graphite, oils, or stearates, preferably graphite. The lubricant is added to the mass to be tableted in a proportion of 0.1 to 5.0 wt.%, preferably 0.5 to 5.0 wt.%, and particularly preferably 1.0 to 4.0 wt.%.

[0031] The mixture according to step a) also contains water. This is usually present in an amount of 1 to 10 wt.%, based on the metal-containing mixture used, preferably 2 to 4 wt.%, and most particularly 3 wt.%.

[0032] The tablets undergo thermal treatment at a temperature between 200 and 800 °C, preferably between 300 and 700 °C, and more preferably between 300 and 500 °C. The duration of this thermal treatment is between 30 minutes and 4 hours, preferably between 1 and 3 hours, and particularly preferably 2 hours.

[0033] The tablets produced by the inventive method have a lateral compressive strength of 100 to 300 N, preferably 100 to 250 N, and particularly preferably 120 to 180 N. Preferably, the tablets produced by tableting have a diameter in the range of 2 to 4 mm, a height in the range of 2 to 4 mm, and a lateral compressive strength in the range of 120 to 180 N.

[0034] The pore volume (measured by mercury porosimetry) of the catalyst body according to the invention is between 100 and 300 mm³ / g, preferably between 150 and 250 mm³ / g.

[0035] The catalyst bodies according to the invention have a specific BET surface area of ​​20 to 60 m² / g, preferably of 30 to 50 m² / g.

[0036] Preferably, the proportion of the pore volume of the pores with a radius of 7.0 to 40.0 nm of the catalyst body according to the invention is between 50 and 95%, preferably between 70 and 90% of the total pore volume.

[0037] The catalyst body obtained by the inventive process is reduced in a further step.

[0038] The reduction is preferably carried out by heating the tableted catalyst body in a reducing atmosphere. The reducing atmosphere is, in particular, hydrogen. The reduction takes place, for example, at a temperature in the range of 150°C to 450°C, preferably in the range of 180°C to 250°C, and particularly preferably in the range of 190°C to 210°C. The reduction takes place, for example, over a period of 1 hour to 10 days, preferably over a period of 2 hours to 72 hours, and particularly preferably over a period of 24 to 48 hours. In a preferred embodiment, the reduction takes place at a temperature in the range of 190°C to 210°C over a period of 24 to 48 hours.

[0039] In a preferred embodiment, the catalyst bodies are stabilized wet or dry after reduction. In wet stabilization, the catalyst bodies are coated with a liquid to minimize contact with oxygen. Suitable liquids include organic liquids and water, preferably organic liquids. Preferred organic liquids are those with a vapor pressure of 0.5 hPa or less at 20°C. Examples of such suitable organic liquids are isodecanol, naphtha, fatty alcohols, hexadecane, 2-ethylhexanol, propylene glycol, and mixtures thereof, particularly isodecanol. In dry stabilization, a mixture of oxygen or an oxygen-containing gas, preferably air, and an inert gas, such as argon or nitrogen, is added to the reduction chamber. The oxygen concentration in the mixture is preferably increased from about 0.04 vol% to about 21 vol%.For example, a mixture of air and inert gas can be added, with the initial air-to-inert gas ratio being approximately 0.2 vol% air to 99.8 vol% inert gas. The air-to-inert gas ratio is then gradually increased (e.g., continuously or stepwise) until, for example, 100 vol% air is added (corresponding to an oxygen concentration of approximately 21 vol%). Without being bound to any theory, it is assumed that the addition of air or oxygen results in the formation of a thin oxide layer with a thickness of, for example, 0.5 to 50 nm, preferably 1 to 20 nm, and particularly preferably 1 to 10 nm on the surface of the catalyst, which protects the catalyst body from further oxidation. During dry stabilization, the reactor temperature is preferably 100°C or less, particularly preferably 20°C to 70°C, and most preferably 30°C to 50°C.The reduction can take place ex situ or in situ in the reaction plant, where the catalyst body is inserted as a catalyst.

[0040] The lateral compressive strength of the catalyst molded bodies in tablet form exhibits values ​​of 50 to 250 N, preferably 60 to 200 N, particularly preferably 70 to 150 N after reduction.

[0041] To determine the stability of the catalyst molded bodies according to the invention against the effects of acid, the molded body is subjected to an acid treatment and the lateral pressure strength of the treated tablets is then determined.

[0042] The catalyst body according to the invention is suitable for use in catalytic hydrogenations of carbonyl groups in organic compounds. Possible reactions include the hydrogenation of diesters (especially maleic acid diesters) to diols, hydrogenation of sugars to polyols, hydrogenation of esters, especially fatty acid esters, hydrogenation of a fatty acid (e.g., by esterification and subsequent hydrogenolysis), hydrogenation of a ketone, hydrogenation of oxoaldehydes to oxo alcohols, and the hydrogenation of furfural. Examples

[0043] The loss on ignition within the scope of the present invention was determined by weighing approximately 1-2 g of a sample of the material to be analyzed and then heating it to 900 °C under room atmosphere and storing it at this temperature for 3 hours. The sample was then cooled under a protective atmosphere and the remaining weight was measured. The difference between the weight before and after the thermal treatment corresponds to the loss on ignition.

[0044] The lateral compressive strength was determined according to DIN EN 1094-5. A statistically sufficient number of tablets (at least 20 tablets) were measured, and the arithmetic mean of the individual measurements was calculated. This mean value corresponds to the lateral compressive strength of a specific sample.

[0045] The determination of chemical elements was carried out using ICP measurement (Inductively Coupled Plasma) according to DIN EN ISO 11885.

[0046] Acid treatment was carried out by mixing a total of 1.5 g of tableted samples with 15 g of acetic acid (10 vol% in H₂O). This mixture was stirred for 30 minutes at room temperature. The tableted sample was then dried in air at 120 °C for 10 hours, and its lateral compressive strength was subsequently measured.

[0047] The specific BET surface areas were determined by nitrogen adsorption according to DIN 66131. ​​The catalyst obtainable by the inventive process preferably has a BET surface area in the range of 20 to 100 m² / g, in particular 30 to 80 m² / g, and most preferably 40 to 60 m² / g.

[0048] The pore volume of the catalyst body was measured using the mercury porosimetry method according to DIN 66133.

[0049] The weight fraction of calcium aluminate in the catalyst body was determined by X-ray diffractometry. A D4 Endeavor from BRUKER was used. For this purpose, the sample was diffracted over a range of 5 to 90°C. Θ (Step sequence 0.020 2°) Θ The reflection intensity was measured (1.5 seconds measurement time per step). CuKα1 radiation (wavelength 1.54060 Å, 40 kV, 35 mA) was used as the radiation source. The sample tray was rotated around its axis at a speed of 30 revolutions / min during the measurement. The resulting spectrum of reflection intensities was quantitatively analyzed using Rietveld refinement, and the proportion of calcium aluminate in the sample was determined. The TOPAS software from BRUKER was used to determine the proportion of the respective crystal phases. Production of the catalyst powder

[0050] Aqueous solution 1 was prepared by dissolving 1250 g of Cu(NO₃)₂·3 H₂O, 220 g of Mn(NO₃)₂·4 H₂O, and 1800 g of Al(NO₃)₃·9 H₂O in 9000 g of distilled water. Solution 2 was prepared by dissolving 1720 g of Na₂CO₃ in 7500 g of distilled water. Both solutions were heated separately to 80 °C with stirring. They were then added to a precipitation vessel with continuous stirring. The addition of both solutions was adjusted so that the combined mixture in the precipitation vessel had a pH of 7 (+ / - 0.2). The resulting precipitate was filtered and washed with distilled water to remove any adhering impurities. The filter cake was resuspended in 8 L of distilled water and spray-dried. The dried powder was then heat-treated for 3 h at 750 °C and served as the starting material for the tableting examples. The relative weight fraction was Cu = 45 wt.%, Mn = 7 wt.% and Al = 18 wt.%, based on the total mass after loss on ignition. This corresponds to a chemical formula of CuMn 0.18 Al 0.94 O2.6. Comparative example 1 (catalyst A)

[0051] Catalyst A was prepared by mixing 500 g of the catalyst powder with 10 g of graphite and then forming tablets with dimensions of 3 mm in height and 3 mm in diameter. The lateral compressive strength of the sample was determined after tableting. The acid treatment damaged all the tablets to such an extent that they were completely broken, making it impossible to determine the lateral compressive strength. Comparative example 2 (catalyst B)

[0052] Catalyst B was prepared by mixing 500 g of the catalyst powder with 10 g of graphite and then forming tablets with dimensions of 4.5 mm in height and 4.5 mm in diameter. The lateral compressive strength of the sample was determined after tableting and acid treatment. The acid treatment damaged all the tablets to such an extent that they were completely broken, making a determination of the lateral compressive strength impossible.

[0053] A portion of the material obtained after tableting was subjected to reduction. The sample was thermally treated in a gas mixture of 2% by volume H₂ and 98% by volume N₂ at a temperature of 200 °C to reduce the CuO to Cu. The sample was then cooled to room temperature under nitrogen and stored in liquid decanol. The lateral compressive strength of this sample was subsequently measured. Example 1 (catalyst 1)

[0054] 500 g of the catalyst powder were mixed with 5 g of calcium aluminate (type SECAR 71, 30 wt% CaO, 70 wt% Al₂O₃), 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. A thermal treatment at 320 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment. Example 2 (catalyst 2)

[0055] 500 g of the catalyst powder were mixed with 15 g of calcium aluminate (type SECAR 71, 30 wt% CaO, 70 wt% Al₂O₃), 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. The tablets were subsequently steam-treated at 100–150 °C for 24 h, followed by a thermal treatment at 320 °C. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample. Example 3 (catalyst 3)

[0056] 500 g of the catalyst powder were mixed with 15 g of calcium aluminate (type SECAR 71, 30 wt% CaO, 70 wt% Al₂O₃), 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 4.5 mm in height and 4.5 mm in diameter. A thermal treatment at 450 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample.

[0057] A portion of the material obtained after tableting was subjected to reduction. The sample was thermally treated in a gas mixture of 2% by volume H₂ and 98% by volume N₂ at a temperature of 200 °C to reduce the CuO to Cu. The sample was then cooled to room temperature under nitrogen and stored in liquid decanol. The lateral compressive strength of this sample was subsequently measured. Example 4 (catalyst 4)

[0058] 500 g of the catalyst powder were mixed with 15 g of calcium aluminate (type SECAR 71, 30 wt% CaO, 70 wt% Al₂O₃), 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. A thermal treatment at 450 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample. Example 5 (catalyst 5)

[0059] 500 g of the catalyst powder were mixed with 15 g of calcium aluminate (type SECAR 71, 30 wt% CaO, 70 wt% Al₂O₃), 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. A thermal treatment at 650 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample. Example 6 (catalyst 6)

[0060] 500 g of the catalyst powder were mixed with 50 g of calcium aluminate (type SECAR 71, 30 wt% CaO, 70 wt% Al₂O₃), 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. A thermal treatment at 450 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample. Example 7 (catalyst 7)

[0061] 500 g of the catalyst powder were mixed with 50 g of calcium aluminate (type SECAR 71, 30 wt% CaO, 70 wt% Al₂O₃), 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. A thermal treatment at 650 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample. Example 8 (catalyst 8) (not according to the invention)

[0062] 500 g of the catalyst powder were mixed with 100 g of calcium aluminate (type SECAR 71, 30 wt% CaO, 70 wt% Al₂O₃), 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. A thermal treatment at 450 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample. Example 9 (catalyst 9) (not according to the invention)

[0063] 500 g of the catalyst powder were mixed with 100 g of calcium aluminate (type SECAR 71, 30 wt% CaO, 70 wt% Al₂O₃), 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. A thermal treatment at 650 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample. Example 10 (catalyst 10)

[0064] The calcium aluminate used in Example 1 was thermally treated at 650 °C for 2 h. Subsequently, 500 g of the catalyst powder was mixed with 15 g of this thermally treated calcium aluminate, 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. A thermal treatment at 450 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample. Example 11 (catalyst 11)

[0065] The calcium aluminate used in Example 1 was thermally treated at 650 °C for 2 h. Subsequently, 500 g of the catalyst powder was mixed with 15 g of this thermally treated calcium aluminate, 10 g of graphite, and 15 g of distilled water. The mixture was then aged for 4 h and formed into tablets measuring 3 mm in height and 3 mm in diameter. A thermal treatment at 650 °C was then performed. The lateral compressive strength of the sample was determined after tableting, after thermal treatment, and after acid treatment of the calcined sample. Example Calcium aluminate [wt%] Temperature of thermal treatment [°C] Side pressure resistance after tableting [N] Lateral pressure strength after thermal treatment [N] Lateral pressure resistance after acid treatment [N] Lateral pressure resistance after reduction [N] Dimensions [mm x mm] Relative pore volume of pores in the range of radii from 40 - 7.0 nm [%] BET surface area [m² / g] Catalyst A - no thermal treatment 85 - 0 0 3 x 3 69,6 57 Catalyst B - No thermal treatment 99 - 0 69 4,5 x 4,5 87,3 57 Catalyst 1 1 320 64 151 129 not determined 3 x 3 71,7 53 Catalyst 2 3 320 73 162 109 not determined 3 x 3 74,8 53 Catalyst 3 3 450 82 230 190 134 4,5 x 4,5 83,1 39 Catalyst 4 3 450 88 175 122 not determined 3 x 3 87,3 41 Catalyst 5 3 650 88 233 170 not determined 3 x 3 87,5 35 Catalyst 6 10 450 66 134 93 not determined 3 x 3 84,7 44 Catalyst 7 10 650 70 175 141 not determined 3 x 3 87,1 36 Catalyst 8 20 450 70 122 90 not determined 3 x 3 82,0 39 Catalyst 9 20 650 71 161 140 not determined 3 x 3 78,0 35 Catalyst 10 3 450 90 216 145 not determined 3 x 3 89,5 40 Catalyst 11 3 450 104 253 165 not determined 3 x 3 86,3 40

[0066] Table 1 clearly shows that the catalysts according to the invention exhibit a significantly higher lateral compressive strength after thermal treatment than the reference catalyst. After acid treatment, the lateral compressive strength decreases for all samples, although the lateral compressive strength of the samples according to the invention remains significantly higher than that of the reference catalysts A and B before acid treatment. This underscores the increased mechanical stability of the catalysts according to the invention, even under the harsh conditions of an acidic environment, such as those encountered during the hydrogenation of carbonyl groups in organic compounds like esters, diesters, aldehydes, or ketones, since the reactants contain acidic impurities.

[0067] The specific surface areas after BET are not significantly affected by the inventive process. The same applies to the relative pore volume of the pores in the range of 40–7.0 nm. This underscores the stability of the catalyst bodies according to the invention with respect to the thermal stress during the thermal treatment.

Claims

1. Catalyst molding comprising a material of the formula CuAlaMnbZncOd , where a is a number between 0 and 2.5, b is a number between 0.001 and 0.6, c is a number between 0 and 2.5, and d is chosen such that the total charge of the molecular formula is zero, characterized in that the catalyst molded body is in tablet form and contains calcium aluminate as a binding material in a weight proportion of 0.5 to 10.0%, based on the catalyst molded body, and the lateral compressive strength is 100-300 N, determined in accordance with DIN EN 1094-5.

2. Catalyst molded body according to claim 1, wherein the calcium aluminate is present in a weight proportion of 0.5 to 5.0%, preferably from 0.5% to less than 5.0%, more preferably from 0.5 to 3.0%, based on the catalyst molded body.

3. Method for producing a catalyst molded body according to one of claims 1 or 2,comprising a material of the formula CuAlaMnbZncOdand containing calcium aluminate as a binder material in a weight proportion of 0.5 to 10.0%, based on the catalyst molded body, comprising the following steps: a) mixing a metal-containing mixture containing copper, manganese, and at least one element selected from zinc and aluminum with calcium aluminate, a lubricant, and water b) Tabletting the mixture according to step a) to obtain a tableted molded body c) Thermal treatment of the tableted shaped bodies at a temperature between 200 and 800 °C for a duration between 30 min and 4 h, where a is between 0 and 2.5, b is between 0.001 and 0.6, and c is between 0 and 2.5, and d is chosen such that the total charge of the sum formula is zero.

4. Method according to claim 3, wherein the metal-containing mixture is a mixed oxide of copper, manganese, and aluminum.

5. Method according to one of claims 3 or 4, wherein the calcium aluminate is present in a weight proportion of 0.5 to 5.0%, preferably from 0.5% to less than 5.0%, more preferably 0.5 to 3.0%, based on the catalyst molded body.

6. Method according to one of claims 3 to 5, wherein the mixture according to step a) is aged for a period of 5 min to 10 h.

7. Method according to one of claims 3 to 6, wherein the thermal treatment takes place between 300 and 500 °C for a duration of between 1 hour and 3 hours.

8. Method according to one of claims 3 to 7, wherein the calcium aluminate used in step a) is essentially present in oxide form.

9. Method according to one of claims 3 to 8, wherein after step c) a reduction of the molded body takes place.

10. Method for the hydrogenation of carbonyl groups in organic compounds using the catalyst molded body according to one of claims 1 or 2 or produced according to a method according to one of claims 3 to 9.