EP2888041A1

EP2888041A1 - Method for treating catalytic converter preforms and catalytic converter preforms with enhanced mechanical strength

Info

Publication number: EP2888041A1
Application number: EP13755994.4A
Authority: EP
Inventors: Thomas Heidemann; Claudia ÖZKOZANOGLU
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2012-08-22
Filing date: 2013-08-20
Publication date: 2015-07-01
Also published as: RU2015109876A; JP2015527194A; RU2638838C2; JP6143867B2; CN104582836B; IN2015DN01366A; WO2014029762A1; CN104582836A

Abstract

The present invention specifies a method for treating catalytic converter preforms, particularly to increase the mechanical strength thereof, said method comprising the following steps: a) provision of prepared catalytic converter preforms; b) immersion of the catalytic converter preforms together with a peptising agent in a volume of liquid not exceeding the theoretical water absorption of the catalytic converter preform; c) thermal treatment of the immersed catalytic converter preforms at 50°C to 250°C; and d) calcination of the thermally treated catalytic converter preforms at 250°C to 600°C. Furthermore, a catalytic converter preform with enhanced mechanical strength is created which can be produced using the method according to the invention. The present invention further relates to the use of catalytic converter preforms according to the invention for the production of amines and in solid bed reactors or fluidized-bed reactors, and to a chemical synthesis method in the presence of catalytic converter preforms according to the present invention.

Description

Process for the treatment of shaped catalyst bodies and shaped catalyst bodies with increased mechanical strength

description

The present invention relates to a process for the treatment of shaped catalyst bodies, in particular to increase their mechanical strength, are impregnated in the finished prepared shaped catalyst body with Peptisierhilfsmitteln and then thermally treated. The invention further relates to shaped catalyst bodies with increased mechanical strength, which can be produced by the process according to the invention, as well as their use.

Catalyst shaped bodies are used in a variety of ways. They are usually in particulate form, e.g. as tablets or extrudates. In order to be able to use such shaped catalyst bodies safely and reliably under industrially relevant conditions, for example in fixed bed reactors and in fluidized bed reactors, they must have sufficient mechanical strength. It should be noted that during use, the shaped catalyst bodies may also lose mechanical strength over time.

According to the state of the art, in order to obtain a sufficient mechanical strength, a large number of methods are available which are used during the respective production processes, so that with the finished preparation of the conventional shaped catalyst bodies the adjustment of the required mechanical strength is usually completed.

Thus, according to the state of the art (see, for example, KP de Jong, "Synthesis of Solid Catalysts", Wiley-VCH, 2009, pp. 173-183), for example in the production of extrudates, the starting materials to be increased are before the actual molding process with so-called Peptisierhilfsmitteln added to form reactive groups on the surface of the solids used, which lead during the molding process and in the optional subsequent thermal treatment step to a network formation and thus to a curing of the resulting shaped catalyst body.There are used as Peptisierhilfsmittel various substances , which can be removed without residue until the end of the respective manufacturing process.

WO 2010/121974 A2 describes inter alia hydroamination catalysts based on zeolites, in particular boron-beta zeolites, which are subjected to various modifications in order to increase the selectivity, the service life and the number of possible regenerations, these modifications being carried out before the finished preparation the corresponding shaped catalyst body, ie before the final calcination. For this purpose, for example, acids or acid mixtures are used to treat the deformed or undeformed material. WO 2004/108280 A1 discloses a method for increasing the cutting hardness of a shaped body, in which a crystalline alumosilicate (zeolite) containing shaped body with a water vapor-containing gas at a temperature of 100 ° C to 600 ° C and an absolute pressure of 0, 1 bar up to 20 bar for a period of at least 20 hours. The mechanical properties of a molded article treated in this way can be improved by at least 20% after calcination.

The processes known in the prior art to provide higher mechanical strength catalyst moldings are therefore limited either to modifications of the original manufacturing process (see, for example, KP de Jong, "Synthesis of Solid Catalysts", Wiley-VCH, 2009, P 173 183) or are very specifically designed for certain catalyst systems (see WO 2010/121974 A2) or lead to an improvement only with greater additional equipment and time (see WO 2004/108280 A1).

Against this background, the object of the invention is to provide a generally applicable method with which the mechanical strength of existing shaped catalyst bodies can be further increased. It is a further object of the invention to provide catalyst moldings with increased mechanical strength.

This object is achieved in a first aspect of the present invention by a process for the treatment of shaped catalyst bodies, which comprises the process steps: a) providing ready-prepared catalyst moldings, b) impregnating the ready-prepared catalyst moldings with a peptizing aid in one Amount of liquid which does not exceed the theoretical water absorption of the catalyst moldings, c) thermally treating the impregnated catalyst moldings at 50 ° C to 250 ° C and d) calcining the thermally treated catalyst moldings at 250 ° C to 600 ° C. This object is also achieved in a first aspect of the present invention by a method for increasing the mechanical strength of shaped catalyst bodies, comprising the steps of: a) providing ready-prepared shaped catalyst bodies, b) impregnating the ready-prepared shaped catalyst bodies c) thermally treating the impregnated catalyst moldings at 50 ° C to 250 ° C; and d) calcining the thermally treated catalyst moldings at 250 ° C to 600 ° C ° C.

The present invention is based on the finding that even ready-prepared shaped catalyst bodies of different shapes and different compositions can be further improved in their mechanical strength even further if they are subjected to the process according to the invention. In addition to freshly prepared shaped catalyst bodies, the process according to the invention can also be applied to commercially available products and even to previously used catalyst bodies which have been regenerated before treatment. The catalyst moldings are impregnated with a Peptisierhilfsmittel, wherein it is important to carry out the impregnation only with a liquid amount of Peptisierhilfsmittel that does not exceed the theoretical water absorption of the catalyst molding. This is also spoken of by the 'incipinet wetness' method, that is, in the impregnation according to the invention, although the catalyst moldings have taken the maximum amount of liquid Peptisierhilfsmittel outwardly but still appear dry, so no liquid passes to the outside.

The theoretical water uptake can be determined by determining the open pore volume of the shaped catalyst bodies, which can be measured by known methods such as water uptake or mercury porosimetry. The impregnation itself can be carried out according to a method familiar to the person skilled in the art. For the process according to the invention, the moldings are preferably initially introduced and the liquid is added at room temperature while the moldings are being subjected to a rotary motion.

The limitation of the amount of liquid of the Peptisierhilfsmittels used, with which the catalyst moldings are impregnated, causes a maximum increase in the mechanical strength. If the catalyst moldings are treated in excess with the Peptisierhilfsmittel, the quantifiable increase decreases significantly until finally only a very small effect is observed, which is shown in the examples and comparative examples given below.

Compared with the ready-prepared catalyst moldings used in the present process, increases in mechanical strength of up to a factor of 3.0 can be achieved. As a measure of the mechanical strength, the cutting hardness and / or lateral compressive strength known to those skilled in the art can be used. Common measuring methods for this purpose are explained below in connection with the examples.

The mechanism leading to the increase of the mechanical strength of shaped catalyst bodies according to the present invention has not yet been clarified with final certainty. It is assumed, however, that new OH groups are created by impregnation with the peptizing aid and the subsequent thermal treatment on the surfaces of the catalyst moldings. These fresh OH groups form new networks in the catalyst moldings when calcining according to the present invention, on the one hand increase the mechanical strength, on the other hand, but do not affect the available pore volume.

Measurements of the pore volume have shown that the pore volume (within the scope of the usual measurement inaccuracies) changes only slightly and tends to even increase, as shown in the examples below.

As further shown below by means of examples and comparative examples, the method according to the invention does not adversely affect the chemical performance of the shaped catalyst bodies in any way. In addition, the inventive method is applicable to a variety of different catalyst materials, as the following examples also show.

Hereinafter, we further specified the present invention. "Finely prepared shaped catalyst bodies" are to be understood as meaning shaped bodies which have been prepared by processes known to the person skilled in the art and are used in this form as shaped catalyst bodies according to the prior art The conventional preparation generally involves providing the starting materials and, if appropriate, auxiliaries and their mixing into a raw material, a shaping of the raw material and one or more thermal treatments for the separation of volatiles and solidification of the moldings (eg calcination). The term molded body comprises both the catalyst support material and the catalytically active component. Optionally, the catalytic active component can fully form the shaped body, that is, the corresponding catalyst does not comprise any additional carrier material.

The peptizing aids for impregnating the shaped catalyst bodies in process step b) can be in solid or liquid form. Solid Peptisierhilfsmittel be dissolved in a suitable solvent and then used to impregnate the moldings, liquid Peptisierhilfsmittel can be used undiluted or as a solution. Suitable peptizing aids for the purposes of the present invention are bases such as ammonia or acids such as nitric acid, formic acid or acetic acid, in particular in aqueous, i. diluted form.

It is preferred to use as peptizing an ammonia solution or a nitric acid solution, in particular an aqueous ammonia solution or an aqueous nitric acid solution. Most preferably, an aqueous ammonia solution is used. In the case of increasing the strength of zeolite shaped bodies, in particular boron-beta-zeolite shaped bodies, an aqueous ammonia solution shows the best effects.

On the other hand, an aqueous solution of nitric acid, for example, has a better effect of increasing the strength of moldings of NiO / CoO / CuO / ZrO ₂ .

The upper limit (maximum value) of the theoretical water absorption of the corresponding shaped catalyst body must not be exceeded or exceeded only insignificantly by the impregnation with the corresponding amount of liquid of the Peptisierhilfsmittels in the present invention. An insignificant excess is understood as a maximum of 5% of the upper limit (maximum value) of the theoretical water absorption. In the context of the present invention, however, the amount of liquid of Peptisierhilfsmittel used should correspond to at least 50% (minimum amount of Peptisierhilfsmittel) based on the upper limit (maximum value) of the theoretical water absorption of the respective shaped catalyst body, preferably at least 90% of the upper limit. In the context of the present invention, it is particularly preferred in step b) to use a quantity of liquid of peptizing aid which corresponds exactly to the theoretical water absorption of the particular shaped catalyst body (ie the upper limit).

In order to form a sufficient amount of new active groups on the surface of the shaped catalyst body, it is preferred, after process step b) the Process step bb) Applying the Peptisierhilfsmittels be carried out for up to 10 hours. Although an exposure time of 1 to 10 hours is preferable, the exposure may be made only for a few minutes, for example, 1 to 30 minutes, or up to 1 hour, depending on the kind and the structure of the catalyst moldings.

It has proved to be advantageous for the quantitative removal as possible of the soaked in step b) in the mold Peptisierhilfsmittels when the thermal treatment in step c) under atmospheric pressure or in vacuo, preferably at 0.1 to 0.9 bar, and / or in a stationary or in a moving bed of the catalyst molding is carried out.

The thermal treatment in process step c) is preferably carried out at 50 ° C to 250 ° C, in particular at 100 ° C to 200 ° C, and serves to remove the Peptisierhilfsmittel after soaking again from the catalyst moldings.

In contrast, calcining in process step d) preferably takes place at 250 ° C. to 600 ° C., in particular at 300 ° C. to 500 ° C. With the calcination, the network of the catalyst-shaped body is further built and thus increases the mechanical strength. At the calcination temperatures to be applied, attention must be paid to the thermal stability of the catalyst materials used, both carrier and active component. Likewise, for a uniform result of calcination, it is desirable to carry out the calcination in process step d) in quiescent or in a moving bed of the catalyst moldings.

If the catalyst shaped body also comprises a carrier material, in principle all carrier materials known to the person skilled in the art can be used. Preferably, the carrier material is selected from Si0 ₂ , Ti0 ₂ , Al ₂ 0 ₃ and Zr0 ₂ . In principle, all catalytically active components known to those skilled in the art may be used as the catalytically active component, for example noble metals such as platinum, palladium, silver, rhodium or non-noble metals such as nickel, cobalt, ruthenium copper, iron or combinations thereof and additionally various doping elements which may be elemental or oxidic may be present.

It is preferred if extrudates and / or tablets and / or granules are used as the shaped catalyst body.

Furthermore, it is preferred to use heterogeneous catalysts as catalyst for the shaped catalyst bodies. In practice, it has been found to be advantageous for a variety of applications when the catalyst of zeolite, in particular boron-beta zeolite, NiO / CoO / CuO / Zr0 ₂ , Ti0 ₂ , CuO / Al ₂ 0 ₃ or Co ₃ 0 ₄ / Si0 _{2 is} selected.

In a second aspect of the invention, the above-mentioned object is achieved by means of shaped catalyst bodies which can be produced by the process according to the invention described above. This ensures that the catalyst moldings are improved in a simple but effective manner in their mechanical strength.

In particular, these shaped catalyst bodies are distinguished by the fact that they have a higher cutting hardness and / or lateral compressive strength compared to the ready-prepared catalyst moldings used by a factor of 1.4. Common measuring methods for this purpose are explained below in connection with the examples.

The cutting hardness and lateral compressive strength of shaped catalyst bodies are a measure of their mechanical strength. For industrial applications in known, for example zeolite catalyzed reactions, a cutting hardness of> 10 N, preferably> 20 N, or a lateral compressive strength of> 10 N, preferably> 20 N, are desirable. In this case, higher cutting hardnesses or lateral compressive strengths tend to be preferred, since under reaction conditions many originally mechanically sufficiently strong catalyst shaped bodies become soft.

Preferably, the catalyst is a boron-beta zeolite and the catalyst moldings have an average cutting hardness of at least 105 N. As a result, it is far superior to the conventional boron-beta zeolite in its mechanical strength. The novel shaped catalyst bodies can preferably be used for the preparation of amines or in fixed bed reactors or fluidized bed reactors.

A further aspect of the present invention relates to a chemical synthesis process in the presence of novel catalyst moldings. In particular, the synthesis involves the preparation of amines by reacting ammonia or primary or secondary amines with olefins at elevated temperatures and pressures. Alternatively, the synthesis is a reaction of unsaturated hydrocarbons, alcohols, carbonyl compounds, nitro compounds or nitriles with hydrogen and / or ammonia. The unsaturated hydrocarbons are in particular alkenes (olefins) and alkynes. Other features, advantages and applications will become apparent from the following description of the preferred, but not limiting embodiments of the invention. All the described features alone or in any combination form the subject matter of the invention, also independent of their summary in the claims or their relations.

The measurement of the cutting hardness was carried out with a device from Zwick-Roell type BZ 2.5 / TS1 S with fixed support plate and freely movable, vertical blade holder whose edge presses the molded body against the fixed plate (pre-load 0.5 N, Vorkraft-speed 10 mm / min, lowering speed 3 mm / min). The freely movable blade holder is connected to a pressure cell for receiving the force. The device is controlled by a computer which registers and evaluates the measured values. Strands of moldings with a predetermined diameter are loaded with a cutting edge (thickness 0.6 mm, plan) with increasing force until breakage of the strands occurs. The force at break is called cutting hardness. The given reading is the mean of a test of 30 moldings. This method is also described in DE 103 26 137 A1, EP 1 996 543 B1 and WO 201 1/048128 A2.

The lateral compressive strength was measured with a testing device from Zwick, Ulm, with a fixed turntable and a freely movable, vertical punch, which presses the shaped body (in the form of tablets, rings or balls) against the fixed turntable. As a result, the moldings are loaded between the two parallel plates on the shell side with increasing force until breakage occurs. The force registered at the break is the lateral compressive strength. The freely movable punch was connected to a pressure cell for receiving the force. The device was controlled by a computer which registered and evaluated the readings. From a number of samples, 25 flawless (i.e., crack-free and no-flaked edges) tablets were taken in tablet form, their lateral crushing strength was determined and then averaged. This method is also described in DE 199 42 300 A1 and EP 1 431 273 A1.

Example 1) Boron-beta-zeolite shaped body, hardening with aqueous ammonia solution

According to Example 1 of WO 2010/121974 A2, a boron-beta-zeolite shaped article which has been distilled with aluminum oxide is produced. The mean cutting hardness is 37 N and the shaped body has a pore volume of 0.42 ml / g (catalyst 1 a) determined by means of mercury porosimetry. This catalyst thus prepared is then in a Rotavapor (trade name of the company. Büchi) soaked with a 10% aqueous ammonia solution to the theoretical water absorption (maximum value) and allowed to stand for 2 h at room temperature. After that, under rotating and in the Vacuum the catalyst at 150 ° C dried. Subsequently, the thus dried catalyst is transferred to a rotary flask and calcined while rotating at 450 ° C for 2 h. The mean cutting hardness of the resulting catalyst (catalyst 1 b) is determined to 105 N, which corresponds to an increase by a factor of 2.83. The catalyst has a pore volume of 0.43 ml / g determined by mercury porosimetry.

Boron-beta-zeolite shaped bodies are particularly suitable for the synthesis of amines, in particular of t-butylamine (tBA).

Each 10 g of the catalysts 1 a and 1 b thus prepared are after crushing to catalyst split in a tubular reactor (6 mm I nnendurchmesser) installed and under isothermal conditions at 270 ° C and a pressure of 270 bar with 43 g / h of a mixture of isobutene and NH ₃ (1 mol: 1.5 mol) and the reaction followed by means of online gas chromatography. Both using catalyst 1 a as well as using catalyst 1 b, a yield of 13.8 - 14.3 g tBA / gfeed at a selectivity of min. 99% achieved. Comparative Example 1) Boron-beta zeolite shaped body, hardening with aqueous ammonia solution

In accordance with Example 1 of WO 2010/121974 A2, a B-beta zeolite shaped body which has been distilled with aluminum oxide is produced. The mean cutting hardness is 37 N (catalyst 1 a). This catalyst prepared in this way is then impregnated in a rotary evaporator with a 10% strength aqueous ammonia solution, which corresponds to twice the theoretical water absorption of the shaped bodies (twice the maximum value), and allowed to stand at room temperature for 2 h. Thereafter, the catalyst is dried at 150 ° C while rotating and under vacuum. Subsequently, the thus dried catalyst is transferred to a rotary flask and calcined while rotating at 450 ° C for 2 h. The mean cutting hardness of the resulting catalyst is determined to 47 N, which corresponds to an increase by a factor of 1.27. Example 2) NiO / CoO / CuO / ZrO ₂ -formkörper, hardening with aqueous ammonia solution

At a pH of 5.7 and a temperature of 70 ° C is a precipitation of a metal salt solution consisting of 29.4 kg nickel nitrate solution (17.4% NiO content), 8.8 kg copper nitrate solution (19.3% CuO content) and 16.3 kg zirconium acetate solution (1 8.7% Zr0 ₂ content) with a 20% sodium carbonate solution. After consumption of the metal salt solution, the pH is adjusted to 7.4 with a sodium carbonate solution. After stirring for 12 h and cooling to room temperature, the resulting Filtered suspension and the filter cake washed with distilled water until a sodium content in the filter cake (after heat treatment at 900 ° C) of <0, 1% is achieved. The washed filter cake is dried at 120 ° C for 12 h and then calcined at 480 ° C for 3 h. The powder thus obtained is mixed with 3% graphite and pressed on a tablet press to 6 x 3 mm tablets. The average lateral compressive strength of this catalyst 2a) is 105 N.

This catalyst thus prepared is then impregnated with a 1 0% aqueous ammonia solution to the theoretical water absorption and allowed to stand for 2 h at room temperature. Thereafter, the catalyst is dried at 150 ° C in a vacuum. Subsequently, the thus dried catalyst is calcined at 450 ° C for 2 h. The average lateral compressive strength of the resulting catalyst 2b) is determined to 260 N, which corresponds to an increase by a factor of 2.47. The catalyst has a pore volume of 0.19 ml / g determined by mercury porosimetry.

NiO / CoO / CuO / ZrO ₂ -formkörper can be used in particular in hydrogenation or amination reactions Comparative Example 2) NiO / CoO / CuO / Zr0 ₂ -formkörper, hardening with aqueous ammonia solution

At a pH of 5.7 and a temperature of 70 ° C is a precipitation of a metal salt solution consisting of 29.4 kg nickel nitrate solution (17.4% NiO content), 8.8 kg copper nitrate solution (19.3% CuO content) and 16.3 kg zirconium acetate solution (1 8.7% Zr0 ₂ content) with a 20% sodium carbonate solution. After consumption of the metal salt solution, the pH is adjusted to 7.4 with a sodium carbonate solution. After stirring for 12 h and cooling to room temperature, the resulting suspension is filtered and the filter cake washed with distilled water until a sodium content in the filter cake (after heat treatment at 900 ° C) of <0, 1% is reached. The washed filter cake is dried at 120 ° C for 12 h and then calcined at 480 ° C for 3 h. The powder thus obtained is mixed with 3% graphite and pressed on a tablet press to 6 x 3 mm tablets. The average lateral compressive strength of this catalyst 2a) is 105 N and the shaped body has a pore volume of 0.18 ml / g determined by mercury porosimetry.

This catalyst thus prepared is then impregnated with a 1 0% aqueous ammonia solution supernatant, which corresponds to twice the theoretical water absorption of the moldings, and allowed to stand for two hours at room temperature. Thereafter, the catalyst is dried at 150 ° C in a vacuum. Subsequently, the thus dried catalyst at 450 ° C. calcined for 2 h. The average lateral compressive strength of the resulting catalyst 2b) is determined to be 1 16 N, which corresponds to an increase by a factor of 1.10.

Example 3) NiO / CoO / CuO / ZrO ₂ shaped bodies, hardening with dilute nitric acid

Catalyst 2a) is soaked in with a 5% aqueous nitric acid solution to the theoretical water absorption and allowed to stand for 2 h at room temperature. Thereafter, the catalyst is dried at 150 ° C in a vacuum. Subsequently, the thus dried catalyst is calcined at 450 ° C for 2 h. The average lateral compressive strength of the resulting catalyst 3) is determined to be 300 N, which corresponds to an increase by a factor of 2.85. The catalyst has a pore volume of 0.21 ml / g determined by mercury porosimetry.

Example 4) Ti0 ₂ shaped body, hardening with dilute nitric acid

7.8kg Ti0 ₂ (S 150 from Finnti, 86%) are processed with 33 g Tylose (Clariant H4000 G4), 65 g stearic acid and 250 g of 3% nitric acid and 2.4 kg water in the Koller to an extrudable mass and formed in the extruder to 1, 5 mm strands. The strands obtained are dried at 120 ° C for 12 h and then calcined at 400 ° C. The mean cutting hardness of this catalyst is 1 1 N and the molding has a pore volume of 0.32 ml / g as determined by mercury porosimetry. This catalyst thus prepared is then impregnated with a 5% aqueous nitric acid solution to the theoretical water absorption and allowed to stand for 2 h at room temperature. Thereafter, the catalyst is dried at 150 ° C in a vacuum. Subsequently, the thus dried catalyst is calcined at 400 ° C for 2 h. The mean cutting hardness of the resulting catalyst 4) is determined to 20 N, which corresponds to an increase by a factor of 1.81. The catalyst has a pore volume of 0.35 ml / g determined by mercury porosimetry.

Ti0 ₂ shaped bodies can be used in particular in CN, CO, CC linking reactions.

Example 5) CuO / Al ₂ O ₃ -formkörper, hardening with dilute nitric acid At a pH of 5.8 and a temperature of 80 ° C, a precipitation of a metal salt solution consisting of 7.1 kg of copper nitrate solution (19.3% CuO content ) and 13.8 kg of aluminum nitrate solution (8, 1% AI ₂ Q ₃ content) with a 20% Sodium carbonate solution performed. After consumption of the metal salt solution, the pH is adjusted to 8.1 with a sodium carbonate solution. After stirring for 12 h and cooling to room temperature, the resulting suspension is filtered and the filter cake washed with distilled water until a sodium content in the filter cake (after 5 heat treatment at 900 ° C) of <1% is reached. The washed filter cake is dried at 120 ° C for 12 h and then calcined at 350 ° C for 3 h. The powder thus obtained is mixed with 3% graphite and pressed on a tablet press to 3 x 3 mm tablets. The average lateral compressive strength of this catalyst 2a) is 56 N and the molding has a pore volume of 0.41 ml / g as determined by mercury porosimetry.

This catalyst thus prepared is then soaked with a 5% aqueous nitric acid solution on the theoretical water absorption and allowed to stand for two hours at room temperature. Thereafter, the catalyst is dried at 15 150 ° C in a vacuum. Subsequently, the thus dried catalyst is transferred to a rotary flask and calcined at 450 ° C for 2 h. The average lateral compressive strength of the resulting catalyst 5) is determined to 81 N, which corresponds to an increase by a factor of 1.44. The catalyst has a pore volume of 0.46 ml / g as determined by mercury porosimetry.

20

Cu07Al ₂ 0 ₃ shaped bodies can be used in particular in hydrogenation reactions.

25 Example 6) Co ₃ 0 ₄ / SiO 2 molding, hardening with dilute nitric acid

At a pH of 7.0 and a temperature of 70 ° C, a precipitation of a metal salt solution consisting of 14.7 kg of cobalt nitrate solution (1 7, 1% Co ₃ 0 ₄ content) is carried out with a 20% sodium carbonate solution. After stirring for 12 h and

30 cooled to room temperature, the resulting suspension is filtered and the filter cake washed with distilled water until a sodium content in the filter cake (after heat treatment at 900 ° C) of <3% is reached. The washed filter cake is dried at 120 ° C for 12 h and then calcined at 500 ° C for 3 h. 2 kg of this powder thus obtained are mixed with 0.69 kg of Silres MSE 100,

35 26.9 g of walocel, 270 g of 56% nitric acid and 250 g of water in the kneader were made into an extrudable mass and molded into 4 mm extrudates using an extruder. The strands obtained are dried at 120 ° C for 12 h and then calcined at 570 ° C. The mean cutting hardness of this catalyst is 59 N.

40

This catalyst thus prepared is then soaked with a 5% aqueous nitric acid solution on the theoretical water absorption and at 2 h at Room temperature allowed to stand. Thereafter, the catalyst is dried at 150 ° C in a vacuum. Subsequently, the thus dried catalyst is calcined at 400 ° C for 2 h. The mean cutting hardness of the resulting catalyst 6) is determined to 90 N, which corresponds to an increase by a factor of 1.52.

Co ₃ 0 ₄ / Si0 ₂ -formkörper can be used in particular in hydrogenation reactions.

evaluation

Example 1) illustrates that the inventive method leads to a significantly increased mechanical strength of the shaped catalyst body. At the same time, the synthesis of t-butylamine in a comparative experiment demonstrates that the increase in mechanical strength can be made without compromising the chemical performance of the catalyst.

Comparative Example 1) shows that the impregnation with the Peptisierhilfsmittel can be advantageously carried out only up to the maximum value of the theoretical water absorption, since excess amounts of liquid lead only to a very low curing effect.

Examples 3) to 6) show that the process according to the invention can also be successfully applied to various other catalyst systems.

Claims

Patent claims

1. Process for the treatment of shaped catalyst bodies, comprising the process steps: a) providing ready-prepared shaped catalyst bodies, b) soaking the fully prepared shaped catalyst bodies with a peptization aid in an amount of liquid which does not exceed the theoretical water absorption of the shaped catalyst bodies , c) thermally treating the soaked shaped catalyst bodies at 50 ° C to 250 ° C and d) calcining the thermally treated shaped catalyst bodies at 250 ° C to 600 ° C.

2. The method according to claim 1, wherein an ammonia solution or a nitric acid solution, in particular an aqueous ammonia solution or an aqueous nitric acid solution, is used as the peptization aid.

3. The method according to claim 1 or 2, after method step b) further comprising method step bb) allowing the peptization aid to take effect for up to 10 hours.

Process according to one of claims 1 to 3, wherein the thermal treatment in process step c) is carried out under normal pressure or in a vacuum, preferably at 0.1 to 0.9 bar and/or in stationary or moving bed of the shaped catalyst bodies.

Process according to one of claims 1 to 4, wherein the calcination in process step d) is carried out in a stationary or moving bed of the shaped catalyst bodies.

Method according to one of claims 1 to 5, wherein extrudates and/or tablets and/or granules are used as shaped catalyst bodies.

7. The method according to any one of claims 1 to 6, wherein heterogeneous catalysts are used as the catalyst for the shaped catalyst bodies.

8. The method according to any one of claims 1 to 7, wherein the catalyst is selected from zeolite, in particular boron beta zeolite, NiO/CoO/CuO/ZrO ₂ , TiO ₂ , CuO/Al ₂ 0 ₃ or Co ₃ 0 ₄ /Si0 ₂ .

9. Catalyst shaped body, producible by the process according to one of claims 1 to 8.

10

10. Catalyst moldings according to claim 9, wherein the catalyst moldings have a cutting hardness and / or lateral pressure resistance that is 1.4 to 3.0 times higher than the fully prepared catalyst moldings used.

15

1 1 . Catalyst shaped bodies according to 9 or 10, wherein the catalyst is a boron-beta zeolite and the catalyst shaped bodies have an average cutting hardness of at least 105 N.

20 12. Use of the shaped catalyst body according to one of claims 9 to 1 1 for the production of amines.

13. Use of the shaped catalyst bodies according to one of claims 9 to 11 in fixed bed reactors or fluidized bed reactors.

25

14. Chemical synthesis process in the presence of shaped catalyst bodies according to one of claims 9 to 1 1.

15. Chemical synthesis process according to claim 14, wherein the synthesis is the production of amines by reacting ammonia or primary or secondary amines with olefins at elevated temperatures and pressures.

16. Chemical synthesis process according to claim 14, wherein the synthesis is a reaction of unsaturated hydrocarbons, alcohols,

Carbonyl compounds, nitro compounds or nitriles with hydrogen and/or ammonia.