EP0900127A1 - Catalyseur pour aromatisation selective - Google Patents

Catalyseur pour aromatisation selective

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Publication number
EP0900127A1
EP0900127A1 EP97919401A EP97919401A EP0900127A1 EP 0900127 A1 EP0900127 A1 EP 0900127A1 EP 97919401 A EP97919401 A EP 97919401A EP 97919401 A EP97919401 A EP 97919401A EP 0900127 A1 EP0900127 A1 EP 0900127A1
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EP
European Patent Office
Prior art keywords
catalyst according
catalyst
compound
aromatics
group
Prior art date
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EP97919401A
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German (de)
English (en)
Inventor
Daniel Heineke
Alfred Hagemeyer
Joachim Wulff-Döring
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BASF SE
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BASF SE
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Publication of EP0900127A1 publication Critical patent/EP0900127A1/fr
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    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C07C5/415—Catalytic processes with metals
    • C07C5/417—Catalytic processes with metals of the platinum group
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group 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
    • B01J23/38—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
    • B01J23/58—Platinum group metals with 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
    • B01J23/38—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
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B01J37/0223—Coating of particles by rotation
    • 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
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C07C5/415—Catalytic processes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • 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
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • 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
    • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • 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
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • 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
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/18—Arsenic, antimony or bismuth
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/36—Rhenium
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/057—Selenium or tellurium; Compounds thereof

Definitions

  • the invention relates to a noble metal-containing catalyst on a ceramic support for the selective production of aromatics from paraffinic / naphthenic hydrocarbon streams with straight-chain, branched and / or cyclic alkyl or alkylene chains of 6 to 12 carbon atoms.
  • the invention relates in particular to the production of C 8 aromatics.
  • the most important source of technically important C 6 to Cs aromatics such as benzene, xylenes or ethylbenzene is catalytic reforming.
  • straight-chain paraffin hydrocarbons are converted into branched paraffin hydrocarbons and aliphatic-aromatic and aromatic hydrocarbons.
  • This process is used on the one hand to increase the knock resistance of petrol fuels, ie the reaction mixtures obtained are generally used as such; on the other hand, the aromatic compounds formed are separated, for example by distillation, and serve as intermediates and building blocks, for example for the production of synthetic rubbers and synthetic fibers.
  • the ethylbenzene formed from components of the C8 fraction is used, for example, to obtain styrene or polystyrene.
  • Catalysts which contain other metals besides platinum, such as Pt-Re / Al 2 0 3 .Si0 2 or Pt / Sn / Al 2 0 3 .Si0 2 are also known; for example, a catalyst based on Pt / Sn / Al 2 0 3 in J. Mol. Catal. £ 8. (1994) 359-376.
  • the carrier materials are mostly aluminosilicates or zeolites.
  • Pt catalysts on L-zeolites (cf. Energy Progress 7, (1987), 215-222) achieve a high aromatic selectivity, which is attributed to the shape selectivity of the support, but with a low space-time yield.
  • multicomponent catalysts such as Pt / Co / Nd (US Pat. No. 4,136,130) or Pt / Co / Re / Ge (US Pat. No. 4,136,017) on (non-zeolitic) chlorinated Al 2 0 3 supports develop higher activity, tend but to the formation of crack products and with it less aromatic selectivity, especially with regard to the formation of C8 aromatics (ethylbenzene; styrene; xylenes).
  • the object of the invention is to create a catalyst which does not have the disadvantages mentioned or has them to a considerably lesser extent and converts C 2 -C 2 -hydrocarbon streams to aromatics in high yield.
  • a special task is to find a catalyst with particular selectivity for ethylbenzene, which is one of the C ⁇ aromatics with the highest added value.
  • the object was achieved by a catalyst based on one or more ceramic oxides of metals from the fourth subgroup (group 4B) of the elements, in particular Zr0 2 and Ti0 2r, a noble metal selected from the elements of the eighth group of the periodic table of the periodic table of the elements , in particular palladium, platinum or rhodium and / or rhenium and / or tin contains.
  • Alkali, alkaline earth or rare earths or their compounds which can be converted into the corresponding oxides at temperatures above 400 ° C.
  • the simultaneous doping with several of the elements mentioned or their connections is possible.
  • Potassium and lanthanum compounds, for example, are well suited.
  • the catalyst can be mixed with sulfur, tellurium, arsenic, antimony or selenium-containing compounds, which in many cases increase the selectivity, presumably through partial "poisoning" (moderators).
  • the catalysts according to the invention have the advantage of higher overall selectivity for aromatics, in particular C 8 aromatics.
  • the catalysts according to the invention enable higher conversion and, associated therewith, a higher aromatic yield than catalysts of the prior art.
  • amphoteric ceramic oxides ie in particular oxides of zircon and titanium or mixtures thereof, can be used to produce the catalysts according to the invention;
  • Corresponding compounds which can be converted into these oxides by calcining are also suitable. These can be made according to known Processes, for example by the sol-gel process, precipitation of the salts, dewatering of the corresponding acids, dry mixing, slurrying or spray drying.
  • the doping with a basic compound can be carried out during production, for example by co-precipitation or subsequently, for example by impregnating the ceramic oxide with an alkali metal or alkaline earth metal compound or a compound of an element of the third subgroup or a rare earth metal compound.
  • the content of alkali or alkaline earth metal, metal of the third main or subgroup, rare earth metal or zinc is generally up to 20% by weight, preferably between 0.1 and 15% by weight, particularly preferably between 0.5 and 10% by weight. %.
  • alkali and alkaline earth metal suppliers use is generally made of compounds which can be converted into the corresponding oxides by calcining. For example, hydroxides, carbonates, oxalates, acetates, nitrates or mixed hydroxycarbonates of the alkali and alkaline earth metals are suitable.
  • the ceramic support is additionally or exclusively doped with a metal of the third main or subgroup, then one should also start from compounds in this case that can be converted into the corresponding oxides by calcining.
  • lanthanum for example lanthanum oxide carbonate, La (OH) 3 , La 2 (CO 3 ) 3 , La (NO 3 ) 3 or lanthanum compounds which contain organic anions, such as La acetate, La formate , or La-Oxalat suitable.
  • the precious metal component can be applied in different ways.
  • the carrier can be impregnated or sprayed with a solution of a corresponding compound of the noble metal or rhenium or tin.
  • Suitable metal salts for the preparation of such solutions are, for example, the nitrates, halides, formates, oxalates, acetates of the noble metal compounds.
  • Complex anions or acids of these complex anions such as H 2 PtCle can also be used.
  • the compounds PdCl 2 , Pd (OAc) 2 , Pd (N0 3 ) 2 and Pt (N0 3 ) 2 have been found.
  • noble metal sols are prepared beforehand in a conventional manner, for example by reducing a metal salt or a mixture of several metal salts in the presence of a stabilizer such as polyvinylpyrrolidone, and then applied to the carrier either by impregnation or spraying.
  • a stabilizer such as polyvinylpyrrolidone
  • the content of the catalyst in elements of the eighth group or rhenium or tin can e.g. 0.005 to 5, preferably 0.01 to 2, particularly preferably 0.1 to 1.5% by weight. If rhenium or tin is additionally used, their ratio to the noble metal component can e.g. 0.1: 1 to 20: 1, preferably 1: 1 to 10: 1.
  • compounds of sulfur, tellurium, arsenic or selenium can be used as moderating additives (according to the common notion of partial poisoning of the catalyst). It is also possible to add carbon monoxide while the catalyst is in operation.
  • sulfur which is expediently applied in the form of ammonium sulfide, (NH 4 ) 2 S, has proven particularly suitable.
  • the molar ratio of noble metal component to poisoning compound can vary from 1: 0 to 1:10, preferably from 1: 1 to 1: 0.05.
  • the catalyst can be fixed in the reactor or e.g. be used in the form of a fluidized bed and have a corresponding shape. Suitable are e.g. Shapes such as grit, tablets, monoliths, balls or extrudates (strands, wagon wheels, stars, rings).
  • the catalyst preparations have a BET surface area of up to 500 m 2 / g, usually from 10 to 300 m 2 / g, particularly preferably from 20 to 300 m 2 / g.
  • the pore volume is generally between 0.1 and 1 ml / g, preferably from 0.15 to 0.6 ml / g, particularly preferably 0.2 to 0.4 ml / g.
  • the average pore diameter of the mesopores which can be determined by mercury penetration analysis, is generally between 8 and 60 nm, preferably between 10 and 40 nm.
  • the proportion of pores with a width of more than 20 nm generally varies between 0 and 60%, the use of supports with a macropore fraction (ie pores of more than 20 nm width) of more than 10% has proven to be advantageous. 5
  • the special reaction is carried out at temperatures from 300 to 800 ° C., preferably 400 to 600 and in particular 400 to 550 ° C., and at pressures from 100 mbar to 100 bar, preferably 1 to 40 bar with an LHSV of 0.01 to 100 h " 1 , preferably 0.1 to 20 h ' 1
  • hydrocarbon mixture to be dehydrogenated
  • diluents such as CO 2 / N 2
  • noble gases or steam can be present.
  • Hydrogen can also be added if required, the volume ratio of hydrogen to hydrocarbon (gases) being from 0.1 to 100, preferably from 1 to 20
  • the added hydrogen can be used to remove carbon which accumulates on the surface of the catalyst as the reaction time progresses.
  • the catalyst In addition to the continuous addition of a gas which prevents the coke from separating during the reaction, there is the possibility of regenerating the catalyst from time to time by passing hydrogen or air over it.
  • the regeneration takes place at temperatures in the range from 300 to 900 ° C., preferably 400 to 800 ° C. with a free oxidizing agent, preferably with air or in a reducing atmosphere, preferably with hydrogen.
  • the regeneration can be carried out at atmospheric, reduced or superatmospheric pressure. Suitable are e.g. Pressures in the range from 500 mbar to 100 bar.
  • the palladium sol was sprayed onto 200 g ZrO 2 tablets (5 x 3 mm tablets) on a heated turntable using a two-component nozzle. The mixture was then dried at 120 ° C. for 72 h. The tablets were impregnated with 45 a solution of 2.96 g of K 2 CO 3 in 47 ml of water for 1 hour in accordance with their water absorption (23.5 ml / 100 g). During the impregnation, it was shaken several times. The mixture was then dried at 120 ° C. for 18 h. 1.1 g of 40% by weight ammonium sulfide ((NH 4 ) 2 S) solution were diluted with water to 47 ml of solution, the pretreated tablets were soaked and dried at 120 ° C. for 16 h.
  • ammonium sulfide ((NH 4 ) 2 S) solution were diluted with water to 47 ml of solution, the pretreated tablets were soaked and dried at 120 ° C. for 16 h.
  • the zirconium dioxide used was in the form of strands and had a BET surface area of 92 m 2 / g, a pore volume of 0.25 ml / g (Hg porosimetry) and a proportion of approximately 30% of pores with more than 0.02 ⁇ m.
  • 200 g of ZrO 2 were soaked with a palladium solution corresponding to their water absorption (27.2 g water / 100 g) until the liquid was absorbed (approx. 30 min).
  • the strands were then dried at 80 ° C. in a rotary evaporator.
  • the strands were then dried at 120 ° C. for 16 h.
  • the strands were slurried in a solution of 3.61 g of K 2 CO 3 in 55 ml of water and, after about 30 minutes, dried again at 80 ° C. in a rotary evaporator. The strands were then dried at 120 ° C. for 28 hours.
  • the strands were slurried in a solution of 3.61 g of K 2 CO 3 in 60 ml of water and, after about 30 minutes, dried again at 80 ° C. in a rotary evaporator. The strands were then dried at 120 ° C. for 28 hours.
  • the zirconium dioxide used was in the form of strands and had a BET surface area of 46 m 2 / g, a pore volume of 0.23 ml / g (Hg porosimetry) and a proportion of approximately 15% of pores with more than 0.02 ⁇ m.
  • 200 g of strands were impregnated with the palladium solution in accordance with their water absorption (26 g water / 100 g). After about 30 minutes, the strands were dried at 80 ° C. in a rotary evaporator. The strands were then dried at 120 ° C. for 14 h.
  • the strands were slurried in a solution of 3.61 g of K 2 CO 3 in 52 ml of water and, after about 30 minutes, dried again at 80 ° C. in a rotary evaporator. The strands were then dried at 120 ° C. for 20 h.
  • zirconium dioxide in the form of a strand (commercial product # 9316321 from Norton; BET surface area 49 m 2 / g; water absorption 30.6 g / 100 g) 0.181 g of Pt (NO 3 ) 2 (commercial product as example 11 ) dissolved in 3.06 ml of water and 0.100 g of Sn (OAc) 2 , dissolved in 3.06 ml of water, and after another hour dried for 16 hours at 120 ° C. and calcined at 650 ° C.
  • the catalyst obtained contains 1% platinum and 0.5% tin.
  • zirconium oxide in the form of a BET surface area 70 m 2 / g; Pore volume 0.28 ml / g; 30% pore fraction with a diameter below 20 nm; crystalline phase monoclinic; Water absorption 30.6 g / 100 g) 0.066 g Pt (N0 3 ) 2 (commercial product as above) and 0.087 g Pd (N0 3 ) 2 dissolved in 3.06 ml water, dried at 120 ° C and calcined at 500 ° C.
  • the catalyst obtained contains 0.5% platinum and palladium.
  • the catalysts according to the invention have a higher selectivity with regard to the total yield of aromatics than the comparative catalyst.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un catalyseur, notamment pour la production sélective d'aromatiques à partir de courants d'hydrocarbures à chaînes alkyle ou alkylène linéaires, ramifiées ou cycliques composées de 6 à 12 atomes de carbone, qui contient, sur un oxyde d'un métal de transition du groupe IVB de la classification périodique des éléments, tel que TiO2 ou ZrO2, au moins un élément sélectionné parmi les éléments du VIIIème groupe secondaire tel que palladium, platine, rhodium, rhénium ou étain, ainsi qu'éventuellement un composé d'un métal alcalin ou alcalino-terreux, un composé du troisième groupe principal ou secondaire ou du zinc ou au moins un composé du groupe soufre, tellure, arsenic, antimoine ou sélénium. L'invention concerne en outre l'utilisation de ce catalyseur pour produire des aromatiques, tels que le benzène d'éthyle ou le xylolène, à partir d'hydrocarbures C6-C12.
EP97919401A 1996-04-26 1997-04-23 Catalyseur pour aromatisation selective Withdrawn EP0900127A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19616736 1996-04-26
DE19616736A DE19616736A1 (de) 1996-04-26 1996-04-26 Katalysator zur selektiven Aromatisierung
PCT/EP1997/002045 WO1997040931A1 (fr) 1996-04-26 1997-04-23 Catalyseur pour aromatisation selective

Publications (1)

Publication Number Publication Date
EP0900127A1 true EP0900127A1 (fr) 1999-03-10

Family

ID=7792547

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97919401A Withdrawn EP0900127A1 (fr) 1996-04-26 1997-04-23 Catalyseur pour aromatisation selective

Country Status (6)

Country Link
EP (1) EP0900127A1 (fr)
JP (1) JP2000512539A (fr)
KR (1) KR20000065043A (fr)
CN (1) CN1216938A (fr)
DE (1) DE19616736A1 (fr)
WO (1) WO1997040931A1 (fr)

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FR2770775B1 (fr) * 1997-11-07 1999-12-24 Oreal Composition pour la teinture d'oxydation des fibres keratiniques comprenant un 3,4-diamino pyrazole 5-substitue et un meta-aminophenol halogene, et procede de teinture
DE19937106A1 (de) * 1999-08-06 2001-02-08 Basf Ag Multikomponenten-Katalysatoren
WO2002051543A1 (fr) * 2000-12-22 2002-07-04 Basf Aktiengesellschaft Catalyseurs multicomposants
DE102005053230A1 (de) * 2005-11-06 2007-05-10 Basf Ag Verfahren zur Aromatisierung von Nichtaromaten und anschließende Dealkylierung von Alkyl-substituierten aromatischen Kohlenwasserstoffen mit Wasserdampf
CN101234349B (zh) * 2007-01-31 2010-09-22 中国石油化工股份有限公司 一种烷烃和/或环烷烃芳构化催化剂及芳构化方法
KR101781656B1 (ko) * 2009-05-20 2017-10-10 바스프 에스이 모놀리스 촉매 및 이의 용도
CN102441412B (zh) * 2010-10-12 2015-02-18 中国石油化工股份有限公司 一种芳构化催化剂及其在高选择性制备对二甲苯中的应用
CN106423255B (zh) * 2015-08-12 2019-01-25 中国石油化工股份有限公司 乙苯催化剂及其制备方法
CN107282089B (zh) * 2016-04-12 2020-03-31 中国石油化工股份有限公司 苯与乙烷烷基化的催化剂
CN107952476B (zh) * 2017-12-13 2021-02-09 中石化炼化工程（集团）股份有限公司 用于醇石脑油耦合制备汽油调和组分的催化剂、制备方法及其应用
CN115518679B (zh) * 2021-06-24 2024-03-26 中国石油化工股份有限公司 一种芳构化催化剂及其制备方法和应用和丁烷芳构化方法

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DE4109502A1 (de) * 1991-03-22 1992-09-24 Degussa Katalysator zur haertung von fettsaeuren und verfahren zu seiner herstellung
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See references of WO9740931A1 *

Also Published As

Publication number Publication date
WO1997040931A1 (fr) 1997-11-06
JP2000512539A (ja) 2000-09-26
KR20000065043A (ko) 2000-11-06
CN1216938A (zh) 1999-05-19
DE19616736A1 (de) 1997-11-06

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