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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/7007—Zeolite Beta
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  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
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  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
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  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
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  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0063—Granulating
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  • B01J37/06—Washing
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  • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes

Definitions

• 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 Peptisierysffenn 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.
• 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.
• zeolites in particular boron-beta zeolites
• these modifications being carried out before the finished preparation the corresponding shaped catalyst body, ie before the final calcination.
• 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 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.
• 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.
• 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 Peptisierysstoff, wherein it is important to carry out the impregnation only with a liquid amount of Peptisierysstoff that does not exceed the theoretical water absorption of the catalyst molding.
• 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.
• 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 method according to the invention does not adversely affect the chemical performance of the shaped catalyst bodies in any way.
• the inventive method is applicable to a variety of different catalyst materials, as the following examples also show.
• 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.
• 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 Peptisierysstoff be dissolved in a suitable solvent and then used to impregnate the moldings, liquid Peptisierysstoff 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.
• an ammonia solution or a nitric acid solution in particular an aqueous ammonia solution or an aqueous nitric acid solution.
• an aqueous ammonia solution is used.
• an aqueous ammonia solution shows the best effects.
• 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 Peptisierysffens 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.
• the amount of liquid of Peptisierysstoff used should correspond to at least 50% (minimum amount of Peptisierystoff) 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.
• the Process step bb) Applying the Peptisierysstoffs be carried out for up to 10 hours.
• 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.
• 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 Peptisierysstoff after soaking again from the catalyst moldings.
• calcining in process step d) preferably takes place at 250 ° C. to 600 ° C., in particular at 300 ° C. to 500 ° C.
• the network of the catalyst-shaped body is further built and thus increases the mechanical strength.
• the thermal stability of the catalyst materials used, both carrier and active component 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.
• the catalyst shaped body also comprises a carrier material
• a carrier material in principle all carrier materials known to the person skilled in the art can be used.
• the carrier material is selected from Si0 2 , Ti0 2 , Al 2 0 3 and Zr0 2 .
• 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.
• extrudates and / or tablets and / or granules are used as the shaped catalyst body.
• heterogeneous catalysts as catalyst for the shaped catalyst bodies.
• 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.
• 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.
• 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.
• a cutting hardness of> 10 N, preferably> 20 N, or a lateral compressive strength of> 10 N, preferably> 20 N are desirable.
• 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.
• the catalyst is a boron-beta zeolite and the catalyst moldings have an average cutting hardness of at least 105 N.
• 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.
• the synthesis involves the preparation of amines by reacting ammonia or primary or secondary amines with olefins at elevated temperatures and pressures.
• 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.
• 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.
• 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 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.
• 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).
• 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 -form redesign, hardening with aqueous ammonia solution
• 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 -form analyses can be used in particular in hydrogenation or amination reactions Comparative Example 2) NiO / CoO / CuO / Zr0 2 -form analyses, hardening with aqueous ammonia solution
• 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.
• the pH is adjusted to 7.4 with a sodium carbonate solution.
• 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.
• 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.
• 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 -form Equity, 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.
• Cu07Al 2 0 3 shaped bodies can be used in particular in hydrogenation reactions.
• 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 -form redesign can be used in particular in hydrogenation reactions.
• Example 1 illustrates that the inventive method leads to a significantly increased mechanical strength of the shaped catalyst body.
• 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 Peptisierysstoff 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.

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• 2013
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