MXPA06009530A - Supported catalyst with a defined pore distribution in the mesopore range - Google Patents

Abstract

The invention relates to a supported catalyst consisting of a support (T) comprising at least 75 wt.%Al2O3 and rhenium compounds as the active component (A). According to the invention, the maximum distribution function of the pore diameter lies in the mesopore range between 0.008 and 0.050µm.

Description

SUSTAINED CATALYST WITH A PORO DISTRIBUTION DEFINITION ON THE MESOPORO SCALE Description The present invention relates to a supported catalyst, processes for producing it, and processes for the metathesis of unsaturated hydrocarbon compounds using the supported catalyst. It is generally known that the pore structure of supported catalysts is of critical importance for its activity. This is particularly true of supported catalysts which are used for the metathesis of non-aromatic unsaturated hydrocarbon compounds. The metathesis of non-aromatic unsaturated hydrocarbon compounds is a long-established method of breaking and reforming CC bonds (eg, Mol.JC Chapter 4.12.2"Alkene Metathesis" in "Handbbok of Heterogeneous Catalysis", - Eds. Ertl. G, Knózinger, H., Weitkamp, J., VCH, Weinheim 1997, Weissermehl, K., Arpe, H.-J., Chapter 3.4"Olefin-Methathese" in "Industrielle Organische Chemie", 4th Edition, VCH Weinheim 1994). Various types of catalysts for a heterogeneously catalyzed metathesis have been described. For the temperature scale of up to about 120 ° C, the use of Re207 or Re (CO)? Or sustained catalysts is customary (Mol, JC, Chapter 4.12.2"Alkene Metathesis" in "Handbook of heterogeneous Catalysis" , Eds. Ertl, G. Kndzinger, H., Veitkamp, J., VCH, Weinheim 1997). DE-C-3823891 and EP-A-90994 describe the preparation of an aluminum oxide having a maximum of the distribution function of the pore diameters in the mesoporous scale to above 0.008 um. Apart from numerous other applications, general use as a support material for catalysts is mentioned. Catalysts containing Re in which no attention has been paid to the sludge structure are described, for example, in US 3641189 and 3642931. However, these catalysts are rapidly deactivated, which makes frequent regeneration necessary. A suspension of the deactivation makes the industrial implementation considerably easier. In addition, a high activity is desirable in order to use the noble metal used as effectively as possible. It was an object of the present invention to provide porous supported catalysts that have a specific pore structure and maintain high activity for a very long period of use. In particular, catalysts which are suitable for the preparation of unsaturated non-aromatic hydrocarbon compounds by metathesis are to be provided. Consequently we have found a supported catalyst comprising a support (S) in which A1203 is present in a proportion of at least 75% in that and a rhenium compound as active component (A), wherein the maximum of the distribution function of the pore diameters in the mesoporous scale is from 0.008 to 0.050 um. The support material (support S) for producing the supported catalysts comprises at least 75% by weight of gamma-Al203. Depending on the calcination temperature, amounts of other phases such as alpha-eta-, delta- or tetra-Al203 may also be present. The ratio of the various phases to each other is not critical, even though the proportion of alpha-A1203 is preferably maintained as low as possible (preferably less than 10%). For the purposes of the present invention, calcination is heating in an atmosphere of oxidizing gas, e.g., a gas atmosphere comprising more than 20 volume% oxygen and otherwise inert constituents. The preferred gas atmosphere is air. In a variant of the production process, the catalysts having the desired pore structure can be obtained by using supports (S) having a maximum of the distribution function of the pore diameters in the mesoporous scale from 0.008 to 0.050. in the production process and the catalyst is produced by customary methods of these supports (S) and an active component (A) using customary auxiliaries, if appropriate. To produce said supports (S) having a maximum of the distribution function of the pore diameters in the mesoporous scale from 0.008 to 0.050 um, a particularly useful process is one in which aluminum alkoxides occur as an intermediate. The synthetic aluminum oxide precursors produced by said route allow the mesoporous size to be adjusted to the specified scale. In accordance with DIN 66 134 of February 1998, published by the Deutsche Institut für Normung e.V., mesopores are pores that have sizes from 2 to 50. In this specific process, an aluminum alkoxide is aged at a water vapor pressure of 1 to 30 bar and a temperature of 100 to 235 ° C for 0.5 to 20 hours while stirring at a circumferential speed of 1.0 to 6.0. m / s to form synthetic aluminum hydroxide. This is then usually dried by a customary method. This process and additional details regarding it are known from DE-C-3823895. In many cases, the supports (S) may be in the form of bodies of spherical configuration. These can be obtained in a particularly advantageous manner by preparing an alumina sol of a synthetic aluminum hydroxide prepared as described above by suspending the synthetic aluminum hydroxide in dilute mineral acid having a concentration of 1 to 5% and subsequently adding 1 to 10% by weight, based on the total weight of the sun, of urea, - introducing the alumina sol by drops to a configuration column whose lower part is filled with aqueous ammonia solution, and drying the spherical particles formed in the column of configuration. The alumina hydrate used here is preferably obtained by hydrolysis of an aluminum alkoxide. The preparation process additional details regarding it are known from EP-A-90994. Apart from aluminum oxide, the support (S) can, if appropriate, also comprise additional customary support materials, preferably materials selected from the group consisting of SiO, aluminosilicates, Ti02, MgO, Ce02 and ZnO. To improve the physical properties of the catalyst, lubricants and additional additives in addition to the actual support material, it can also be mixed, eg, graphite, cement, gypsum or mica. Suitable supports (S) typically have a specific surface area of less than 280 m2 / g, preferably from 70 to 250 m2 / g, particularly preferably 100-200 m2 / g- The appropriate pore volumes (determined by means of mercury porosimetry) are usually in the range of 0.25 to 1.3 ml / g, preferably 0.35 to 1.0 ml / g. The preferred water absorption is 0.4 to 1.5 ml / g. The determination of the pore size and volume and its distribution is carried out in accordance with DIN 66134 of February 1998 and DIN 66133 of 1993, published by the Deutsche Institut für Normung e.V. If appropriate, the support may additionally have been treated with acids. The active component (A) applied to the support (S) comprises at least one rhenium compound. Suitable compounds include sulfides, oxides, nitrides, carbonyls, halides and acids. Particular preference is given to ammonium perrhenate or perrhenic acid and rhenium heptoxide. The rhenium component can be applied to the support material by all customary methods, preferably to the finished shaped support bodies. These include, for example, methods such as impregnation in an excess of "dry impregnation" solution (i.e., calculated in accordance with the particular water absorption), sublimation (especially for carbonyls). If necessary, the water is preferably used as a solvent for the rhenium component, but it is also possible to use organic solvents such as alcohols or dioxane. In addition to the rhenium component, the active component (A) may further comprise a promoter, ie, one or more additional compounds that optimize the activity or selectivity of the finished catalyst. These compounds are selected from the group consisting of phosphorous oxide, Fex03, tantalum oxide, Zr02, Si02, niobium oxide, molybdenum and tungsten compounds, oxides of the elements of the lanthanide series, vanadium oxide, alkali metal, alkaline earth metal, lead and tin compounds. These compounds can be applied before, after or simultaneously with the rhenium component. The proportion of active component (A) in the supported catalyst is usually from 0.1 to 30% by weight. As the active component, preference is given to rhenium oxide in an amount of 0.5 to 15% by weight. Rhenium oxide is particularly preferably present in crystallites less than 1 mm above the surface. This corresponds to rhenium surface areas (determined by N20 chimisorption) greater than 0.4 m2 / g, as described in DE 19,837,203 for coated catalysts. In the supported catalyst of the invention, the total pore volume measured by means of mercury porosimetry on the scale of 300 to 0.003 μm is generally greater than 0.2 ml / g, preferably 0.3 ml / g, particularly preferably 0.5 ml / g. g, and the sum of the surface areas of these pores is greater than 30 m2 / g, preferably greater than 130 m2 / g, but less than 250 m2 / g- The determination of the pore size and volume and its distribution takes carried out in accordance with DIN 66133 of June 1993 and DIN 66134 of February 1998, published by the Deutsche Institut für Normung eV The production of the catalyst of the invention can be carried out in three different ways. The first method is already mentioned above in the description of appropriate supports (S). Here, the supports (S) that have a maximum of the distribution function of the pore diameter in the mesoporous scale of 0.008 to 0.050 μm are used and the supporting catalysts are otherwise produced by customary methods. The second method comprises a) in step (a), producing a raw mixture (a) comprising a finely divided support (S) towards which a customary active component may have been applied if appropriate, a pore-forming material (P), customary auxiliaries and if appropriate an appropriate active component, b2) in step (bl), form shaped bodies as is customary for supported catalysts of the raw mixture (a) and, either simultaneously or in a separate process Subsequently, remove the material (P) of pore formation by heating, cl) in step (cl), if appropriate, apply an active component (A) to the configured bodies, with step (cl) being mandatory if the production of the raw mixture (a) in step (A1) has been carried out without using the active component (A) or a support (S) to which an active component (A) has already been applied and otherwise optional The above mentioned sequence of steps covers the embodiments: (i) the total amount of the active component (A) is used in the raw mixture (a) in step (a), either as a result of being added separately to the raw mixture (a) or as a result of the same having previously been applied to the customary support (S), (ii) only part of the total amount of the active component (A) is used in the raw mixture (a) in step (a), (iii) the active component (a) A is still not used in the raw mixture (a) in step (al). In the case of mode (i), step (cl) is not measured. In the case of mode (ii), it is necessary to add the missing part of the active component by means of step (cl). In the case of mode (iii), it is necessary to use the total amount of the active component (A) in step (cl). In the finely divided supports (S) used in this second method, the average particle size is generally 30 to 120 μm, preferably being given to 30% by weight of the particles having a particle size of more than 60 μm . The particle size is determined by conventional methods, e.g., sieve analysis. The preferred pore-forming materials (P) are inorganic or organic compounds that decompose at temperatures below 500 ° C, preferably below 450 ° C, and leave no residue in the catalyst. Suitable inorganic pore-forming materials are, for example, carbonates, hydrogencarbonates or oxalates, in particular as ammonium salts. Suitable organic pore formers are tartaric acid, oxalic acid / citric acid, ammonium nitrate, ammonium oxalate, guanidinium salts, urotropin, proteins such as gelatoin, hydrocarbons such as glucose, sucrose and soluble starch, polytetrahydrofuran, surfactants, sulphonic acids, polyvinyl alcohol, methylcellulose, polyalcohols, lactic acid, polyethylene oxides, polymethylene oxides, polypropylene oxides, polyolefins, nut shell powders, polyacrylates, carbonates, hydrogencarbonates, fats, waxes, fatty acids, alginates, fibers textiles, plant fibers and oxalates. The term polyalcohols encompasses sugars, starches, flour, celluloses and cellulose derivatives. The term plant fibers also encompasses paper pulp. The pore formers used usually have average particle sizes of more than 10 nm, preferably more than 100 nm, particularly preferably more than 1 μm. The particle size is determined by conventional methods, e.g., sieve analysis. The process for producing the catalysts of the invention may vary. In one embodiment, the raw mixture (a9) is prepared as a powder mixture by mechanical mixing of the starting materials and the shaped bodies are produced by pressing the powder mixture.Additional auxiliaries and additives serving to improve the processability are also possible. of the catalyst or having a favorable effect on the physical properties of the catalyst, eg, graphite, cement, copper powder. In a further embodiment, the crude mixture (a) is prepared as an extrudable suspension in which the support (S) and the pore former (P) form a discontinuous phase and a customary suspension medium forms the continuous phase and the active component (A), -if present, dissolved or suspended in the continuous phase. Suitable suspending media are mineral acids, water, or C2-C4 carboxylic acids, e.g., nitric acid, acetic acid or formic acid. The suspension is usually produced from the aforementioned starting materials by means of kneading or, preferably, by grinding processes. The extrudable suspension is usually converted to a moldable supported catalyst precursor by configuring the extrudable suspension to form shaped bodies as is customary for supported catalysts and subsequently to cure the shaped bodies by evaporating the suspension medium in a customary manner. This usually occurs at temperatures of 50 to 200 ° C. To remove the pore former (P), the shaped bodies are generally heated in an atmosphere containing oxygen at a temperature of 250 to 1100 ° C, preferably 300 to 850 ° C. If the removal of the pore former (P) is carried out at temperatures below 500 ° C, the shaped body obtained in this way is subsequently calcined at temperatures of 500 to 1100 ° C, preferably 500 to 850 ° C. For the purposes of the present invention, the calcination is heating in an atmosphere of oxidizing gas, e.g., a gas atmosphere comprising oxygen and otherwise inert constituents. The preferred gas atmosphere is air. The active component (A) is preferably applied to the bodies formed after the removal of the pore-forming material. This is achieved by customary methods, e.g., by spraying it (eg, perrhenic acid or ammonium perrhenate), if appropriate as a solution in a solvent, to the configured body, eg, in a Spraying drum, and first releasing the support which has previously been treated in this manner from the solvent at a temperature of 50 to 200 ° C and subsequently calcining it at a temperature of 500 to 1100 ° C, preferably from 500 to 850 ° C. The third method for producing the catalyst of the invention comprises a2) in step (a2), preparing a slurry that can be processed in a tray mill and in which a customary suspension medium forms the continuous phase and a support (S ) that has a maximum of the distribution function of the pore diameter in the mesoporous scale from 0.002 to 0.008 um is present in the discontinuous phase and, if appropriate, the active component (A) and customary auxiliaries dissolve or suspend in the continuous phase, b2) in step (b2), treat this suspension in a tray mill until the fine surface structure of the support (S) suspended therein has been altered to such an extent that the shaped bodies produced from the suspension have, after drying, a maximum of the distribution function of the pore diameters in the mesoporous scale from 0.008 to 0.050 um. The treatment time in step (b2) depends on a number of parameters, including the degree of filling of the tray mill and the treatment time. Basically, the incremental treatment time results in the maximum of the distribution function of the pore diameters in the mesoporous scale that moves to higher values. The appropriate treatment time, therefore, can be easily determined by means of a few rapid tests or by examining samples. After step (b2), the shaped bodies are produced from the suspension by means of customary methods, e.g., by extrusion, and the active component (A) is applied to these by one of the methods described above. The catalyst precursor obtained in this way is dried and then calcined.

The supported catalysts of the invention are particularly useful for preparing a compound having a non-aromatic CC double bond or CC tiple bond (compound A) of another compound or mixture of other compounds having a non-aromatic double bond of cC or linkage triple of CC (compound B), which comprises bringing the compound (B) into contact with a catalyst supported according to the invention at a temperature of 50 to 500 ° C. Such processes are generally known and described, for example, in "Industrielle Organische Chemie", Klau Weissermel, Han-Jürgen Erpel, 5th Edition, Verlag Wiley, VCH, 1998, Chapter 3.4, and "Handbook of Heterogeneous Catalysius", edited by G. Ertl, H. Knózinger and J. Weitkamp, Volume 5, VCH Verlagsgesellschaft mbH, Weinheim, Chapter 4.12.2, Alkene Metathesis, pages 2387 to 2399. However, they can also be used for the metathesis of unsaturated esters, nitriles, ketones, aldehydes, acids or ethers, as described, for example, in Xiaoding, X., Imhoff, P., von den Aard, CN, and Mol, J. C, J. Chem. Soc., Chem. Comm. . (985), p. 273. In the reaction of substituted olefins, a cocatalyst, for example a tin alkyl, lead alkyl or aluminum alkyl, is preferably used to achieve a further increase in activity.

Here, the supported catalysts of the invention can be used in the same way as known metathesis catalysts. The catalysts of the invention can be used particularly advantageously in metathesis processes to prepare propene by metathesis of a mixture comprising 2-butene and ethylene or 1-butene and 2-butenes, or to prepare 3-hexene and ethylene by metathesis of 1-butene. Appropriate processes are described in detail in DE-A-19813720, EP-A-1134271, WO 02/083609, DE-A-10143160. For the aforementioned starting compounds of C4, they are usually supplied in the form of a raffinate II. The term "refined II" refers to C4 fractions which generally have a butene content of 30 to 100% by weight, preferably 40 to 98% by weight. Apart from butenes, saturated C4 alkanes, in particular, may also be present. The manner in which these refinings II are obtained is generally known and described, for example, in EP-A-1134271. In particular, it is possible to use olefin mixtures comprising 1-butene or 1-butene which is obtained by distilling a 1-butene-rich fraction of the raffinate II. 1-Butene can also be obtained from the remaining 2-butene-rich fraction by subjecting the 2-butene-rich fraction to an isomerization reaction and subsequently fractionally distilling the product to provide a fraction rich in 1-butene and a rich fraction. in 2-butene. This process is described in DE-A-10311139. The rhenium-containing catalysts of the invention are particularly useful for reactions in the liquid phase at temperatures of 10 to 150 ° C and a pressure of 5 to 100 bar. Experimental part Example 1: Production of a catalyst according to the invention (A-84616). 1 kg of aluminum oxide powder (BASF DI0-10, 80.6% A1203) was mixed with 30 g of 85% strength formic acid and 712 g of water in a kneader. 15 minutes before the end of the kneading time (6 h), 50 g of Walocel (methylcellulose having an average molecular weight of 10,000 of Wolff Walsrode AG, D-29655 Walsrode) were added as pore-forming material. The mass was subsequently processed in an extruder to form 1.5 mm extrudates and dried at 120 ° C for 5 hours. The extrudates were then heated in air at 720 ° C for a period of 3 hours and at 750 ° C for an additional 15 minutes. This temperature was maintained for 3 hours. The intermediates produced in this way have a surface area of 172 m2 / g, a water absorption of 0.83 ml / g and a porosity (Hg porosimetry) of 0.76 ml / g- 730 g of the precursor were impregnated by spraying 107 g of perrhenic acid (70.4% of Re), made with water at 0.545 1, in an impregnation drum. After being allowed to stand for 5 hours, the catalyst was first dried at 120 ° C for 6 hours, subsequently heated at 520 ° C for a period of 2 hours and at 550 ° C for an additional 15 minutes and calcined in air at this temperature for 2 hours. The finished catalyst comprised 98% Re207 and had a water absorption of 0.76 ml / g. The cumulative total surface area of the pores determined by means of Hg porosimetry on the measurement scale of 300 to 0.003 um is 152 m2 / g. The volume of pro was 0.69 ml / g. The maximum in the pore distribution in the mesoporous scale was 9.6 nm. Example 2: Production of a comparative catalyst (B-84911). 5.1 kg of A1203 support extrusions of 1.5 mm, commercial (BASF D10-10 SI .5 BET 200 m2 / g, water absorption 0.77 ml / g, porosity (Hg porosimetry) 0.61 ml7g) whose raw material had been prepared by a conventional process by means of acid digestion of an aluminum hydroxide with subsequent aspersion calcination they were impregnated by spraying 781 g of perrhenic acid (70.4% of Re), made with water to 3473 1, in an impregnation drum. After being allowed to stand for 3 hours, the catalyst was first dried at 120 ° C for 6 hours, subsequently heated at 520 ° C for a period of 2 hours and at 550 ° C for an additional 15 minutes and calcined in air at this temperature for 2 hours. The finished catalyst comprised 9.8% Re207 and had a water absorption of 0.66 ml / g. The cumulative total surface area of the pores determined by means of Hg porosimetry in the measurement scale of 300 to 0.003 um was 173 m2 / g- The pore volume was 0.58 ml / g. The maximum in the pore distribution in the mesoporous scale is at 6.5 nm. Example 3: Production of a catalyst according to the invention (C-85277) 6.4 kg of an aluminum oxide powder (BASF D10-10) were mixed with 195.1 g of formic acid and 2.4 1 of water in a tray mill . After 50 minutes, 0.0332 1 of 25% strength ammonia and 300 ml of water were added. 15 minutes before the end of the kneading time, 320 g of Walocel (methylcellulose having an average molecular weight of 10,000 of Wolff Walsrode AG, D-29655 Walsrode) were added as pore-forming material. The total time of kneading was 2 hours. The mass was subsequently processed in an extruder to form 1.5 mm extrudates and dried in air at 120 ° C for 16 hours. The shaped bodies were then brought to 670 ° C for a period of 3 hours and at 700 ° C for an additional 15 minutes and calcined in air under these conditions for 2 hours. The intermediates produced in this way have a surface area of 185 m2 / g, a water absorption of 0.69 ml / g and a porosity (porosimetry of, Hg) of 0.57 ml / g. 318 g of the intermediate were impregnated with aqueous perrhenic acid by spraying. After being allowed to stand for 5 hours, the catalyst was first dried at 120 ° C for 6 hours, subsequently heated at 520 ° C for a period of 2 hours and at 550 ° C for an additional 15 minutes and calcined in air at this temperature for 2 hours. The finished catalyst comprised 9.9% Re207 and had a water absorption of 0.62 ml / g. The cumulative total surface area of the pores determined by means of Hg porosimetry on the measurement scale of 300 to 0.003 um was 155 m2 / g. The pore volume was 0.51 ml / g. The maximum of the pore distribution on the mesoporous scale was at 8.9 nm. Example 4: Production of a catalyst according to the invention (D-85403) 1.5 mm catalyst extrudates (BASF D10-10) were produced by the same conventional process described in Example 2. However, in the production of the dough for setting, the tray milling time was increased by 65% and the tray mill lots were made 6% smaller. Otherwise, the procedure was as in Example 2. The finished catalyst comprised 9.5% Re207 and had a water absorption of 0.61 ml / g. The cumulative total surface area of the pores determined by means of Hg porosimetry in the measurement scale of 300 to 0.003 um is 185 m2 / g. The pore volume was 0.51 ml / g. The maximum of the pore distribution in the mesoporous scale was 8.0 n. Example 5: Production of a catalyst according to the invention (E-85534) As supports, use was made of 220 g of 1 mm A1203 spheres (Alumina Spheres 1/160) from Sasol (Sasol Germany GmbH, Hamburg) which have been produced by a special process initiating aluminum alkoxides, which first make possible higher purities and secondly makes it possible to produce specific pore structures. The support was impregnated with perrhenic acid as in the previous examples, dried and calcined. The finished catalyst comprised 9.4% of Re207. The cumulative total surface area of the pores determined by means of Hg porosimetry in the measurement scale of 300 to 0.003 um was 166 m2 / g. The pore volume was 0.42 ml 7g. The maximum of the pore distribution in the mesoporous scale was 9.2 nm. Example 6: Production of a catalyst according to the invention (F-86850) As supports, use was made of 2.4 kg of product D10-21 of BASF in the form of extruded 1.5 mm. The starting material for the supports was, as in Example 5, prepared by a special process starting from aluminum alkoxides. The support was impregnated with perrhenic acid as in the previous examples, dried and calcined. The finished catalyst comprised 8.95 of Re207. The cumulative total surface area of the pores determined by means of Hg porosimetry in the measurement scale of 300 to 0.003 um is 158 m2 / g. The pore volume was 0.52 ml 7g. The maximum of the pore distribution in the mesoporous scale was at 9.9 nm. Example 7: Production of a comparative catalyst (G-85869) A catalyst was produced by an analogous method to Example 2. The catalyst comprised 9.1 wt% of Re207. The cumulative total surface area of the pores determined by means of Hg porosimetry on the measurement scale of 300 to 0.003 um was 167 m2 / g. The pore volume was 0.50 ml / g. The maximum of the pore distribution on the mesoporous scale was at 7.0 nm. Example 8: Production of a catalyst according to the invention (H-85893) A catalyst was produced by a method analogous to Example 5, but a Sasol material, "extruded from A120) 3, 1.5 / 150 Z600100", in the 1.5mm extruded form is used as a support. The catalyst comprised 9.5% by weight of Re207. The cumulative total surface area of the pores determined by means of Hg porosimetry in the measurement scale from 300 to 0.003 um was 136 m2 / g. The pore volume was 0.75 ml / g. The maximum of the pore distribution in the mesoporous scale was at 21.0 nm. Example A-H: Measurement of catalyst activity 10-15 g of catalyst were installed in each case in a tube reactor. The feed consisted of 150-200 g / h of a mixture of about 85-90% linear butenes, about 2.5% isobutene and butanes as equilibrium (refined II). Since the composition of the feed can fluctuate greatly, especially with respect to contamination with dienes that severely poison the catalyst and thus lead to rapid deactivation, only the measurements that were carried out using the same batch of raffinate II can be compare each other Which below (i), (ii) and (iii) in each case they relate to two different batches of raffinate II. The reaction conditions are 40 ° C and 35 bar in each case. The composition of the stream leaving the reactor was monitored by means of on-line GC. As representative of the numerous components, the quantities of the most important or major products, ie, propene, trans-2-pentene and trans-3-hexene at different times of measurement have been shown in the table below. All the products not shown, (ethylene, cis-2-pentene, cis-3-hexene, 2-methyl-2-butene and 2-methyl-2-pentene) in principle present similar changes over time and comparable differences in times of operating relatively low. A repetition measurement carried out in Example C shows that the differences measured between the catalysts according to the invention and the comparative examples are significantly greater than the measurement inaccuracies. i) 84616 (of con. with inv.) - Ex. A 84911 (comp) - Ex. Bl t Propene trans-2- trans-2- Propene trans-2- trans-3- [h] [% in Pentene Hexane [% in Pentene Hexene weight] [% in [% by weight [% in [% by weight] weight] weight] weight] 4 14.3 14.1 2.8 12.6 12.6 2.3 9 12.1 11.0 1.7 9.0 9.1 1.2 17 7.7 7.8 0.8 6.3 6.5 0.6 26 6.28 ("52%) 6.9 (-51%) 0.7 (-75%) ^ g (- 61%) 5 _, (-60%) Q ^ 4 (-83% =) ii) 85277 (from con with inv.) - Ej Cl Repeat of 85277 (according to inv) Ej C2 T Propeno trans- 2- trans-3- Propene trans-2- trans-3- [h] [% in Pentene Hexeno [% in Pentene Hexeno weight] [% in [% by weight] [% in [% in 4 17.4 16.5 4.8 17.6 16.9 5.1 9 16.6 15.5. 4.2 17.1 16.4 4.8 17 15.2 < ~ 13%) 14.3 (-135) 3.5-27%) 16.7 < ~ 5%) 15.7 (-7%) 4.3 ("16%) 85403 (from con with inv.) - Ex. D 84911 (comp.) - Ex. B2 t Propene trans-2- trans-3- Propene trans -2- trans-3- [h] [% in Pentene Hexene [% in Pentene Hexene weight] [% in [% by weight [% in [% by weight] weight] weight] weight] 3 17.3 16.4 4.8 17.0 16.5 4.9 9 16.1 15.1 3.9 14.8 14.1 3.4 17 13.1 (~ 23%) 12.7 (-23%) 2.7 ('4% 11.8 (-31%) 11.6 (-30%) 2.3Í53%) 85534 (of con. With inv.) -Ej E 85850 (of con. With inv) Ex. F t Propene trans-2- trans-3- Propene trans-2- trans-3- [h] [% in Pentene Hexeno [% in Pentene Hexeno weight] [% in [% by weight] [% in [% by weight] weight] weight] weight] 4 15.7 18.6 7.9 16.8 18.5 5.3 9 15.6 18.7 7.8 16.2 17.7 4.8 17 15.7 * '18.7 *' 7.8 * '15.6 ("-7%) 17.9 (-9%) 4-7 e-i 13%) *) No deactivation could be detected within the supervised period of time III) 85869 (com.) - Ex. G 85893 (from con. With inv.) Ex.H t Propene trans-2- trans-3- Propene trans-2- trans-3- [h] [% in Pentene Hexene [% in Pentene Hexene weight [% in [ % by weight] [% in [% by weight] weight] weight] weight] 4 16.1 16.3 4.4 16.8 18.1 4.9 9 13.4 13.2 4.1 15.8 16.7 3.9 17 10.4 (-35%) 10.9 ("-33%) 2.0 (-55%) 13.7 (-18%) 13.7 ° (24%) 2-4 ( -5i%) It can be seen that the catalysts of the invention show a slower overall deactivation rate and sometimes they also exhibit higher initial activities, so that more products are present in the output stream after a prolonged operating time, which significantly increases the performance of the box.

Claims (15)

1. CLAIMS. 1. - A supported catalyst comprising a support (S) in which A1203 is present in a proportion of at least 75% by weight of rhenium compounds as active component (A), wherein the maximum of the distribution function of The pore diameters in the mesoporous scale are from 0.008 to 0.050 um.
2. 2. The sustained catalyst according to claim 1, wherein the support (S) comprises A1203 together with compounds selected from the group consisting of Si02, aluminosilicates, Ti02, Zn02, MgO, Ce02 and ZnO.
3. 3. The sustained catalyst according to claim 1 or 2, wherein the active component (A) comprises rhenium oxide together with a promoter selected from the group consisting of phosphorous oxide, Fe203, tantalum oxide, Zr02, Si02, niobium oxide, oxides of the elements of the lanthanide series, vanadium oxide, molybdenum, tungsten, alkaline earth metal and tin compounds.
4. 4. The catalyst supported according to any of claims 2 to 3, wherein the amount of rhenium compound is selected such that the supported catalyst comprises 0.01 to 1 mmol of rhenium per gram of supported catalyst.
5. 5. A process for producing a sustained catalyst according to any of claims 1 to 4, comprising: al) in step (al), producing a crude mixture (a) comprising the support (S) to which the active component (A) may have been applied if appropriate, a pore-forming material (P), if appropriate customary auxiliaries and if appropriate an active component customary, - bl) in step (bl), form shaped bodies as are used for catalysts supported by a crude mixture (a) and, either simultaneously or in a subsequent separate process, remove the pore-forming material (P) by heating, cl) in step (cl), if it is appropriate to apply the active component (A) to the shaped bodies, with step (cl) being mandatory if the production of the raw mixture (a) in step (a) has been carried out without using the active component (A) ) or a support (S) to which an active component or (A) has already been applied and otherwise being optional.
6. 6. The process according to claim 5, wherein the pore-forming material (P) is selected from the group consisting of tartaric acid, oxalic acid, citric acid, ammonium nitrate, ammonium oxalate, guanidinium salts , urotropin, proteins such as gelatin, carbohydrates such as glucose, sucrose and soluble starch, polytetrahydrofuran, surfactants, sulfonic acids, polyvinyl alcohol, methylcellulose, polyalcohols, lactic acid, polyethylene oxides, polymethylene oxides, polypropylene oxides, polyolefins , nut shell powders, polyacrylates, carbonates, hydrogen carbonates, fats, waxes, fatty acids, alginates, textile fibers, plant pomace and oxalates.
7. 7. - The process according to claim 5 or 6, wherein the raw mixture (a) is prepared as a pulverized mixture and the bodies configured and produced by pressing the powder mixture.
8. 8. - The process according to any of claims 5 to 7, wherein the raw mixture (a) is prepared as an extrudable suspension in which the support (S) and the pore former (P) form a discontinuous phase and a customary suspension medium forms the continuous phase and the active component (A), if present, is dissolved or suspended in the continuous phase.
9. 9. The process according to any of claims 5 to 8, wherein the raw mixture (a) prepared as an extrudable suspension in step (a) is converted in step (b) to a prefabricated moldable supported catalyst by forming the extrudable suspension to form shaped bodies as is customary for supported catalysts and subsequently to cure the shaped bodies by evaporating the suspension medium.
10. 10. A process for producing the sustained catalyst according to any of claims 1 to 4, which comprises producing the supported catalyst by customary methods of a support (S) having a maximum of the distribution function of the pore diameters in the mesoporous scale from 0.008 to 0.050 um and an active component (A) using auxiliaries accustomed if appropriate.
11. 11. The process according to claim 10, wherein the support (S) that has a maximum of the distribution function of the pore diameters in the mesoporous scale from 0.008 to 0.050 μm is produced by aging an alkoxide of aluminum at a water vapor pressure of 1 to 30 bar and a temperature of 100 to 235 ° C for 0.5 to 20 hours while stirring at a circumferential speed of 1.0 to 6.0 m / s and drying and if appropriate setting the resulting synthetic aluminum hydroxide by a customary method.
12. 12. The process according to claim 11, wherein the supports (S) that have a maximum of the distribution function of the pore diameters in the mesoporous scale of 0.008 to 0.050 um are produced: - preparing a alumina sol of a synthetic aluminum hydroxide prepared according to claim 11 by suspending the alumina hydrate in dilute mineral acid having a concentration of 1 to 5% and subsequently * adding from 1 to 10% by weight, based on the weight total of the urea sol, introducing the alumina sol drops to a configuration column whose lower part is filled with aqueous ammonia solution, and - drying the spherical particles formed in the configuration column.
13. 13. A process for producing the supported catalyst according to any of claims 1 to 4, comprising A2) in step (a2), preparing a suspension that can be processed in a tray mill and in which a medium of suspension customary forms the continuous phase and a support (S) that has a maximum of the distribution function of the pore diameters in the mesoporous scale of

    0. 002 to 0.008 um is present in the discontinuous phase and, if appropriate, the active component (A) and customary auxiliaries are dissolved or suspended in the continuous phase, B2) in step (b2), treating this suspension in a mill of trays until the fine surface structure of the support (S) suspended therein has been altered to a degree that the shaped bodies produced from the suspension have, after drying, a maximum of the distribution function of the pore diameters in the mesoporous scale from 0.008 to 0.050 um.
14. 14. A process for preparing a compound having a non-aromatic dc double bond or CC triple bond (compound A) of another compound or mixture of other compounds having a non-aromatic dc double bond or dc triple bond (compound B), which comprises bringing the compound (B) into contact with a supported catalyst according to any of claims 1 to 4 at a temperature of 50 to 500 ° C.
15. 15. The process according to claim 14, wherein the compound (B) is 1-butene or a mixture of butenes comprising 1-butene.