WO2007009904A1 - Catalyseur a repartition bimodale des particules de la matiere catalytiquement active, procede pour sa production et sa regeneration et utilisation de ce catalyseur - Google Patents

Catalyseur a repartition bimodale des particules de la matiere catalytiquement active, procede pour sa production et sa regeneration et utilisation de ce catalyseur Download PDF

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WO2007009904A1
WO2007009904A1 PCT/EP2006/064073 EP2006064073W WO2007009904A1 WO 2007009904 A1 WO2007009904 A1 WO 2007009904A1 EP 2006064073 W EP2006064073 W EP 2006064073W WO 2007009904 A1 WO2007009904 A1 WO 2007009904A1
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catalytically active
active material
catalyst
particles
carrier
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PCT/EP2006/064073
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German (de)
English (en)
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Stefan Kotrel
Peter Lechtken
Gerd Rohrbacher
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Basf Aktiengesellschaft
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Priority to EP06792487A priority Critical patent/EP1907120A1/fr
Publication of WO2007009904A1 publication Critical patent/WO2007009904A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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

  • Catalyst with bimodal distribution of the particles of the catalytically active material process for its preparation and for its regeneration and use of the catalyst.
  • the subject of the present invention is a catalyst containing a carrier and a catalytically active material.
  • the particles of the catalytically active material are bimodal size distributed.
  • the fraction of the larger particles of the catalytically active material and the fraction of the smaller particles of the catalytically active material are uniformly mixed in the catalytically active layer of the catalyst.
  • the catalytically active material is 50% by weight or less based on the catalyst.
  • the invention further relates to a process for the preparation or regeneration of a catalyst according to the invention.
  • a catalytically active material located on a support is coagulated in a first step.
  • a further catalytically active material is applied to the carrier.
  • the invention further relates to the use of the catalytically active material for the dehydrogenation of five- or six-membered carbon-containing molecule rings to aromatic compounds.
  • Catalysts with a bimodal size distribution of the catalytically active material are known, for example Sayari et al. (Journal of Electron Spectroscopy and Related Phenomena, 58 (4) (1992) 285 to 298). Sayari et al. but suggest that a bimodal size distribution with a fraction of the smaller particles of the catalytically active material, which is homogeneously distributed over the carrier, and a fraction of the larger particles of the catalytically active material, which are arranged only on the outer surface of the carrier material systematically occurs in the catalysts.
  • Tsang et al. shows a carbon nanotube catalyst with palladium as the catalytically active Material.
  • the outside on the nanotubes arranged palladium particles have a diameter of 20 to 28 nm.
  • the smaller palladium particles arranged on the inside of the nanotube have a mean diameter of approximately 2.6 nm.
  • the good catalytic activity is attributed to the smaller palladium particles located on the inside of the nanotube.
  • DE 19 900 176 describes a catalyst with a bimodal size distribution of the catalytically active material.
  • the catalytically active material is nickel. Zirconium is used as a carrier.
  • the nickel content of the catalyst is 60% or more.
  • EP 1 205 240 discloses palladium as a catalytically active material and ⁇ -alumina as a carrier. A coagulated metal phase coats the particles of the catalytically active material. A bimodal size distribution of the particles of the catalytically active material is considered to be negative, since it can not achieve the desired sweep ratio for optimum catalytic activity. Instead, a monomodal size distribution of the metal-coated catalytically active material is recommended.
  • a deactivated catalyst can be regenerated. It is generally endeavored to prevent coagulation of the catalytically active material, for example by a glow of the carrier, since the coagulated particles of the catalytically active material in principle show a poorer catalytic activity.
  • the support of the catalyst should continue to have a low abrasion.
  • consuming carrier to be produced should be regenerated again.
  • the process should be as cost-effective as possible by a few process steps and the dispensability of chemical substances such as solvents.
  • a repeated regeneration of the carrier material should be possible.
  • This object is achieved according to the invention by providing the catalyst described at the outset and a process for the preparation or regeneration of the catalyst according to the invention.
  • the catalytically active material may be a substance of Groups 7 to 11 of the Periodic Table.
  • the periodic table according to IUPAC applies at the time of February 4, 2005. This means in particular the elements Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au.
  • the catalytically active material is palladium.
  • the catalytically active material can be applied to the support in all forms. The application is possible in metallic or in elementary form, for example by vapor deposition. The catalytically active material can also be applied in a covalently bonded form. It is also possible to apply in an electrostatically bound form. An example is the application in the form of a salt or in the form of a complex of the catalytically active material.
  • the further catalytically active material can be applied to the support, for example by the method described in DE 19 533 665.
  • An oxide support is preferably impregnated with an aqueous nitric acid Pd (NO 3) 2 solution.
  • the Pd content of a Pd (NO 3) 2 solution is generally from 5% by weight to 20% by weight, preferably from 10% by weight to 15% by weight, particularly preferably from 11% by weight to 13 Wt .-% based on the solution.
  • each impregnation step with a Pd (NO 3) 2 solution increases the Pd content of the support by 1% by weight or less, preferably from 0.1% by weight to 0.5% by weight, based on the carrier.
  • the impregnation can also be carried out with other Pd salts or complexes known to the person skilled in the art, such as nitrosyl nitrates, halides, carbonates, carboxylates, acetylacetonates, chloro complexes, nitrite complexes or amine complexes.
  • Pd salts or complexes known to the person skilled in the art, such as nitrosyl nitrates, halides, carbonates, carboxylates, acetylacetonates, chloro complexes, nitrite complexes or amine complexes.
  • the catalytically active material is generally present in the active form on the carrier. This active form depends on the particular catalytically active material.
  • the catalytically active material is generally active in the reduced form.
  • the catalytically active material must therefore be reduced in the case of covalently or electrostatically bonded forms of the catalytically active material, as a rule.
  • This reduction can, for example, by heat treatment under pure H 2 , for example at Pd (NO 3 ) 2 at 230 0 C to 300 0 C, preferably at 240 0 C to 260 0 C for 2 to 3 h, preferably for 1 h to 3 h respectively.
  • the reduction is also possible by CO, hydrazine and all other reduction methods known in the art.
  • catalytically active material for example Pd
  • a plurality of catalytically active elements for example two, three or four different elements, to be applied in covalent or in electrostatically bound or in elemental form to the support.
  • the catalytically active material is generally present in such amounts as to ensure catalytic activity. This depends on the respective catalytic active material for example in Pd usually at a content of the catalytically active material of 0.1 wt .-% or more preferably at 0.3 wt .-% and particularly preferably at 0.5 wt .-% or more based on the Catalyst the case.
  • the catalytically active material is 50% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, and more preferably 1% by weight or less, based on the catalyst.
  • a carrier according to the invention is generally a solid that is heat stable up to the sintering temperature of the catalytically active material.
  • a support according to the invention may be selected from the group metal oxides, nitrites, carbides, silicates, aluminosilicates, spinels or carbons.
  • a carrier according to the invention can also consist of more than just one material.
  • the metal oxides are preferably used as a carrier according to the invention.
  • the preferred carriers in the context of the present invention are 0C-Al 2 O 3 or ZrO 2.
  • An ⁇ -AbCv support according to the invention is preferably prepared according to DE 19 533 665.
  • the support generally has a BET specific surface area of from 1 m 2 / g to 10 m 2 / g, preferably from 4 m 2 / g to 8 m 2 / g, a pore diameter of 5 nm to 300 ⁇ m, preferably 20 nm to 50 microns and especially from 20 nm to 10 microns and a pore volume of 0.1 cm 3 / g to 0.5 cm 3 / g, preferably from 0.2 cm 3 / g to 0.3 cm 3 / g.
  • the catalyst is formed as a shell catalyst.
  • shell-type catalyst is to be understood as meaning a catalyst in which the catalytically active material occurs only in the outer layer.
  • This outer layer is understood to mean the outer 600 ⁇ m or less, preferably the outer 400 ⁇ m or less and in particular the outer 200 ⁇ m of the carrier.
  • a bimodal size distribution of the particles of the catalytically active material is present when the mean diameters of the particles of the catalytically active material are distributed such that they form two maximas.
  • the standard DIN 66136-3 is applicable for chemisorption with regard to the metals platinum and copper.
  • DIN 66136-3 is applied to Pd in the context of the present invention.
  • the chemisorption is preferably carried out with a single Anaylsegas.
  • This analysis gas is preferably CO.
  • Helium can be used preferably as a carrier gas for the CO.
  • a comparison of the thermal conductivity detector signal of an injection (loop) with the signal of a manually performed injection serves as a calibration (gas syringe).
  • the gravimetric control can be done by filling the loop with water. This is described in point 3.4.1 of DIN 66136-3.
  • the ramp is preferably 5 ° C / min.
  • the H 2 can then preferably be washed away with helium.
  • the dispersity and the mean diameter of the particles of the fraction of the smaller particles of the catalytically active material of a catalyst according to the invention can be determined, for example, in particular in the case of Pd as the catalytically active material, as follows.
  • the catalytically active material is first applied to the support, for example in the manner described in Comparative Example 1. This is followed by a CO chemisorption measurement. This CO chemisorption measurement gives the mean diameter and dispersity of the particles of the fraction of the smaller particles of the catalytically active material.
  • Such a value can be seen, for example, in Table 2 for Inventive Example 1 on the catalysis analyzers ⁇ 2 to ⁇ .
  • the dispersity and the mean diameter of the particles of the fraction of the larger particles of the catalytically active material can be determined, for example, in particular in the case of Pd as the catalytically active material as follows.
  • the example given in Example 1 The method of calcination leads to coagulation of the particles of the catalytically active material.
  • a subsequent CO chemisorption measurement according to the method described above then gives the dispersity and the average diameter of the particles of the fraction of the larger particles of the catalytically active material.
  • Such a value can be seen, for example, in the first row of Table 2, for example, 1 in the catalyst V5.
  • the fixation of the catalyst can take place by embedding in synthetic resin.
  • the ultrathin sections (floated on water) can be made with a Microtom Leica Ultracut from the manufacturer Leica.
  • the verification of the catalytically active material can be carried out by an EDXS (Energy Dispersive X-Ray Spectroscopy).
  • the EDXS is particularly suitable for a core charge of greater than 7.
  • HAADF STEM images High Angle Annular Dark Field Scanning TEM
  • the transmission electron micrographs show two different fractions of the particles of the catalytically active material.
  • the maximum of the particles of the smaller fraction of the catalytically active material from 1 nm to 10 nm, more preferably from 3 nm to 7 nm. In another embodiment of the invention, the maximum of the larger fraction of the particles of the catalytically active material from 50 nm to 100 nm, preferably from 60 nm to 80 nm.
  • the dispersity of the particles of the smaller fraction of the catalytically active material is 10% or more, preferably 15% or more and particularly preferably 20% or more and in particular 25% or more.
  • the dispersity of the particles of the larger fraction of the catalytically active material is generally 10% or less, preferably 5% or less, and more preferably 2% or less.
  • the measurement of this Maximas takes place by CO chemisorption according to DIN 66136-3. In the context of the present invention, this is also applied correspondingly to Pd.
  • the CO chemisorption is carried out with a single analysis gas, the CO. This is the so-called CO chemisorption.
  • Helium is used as a carrier gas for the CO.
  • a comparison of the thermal conductivity detector signal of an injection (loop) with the signal of a manually performed injection serves as calibration (gas syringe).
  • the gravimetric control is done by filling the loop with water. This is described in point 3.4.1 of DIN 66136-3.
  • the catalyst is reduced before the CO Chemisorptionsunk at 200 0 C for 30 min under hfe.
  • the ramp is 5 ° C / min.
  • N is the number of Pd atoms on the surface of a Pd particle. N is determined by the CO absorption amount per g of catalyst measured in CO chemisorption.
  • Vpd effective volume of a Pd atom in a Pd particle apd effective area of a Pd atom located on the surface of a Pd particle Dpd dispersity with respect to the last impregnation with Pd see Table 2 for example
  • vpd molecular weight of Pd / (density of Pd * Avogadro constant)
  • the average diameter of the fraction of the larger particles of the catalytically active material is ten times or more of the mean diameter of the fraction of the smaller particles of the catalytically active material. The measurement of this diameter of the fraction of the smaller particles of the catalytically active material takes place after the same CO chemisorption and after the same evaluation, after which the measurement of the Maximas took place.
  • the fraction of the larger particles and the fraction of the smaller particles of the catalytically active material are monodisperse.
  • monodisperse means a small deviation from the mean value of the diameters within a fraction of the particles of the catalytically active material.
  • a low deviation is generally present when the average diameter of the particles of the catalytically active material measured by CO chemisorption is 20% or less, preferably 15% or less, and more preferably 10% or less and in particular 5% or less exceeded or by 20% or less, preferably by 15% or less and more preferably by 10% or less and in particular by 5% or less.
  • This undershoot or overshoot can also be detected, for example, by the transmission electron microscopy described above.
  • a monodisperse distribution according to the invention of the diameter of the particles of the fraction of the larger particles of the catalytically active material and the fraction of the smaller particles of the catalytically active material can be seen, for example, in Example 1, FIG.
  • the particles of the catalytically active material are spheroidal with a ratio of the smallest to the largest diameter of a particle of from 0.5 to 1, preferably from 0.7 to 1 and particularly preferably from 0.9 to 1 before.
  • a uniform mixing of the fractions of the smaller particles and the larger particles of the catalytically active material is understood in the context of the present invention that the particles have no size-dependent preferred arrangement.
  • the particle size of the catalytically active material thus generally does not determine the arrangement on the carrier. In general, therefore, no surfaces can be observed on the surface of the support on which only particles of the fraction of the larger particles of the catalytically active material occur. In general, no surfaces can be observed on the surface of the carrier on which only particles of the fraction of the smaller particles of the catalytically active material occur.
  • a natural limit is the surface structure of the catalyst. The distribution is therefore generally uniform considering the physical limits imposed by the surface structure of the carrier.
  • the physical structure of the carrier allows a uniform distribution of the particles of the fraction of the larger particles and the fraction of the smaller particles of the catalytically active material in the catalytically active layer of the catalyst. This may not be the case for zeolites or nanotubes, for example.
  • FIG. 2 shows that the particles of catalytically active material are evenly distributed on the surface of the carrier. There are no surfaces of the catalyst to see on which preferably only the particles of the fraction of the smaller particles of the catalytically active material or only the larger particles of the catalytically active material occur.
  • Another object of the present invention is a process for the preparation of a catalyst according to the invention.
  • a catalytically active material located on a carrier is coagulated on the carrier in a first step.
  • a catalytically active material is applied to this carrier with the coagulated catalytically active material.
  • coagulation takes place by sintering the catalytically active material supported on a support.
  • sintering is meant a thermal treatment at 50% or more, preferably at 60% or more based on the absolute melting temperature.
  • the coagulation of the particles of the catalytically active material can also be carried out at elevated temperatures.
  • a coagulation of the particles of the catalytically active material by sintering of the catalytically active material is generally carried out until the particles of the catalytically active material are coagulated.
  • the duration of sintering is generally dependent on the type of catalytically active material.
  • the particles can also be coagulated by calcining, for example for 2 hours, at temperatures of 900 ° C. or more on a support. However, it can also be sintered shorter or longer depending on the catalytically active material.
  • the carrier used is preferably an ⁇ -AbOs carrier prepared according to DE 19 533 665, which was preferably impregnated with palladium salt solution. It is preferably a CIM carrier.
  • CIM carrier is to be understood as meaning oxidic carrier which is produced by sintering an oxide powder with the aid of a polymer former. Details of the preparation teach either DE 19 533 468 or DE 19 533 665.
  • the removal of the polymeric binder can be carried out either by calcination or by debindering with other oxidants such as nitric acid.
  • ⁇ -AbOs CIM carrier for example, OC-Al2O3 powder having a particle size of 0.2 .mu.m to 4 .mu.m, preferably from 0.5 .mu.m to 1, 0 .mu.m kneaded with a polymer former, melted and over a Schwerwalzene extruder to a granulate having the size of 1 mm to 10 mm, preferably processed from 3 mm to 6 mm.
  • the green compact is preferably freed from the polymeric binder by pyrolysis and then calcined.
  • a resulting CIM support is characterized by a particularly narrow pore radius distribution.
  • the finished carrier can then in particular be impregnated with a palladium salt solution, particularly preferably with Pd (NO 3) 2.
  • a palladium salt solution particularly preferably with Pd (NO 3) 2.
  • the Pd content of the Pd (NC "3) 2 can vary within wide limits
  • the palladium content of the palladium nitrate solution is 0.05% by weight to 2% by weight, particularly preferably 0.12% by weight. -% to 0.14 wt .-% based on the catalyst of the invention.
  • the soaked catalyst can then be dried.
  • the drying can be carried out with a variety of suitable drying methods.
  • the drying is preferably carried out gently for the carrier. This is the case, for example, during drying with gentle heating in a weak stream of air with constant rotation.
  • the residual moisture of the carrier is generally 1% by weight or less based on the carrier ⁇ .
  • Sintering of the catalytically active material on the carrier can lead to stresses and cracks in the carrier. These stresses and cracks can be removed, for example, by annealing following drying. Annealing may also serve to decompose the nitrates to the corresponding oxides. Annealing means heating the catalyst for an extended period of time. The temperature profile during annealing is preferably determined as a function of the material of the carrier and of the catalytically active material of a catalyst according to the invention.
  • a produced according to DE 19533665 ⁇ subscriptions CIM support which has been preferably impregnated with palladium salt solution, for example, heated in 2 hours to 350 0 C and are annealed for a further 4 h at this temperature.
  • another catalytically active material can be any catalytically active material.
  • the catalytically active materials listed above are preferably used.
  • a particularly preferred catalytically active material is Pd.
  • catalytically active material is in a preferred embodiment, the material chemically same catalytically active material as the coagulated catalytically active material.
  • Pd is coagulated and Pd applied as another catalytically active material.
  • Coagulation of the catalytically active material and the subsequent application of a catalytically active material can take place once. However, the coagulation and the subsequent application of the catalytically active material can also take place two, three, four, five, six, seven, eight, nine, or ten times or more than ten times. In this case, the content of the catalytically active material of the carrier increases. Coagulation and application of another catalytically active material is generally possible until the catalytically active material is present in economically unviable amounts in the catalyst.
  • a fresh catalyst is to be understood as meaning, in particular, a catalyst which has not yet been used for catalysis. It is generally a newly prepared catalyst without significant impurities by by-products of the reaction to be catalyzed and in particular without organic deposits.
  • a deactivated catalyst is understood as meaning a catalyst which has been prepared, for example, by the process described in DE 19 533 665, has been impregnated with palladium on an industrial scale and, for example, for more than 50 days in a large-scale plant at a feed load of 0.12 kg 2,3,6-trimethylphenol per liter of catalyst per hour was in use.
  • Deactivation means, in particular, that the catalytic activity of a catalyst has fallen below an economically viable level, so that the catalyst would have to be replaced in large-scale operation. This is generally the case for a selectivity for the desired reaction product of 80% or less.
  • such a deactivated catalyst is regenerated by coagulating the catalytically active material present on the carrier and, in a further step, by applying a further catalytically active material to the carrier.
  • the coagulation is carried out, for example, by a heat treatment at the sintering temperature of the catalytically active material of a catalyst according to the invention.
  • the sintering is usually carried out over such a period of time, which allows coagulation of the particles of the catalytically active material.
  • a deactivated ⁇ -AbCvTräger which was prepared according to DE 19 533 665, can be regenerated by the annealing at an unusually high temperature of 900 0 C over a period of 2 h.
  • Another catalytically active material is applied in a further step on the carrier thus regenerated.
  • regeneration is possible according to the invention. But it can also take several regenerations.
  • a deactivated catalyst can be regenerated by the process according to the invention and then used during operation until a further deactivation is carried out. Then, the catalyst deactivated for the second time can be regenerated by the method according to the invention, so that it can be used a second time. There are two, three, four, five, six, seven, eight, nine, but also ten or more regeneration steps possible.
  • a catalyst prepared according to DE 19 533 665 and regenerated or treated by the process according to the invention surprisingly shows no further losses in the catalytic performance in a further embodiment.
  • the catalytic performance in this context primarily describes the catalytic performance via a stress test, as described in Example 4 according to the invention.
  • a catalyst regenerated by the process according to the invention even has a better catalytic performance than a fresh catalyst.
  • a catalyst prepared according to the process of the invention and prepared according to the process of the invention can, for example, in the dehydrogenation of 2,3,6-trimethyl-2-cyclohexene-1-one, have a selectivity to 2,3,6-trimethylphenol of 98%. or more.
  • This surprisingly good catalytic performance of an inventively regenerated catalyst is still present in a further embodiment, even after a load on the catalyst.
  • the catalytic performance is generally not significantly degraded by a load compared to a fresh catalyst.
  • the carrier regenerated according to the invention thus generally shows no significant lent other aging phenomena or even a better aging behavior than a fresh catalyst.
  • the inventive method for regenerating a deactivated catalyst is generally inexpensive, since only a few process steps are used. Furthermore, additional chemical substances, such as solvents, are usually dispensable.
  • a catalyst produced by the process according to the invention has an improved service life in industrial operation.
  • An improved service life generally means a service life of 30 days or more, in particular of 40 days or more, more preferably of 50 days or more and in particular of 50 days to 60 days in the case of the feed quantity described above.
  • a catalyst regenerated according to the invention or prepared according to DE 19 533 665 can, for example, have a 2,3,6-trimethylphenol selectivity in the 2,3,6-trimethyl-2-cyclohexene-1-one hydrogenation of 95% or more in a Have a service life of 50 days.
  • This long service life of a catalyst regenerated according to the invention can be achieved in another embodiment without a significant drop in the catalytic performance.
  • the catalyst according to the invention exhibits reduced abrasion.
  • a reduced abrasion is understood to mean the dust produced by a mechanical movement.
  • Abrasion tendency of a catalyst is generally measured in a rotary drum test according to ASTM 4058.
  • the inventive method allows in a further embodiment, a cost-effective production of a catalyst according to the invention.
  • the same carrier can be used several times. For example, one, two, three, four, five, six, seven, eight, nine, but also ten or more regeneration cycles are possible.
  • the process according to the invention of preparing or regenerating a catalyst according to the invention can enable a reuse of a catalyst of a desired quality.
  • the method according to the invention thus makes, in a further embodiment, independent of the variations in quality of a catalyst preparation, for example according to DE 19 533 665.
  • the process according to the invention furthermore makes possible a cost-effective recovery of the catalytically active material.
  • a repeated regeneration of a catalyst according to the invention leads to an enrichment of the catalytically active material on the support.
  • Such enriched catalytically active material can then be recovered inexpensively.
  • a catalyst according to the invention or a catalyst prepared or regenerated by the process according to the invention can generally be used as a function of the catalytically active material and of the carrier for a large number of reaction types.
  • a catalyst according to the invention or a catalyst prepared or regenerated by the novel process for the dehydrogenation of 5- or 6-membered carbon-containing molecular rings can be used to form aromatic compounds.
  • the embodiment of a catalyst prepared according to DE 19 533 655 can be used for this purpose.
  • a catalyst prepared in particular according to DE 19 533 665 and prepared or regenerated by the process according to the invention is used for the preparation of substituted aromatics and heteroaromatics by the catalytic dehydrogenation of non-aromatic, six-membered rings.
  • a catalyst prepared in particular according to DE 19 533 665 and prepared or regenerated by the process according to the invention can be used for the dehydrogenation of 2,3,6-trimethyl-2-cyclohexene-1-one to 2,3,6-trimethylphenol.
  • a catalyst prepared in particular according to DE 19 533 665 and prepared or regenerated by the process according to the invention can be used in a further preferred embodiment for the dehydrogenation of 3-methylpiperidine to 3-picoline.
  • Carrier ⁇ -AbCvTräger prepared according to DE 19 533 665 with a BET specific surface area of about 7 m 2 / g, a pore diameter of 100 nm and a pore volume of 0.23 cm 3 / g
  • Carrier ⁇ commercially available ZrO 2 support with a BET specific surface area of 70 m 2 / g, a pore diameter of 20 nm and a pore volume of 0.27 cm 3 / g
  • Catalytically Active Material Pd served as a catalytically active material in all experiments
  • Comparative Catalysts V1 to V4 a carrier ⁇ with Pd, wherein the Pd was first applied to the support ⁇ by the method in Comparative Example 1.
  • Catalysts according to the invention ⁇ 1 to ⁇ 8 a carrier ⁇ with Pd, wherein the Pd was first applied by the method in Comparative Example 1. This support was additionally treated according to Example 1 of the invention.
  • Inventive catalyst ⁇ a carrier ⁇ with Pd, the Pd being first applied by the method in Comparative Example 1. This support was additionally treated according to Example 1 of the invention.
  • Table 1 Overview of the comparative catalysts and the catalysts of the invention
  • Comparative Example 1 Preparation of a Comparative Catalyst V1
  • the starting material was a support ⁇ , to which no catalytically active material had yet been applied.
  • This carrier ⁇ was first annealed at 950 0 C in air.
  • the support ⁇ was then impregnated with a Pd (NO 3) 2 solution having a Pd content of 0.13% by weight, based on the support ⁇ .
  • the impregnation volume corresponded to 95% based on the water absorption of the carrier ⁇ .
  • the moist catalyst was then dried at 120 0 C to a residual moisture content of 0.2 wt .-% based on the catalyst.
  • Figure 1 shows a TEM brightfield image in review of such a catalyst.
  • a FEI-Tecnai F20 from the manufacturer FEI, Holland was used as the measuring device for such a field emission source TEM.
  • the fixation of the catalyst was carried out by embedding in synthetic resin.
  • the ultrathin sections (floated on water) were made with a microtome Leica Ultracut manufacturer Leica.
  • EDXS Electronic Dispersive X-Ray Spectroscopy
  • Comparative Example 2 Selectivity of Comparative Catalyst V 2 After Loading Comparative Catalyst C 2 was prepared according to Comparative Example 1. Comparative catalyst V2 was used for more than 50 days in a large-scale plant for the dehydrogenation of TCMH to TMP at a feed of 0.12 kg TMCH per liter of catalyst per hour. This comparative catalyst V2 was heated in 2 hours to 450 0 C and annealed for 5 hours at 450 0 C. An activity test according to Inventive Example 4 was carried out. The TMP selectivity was 89.8%.
  • a support was covered with a ß Pd (NC "3) 2 solution having a Pd content of 0.13 wt .-% to the carrier impregnated ß
  • the comparative catalyst was V3. Doing to 120 0 C (2.3 ° C / heated min). this temperature was maintained for 6 h. The comparative catalyst V3 was then heated to 450 0 C (2.6 ° C / min) and calcined for 135 min at this temperature.
  • Comparative Example 4 Preparation of a Comparative Catalyst V4 Which Has a Larger Loading
  • a support ⁇ was heated in 2 h in air at 900 0 C and calcined at 900 0 C for a further 2 h.
  • This support ⁇ was impregnated after cooling with a Pd (NO3) 2 solution having a Pd content of 0.26 wt .-% (V4.1).
  • Another carrier ⁇ was also soaked after cooling with a Pd (NO3) 2 solution having a Pd content of 0.52 wt% (V4.2).
  • the wt .-% information refers to the carrier ⁇ .
  • the impregnation volume corresponded to 95% based on the water absorption of the carrier ⁇ .
  • the wet comparative catalysts V4 were then dried with slight warming in a small stream of air and thereby constantly rotated.
  • the comparative catalysts V4 were then dried for 2 h at 120 0 C, heated in 2 h at 350 0 C and annealed for a further 4 h at this temperature.
  • a comparative catalyst 1 was heated in 2 h in air at 900 0 C and calcined at 900 0 C for a further 2 h. After cooling, the catalyst thus obtained was impregnated with a Pd (NO 3 ) 2 solution having a Pd content of 0.13% by weight, based on the carrier ⁇ . The impregnation volume corresponded to 95% based on the water absorption of the carrier ⁇ . The catalyst thus impregnated was then dried with slight warming (at 40 to 50 0 C for 10 min) in a weak stream of air and thereby constantly rotated. Thereafter, the catalyst was dried for 2 h at 120 0 C, heated in 2 h at 350 0 C and annealed for a further 4 h at this temperature.
  • Figure 2 shows the TEM image of a catalyst according to the invention ⁇ 1.
  • the TEM image was prepared as described in Example 1.
  • the catalyst ⁇ 1 according to the invention consequently exhibits a bimodal distribution of the particles of the catalytically active material.
  • Example 2 Pd content, Pd surface area and size distribution of the catalysts ⁇ 2 to ⁇ 8 regenerated according to the invention.
  • a comparative catalyst V1 was used for longer than 50 days in a large-scale plant for the dehydrogenation of TMCH to TMP in use 0.12 kg TMCH per liter of catalyst per hour.
  • This catalyst was then annealed by the method of Example 1 according to the invention and impregnated with Pd (NC "3) 2 solution The annealing and subsequent soaking were repeated a total of 7 times on the same catalyst
  • a sample for measurement was taken after each annealing and after every other potions retained (inventively regenerated catalysts ⁇ 2 to ⁇ ). The measurement results after each annealing and after each subsequent impregnation are shown in Table 2.
  • Table 2 Pd content, catalytic performance, Pd surface area and average measured by CO chemisorption
  • TMP means 2, 3, 6-trimethylphenol.
  • the TMP selectivity was measured before a load drive according to Example 4 and after a
  • the “total" dispersity describes the percentage of Pd atoms present on the surface of the Pd metal particles, based on the total number of Pd atoms present on the support Proportion of Pd atoms located on the surface of the Pd metal particles, based on the number of Pd atoms that were re-applied to the support by post-soaking.
  • the metal surfaces of the catalysts according to the invention and of the comparative experiment were determined by CO chemisorption according to DIN 66136-3.
  • the standard DIN 66136-3 is applicable for chemisorption with regard to the metals platinum and copper.
  • DIN 66136-3 is correspondingly applied to Pd in the context of the present invention.
  • the chemisorption is carried out with a single Anayl- segas. This analysis gas was CO. It was the so-called CO chemisorption. Helium was used as carrier gas for the CO.
  • a comparison of the thermal conductivity detector signal of an injection (loop) with the signal of a manually performed injection served as a calibration (gas syringe). The gravimetric control was done by filling the loop with water.
  • dispersity is to be understood as meaning the percentage of those Pd atoms of a catalyst according to the invention which are located on the surface of the Pd particles, based on the total Pd amount of a catalyst according to the invention.
  • the diameter of the individual Pd particles was calculated from the dispersity according to Anderson (Anderson, JR, Structure of Metallic Catalysts, Academic Press, London 1975, p. It was assumed that the Pd particles are purely spherical particles.
  • N is the number of Pd atoms on the surface of a Pd particle. N is determined by the CO absorption amount measured in CO chemisorption per g of catalyst.
  • Dpd dispersity based on the last impregnation with Pd see Table 2 for example 1.
  • dpd diameter According to Anderson p. 296, apd was assumed to be 1.27 * 10 19 atoms per m 2 .
  • vpd is calculated according to the formula:
  • vpd molecular weight of Pd / (density of Pd * Avogadro constant)
  • the calculated value of 62 nm was confirmed by the large Pd particles with a diameter of 40 nm to 80 nm found in the TEM image in Figure 2.
  • Table 1 shows the “total” dispersity, which relates to the total amount of Pd of a catalyst according to the invention: Table 1 also shows the "post-saturation” dispersity, which relates only to the impregnated amount of Pd of a catalyst according to the invention. In each case, 0.13% by weight of Pd, based on the catalyst material, was impregnated. The measured metal surface of the Pd remains approximately the same for the subsequent impregnation and annealing steps. The calculated from the dispersity "Nachtränkung" diameter of the Pd particles of a catalyst according to the invention confirmed the found in Figure 2 smaller Pd particles with a diameter of about 1 nm to 5 nm.
  • Example 3 Preparation of a catalyst ⁇ according to the invention with a carrier ⁇
  • a comparative catalyst V3 with a Pd content of 1 wt .-% based on the support ß was heated in 2 h in air at 900 0 C and calcined at 900 0 C for a further 2 h. After cooling, the catalyst thus obtained was impregnated with a Pd (NO 3) 2 solution having a Pd content of 1% by weight, based on the support ⁇ . The impregnation volume corresponded to 95% of the water absorption of the carrier ß. The moist catalyst ⁇ was then dried with gentle heating in a gentle stream of air. This catalyst was then dried for 2 h at 120 0 C, heated in 127 min at 450 0 C and annealed for a further 135 min at this temperature.
  • Example 4 TMP selectivity of a catalyst according to the invention ⁇ 1 and of a comparative catalyst V1 after a load
  • a comparative catalyst V1 and a catalyst ⁇ 1 according to the invention were investigated in a tubular reactor with an inner diameter of 21 mm for the respective activity with respect to the TMCH dehydrogenation.
  • 35 ml of the catalyst was placed in a tubular reactor and activated for 2 h at 250 0 C under pure hfe.
  • the TMCH dosage was then switched on at normal pressure and 300 0 C and on 30 ml / h.
  • the receiver flask for the product collection was changed after a break-in period of 1 h and the formed reaction product, TMP, collected for one hour, then weighed and analyzed for the TMCH, anone and TMP content (sample "before loading").
  • the amount of feed was then increased to twice the value for one load run after one hour each time and the original piston for the product collection was changed, and after two times the load was increased, the initial load was continued for another hour ("after load” sample).
  • Product quality before and after this load was compared.
  • the inventive catalyst ⁇ 1 showed a TMCH selectivity of 97.2% before the load and 96.2% after the load.
  • Comparative catalyst V1 achieved only TMP selectivity of 93.9% before loading and 91.9% after loading under the same experimental conditions.
  • TMP selectivity was measured by a Hewlett-Packard HP 5890 Siries 2 gas chromatograph flow injection method.
  • Table 3 TMP selectivity of a comparative catalyst V1 and a catalyst according to the invention ⁇ 1 before and after the loading described in Example 4.
  • Example 5 TMP Selectivity of the Inventive Catalysts ⁇ 2 to ⁇ 8
  • the catalysts ⁇ 2 to ⁇ 8 regenerated according to the invention were subjected to the test described in Example 4. Table 2 shows the results obtained.
  • Example 6 Cyclohexanone dehydrogenation activity of a catalyst according to the invention and of a comparative catalyst
  • a comparative catalyst V1 and a catalyst ⁇ 1 according to the invention were investigated in the apparatus of Inventive Example 4 for their activity with respect to the dehydrogenation of cyclohexanone to the phenol. All parameters (pressure, temperature, H2 flow, reduction) apart from the set feed loads were identical to the conditions in Example 4 according to the invention.
  • the feed load was halved in two steps. Subsequently, the experiment was completed with the original load. Each load was held for 1 hour. Table 4 shows the phenol and cyclohexanone concentrations of the dehydrogenation product as a function of catalyst loading.
  • Example 7 Catalytic Performance of a catalyst according to the invention ⁇ and a comparative catalyst V3 for the dehydrogenation of 3-MPIP to 3-PIC.
  • the comparative catalyst V3 and the catalyst ⁇ of the invention were investigated for the dehydrogenation of 3-MPIP to 3-PIC.
  • 100 ml of the respective catalyst was charged to a reactor. This was followed by activation for 4 h at 100 ° C. in a 20% by volume H 2 (in N 2 ) atmosphere and then at 200 ° C. under pure H 2 for 3 h. Subsequently, at normal pressure and 265 ° C, the 3-MPIP dosage was turned on and set to 30 ml / h. An additional 4 l / h of H 2 and 16 l / h of N 2 were passed over the catalyst bed.
  • Table 5 3-PIC selectivity of a comparative catalyst V3 and a catalyst according to the invention ⁇ before and after the loading described in Example 7.
  • Example 8 Residual selectivity of a catalyst according to the invention ⁇ 1 and a comparative catalyst V1 after loading
  • the inventive catalyst ⁇ 1 and the comparative catalyst V1 were used in a production plant successively in two production campaigns.
  • the reactor temperature was kept constant at 306 ⁇ 2 ° C, the feed with TMCH was 700 to 800 kg / h. After 50 days, the following results were obtained.
  • the comparative catalyst V1 led to a residual selectivity of 87.4% at a production rate of 720 l.
  • the catalyst ⁇ 1 according to the invention led to a residual selectivity of 96.6% at a production rate of 754 l.

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Abstract

L'invention concerne un catalyseur contenant un support, ainsi qu'une matière catalytiquement active dont les particules sont réparties dimensionnellement de manière bimodale. La fraction des particules plus grandes de la matière catalytiquement active et la fraction des particules plus petites de la matière catalytiquement active sont présentes de manière uniformément mélangée dans la couche catalytiquement active du catalyseur. La matière catalytiquement active représente au plus 50 % en poids par rapport au catalyseur. L'invention concerne également un procédé pour la production ou la régénération d'un catalyseur selon l'invention. Selon ce procédé, une matière catalytiquement active située sur un support est coagulée lors d'une première étape et une autre matière catalytiquement active est appliquée sur le support lors d'une étape suivante. L'invention concerne en outre l'utilisation de la matière catalytiquement active pour la déshydrogénation de cycles moléculaires carbonés à cinq ou six chaînons afin d'obtenir des composés aromatiques.
PCT/EP2006/064073 2005-07-18 2006-07-11 Catalyseur a repartition bimodale des particules de la matiere catalytiquement active, procede pour sa production et sa regeneration et utilisation de ce catalyseur WO2007009904A1 (fr)

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US9061270B2 (en) 2010-02-05 2015-06-23 Exxonmobil Chemical Patents Inc. Cyclohexanone dehydrogenation catalyst and process
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CN107935832A (zh) * 2017-12-30 2018-04-20 郑州智谷工业技术有限公司 一种利用醇脱氢制备醛或半缩醛的方法
CN113058597B (zh) * 2021-03-18 2023-10-27 北京工业大学 一种负载型铂基三效催化剂再生方法

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US8487140B2 (en) 2008-08-29 2013-07-16 Exxonmobil Chemical Patents Inc. Process for producing phenol
US9249077B2 (en) 2009-07-14 2016-02-02 Exxonmobil Chemical Patents Inc. Dehydrogenation process
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