EP1919614A1 - Catalyseur pour deshydrater ou hydrater des hydrocarbures contenant une substance catalytique secondaire - Google Patents

Catalyseur pour deshydrater ou hydrater des hydrocarbures contenant une substance catalytique secondaire

Info

Publication number
EP1919614A1
EP1919614A1 EP06792498A EP06792498A EP1919614A1 EP 1919614 A1 EP1919614 A1 EP 1919614A1 EP 06792498 A EP06792498 A EP 06792498A EP 06792498 A EP06792498 A EP 06792498A EP 1919614 A1 EP1919614 A1 EP 1919614A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
catalyst material
catalysts
hydrogenation
dehydrogenation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP06792498A
Other languages
German (de)
English (en)
Inventor
Christian Walsdorff
Christophe Houssin
Gerald Vorberg
Reinhard KÖRNER
Otto Hofstadt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1919614A1 publication Critical patent/EP1919614A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a catalyst for the dehydrogenation or hydrogenation of hydrocarbons containing 10 to 70 wt .-% ground, secondary catalyst material of a used (de) hydrogenation catalyst containing iron oxide and 30 to 90 wt .-% of the corresponding fresh catalyst material containing iron oxide, wherein the iron oxide of fresh catalyst material predominantly in the form of hematite or potassium ferrite phases. Furthermore, the invention relates to a process for the preparation of the catalyst according to the invention. Furthermore, the invention relates to a process for the dehydrogenation or hydrogenation of hydrocarbons using the catalyst according to the invention.
  • DD 268 631 A1 describes dehydrogenation catalysts, wherein the catalysts
  • Waste 1 and 2 arise, for example, in the production of pigments for data carriers due to the high quality requirements with regard to the magnetic properties.
  • a conversion of about 40% with a selectivity of about 92% is achieved in the dehydrogenation of ethylbenzene to styrene.
  • WO 94/11104 discloses a process for the preparation of iron, potassium and cerium containing dehydrogenation catalysts from such used catalysts by milling the used material, optionally cleaning, restoring the original effect by adjusting the composition and restoring the external form by adding the ground used Material is added to an effective amount of potassium and such an amount of cerium, so that the total amount of cerium is higher than the original amount.
  • the used material is calcined prior to grinding in the presence of oxygen.
  • the process described dehydrogenation catalysts are obtained which in the dehydrogenation of ethylbenzene to styrene at a conversion of 70% reach a selectivity of 94 to 95%.
  • DE 103 05 650 A1 describes the regeneration of mixed oxide catalysts which are used in the ammoxidation for the preparation of nitriles.
  • the deactivated catalyst is optionally ground and calcined at 300 to 900 0 C under sow erstoff.
  • the described (de) hydrogenation catalysts are typically offered in the form of strands, rings, tablets, ring tablets, extrudates, honeycomb bodies or similar shaped bodies.
  • the active composition of the catalysts mentioned contains predominantly metals selected from the group consisting of iron, alkali compounds, in particular potassium, molybdenum, magnesium, calcium, cerium, tungsten, titanium, vanadium, copper, manganese, nickel, zinc, palladium, platinum, cobalt, aluminum , Tin, silicon, lead, ruthenium, silver, gold, zirconium, rhodium, lanthanum, chromium, cadmium or barium.
  • the fresh feedstocks in the form of metal oxides, nitrates, carbonates, hydroxides or the like are mixed directly in a mixer, kneader or MixMuller. Furthermore, the starting materials can also be slurried in a spray mixture and processed in a spray dryer into a spray powder. The extrudable mass is then extruded, dried and calcined.
  • the fresh starting materials are obtained via precipitation reactions, processed in a spray dryer into a spray powder, calcined and deformed, or first deformed and then calcined.
  • the catalyst When a catalytic converter is operated after a period of typically two to five years in a technical plant, such as isoprene, butadiene or styrene Plant, the catalyst has undergone a number of changes.
  • the removed catalyst usually has iron oxide in a reduced form, ie as magnetite.
  • Part of the catalysts removed is usually depleted of potassium compounds, while in other areas, in particular in the interior of the shaped catalyst body, an accumulation of potassium compounds may also be present in the form of separate deposits between the catalyst strands.
  • the potassium is typically in the form of potassium carbonate or potassium bicarbonate.
  • the degraded catalysts usually have virtually no organic hydrocarbons or coke deposits, ie carbon, which is not present as carbonate or bicarbonate on.
  • the Cerkistallitility the expansion catalysts is about 40 to 60 nm.
  • the shaped catalyst bodies are often damaged by the mechanical stresses during installation, operation and removal. Furthermore, the catalyzed catalyst may contain a high proportion of dust or debris.
  • the catalysts prepared using secondary catalyst material should have comparable properties, in particular with regard to activity, selectivity and, in particular, mechanical hardness, as are the catalysts of the prior art.
  • the secondary catalyst material should be directly usable without the addition of doping elements.
  • the invention relates to catalysts for the dehydrogenation or hydrogenation of hydrocarbons containing 10 to 70 wt .-% ground, secondary catalyst material of a used (de) hydrogenation catalyst containing iron oxide and 30 to 90 wt .-% of the corresponding fresh catalyst material containing iron oxide, wherein the iron oxide of the fresh catalyst material is present predominantly in the form of hematite or potassium ferrite phases.
  • secondary catalyst material is understood in the present invention to be used / used / deactivated, optionally treated catalyst material, and the secondary catalyst material has thus already been incorporated into a chemical plant which operates the chemical plant for a period of several days to several years
  • the secondary catalyst material was operated for a typical lifetime of (de) hydrogenation catalysts of 1 to 3 years.
  • the secondary catalyst material advantageously has no organic hydrocarbons or coke deposits.
  • such deposits should advantageously constitute less than 2% by weight, preferably less than 1% by weight, in particular less than 0.1% by weight, based on the secondary catalyst material.
  • a small amount of deposits can be achieved by a special shutdown of the isoprene, butadiene or styrene plant known to those skilled in the art.
  • the temperature is lowered to 580 to 610 0 C when shutting down a system.
  • the ethylbenzene feed is reduced to give a steam / ethylbenzene weight ratio of at least 2/1.
  • the temperature is lowered further to 550 to 575 ° C and at the same time the ethylbenzene feed is gradually reduced and finally switched off.
  • the nitrogen cycle is switched on and the temperature continues to be countersunk to a minimum of 360 0 C, preferably from 400 0 C.
  • the temperature is lowered to 50 0 C under nitrogen. At least 30 0 C, preferably at about 50 0 C controlled air is added.
  • thermocouples which detect local temperature increases, ie re-oxidation. If no temperature increases can be detected, then the further addition of air can take place until no further temperature increases are more noticeable. Finally, it is cooled with air and nitrogen or only with air.
  • the recovered secondary catalyst material is subjected to a thermal treatment under oxygen-containing atmosphere prior to reuse.
  • the thermal treatment is advantageously carried out at temperatures of 100 to 1500 0 C, preferably from 300 to 1200 0 C, more preferably from 500 to 1000 0 C, further preferably from 700 to 1000 0 C and in particular from 850 to 1000 0 C, performed.
  • the thermal treatment is carried out for a period of 30 minutes to 10 hours, preferably for a period of 1 to 3 hours.
  • the iron is advantageously present after the thermal treatment substantially in the form of hematite, magnetite and potassium ferrite phases.
  • the secondary catalyst material therefore advantageously has iron predominantly in the form of Hematite and magnetite, where x is advantageously between 1 and 11 and y is advantageously between 2 and 17.
  • Preferred potassium ferrite phases are K2FeioOi6 and KFeÜ2.
  • the iron oxide is advantageously present at 15 to 85% by weight, based on the sum of the iron oxides, in the form of K 2 Fe x O y , advantageously from 20 to 60% by weight.
  • the remaining iron oxides are advantageously present as hematite and / or magnetite.
  • the secondary catalyst material advantageously has a cerium crystallite size of 15 to 90 nm, preferably 40 to 60 nm.
  • oxygen-containing gas air is preferably used.
  • their composition may vary within the limits known to those skilled in the art. Particular preference is given to using lean air.
  • the thermal treatment may be carried out batchwise or continuously in various apparatuses, for example in ovens or rotary kilns. Preferably, the thermal treatment is carried out continuously in rotary tubes. In particular, in heavily pulverized or powder-containing expansion catalyst, it may be useful to carry out the calcination in a rotary kiln equipped with knockers. Furthermore, the oxidative treatment may also be carried out prior to the removal of the secondary catalyst material directly in the production plant.
  • the secondary catalyst material is advantageously ground, if appropriate after a thermal treatment, in suitable mills.
  • the material can be comminuted, for example, with a spiral jet mill.
  • the grinding gas pressure during grinding is typically 1 to 10 bar.
  • the grinding throughput is usually at 1 to 30 kg / h.
  • the mean particle diameters have a value in the range from 1 to 700 ⁇ m, preferably 5 to 500 ⁇ m, in particular 10 to 200 ⁇ m.
  • the milled secondary catalyst powder can then be used for the preparation of new catalysts.
  • the catalyst according to the invention advantageously contains 15 to 70% by weight ground, secondary catalyst material, based on the total catalyst material, and 30 to 85% by weight of the corresponding fresh catalyst material, based on the Total catalyst material, preferably 25 to 65 wt .-% ground, secondary catalyst lysatormaterial and 35 to 75 wt .-% of the corresponding fresh catalyst matrials, in particular 35 to 55 wt .-% ground, secondary catalyst material and 45 to 65 parts by weight. % of the corresponding fresh catalyst material.
  • the catalyst according to the invention advantageously contains exclusively secondary and fresh catalyst material in the stated ratios.
  • the bulk density of the catalyst according to the invention is advantageously 1.2 to 2 kg / l, in particular 1.3 to 1.7 kg / l.
  • the shaking weight is advantageously 1 to 1.7 kg / l, in particular 1.1 to 1.5 kg / l.
  • the catalytic composition of the fresh feeds corresponds to the catalytic composition known in the art for (de) hydrogenation catalysts.
  • the amount and the typical composition of the fresh feedstock can be changed.
  • the catalysts according to the invention advantageously contain starting materials in the form of oxides, nitrates, carbonates, hydroxides and the like, preferably in the form of oxides, in particular iron, preferably as iron oxide, advantageously in an amount of 40 to 90 wt .-% based on the sum of all starting materials , Furthermore, the catalysts of the invention advantageously contain alkali metal compound (s), preferably potassium compound (s) such as potassium oxide, suitably in an amount of 1 to 40 wt .-% based on the sum of all starting materials. Typically, the catalysts of the invention advantageously contain a number of promoters, depending on their field of use.
  • the catalyst according to the invention is particularly suitable for the dehydrogenation of hydrocarbons which have at least one saturated functional group, for example alkenes to the corresponding 1,3-alkadienes, preferably alkylaromatic compounds to the corresponding alkenylaromatic compounds.
  • Suitable alkylaromatic compounds are all aromatic and heteroaromatic alkyl compounds, preferred are those in which the alkyl radical is unbranched or branched and contains two to six carbon atoms.
  • Suitable aromatic radicals are mono-, di- or trinuclear, preferably mono- or binuclear, particularly preferably monocyclic aromatics.
  • isopropylbenzene cumene
  • ethylbenzene 1,1-diphenylbenzene and 1,2-diphenylethane
  • bibenzyl preferably isopropylbenzene (cumene), ethylbenzene and 1,1-diphenylbenzene, particularly preferably ethylbenzene.
  • heteroaromatic radicals are mono-, di- or trinuclear, preferably one or two- Ruminent, particularly preferably mononuclear, five-membered heteroaromatic compounds having one to three nitrogen atoms and / or one oxygen or sulfur atom, mono-, di- or trinuclear, preferably mononuclear or dinuclear, particularly preferably mononuclear, six-membered heteroaromatic compounds having one to three nitrogen atoms as heteroatoms, in particular pyridines, such as 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine and 5-ethyl-2-methylpyridine, preferably 2-ethylpyridine and 5-ethyl-2-methylpyridine.
  • pyridines such as 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine and 5-ethyl-2-methylpyridine, preferably 2-ethylpyridine and 5-ethyl-2-methylpyridine.
  • Suitable promoters for the catalysts according to the invention are, in addition to cerium compounds, compounds of calcium, magnesium, molybdenum, tungsten, chromium and titanium.
  • Vanadium, copper, manganese, nickel, zinc, palladium, platinum, cobalt, aluminum, tin, silicon, lead, ruthenium, silver, gold, zirconium, rhodium, lanthanum, chromium, cadmium, barium or mixtures thereof are also suitable as further promoters .
  • Copper oxide corresponding to 0 - 80 wt .-% CuO, aluminum corresponding to 0 - 80 wt .-% Al2O3 and iron, corresponding to 0 - 90 wt .-% Fe 2 O 3 furthermore, copper oxide corresponding to 0 - 80 wt .-% CuO, aluminum corresponding to 0 - 80 wt .-% Al2O3 and iron, corresponding to 0 - 90 wt .-% Fe 2 O 3 further
  • the dehydrogenation catalyst according to the invention particularly preferably has the following composition with respect to the sum of the fresh and secondary starting materials:
  • Iron corresponding to 40-90% by weight of Fe 2 O 3
  • potassium corresponding to 1-40% by weight as K 2 O
  • Cerium corresponding to 1-25% by weight of Ce 2 O 4 , in particular 5-15% by weight of Ce 2 O 4 , magnesium, corresponding to 0-10% by weight of MgO,
  • Vanadium corresponding to 0 - 10 wt .-% V2O5 wherein said components add up to 100 wt .-%.
  • the weight ratio of potassium (calculated as K 2 O) to iron oxide (calculated as Fe 2 U 3) is generally 0.01: 1 to 2: 1, preferably from 0.1: 1 to 1: 1.
  • the catalysts preferably contain further promoters (calculated as oxides) in a weight ratio to the iron oxide of from 0.01: 1 to 1: 1, preferably from 0.02: 1 to 0.5: 1.
  • no doping elements are added to the secondary catalyst material.
  • the invention further relates to catalyst beds which consist of at least 25% by weight of catalyst according to the invention, based on the total amount of catalyst of the corresponding catalyst bed.
  • the catalyst beds consist of at least 30% by weight, preferably at least 50% by weight, of catalysts according to the invention.
  • the catalysts of the invention may be uniformly mixed with prior art catalysts dispersed throughout the catalyst bed or concentrated at one or more locations.
  • a catalyst system consisting of several reactors, i. consists of several catalyst beds, for example, one or more reactor (s) is filled with the catalysts of the invention and the remaining reactors with the catalysts of the prior art. Preference is given to using exclusively catalysts according to the invention.
  • the invention further relates to the process for the preparation of the catalyst according to the invention, which is characterized in that secondary catalyst material of a used (de) hydrogenation catalyst is optionally calcined and then ground and then in a ratio of 1: 9 to 7: 3 with fresh starting materials of the corresponding (De) hydrogenation catalyst is mixed, deformed and calcined.
  • the secondary catalyst material prior to milling and mixing with the fresh feedstock to a thermal treatment under oxygen atmosphere at 100 stoff Anlagenr is advantageously subjected to 1500 0 C.
  • the mixing of the secondary catalyst powder with the fresh starting materials is advantageously carried out in a mixer, for example in a Mix-Müller.
  • the shaping and calcination is expediently carried out as described in the prior art (see, for example, DE-A 101 54 718).
  • the catalysts according to the invention can be used as starting materials in addition to the secondary catalyst powder compounds of the promoters, such as those present in the finished catalyst, or compounds that convert during the manufacturing process in compounds as present in the finished catalyst.
  • Auxiliaries may also be added to the starting materials in order to improve processability, mechanical strength or pore structure. Examples of such substances are potato starch, cellulose, stearic acid, graphite and / or Portland cement.
  • the starting materials can be mixed directly in a mixer, kneader or preferably a Mix-Muller.
  • the starting materials can also be slurried in a spray mixture and processed in a spray dryer into a spray powder.
  • the starting materials are preferably processed in a Mix-Muller or kneader with the addition of water to form an extrudable mass.
  • the extrudable mass is then extruded, dried and calcined.
  • Preferred catalyst forms are strands, rings, tablets, ring tablets, extrudates or honeycombs. Particular preference is given to shaped catalyst bodies or catalyst extrudates having a diameter and a height of less than or equal to 10 mm.
  • Preferred strand molds comprise catalyst spheres with a diameter of less than 6 mm or catalyst honeycomb bodies with a cell diameter of less than 5 mm or extrudates with 2 to 10 mm diameter, in particular 2.5 to 6 mm.
  • the cross-section of the extrudates may be round or in other forms.
  • Particularly preferred are extrudates with rotationally symmetrical cross-section, in particular with a diameter of 2 to 4 mm, preferably of 3 mm, and extrudates with a star-shaped or those with a gear-toothed ("toothed-wheel") cross-section, in particular with diameters of 3 to 7, preferably 3.5 mm, 4.5 mm or 6 mm.
  • the shaping of the catalysts can also be achieved by a
  • the extruded or optionally tabletted shaped catalyst bodies are then usually dried and subjected to calcination.
  • the drying is preferably carried out on a belt dryer at temperatures between 100 and 200 0 C.
  • the calcination is preferably carried out in a rotary kiln at temperatures between 500 and 1000 ° C., preferably between 700 and 1000 ° C., in particular between 800 and 950 ° C., and particularly preferably between 850 and 900 ° C.
  • carbonate-containing feedstocks convert to oxides. Potassium and iron oxides typically form mixed potassium ferrite crystal structures in the most preferred temperature range.
  • the dehydrogenation of hydrocarbons can be carried out by all methods known to those skilled in the art. Preference is given to the dehydrogenation of alkylaromatics to alkenylaromatics in adiabatic or isothermal processes, in particular in US Pat adiabatic method.
  • the reaction is usually distributed to several series-connected reactors, preferably radial flow reactors. Preferably, two to four reactors are connected in series. In each reactor is a fixed bed with dehydrogenation catalysts.
  • ethylbenzene In the dehydrogenation of ethylbenzene to styrene, as is generally practiced today in so-called adiabatic multi-stage method, is typically ethylbenzene together with water vapor, advantageously in an amount of less than 30 wt .-% based on ethylbenzene, to temperatures around 500 0 C. heated by means of a heat exchanger and mixed directly before entering the first reactor with superheated steam from a steam superheater, so that the desired inlet temperature in the first reactor is usually between 600 and 650 0 C.
  • the mass ratio of water vapor (total steam) to ethylbenzene when entering the bed of the dehydrogenation catalyst in the first reactor is advantageously 0.7: 1 to 2.5: 1. Preference is given to using a steam / ethylbenzene ratio of 0.75: 1 to 1.8: 1, in particular 0.8: 1 to 1.5: 1.
  • the process is preferably operated at reduced pressure, typical reactor pressures are in the range of 300 to 1000 mbar.
  • the preferably hollow-cylindrical catalyst beds (radial flow reactors) are flowed through from the inside to the outside.
  • the reaction mixture Before entering the next reactor, the reaction mixture is advantageously brought back to temperatures of usually 600 and 650 0 C via a heat exchanger by means of superheated steam.
  • the pressure at the outlet of the last reactor should not be more than 700 mbar, more preferably not more than 600 mbar and in particular not more than 500 mbar.
  • a bed of an oxidation catalyst with oxygen supply for combustion of a subset of the hydrogen formed in the previous reactor may be configured, as described for example in WO 2005/097715 and in the German application with WO 2006/018133.
  • the unsaturated compounds obtainable in the process according to the invention for example alkenylaromatics or 1,3-alkadienes, can advantageously be polymerized to give plastics or used as building blocks for organic-chemical syntheses.
  • the catalyst according to the invention has significantly lower production costs at a comparable activity and selectivity through the use of secondary catalyst material. Furthermore, the cost of disposal of the secondary catalyst material can be reduced.
  • Example 1 Process for the dehydrogenation of ethylbenzene
  • Example A Inventive catalyst
  • Secondary styrene catalyst strands were calcined at a temperature of 700 ° C. under an oxygen-containing atmosphere for 90 minutes.
  • the thermally treated secondary catalyst strands were milled to give a particle distribution of 1 to 700 microns. An elemental analysis was performed.
  • Magnesium corresponding to 2.1% by weight of MgO
  • Molybdenum corresponding to 2.4% by weight of MoO 3 , iron, corresponding to Fe 2 O 3 , difference to 100% by weight (calculated)
  • the catalyst powder was processed according to Example 8 of DE-A 101 54 718 into catalyst strands.
  • Example B Inventive catalyst
  • Catalyst strands according to Example 1 were prepared from secondary catalyst material, wherein the secondary catalyst material was not subjected to thermal treatment.
  • Table 1 Test conditions and results of the dehydrogenation of ethylbenzene to styrene under isothermal conditions

Landscapes

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

Abstract

La présente invention concerne un catalyseur pour déshydrater ou hydrater des hydrocarbures contenant 10 à 70 % en poids d'une substance catalytique secondaire broyée d'un catalyseur d'hydratation/déshydratation usagé contenant de l'oxyde de fer, et 30 à 90 % en poids de la matière catalytique vierge correspondante contenant de l'oxyde de fer. Selon l'invention, l'oxyde de fer de la matière catalytique vierge se présente principalement sous la forme d'hématite ou de phases de ferrite de potassium. L'invention a également pour objet un procédé pour produire le catalyseur de l'invention, ainsi qu'un procédé pour déshydrater ou hydrater des hydrocarbures par utilisation du catalyseur de l'invention.
EP06792498A 2005-07-22 2006-07-13 Catalyseur pour deshydrater ou hydrater des hydrocarbures contenant une substance catalytique secondaire Ceased EP1919614A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005034978 2005-07-22
PCT/EP2006/064178 WO2007009927A1 (fr) 2005-07-22 2006-07-13 Catalyseur pour deshydrater ou hydrater des hydrocarbures contenant une substance catalytique secondaire

Publications (1)

Publication Number Publication Date
EP1919614A1 true EP1919614A1 (fr) 2008-05-14

Family

ID=37052551

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06792498A Ceased EP1919614A1 (fr) 2005-07-22 2006-07-13 Catalyseur pour deshydrater ou hydrater des hydrocarbures contenant une substance catalytique secondaire

Country Status (4)

Country Link
US (1) US8003837B2 (fr)
EP (1) EP1919614A1 (fr)
JP (1) JP4934134B2 (fr)
WO (1) WO2007009927A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL1957197T3 (pl) * 2005-10-26 2017-04-28 Albemarle Netherlands B.V. Kompozycja katalizatora nieosadzonego na nośniku i sposób jej wytwarzania
WO2008003731A1 (fr) * 2006-07-07 2008-01-10 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'un catalyseur
US8119559B2 (en) * 2007-05-03 2012-02-21 Basf Corporation Catalyst, its preparation and use
JP5691779B2 (ja) * 2010-12-07 2015-04-01 株式会社デンソー 排ガス浄化装置
US20130165723A1 (en) * 2011-12-22 2013-06-27 Basf Se Catalyst for the dehydrogenation of hydrocarbons
JP5992051B2 (ja) * 2012-10-01 2016-09-14 旭化成株式会社 アンモ酸化反応の停止方法
KR101953919B1 (ko) * 2012-12-18 2019-03-04 에스케이이노베이션 주식회사 혼성 망간 페라이트 허니컴형 촉매, 이의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법
PL3140039T3 (pl) * 2014-05-09 2021-01-25 Basf Se Ulepszony katalizator do odwodorniania węglowodorów
EP3140267B1 (fr) * 2014-05-09 2021-03-31 Basf Se Catalyseur pour la déshydrogénation d'hydrocarbures
KR101701973B1 (ko) * 2015-06-05 2017-02-03 금호석유화학 주식회사 페라이트 금속 산화물 촉매의 제조방법
BR102016022962B1 (pt) * 2016-10-03 2021-10-26 Petróleo Brasileiro S.A. - Petrobras Processo de preparação de um catalisador de ferro-cromo promovido com platina, e, catalisador composto de ferro-cromo promovido com platina
CN108203365B (zh) * 2016-12-16 2021-01-29 中国石油天然气股份有限公司 用于乙苯脱氢制苯乙烯的方法
RU2705574C1 (ru) * 2018-02-27 2019-11-08 Индийская Нефтяная Корпорация Лимитэд Каталитическая композиция для превращения алканов в алкены и способ ее получения
CA3226611A1 (fr) * 2021-07-26 2023-02-02 Kabu Walter MAKGERU Composition de carburant pour combustion

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242483A (en) * 1992-08-05 1993-09-07 Intevep, S.A. Process for the production of vanadium-containing steel alloys
WO2005105305A1 (fr) * 2004-04-15 2005-11-10 Shell Internationale Research Maatschappij B.V. Particule taillee et procede de deshydrogenation l'utilisant

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB626742A (en) 1947-02-14 1949-07-20 Standard Oil Dev Co Improvements in or relating to the catalytic synthesis of hydrocarbons
CA1074773A (fr) * 1975-07-03 1980-04-01 Gregor H. Riesser Catalyseur et procede de deshydrogenation
DD130793B1 (de) 1977-03-28 1981-09-30 Manfred Weber Verfahren zur rejuvenierung gebrauchter hydrospaltkatalysatoren
CA1108114A (fr) * 1977-04-14 1981-09-01 Gregor H. Riesser Catalyseur de dehydrogenation
DD268631A1 (de) 1987-10-12 1989-06-07 Buna Chem Werke Veb Dehydrierungskatalysator fuer die styrensynthese
US4888316A (en) * 1988-11-21 1989-12-19 Phillips Petroleum Company Preparation of hydrotreating catalyst from spent catalyst
DE4006918A1 (de) 1990-03-06 1991-09-12 Basf Ag Verfahren zum aufarbeiten von katalysatoren
DE4237740A1 (de) 1992-11-09 1994-05-11 Basf Ag Verfahren zur Herstellung von Eisen, Kalium und Cer enthaltenden Katalysatoren
DE10154718A1 (de) 2001-11-09 2003-05-22 Basf Ag Eisenoxide mit höherem Veredelungsgrad
JP4383055B2 (ja) * 2001-04-10 2009-12-16 ビーエーエスエフ ソシエタス・ヨーロピア 改質鉄酸化物
TWI267401B (en) * 2002-01-30 2006-12-01 Shell Int Research A catalyst, its preparation and its use in a dehydrogenation process
DE10305650A1 (de) 2003-02-12 2004-08-26 Reilly Industries, Inc., Indianapolis Verfahren zur Regenerierung von Mischoxidkatalysatoren
DE102004015800A1 (de) 2004-03-29 2005-10-20 Basf Ag Katalysator für die Oxidation von Wasserstoff, sowie Verfahren zur Dehydrierung von Kohlenwasserstoffen
DE102004039603A1 (de) 2004-08-13 2006-02-23 Basf Ag Katalysator enthaltend Eisenoxid(e), Alkalimetallverbindung(en) und Ceroxid(e)
KR20070086102A (ko) 2004-12-23 2007-08-27 쉘 인터내셔날 리써취 마트샤피지 비.브이. 폐 촉매로부터 촉매 지지체의 제조 방법
EP2083569A1 (fr) 2008-01-22 2009-07-29 Avaya Inc. Profils personnels de décodeurs (STB) à plateforme d'application à câble ouvert et applications de communications

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242483A (en) * 1992-08-05 1993-09-07 Intevep, S.A. Process for the production of vanadium-containing steel alloys
WO2005105305A1 (fr) * 2004-04-15 2005-11-10 Shell Internationale Research Maatschappij B.V. Particule taillee et procede de deshydrogenation l'utilisant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2007009927A1 *

Also Published As

Publication number Publication date
JP4934134B2 (ja) 2012-05-16
WO2007009927A1 (fr) 2007-01-25
US20080200739A1 (en) 2008-08-21
JP2009502451A (ja) 2009-01-29
US8003837B2 (en) 2011-08-23

Similar Documents

Publication Publication Date Title
EP1919614A1 (fr) Catalyseur pour deshydrater ou hydrater des hydrocarbures contenant une substance catalytique secondaire
DE2815812C2 (de) Katalysator für die Dehydrierung von Kohlenwasserstoffen zu ungesättigten Kohlenwasserstoffen und seine Verwendung für die Dehydrierung in Gegenwart von Dampf
DE69533409T2 (de) Verfahren zur herstellung eines dehydrierungskatalysators
EP2134465B1 (fr) Procédé de fabrication d'un catalyseur composé d'un corps support et d'une masse à activité catalytique appliquée sur la surface du corps support
EP1289919B1 (fr) Procede de production d'acroleine et/ou d'acide acrylique
DE102012019123B4 (de) Hydrierkatalysator und Verfahren zu dessen Herstellung durch die Verwendung von unkalziniertem Ausgangsmaterial
DE10060099A1 (de) Regenerierung eines Dehydrierkatalysators
EP2953720B1 (fr) Procédé de fabrication d'une masse à activité catalytique qui constitue un mélange entre un oxyde de plusieurs éléments, lequel contient les éléments mo et v, et au moins un oxyde du molybdène
EP3019458B1 (fr) Procédé de déshydrogénation oxydative de n-butènes pour donner du butadiène
EP0609751B1 (fr) Procédé de régénération d'un catalyseur d'oxydation usagé constitue d'un mélange d'oxydes dans le cadre de l'oxydation catalytique en phase gazeuse de composés organiques inférieurs
EP0394842B1 (fr) Catalyseur pour l'hydrogénation de composés aliphatiques insaturés
DE60312484T2 (de) Auf eisenoxid basierender katalysator, seine herstellung und seine verwendung bei einem dehydrierungsverfahren
WO2015144548A1 (fr) Catalyseur d'hydrogénation et son procédé de fabrication
WO1999049966A1 (fr) Catalyseur pour deshydrogener du benzene d'ethyle en styrene
EP2271424A2 (fr) Catalyseur en coquille contenant un oxyde multimétallique renfermant du molybdène
DE102017121709A1 (de) Synthese eines MoVNbTe-Schalenkatalysators für die oxidative Dehydrierung von Ethan zu Ehtylen
EP3140267B1 (fr) Catalyseur pour la déshydrogénation d'hydrocarbures
EP0009068B1 (fr) Catalyseurs à lit fluidisé pour préparer synthétiquement du gaz naturel par méthanisation du monoxyde de carbone
DE102012012510B4 (de) Graphithaltiger Katalysatorformkörper, dessen Herstellverfahren sowie Verwendung
DE60307844T2 (de) Verfahren zur dehydrierung eines ungesättigten kohlenwasserstoffs
EP3470139B1 (fr) Procédé de déshydrogénation catalytique d'hydrocarbures
DE1817692B2 (de) Verfahren zur Dehydrierung von Monoolefinen und/oder alkylierten aromatische Kohlenwasserstoffen Ausscheidung aus 1800929
WO2016177764A1 (fr) Procédé de fabrication de catalyseurs contenant du chrome pour la déshydrogénation oxydante de n-butènes en butadiène sans formation d'intermédiaires cr(vi)
DE1052979B (de) Verfahren zur Entfernung von Acetylen aus einem vorwiegend AEthylen enthaltenden Gasgemisch durch selektive Hydrierung
WO2006018133A1 (fr) Catalyseur contenant un(des) oxyde(s) de fer, un(des) compose(s) de metal alcalin et un(des) oxyde(s) de cerium

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080222

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20080904

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20120526