EP1919614A1 - Catalyst for the dehydrogenation or hydrogenation of hydrocarbons containing secondary catalyst material - Google Patents

Catalyst for the dehydrogenation or hydrogenation of hydrocarbons containing secondary catalyst material

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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)
French (fr)
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1919614A1 publication Critical patent/EP1919614A1/en
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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

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  • Physics & Mathematics (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a catalyst for the dehydrogenation or hydrogenation of hydrocarbons containing between 10 and 70 wt. % milled, secondary catalyst material of a used (de)hydrogenation catalyst that contains iron oxide and between 30 and 90 wt. % of the corresponding fresh catalyst material containing iron oxide, said iron oxide of the fresh catalyst material being predominantly in the form of hematite or potassium ferrite. The invention also relates to a method for producing the catalyst and to a method for dehydrogenating or hydrogenating hydrocarbons using the catalyst provided by the invention.

Description

Katalysator zur Dehydrierung oder Hydrierung von Kohlenwasserstoffen enthaltend sekundäres KatalysatormaterialCatalyst for dehydrogenating or hydrogenating hydrocarbons containing secondary catalyst material
Beschreibungdescription
Die Erfindung betrifft einen Katalysator zur Dehydrierung oder Hydrierung von Kohlenwasserstoffen enthaltend 10 bis 70 Gew.-% gemahlenes, sekundäres Katalysatormaterial eines gebrauchten (De)Hydrierkatalysators enthaltend Eisenoxid und 30 bis 90 Gew.-% des korrespondierenden frischen Katalysatormaterials enthaltend Eisenoxid, wobei das Eisenoxid des frischen Katalysatormaterials überwiegend in Form von Hä- matit oder Kaliumferritphasen vorliegt. Ferner betrifft die Erfindung ein Verfahren zur Herstellung des erfindungsgemäßen Katalysators. Des weiteren betrifft die Erfindung ein Verfahren zur Dehydrierung oder Hydrierung von Kohlenwasserstoffen unter Verwendung des erfindungsgemäßen Katalysators.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.
Die Regenerierung von sekundärem Katalysatormaterial ist seit Jahren in der chemischen Industrie von besonderem Interesse, da die Wiederverwendung eine Ressourcen- und Kosteneinsparung in sich birgt.The regeneration of secondary catalyst material has been of particular interest in the chemical industry for years, because reuse saves resources and costs.
Auf dem Gebiet der Dehydrierkatalysatoren findet sich folgender Stand der Technik:In the field of dehydrogenation catalysts, the following state of the art can be found:
DD 268 631 A1 beschreibt Dehydrierkatalysatoren, wobei die Katalysatoren ausDD 268 631 A1 describes dehydrogenation catalysts, wherein the catalysts
50 bis 90 Teilen Abfalleisenoxiden mit der Zusammensetzung 10 bis 40 % Magnetit, 50 bis 80 % Goethit und 10 bis 30 % Lepidocrocit (Abfall 1), 1 bis 20 Teilen Abfalleisen- oxiden mit der Zusammensetzung 85 bis 95 % Magnetit (Abfall 2) und 5 bis 15 %50 to 90 parts of waste iron oxides having the composition 10 to 40% magnetite, 50 to 80% goethite and 10 to 30% lepidocrocite (waste 1), 1 to 20 parts of waste iron oxides having the composition 85 to 95% magnetite (waste 2) and 5 to 15%
Wüstit und 49 bis 10 Teile gemahlenen Styrenaltkatalysator bestehen. Eine thermische Behandlung der gemahlenen Altkatalysatoren wird nicht beschrieben; dieser wird vor der Weiterverarbeitung lediglich mit den anderen Abfällen gemischt. Abfall 1 und 2 entsteht beispielsweise bei der Produktion von Pigmenten für Datenträger aufgrund der hohen qualitativen Anforderungen bezüglich der magnetischen Eigenschaften. Mit dem beschriebenen Dehydrierkatalysator wird bei der Dehydrierung von Ethylbenzol zu Sty- rol ein Umsatz von ca. 40 % bei einer Selektivität von ca. 92 % erreicht.Wüstit and 49 to 10 parts of ground styrenated catalyst consist. A thermal treatment of the ground old catalysts is not described; this is only mixed with the other waste before further processing. 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. With the described dehydrogenation catalyst, a conversion of about 40% with a selectivity of about 92% is achieved in the dehydrogenation of ethylbenzene to styrene.
WO 94/11104 offenbart ein Verfahren zur Herstellung von Eisen, Kalium und Cer ent- haltenden Dehydrierkatalysatoren aus ebensolchen gebrauchten Katalysatoren durch Vermählen des gebrauchten Materials, gegebenenfalls Reinigung, Wiederherstellen der ursprünglichen Wirkung durch Einstellen der Zusammensetzung und Wiederherstellen der äußeren Form, indem dem vermahlenen gebrauchten Material eine wirksame Menge an Kalium und eine solche Menge an Cer zugesetzt wird, so dass die Ge- samtmenge an Cer höher als die ursprünglich vorhandene Menge. Gegebenenfalls wird das gebrauchte Material vor dem Vermählen in Gegenwart von Sauerstoff kalziniert. Durch das beschriebene Verfahren werden Dehydrierkatalysatoren erhalten, die bei der Dehydrierung von Ethylbenzol zu Styrol bei einem Umsatz von 70 % eine Selektivität von 94 bis 95 % erreichen.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. Optionally, 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%.
Auch bei anderen katalytischen Verfahren, wie beispielweise bei der Entfernung von Stickoxiden aus Verbrennungsabgasen durch Umsetzung mit Ammoniak bei erhöhter Temperatur, wird eine Regenerierung des gebrauchten Katalysatormaterials beschrieben (DE 40 06 918 A1), indem man die gebrauchten Katalysatoren auf Korngrößen von 5 bis 20 μm vermahlt und das erhaltende Pulver bei der Herstellung von Katalysatoren mit frischem Ausgangsmaterial in Mengen von bis zu 80 Gew.-%, bezogen auf das gesamte eingesetzte Material, vor der Verformung zusetzt.In other catalytic processes, such as in the removal of nitrogen oxides from combustion exhaust gases by reaction with ammonia at elevated temperature, a regeneration of the used catalyst material is described (DE 40 06 918 A1) by the used catalysts to particle sizes of 5 to 20 microns grinding and adding the obtained powder in the preparation of catalysts with fresh starting material in amounts of up to 80 wt .-%, based on the total material used, prior to deformation.
In DE 103 05 650 A1 wird die Regenerierung von Mischoxidkatalysatoren, die bei der Ammonoxidation zur Herstellung von Nitrilen eingesetzt werden, beschrieben. Der deaktivierte Katalysator wird gegebenenfalls gemahlen und bei 300 bis 9000C unter Sau- erstoff kalziniert.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.
Im Stand der Technik sind verschiedene Katalysatoren und Verfahren zur Dehydrierung und Hydrierung von Kohlenwasserstoffen beschrieben. Die beschriebenen (De)Hydrierkatalysatoren werden typischerweise in Form von Strängen, Ringen, Tab- letten, Ringtabletten, Extrudaten, Wabenkörpern oder ähnlichen Formkörpern angeboten. Die Aktivmasse der genannten Katalysatoren beinhaltet vorwiegend Metalle ausgewählt aus der Gruppe bestehend aus Eisen, Alkaliverbindungen, insbesondere Kalium, Molybdän, Magnesium, Calcium, Cer, Wolfram, Titan, Vanadium, Kupfer, Mangan, Nickel, Zink, Palladium, Platin, Kobalt, Aluminium, Zinn, Silizium, Blei, Ruthenium, SiI- ber, Gold, Zirkonium, Rhodium, Lanthan, Chrom, Cadmium oder Barium.Various catalysts and processes for the dehydrogenation and hydrogenation of hydrocarbons are described in the prior art. 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.
Die (De)Hydrier-Katalysatoren werden in jüngerem Stand der Technik und im industriellen Maßstab allerdings nach wie vor nach folgenden Verfahren hergestellt (siehe u.a. EP-A 1 379 470):However, the (de) hydrogenation catalysts are still produced in the more recent state of the art and on an industrial scale by the following processes (see, inter alia, EP-A 1 379 470):
a) Die frischen Einsatzstoffe in Form von Metalloxiden, -nitraten, -carbonate, -hydroxide oder dergleichen werden direkt in einem Mischer, Kneter oder Mix- Muller gemischt. Ferner können die Einsatzstoffe auch in einer Sprühmaische aufgeschlämmt und in einem Sprühtrockner zu einem Sprühpulver verarbeitet werden. Die extrudierbare Masse wird anschließend extrudiert, getrocknet und kalziniert. b) Die frischen Einsatzstoffe werden via Fällungsreaktionen gewonnen, in einem Sprühtrockner zu einem Sprühpulver verarbeitet, kalzinert und verformt, bzw. erst verformt und dann kalziniert.a) 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. b) 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.
Wenn ein Katalysator nach einer Laufzeit von typischerweise zwei bis fünf Jahren Betrieb in einer technischen Anlage, wie beispielsweise Isopren-, Butadien- oder Styrol- Anlage, ausgebaut wird, hat der Katalysator eine Reihe von Veränderungen erfahren. Der ausgebaute Katalysator weist in der Regel Eisenoxid in einer reduzierten Form, d.h. als Magnetit auf. Ein Teil der ausgebauten Katalysatoren ist in der Regel an Kaliumverbindungen verarmt, während in anderen Bereichen, insbesondere im Inneren der Katalysatorformkörper, eine Anreicherung von Kaliumverbindungen auch in Form von separaten Ablagerungen zwischen den Katalysatorsträngen vorliegen kann. Das Kalium liegt typischerweise in Form von Kaliumcarbonat oder Kaliumhydrogencarbonat vor. Die ausgebauten Katalysatoren weisen in der Regel praktisch keinerlei organische Kohlenwasserstoffe oder Koksablagerungen, d.h. Kohlenstoff, der nicht als Carbonat oder Hydrogencarbonat vorliegt, auf. Die Cerkistallitgröße der Ausbaukatalysatoren liegt bei ungefähr 40 bis 60 nm.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 Cerkistallitgröße the expansion catalysts is about 40 to 60 nm.
Die Katalysatorformkörper sind oftmals durch die mechanischen Belastungen beim Einbau, Betrieb und Ausbau geschädigt. Ferner kann der ausgebaute Katalysator ei- nen hohen Anteil von Staub oder Bruchstücken enthalten.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.
Aufgrund der aufgezeigten Veränderungen des sekundären Katalysatormaterials und den allgemeinen Schwierigkeiten beim Verarbeiten von sekundärem Katalysatormaterial, insbesondere beim Verstrangen, wurden bislang bei den industriellen (De)Hydrierungsverfahren überwiegend Katalysatoren eingesetzt, die aus frischen Einsatzstoffen hergestellt wurden.Due to the demonstrated changes in the secondary catalyst material and the general difficulties in processing secondary catalyst material, especially in Verstrangen, have been used in the industrial (de) hydrogenation predominantly catalysts, which were prepared from fresh feeds.
Angesichts hoher Rohstoffpreise und steigender Anforderungen an die Nachhaltigkeit wirtschaftlichen Handelns stehen Verfahren zur Verwendung von Sekundär-Rohstoffen zunehmend im Fokus der chemischen Forschung. Ferner werden an die Entsorgung von gebrauchten Katalysatoren aus der chemischen Industrie zunehmend höhere Anforderungen gestellt.In view of high raw material prices and increasing demands on the sustainability of economic activity, methods for the use of secondary raw materials are increasingly becoming the focus of chemical research. Furthermore, the disposal of used catalysts from the chemical industry increasingly demanding.
Der vorliegenden Erfindung lag deshalb die Aufgabe zugrunde, ein Verfahren aufzufin- den, um Katalysatoren für bedeutsame Prozesse in der chemischen Industrie unter Verwendung von sekundärem Katalysatormaterial als Einsatzstoff herzustellen. Insbesondere war es Aufgabe der vorliegenden Erfindung, Katalysatoren enthaltend Eisenoxide unter Verwendung von sekundärem Katalysatormaterial herzustellen. Die unter Verwendung von sekundärem Katalysatormaterial hergestellten Katalysatoren sollten vergleichbare Eigenschaften insbesondere hinsichtlich der Aktivität, Selektivität und insbesondere mechanischer Härte aufweisen wie die Katalysatoren aus dem Stand der Technik. Ferner soll das sekundäre Katalysatormaterial ohne Zugabe von Dotierelementen direkt verwendbar sein.It is an object of the present invention to provide a process for producing catalysts for significant processes in the chemical industry using secondary catalyst material as a feedstock. In particular, it was an object of the present invention to produce catalysts containing iron oxides using secondary catalyst material. 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. Furthermore, the secondary catalyst material should be directly usable without the addition of doping elements.
Die Erfindung betrifft demnach Katalysatoren zur Dehydrierung oder Hydrierung von Kohlenwasserstoffen enthaltend 10 bis 70 Gew.-% gemahlenes, sekundäres Katalysatormaterial eines gebrauchten (De)Hydrierkatalysators enthaltend Eisenoxid und 30 bis 90 Gew.-% des korrespondierenden frischen Katalysatormaterials enthaltend Eisenoxid, wobei das Eisenoxid des frischen Katalysatormaterials überwiegend in Form von Hämatit oder Kaliumferritphasen vorliegt.Accordingly, 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.
Unter dem Begriff „sekundäres Katalysatormaterial" wird in der vorliegenden Erfindung bereits gebrauchtes/verwendetes/deaktiviertes, gegebenenfalls aufbereitetes Katalysatormaterial verstanden. Das sekundäre Katalysatormaterial wurde somit bereits einmal in eine chemische Anlage eingebaut, die chemische Anlage für einen Zeitraum von mehreren Tagen bis mehreren Jahren betrieben und das Katalysatormaterial wieder ausgebaut. Insbesondere wurde das sekundäre Katalysatormaterial für eine typische Lebenszeit von (De)Hydrierkatalysatoren von 1 bis 3 Jahren betrieben.The term "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 In particular, the secondary catalyst material was operated for a typical lifetime of (de) hydrogenation catalysts of 1 to 3 years.
Das sekundäre Katalysatormaterial weist vorteilhaft keine organischen Kohlenwasserstoffe oder Koksablagerungen auf. In Summe sollten solche Ablagerungen vorteilhaft weniger als 2 Gew.-%, bevorzugt weniger als 1 Gew.-%, insbesondere weniger als 0,1 Gew.-% bezogen auf das sekundäre Katalysatormaterial ausmachen.The secondary catalyst material advantageously has no organic hydrocarbons or coke deposits. In sum, 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.
Eine geringe Menge an Ablagerungen kann durch ein spezielles, dem Fachmann bekanntes, Herunterfahren der Isopren-, Butadien- oder Styrol-Anlage erreicht werden.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.
Vorteilhaft wird beim Herunterfahren einer Anlage die Temperatur auf 580 bis 6100C verringert. Anschließend wird der Ethylbenzol-Feed verringert, so dass ein Dampf/Ethylbenzol-Gewichtsverhältnis von mindestens 2/1 entsteht. Nach dem Abstellen des Vakuums wird die Temperatur weiter auf 550 bis 575°C abgesenkt und gleich- zeitige wird stufenweise der Ethylbenzol-Feed verringert und schließlich abgeschaltet. Anschließend wird der Stickstoff-Kreislauf eingeschaltet und die Temperatur weiter bis auf minimal 3600C angesenkt, bevorzugt 4000C. Nach dem Abstellen des Dampfkreislaufes wird die Temperatur unter Stickstoff auf 500C abgesenkt. Bei mindestens 300C, bevorzugt bei ca. 500C wird kontrolliert Luft zugegeben. Die Kontrolle erfolgt mit Hilfe von Thermoelemente, die lokale Temperaturerhöhungen, d.h. Re-oxidation, feststellen. Wenn keine Temperaturerhöhungen mehr erkennbar ist, dann kann die weitere Zugabe von Luft erfolgen, bis keine weiteren Temperaturerhöhungen mehr erkennbar sind. Abschließend wird mit Luft und Stickstoff oder nur mit Luft abgekühlt.Advantageously, the temperature is lowered to 580 to 610 0 C when shutting down a system. Subsequently, the ethylbenzene feed is reduced to give a steam / ethylbenzene weight ratio of at least 2/1. After switching off the vacuum, 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. Subsequently, 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. After stopping the steam cycle, 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. The control takes place with the help of 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.
Vorteilhaft wird das ausgebaute sekundäre Katalysatormaterial vor der Neuverwendung einer thermischen Behandlung unter sauerstoffhaltiger Atmosphäre ausgesetzt. Die thermische Behandlung wird vorteilhaft bei Temperaturen von 100 bis 15000C, bevorzugt von 300 bis 12000C, besonders bevorzugt von 500 bis 10000C, ferner bevorzugt von 700 bis 10000C und insbesondere von 850 bis 10000C, durchgeführt. Zweckmäßigerweise wird die thermische Behandlung für einen Zeitraum von 30 Minuten bis 10 Stunden durchgeführt, bevorzugt für einen Zeitraum von 1 bis 3 Stunden. Das Eisen liegt nach der thermischen Behandlung vorteilhaft im wesentlichen in Form von Hämatit, Magnetit und Kaliumferritphasen vor. Das sekundäre Katalysatormaterial weist demnach vorteilhaft Eisen überwiegend in Form von Hämatit und Magnetit auf, wobei x vorteilhaft zwischen 1 und 11 und y vorteilhaft zwischen 2 und 17 liegt. Bevorzugte Kaliumferritphasen sind K2FeioOi6 und KFeÜ2. Das Eisenoxid liegt vorteilhaft mit 15 bis 85 Gew.-%, bezogen auf die Summe der Eisenoxide, in Form von K2FexOy vor, vorteilhaft mit 20 bis 60 Gew.-%. Die restlichen Eisenoxide liegen vorteilhaft als Hämatit und/oder Magnetit vor.Advantageously, 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. Conveniently, 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.
Das sekundäre Katalysatormaterial weist nach der thermischen Behandlung vorteilhaft eine Cerkristallitgröße von 15 bis 90 nm, bevorzugt von 40 bis 60 nm auf.After the thermal treatment, the secondary catalyst material advantageously has a cerium crystallite size of 15 to 90 nm, preferably 40 to 60 nm.
Als sauerstoffhaltiges Gas wird bevorzugt Luft eingesetzt. Je nach Quelle, aus der die Luft stammt, kann deren Zusammensetzung im Rahmen der dem Fachmann geläufi- gen Grenzen schwanken. Besonders bevorzugt wird Magerluft verwendet.As the oxygen-containing gas, air is preferably used. Depending on the source from which the air originates, their composition may vary within the limits known to those skilled in the art. Particular preference is given to using lean air.
Die thermische Behandlung kann diskontinuierlich oder kontinuierlich in verschiedenen Vorrichtungen, beispielsweise in Hordenöfen oder Drehrohren durchgeführt werden. Bevorzugt wird die thermische Behandlung kontinuierlich in Drehrohren durchgeführt. Insbesondere bei stark pulverisiertem oder pulverhaltigem Ausbau-Katalysator kann es sinnvoll sein, die Kalzination in einem mit Klopfern ausgestatteten Drehrohr durchzuführen. Ferner kann die oxidative Behandlung auch vor dem Ausbau des sekundären Katalysatormaterials direkt in der Produktionsanlage durchgeführt werden.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.
Das sekundäre Katalysatormaterial wird vorteilhaft, gegebenenfalls nach einer thermischen Behandlung, in geeigneten Mühlen gemahlen. Gegebenenfalls kann es von Vorteil sein, das Material zunächst vorzubrechen. Diese Vorbrechung kann beispielsweise in Daumenbrecher oder Hammermühlen mit beispielsweise einem 3 mm Quadratloch- Sieb bei beispielsweise 3000 Umdrehungen pro Minute erfolgen. Anschließend kann das Material beispielsweise mit einer Spiralstrahlmühle endzerkleinert werden. Das Mahlgasdruck beträgt beim Zermahlen typischerweise 1 bis 10 bar. Der Mahldurchsatz liegt in der Regel bei 1 bis 30 kg/h.The secondary catalyst material is advantageously ground, if appropriate after a thermal treatment, in suitable mills. Optionally, it may be advantageous to pre-break the material first. This break can be done, for example, in thumb crushers or hammer mills with, for example, a 3 mm square hole sieve at, for example, 3000 revolutions per minute. Subsequently, 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.
Die mittleren Partikeldurchmesser weisen einen Wert im Bereich von 1 bis 700 μm auf, bevorzugt 5 bis 500 μm, insbesondere 10 bis 200 μm.The mean particle diameters have a value in the range from 1 to 700 μm, preferably 5 to 500 μm, in particular 10 to 200 μm.
Das gemahlene sekundäre Katalysatorpulver kann anschließend für die Herstellung von neuen Katalysatoren verwendet werden.The milled secondary catalyst powder can then be used for the preparation of new catalysts.
Der erfindungsgemäße Katalysator enthält vorteilhaft 15 bis 70 Gew.-% gemahlenes, sekundäre Katalysatormaterial, bezogen auf das Gesamtkatalysatormaterial, und 30 bis 85 Gew.-% des korrespondierenden frischen Katalysatormaterials, bezogen auf das Gesamtkatalysatormaterial, bevorzugt 25 bis 65 Gew.-% gemahlenes, sekundäre Kata- lysatormaterial und 35 bis 75 Gew.-% des korrespondierenden frischen Katalysatorma- terials, insbesondere 35 bis 55 Gew.-% gemahlenes, sekundäre Katalysatormaterial und 45 bis 65 Gew.-% des korrespondierenden frischen Katalysatormaterials.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.
Der erfindungsgemäße Katalysator enthält vorteilhaft ausschließlich sekundäres und frisches Katalysatormaterial in den genannten Verhältnissen.The catalyst according to the invention advantageously contains exclusively secondary and fresh catalyst material in the stated ratios.
Das Schüttgewicht des erfindungsgemäßen Katalysators beträgt vorteilhaft 1 ,2 bis 2 kg/l, insbesondere 1,3 bis 1 ,7 kg/l. Das Rüttelgewicht beträgt vorteilhaft 1 bis 1 ,7 kg/l, insbesondere 1 ,1 bis 1 ,5 kg/l.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.
Gegebenenfalls wird an dem gemahlenen sekundären Katalysatorpulver eine Elementaranalyse durchgeführt. Normalerweise entspricht die katalytische Zusammensetzung der frischen Einsatzstoffe der aus dem Stand der Technik für (De)Hydrierkatalysatoren bekannten katalytischen Zusammensetzung. In Ausnahmefällen kann aufgrund der analysierten Zusammensetzung des gemahlenen sekundären Katalysatorpulvers die Menge und die typische Zusammensetzung der frischen Einsatzstoffe geändert werden.Optionally, elemental analysis is performed on the ground secondary catalyst powder. Normally, the catalytic composition of the fresh feeds corresponds to the catalytic composition known in the art for (de) hydrogenation catalysts. In exceptional cases, due to the analyzed composition of the ground secondary catalyst powder, the amount and the typical composition of the fresh feedstock can be changed.
Die erfindungsgemäßen Katalysatoren enthalten vorteilhaft Einsatzstoffe in Form von Oxiden, Nitraten, Carbonaten, Hydroxiden und dergleichen, bevorzugt in Form von Oxiden, insbesondere Eisen, bevorzugt als Eisenoxid, zweckmäßigerweise in einer Menge von 40 bis 90 Gew.-% bezogen auf die Summe aller Einsatzstoffe. Ferner ent- halten die erfindungsgemäßen Katalysatoren vorteilhaft Alkalimetallverbindung(en), bevorzugt Kaliumverbindung(en) wie beispielsweise Kaliumoxid, zweckmäßigerweise in einer Menge von 1 bis 40 Gew.-% bezogen auf die Summe aller Einsatzstoffe. Typischerweise enthalten die erfindungsgemäßen Katalysatoren vorteilhaft eine Reihe von Promotoren in Abhängigkeit von ihrem Einsatzgebiet.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.
Der erfindungsgemäße Katalysator eignet sich insbesondere zur Dehydrierung von Kohlenwasserstoffen, die mindestens eine gesättigte funktionelle Gruppe aufweisen, beispielsweise Alkenen zu den entsprechenden 1 ,3-Alkadienen, bevorzugt alkylaroma- tischen Verbindungen zu den entsprechenden alkenylaromatischen Verbindungen. Als alkylaromatische Verbindungen eignen sich alle aromatischen und heteroaromatischen Alkylverbindungen, bevorzugt sind solche, in denen der Alkylrest unverzweigt oder verzweigt ist und zwei bis sechs C-Atome enthält. Als aromatische Reste eignen sich ein-, zwei- oder dreikernige, bevorzugt ein- oder zweikernige, besonders bevorzugt einkernige Aromaten. Beispielhaft seien Isopropylbenzol (Cumol), Ethylbenzol, 1 ,1-Diphenyl- benzol und 1 ,2-Diphenylethan (Bibenzyl), bevorzugt Isopropylbenzol (Cumol), Ethylbenzol und 1 ,1-Diphenylbenzol, besonders bevorzugt Ethylbenzol genannt. Als heteroaromatische Reste eignen sich ein-, zwei- oder dreikernige, bevorzugt ein- oder zwei- kernige, besonders bevorzugt einkernige Fünfring-Heteroaromaten mit ein bis drei Stickstoffatomen und/oder einem Sauerstoff- oder Schwefelatom, ein-, zwei- oder dreikernige, bevorzugt ein- oder zweikernige, besonders bevorzugt einkernige Sechsring- Heteroaromaten mit ein bis drei Stickstoffatome als Heteroatome, insbesondere Pyridi- ne, wie 2-Ethylpyridin, 3-Ethylpyridin, 4-Ethylpyridin und 5-Ethyl-2-methylpyridin, bevorzugt 2-Ethylpyridin und 5-Ethyl-2-methylpyridin.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. Examples which may be mentioned are isopropylbenzene (cumene), ethylbenzene, 1,1-diphenylbenzene and 1,2-diphenylethane (bibenzyl), preferably isopropylbenzene (cumene), ethylbenzene and 1,1-diphenylbenzene, particularly preferably ethylbenzene. As 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.
Beispielsweise sei die Dehydrierung von Ethylbenzol zu Styrol, von Cumol zu α- Methyl-Styrol, von Buten zu Butadien und von Isopenten zu Isopentadien (Isopren), insbesondere die Dehydrierung von Ethylbenzol zu Styrol, genannt.For example, the dehydrogenation of ethylbenzene to styrene, of cumene to α-methyl-styrene, of butene to butadiene and of isopentene to isopentadiene (isoprene), in particular the dehydrogenation of ethylbenzene to styrene, called.
Als Promotoren für die erfindungsgemäßen Katalysatoren eignen sich neben Cer- Verbindungen vorteilhaft Verbindungen von Calcium, Magnesium, Molybdän, Wolfram, Chrom und Titan.Suitable promoters for the catalysts according to the invention are, in addition to cerium compounds, compounds of calcium, magnesium, molybdenum, tungsten, chromium and titanium.
Als weitere Promotoren sind ferner Vanadium, Kupfer, Mangan, Nickel, Zink, Palladium, Platin, Kobalt, Aluminium, Zinn, Silizium, Blei, Ruthenium, Silber, Gold, Zirkonium, Rhodium, Lanthan, Chrom, Cadmium, Barium oder Mischungen hieraus geeignet.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 ,
Der erfindungsgemäße Hydier-Katalysator weist vorteilhaft folgende Zusammensetzung im Bezug auf die Summe der frischen und sekundären Einsatzstoffe auf:The hydrogenation catalyst according to the invention advantageously has the following composition with respect to the sum of the fresh and secondary feedstocks:
Kupferoxid entsprechend 0 - 80 Gew.-% CuO, Aluminium entsprechend 0 - 80 Gew.-% AI2O3 und Eisen, entsprechend 0 - 90 Gew.-% Fe2O3 fernerCopper 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
Oxide ausgewählt aus der Gruppe bestehend ausOxides selected from the group consisting of
Kalium, Cer, Magnesium, Calcium, Lanthans, Wolframs, Molybdäns, Titans, Zinn, Vanadium, Mangan, Nickel, Zink, Palladium, Platin, Kobalt, Zinn, Silizium, Blei, Ruthenium, Silber, Gold, Zirkonium, Rhodium, Chrom, Cadmium, Barium, entsprechend 0 - 20 Gew.-% wobei sich die genannten Komponenten auf 100 Gew.-% addieren.Potassium, cerium, magnesium, calcium, lanthanum, tungsten, molybdenum, titanium, tin, vanadium, manganese, nickel, zinc, palladium, platinum, cobalt, tin, silicon, lead, ruthenium, silver, gold, zirconium, rhodium, chromium, Cadmium, barium, corresponding to 0 - 20 wt .-% wherein said components add up to 100 wt .-%.
Der erfindungsgemäße Dehydrier-Katalysator weist besonders bevorzugt folgende Zusammensetzung im Bezug auf die Summe der frischen und sekundären Einsatzstof- fe auf: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:
Eisen, entsprechend 40 - 90 Gew.-% Fe2O3, Kalium, entsprechend 1 - 40 Gew.-% als K2O,Iron, corresponding to 40-90% by weight of Fe 2 O 3 , potassium, corresponding to 1-40% by weight as K 2 O,
Cer, entsprechend 1 - 25 Gew.-% Ce2O4, insbesondere 5 - 15 Gew.-% Ce2O4, Magnesium, entsprechend 0 - 10 Gew.-% MgO,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,
Calcium, entsprechend 0 - 10 Gew.-% CaO, Wolfram, entsprechend 0 - 10 Gew.-% WO3, Molybdän, entsprechend 0 - 10 Gew.-% Moθ3,Calcium, corresponding to 0-10% by weight of CaO, tungsten, corresponding to 0-10% by weight of WO 3 , Molybdenum, corresponding to 0-10% by weight MoO 3,
Vanadium, entsprechend 0 - 10 Gew.-% V2O5 wobei sich die genannten Komponenten auf 100 Gew.-% addieren.Vanadium, corresponding to 0 - 10 wt .-% V2O5 wherein said components add up to 100 wt .-%.
Das Gewichtsverhältnis von Kalium (berechnet als K2O) zu Eisenoxid (berechnet als Fe2Ü3) beträgt in der Regel 0,01 :1 bis 2:1, bevorzugt von 0,1 :1 bis 1 :1. Bevorzugt enthalten die Katalysatoren darüber hinaus weitere Promotoren (berechnet als Oxide) in einem Gewichtsverhältnis zum Eisenoxid von 0,01 :1 bis 1 :1 , bevorzugt von 0,02:1 bis 0,5:1.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. In addition, 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.
Bevorzugt werden dem sekundären Katalysatormaterial keine Dotierelemente zugesetzt.Preferably, no doping elements are added to the secondary catalyst material.
Die Erfindung betrifft ferner Katalysatorbetten, die zu mindestens 25 Gew.-% aus erfin- dungsgemäßen Katalysator, bezogen auf die gesamte Katalysatormenge des entsprechenden Katalysatorbettes, bestehen. Vorteilhaft bestehen die Katalysatorbetten aus mindestens 30 Gew.-%, bevorzugt mindestens 50 Gew.-% aus erfindungsgemäßen Katalysatoren. Die erfindungsgemäßen Katalysatoren können gleichmäßig mit Katalysatoren aus dem Stand der Technik vermischt über das Katalysatorbett verteilt oder an einem oder mehreren Orten konzentriert sein. Bei einem Katalysatorsystem, das aus mehreren Reaktoren, d.h. mehreren Katalysatorbetten besteht, wird beispielsweise ein oder mehrere Reaktor(en) mit den erfindungsgemäßen Katalysatoren gefüllt und die verbleibenden Reaktoren mit den Katalysatoren aus dem Stand der Technik. Bevorzugt werden ausschließlich erfindungsgemäße Katalysatoren eingesetzt.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. Advantageously, 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. In 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.
Die Erfindung betrifft ferner das Verfahren zur Herstellung des erfindungsgemäßen Katalysators, das dadurch gekennzeichnet ist, dass sekundäres Katalysatormaterial eines gebrauchten (De)Hydrierkatalysator gegebenenfalls kalziniert und dann gemahlen wird und anschließend in einem Verhältnis von 1 :9 bis 7:3 mit frischen Einsatzstoffen des korrespondierenden (De) Hydrierkatalysators vermischt, verformt und kalziniert wird.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.
Vorteilhaft wird das sekundäre Katalysatormaterial vor dem Vermählen und dem Vermischen mit den frischen Einsatzstoffen einer thermischen Behandlung unter sauer- stoffhaltiger Atmosphäre bei 100 bis 15000C unterzogen.The secondary catalyst material prior to milling and mixing with the fresh feedstock to a thermal treatment under oxygen atmosphere at 100 stoffhaltiger is advantageously subjected to 1500 0 C.
Das Vermischen des sekundären Katalysatorpulvers mit den frischen Einsatzstoffen erfolgt vorteilhaft in einem Mischer, beispielsweise in einem Mix-Müller.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.
Das Verformen und Kalzinieren erfolgt zweckmäßigerweise wie im Stand der Technik beschrieben (siehe beispielsweise DE-A 101 54 718). Zur Herstellung der erfindungsgemäßen Katalysatoren können als Einsatzstoffe neben dem sekundären Katalysatorpulver Verbindungen der Promotoren, wie sie im fertigen Katalysator vorliegen, eingesetzt werden, oder Verbindungen, die sich während des Herstellungsprozess in Verbindungen, wie sie im fertigen Katalysator vorliegen, um- wandeln. Den Einsatzstoffen können auch Hilfsstoffe zugesetzt werden, um die Verar- beitbarkeit, die mechanische Festigkeit oder die Porenstruktur zu verbessern. Beispiele für solche Stoffe sind Kartoffelstärke, Zellulose, Stearinsäure, Graphit und/oder Portland-Zement. Die Einsatzstoffe können direkt in einem Mischer, Kneter oder vorzugsweise einem Mix-Muller gemischt werden. Ferner können die Einsatzstoffe auch in einer Sprühmaische aufgeschlämmt und in einem Sprühtrockner zu einem Sprühpulver verarbeitet werden. Die Einsatzstoffe werden vorzugsweise in einem Mix-Muller oder Kneter unter Zugabe von Wasser zu einer extrudierbaren Masse verarbeitet. Die extru- dierbare Masse wird anschließend extrudiert, getrocknet und kalziniert. Bevorzugte Katalysatorformen sind Stränge, Ringe, Tabletten, Ringtablette, Extrudate oder Wa- benkörper. Besonders bevorzugt sind Katalysatorformkörper oder Katalysatorextrudate mit einem Durchmesser und einer Höhe von kleiner gleich 10 mm. Bevorzugte Strangformen umfassen Katalysatorkugeln mit einem Durchmesser von kleiner 6 mm oder Katalysatorwabenkörper mit einem Zellendurchmesser von kleiner 5 mm oder Extrudate mit 2 bis 10 mm Durchmesser, insbesondere 2,5 bis 6 mm. Der Querschnitt der Extrudate kann rund oder in anderen Formen ausgeführt sein. Besonders bevorzugt sind Extrudate mit rotationssymmetrischem Querschnitt, insbesondere mit einem Durchmesser von 2 bis 4 mm, bevorzugt von 3 mm, sowie Extrudate mit einem sternförmigen oder solche mit einem zahnradförmigen ("toothed-wheel") Querschnitt, insbesondere mit Durchmessern von 3 bis 7, bevorzugt 3,5 mm, 4,5 mm oder 6 mm. Alter- nativ zu einer Extrusion kann die Formgebung der Katalysatoren auch durch eineThe shaping and calcination is expediently carried out as described in the prior art (see, for example, DE-A 101 54 718). For the preparation of 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. Furthermore, 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. As an alternative to extrusion, the shaping of the catalysts can also be achieved by a
Tablettierung erfolgen. Die extrudierten oder gegebenenfalls tablettierten Katalysatorformkörper werden anschließend in der Regel getrocknet und einer Kalzinierung unterzogen. Die Trocknung wird vorzugsweise auf einem Bandtrockner bei Temperaturen zwischen 100 und 2000C durchgeführt. Die Kalzinierung wird vorzugsweise in einem Drehrohr bei Temperaturen zwischen 500 und 10000C, bevorzugt zwischen 700 und 10000C, insbesondere zwischen 800 und 9500C, und besonders bevorzugt zwischen 850 und 9000C durchgeführt. Insbesondere bei der Kalzinierung im besonders bevorzugten Temperaturbereich wandeln sich carbonathaltige Einsatzstoffe in Oxide um. Kalium- und Eisenoxid bilden im besonders bevorzugten Temperaturbereich typi- scherweise gemischte Kaliumferrit-Kristallstrukturen aus.Tableting done. 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. Particularly in the calcination in the particularly preferred temperature range, carbonate-containing feedstocks convert to oxides. Potassium and iron oxides typically form mixed potassium ferrite crystal structures in the most preferred temperature range.
Die Erfindung wird im folgenden am Beispiel des Verfahrens zur Dehydrierung von Ethylbenzol zu Styrol im Detail erläutert.The invention is explained in detail below using the example of the process for the dehydrogenation of ethylbenzene to styrene.
Die Dehydrierung von Kohlenwasserstoffen kann nach allen dem Fachmann bekannten Verfahren durchgeführt werden. Bevorzugt wird die Dehydrierung von Alkylaroma- ten zu Alkenylaromaten in adiabaten oder isothermen Verfahren, insbesondere in adiabaten Verfahren, durchgeführt. Die Reaktion wird in der Regel auf mehrere in Reihe geschaltete Reaktoren, vorzugsweise Radialstromreaktoren, verteilt. Bevorzugt sind zwei bis vier Reaktoren in Reihe geschaltet. In jedem Reaktor befindet sich ein Festbett mit Dehydrierkatalysatoren.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.
Bei der Dehydrierung von Ethylbenzol zu Styrol, wie sie heute in der Regel in sogenannten adiabaten Verfahren mehrstufig ausgeübt wird, wird typischerweise Ethylbenzol zusammen mit Wasserdampf, vorteilhaft in einer Menge von kleiner 30 Gew.-% bezogen auf Ethylbenzol, auf Temperaturen um 5000C mittels eines Wärmetauschers erhitzt und direkt vor dem Eintritt in den ersten Reaktor mit überhitztem Wasserdampf aus einem Dampfüberhitzer gemischt, so dass die gewünschte Eintrittstemperatur im ersten Reaktor üblicherweise zwischen 600 und 6500C liegt. Das Massen-Verhältnis Wasserdampf (Gesamtwasserdampf) zu Ethylbenzol liegt bei Eintritt in die Schüttung des Dehydrierungskatalysators im ersten Reaktor vorteilhaft bei 0,7:1 bis 2,5:1. Bevor- zugt wird bei einem Wasserdampf/Ethylbenzol-Verhältnis von 0,75:1 bis 1 ,8:1 gearbeitet, insbesondere 0,8:1 bis 1 ,5:1. Das Verfahren wird bevorzugt bei reduziertem Druck betrieben, typische Reaktordrücke liegen im Bereich von 300 bis 1000 mbar. Die Raumgeschwindigkeit (LHSV = liquid hourly space velocity) bezogen auf das aktive Volumen der Betten (also das Volumen der Betten abzüglich etwaiger nicht oder kaum durchströmter Totzonen) mit Dehydrierkatalysator liegt in der Regel bei 0,2 bis 0,7 1/h, bevorzugt 0,3 bis 0,6 1/h und insbesondere 0,32 bis 0,58 1/h. Die vorzugsweise hohl- zylinderförmig angeordneten Katalysatorbetten (Radialstromreaktoren) werden von innen nach außen durchströmt.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 space velocity (LHSV = liquid hourly space velocity) based on the active volume of the beds (ie the volume of the beds less any dead or hardly flown dead zones) with dehydrogenation catalyst is usually 0.2 to 0.7 1 / h, preferably 0.3 to 0.6 l / h and in particular 0.32 to 0.58 l / h. The preferably hollow-cylindrical catalyst beds (radial flow reactors) are flowed through from the inside to the outside.
Vor Eintritt in den nächsten Reaktor wird das Reaktionsgemisch vorteilhaft über einen Wärmetauscher mittels überhitztem Dampf erneut auf Temperaturen von üblicherweise 600 und 6500C gebracht. Bevorzugt sollte der Druck am Ausgang des letzten Reaktors nicht mehr als 700 mbar, besonders bevorzugt nicht mehr als 600 mbar und insbesondere nicht mehr als 500 mbar betragen.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. Preferably, 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.
Alternativ kann an Stelle des Wärmetauschers am Eingang des zweiten und gegebenenfalls folgende Reaktoren auch eine Schüttung eines Oxidationskatalysators mit Sauerstoffzufuhr zur Verbrennung einer Teilmenge des im vorangegangenen Reaktor gebildeten Wasserstoffs eingerichtet sein, wie sie beispielsweise in der WO 2005/097715 und in der deutschen Anmeldung mit der WO 2006/018133 ist.Alternatively, instead of the heat exchanger at the entrance of the second and optionally subsequent reactors, 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.
Die bei dem erfindungsgemäßen Verfahren erhältlichen ungesättigten Verbindungen, beispielsweise Alkenylaromaten oder 1 ,3-Alkadiene, können vorteilhaft zu Kunststoffen polymerisiert oder als Bausteine für organisch-chemische Synthesen eingesetzt wer- den. Der erfindungsgemäße Katalysator weist bei einer vergleichbaren Aktivität und Selektivität durch die Verwendung von sekundärem Katalysatormaterial deutlich geringere Herstellkosten auf. Ferner können die Kosten für die Entsorgung des sekundären Katalysatormaterials reduziert werden.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.
BeispieleExamples
Beispiel 1 : Verfahren zur Dehydrierung von EthylbenzolExample 1: Process for the dehydrogenation of ethylbenzene
Beispiel A: Erfindungsgemäßer KatalysatorExample A: Inventive catalyst
Sekundäre Styrol-Katalysatorstränge wurden bei einer Temperatur von 7000C unter sauerstoffhaltiger Atmosphäre für 90 Minuten kalziniert. Die thermisch behandelten sekundären Katalysatorstränge wurden gemahlen, um eine Partikelverteilung von 1 bis 700 μm zu erhalten. Es wurde eine Elementaranalyse durchgeführt.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.
Sekundäres Katalysatorpulver und frische Einsatzstoffe wurden in einem Verhältnis von 40 : 60 Gew.-% gemischt, so dass der erhaltende Katalysator folgende Zusammensetzung aufwies:Secondary catalyst powder and fresh feeds were mixed in a ratio of 40:60 wt% such that the resulting catalyst had the following composition:
Kalium, entsprechend 9,3 Gew.-% als K2O,Potassium, corresponding to 9.3 wt .-% as K 2 O,
Cer, entsprechend 10,7 Gew.-% Ce2O4,Cerium, corresponding to 10.7% by weight of Ce 2 O 4 ,
Magnesium, entsprechend 2,1 Gew.-% MgO,Magnesium, corresponding to 2.1% by weight of MgO,
Calcium, entsprechend 2,2 Gew.-% CaO,Calcium, corresponding to 2.2% by weight of CaO,
Molybdän, entsprechend 2,4 Gew.-% MoO3, Eisen, entsprechend Fe2O3, Differenz zu 100 Gew.-% (rechnerisch)Molybdenum, corresponding to 2.4% by weight of MoO 3 , iron, corresponding to Fe 2 O 3 , difference to 100% by weight (calculated)
Das Katalysatorpulver wurde gemäß Beispiel 8 der DE-A 101 54 718 zu Katalysatorstränge verarbeitet.The catalyst powder was processed according to Example 8 of DE-A 101 54 718 into catalyst strands.
Beispiel B: Erfindungsgemäßer KatalysatorExample B: Inventive catalyst
Es wurden Katalysatorstränge gemäß Beispiel 1 aus sekundärem Katalysatormaterial hergestellt, wobei das sekundäre Katalysatormaterial keiner thermischen Behandlung ausgesetzt wurde.Catalyst strands according to Example 1 were prepared from secondary catalyst material, wherein the secondary catalyst material was not subjected to thermal treatment.
Beispiel C: VergleichsbeispielExample C: Comparative Example
Es wurden Katalysatoren gemäß dem Beispiel 8 der DE-A 101 54 718 hergestellt. Dehydrierung von Ethylbenzol zu Styrol:Catalysts according to Example 8 of DE-A 101 54 718 were prepared. Dehydrogenation of ethylbenzene to styrene:
a) Dehydrierung unter isothermen Bedingungena) dehydrogenation under isothermal conditions
In einer einstufigen isothermen Test-Anlage wurden jeweils 13,3 ml des Katalysators aus den Beispielen A bis C unter den in Tabelle 1 angegebenen Bedingungen getestet.In a single-stage isothermal test system, 13.3 ml of the catalyst from Examples A to C were tested under the conditions given in Table 1.
Tabelle 1 : Versuchsbedingungen und Ergebnisse der Dehydrierung von Ethylbenzol zu Styrol unter isothermen BedingungenTable 1: Test conditions and results of the dehydrogenation of ethylbenzene to styrene under isothermal conditions
b) Dehydrierung unter adiabatischen Bedingungen b) dehydration under adiabatic conditions
In einer zweistufigen adiabatischen Test-Anlage wurden jeweils 434 ml des Katalysators aus den Beispielen A und C pro Reaktor unter den in Tabelle 2 angegebenen Bedingungen getestet.In a two-stage adiabatic test system, in each case 434 ml of the catalyst from Examples A and C per reactor were tested under the conditions given in Table 2.
Tabelle 2: Versuchsbedingungen und Ergebnisse der Dehydrierung von Ethylbenzol zu Styrol unter adiabatischen BedingungenTable 2: Experimental conditions and results of dehydrogenation of ethylbenzene to styrene under adiabatic conditions
Beispiel 2: Performance-Beurteilung von Katalysatoren unterschiedlicher Mischungsverhältnisse zwischen sekundären und frischem Katalysatormaterial Example 2: Performance assessment of catalysts of different mixing ratios between secondary and fresh catalyst material
Um die Performance der einzelnen Katalysatoren zu bewerten, wurden folgende Parameter berücksichtigt:In order to evaluate the performance of the individual catalysts, the following parameters were taken into account:
1. Schnitthärte (SH)1. Cutting hardness (SH)
2. Verformbarkeit (V) mittels (Masse der erhaltenden geformten Strän- ge)/(eingesetzte Gesamtmasse)2. Deformability (V) by means of (mass of the resulting formed strands) / (total mass used)
3. Ausbeute (A)3. Yield (A)
4. Wirtschaftlichkeit (W) mittels Berücksichtigung der jeweiligen eingesparten Materialkosten und der entstehenden Kosten durch Vermahlung und Kalzinierung des sekundären Katalysatormaterials und Lagerung dieses regenerierten Materials 5. Performance mittels Multiplikation der Faktoren 1 bis 4/1004. Economic efficiency (W) by taking into account the respective saved material costs and the resulting costs by grinding and calcination of the secondary catalyst material and storage of this regenerated material 5. Performance by multiplying the factors 1 to 4/100
In der Tabelle 3 sind die genannten Faktoren für die jeweiligen Katalysatoren aufgelistet, die Figur 1 zeigt die ermittelte Performance in Abhängigkeit vom Mischungsverhältnis.In Table 3, the factors mentioned for the respective catalysts are listed, Figure 1 shows the determined performance as a function of the mixing ratio.
Für die Ermittlung der Ausbeute wurde die Dehydrierung von Ethylbenzol zu Styrol unter isothermen Bedingungen gemäß Beispiel a durchgeführt.For the determination of the yield, the dehydrogenation of ethylbenzene to styrene was carried out under isothermal conditions according to Example a.
Tabelle 3: Performancedaten unterschiedlicher KatalysatorenTable 3: Performance data of different catalysts

Claims

Patentansprüche claims
1. Katalysator zur Dehydrierung oder Hydrierung von Kohlenwasserstoffen enthaltend 10 bis 70 Gew.-% gemahlenes, sekundäres Katalysatormaterial eines ge- brauchten (De)Hydrierkatalysators enthaltend Eisenoxid und 30 bis 90 Gew.-% des korrespondierenden frischen Katalysatormaterials enthaltend Eisenoxid, wobei das Eisenoxid des frischen Katalysatormaterials überwiegend in Form von Hämatit oder Kaliumferritphasen vorliegt.1. A catalyst for dehydrogenating or hydrogenating 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.
2. Katalysator nach Anspruch 1 , wobei der Katalysator bei Temperaturen von 500 bis 10000C kalziniertes und anschließend gemahlenes sekundäres Katalysatormaterials enthält.2. Catalyst according to claim 1, wherein the catalyst at temperatures of 500 to 1000 0 C calcined and then ground secondary catalyst material.
3. Katalysator nach Anspruch 1 , wobei der Katalysator bei Temperaturen von 700 bis 10000C kalziniertes und anschließend gemahlenes sekundäres Katalysatormaterial enthält.3. Catalyst according to claim 1, wherein the catalyst at temperatures of 700 to 1000 0 C calcined and then ground secondary catalyst material.
4. Katalysator nach den Ansprüchen 1 bis 3, wobei das Eisenoxid des sekundären Katalysatormaterials 15 bis 85 Gew.-% bezogen auf die Summe der Ei- senoxide, und als Rest Hämatit und/oder Magnetit enthält.4. The catalyst according to claims 1 to 3, wherein the iron oxide of the secondary catalyst material 15 to 85 wt .-% based on the sum of the iron oxides, and the remainder contains hematite and / or magnetite.
5. Katalysator nach den Ansprüchen 1 bis 4, wobei der Katalysator 25 bis 65 Gew.- % gemahlenes, sekundäres Katalysatormaterial und 35 bis 75 Gew.-% des korrespondierenden frischen Katalysatormaterials enthält.5. Catalyst according to claims 1 to 4, wherein the catalyst contains 25 to 65% by weight ground, secondary catalyst material and 35 to 75 wt .-% of the corresponding fresh catalyst material.
6. Verfahren zur Herstellung des Katalysators nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, dass sekundäres Katalysatormaterial eines gebrauchten (De)Hydrierkatalysator gegebenenfalls kalziniert und dann gemahlen wird und anschließend in einem Verhältnis von 1 :9 bis 7:3 mit frischen Einsatzstoffen des korrespondierenden (De)Hydrierkatalysators vermischt, verformt und kalziniert wird.6. A process for the preparation of the catalyst according to claims 1 to 5, 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.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das sekundäre Katalysatormaterial unter sauerstoffhaltiger Atmosphäre bei Temperaturen von 500 bis 10000C kalziniert wird.7. The method according to claim 6, characterized in that the secondary catalyst material is calcined under oxygen-containing atmosphere at temperatures of 500 to 1000 0 C.
8. Verfahren nach den Ansprüchen 6 oder 7, dadurch gekennzeichnet, dass dem sekundären Katalysatormaterial keine Dotiermetalle zugesetzt werden.8. The method according to claims 6 or 7, characterized in that no doping metals are added to the secondary catalyst material.
9. Verfahren nach den Ansprüchen 6 bis 8, dadurch gekennzeichnet, dass das sekundäre Katalysatormaterial in einem Verhältnis von 2,5:7,5 bis 6,5:3,5 mit fri- sehen Einsatzstoffen des korrespondierenden (De)Hydrierkatalysators vermischt, verformt und kalziniert wird.9. The method according to claims 6 to 8, characterized in that the secondary catalyst material in a ratio of 2.5: 7.5 to 6.5: 3.5 with fri- see starting materials of the corresponding (de) hydrogenation catalyst mixed, deformed and calcined.
10. Katalysatorbett, das mindestens 25 Gew.-% Katalysatoren gemäß den Ansprü- chen 1 bis 5 enthält.10. Catalyst bed containing at least 25 wt .-% catalysts according to claims 1 to 5.
11. Verfahren zur Dehydrierung oder Hydrierung von Kohlenwasserstoffen unter Verwendung von Katalysatoren gemäß der Ansprüche 1 bis 5. 11. A process for the dehydrogenation or hydrogenation of hydrocarbons using catalysts according to claims 1 to 5.
EP06792498A 2005-07-22 2006-07-13 Catalyst for the dehydrogenation or hydrogenation of hydrocarbons containing secondary catalyst material Ceased EP1919614A1 (en)

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