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WO2006018133A1 - Catalyseur contenant un(des) oxyde(s) de fer, un(des) compose(s) de metal alcalin et un(des) oxyde(s) de cerium - Google Patents

Catalyseur contenant un(des) oxyde(s) de fer, un(des) compose(s) de metal alcalin et un(des) oxyde(s) de cerium Download PDF

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Publication number
WO2006018133A1
WO2006018133A1 PCT/EP2005/008406 EP2005008406W WO2006018133A1 WO 2006018133 A1 WO2006018133 A1 WO 2006018133A1 EP 2005008406 W EP2005008406 W EP 2005008406W WO 2006018133 A1 WO2006018133 A1 WO 2006018133A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
cerium
oxide
dehydrogenation
hydrate
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Ceased
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PCT/EP2005/008406
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German (de)
English (en)
Inventor
Christian Walsdorff
Otto Hofstadt
Gerald Vorberg
Reinhard KÖRNER
Harald Freiberger
Christophe Houssin
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BASF SE
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BASF SE
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Filing date
Publication date
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Publication of WO2006018133A1 publication Critical patent/WO2006018133A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J23/83—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 rare earths or actinides
    • 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
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • 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)
    • 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
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36

Definitions

  • the invention relates to a catalyst containing iron oxide (s), alkali metal compound (s) and cerium oxide (s), wherein in the preparation of the catalyst as Cer component (s) Cercarbonat hydrate (s) having a BET surface area of less than 0.30 m 2 / g are used.
  • the invention further relates to a catalyst bed which consists of at least 25% by weight of catalysts which contain iron oxide (s), alkali metal compound (s) and cerium oxide (s), in the preparation of the catalysts as cerium component (n) Cercarbonate hydrate (s) having a BET surface area of less than 0.30 m 2 / g are used.
  • the invention relates to a process for the dehydrogenation of alkylaromatic compounds.
  • EP-A 177 832 describes dehydrogenation catalysts comprising iron oxide, potassium oxide, molybdenum oxide, magnesium oxide, calcium oxide and cerium oxide, which is prepared using commercially available ceria as starting material.
  • EP-A 894 528 discloses dehydrogenation catalysts which also contain iron oxide, potassium oxide, molybdenum oxide, magnesium oxide, calcium oxide and cerium oxide using aqueous cerium nitrate solution as the feedstock.
  • cerium nitrate as starting material has the disadvantage that nitrogen oxides are liberated during the calcination of the catalyst.
  • DE-A 101 54 718 describes catalysts comprising iron oxide, potassium oxide, molybdenum oxide, magnesium oxide, calcium oxide and cerium oxide, which is prepared using cerium carbonate hydrate.
  • Cerium oxides are generally used in an amount of 5 to 60% by weight as carbonates, oxides, nitrates or hydroxides. it is described that by cerium Polari ⁇ tion of the Fe-O bond and obstruction of reaction of Fe 3+ to Fe 3 O 4 ty the Aktivi ⁇ and increased stability of the K-Fe phases.
  • the object of the invention was therefore to show a catalyst for the dehydrogenation of alkylaromatic compounds, which has improved alkylaromatic conversion with improved or constant alkenyl aromatic selectivity. Furthermore, the object was to reduce the benzene selectivity for the same or improved activity.
  • Lower benzene selectivity generally leads to a reduced amount of dehydrogenation gas because of the parallel reduced formation of, in particular, ethylene and carbon dioxide. This is particularly important in styrene plants with limited vacuum compressor performance of importance.
  • the object has been achieved with the aid of a catalyst comprising iron oxide (s), alkali compound (s) and cerium oxide (e), in which case the preparation of the catalyst as cerium component (s) comprises cercarbonate hydrate (e) having a BET surface area be used of less than 0.30 m 2 / g.
  • the BET surface area of the starting material cercarbonate hydrate is preferably less than 0.25 m 2 / g, in particular, the BET surface area of the cercarbonate hydrates is from 0.01 to 0.20 m 2 / g. A suitable method for measuring the BET surface area is described below.
  • the sulfur content of the cercarbonate hydrate used according to the invention is advantageously less than 100 ppm by weight, in particular less than 20 ppm by weight.
  • FIG. 3 shows, by way of example, scanning electron microscopy (SEM) images of rhodia cercarbonate hydrates used according to the invention.
  • Fig. 1 Wildhelm Priem GmbH & Co. KG
  • Fig. 2 Talbacher Auermet
  • the surfaces of the cercarbonate hydrates used according to the invention have, in comparison with the cercarbonate hydrates used in the prior art, larger crystals and in particular a significantly reduced proportion of smaller crystals grown on.
  • Cercarbonate hydrate is a pasty solid with varying water content.
  • the cercarbonate hydrate to be used according to the invention has a composition of approximately (Ce) 2 (CO 3 ) 3 .8H 2 O and an XRD structure analogous to lanthanite (Gmelin Handbook Rare Earth A7 p.191).
  • the use of more highly dehydrated cerium carbonates, in particular commercially available so-called dry cerium carbonates, is less preferred and generally leads to catalysts with reduced performance properties.
  • Cercarbonate hydrate can be obtained from numerous suppliers, for example from Schwarzacher Auermet principless GmbH in Austria, Wilhelm Priem GmbH & Co. KG in Germany or Rhodia in France.
  • the BET surface area of the cercarbonate hydrates varies widely and is 0.38 m 2 / g (Wilhelm Priem GmbH & Co. KG), 0.35 m 2 / g (Treibacher Auermet) and 0.18 m 2 / g. g (Rhodia).
  • catalysts are used whose preparation as cerium component at least 25 wt .-% ceric carbonate hydrate with a BET surface area of less than 0.30 m 2 / g are used.
  • the remaining up to 75 wt .-% may be Cercar ⁇ carbonate hydrates with a higher BET surface area or other cerium compounds such as cerium nitrates, oxides or hydroxides.
  • the invention further relates to catalyst beds which consist of at least 25% by weight of catalyst according to the invention.
  • the catalyst beds consist of at least 30% by weight, preferably at least 50% by weight, of catalysts according to the invention.
  • the catalysts of the invention may be evenly distributed over the catalyst bed or concentrated at one or more locations.
  • the catalysts according to the invention are used uniformly distributed over the entire dehydrogenation catalyst bed, in particular without the use of a further dehydrogenation catalyst from the prior art.
  • the catalyst according to the invention is particularly suitable for the dehydrogenation of hydrocarbons which have at least one saturated functional group, for example alkenes to the corresponding 1,3-alkadienes, preferably alkylaromatic compounds to the corresponding alkenylaromatic compounds.
  • Suitable alkylaromatic compounds are all aromatic and heteroaromatic alkyl compounds, preference is given to those in which the alkyl radical is unbranched or branched and contains two to six C atoms.
  • Suitable aromatic radicals are mono-, di- or trinuclear, preferably mono- or binuclear, particularly preferably einker ⁇ nige aromatics.
  • isopropylbenzene (cumene), ethylbenzene, 1, 1-diphenyl benzene and 1,2-diphenylethane (bibenzyl), preferably isopropylbenzene (cumene), ethylbenzene and 1,1-diphenylbenzene, more preferably ethylbenzene.
  • Suitable heteroaromatic radicals are mono-, di- or trinuclear, preferably mononuclear or dinuclear, particularly preferably mononuclear, five-membered heteroaromatic compounds having one to three nitrogen atoms and / or one oxygen atom or one sulfur atom, one, two or three ⁇ Ripe, preferably mono- or binuclear, particularly preferably mononuclear, six-membered heteroaromatic having one to three nitrogen atoms as heteroatoms, in particular pyridines, such as 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine and 5-ethyl-2-methylpyridine, be ⁇ preferably 2-ethylpyridine and 5-ethyl-2-methylpyridine.
  • the catalysts according to the invention typically contain a number of promoters, depending on their field of use. Suitable promoters for a dehydrogenation catalyst are, in addition to cerium compounds, advantageously compounds of calcium, magnesium, molybdenum, tungsten, chromium and titanium.
  • the weight ratio of potassium (calculated as K 2 O) to iron oxide (calculated as Fe 2 O 3 ) is generally from 0.01: 1 to 2: 1, preferably from 0.1: 1 to 1: 1.
  • the catalysts preferably contain further promoters (calculated as oxides) in a weight ratio to the iron oxide of from 0.01: 1 to 1: 1, preferably from 0.02: 1 to 0.5: 1.
  • the catalyst according to the invention has in particular the following composition:
  • Iron corresponding to 40-90% by weight of Fe 2 O 3
  • potassium corresponding to 1-40% by weight as K 2 O
  • Cerium corresponding to 1 to 25% by weight of Ce 2 O 4 , in particular 5 to 15% by weight of Ce 2 O 4 ,
  • Magnesium corresponding to 0-10% by weight of MgO
  • Tungsten corresponding to 0-10% by weight of WO 3
  • molybdenum corresponding to 0-10% by weight of MoO 3
  • Vanadium corresponding to 0 - 10 wt .-% V 2 O 5 wherein said components add up to 100 wt .-%.
  • the starting materials used can be compounds of the promoters present in the finished catalyst, or compounds which convert during the preparation process into compounds present in the finished catalyst.
  • the starting materials can also Additives may be added to improve processability, mechanical strength or pore structure. Examples of such substances are potato starch, celluloses, stearic acid, graphite and / or Portland cement.
  • the starting materials can be mixed directly in a mixer, kneader or preferably a Mix-Muller.
  • the starting materials can also be slurried in a spray mixture and processed in a spray dryer to form a spray powder.
  • the starting materials are preferably processed in a Mix-Muller or kneader with the addition of water to form an extrudable mass.
  • the extrudable mass is then extruded, dried and calcined.
  • Preferred strand forms comprise extrudates of 2 to 10 mm in diameter, in particular 2.5 to 6 mm.
  • the cross-section of the extrudates may be round or in other forms.
  • extrudates with rotationally symmetrical cross section in particular with a diameter of 2 to 4 mm, preferably of 3 mm, as well as extrudates with a star-shaped or those with a gear-toothed ("toothed-wheel") cross section, in particular with a diameter of 3 to 7, preferably 3.5 mm, 4.5 mm or 6 mm.
  • the shaping of the catalysts can also be carried out by tableting.
  • the extruded or optionally tabletted shaped catalyst bodies are then usually dried and subjected to calcining. The drying is preferably carried out on a belt dryer at temperatures between 100 and 200 0 C.
  • the calcination is preferably in a rotary kiln at temperatures between 500 and 1000 0 C, preferably between 700 and 1000 ° C, in particular zwi ⁇ rule 800 and 950 0 C, and particularly preferably 850 to 900 0 C fürge leads.
  • carbonate-containing feedstocks convert to oxides.
  • Potassium and iron oxides typically form mixed potassium ferrite crystal structures in the most preferred temperature range.
  • the dehydrogenation of hydrocarbons can be carried out by all methods known to the person skilled in the art.
  • the dehydrogenation of alkylaromatics to alkenylaromatics is preferably carried out in adiabatic or isothermal processes, in particular in adiabatic processes.
  • the reaction is generally distributed to several reactors in series, preferably radial flow reactors. Preferably, two to four reactors are connected in series. In each reactor is a Fest ⁇ bed with dehydrogenation catalysts.
  • ethylbenzene In the dehydrogenation of ethylbenzene to styrene, as is generally practiced today in multi-stage processes in so-called adiabatic processes, ethylbenzene is typically heated to temperatures together with steam, advantageously in an amount of less than 30% by weight, based on ethylbenzene around 500 0 C by means of a heat exchanger heated and mixed directly before entering the first reactor with superheated steam from a steam superheater, so that the desired inlet temperature in the first reactor is usually between 600 and 650 ° C.
  • the mass ratio of water vapor (total steam) to ethylbenzene when entering the bed of the dehydrogenation catalyst in the first reactor is advantageously 0.7: 1 to 2.5: 1.
  • the process is preferably operated at reduced pressure, typical reactor pressures are in the range of 300 to 1000 mbar.
  • the preferably hollow-cylindrical catalyst beds (radial flow reactors) are flowed through from the inside to the outside.
  • the reaction mixture Before entering the next reactor, the reaction mixture is advantageously brought back to temperatures of usually 600 and 650 0 C via a heat exchanger by means of superheated steam.
  • the pressure at the outlet of the last reactor should not be more than 700 mbar, more preferably not more than 600 mbar and in particular not more than 500 mbar.
  • a bed of an oxidation catalyst with oxygen supply for combustion of a subset of the hydrogen formed in the previous reactor can be set up, as for example in the German An ⁇ message with the application file number 102004015800.2 is described.
  • the volume ratio of the Schüttun ⁇ conditions of oxidation catalyst and dehydrogenation catalyst per reactor is generally 0.1: 1 to 1: 1.
  • an integrated oxidation catalyst this is preferably arranged upstream of the dehydrogenation catalysts in the flow direction.
  • Radial-flow reactors are preferably used in an integrated oxidation process in which the beds (catalyst beds) of oxidation and dehydrogenation catalysts are arranged concentrically with one another and optionally separated from one another by cylindrical sieves (screens). The oxidation catalyst is then used as the inner of the two concentrically arranged approximately hollow-cylindrical Schüt ⁇ lines.
  • the unsaturated compounds obtainable in the process according to the invention for example alkenylaromatics or 1,3-alkadienes, can advantageously be plastics polymerized or used as building blocks for organic-chemical syntheses were ⁇ the.
  • SEM scanning electron microscopy
  • FIG. 3 shows scanning electron microscopy (SEM) images of the rhodia cercarbonate hydrates from their Chinese production site (Lyang Rhodia).
  • the company Rhodia has recently moved the production of the Cercarbonate Hydrate from a production site in France to a production site in China. Individual batches from the production of the French site that we examined did not show the properties of the invention in the past.
  • the measurement of the dead volume was therefore carried out with evacuated sample cooled in liquid nitrogen.
  • the weighed samples were built into the sample containers of the device. These were then evacuated at room temperature to a pressure ⁇ 2 torr and refilled with helium to a pressure> 300 torr. This was repeated five times. After the fifth evacuation, the sample containers were immersed in Deward vessels filled with liquid nitrogen so that the samples were completely submerged. It was waited five minutes. After closing the valves, the measurements were started.
  • the ball of the sample container was completely filled with the Cercarbonate hydrate in order to minimize any influence on the measurement result in view of the small BET surface areas, if possible by means of dead volume effects.
  • Example 1 (according to the invention):
  • a catalyst was prepared analogously to the comparative example using the cerium carbonate hydrate of FIG. 3 (Rhodia company).
  • Magnesium corresponding to 2.1% by weight of MgO
  • Molybdenum corresponding to 2.4% by weight MoO 3 .

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

Abstract

L'invention concerne un catalyseur contenant un(des) oxyde(s) de fer, un(des) composé(s) de métal alcalin et un(des) oxyde(s) de cérium. Lors de la production du catalyseur, le(s) constituant(s) utilisé(s) est(sont) de l'hydrate/des hydrates de carbonate de cérium, avec une surface BET inférieure à 0,30 m2/g. L'invention concerne en outre un lit catalyseur consistant au moins à 25 % en catalyseurs, qui contiennent de l'oxyde/des oxydes de fer, un(des) composé(s) de métal alcalin et de l'oxyde/des oxydes de cérium. Lors de la production des catalyseurs, le(s) constituant(s) utilisé(s) est(sont) de l'hydrate/des hydrates de carbonate de cérium, avec une surface BET inférieure à 0,30 m2/g. L'invention concerne par ailleurs un procédé pour déshydrogéner des composés alkylaromatiques.
PCT/EP2005/008406 2004-08-13 2005-08-03 Catalyseur contenant un(des) oxyde(s) de fer, un(des) compose(s) de metal alcalin et un(des) oxyde(s) de cerium Ceased WO2006018133A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004039603A DE102004039603A1 (de) 2004-08-13 2004-08-13 Katalysator enthaltend Eisenoxid(e), Alkalimetallverbindung(en) und Ceroxid(e)
DE102004039603.5 2004-08-13

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WO2006018133A1 true WO2006018133A1 (fr) 2006-02-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8003837B2 (en) 2005-07-22 2011-08-23 Basf Se Catalysts for dehydrogenation and/or hydrogenation of hydrocarbons, processes for preparing the same, and uses therefor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0177832A2 (fr) * 1984-10-11 1986-04-16 Nissan Girdler Catalyst Co., Ltd. Catalyseur de déshydrogénation
EP0502510A1 (fr) * 1991-03-05 1992-09-09 Nissan Girdler Catalyst Co., Ltd. Catalyseur de déshydrogénation d'hydrocarbures alkyl- aromatiques et procédé de préparation dudit catalyseur
WO1996018458A1 (fr) * 1994-12-14 1996-06-20 Shell Internationale Research Maatschappij B.V. Catalyseur de deshydrogenation et procede associe
EP0894528A2 (fr) * 1997-08-01 1999-02-03 Süd Chemie Mt S.R.L. Catalysateur à base de ferrate de potassium pour la déshydrogénation de l'ethylbenzène en styrène
DE10154718A1 (de) * 2001-11-09 2003-05-22 Basf Ag Eisenoxide mit höherem Veredelungsgrad

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0177832A2 (fr) * 1984-10-11 1986-04-16 Nissan Girdler Catalyst Co., Ltd. Catalyseur de déshydrogénation
EP0502510A1 (fr) * 1991-03-05 1992-09-09 Nissan Girdler Catalyst Co., Ltd. Catalyseur de déshydrogénation d'hydrocarbures alkyl- aromatiques et procédé de préparation dudit catalyseur
WO1996018458A1 (fr) * 1994-12-14 1996-06-20 Shell Internationale Research Maatschappij B.V. Catalyseur de deshydrogenation et procede associe
EP0894528A2 (fr) * 1997-08-01 1999-02-03 Süd Chemie Mt S.R.L. Catalysateur à base de ferrate de potassium pour la déshydrogénation de l'ethylbenzène en styrène
DE10154718A1 (de) * 2001-11-09 2003-05-22 Basf Ag Eisenoxide mit höherem Veredelungsgrad

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8003837B2 (en) 2005-07-22 2011-08-23 Basf Se Catalysts for dehydrogenation and/or hydrogenation of hydrocarbons, processes for preparing the same, and uses therefor

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