EP1722892A1 - Catalyseur supporte dont les pores sont repartis de maniere definie dans la gamme des mesopores - Google Patents

Catalyseur supporte dont les pores sont repartis de maniere definie dans la gamme des mesopores

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Publication number
EP1722892A1
EP1722892A1 EP05715490A EP05715490A EP1722892A1 EP 1722892 A1 EP1722892 A1 EP 1722892A1 EP 05715490 A EP05715490 A EP 05715490A EP 05715490 A EP05715490 A EP 05715490A EP 1722892 A1 EP1722892 A1 EP 1722892A1
Authority
EP
European Patent Office
Prior art keywords
active component
supported catalyst
pore
customary
maximum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05715490A
Other languages
German (de)
English (en)
Inventor
Markus Schubert
Jürgen STEPHAN
Volker BÖHM
Andreas Brodhagen
Frank Poplow
Christian Weichert
Holger Borchert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1722892A1 publication Critical patent/EP1722892A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/36—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution

Definitions

  • the present invention relates to a supported catalyst, processes for its preparation and processes for the metathesis of non-aromatic unsaturated hydrocarbon compounds using the supported catalyst.
  • Re-containing catalysts for which no attention has been paid to the pore structure, are e.g. in US 3641189 and 3642931. However, these catalysts quickly deactivate, which necessitates frequent regeneration. Slowing down the deactivation considerably simplifies the technical implementation. In addition, a high level of activity is desirable in order to use the precious metal used as effectively as possible.
  • ren are provided which are suitable for the production of non-aromatic unsaturated hydrocarbon compounds by metathesis.
  • a supported catalyst was composed of a support (T) which consists of at least 75% by weight of Al 2 O 3 and contains a rhenium compound as active component (A), the maximum of the distribution function of the pore diameter in the mesopore range being from 0.008 to 0.050 ⁇ m is found.
  • At least 75% by weight of gamma-Al 2 O 3 is used as the support material (support T) for the preparation of the supported catalysts.
  • portions of other phases such as. B. alpha-, eta-, delta- or theta-AI 2 O 3 may be included.
  • the ratio of the different phases to one another is not critical, only the alpha-Al 2 O 3 content will preferably be kept as low as possible (preferably less than 10%).
  • Calcining is understood to mean heating in an oxidative gas atmosphere, for example a gas atmosphere which contains more than 20 vol.% Oxygen and otherwise inert constituents.
  • the preferred gas atmosphere is air.
  • the catalysts with the desired pore structure can be obtained according to a production variant by using supports (T) with a maximum of the distribution function of the pore diameters in the mesopore range from 0.008 to 0.050 ⁇ m during manufacture and consisting of these supports (T) and an active component (A ) if necessary using customary auxiliaries, the catalyst is produced by customary processes.
  • an aluminum alcoholate at a water vapor pressure of 1 to 30 bar and a temperature of 100 to 235 ° C in a period of 0.5 to 20 hours with stirring at a peripheral speed of 1.0 to 6.0 m / s aged, producing a synthetic aluminum hydroxide.
  • This is then usually dried using a customary method. This method and further details on this are known from DE-C-3823895.
  • the carriers (T) should be in the form of spherical shaped bodies. These can be obtained particularly cheaply by produces an alumina sol from the synthetic aluminum hydroxide prepared as described above by suspending the synthetic aluminum hydroxide in dilute mineral acid at a concentration of 1 to 5% and then adding 1 to 10% by weight, based on the total sol weight, of urea to the alumina sol a shaped column, which is filled in the lower part with aqueous ammonia solution, drips in
  • the alumina hydrate used is preferably obtained by hydrolysis of an aluminum alcoholate. This manufacturing process and further details are known from EP-A-90994.
  • the support (T) is optionally given other customary support materials, preferably those from the group of SiO 2 , aluminosilicates, TiO 2 , ZrO 2 , MgO, CeO 2 , or ZnO.
  • lubricants and additives can also be added in addition to the actual support material, such as. B. graphite, cement, plaster or muscovite.
  • Suitable carriers typically have a specific surface area of less than 280 m 2 / g, preferably 70 to 250 m 2 / g, particularly preferably 100-200 m 2 / g.
  • Suitable pore volumes are usually between 0.25 and 1.3 ml / g, preferably between 0.35 and 1.0 ml / g.
  • the preferred water absorption is 0.4 to 1.5 ml / g.
  • the pore size and volume and their distribution are determined in accordance with DIN 66134 from February 1998 and DIN 66133 from 1993, published by the German Institute for Standardization
  • the carrier may optionally have been additionally treated with acids.
  • the active component (A) applied to the support (T) contains at least one compound of rhenium, the sulfides, oxides, nitrides, carbonyls, halides or acids being suitable. Ammonium perrhenate or, perrhenic acid and rhenium heptoxide are particularly preferred.
  • the rhenium component can be applied to the carrier material in all customary processes, preferably to the finished carrier moldings. These include, for example, methods such as impregnation in the supernatant solution, so-called dry soaks (ie calculated on the respective water absorption), sublimation (especially for carbonyls). If necessary, water is preferably used as the solvent for the rhenium component, but organic solvents such as, for. B.
  • the active component (A) can also comprise a promoter, ie one or more further compounds which optimize the activity or selectivity of the finished catalyst. These compounds are selected from the group consisting of phosphorus oxide, Fe 2 O 3 , tantalum oxide, ZrO 2 , SiO 2 , niobium oxide, molybdenum and tungsten compounds, oxides of the elements from the lanthanide series, vanadium oxide, alkali metal, alkaline earth metal, lead or tin compounds. These compounds can be applied before, after or simultaneously with the rhenium component.
  • a promoter ie one or more further compounds which optimize the activity or selectivity of the finished catalyst. These compounds are selected from the group consisting of phosphorus oxide, Fe 2 O 3 , tantalum oxide, ZrO 2 , SiO 2 , niobium oxide, molybdenum and tungsten compounds, oxides of the elements from the lanthanide series, vanadium oxide, alkali metal, alkaline earth metal, lead
  • the proportion of active components (A) in the supported catalyst is usually 0.1 to 30% by weight.
  • Rhenium oxide is preferred as the active component in an amount of 0.5 to 15% by weight.
  • the rhenium oxide is particularly preferably present in crystallites which are smaller than 1 nm on the surface. This goes hand in hand with rhenium surfaces (determined by means of N 2 O chemisorption) which are greater than 0.4 m 2 / g, as stated in DE 19,837,203 for coated catalysts.
  • the total pore volume of 300 to 0.003 ⁇ m measured by means of mercury porosimetry is generally greater than 0.2, preferably 0.3, particularly preferably 0.5 ml / g and the sum of the surfaces of these pores is greater than 30, preferably greater than 130 m 2 / g, but less than 250 m 2 / g.
  • the pore size and volume and their distribution are determined in accordance with DIN 66133 from June 1993 and DIN 66134 from February 1998, published by the German Institute for Standardization
  • the catalyst according to the invention can be produced in three different ways.
  • the supports (T) are used with a maximum of the distribution function of the pore diameters in the area of the mesopores at 0.008 to 0.050 ⁇ m, and the supported catalyst is otherwise produced by customary methods.
  • T finely divided carrier
  • P pore-forming material
  • step (b1) in step (b1) forms shaped bodies from the raw mixture (a), as are customary for supported catalysts, and the pore-forming material (P) is removed either by annealing or in a subsequent separate working process, d) in step d) if appropriate, an active component (A) is applied to the moldings, this step (d) being mandatory, provided in step (a1) the preparation of the raw mixture (a) without the active component (A) or a carrier being used (T), to which an active component (A) has already been applied, and is otherwise optional.
  • step (a1) the total amount of active component (A) is already used in the raw mixture (a), be it that it is added to the raw mixture (a) separately or be it that it is already applied to the customary carrier (T), (ii) in step (a1) only part of the total amount of active component (A) is used in the raw mixture (a), (iii) in step (a1) the active component (A) has not yet been used in the raw mixture (a).
  • step (d) is omitted.
  • step (ii) it is necessary to add the missing part of the active component through step (d).
  • step (iii) it is necessary to use the total amount of active component (A) in step (d).
  • the average grain size is generally 30 to 120 / m, preferably 30% by weight having a grain size of more than 60 ⁇ m.
  • the grain size is determined using conventional methods, e.g. Sieve analysis determined.
  • Suitable pore-forming materials are preferably inorganic or organic compounds which decompose at temperatures below 500 ° C., preferably below 450 ° C., and which leave no residues in the catalyst.
  • Suitable pore-forming inorganic materials are, for example, carbonates, hydrogen carbonates 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 gelatin, carbohydrates such as glucose, sucrose and soluble starch, polytetrahydrofuran, surfactants, sulfonic acids, polyvinyl alcohol, methyl cellulose, polyalcohols, polyalcohols, polyalcohols, polyalcohols, polyalcohols - methylene oxides, polypropylene oxides, polyolefins, nutshell powder, polyacrylates, carbonates, hydrogen carbonates, fats, waxes, fatty acids, alginates, textile fibers, vegetable fibers, and oxalates.
  • polyalcohols includes sugars, starches, flour, celluloses and derivatized celluloses.
  • plant fibers also includes paper pulp, the so-called 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 ⁇ m. The particle size is determined using conventional methods, e.g. Sieve analysis determined.
  • the process for the preparation of the catalysts according to the invention can vary: In one embodiment, the procedure is such that the raw mixture (a) is made available as a powder mixture by mechanical mixing of the starting materials, and the molded articles are produced by pressing the powder mixture. It is also possible to add further auxiliaries and additives which serve to improve the processability of the catalyst or which have a favorable effect on the physical properties of the catalyst, for example graphite, cement, copper powder
  • the raw mixture (a) is provided as an extrudable suspension in which the carrier (T) and the pore former (P) form a discontinuous phase and a customary suspending agent forms the continuous phase and the active component (A), if present, is dissolved or suspended in the continuous phase.
  • Suitable suspending agents are mineral acids, water or d- to C 4 -carboxylic acids, for example nitric acid, acetic acid or formic acid.
  • the suspension is usually produced from the aforementioned starting materials by means of kneading or, preferably, Koller processes.
  • a deformable supported catalyst precursor is usually produced from the extrudable suspension by forming the extrudable suspension into shaped bodies, as are customary for supported catalysts, and then curing the shaped bodies by usually evaporating the suspending agent. Generally this happens at temperatures from 50 to 200 ° C.
  • the shaped bodies are generally tempered in an oxygen-containing atmosphere at a temperature of 250 to 1100, preferably 300 to 850 ° C.
  • the shaped body thus obtained is still calcined at temperatures from 500 to 1100 ° C., preferably from 500 to 850 ° C.
  • Calcination is understood to mean heating in an oxidative gas atmosphere, e.g. a gas atmosphere containing oxygen and otherwise inert components.
  • oxidative gas atmosphere e.g. a gas atmosphere containing oxygen and otherwise inert components.
  • the preferred gas atmosphere is air.
  • the active component (A) is preferably applied to the moldings after the pore-forming material has been removed. This is done according to customary methods, for example by spraying (for example perrhenic acid or ammonium perrhenate), optionally dissolved in a solvent, onto the shaped body, for example in a spray drum, and first removing the pretreated carrier at a temperature of 50 to 200 ° C. from the solution. freed solvent and then calcined at a temperature of 500 to 1100 ° C, preferably from 500 to 850 ° C.
  • the procedure is as follows:
  • step (a2) in step (a2) produces a suspension which can be processed in a pan, in which a conventional suspension medium forms the continuous phase and a carrier (T) with a maximum of the distribution function of the pore diameters in the region of the mesopores at 0.002 to 0.008 ⁇ m in the discontinuous phase is contained and optionally the active component (A), and conventional auxiliaries are dissolved or suspended in the continuous phase
  • this suspension is treated in a pan until the surface fine structure of the carrier (T) suspended therein has changed to such an extent that moldings produced from the suspension have a maximum of the distribution function of the pore diameter in the region of the mesopores after drying have at 0.008 to 0.050 ⁇ m.
  • the duration of treatment in step (b2) depends on several parameters, including the degree of filling of the pan and the duration of treatment. Basically, as the duration of treatment increases, the maximum of the distribution function of the pore diameters in the area of the mesopores shifts to higher values. The appropriate treatment duration can therefore be easily determined by a few puncture tests or by examining samples.
  • step (b2) the suspension is removed using customary methods, e.g. produced by extrusion, moldings to which the active component (A) is applied by one of the methods described above.
  • the catalyst precursor thus obtained is calcined after drying.
  • the supported catalysts according to the invention are particularly suitable for the production of a compound with a non-aromatic C-C double bond or C-C-
  • esters 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 Aardweg, CN, and Mol, J. C, J Chem. Soc, Chem. Comm. (1985), p. 273 is described.
  • a so-called cocatalyst for example tin, lead or aluminum alkyls, is frequently used in the reaction of substituted olefins in order to additionally increase the activity.
  • the supported catalysts according to the invention can be used in the same way as the known metathesis catalysts.
  • the catalysts of the invention can be used particularly advantageously in metathesis processes for the production of propene by metathesis of a mixture which contains 2-butene and ethylene or 1-butene and 2-butenes, and of 3-hexene and ethylene by metathesis of 1-butene.
  • Corresponding methods are described in detail in DE-A-19813720, EP-A-1134271, WO 02/083609, DE-A-10143160.
  • the aforementioned C 4 starting compounds are usually provided in the form of a so-called raffinate II.
  • the Raffinate II is
  • C 4 cuts which generally have a butene content of 30 to 100, preferably 40 to 98,% by weight.
  • saturated C 4 alkanes can also be present.
  • the extraction of such raffinates II is generally known and is described, for example, in EP-A-1134271.
  • 1-butene-containing olefin mixtures or 1-butene can be used, which is obtained by distilling off a 1-butene-rich fraction from raffinate II.
  • 1-Butene can also be obtained from the remaining fraction rich in 2-butenes by subjecting the 2-butene-rich fraction to an isomerization reaction and then separating by distillation into a 1-butene and a 2-butene-rich fraction. This process is described in DE-A-10311139.
  • the rhenium-containing catalysts according to the invention are particularly suitable for reactions in the liquid phase, at temperatures from 10 to 150 ° C. and a pressure from 5 to 100 bar.
  • Example 1 Preparation of a catalyst according to the invention (A-84616)
  • the intermediate produced in this way had a surface area of 172 m 2 / g, a water absorption of 0.83 ml / g and a porosity (Hg porosimetry) of 0.76 ml / g.
  • the pore volume was 0.69 ml / g.
  • Example 2 Preparation of a comparative catalyst (B-84911)
  • the pore volume was 0.58 ml / g.
  • the maximum in the pore distribution in the area of the mesopores is 6.5 nm.
  • Example 3 Preparation of a catalyst according to the invention (C-85277)
  • the so Intermediate produced had a surface area of 185 m 2 / g, a water absorption of 0.69 ml / g and a porosity (Hg porosimetry) of 0.57 ml / g. 318 g of the intermediate were spray-impregnated with aqueous perrhenic acid. After a rest period of 5 hours, the catalyst is first dried at 120 ° C. for 6 hours, then heated to 520 ° C. for 2 hours and to 550 ° C. in a further 15 minutes, and calcined in air at this temperature for 2 hours. The finished catalyst contained 9.9% Re 2 O 7 and had a water absorption of 0.62 ml / g.
  • the pore volume was 0.51 ml / g.
  • the maximum pore distribution in the mesopore range was 8.9 nm.
  • 1.5 mm catalyst strands (BASF D10-10) were produced by the same conventional method described in Example 2. However, during the production of the dough for the deformation, the koller time was extended by 65% and the koller approaches reduced by 6%. Otherwise the procedure was as in Example 2.
  • the finished catalyst contained 9.5% Re 2 O 7 and had a water absorption of 0.61 ml / g.
  • the pore volume was 0.51 ml / g.
  • the maximum pore distribution in the mesopore range was 8.0 nm.
  • the pore volume was 0.42 ml / g.
  • Measuring range between 300 and 0.003 ⁇ m is 158 m 2 / g.
  • the pore volume was
  • Example 7 Preparation of a comparative catalyst (G - 85869)
  • a catalyst was produced as in Example 2.
  • the catalyst contained 9.1% by weight of Re 2 O 7 .
  • the total cumulative surface area of the pores determined by means of mercury porosimetry in the measuring range between 300 and 0.003 ⁇ m was 167 m 2 / g.
  • the pore volume was 0.50 ml / g.
  • the maximum in the pore distribution in the area of the mesopores was 7.0 nm.
  • Example 8 Preparation of a catalyst according to the invention (H-85893)
  • a catalyst was used analogously to Example 5, but a material from Sasol, “Al 2 O 3 extrudates, 1.5 / 150 Z600100”, was used as the support in the form of 1.5 mm strands.
  • the catalyst contained 9.5 wt% Re 2 O 7.
  • the pore volume was 0.75 ml / g.
  • the maximum in the pore distribution in the area of the mesopores was included 21.0 nm.
  • the catalysts of the invention are generally more slowly deactivated and z. Some also show higher initial activities, so that after a longer period of time there are still more products in the outlet stream, which significantly increases the overall yield.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un catalyseur supporté constitué d'un support (T) qui comprend au moins 75 % en poids d'Al2O3 ainsi que des composés rhénium en tant que composants actifs (A). Selon l'invention, le maximum de la fonction de répartition des diamètres des pores se situe dans la gamme des mésopores qui est comprise entre 0,008 et 0,050 νm.
EP05715490A 2004-02-28 2005-02-24 Catalyseur supporte dont les pores sont repartis de maniere definie dans la gamme des mesopores Withdrawn EP1722892A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004009805A DE102004009805A1 (de) 2004-02-28 2004-02-28 Trägerkatalysator definierter Porenverteilung im Bereich der Mesoporen
PCT/EP2005/001912 WO2005082532A1 (fr) 2004-02-28 2005-02-24 Catalyseur supporte dont les pores sont repartis de maniere definie dans la gamme des mesopores

Publications (1)

Publication Number Publication Date
EP1722892A1 true EP1722892A1 (fr) 2006-11-22

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EP05715490A Withdrawn EP1722892A1 (fr) 2004-02-28 2005-02-24 Catalyseur supporte dont les pores sont repartis de maniere definie dans la gamme des mesopores

Country Status (7)

Country Link
US (1) US20070191212A1 (fr)
EP (1) EP1722892A1 (fr)
KR (1) KR20060126573A (fr)
CN (1) CN1925914A (fr)
CA (1) CA2557273A1 (fr)
DE (1) DE102004009805A1 (fr)
WO (1) WO2005082532A1 (fr)

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WO2010101637A2 (fr) * 2009-03-02 2010-09-10 Sud-Chemie Inc. Conversion de sucre, de polysaccharide, ou de glycérol en produits chimiques utiles au moyen d'un catalyseur supporté d'oxyde de zirconium activé
US8324440B2 (en) * 2010-02-05 2012-12-04 Uop Llc Support properties of silica supported catalysts and their use in olefin metathesis
US8895795B2 (en) * 2010-02-05 2014-11-25 Uop Llc Acid washed silica supported catalysts and their use in olefin metathesis
US8935891B2 (en) 2011-06-09 2015-01-20 Uop Llc Olefin metathesis catalyst containing tungsten fluorine bonds
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DE102004009805A1 (de) 2005-09-15
WO2005082532A1 (fr) 2005-09-09
US20070191212A1 (en) 2007-08-16
CA2557273A1 (fr) 2005-09-09
KR20060126573A (ko) 2006-12-07

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