EP2512658A2 - Katalysator und verfahren zur hydrierung von aromaten - Google Patents

Katalysator und verfahren zur hydrierung von aromaten

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Publication number
EP2512658A2
EP2512658A2 EP10792900A EP10792900A EP2512658A2 EP 2512658 A2 EP2512658 A2 EP 2512658A2 EP 10792900 A EP10792900 A EP 10792900A EP 10792900 A EP10792900 A EP 10792900A EP 2512658 A2 EP2512658 A2 EP 2512658A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydrogenation
group
active metal
hydrogenated
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.)
Withdrawn
Application number
EP10792900A
Other languages
German (de)
English (en)
French (fr)
Inventor
Lucia KÖNIGSMANN
Daniela Mirk
Thomas Heidemann
Michael Hesse
Martin Bock
Mario Emmeluth
Jutta Bickelhaupt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10792900A priority Critical patent/EP2512658A2/de
Publication of EP2512658A2 publication Critical patent/EP2512658A2/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J35/31—Density
    • 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
    • B01J35/31—Density
    • B01J35/32—Bulk density
    • 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
    • B01J35/392—Metal surface area
    • 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
    • B01J35/397—Egg shell like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • 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
    • 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
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
    • C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
    • 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
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a coated catalyst comprising an active metal selected from the group consisting of ruthenium, rhodium, palladium, platinum and mixtures thereof, applied to a support material comprising silicon dioxide, wherein the pore volume of the support material is 0.6 to 1, 0 ml / g, determined by Hg porosimetry, the BET surface area is 280 to 500 m 2 / g, and at least 90% of the pores present have a diameter of 6 to 12 nm, a method for producing this A coated catalyst, a process for hydrogenating an organic compound containing at least one hydrogenatable group using the coated catalyst, and the use of the coated catalyst for the hydrogenation of an organic compound.
  • a coated catalyst which contains as active metal ruthenium alone or together with at least one further metal of transition groups IB, VIIB or VIII of the Periodic Table of the Elements, applied to a support comprising silicon dioxide as support material. Further disclosed is a process for producing this coated catalyst, a process for hydrogenating an organic compound containing hydrogenatable groups, and the use of the corresponding catalyst in the hydrogenation of organic compounds containing a hydrogenatable group.
  • the coated catalyst used in this process is characterized in that the active metal to a particularly high proportion in a penetration depth of 300 to 1000 ⁇ , relative to the substrate surface, is present.
  • the catalyst according to this document can a shell catalyst, wherein the surface area of the support material, measured by the BET method, is generally 10 to 500 m 2 / g, the pore volume is generally 0.3 to 1.2 ml / g.
  • Suitable active metals include rhodium, ruthenium, palladium or platinum.
  • the support material according to this document is nanoporous, wherein nanopores with a pore size in the range of 1 to 500 nm are present.
  • WO 99/32427 discloses a process for the hydrogenation of benzene polycarboxylic acids or derivatives thereof using a macroporous catalyst.
  • This catalyst contains as the active metal ruthenium alone or together with at least one metal of the I, VII. Or VIII. Subgroup of the Periodic Table, applied to a support, wherein the support has macropores.
  • the pores of the carrier material have an average diameter of at least 50 nm and a BET surface area of at most 30 m 2 / g.
  • EP 0 814 098 B1 discloses a process for reacting an organic compound in the presence of a supported ruthenium catalyst.
  • the catalyst according to this document is characterized in that it comprises as active metal ruthenium alone or together with at least one metal of the I, VII or VIII subgroup of the periodic table in an amount of 0.01 to 30 wt .-% based on the total weight of the catalyst supported on a support, wherein 10 to 50% of the pore volume of the support is formed by macropores having a diameter in the range of 50 nm to 10,000 nm.
  • EP 1 266 882 B1 discloses a process for the preparation of cyclohexanedicarboxylic acid esters by hydrogenating the corresponding benzenedicarboxylic acid esters in the presence of a suitable catalyst.
  • the catalyst according to this document contains as active metal nickel in an amount of 5 to about 70 wt .-%.
  • WO 2004/009526 A1 also discloses a microporous catalyst and a process for the hydrogenation of aromatic compounds using this catalyst.
  • the cited document mentions catalysts which have an average pore diameter of 5 to 20 nm and a BET surface area> 50 m 2 / g.
  • the amount of active metal ruthenium is 0.1 to 30 wt .-%, and the BET surface area is between 1 and 350 m 2 / g.
  • the pore volume of the carrier material used, for example silicon dioxide, is at low values of 0.28 to 0.43 ml / g.
  • WO 03/103830 A1 discloses a catalyst and a process for the hydrogenation of aromatic compounds using this catalyst.
  • the catalyst according to this document contains as active material at least one metal of VIII.
  • Subgroup and a support material having an average pore diameter of 25 to 50 nm and a specific surface area of> 30 m 2 / g.
  • DE 196 24 835 A1 discloses a process for the hydrogenation of polymers with ruthenium or palladium catalysts.
  • the support material of the catalyst according to this document has a specific pore size distribution, wherein 10 to 50% of the pore volume of the support of macropores having a pore diameter in the range of 50 nm to 10,000 nm and 50 to 90% of the pore volume of the support of mesopores having a pore diameter in Range of 2 to 50 nm are formed.
  • the catalyst according to this document is a full catalyst, i. h., That the active metal is distributed over the entire cross-section of the catalyst particles.
  • the catalysts which are already known from the prior art, as well as the processes for the hydrogenation of aromatic compound using these catalysts are still in need of improvement.
  • the conversion should be increased to the desired target compound, for example a carbocyclic aliphatic compound derived from the corresponding aromatic compound.
  • the selectivity of the catalysts can be further increased with respect to the desired product.
  • Further inventive solutions of the stated objects are a process for the preparation of this catalyst, and a process for the hydrogenation of organic compounds which have at least one hydrogenatable group.
  • the solution of the stated object is based on a coated catalyst containing an active metal selected from the group consisting of ruthenium, rhodium, palladium, platinum and mixtures thereof, which has a very specific combination of certain characteristics, the catalyst a particularly high activity and selectivity, for example the hydrogenation of organic compounds.
  • the coated catalyst according to the invention contains an active metal selected from the group consisting of ruthenium, rhodium, palladium, platinum and mixtures thereof, preferably ruthenium, very particularly preferably ruthenium as the only active metal.
  • the amount of the active metal is generally ⁇ 1 wt .-%, preferably 0.1 to 0.5 wt .-%, particularly preferably 0.25 to 0.35 wt .-%, based on the total weight of catalyst.
  • the present invention therefore preferably relates to the coated catalyst according to the invention, wherein the amount of the active metal is 0.1 to 0.5 wt .-%, particularly preferably 0.25 to 0.35 wt .-%, based on the total weight of the catalyst.
  • Shell catalysts are known per se to those skilled in the art.
  • the term "shell catalyst” means that the existing at least one active metal, preferably ruthenium, is for the most part present in an outer shell of the support material.
  • the shell catalysts according to the invention are preferably 40 to 70 wt .-%, more preferably 50 to 60 wt .-% of the active metal, based on the total amount of the active metal, in the shell of the catalyst to a penetration depth of 200 ⁇ before.
  • the above data are obtained by SEM (electron probe microanalysis) - EDXS (energy dispersive X-ray spectroscopy) and represent averaged values.
  • the coated catalyst according to the invention is preferably characterized in that the predominant amount of the active metal in the shell is present up to a penetration depth of preferably 200 ⁇ m, ie near the surface of the coated catalyst. In contrast, there is preferably no or only a very small amount of the active metal in the interior (core) of the catalyst.
  • the catalyst according to the invention - despite the small amount of active metal - due to the special combination of certain features a very high activity in the hydrogenation of organic compounds containing at least one hydrogenatable groups, especially in the hydrogenation of carbocyclic aromatic groups , with very good selectivities. In particular, the activity of the catalyst according to the invention does not decrease over a long hydrogenation period.
  • a coated catalyst according to the invention in which no active metal can be detected inside the catalyst, i. Active metal is present only in the outermost shell, for example in a zone up to a penetration depth of up to 500 ⁇ m.
  • the amount of the active metal, based on the concentration ratio of active metal to Si, on the surface of the shell catalyst 2 to 25%, preferably 4 to 10%, particularly preferably 4 to 6%, determined by means of SEM EPMA - EDXS.
  • the surface analysis is carried out by means of area analyzes of areas of 800 ⁇ x 2000 ⁇ and with an information depth of about 2 ⁇ .
  • the elemental composition is determined in% by weight (normalized to 100% by weight).
  • the mean concentration ratio (active metal / Si) is averaged over 10 measuring ranges.
  • the surface of the shell catalyst is understood to be the outer shell of the catalyst up to a penetration depth of approximately 2 ⁇ m. This penetration depth corresponds to the information depth in the above-mentioned surface analysis.
  • a coated catalyst in which the amount of the active metal, based on the weight ratio of active metal to Si (wt / wt in%), at the surface of the shell catalyst is 4 to 6%, in a penetration depth of 50 ⁇ 1, 5 to 3% and in the range of 50 to 150 ⁇ penetration 0.5 to 2%, determined by means of SEM EPMA (EDXS), is.
  • the stated values represent averaged values.
  • the size of the active metal particles preferably decreases with increasing penetration, as determined by (FEG) TEM analysis.
  • the active metal is preferably partially or completely crystalline in the coated catalyst according to the invention.
  • very finely crystalline active metal can be detected in the shell of the coated catalyst according to the invention by means of SAD (Selected Area Diffraction).
  • the content of alkaline earth metal ion (s) (M 2+ ) in the catalyst is preferably from 0.01 to 1% by weight, in particular from 0.05 to 0.5% by weight, very particularly preferably from 0.1 to 0.25% by weight .-%, each based on the weight of the silica support material.
  • An essential constituent of the catalysts according to the invention is the support material containing silicon dioxide, preferably amorphous silicon dioxide.
  • amorphous in this context means that the proportion of crystalline silicon dioxide phases makes up less than 10% by weight of the carrier material.
  • the support materials used for the preparation of the catalysts may have superstructures, which are formed by regular arrangement of pores in the carrier material.
  • Suitable support materials are in principle amorphous silicon dioxide types which consist of at least 90% by weight of silicon dioxide, the remaining 10% by weight, preferably not more than 5% by weight, of the support material also being another oxidic material can, for.
  • MgO, CaO, Ti0 2 , Zr0 2 and / or Al 2 0 3 are examples of amorphous silicon dioxide types which consist of at least 90% by weight of silicon dioxide, the remaining 10% by weight, preferably not more than 5% by weight, of the support material also being another oxidic material can, for.
  • MgO, CaO, Ti0 2 , Zr0 2 and / or Al 2 0 3 As MgO, CaO, Ti0 2 , Zr0 2 and / or Al 2 0 3 .
  • the support material is halogen-free, in particular chlorine-free, ie the content of halogen in the support material is generally less than 500 ppm by weight, z. In the range of 0 to 400 ppm by weight.
  • preference is given to a coated catalyst which contains less than 0.05% by weight of halide (determined by ion chromatography), based on the total weight of the catalyst.
  • the halide content of the support material is particularly preferably below the analytical detection limit.
  • support materials containing silicon dioxide which have a specific surface area in the range from 280 to 500 m 2 / g, particularly preferably 280 to 400 m 2 / g, very particularly preferably 300 to 350 m 2 / g (BET surface area to DIN 66131). exhibit. They may have been both natural and artificial.
  • suitable amorphous support materials based on silica are silica gels, kieselguhr, fumed silicas and precipitated silicas.
  • the catalysts comprise silica gels as support materials.
  • the pore volume of the carrier material is 0.6 to 1.0 ml / g, preferably 0.65 to 0.9 ml / g, for example 0.7 to 0.8 ml / g, determined by Hg porosimetry (DIN 66133).
  • at least 90% of the pores present have a pore diameter of 6 to 12 nm, preferably 7 to 11 nm, particularly preferably 8 to 10 nm.
  • the pore diameter can be determined by methods known to those skilled in the art, for example by Hg porosimetry or N 2 physisorption.
  • at least 95%, more preferably at least 98%, of the pores present have a pore diameter of 6 to 12 nm, preferably 7 to 11 nm, particularly preferably 8 to 10 nm.
  • the shell catalyst according to the invention in a preferred embodiment, there are no pores which are smaller than 5 nm. Furthermore, in the coated catalyst according to the invention there are no pores which are greater than 25 nm, in particular greater than 15 nm. In this context, "no pores” means that no pores having these diameters are found by customary measuring methods, for example Hg-porosimetry or N 2 physisorption The maceration of the coated catalyst according to the invention does not involve macropores, but exclusively mesopores within the scope of the measuring accuracy of the analytics used ,
  • the coated catalyst according to the invention in fixed catalyst beds, one usually uses shaped bodies of the support material, which are eg. B. by extrusion, extrusion or tabletting are available and the z.
  • shaped bodies of the support material which are eg. B. by extrusion, extrusion or tabletting are available and the z.
  • balls e.g. B. by extrusion, extrusion or tabletting are available and the z.
  • balls e. B. by extrusion, extrusion or tabletting are available and the z.
  • balls e. B. by extrusion, extrusion or tabletting are available and the z.
  • balls e. B. by extrusion, extrusion or tabletting are available and the z.
  • balls e. B. by extrusion, extrusion or tabletting are available and the z.
  • the dimensions of these moldings usually range from 0.5 mm to 25 mm.
  • Methods for measuring the dispersity of the active metal are known per se to those skilled in the art, for example by pulse demisorption, where the determination of the noble metal dispersion (specific metal surface, crystallite size) is carried out with a CO pulse method (DIN 66136 (1 -3)).
  • the present invention therefore preferably relates to a coated catalyst according to the invention, wherein the dispersity of the active metal is 30 to 60%, particularly preferably 30 to 50%.
  • the surface of the active metal is preferably 0.2 to 0.8 m 2 / g, particularly preferably 0.3 to 0.7 m 2 / g. Methods for measuring the surface of the active metal are known per se to those skilled in the art.
  • the present invention therefore preferably relates to a shell catalyst according to the invention, wherein the surface of the active metal is 0.2 to 0.8 m 2 / g, particularly preferably 0.3 to 0.7 m 2 / g.
  • the coated catalyst according to the invention preferably has a packing density of 400 to 600 g / l, more preferably 450 to 550 g / l.
  • the present invention therefore preferably relates to a coated catalyst according to the invention which has a packing density of 400 to 600 g / l, more preferably 450 to 550 g / l.
  • the coated catalyst according to the invention is used in the hydrogenation of organic compounds, the very specific combination of features of the silica-containing carrier material with a specific pore volume, a BET specific surface area and a very specific pore diameter gives it a particularly high activity and selectivity with respect to the desired products.
  • the present invention therefore preferably relates to a coated catalyst according to the invention comprising ruthenium as active metal applied to a support material containing silicon dioxide, the pore volume of the support material being 0.6 to 1.0 ml / g, preferably 0.65 to 0.9 ml / g, for example 0.7 to 0.8 ml / g, determined by Hg porosimetry (DIN 66133) and N 2 adsorption (DIN 66131), the BET surface area 280 to 500 m 2 / g, preferably 280 to 400 m 2 / g, particularly preferably 300 to 350 m 2 / g, (BET surface area according to DIN 66131), and at least 90%, preferably at least 95%, particularly preferably at least 98%, of the pores present Diameter of 6 to 12 nm, preferably 7 to 1 1 nm, more preferably 8 bi 10 nm.
  • the preparation of the coated catalysts according to the invention is preferably carried out by first soaking the carrier material with a solution containing a precursor compound of the active metal or several times, drying the resulting solid and then reducing it.
  • the individual process steps are described in more detail below.
  • a further subject of the present application is thus a process for the preparation of a coated catalyst according to one of claims 1 to 5, comprising the steps: one or more impregnation of the support material containing silica with a solution containing at least one precursor compound of the active metal, followed by drying,
  • step (A) a single or multiple impregnation of the carrier material containing silicon dioxide with a solution containing at least one precursor compound of the active metal.
  • all precursor compounds of the active metal are suitable, which can be converted in the process conditions of the invention into metallic active metal, for example, nitrates, acetonates and acetates, acetates being preferred.
  • the active metal is ruthenium, for example, ruthenium (III) acetate is preferred.
  • Further preferred precursor compounds are palladium (II) acetate, platinum (II) acetate and / or rhodium (II) acetate.
  • Suitable solvents for providing the solution containing at least one precursor compound are water or mixtures of water or solvent with up to 50 vol .-% of one or more water or solvent-miscible organic solvents, eg. B.
  • acetic acid or glacial acetic acid may also be used. All mixtures should be chosen so that there is a solution or phase.
  • Preferred solvents are acetic acid, water or mixtures thereof. Particular preference is given to using a mixture of water and acetic acid as solvent, since ruthenium (III) acetate is usually present dissolved in acetic acid or glacial acetic acid.
  • the catalyst according to the invention can also be prepared without the use of water.
  • the impregnation of the carrier material can take place in different ways and depends in a known manner on the shape of the carrier material. For example, one can spray or rinse the support material with the solution of the precursor compound or suspend the support material in the solution of the precursor compound. For example, it is possible to suspend the support material in an aqueous solution of the active metal precursor compound and to filter off the aqueous supernatant after a certain time. On the recorded amount of liquid and the active metal concentration of the solution then the active metal content of the catalyst can be controlled in a simple manner.
  • the impregnation of the carrier material can also be carried out, for example, by treating the carrier with a defined amount of the solution of the active metal precursor compound which corresponds to the maximum amount of liquid that can absorb the carrier material.
  • Suitable apparatuses for this purpose are the apparatuses commonly used for mixing liquids with solids (see Vauck / Müller, Basic Operations of Chemical Process Engineering, 10th edition, Deutscher Verlag für Grundstoffindustrie, 1994, p. 405 et seq.), For example tumble dryers, tumbling drums, drum mixers , Paddle mixer and the like. Monolithic carriers are usually rinsed with the aqueous solutions of the active metal precursor compound.
  • the solutions used for impregnating are preferably low in halogen, in particular low in chlorine, ie they contain no or less than 500 ppm by weight, in particular less than 100 ppm by weight of halogen, eg 0 to ⁇ 80 ppm by weight of halogen, based on the total weight of the solution.
  • the concentration of the active metal precursor compound in the solutions depends of course on the amount of active metal precursor compound to be applied and the absorption capacity of the carrier material for the solution and is ⁇ 20% by weight, preferably 0.01 to 6% by weight, particularly preferably 0, 1 to 1, 1 wt .-%, based on the total mass of the solution used.
  • the drying can be carried out by the usual methods of drying solids while maintaining the upper temperature limits mentioned below.
  • the observance of the upper limit of the drying temperatures is for the quality, i. the activity of the catalyst important. Exceeding the drying temperatures given below results in a significant loss of activity. Calcination of the support at higher temperatures, e.g. Above 300 ° C or even 400 ° C, as proposed in the prior art, is not only superfluous but also adversely affects the activity of the catalyst.
  • the drying is preferably carried out at elevated temperature, preferably at ⁇ 180 ° C, especially at ⁇ 160 ° C, and at least 40 ° C, especially at least 70 ° C, especially at least 100 ° C, especially in the range of 1 10 ° C to 150 ° C.
  • the drying of the impregnated with the active metal precursor compound solid is usually carried out under atmospheric pressure and to promote the drying, a reduced pressure can be applied. Frequently, to promote drying, a gas stream will be passed over or through the material to be dried, e.g. Air or nitrogen.
  • the drying time naturally depends on the desired degree of drying and the drying temperature and is preferably in the range of 1 h to 30 h, preferably in the range of 2 to 10 h.
  • the drying of the treated support material is preferably carried out to such an extent that the content of water or of volatile solvent constituents before the subsequent reduction is less than 5% by weight, in particular not more than 2% by weight, based on the total weight of the solid.
  • the stated proportions by weight in this case relate to the weight loss of the solid, determined at a temperature of 160 ° C., a pressure of 1 bar and a duration of 10 minutes. In this way, the activity of the catalysts used according to the invention can be further increased.
  • the conversion of the solid obtained after drying into its catalytically active form is carried out by reducing the solid at temperatures in the range of generally from 150 ° C. to 450 ° C., preferably from 250 ° C. to 350 ° C., in a manner known per se.
  • the support material is brought into contact with hydrogen or a mixture of hydrogen and an inert gas at the above-indicated temperatures.
  • the hydrogen absolute pressure is of minor importance for the result of the reduction and can be varied, for example, in the range from 0.2 bar to 1.5 bar.
  • the hydrogenation of the catalyst material is carried out at normal hydrogen pressure in the hydrogen stream.
  • the reduction is carried out by moving the solid, for example by reducing the solid in a rotary kiln or a rotary kiln. In this way, the activity of the catalysts according to the invention can be further increased.
  • the hydrogen used is preferably free of catalyst poisons, such as CO- and S-containing compounds, eg H 2 S, COS and others.
  • the reduction can also be carried out by means of organic reducing reagents such as hydrazine, formaldehyde, formates or acetates.
  • the catalyst can be passivated in a known manner to improve the handling, for example by briefly mixing the catalyst with an oxygen-containing gas, for example air, but preferably with an inert gas mixture containing 1 to 10% by volume of oxygen , treated. Also, C0 2 or C0 2/02-mixtures can be applied here.
  • the active catalyst may also be stored under an inert organic solvent, eg ethylene glycol.
  • the active metal catalyst precursor e.g. as prepared above or prepared as described in WO-A2-02 / 100538 (BASF AG)
  • the active metal catalyst precursor are impregnated with a solution of one or more alkaline earth metal (II) salts.
  • Suitable alkaline earth metal (II) salts are corresponding nitrates, in particular magnesium nitrate and calcium nitrate.
  • a suitable solvent for the alkaline earth metal (II) salts in this impregnation step is water.
  • the concentration of the alkaline earth metal (II) salt in the solvent is, for example, 0.01 to 1 mol / liter. Due to the manufacturing process, the active metal is present in the catalysts according to the invention as metallic active metal.
  • the halide content, in particular chloride content, of the shell catalysts of the invention is also below 0.05 wt .-% (0 to ⁇ 500 ppm by weight, eg im Range of 0-400 wppm) based on the total weight of the catalyst.
  • the chloride content is e.g. determined by ion chromatography with the method described below.
  • the support material preferably contains not more than 1% by weight and in particular not more than 0.5% by weight and in particular not more than 0.2% by weight of aluminum oxide, calculated as Al 2 O 3 .
  • the concentration of Al (III) and Fe (II and / or III) in total is preferably less than 300 ppm, more preferably less than 200 ppm, and is e.g. in the range of 0 to 180 ppm.
  • the proportion of alkali metal oxide preferably results from the preparation of the support material and can be up to 2 wt .-%. It is preferably less than 1% by weight. Also suitable are alkali metal oxide-free carrier (0 to ⁇ 0.1 wt .-%). The proportion of MgO, CaO, TiO 2 or ZrO 2 can make up to 10 wt .-% of the support material and is preferably not more than 5 wt .-%. Also suitable are support materials which contain no detectable amounts of these metal oxides (0 to ⁇ 0.1 wt .-%).
  • the coated catalyst of the invention is preferably used as a hydrogenation catalyst. It is particularly suitable for the hydrogenation of organic compounds containing at least one hydrogenatable group.
  • the hydrogenatable groups may be groups having the following structural units: CC double bonds, CC triple bonds, aromatic groups, CN double bonds, CN triple bonds, CO double bonds, NO double bonds, CS double bonds, N0 2 Groups, wherein the groups may also be contained in polymers or cyclic structures, for. B. in unsaturated heterocycles.
  • the hydrogenatable groups can each occur individually or multiply in the organic compounds. It is also possible that the organic compounds have two or more different of said hydrogenatable groups. Depending on the hydrogenation conditions, it is possible in the last case that only one or more of the hydrogenatable groups are hydrogenated.
  • the coated catalyst according to the invention for the hydrogenation of benzene to cyclohexane thus the typical cyclohexane specifications that require a benzene residual content of ⁇ 100 ppm (equivalent to a benzene conversion of> 99.99%), complied.
  • the benzene conversion in a hydrogenation of benzene with the shell catalyst of the invention > 99.995%.
  • the conversion in a hydrogenation of aromatic dicarboxylic acid esters, in particular phthalic acid esters, with the coated catalyst according to the invention > 99.995%.
  • a further subject of the present application is therefore a process for the hydrogenation of an organic compound which comprises at least one hydrogenatable group. preferably, for hydrogenating a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group or for hydrogenating aldehydes to the corresponding alcohols, most preferably for hydrogenating a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, wherein the organic compound with at least one reducing agent and a shell catalyst according to the invention is brought into contact.
  • the present invention also relates to the use of the coated catalyst of the invention in a process for the hydrogenation of an organic compound containing at least one hydrogenatable group.
  • the present invention relates to this use according to the invention wherein a carbocyclic aromatic group is hydrogenated to the corresponding carbocyclic aliphatic group or aldehydes to the corresponding alcohols.
  • the carbocyclic aromatic group is preferably part of an aromatic hydrocarbon having the following general formula:
  • A is selected from phenyl, diphenyl, benzyl, dibenzyl, naphthyl, anthracene, pyridyl and quinoline, more preferably A is phenyl;
  • n is preferably 0 to 4; independently of the ring size, n is more preferably 0 to 3, most preferably 0 to 2 and especially 0 to 1; the other carbon atoms or heteroatoms of A carrying no substituents B carry hydrogen atoms or optionally no substituents;
  • alkyl is independently selected from the group consisting of alkyl, alkenyl, alkynyl, substituted alkyl, substituted alkenyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, heteroalkenyl, substituted heteroalkenyl, heteroalkynyl, substituted heteroalkynyl, cycloalkyl, cycloalkenyl, substituted cycloalkyl, substituted cycloalkenyl, COOR wherein R is H, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl or substituted aryl, halogen, hydroxy, alkoxy, aryloxy, carbonyl, amino, amido, thio and phosphino; preferably B is independently selected from Ci -6 alkyl, Ci -6 alkenyl, Ci -6 alkynyl, C 3- 8 cycloalkyl, C 3- 8 cycloalkenyl
  • alkyl according to the present application is to be understood as meaning branched or linear, saturated acyclic hydrocarbon radicals.
  • suitable alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, etc.
  • COOR R is H or branched or linear alkyl, H or C preferably 12 alkyl.
  • Preferred alkyl groups are C 4-10 -alkyl groups, more preferably C 8 -10-alkyl groups. These may be branched or unbranched and are preferably branched.
  • the alkyl groups having more than three carbon atoms may be mixtures of isomers of different alkyl groups having the same carbon number.
  • One example is a C 9 -alkyl group, which may be an isononyl group, ie an isomer mixture of various C 9 -alkyl groups. The same applies, for example, to a C 8 -alkyl group.
  • Such isomer mixtures are obtained starting from the alcohols corresponding to the alkyl groups, which are obtained as isomer mixtures on the basis of their preparation process known to the person skilled in the art.
  • Alkenyl according to the present application is to be understood as meaning branched or unbranched acyclic hydrocarbon radicals which have at least one carbon-carbon double bond. Suitable alkenyl radicals are, for example, 2-propenyl, vinyl, etc.
  • the alkenyl radicals preferably have 2 to 50 carbon atoms, particularly preferably 2 to 20 carbon atoms, very particularly preferably 2 to 6 carbon atoms and in particular 2 to 3 carbon atoms.
  • the term alkenyl is to be understood as meaning those radicals which have either an cis or a trans orientation (alternatively E or Z orientation).
  • Alkynyl according to the present application is to be understood as meaning branched or unbranched acyclic hydrocarbon radicals which have at least one carbon-carbon triple bond.
  • the alkynyl radicals preferably have 2 to 50 carbon atoms, particularly preferably 2 to 20 carbon atoms, very particularly preferably 1 to 6 carbon atoms and in particular 2 to 3 carbon atoms.
  • Substituted alkyl, substituted alkenyl and substituted alkynyl are alkyl-alkenyl and alkynyl radicals in which one or more hydrogen atoms bound to one carbon atom of these radicals are replaced by another group.
  • heteroalkyl heteroalkenyl and heteroalkynyl are meant alkyl-alkenyl and alkynyl radicals wherein one or more of the carbon atoms in the carbon chain is selected from N, O and a heteroatom S are replaced.
  • the bond between the heteroatom and another carbon atom may be saturated or optionally unsaturated.
  • Cycloalkyl according to the present application is to be understood as meaning saturated cyclic nonaromatic hydrocarbon radicals which are composed of a single ring or several condensed rings.
  • Suitable cycloalkyl radicals are, for example, cyclopentyl, cyclohexyl, cyclooctanyl, bicyclooctyl, etc.
  • the cycloalkyl radicals preferably have between 3 and 50 carbon atoms, particularly preferably between 3 and 20 carbon atoms, very particularly preferably between 3 and 8 carbon atoms and in particular between 3 and 6 carbon atoms.
  • cycloalkenyl By cycloalkenyl, according to the present application, partially unsaturated, cyclic non-aromatic hydrocarbon radicals are to be understood which have a single or multiple condensed rings. Suitable cycloalkenyl radicals are, for example, cyclopentenyl, cyclohexenyl, cyclooctenyl etc.
  • the cycloalkenyl radicals preferably have 3 to 50 carbon atoms, particularly preferably 3 to 20 carbon atoms, very particularly preferably 3 to 8 carbon atoms and in particular 3 to 6 carbon atoms.
  • Substituted cycloalkyl and substituted cycloalkenyl radicals are cycloalkyl and cycloalkenyl radicals in which one or more hydrogen atoms of any carbon atom of the carbon ring are replaced by another group.
  • Such other groups are, for example, halogen, alkyl, alkenyl, alkynyl, substituted alkyl, substituted alkenyl, substituted alkynyl, aryl, substituted aryl, cycloalkyl, cycloalkenyl, substituted cycloalkyl, substituted cycloalkenyl, an aliphatic heterocyclic radical, a substituted aliphatic heterocyclic radical, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, seleno and combinations thereof.
  • substituted cycloalkyl and cycloalkenyl radicals are 4-dimethylaminocyclohexyl, 4,5-dibromocyclohept-4-enyl and others
  • aryl is to be understood as meaning aromatic radicals which have a single aromatic ring or a plurality of aromatic rings which are condensed, linked via a covalent bond or are bonded by a suitable moiety, eg. Example, a methylene or ethylene unit are linked.
  • suitable moieties may also be carbonyl moieties, such as in benzophenone, or oxygen moieties, such as in diphenyl ether, or nitrogen moieties, such as in diphenylamine.
  • the aromatic ring or the aromatic rings are, for example, phenyl, naphthyl, diphenyl, diphenyl ether, diphenylamine and benzophenone.
  • the aryl radicals preferably have 6 to 50 carbon atoms, particularly preferably 6 to 20 carbon atoms, very particularly preferably 6 to 8 carbon atoms.
  • Substituted aryl radicals are aryl radicals wherein one or more hydrogen atoms attached to carbon atoms of the aryl radical are replaced by one or more other groups.
  • Suitable groups include alkyl, alkenyl, alkynyl, substituted alkyl, substituted alkenyl, substituted alkynyl, cycloalkyl, cycloalkenyl, substituted cycloalkyl, substituted cycloalkenyl, heterocyclo, substituted heterocyclo, halogen, halo-substituted alkyl (e.g., CF 3 ), hydroxy, amino , Phosphino, alkoxy, thio and both saturated and unsaturated cyclic hydrocarbons, which may be fused to the aromatic ring or to the aromatic rings or may be linked by a bond, or may be linked to one another via a suitable group.
  • Suitable groups have already been mentioned above.
  • Heteroaryl radicals are to be understood as those aryl radicals in which one or more of the carbon atoms of the aromatic ring of the aryl radical has been replaced by a heteroatom selected from N, O and S.
  • Substituted heteroaryl radicals are understood as meaning those substituted aryl radicals in which one or more of the carbon atoms of the aromatic ring of the substituted aryl radical has been replaced by a heteroatom selected from N, O and S.
  • Heterocyclo means a saturated, partially unsaturated or unsaturated cyclic radical in which one or more carbon atoms of the radical are represented by a heteroatom, e.g. N, O or S are substituted (the term "heterocyclo" also includes the abovementioned heteroaryl radicals.)
  • heterocyclo radicals are piperazinyl, morpholinyl, tetrahydropyranyl, Tetrahydrofuranyl, piperidinyl, pyrrolidinyl, oxazolinyl, pyridyl, pyrazyl, pyridazyl, pyrimidyl.
  • Substituted heterocyclo radicals are those heterocyclo radicals in which one or more hydrogen atoms which are bonded to one of the ring atoms are replaced by another group.
  • Other suitable groups include halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, seleno, and combinations thereof.
  • Alkoxy radicals are radicals of the general formula -OZ 1 , where Z 1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, silyl and combinations thereof.
  • Suitable alkoxy radicals are, for example, methoxy, ethoxy, benzyloxy, t-butoxy, etc.
  • aryloxy means those radicals of the general formula -OZ 1 , wherein Z 1 is selected from aryl, substituted aryl, heteroaryl, substituted heteroaryl and Combinations of it.
  • Suitable aryloxy groups are phenoxy, substituted phenoxy, 2-pyridinoxy, 8-quinolinoxy, etc.
  • A is phenyl
  • n is 0 to 3
  • the hydrogenation process according to the invention is preferably carried out in such a way that the phenyl group is completely hydrogenated to the corresponding cyclohexyl group.
  • Preferred compounds which are hydrogenated according to the invention to their corresponding cyclohexyl derivatives are mentioned below.
  • the aromatic hydrocarbon is selected from the group consisting of benzene and alkyl-substituted benzenes such as toluene, ethylbenzene, xylene (mixture of o, m, p or isomers) and mesitylol (1, 2,4 or 1, 3,5 or mixture of isomers).
  • benzene is preferably hydrogenated to cyclohexane and the alkyl-substituted benzenes such as toluene, ethylbenzene, xylene and mesitylol to alkyl-substituted cyclohexanes such as methylcyclohexane, ethylcyclohexane, dimethylcyclohexane and trimethylcyclohexane. It is also possible to hydrogenate any desired mixtures of the aforementioned aromatic hydrocarbons to mixtures of the corresponding cyclohexanes.
  • any mixtures containing two or three compounds selected from benzene, toluene and xylene can be hydrogenated to mixtures containing two or three compounds selected from cyclohexane, methylcyclohexane and dimethylcyclohexane.
  • the aromatic hydrocarbon is selected from the group consisting of phenol, alkyl-substituted phenols such as 4-tert-butylphenol and 4-nonylphenol, bis (p-hydroxyphenyl) methane and bis (p-hydroxyphenyl ) dimethyl methane.
  • phenol to cyclohexanol the alkyl-substituted phenols such as 4-tert-butylphenol and 4-nonylphenol
  • alkyl-substituted cyclohexanols such as 4-tert-butylcyclohexanol and 4-nonylcyclohexanol
  • bis (p-hydroxyphenyl) methane to bis in the inventive method are preferred (p-hydroxycyclohexyl) methane and bis (p-hydroxyphenyl) dimethylmethane hydrogenated to bis (p-hydroxycyclohexyl) dimethylmethane.
  • the aromatic hydrocarbon is selected from the group consisting of aniline, alkyl-substituted aniline, ⁇ , ⁇ -dialkylaniline, diaminobenzene, bis (p-aminophenyl) methane and bis (p-aminotolyl) methane.
  • aniline to cyclohexylamine alkyl-substituted aniline to alkyl-substituted cyclohexylamine, ⁇ , ⁇ -dialkylaniline to N, N-dialkylcyclohexylamine, diaminobenzene to diaminocyclohexane, bis (p-aminophenyl) methane to bis (p-aminocyclohexyl) methane and bis (p-aminotolyl) methane hydrogenated to bis (p-amino-methylcyclohexyl) methane.
  • the aromatic hydrocarbon is selected from the group consisting of aromatic carboxylic acids such as phthalic acid and aromatic Carbonchureestern such as C i 2 alkyl esters of phthalic acid, wherein said Ci-i2 alkyl radicals may be linear or branched, for example, dimethyl phthalate, di-2-propylheptylphthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, diisononyl phthalate.
  • aromatic carboxylic acids such as phthalic to cycloaliphatic carboxylic acids such as tetrahydrophthalic acid and aromatic carboxylic acid esters such as Ci-i 2 alkyl esters of phthalic to aliphatic carboxylic acid esters such as C-12-alkyl esters of tetrahydrophthalic eg dimethyl phthalate to Dimethylcyclohexandicarboxylat, di-2-propylheptylphthalat to di-2-propylheptylcyclohexandicarboxylat, di-2-ethylhexylphthalat to di-2-ethylhexylcyclo-hexanedicarboxylate, dioctyl phthalate to Dioctylcyclohexandicarboxylat and diisononyl phthalate to diisononyl-cyclohexanedicarboxylate, hydrogenated.
  • aromatic carboxylic acids such as phthalic to
  • the organic compound which has at least one carbocyclic aromatic group selected from the group consisting of benzene, alkyl-substituted benzenes, phenol, alkyl-substituted phenols, aniline, alkyl-substituted aniline, N, N-dialkylaniline, Diaminobenzene, bis (p-aminophenyl) methane, bis (p-aminotolyl) methane, aromatic carboxylic acids, aromatic carboxylic esters and mixtures thereof.
  • carbocyclic aromatic group selected from the group consisting of benzene, alkyl-substituted benzenes, phenol, alkyl-substituted phenols, aniline, alkyl-substituted aniline, N, N-dialkylaniline, Diaminobenzene, bis (p-aminophenyl) methane, bis (p-aminotolyl) methane, aromatic carboxylic acids, aromatic
  • the organic compound which comprises at least one organic compound which has at least one carboelomatic aromatic group selected from the group consisting of benzene, diisononyl phthalate, benzoic acid, 2-methylphenol, bisphenol A, cuminaldehyde, aniline, methylenedianiline, ortho Toluidine base, xylidine base and mixtures thereof.
  • the present application relates to a process for the hydrogenation of aldehydes to the corresponding alcohols.
  • Preferred aldehydes are mono- and disaccharides such as glucose, lactose and xylose.
  • the mono- and disaccharides are hydrogenated to the corresponding sugar alcohols, e.g. glucose is hydrogenated to sorbitol, lactose to lactitol and xylose to xylitol.
  • Suitable mono- and disaccharides and suitable hydrogenation conditions are, for.
  • the coated catalyst according to the present invention is used.
  • the hydrogenation process according to the invention is a selective process for the hydrogenation of organic compounds containing hydrogenatable groups, preferably for the hydrogenation of a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, with high yields and space-time yields, [product amount / (catalyst volume ⁇ time) ] (kg / (l Ka t ⁇ h)), [ amount of product / (reactor volume ⁇ time)] (kg / (l reac tor ⁇ h)), based on the catalyst used and in which the Catalysts without workup can be used several times for hydrogenations. In particular, long catalyst life times are achieved in the hydrogenation process according to the invention.
  • the hydrogenation process according to the invention can be carried out in the liquid phase or in the gas
  • the hydrogenation process of the invention may be carried out in the absence of a solvent or diluent or the presence of a solvent or diluent, i. it is not necessary to carry out the hydrogenation in solution.
  • solvent or diluent may be used as solvent or diluent.
  • the solvents or diluents are basically additionally those which are capable of dissolving as completely as possible the organic compound to be hydrogenated or which are completely mixed with it and which are inert under the hydrogenation conditions, ie are not hydrogenated.
  • Suitable solvents are cyclic and acyclic ethers, for example tetrahydrofuran, dioxane, methyl tert-butyl ether, dimethoxyethane, dimethoxypropane, dimethyldiethylene glycol, aliphatic alcohols such as methanol, ethanol, n- or isopropanol, n-, 2-, iso- or tert Butanol, carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate or butyl acetate, and aliphatic Etheralkohole such as methoxypropanol and cycloaliphatic compounds such as cyclohexane, methylcyclohexane and dimethylcyclohexane.
  • aliphatic alcohols such as methanol, ethanol, n- or isopropanol, n-, 2-, iso- or tert Butanol
  • the amount of solvent or diluent used is not particularly limited and can be freely selected as needed, but those amounts are preferred which lead to a 3 to 70 wt .-% solution of the organic compound intended for hydrogenation.
  • the use of a diluent is advantageous in order to avoid excessive heat of reaction in the hydrogenation process. Excessive heat of reaction can lead to deactivation of the catalyst and is therefore undesirable. Therefore, careful temperature control is useful in the hydrogenation process of the present invention. Suitable hydrogenation temperatures are mentioned below.
  • the product formed during the hydrogenation is preferably used as solvent, optionally in addition to other solvents or diluents.
  • a part of the product formed in the process can be admixed with the aromatic still to be hydrogenated.
  • cyclohexane is thus used as solvent in a particularly preferred embodiment.
  • the corresponding cyclohexanedicarboxylic acid dialkyl esters are preferably used as solvent.
  • the present invention relates to a hydrogenation of the type in question, wherein benzene is hydrogenated in the presence of the catalyst according to the invention to cyclohexane.
  • the actual hydrogenation is usually carried out in analogy to the known hydrogenation for the hydrogenation of organic compounds, the hydrogenatable groups preferably for the hydrogenation of a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, as described in the aforementioned prior art.
  • the organic compound is brought into contact as liquid phase or gas phase, preferably as liquid phase, with the catalyst in the presence of hydrogen.
  • the liquid phase can be passed through a fluid catalytic bed (fluid bed mode) or a fixed catalyst bed (fixed bed mode).
  • the present invention therefore preferably relates to the process according to the invention. wherein the hydrogenation is carried out in a fixed bed reactor.
  • the hydrogenation can be configured both continuously and discontinuously, wherein the continuous process procedure is preferred.
  • the process according to the invention is carried out in trickle-bed reactors or in flooded mode according to the fixed-bed procedure.
  • the hydrogen can be passed both in cocurrent with the solution of the educt to be hydrogenated and in countercurrent over the catalyst.
  • Suitable apparatus for carrying out hydrogenation after hydrogenation on the catalyst fluidized bed and on the fixed catalyst bed are known in the art, e.g. from Ullmanns Enzyklopadie der Technischen Chemie, 4th Edition, Vol. 13, p. 135 ff., and P.N. Rylander, "Hydrogenation and Dehydrogenation” in Ulmann's Encyclopedia of Industrial Chemistry, 5th ed. on CD-ROM.
  • the hydrogenation according to the invention can be carried out both at normal hydrogen pressure and at elevated hydrogen pressure, e.g. be carried out at a hydrogen absolute pressure of at least 1, 1 bar, preferably at least 2 bar. In general, the absolute hydrogen pressure will not exceed 325 bar, preferably 300 bar.
  • the hydrogen absolute pressure is particularly preferably in the range from 1.1 to 300 bar, very particularly preferably in the range from 5 to 40 bar.
  • the hydrogenation of benzene occurs e.g. at a hydrogen pressure of generally ⁇ 50 bar, preferably 10 bar to 45 bar, particularly preferably 15 to 40 bar.
  • the reaction temperatures in the process according to the invention are generally at least 30.degree. C. and frequently will not exceed 250.degree.
  • the hydrogenation process is preferably carried out at temperatures in the range from 50 to 200.degree. C., particularly preferably from 70 to 180.degree. C., and very particularly preferably in the range from 80 to 160.degree.
  • the hydrogenation of benzene is carried out, for example, at temperatures in the range of generally from 75 ° C to 170 ° C, preferably from 80 ° C to 160 ° C.
  • Hydrogen-containing gases which contain no catalyst poisons such as carbon monoxide or sulfur-containing gases such as H 2 S or COS, eg.
  • mixtures of hydrogen with inert gases such as nitrogen or reformer exhaust gases, which usually still contain volatile hydrocarbons. Preference is given to using pure hydrogen (purity> 99.9% by volume, especially> 99.95% by volume, in particular> 99.99% by volume).
  • the starting material to be hydrogenated in an amount of 0.05 to 3 kg / (l (catalyst) « h), in particular 0.15 to 2 kg / (l (catalyst) « h) on lead the catalyst.
  • the catalysts used in this process can be regenerated with decreasing activity according to the usual for noble metal catalysts such as ruthenium catalysts, known in the art methods.
  • noble metal catalysts such as ruthenium catalysts
  • a solvent for. As water, rinse.
  • the hydrogenation-containing organic compounds (preferred compounds mentioned above) used in the hydrogenation process according to the invention in a preferred embodiment of the process according to the invention have a sulfur content of generally ⁇ 2 mg / kg, preferably ⁇ 1 mg / kg, more preferably ⁇ 0 , 5 mg / kg, most preferably ⁇ 0.2 mg / kg, and especially ⁇ 0.1 mg / kg.
  • the method for determining the sulfur content is mentioned below.
  • a sulfur content of ⁇ 0.1 mg / kg means that no sulfur in the feedstock such as e.g. Benzene is detected.
  • the hydrogenation process according to the invention is preferably characterized in the case of the preferred hydrogenation of carbocyclic aromatic groups to the corresponding carbocyclic aliphatic groups by the complete hydrogenation of the aromatic nuclei of the organic compounds with carbocyclic aromatic groups, the degree of hydrogenation generally being> 98%, preferably at> 99%, particularly preferably> 99.5%, very particularly preferably> 99.9%, in particular> 99.99% and especially> 99.995%.
  • the degree of hydrogenation is determined by gas chromatography.
  • the degree of hydrogenation is determined by means of UVA / IS spectrometry.
  • a particularly preferred embodiment of the hydrogenation process according to the invention relates to the hydrogenation of benzene to cyclohexane.
  • the hydrogenation process according to the invention is therefore described in more detail below using the example of benzene hydrogenation.
  • the hydrogenation of benzene is generally in the liquid phase. It can be carried out continuously or discontinuously, continuous operation being preferred.
  • the benzene hydrogenation according to the invention is generally carried out at a temperature of 75 ° C to 170 ° C, preferably 80 ° C to 160 ° C.
  • the pressure is generally ⁇ 50 bar, preferably 10 to 45 bar, more preferably 15 to 40 bar, most preferably 18 to 38 bar.
  • the benzene used in the hydrogenation process according to the invention in a preferred embodiment of the method according to the invention has a sulfur content of generally ⁇ 2 mg / kg, preferably ⁇ 1 mg / kg, more preferably ⁇ 0.5 mg / kg, most preferably ⁇ 0.2 mg / kg, and in particular ⁇ 0.1 mg / kg.
  • the method for determining the sulfur content is mentioned below.
  • a sulfur content of ⁇ 0.1 mg / kg means that no sulfur is detected in benzene using the method of measurement given below.
  • the hydrogenation may generally be carried out in the fluid bed or fixed bed mode, with preference being given to carrying out in the fixed bed mode.
  • the hydrogenation process according to the invention is particularly preferably carried out with liquid circulation, wherein the hydrogenation heat can be removed and used via a heat exchanger.
  • the feed / circulation ratio is generally from 1: 5 to 1:40, preferably from 1:10 to 1:30.
  • an after-reaction of the hydrogenation can take place.
  • the reactor can be operated with liquid phase hydrogenation in trickle mode or flooded.
  • the reactor is filled with the catalyst according to the invention or with another catalyst known to the person skilled in the art.
  • Hydrogenated products can thus be obtained with the aid of the process according to the invention which contain no or very low residual contents of the starting materials to be hydrogenated.
  • Example 1 Catalyst Preparation Example 1.1 (Inventive)
  • Si0 2 support AF125, spheres 3-5 mm, BET 337 m 2 / g, shaking density 0.49 kg / l, water absorption (WA) 0.83 ml / g, and ruthenium (III) acetate in acetic acid of Umicore 200 g carrier is presented in a round bottom flask. 14.25% Ru acetate solution. is weighed into a measuring cylinder and with dist. H 2 0 diluted to 150 ml (90% WA). The solution is quartered. The support material is placed on a rotary evaporator and the first of the four impregnations is pumped onto the support material with a slight vacuum at 3-6 rpm.
  • the impregnated material is dried in a rotary kiln at 140 ° C, reduced 3h / 200 ° C (20 l / h H 2 , 10 l / h N 2 ) and passivated (at RT (5% air in N 2 , 2h)).
  • the novel catalyst A thus obtained contains 0.34% by weight of Ru
  • Catalyst B is prepared as described in WO 2006/136451, (0.35% Ru / Si0 2 )
  • Catalyst C is prepared as described in EP 1 042 273 (0.5% Ru / Al 2 O 3 )
  • Example 2 Hydrogenation
  • Example 2.1 Hydrogenation of benzene
  • a continuously operated plant consisting of two tubular reactors connected in series (main reactor (HR) 160 mL and postreactor (NR) 100 mL) is treated with the same procedure described in Example 1 .1.
  • prepared catalyst A (HR: 54.3 g, NR: 33.5 g).
  • the main reactor is operated in trickle mode with circulation, the secondary reactor in straight pass in the swamp mode.
  • Palatinol N diisononyl phthalate, CAS No.
  • Example 2.4 Hydrogenation of diisononyl phthalate to di-isononylcyclohexanedicarboxylic acid ester (DINCH) with catalyst C
  • a continuously operated plant consisting of a tubular reactor (160 ml) is treated with the catalyst C prepared in Example 1 .3 (0.5% Ru on Al 2 O 3 ) (78.0 g). filled.
  • the reactor is operated in trickle mode with circulation (liquid load 10 m / h).
  • the conversion of palatinol N is 94.9%, the selectivity based on DINCH is 98.5%.
  • the cis / trans ratio is 96 / 4-90 / 10.
  • Example 2.9 Hydrogenation of bisphenol A 3.6 g of the catalyst A prepared according to Example 1 .1 are placed in a 300 ml pressure reactor and placed in a catalyst insert basket, and 100 g of a 30% strength solution of bisphenol A in n-butanol are added. The hydrogenation is carried out with pure hydrogen at a constant pressure of 200 bar and a temperature of 180 ° C. It is hydrogenated for 24 h. The reactor is subsequently expanded. The conversion of bisphenol A is 100% (GC column: RTX 65, length 30 m, layer thickness 0.5 ⁇ m, temperature program: from 280 ° C. 40 minutes isothermal). The selectivity of ring hydrogenated bisphenol A is 85.77 FI .-%. As minor components about 14.23 FI .-% low boilers (components with a lower boiling point than ring hydrogenated bisphenol A) can be detected.
  • a 300 ml pressure reactor 3.5 g of the catalyst B prepared according to Example 1.2 are placed in a catalyst insert basket and mixed with 100 g of cuminaldehyde.
  • the hydrogenation is carried out with pure hydrogen at a constant pressure of 200 bar and a temperature of 160 ° C. It is hydrogenated until hydrogen is no longer absorbed (20 hours).
  • the reactor is subsequently expanded.
  • the conversion of cuminaldehyde is 100% (GC column: DB wax, length 30 m, layer thickness 0.25 ⁇ m, temperature program: from 60 ° C at 2.5 ° C / min to 240 ° C).
  • the selectivity to isopropylcyclohexylmethanol is 60.6 FI .-%.
  • minor components about 30.5 FI .-% low boilers (components with a lower boiling point than isopropylcyclohexanol) can be detected.
  • Toluidine base is 100% (GC column: DB-1, length 30 m, layer thickness 1 ⁇ , temperature program: from 150 ° C at 8 ° C / min to 280 ° C.)
  • the selectivity of dimethyldicykan (2,2'-dimethyl -4,4'-methylenebis (cyclohexylamine) is 89.1% by FI.
  • Example 2.15 Hydrogenation of ortho-toluidine base to dimethyl dicycane with catalyst C
  • a 1.2 L pressure reactor 5 g of the catalyst A prepared according to Example 1.1 are placed in a catalyst insert basket and treated with 700 g of a 25% solution of xylidine base (2,2 ', 6,6'-tetremethyl-4,4
  • the hydrogenation is carried out with pure hydrogen at a constant pressure of 200 bar and a temperature of 220 ° C. It is hydrogenated for 2 hours and then the reactor is let down.
  • the conversion of xylidine base is 100 % (GC column: DB1, length 30 m, layer thickness 0.25 ⁇ m, temperature program: from 150 ° C.
  • the butene dimerization is carried out continuously in an adiabatic reactor consisting of two partial reactors (length: 4 m each, diameter: 80 cm each) with intermediate cooling at 30 bar.
  • the feedstock used is a raffinate II having the following composition: i-butane: 2% by weight
  • Butene-2-cis 17% by weight
  • the catalyst used is a material according to DE 4 339 713 consisting of 50 wt .-% NiO, 12.5 wt .-% Ti0 2 , 33.5 wt .-% Si0 2 and 4 wt .-% Al 2 0 3 in the form of 5x5 mm tablets.
  • the reaction is carried out at a rate of 0.375 kg of raffinate II / l of catalyst * h, a recycle C 4 / raffinate II of 3, an inlet temperature on the 1.
  • the conversion based on the butenes contained in the raffinate II is 83.1%; the selectivity to the desired octenes was 83.3%.
  • the octene fraction is separated from unreacted raffinate II and the high boilers.
  • Process step 2 (hydroformylation and subsequent hydrogenation): 750 g of the octene mixture prepared in process step 1 are charged discontinuously in an autoclave with 0.13 wt .-% Dikobaltoktacarbonyl Co 2 (CO) 8 as a catalyst with the addition of 75 g of water at 185 ° C and reacted under a synthesis gas pressure of 280 bar at a mixing ratio of H 2 to CO of 60/40 5 hours. The consumption of synthesis gas, to recognize a pressure drop in the autoclave is supplemented by repressing.
  • CO Dikobaltoktacarbonyl Co 2
  • the reaction effluent is freed from the cobalt catalyst with 10% by weight acetic acid by passing in air, and the organic product phase is hydrogenated with Raney nickel at 125 ° C. and a hydrogen pressure of 280 bar for 10 h.
  • the isononanol fraction is separated from the C8 paraffins and the high boilers.
  • Process step 3 (esterification): In the third process step, 865.74 g of the isononanol fraction obtained in process step 2 (20% excess with respect to phthalic anhydride) with 370.30 g of phthalic anhydride and 0.42 g of isopropyl butyl titanate as catalyst in a 2 l autoclave under N 2 -einperlung (10 l / h) reacted at a stirring speed of 500 U / min and a reaction temperature of 230 ° C. The reaction water formed is continuously removed from the reaction mixture with the N 2 stream. The reaction time is 180 min. Subsequently, the excess isononanol is distilled off at a vacuum of 50 mbar.
  • the purified diisononyl phthalate is then dried for 30 minutes at 150 ° C / 50 mbar by passing an N 2 - stream (2 l / h), then stirred with activated charcoal for 5 min and suction filtered through a suction filter with filter aid Supra-Theorit 5 (temperature 80 ° C).
  • the diisononyl phthalate thus obtained has a density of 0.973 g / cm 3 , a viscosity of 73.0 mPa * s, a refractive index n D 20 of 1.4853, an acid number of 0.03 mg KOH / g, a water content of 0, 03% and GC purity of 99.83%.

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US20120296111A1 (en) 2012-11-22
CN102753266B (zh) 2015-09-02
JP5745538B2 (ja) 2015-07-08
US9084983B2 (en) 2015-07-21
KR20120092197A (ko) 2012-08-20
KR101833077B1 (ko) 2018-02-27

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