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WO1996033802A1 - Catalyseur de deshydrogenation et d'aromatisation selectives d'hydrocarbures aliphatiques ou alicycliques - Google Patents

Catalyseur de deshydrogenation et d'aromatisation selectives d'hydrocarbures aliphatiques ou alicycliques Download PDF

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Publication number
WO1996033802A1
WO1996033802A1 PCT/DE1996/000776 DE9600776W WO9633802A1 WO 1996033802 A1 WO1996033802 A1 WO 1996033802A1 DE 9600776 W DE9600776 W DE 9600776W WO 9633802 A1 WO9633802 A1 WO 9633802A1
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Prior art keywords
catalyst
hydrogen
carbon
oxide
sol
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PCT/DE1996/000776
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German (de)
English (en)
Inventor
Heiner Lieske
Dang Lanh Hoang
Henry Preiss
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INSTITUT FüR ANGEWANDTE CHEMIE BERLIN-ADLERSHOF E.V.
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Publication of WO1996033802A1 publication Critical patent/WO1996033802A1/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
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • 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
    • C07C5/412—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
    • 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
    • B01J35/613—10-100 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
    • B01J35/61—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
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • 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
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/18—Carbon
    • 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
    • C07C2523/20—Vanadium, niobium or tantalum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a selective catalyst for the aromatization of aliphatic or alicyclic hydrocarbons with at least 6 carbon atoms in the chain and for the dehydrogenation of alkanes to alkenes, process for the preparation of the catalyst and its use.
  • C 6 -C 8 aromatics such as toluene, ethylbenzene, p-xylene and o-xylene are important aromatic hydrocarbons, which are the main constituents of high-octane fuels and are also used as starting materials for a variety of synthesis reactions in the chemical industry. Flavoring is therefore one of the most important petrochemical processes for upgrading paraffinic hydrocarbons. Because catalysts are indispensable for the technical implementation of the aromatization processes, the development of effective catalysts is a constant requirement for catalysis research. For decades, C 6 -C 8 aromatics have been obtained from hydrocarbon fractions containing mainly C 6 -C 8 paraffins using the known reforming process or its modifications.
  • the object of the invention is to provide new catalysts with high selectivity for aromatization reactions, to provide a process for their preparation and to enable their use in a catalytic aromatization process. Another object is to provide a catalyst for aromatization reactions which enables a high space-time yield.
  • Another object is to provide a catalyst for dehydrogenation reactions, in particular for dehydrogenation reactions from alkanes to alkenes.
  • Another object is to provide a long-lasting catalyst which can be produced from inexpensive raw materials.
  • SUMMARY OF THE INVENTION According to the invention, this object is achieved with a porous composite which is effective as a selective dehydrogenation and aromatization catalyst and comprises at least one oxide of a transition metal of IV., V. or VI. Subgroup of the Periodic Table of the Elements and Carbon, the catalyst having a BET surface area of 20 to 1000 m 2 / g. O 96/33802 PO7DE96 / 00776
  • the catalyst has the ability to reversibly absorb hydrogen in the temperature range 400 to 700 ° C.
  • the catalyst predominantly has no strongly acidic or strongly basic or strongly acidic and strongly basic centers on its surfaces.
  • the invention further relates to a catalyst as it is obtained when (i) a mixture of at least one compound from the group of oxides or mixed oxides or the compounds of a transition metal of IV., V. or VI. Subgroup and
  • Another object of the invention is a catalyst as it is obtained when from (i) an aqueous solution or an aqueous-alcoholic solution or a sol of a pyrolyzable carbon compound, (ii) an aqueous or aqueous-alcoholic sol with at least one Oxide, hydroxide, alkoxide or an oxygen acid of a transition metal of VI., V. or VI. Subgroup and (iii) a stabilizing complexing agent, a mixed sol is formed by a sol-gel process, this is formed after removal of the solvent and drying and is pyrolyzed at a temperature of 800 ° C. to 1400 ° C.
  • the molded body formed contains oxide particles, has a surface determinable by the BET method in the range from 30 to 300 m 2 / Qf and in the temperature range from 400 to 700 ° C the ability to reversible uptake of hydrogen.
  • the catalyst for the selective dehydrogenation and aromatization of aliphatic or alicyclic hydrocarbons comprises a porous composite which consists of at least one oxide of a transition metal of IV., V. or VI. Subgroup of the periodic table of elements and carbon consists, wherein the catalyst has a surface by the BET method (J.Amer.Chem.Soc. 60 (1938) 309) of 20 to 1000 m 2 / g.
  • Suitable transition metal elements are Ti, Zr, Hf, V, Nb, Ta, Cr, W or Mo, in particular zirconium, titanium, tantalum or niobium. Mixtures of these elements can also be used.
  • the surface determined by the BET method (J.Amer.Chem.Soc. 60 (1938) 309), is preferably in the range from 50 to 900 m 2 / g, in particular 100 to 800 m 2 / g.
  • a composite is a coked product in which either the oxide of the transition metal is incorporated in a carbon framework structure or is present thereon in a fine, as uniform as possible distribution, or in which carbon is incorporated in a framework structure of the transition metal oxide . It is preferably an unsupported composite of the structure mentioned, but supports can also be used, for example those made from one of the less effective oxides of the transition metals according to the invention or other conventional supports such as A1 2 0 3 or SiO 2 . As essential feature for the identification of an effective structure of the composite was found that this in the temperature range 400 to 700 * C has the ability to reversi ⁇ blen uptake of hydrogen.
  • the catalyst on its surfaces predominantly has no strongly acidic or strongly basic or strongly acidic and strongly basic centers. This resulted, among other things, in acidity measurements using the temperature raturation-programmed desorption using ammonia (TPDA) or carbon dioxide.
  • TPDA temperature raturation-programmed desorption using ammonia
  • carbon dioxide carbon dioxide
  • advantageously effective composites have a porous framework structure and the pores are in the range from 1.5 to 5 nm, preferably the most common pore radius is between 1.5 and 3 nm.
  • the porous framework structure can also deviate therefrom most common pore radii.
  • the ability of the catalyst to absorb hydrogen and the ability to essentially completely release it again after subsequent purging with inert gas is an important distinguishing feature with which the suitability according to the invention is qualitative even during production, without corresponding catalytic tests can be predicted.
  • This property of the catalyst has not yet been elucidated in its connection with the catalytic activity, but is a means suitable for predicting the activity according to the invention and thus for the development of catalysts within the scope of the invention.
  • the selective dehydrogenation and aromatization catalyst can generally be prepared in such a way that
  • the hydroxides, alkoxides or oxygen acids of the elements Ti, Zr, Hf, V, Nb, Ta, Cr, W or Mo are used, in particular those of zirconium, titanium, hafnium, tantalum or niobium.
  • the sol-gel process in which
  • a mixed sol is formed from one or more stabilizing complexing agents, converted into a gel by removal of the solvent and drying, brought into a form which can be used practically as a catalyst and thermally at about 800 * C to 1400 * C is treated under an inert gas atmosphere in order to obtain composite molded articles with a porous carbon structure by pyrolysis of the carbon compounds together with the transition metal oxides.
  • a coked product (composite) is obtained from a hydrosol, which is present as a hydrogel after drying, and the subsequent pyrolysis, in which the transition metal compound (s) are present in a fine distribution, preferably uniform distribution, in a carbon skeleton is or are installed.
  • pechic acid e.g. prepared according to FUEL, 73 (1994) - 243
  • carbohydrate such as sucrose.
  • Low viscosity polyacrylic acid can also be used.
  • complexing agents serve to precipitate poorly soluble transition metal compounds from the solution or to avoid the sol.
  • the addition of the complexing agents is therefore advantageously carried out already in the hydrolysis of a hydrolyzable compound of these elements, preferably an alkoxy compound, or in the peptization of a transition metal oxide or hydroxide.
  • Advantageous transition metal compounds are, for example, those which can form solutions or brine. These include, for example, oxo acids, alkoxides, inorganic salts of organic acids, sols of peroxy acids, e.g. Zirconium (IV) propoxide, niobium (V) ethoxide, tetrabutyl orthotitanate, tetraisopropyl orthotitanate, niobium oxide hydrate, tantalum (V) ethoxide, molybdenum (VI) oxide, vanadium (V) oxide, tungstic acid etc.
  • oxo acids e.g. Zirconium (IV) propoxide, niobium (V) ethoxide, tetrabutyl orthotitanate, tetraisopropyl orthotitanate, niobium oxide hydrate, tantalum (V) ethoxide, molybdenum (VI) oxide, vana
  • a further possibility for producing the composite consists of a strongly carbon-old substance, such as activated carbon or certain porous polymers or polymer powder, with an aqueous and / or alcoholic solution of oxides, hydroxides, alkoxides or oxygen acids of transition metals of VI. V. or VI. Verbindun- this gene to impregnate subgroup of the Periodic Table of the Elements or mixtures and thereafter thermal treatment in inert gas at temperatures Tem ⁇ 800-1400 * C. This gives surfaces of the catalyst up to 850 m 2 / g and above.
  • Carbon is understood to mean both a highly carbon-containing substance and pure carbon up to graphitic carbon, such as are produced in further temperature treatment.
  • the oxides formed are often crystalline and can be detected by X-ray diffraction.
  • an inert gas such as argon or helium can be used as the inert gas for the thermal treatment.
  • the shaped composite according to the invention is subjected to a hydrogen treatment either alone with hydrogen gas or with a gas which contains hydrogen. This hydrogen treatment is carried out over a period of 5 minutes to several hours. This treatment is preferably carried out for 30 to 90 minutes. Without this process measure or if the hydrogen saturation is too low, the catalytic activity is not sufficient, ie the yield of target products is too low.
  • Haldrogen-containing gas is understood to mean a gas in which the part which is not hydrogen essentially does not react with the hydrogen and the catalyst under the given conditions.
  • the catalyst has the property of completely releasing the hydrogen taken up when, for example, an inert gas is passed through it. This property, which is important for the purpose according to the invention, is measured by the so-called temperature-programmed reduction (TPR) and the temperature-programmed desorption of hydrogen (TPDH).
  • TPR temperature-programmed reduction
  • TPDH temperature-programmed desorption of hydrogen
  • the catalyst according to the invention is suitable for the selective catalytic production of aromatics from aliphatic and / or alicyclic hydrocarbons and for the dehydrogenation of alkanes to alkenes.
  • the invention therefore also relates to the use of the selective catalysts described above for the catalytic conversion of aliphatic or alicyclic hydrocarbons having at least 6 carbon atoms in the longest chain into benzene or alkyl-substituted benzenes.
  • the catalyst is particularly suitable for the catalytic conversion of saturated or unsaturated hydrocarbons having 6 to 12 carbon atoms in the chain.
  • the saturated hydrocarbons are at least 6 to 12, preferably at least 6 to 10, in particular at least 6 to 8 carbon atoms preferred in the longest chain.
  • n-hexane in benzene, n-heptane in toluene and n-octane in o-xylene and ethylbenzene and their mixtures are converted with great selectivity.
  • this new class of aromatization catalysts for example when converting n-octane to alkyl aromatics with an inventive zirconium oxide / C-containing catalyst, increases the C 6 -C B aromatics selectivity reached from 61 to 84%.
  • the resulting aromatic fraction in the catalyst according to the invention consisted of approximately 85% o-xylene and ethylbenzene and only 4.4% of the physiologically questionable benzene. In contrast, only 33.4% C ⁇ aromatics were formed on Pt / Al 2 0 3 , but about 30% benzene.
  • the aromatic fraction In the n-hexane conversion with a Zr0 2 / C catalyst, the aromatic fraction consists of 100% benzene, while a platinum catalyst forms a mixture of C 6 , C 7 and C 8 aromatics.
  • the process according to the invention for the production of aromatic hydrocarbons is carried out in complete analogy to the customary reforming and aromatization processes (for example Gates et al., Chemistry of Catalytic Processes, NY 1979; Ullmans Encyclopedia of Industrial Chemistry, Volume 10, Verlag Chemie, Weinheim, 1975 ) carried out.
  • the reaction temperatures are advantageously 450 to 580 ° C, preferably 500 to 560 ° C, and the reaction pressure up to 30 bar, preferably 1 - 20 bar.
  • the semi-regenerative or cyclic reforming processes described in the literature can also be used in adiabatic working fixed-bed reactors.
  • the space velocity LHSV volume of liquid hydrocarbon per volume of catalyst and hour
  • LHSV volume of liquid hydrocarbon per volume of catalyst and hour
  • the space velocity LHSV can be between 0.8 and 3 h "1 , preferably about 1 h " 1 , and the H 2 / hydrocarbon molar ratio between 4 and 15 is preferred 10 - 12, can be varied.
  • Axial or radial flow reactors can be used. After leaving the reactor, the reaction mixture is cooled in heat exchangers, whereupon formed and unreacted hydrocarbons are condensed. Phase separation then takes place in the gas separator.
  • a very high percentage of the liquid phase consists of aromatic hydrocarbons, which are separated and purified by conventional methods, for example by distillation.
  • the gas phase consists of 70-85% hydrogen, which can be circulated via compressors.
  • the new catalysts show outstanding selectivity and an increase in yield when converting n-alkanes into aromatic compounds. They are also particularly economical because of their ease of manufacture and the relatively inexpensive components.
  • Another advantage is that the formation of the physiologically questionable benzene can be almost completely suppressed with starting products with 7 carbon atoms in the chain. Furthermore, the yield of valuable materials is increased to the disadvantage of by-products that would otherwise occur.
  • the catalysts according to the invention can also be used for the dehydrogenation of alkanes to alkenes, in particular for the dehydrogenation of C 3 -C 5 -alkanes.
  • i-butene is obtained from i-butane after catalytic conversion in very good yield.
  • the invention will be explained in more detail below by examples.
  • the catalysts of the invention are characterized as follows: "transition metal oxide / C source / temperature of the thermal treatment in Ar"
  • C sources P (pechic acid), (S) sucrose, AK (activated carbon);
  • a "zirconium oxide sol” was produced by hydrolysis of 0.01 mol of zirconium (IV) propylate dissolved in 12.5 ml of methanol and 1.5 g of acetylacetone with 25 ml of distilled water with ice cooling. posed. A solution of 0.32 g of "pitch acid”, 0.32 g of glycerol and 2.5 ml of distilled water in 10 ml of methanol was added dropwise to this sol while stirring with ice cooling. Pechic acid had previously been prepared according to FUEL, 73 (1994) 243.
  • the methanol was largely evaporated by heating to about 60 * C.
  • the binary gel formed can be deformed after partial drying by extrusion or tableting. It was transferred to a xerogel by drying at 110'C.
  • the xerogel can be crushed into fragments of considerable strength as desired.
  • the xerogel was thermally treated at 900 * C in an argon atmosphere for 1 h. Shape and strength are retained.
  • the catalyst ZrO 2 / P / 900 obtained has a BET specific surface area of 143 m 2 and a most common pore radius of 1.9 nm. According to the X-ray structure analysis, the zirconium is present as a crystalline oxide with a predominantly tetragonal structure. The average crystallite size is 6.8 nm.
  • Example 2
  • the ZrO 2 / S / 900 catalyst obtained has a BET specific surface area of 126 m 2 and a most common pore radius of 2.4 nm. According to the X-ray structure analysis, the zirconium is predominantly as a crystalline oxide tetragonal structure. The average crystallite size is 4.5 nm.
  • the catalyst has a specific surface area of 840m 2 / g.
  • Example 4 Characterization of a Catalyst According to the Invention by Measuring the Hydrogen Absorption Capacity Using Temperature-Programmed Reduction (TPR) and Temperature-Programmed Desorption of Hydrogen (TPDH)
  • TPR and TPDH measurements were carried out in an apparatus corresponding to that described by Robertson et al. [J. Catal. 37 (1975) 424].
  • 500 mg of the catalyst ZrO 2 / P / 900 were thermally treated in an argon stream at 300'C lh. After cooling to room temperature, the sample was heated for the purpose of a first absorption of hydrogen in a 5% H 2 -in-Ar-stream at a heating rate of locomotive / min to a final temperature of 750 * C. The sample was then cooled to room temperature in a H 2 / Ar stream. The H 2 / Ar stream was then replaced by Ar and the sample in the Ar stream was linearly heated at 1OK / min to 800 ° C.
  • the sample was again heated linearly in the 5% H 2 -in-Ar current up to 750 ° C.
  • the hydrogen consumption which occurred was detected by cathometry and gave the TPR result, characterized by the hydrogen consumption given in Table 1 and the peak maximum temperature was linearly heated in the Ar stream to 800 ° C.
  • the amount of desorbing the hydrogen was again recorded continuously and gave the TPDH result in Table 1.
  • the TPR and TPDH results are a measure of the reversible hydrogen uptake and release capacity of the catalyst in the range of the reaction temperatures of the catalytic reactions.
  • Catalytic testing of a catalyst according to the invention was carried out in a temperature-controlled quartz flow reactor with a diameter of 8 mm, which was heated by means of a radiation furnace.
  • a sample of 500 mg of the catalyst ZrO 2 / P / 900 prepared in accordance with Example 1 and a grain size of 0.3 mm to 0.8 mm was treated in the reactor for 1 h at 550 ° C. in flowing hydrogen. Thereafter, it was treated with hydrocarbon at the same temperature ⁇ Substance of saturated hydrogen flow, see Tables 2 and 3, over the catalyst. After 1 h the reaction reached a steady state.
  • reaction products were carried out on-line gas chromatography, the gas chromatography separation of the aromatics and the other ⁇ - ⁇ - Hydrocarbons were carried out on a benton 34 column and the low-boiling C.-C 4 reaction products on an alumina column, and the degree of conversion U and the selectivity S were calculated accordingly
  • This catalyst was prepared analogously to Example 1, characterized analogously to Example 4 and examined catalytically analogously to Example 5.
  • the catalyst has a BET surface area of 308m 2 , a most common pore radius of 5.0nm and a Ti0 2 particle size of 4.7nm.
  • This catalyst was prepared analogously to Example 2, characterized analogously to Example 4 and analogously to Example 5 examined catalytically.
  • the catalyst has a BET surface area of 126m 2 , a most common pore radius of 2.4nm and a Zr0 2 particle size of 4.5nm.
  • This catalyst was prepared as described in Example 3, characterized analogously to Example 4 and examined catalytically analogously to Example 5.
  • the catalyst has a BET surface area of 840m 2 .
  • This catalyst was prepared analogously to Example 1, characterized analogously to Example 4 and examined catalytically analogously to Example 5.
  • the catalyst has a BET surface area of 185 m 2 .
  • This comparative catalyst was a classic reforming catalyst which was produced by impregnating a ⁇ -Al 2 0 3 with a specific surface area of 300 m 2 / g with hexachloroplatinic (IV) acid. The platinum content was 0.5%. After the impregnation, the catalyst was calcined in air at 500 ° C. and then reduced in hydrogen for 1 hour. The catalytic testing was carried out analogously to Example 5.
  • This catalyst is a classic catalyst for aromatizing light hydrocarbons.
  • the catalyst was prepared by impregnating HZSM-5 with a 0.05 molar aqueous solution of Ga (N0 3 ) 3 . He was then heated in air gradually to 500 * C and lh left at 500 "C. In this form it was used as a catalyst.

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

Abstract

L'invention concerne un catalyseur sélectif d'aromatisation d'hydrocarbures aliphatiques ou alicycliques ayant au moins 6 atomes de carbone dans la chaîne la plus longue, et de déshydrogénation d'alcanes en alcènes. Le nouveau catalyseur est un composite poreux composé d'un oxyde d'un métal de transition du sous-groupe IV, V ou VI de la classification périodique des éléments, et de carbone, le catalyseur ayant une surface comprise entre 20 et 1000 m2/g. Le procédé se caractérise en ce qu'un mélange d'oxydes, d'hydroxydes, d'alcoxydes ou de composés d'un métal de transition pouvant être convertis en oxyde, ainsi que du carbone sont soumis à un traitement thermique dans une plage de températures allant de 800 à 1400 °C, pour former un composite poreux, et sont ensuite traités avec de l'hydrogène ou un gaz contenant de l'hydrogène. L'invention concerne également la production de ce type de catalyseurs par procédé sol-gel. Ces catalyseurs s'utilisent de préférence dans la production de toluène, d'o-xylène et d'éthylbenzène ayant une excellente sélectivité.
PCT/DE1996/000776 1995-04-28 1996-04-26 Catalyseur de deshydrogenation et d'aromatisation selectives d'hydrocarbures aliphatiques ou alicycliques WO1996033802A1 (fr)

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DE19516318.4 1995-04-28
DE19516318A DE19516318A1 (de) 1995-04-28 1995-04-28 Selektiver Aromatisierungskatalysator, Verfahren zur Herstellung und Verwendung

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DE19612000A1 (de) * 1996-03-18 1997-09-25 Inst Angewandte Chemie Berlin Katalysator zur Aromatisierung von aliphatischen und alicyclischen Kohlenwasserstoffen
DE19616736A1 (de) * 1996-04-26 1997-11-06 Basf Ag Katalysator zur selektiven Aromatisierung
DE19616738A1 (de) * 1996-04-26 1997-10-30 Basf Ag Katalysator und seine Verwendung zur Dehydrierung von paraffinischen/naphthenischen Kohlenwasserstoffen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865750A (en) * 1971-12-27 1975-02-11 Exxon Research Engineering Co Titanium carbide catalysts, and the catalyst compositions
EP0120798A1 (fr) * 1983-03-25 1984-10-03 Eurotungstene Poudres S.A. Catalyseurs de reformage à base de carbures de tungstène et de molybdène, et leur méthode d'utilisation
US5384027A (en) * 1993-11-09 1995-01-24 Akzo Nobel N.V. Reforming hydrocarbons using transition metal carbide catalyst and gaseous oxygen
WO1995032150A1 (fr) * 1994-05-20 1995-11-30 Akzo Nobel Nv Preparation d'un catalyseur au carbure metallique situe sur un support au carbone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865750A (en) * 1971-12-27 1975-02-11 Exxon Research Engineering Co Titanium carbide catalysts, and the catalyst compositions
EP0120798A1 (fr) * 1983-03-25 1984-10-03 Eurotungstene Poudres S.A. Catalyseurs de reformage à base de carbures de tungstène et de molybdène, et leur méthode d'utilisation
US5384027A (en) * 1993-11-09 1995-01-24 Akzo Nobel N.V. Reforming hydrocarbons using transition metal carbide catalyst and gaseous oxygen
WO1995032150A1 (fr) * 1994-05-20 1995-11-30 Akzo Nobel Nv Preparation d'un catalyseur au carbure metallique situe sur un support au carbone

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