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WO2007051854A2 - Procede d'aromatisation d'hydrocarbures non aromatiques a la vapeur d'eau - Google Patents

Procede d'aromatisation d'hydrocarbures non aromatiques a la vapeur d'eau Download PDF

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Publication number
WO2007051854A2
WO2007051854A2 PCT/EP2006/068131 EP2006068131W WO2007051854A2 WO 2007051854 A2 WO2007051854 A2 WO 2007051854A2 EP 2006068131 W EP2006068131 W EP 2006068131W WO 2007051854 A2 WO2007051854 A2 WO 2007051854A2
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WIPO (PCT)
Prior art keywords
catalyst
weight
zirconia
tin
platinum
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PCT/EP2006/068131
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German (de)
English (en)
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WO2007051854A3 (fr
Inventor
Michael Koch
Götz-Peter SCHINDLER
Dirk Neumann
Hartmut Hibst
Armin Lange De Oliveira
Jens Klein
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BASF SE
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BASF SE
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Publication of WO2007051854A3 publication Critical patent/WO2007051854A3/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
    • 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
    • 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
    • B01J23/63—Platinum group metals 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
    • C07C5/373—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
    • 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
    • B01J21/066—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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/62—Platinum group metals with gallium, indium, thallium, 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/63—Platinum group metals with rare earths or actinides

Definitions

  • the present invention relates to a process for the aromatization of non-aromatic hydrocarbons having 6 or more carbon atoms in the presence of water vapor and a catalyst.
  • EP 454 022 teaches a carrier which also contains calcium aluminate in addition to zinc aluminate, which leads to an increase in activity and selectivity of the catalyst.
  • DE 196 16 736 which contain at least one element selected from the elements of group VIII of the Periodic Table and / or rhenium and / or tin on a titania or zirconia support, from paraffinic / naphthenic hydrocarbon streams aromatic hydrocarbons can be produced.
  • the examples of DE 196 16 736 disclose the reaction of n-octane pulsed with an inert gas (helium) in the absence of water vapor on a catalyst containing palladium and potassium on a zirconia support.
  • WO 02/051547 (BASF AG) describes catalysts with bimodal pore distribution which comprise a) 10 to 99.9% by weight zirconium dioxide and b) 0 to 60% by weight aluminum oxide, silicon dioxide and / or titanium dioxide and c) 0, 1 to 10 wt .-% of at least one element of the first or second main group, an element of the third subgroup, an element of the eighth subgroup of the Periodic Table of the Elements, lanthanum and / or pear contain, with the proviso that the sum of the weight percent 100 results.
  • WO 02/051543 (BASF AG) describes multicomponent catalysts which comprise a) platinum and tin and b) gallium, indium, cobalt and / or germanium, c) optionally scandium, yttrium and / or lanthanum and d) optionally alkali metal and or alkaline earth metals on a zirconia support optionally containing Si ⁇ 2, Al2O3 and / or HO2 included.
  • WO 02/051540 (BASF AG) describes catalysts which contain a) from 10 to 99% by weight of zirconium dioxide and / or titanium dioxide and b) from 0.1 to 30% by weight of silica and c) from 0 to 60% by weight. % Of alumina and d) 0.1 to 10% by weight of at least one element of the first or second main group, of a third subgroup element, of an element of the eighth subgroup of the Periodic Table of the Elements and / or tin, with the proviso that the sum of the percentages by weight gives 100, a process for the dehydrogenation of C2 to Ci6 hydrocarbons and the use of these catalysts and a method for producing these catalysts.
  • the object of the present invention is to provide a process for the aromatization of non-aromatic hydrocarbons, which allows the aromatization of non-aromatic hydrocarbons on a catalyst in the presence of water vapor, wherein the catalyst shows improved activity and / or selectivity.
  • non-aromatic hydrocarbons can be aromatized.
  • the non-aromatic hydrocarbons usually have at least 6 carbon atoms, usually 6 to 20 carbon atoms.
  • the non-aromatic hydrocarbons are paraffins, naphthenes or mixtures thereof.
  • the feed stream usually used contains as a rule aromatic and non-aromatic hydrocarbons having 6 to 20, preferably 7 to 20, in particular 7 to 12 carbon atoms.
  • the proportion of non-aromatic compounds is at least 1 wt .-%, preferably at least 5 wt .-% and in particular at least 10 wt .-%.
  • the proportion of non-aromatics is from 5 to 80% by weight, preferably from 10 to 50% by weight and in particular from 10 to 30% by weight.
  • the feed contains only non-aromatic hydrocarbons.
  • the non-aromatic hydrocarbons may also include olefins on a case-by-case basis; their proportion is usually below 1 wt .-%.
  • the feed stream may contain up to 40% by weight, preferably up to 10% by weight, more preferably up to 2% by weight, of hydrocarbons having 5 and / or 6 carbon atoms.
  • the so-called BTX cut which is obtained in steam cracking can also be used as the feed stream.
  • the feed stream may contain sulfur containing compounds, such as e.g. Mercaptans, thiophene, benzothiophene, alkyl-substituted thiophenes and / or benzothiophenes.
  • sulfur containing compounds such as e.g. Mercaptans, thiophene, benzothiophene, alkyl-substituted thiophenes and / or benzothiophenes.
  • the sulfur content of the feed stream may be up to 100 ppm, usually 10 ppm or less, more preferably 2 ppm or less.
  • the aromatization is usually carried out between 300 and 800 ° C, preferably between 400 to 700 ° C, in particular between 500 and 600 ° C.
  • the pressure is in this case in a range of 1 to 50 bar, preferably from 3 to 30 bar, in particular from 5 to 25 bar.
  • the LHSV Liquid Hourly Space Velocity
  • the LHSV is usually 0.1 to 10 parts by volume of feed stream per part by volume of catalyst per hour (l / l »h), preferably 0.5 to 5 l / l» h, especially at 1 to 3 (l / l »h).
  • the molar ratio of water vapor / carbon is generally from 0.01 to 10, preferably from 0.1 to 5, in particular from 0.2 to 2.
  • the catalysts used in the invention comprise a) a zirconia-containing support; b) platinum, in particular 0.01 to 5 wt .-%, based on the total weight of the catalyst; c) tin, in particular 0.01 to 20 wt .-%, based on the total weight of the catalyst; wherein the weight ratio of tin to platinum is at least 1.
  • the catalyst used contains as component a) a zirconia-containing carrier.
  • a stabilized zirconia-containing carrier It is also possible to use a stabilized zirconia-containing carrier.
  • Suitable stabilizers are all compounds which stabilize the tetragonal or monoclinic structure of the zirconium oxide.
  • the stabilizers are used which cause and / or stabilize the tetragonal structure of the zirconium oxide.
  • the stabilized zirconia-containing carrier contains cerium, lanthanum and / or silicon, preferably cerium and / or lanthanum.
  • the stabilized zirconia-containing carrier contains, in particular, cerium (III) oxide, lanthanum (III) oxide and / or silicon (IV) oxide, preferably cerium (III) oxide and / or lanthanum (III) oxide.
  • the stabilized zirconia-containing carrier usually contains up to 40% by weight, preferably 10 to 30% by weight, especially 15 to 30% by weight, based on the weight of Zirconium oxide, cerium (III) oxide.
  • the stabilized zirconia-containing support usually contains up to 20% by weight, preferably from 2 to 15% by weight, in particular from 5 to 15% by weight, based on the weight of zirconium oxide , Lanthanum (III) oxide.
  • the stabilized zirconium oxide-containing support usually contains up to 10% by weight, preferably 1 to 7% by weight, in particular 2 to 5% by weight, based on the weight of Zirconium oxide, silicon (IV) oxide.
  • the stabilized zirconia-containing carrier usually contains up to 40% by weight, preferably 5 to 30% by weight. %, in particular 10 to 25 wt .-%, based on the weight of zirconium oxide, cerium (III) oxide and usually up to 20 wt .-%, preferably 1 to 15 wt .-%, in particular 2 to 10 wt. -%, based on the weight of zirconium oxide, lanthanum (III) oxide.
  • the zirconia-containing carrier may also contain adjuvants. These are suitable for facilitating the shaping of the zirconia-containing support.
  • auxiliaries are, for example, graphite, waxes, silicon dioxide and aluminum oxide. These aids can either be self-added or in the form of their own
  • silica precursors such as e.g. Tetraalkyl orthosilicates and colloidal silica
  • alumina precursors e.g. Boehmite
  • Pural® Pural®
  • auxiliaries are graphite, waxes and aluminum oxides, in particular aluminum oxides.
  • the zirconia-containing carrier can contain up to 40% by weight, based on the total weight of the zirconia-containing carrier, of auxiliaries.
  • the zirconium oxide-containing support comprises from 5 to 40% by weight, preferably from 10 to 35% by weight, based on the total weight of the zirconium oxide support, of auxiliaries.
  • the catalyst contains as component b) 0.01 to 5 wt .-%, based on the total weight of the catalyst, platinum. In a preferred embodiment, the catalyst contains 0.1 to 2 wt .-%, preferably 0.3 to 1 wt .-%, based on the total weight of the catalyst, platinum. Furthermore, the catalyst contains as component c) 0.01 to 20 wt .-%, based on the total weight of the catalyst, tin. In a preferred embodiment, the catalyst contains 0.5 to 10 wt .-%, preferably 1 to 5 wt .-%, based on the total weight of the catalyst, tin.
  • the weight ratio of tin to platinum is generally at least 1, preferably at least 2, in particular at least 3.
  • the catalyst contains at least one further promoter as component d).
  • promoters are metals selected from the group of scandium, yttrium, lanthanum, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, rhodium, iron, ruthenium, cobalt, iridium, nickel, palladium, copper, Silver, gold, zinc, indium, germanium, lead, arsenic, antimony, bismuth, cerium, praseodymium, neodymium and europium, or mixtures thereof.
  • vanadium, chromium, rhenium, iron, nickel, copper or mixtures thereof are used as promoters.
  • vanadium, chromium, copper or mixtures thereof are used.
  • a further promoter from the above-mentioned group is used.
  • two further promoters from the above-mentioned group are used.
  • the catalyst contains 0.01 to 20 wt .-%, preferably 0.1 to 15 wt .-%, in particular 0.5 to 10 wt .-%, based on the total weight of the catalyst, further promoter.
  • the catalyst contains as component e) at least one metal whose metal compound is alkaline, preferably at least one metal oxide which reacts alkaline, in particular at least one oxide of an alkali metal, alkaline earth metal or lanthanum.
  • alkali metal are preferably potassium or cesium and as the alkaline earth metal, preferably barium into consideration.
  • oxides of potassium or lanthanum are used.
  • a metal compound wherein the metal in question selected from the group of alkali metals, alkaline earth metals and Lanthanum, and which is alkaline, preferably a metal oxide, as listed above, used.
  • two metal compounds wherein the metals in question are selected from the group of alkali metals, alkaline earth metals and lanthanum, and which react alkaline, preferably two metal oxides as listed above, are used.
  • the catalyst contains 0.01 to 20 wt .-%, preferably 0.1 to 15 wt .-%, in particular 0.5 to 10 wt .-%, based on the total weight of the catalyst, of at least one metal whose metal compound used is alkaline, preferably, this metal compound contains an alkali metal, alkaline earth metal or lanthanum.
  • the catalyst usually has a BET surface area (determined to DIN 66131) of up to 500 m 2 / g, preferably from 10 to 300 m 2 / g, in particular from 20 to 200 m 2 / g.
  • the pore volume of the catalyst is 0.1 to 1 ml / g, preferably 0.15 to 0.6 ml / g, in particular 0.2 to 0.4 ml / g.
  • the zirconium oxide phases of the catalyst are usually tetragonal and / or monoclinic (determined by X-ray diffraction (XRD)).
  • the catalyst comprises a) a zirconia-containing carrier; b) 0.01 to 5 wt .-%, based on the total weight of the catalyst, platinum; c) 0.01 to 20 wt .-%, based on the total weight of the catalyst, tin; d) at least one further promoter; wherein the weight ratio of tin to platinum is at least 1.
  • the catalyst comprises a) a zirconia-containing carrier; b) 0.01 to 5 wt .-%, based on the total weight of the catalyst, platinum; c) 0.01 to 20 wt .-%, based on the total weight of the catalyst, tin; e) at least one metal whose metal compound is alkaline; wherein the weight ratio of tin to platinum is at least 1.
  • the catalyst comprises a) a zirconia-containing carrier; b) 0.01 to 5 wt .-%, based on the total weight of the catalyst, platinum; c) 0.01 to 20 wt .-%, based on the total weight of the catalyst, tin; d) at least one further promoter; e) at least one metal whose metal compound is alkaline; wherein the weight ratio of tin to platinum is at least 1.
  • the catalyst comprises a) a zirconia-containing support consisting essentially of zirconium oxide; b) 0.01 to 5 wt .-%, based on the total weight of the catalyst, platinum; c) 0.01 to 20 wt .-%, based on the total weight of the catalyst, tin; e) at least one metal whose metal compound is alkaline; wherein the weight ratio of tin to platinum is at least 1.
  • the catalyst comprises a) a zirconium oxide-containing support which contains a1) at least one stabilizer; b) 0.01 to 5 wt .-%, based on the total weight of the catalyst, platinum; c) 0.01 to 20 wt .-%, based on the total weight of the catalyst, tin; e) at least one metal whose metal compound is alkaline; wherein the weight ratio of tin to platinum is at least 1.
  • the catalyst comprises a) a zirconium oxide-containing support which a1) at least one stabilizer; a2) an adjuvant; contains; b) 0.01 to 5 wt .-%, based on the total weight of the catalyst, platinum; c) 0.01 to 20 wt .-%, based on the total weight of the catalyst, tin; e) at least one metal whose metal compound is alkaline; wherein the weight ratio of tin to platinum is at least 1.
  • the catalyst of the present invention contains ⁇ 0.05% by weight of a component selected from gallium, indium, cobalt and germanium or a mixture thereof.
  • the catalyst according to the invention is essentially free of gallium, indium, cobalt and germanium or a mixture thereof.
  • the term "substantially free of” means that the said component or the components mentioned are present in an amount of ⁇ 0.05% by weight and furthermore do not alter the properties of the catalyst.
  • the catalyst according to the invention contains no component from the group gallium, indium, cobalt and germanium or a mixture thereof.
  • the preparation of the catalyst can be carried out by conventional methods known to the person skilled in the art.
  • the zirconia-containing support from corresponding compounds which convert to zirconia upon calcining.
  • hydroxides, carbonates and carboxylates are suitable.
  • the zirconium oxide or the corresponding precursor, which is converted into zirconium oxide during calcining can be prepared by methods known per se, such as e.g. by the sol-gel method, by precipitation, dehydration of the corresponding carboxylates, dry mixing, slurrying or spray-drying.
  • the precipitation usually employs soluble zirconium salts, e.g. the corresponding halides, preferably chloride, alkoxides, nitrate, etc., preferably nitrate.
  • Stabilized zirconia-containing supports can i.a. can be prepared by reacting the zirconia described above or the corresponding precursor with soluble salts of the stabilizers, such as. the corresponding halides, preferably chlorides, alkoxides, nitrates, etc., soaks.
  • soluble salts of the stabilizers such as. the corresponding halides, preferably chlorides, alkoxides, nitrates, etc.
  • Suitable soluble salts of the stabilizers are, in turn, generally suitable halides, preferably chlorides, alkoxides, nitrates, etc.
  • the stabilized zirconium oxide-containing support from compounds which convert to zirconium oxide or cerium (III) oxide, lanthanum (III) oxide, silicon (IV) oxide on calcination.
  • compounds which convert to zirconium oxide or cerium (III) oxide, lanthanum (III) oxide, silicon (IV) oxide on calcination.
  • hydroxides, carbonates and carboxylates are suitable. These are for example precipitated together, spray-dried together etc.
  • the zirconia described above, the stabilized zirconia described above or the corresponding precursors can be mixed with auxiliaries which are suitable for facilitating the shaping of the zirconia support. Subsequently, the shaping takes place.
  • auxiliaries which are suitable for facilitating the shaping of the zirconia support. Subsequently, the shaping takes place.
  • strands, tablets, spheres, chippings, monoliths, etc. are prepared by the usual methods.
  • the zirconium oxide described above, the stabilized zirconium oxide described above or the corresponding precursors, which are optionally mixed with auxiliaries, are calcined. This is usually done with air or a mixture of air and nitrogen, at a temperature of 300 to 800 ° C, preferably at 500 to 600 ° C. It may be advantageous to add water vapor to the air or to the air / nitrogen mixture.
  • the carrier is impregnated with a solution of suitable platinum precursors or suitable tin precursors.
  • the impregnation can be carried out by the incipient-wetness method, in which case the porous volume (pore volume) of the support is filled up with approximately the same volume of impregnating solution and, optionally after a ripening, the support is dried; or one works with a surplus of solution, wherein the volume of this solution is greater than the porous volume (pore volume) of the carrier.
  • the carrier is mixed with in the impregnating solution and stirred for a sufficient time.
  • the carrier with a solution of the platinum precursor or of the tin precursor.
  • the order of the impregnations does not matter. But it may also be advantageous to apply the individual precursors in a certain order. It is also possible to impregnate with a solution containing both the platinum and the tin precursor.
  • Suitable platinum precursors are platinum salts, i.a. Halides, in particular chloride, nitrate, acetate, alkaline carbonates, formate, oxalate, citrate, tartrate, but also platinum complexes.
  • the latter can contain as neutral ligands Lewis bases such as amines or phosphines and as anionic ligands halides such as chloride, bromide or nitrate, etc.
  • Suitable tin precursors are tin salts, in particular tin (II) salts, i.a. Halides, especially chloride, sulfate, acetate, formate, oxalate, citrate, tartrate, but also alkali and / or Erdalkalistannate such. Sodium stannate.
  • Catalysts containing one or more further promoters are prepared by applying the promoter precursor or promoter precursors in analogy to the platinum or tin plating processes.
  • Suitable promoter precursors include i.a. Halides, in particular chlorides, nitrates, acetates, alkaline carbonates, formates, oxalates, citrates, tartrates, corresponding organometallic compounds, but also promoter complexes.
  • the latter may contain, as ligands, acetylacetonate, amino alcohols, carboxylates, such as oxalates, citrates, etc., or hydroxycarboxylic acid salts, etc.
  • the corresponding promoter precursor can be applied together with the platinum and / or tin precursor. the. But it is also possible to apply them one after the other. It may also be advantageous to apply the individual precursors in a certain order.
  • the promoter precursors can be applied together or separately. It is also possible to apply the platinum and / or tin precursor together or separately with one or more promoter precursors. In the case of a separate application, it may also be advantageous to apply the individual precursors in a certain order.
  • catalysts which contain at least one metal whose metal compound is alkaline
  • the alkaline metal precursor or the alkaline metal precursors are applied in analogy to the processes for platinum or tin plating.
  • alkaline metal precursors are usually used compounds which convert to the corresponding oxides during calcining. Suitable for this are hydroxides, carbonates, carboxylates, e.g. Formates, acetates, oxalates, nitrates, hydroxycarbonates etc.
  • the respective precursors can be applied together or separately. In the case of a separate application, it may also be advantageous to apply the individual precursors in a certain order.
  • the zirconium oxide-containing support on which the platinum precursor, the tin precursor and optionally the promoter precursor (s) and, if appropriate, the alkali metal precursor (s) are applied is calcined.
  • the calcination is usually carried out with air or a mixture of air and nitrogen, at a temperature of 300 to 800 ° C, preferably at 400 to 600 ° C. It may be advantageous to add water vapor to the air or to the air / nitrogen mixture.
  • the catalyst thus obtained is usually activated before it is used in the aromatization of non-aromatics.
  • it is treated with hydrogen or a mixture of hydrogen and nitrogen at temperatures of 100 to 800 ° C, preferably at 400 to 600 ° C.
  • it may be advantageous to start with a low hydrogen content in the hydrogen / nitrogen mixture and to increase the hydrogen content continuously during the activation process.
  • the activation of the catalyst is usually carried out in the reactor in which the aromatization of non-aromatics is to take place. However, it is also possible to carry out the activation of the catalyst before installation in the corresponding reactor. However, it is also possible to use the catalyst without prior activation in the aromatization of non-aromatics.
  • Coke and / or coke precursors may form at the active centers and in the pores of the catalyst.
  • Coke is usually high-boiling unsaturated hydrocarbons.
  • Coke precursors are typically low boiling alkenes, alkynes and / or saturated high molecular weight hydrocarbons.
  • the deposition of the coke or coke precursor causes the activity and / or selectivity of the catalyst is adversely affected.
  • the aim of the regeneration is the removal of the coke or the coke precursor without adversely affecting the physical properties of the catalyst.
  • the coke precursors can be removed by evaporation in the presence of an intergas at elevated temperature (T> 250 ° C.) and / or hydrogenation in the presence of a hydrogen-containing gas mixture and / or combustion in the presence of an oxygen-containing gas mixture.
  • the regeneration of the catalyst can be carried out in-situ or ex-situ, preference is given to in situ regeneration.
  • the inlet temperature for the oxidative regeneration is usually between 350 and 550 ° C.
  • the oxygen concentration of the oxygen-containing gas mixture is usually between 0.1 and 10 vol .-%.
  • the pressure is typically between 0.1 and 10 bar.
  • the oxidative regeneration of the catalyst is carried out in the presence of water vapor.
  • the reaction product obtained by the process according to the invention is rich in hydrogen and aromatic hydrocarbons.
  • the aromatic hydrocarbons formed are separated by conventional methods.
  • the feed used and the water are evaporated in an evaporator at 100 to 400 ° C, this steam brought in a preheater to the desired reaction temperature, preferably at 400 to 700 ° C, in particular at 500 to 600 ° C is located, and then introduced into the reactor.
  • the heating can be done eg in a fired oven. It may be useful to use the heat obtained in the condensation of the product gas obtained at least partially for heating or vaporizing the feed and the water.
  • the reactors used are generally fixed-bed reactors, tube-bundle reactors or fluid-bed reactors.
  • the fixed bed reactor will operate in adiabatic mode or the tube bundle reactor in isothermal mode.
  • the introduction of the heat can take place both inside and outside the reactor.
  • the heat is supplied outside the reactor, this preferably takes place via a heat exchanger.
  • the heat within the reactor by reaction of the hydrogen formed in the aromatization and / or the remaining hydrocarbons and / or the hydrogen formed in the aromatization and / or the remaining hydrocarbons and / or in the aromatization produced methane and / or formed during the aromatization coke with oxygen.
  • air, oxygen and / or an oxygen-containing gas are fed into the reactor.
  • the process according to the invention can be carried out in a reactor, but it is also possible to carry out the reaction in several reactors connected in series (Reactor cascade) to carry out, if necessary, intermediate heating (s) are inserted between the individual reactors.
  • the autothermal procedure by supplying air, oxygen or an oxygen-containing gas or a reactor cascade with intermediate heating is particularly useful if the feed stream contains a larger amount of non-aromatic hydrocarbons, especially if their proportion is> 30 wt .-%.
  • the reaction product obtained according to the process of the invention is passed from the reactor to a heat exchanger where it is cooled.
  • the forming liquid phase which contains the aromatic hydrocarbon, or a mixture of aromatic hydrocarbons, is fed to a phase separator and the organic phase separated from the water phase. If desired, the organic phase containing the aromatic hydrocarbon or a mixture of aromatic hydrocarbons may be further purified, for example by distillation.
  • the present invention relates to the aforementioned catalysts.
  • the preferred embodiments with respect to the catalyst are analogous to those given with respect to the process with respect to the catalyst.
  • the zirconia-containing carrier contains a stabilizer which in turn contains cerium and / or lanthanum.
  • the zirconia-containing support contains up to 1.5% by weight of silica based on the total weight of the catalyst.
  • the catalyst contains as component e) as metal compound only potassium-containing compounds.
  • the catalyst does not contain cesium.
  • the catalyst contains no further promoter.
  • Example 2 Pt, Sn, La, K / ZrO 2 (Inventive) Catalyst (1B) contains 0.6% Pt, 2.4% Sn, 5% La and 1% K.
  • Example 3 Pt, Sn, La, / La-Ce-ZrO 2 (Inventive)
  • the catalyst (1 C) contains 0.6% Pt, 2.4% Sn.
  • Example 4 Pt, Sn, La / La-Ce-ZrO 2 (According to the Invention)
  • the catalyst (1 D) contains 0.6% Pt, 2.4% Sn.
  • Example 5 Pt, Sn, La / La-Ce-ZrO 2 (Inventive)
  • the catalyst (1 E) contains 0.6% Pt and 2.4% Sn.
  • the catalytic tests were carried out in a 100 ml fixed bed reactor, which was filled with 20 ml of catalyst and steatite as inert material.
  • the starting materials mixture of non-aromatic and aromatic hydrocarbons, water
  • the product mixture was condensed out in a separator.
  • the two liquid phases water, organic phase
  • the catalysts were activated before starting the reaction with H 2 at 500 ° C over a period of 1 h.
  • All catalysts were prepared by impregnation to the maximum solvent consumption (incipient wetness). For this purpose, the combined stock solutions of the maximum three starting compounds were combined and diluted with solvent accordingly. Some catalysts were pre-impregnated with bis (ethanol-ammonium) hexahydroxo-platinate (EA-Pt) solution, which was also diluted to give maximum solvent uptake. In a subsequent step, these catalysts were after drying at 80 ° C for several hours with the Sn-oxalate solution and optionally La-nitrate solution again impregnated to the maximum solvent uptake.
  • EA-Pt bis (ethanol-ammonium) hexahydroxo-platinate
  • All catalysts were dried after impregnation for at least six hours at 80 ° C and then calcined at 500 ° C under air for three hours.

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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)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé d'aromatisation d'hydrocarbures non aromatiques présentant au moins 6 atomes de carbone en présence de vapeur d'eau et d'un catalyseur contenant un support d'oxyde de zirconium ainsi que de l'étain et du platine en proportion d'au moins 1/1. Cette invention concerne également le catalyseur susmentionné.
PCT/EP2006/068131 2005-11-06 2006-11-06 Procede d'aromatisation d'hydrocarbures non aromatiques a la vapeur d'eau Ceased WO2007051854A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005053233.0 2005-11-06
DE102005053233A DE102005053233A1 (de) 2005-11-06 2005-11-06 Verfahren zur Aromatisierung von Nichtaromatischen Kohlenwasserstoffen mit Wasserdampf

Publications (2)

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WO2007051854A2 true WO2007051854A2 (fr) 2007-05-10
WO2007051854A3 WO2007051854A3 (fr) 2007-07-26

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009074291A1 (fr) 2007-12-10 2009-06-18 Nxp B.V. Améliorations apportées à systèmes de réception de diversité ou relatives à ceux-ci
CN112742383A (zh) * 2021-02-03 2021-05-04 成都市丽睿科技有限公司 一种金属合金催化剂的制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632503A (en) * 1969-09-10 1972-01-04 Universal Oil Prod Co Catalytic composite of platinum tin and germanium with carrier material and reforming therewith
DE19727021A1 (de) * 1997-06-25 1999-01-07 Basf Ag Verfahren zur Herstellung von C8-Aromaten aus Butenen
DE10047642A1 (de) * 2000-09-26 2002-04-11 Basf Ag Verfahren zur Dehydrierung von Kohlenwasserstoffen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009074291A1 (fr) 2007-12-10 2009-06-18 Nxp B.V. Améliorations apportées à systèmes de réception de diversité ou relatives à ceux-ci
CN112742383A (zh) * 2021-02-03 2021-05-04 成都市丽睿科技有限公司 一种金属合金催化剂的制备方法

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DE102005053233A1 (de) 2007-05-10

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