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• • 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
  • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
  • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8926—Copper and noble 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
  • B01J35/51—Spheres
• • 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
  • 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
• • 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
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/638—Pore volume more than 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
  • B01J35/64—Pore diameter
  • B01J35/651—50-500 nm
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/09—Geometrical isomers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides

Definitions

• the goal of the present invention was to find a new catalytic system with improved properties in selective hydrogenation of organic starting material.
• Catalytic selective hydrogenations are important processes in the fine chemicals industry.
• the obtained products can be used as such (i.e. as flavor or fragrance compounds) or they can be used as intermediates for the production of other important compounds.
• a catalytic system comprising porous glass- particles, which are impregnated with Cu- and Pd- nanoparticles and which are coated with at least one ionic liquid, shows improved properties in selective catalytic hydrogenations.
• the glass particles are doped with Cu-nanoparticles as well as with Pd-nanoparticles and the so doped (impregnated) glass particles are then coated with a layer of at least one ionic liquid.
• the present invention relates to a catalytic system (I) comprising porous glass particles, which are impregnated with Cu- and Pd- nanoparticles and which are coated with at least one ionic liquid.
• Glass is a well known composition.
• the glass used as carrier material for the embodiment of the present invention has a high amount of Si0 2 .
• the glass particles are used as carrier material for the catalytic system.
• the porous glass particles used in the catalytic system according to the present invention have a Si0 2 content of at least 90 weight-% (wt-%), based on the total weight of the glass particles.
• the glass particles can have any shape and size.
• the porous glass particles, which are used as carriers are spheric and/or sphere-like.
• the present invention relates to a catalytic system (II), which is catalytic system (I), wherein the glass particles are spheric and/or sphere-like.
• the porous glass particles which are used as carriers particles have an average particle diameter of 50 ⁇ to 500 ⁇ , more preferably 75 ⁇ to 300 ⁇ .
• diameter means the longest dimension of the particles. The diameter can be measured by any commonly known method, such as microscope counting, Coulter counter or dynamic light scattering.
• the present invention relates to a catalytic system (III), which is catalytic system (I) or (II), wherein the glass particles have an average particle diameter of 50 ⁇ to 500 ⁇ (preferably 75 ⁇ to 300 ⁇ ).
• the porous glass particles, which are used as carriers particles have an average pore size of 20 nm to 100 nm, more preferably 30 nm to 75 nm.
• the porous glass particles, which are used as carriers particles have a specific surface area of 50 m 2 g "1 to 300 m 2 g " ⁇ preferably 60 m 2 g "1 to 200m 2 g "1 .
• the specific surface area is measured by using well known methods, such as BET.
• the present invention relates to a catalytic system (V), which is catalytic system (I), (II), (III) or (IV), wherein the glass particles have a specific surface area of 50 m 2 g "1 to 300 m 2 g "1 , preferably 60 m 2 g "1 to 200 m 2 g "1 .
• the porous glass particles which are used as carriers particles have a pore volume of 1000 mm 3 g "1 to 2000 mm 3 g " ⁇ more preferably 1200 mm 3 g "1 to 1600 mm 3 g "1 .
• the pore volume is measured by using well known methods, such as BET.
• the present invention relates to a catalytic system (VI), which is catalytic system (I), (II), (III), (IV) or (V), wherein the glass particles have a pore volume of 1000 mm 3 g "1 to 2000 mm 3 g "1 , preferably 1200 mm 3 g "1 to 1600 mm 3 g "1 .
• Suitable glass particles are available commercially from various companies.
• TRISPOR ® , TRISOPERL ® and VITRADENT ® are examples for suitable glass particles and they are produced and sold by Biosearch Technolgies Inc, VitraBio (Steinach, Germany).
• porous glass particles are impregnated by Cu and Pd nanoparticles.
• the molar ratio of Cu-nanoparticles to Pd-nanoparticles (on the porous glass) is 10:1 to 1 :10, more preferably 1 :1 to 1 :8. Therefore the present invention relates to a catalytic system (VII), which is catalytic system (I), (II), (III), (IV), (V) or (VI), wherein the ratio of Cu-nanoparticles to Pd-nanoparticles is 10:1 to 1 :10, preferably 1 :1 to 1 :8, more preferably 1 :1 to 1 :5.
• the total metal nanoparticle loading (Cu and Pd) is 0.001 to 1 .0 mmolg "1 , more preferably 0.01 - 0.6 mmolg "1 .
• the loading is determined by commonly known and used methods, such as ICP-OES (inductively coupled plasma optical emission spectrometry). Therefore the present invention relates to a catalytic system (VIII), which is catalytic system (I), (II), (III), (IV), (V), (VI) or (VII), wherein the metal nanoparticle loading is 0.001 - 1.0 mmolg "1 , preferably 0.01 - 0.6 mmolg "1 .
• the Pd-nanoparticles have an average particle size of between 0.5 and 20 nm, preferably of between 2 and 15 nm.
• the Cu-nanoparticles are smaller than the Pd-nanoparticles.
• the present invention relates to a catalytic system (VIM'), which is catalytic sys- tern (I), (II), (III), (IV), (V), (VI), (VII) or (VIII), wherein the Pd-nanoparticles have an average particle size of between 0.5 and 20 nm, preferably between of 2 and 15 nm.
• the catalytic system according to the present invention is coated with a layer of one or more ionic liquid, such as 1 -ethyl-3-methylimidazolium acetate, 1 -ethyl-3- methylimidazolium dimethyl phosphate 1 -ethyl-3-methylimidazolium dicyanamide, 1 -ethyl- 3-methylimidazolium diethylphosphate, and 1 -ethyl-3-methylimidazolium trifluoroacetate.
• one or more ionic liquid such as 1 -ethyl-3-methylimidazolium acetate, 1 -ethyl-3- methylimidazolium dimethyl phosphate 1 -ethyl-3-methylimidazolium dicyanamide, 1 -ethyl- 3-methylimidazolium diethylphosphate, and 1 -ethyl-3-methylimidazolium trifluoroacetate.
• the present invention relates to a catalytic system (IX), which is catalytic system (I), (II), (III), (IV), (V), (VI), (VII), (VIII) or (VIII'), wherein the at least one ionic liquid is cho- sen form the group consisting of ionic liquid 1 -ethyl-3-methylimidazolium acetate, 1 -ethyl- 3-methylimidazolium dimethyl phosphate, 1 -ethyl-3-methylimidazolium dicyanamide, 1 - ethyl-3-methylimidazolium diethylphosphate, and 1 -ethyl-3-methylimidazolium trifluoro- acetate, preferred is 1 -ethyl-3-methylimidazolium acetate.
• the catalytic system according to the present invention comprise the ionic liquid layer in an amount of 2 - 20 wt-%, based on the total weight of the catalytic system, preferably 5 - 1 5 wt-%.
• the present invention relates to a catalytic system (X), which is catalytic system (I), (II), (III), (IV), (V), (VI), (VII), (VII I), (VIII') or (IX), wherein the amount of ionic liquid lay- er is 2 - 20 wt-%, preferably 5 - 15 wt-%, based on the total amount of the catalytic system.
• the invention also relates to the process of production of catalytic systems (I), (I I), (III), (IV), (V), (VI), (VII), (VIII), (VI II'), (IX) and (X) as described above.
• the catalytic systems are produced by impregnating the glass particles with the Cu and Pd nanoparticles (step a) and then coating it with a layer of at least one ionic liquid (step b).
• the impregnating (step a) of the porous glass particles with the Cu and Pd nanoparticles can be done by methods known to person skilled in the art.
• the Cu and Pd-nanoparticles are applied (impregnated, doped) by wet- impregnation.
• the glass particles are put into a solvent (or a mixture of solvents).
• the Cu and the Pd are added afterwards in the form of a salt, which dissolves in the solvent (or solvent mixture).
• the solvent is then removed (usually by heating optionally by applying reduced pressure) and the impregnated glass particles are then calcined at elevated temperature.
• step a1 it is possible to add the Cu and the Pd salts together to the glass particles (step a1) or to add the Cu salt first and then the Pd salt (step a2) or to add the Pd salt first and then the Cu salt (step aS). Furthermore it is also possible to add the Cu salt first then calcine the so obtained glass particles at elevated temperature; suspend the so treated glass particles in a suitable solvent and add the Pd salt and calcine again at elevated temperature (step a'1).
• step a'2 Furthermore it is also possible to add the Pd salt first then calcine the so obtained glass particles at elevated temperature; suspend the so treated glass particles in a suitable solvent and add the Cu salt and calcine again at elevated temperature (step a'2).
• Suitable solvents for the wet-impregnation step(s) are solvents which are inert and where- in the Pd salts and Cu salts are soluble, such as i.e. acetone.
• Suitable Cu salts and Pd salts are Pd(ll)salts and Cu(ll) salts, such as i.e. Pd(ll)acetate (Pd(OAc) 2 ), Pd(l l)acetylacetonate ((Pd(acac)), Pd(ll)chloride (PdCI 2 ),
• Cu(l l)acetylacetonate Cu(acac)
• Cu(l l)acetate Cu(OAc) 2
• Cu(l l)chloride CuCI 2 ).
• Step a'2 is preferred.
• step b the particles of step a are coated by a ionic liquid or a mixture of ionic liquids. This is usually done by a wet impregnation.
• the particles obtained by any of the steps a is put in a solution of at least one ionic liquid in a suitable solvent (such as acetone) and afterwards the mixture is treated in a ultrasonic bath to degas the porous carrier and then the solvent is removed (for example by evaporation under reduced pressure at slightly elevated temperature).
• a suitable solvent such as acetone
• the catalytic system according to the present invention is then obtained.
• the catalytic systems (I), (II), (III), (IV), (V), (VI), (VI I), (VIII), (VII I'), (IX) and (X) are used in selective catalytic hydrogenations.
• the catalytic systems (I), (II), (I II), (IV) , (V), (VI), (VII), (VIII), (VIII'), (IX) and (X) are used for the hydrogenations of carbon-carbon triple bonds to carbon-carbon double bonds.
• a preferred embodiment of the present invention is the use of a catalytic systems (I), (I I), (III), (IV), (V), (VI), (VI I), (VIII), (VI II'), (IX) and/or (X) in the selective hydrogenation of a compound of formula (A)
• Pn is a linear or branched C 1 -C35 alkyl or linear or branched C5-C35 alkenyl moiety, wherein the C-chains can be substituted, and
• R 2 is a linear or branched C 1 -C4 alkyl, wherein the C-chain can be substituted.
• Preferred compounds of formula (A) are the following compounds of formula (Aa) - (Ac)
• aromatic compounds having carbon carbon triple bonds can be hydro- genated selectively by using a catalytic systems (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (VIII'), (IX) and/or (X).
• a catalytic systems I, (II), (III), (IV), (V), (VI), (VII), (VIII), (VIII'), (IX) and/or (X).
• R is H or C 6 H 5 .
• the hydrogenation can be carried out with or without solvents.
• Suitable (and preferred) solvents are hydro- carbons, such as hexane, cyclohexane, methylcyclohexane, heptane, toluene and xylene.
• the hydrogenation can be carried out at a broad range of temperature and pressure.
• the selective catalytic hydrogenation in accordance with the present invention can be car- ried out under conditions conventionally used for hydrogenations.
• the selective catalytic hydrogenation is carried out at a pressure of about 0.1 to about 6 MPa and at a temperature of about 0°C to about 200°C.
• the selective catalytic hydrogenation can be carried out batch wise or in continuous mode.
• the pressure used for the selective catalytic hydrogenation is between 0.1 and 3 MPa, more preferably between 0.1 and 1.5 MPa, even more preferably between 0.15 and 1 MPa and most preferably between 0.2 and 0.8 MPa.
• the reaction temperature for the selective catalytic hydrogenation is between 0°C and 150°C, more preferably between 20°C and 120°C, even more preferably between 40°C and 90°.
• the compounds obtained by the hydrogenation process according to the present inven- tion can be used as such (for example as flavor or fragrance compounds) or can be used as an intermediate for further reactions.
• porous glass beads TRISOPERL Charge PG L 13/05 (VitraBio GmbH, Steinach, Germany); particle diameter: 100-200 ⁇ , pore size: 48.4 nm, pore volume: 141 0 mm 3 g "1 , surface area: 1 23.9 m 2 g "1 .
• step 1 5 g of Pd/TP of step 1 were given to a solution of 0.1 1 5 mmol Cu(acac) 2 (29.45 mg) in 250 ml acetone. The mixture was treated 10 min in an ultrasound bath to degas the porous support. The solvent was evaporated at 500 mbar, 40 °C, and 90 rpm. Finally, the catalyst was calcined at 300 °C for 2 h.
• the following catalytic system were prepared as well in analogy to Example 1 .
• the Cu and the Pd amount was varied. All the other reaction conditions and amounts have not been amended. So the ionic liquid is 1 -ethyl-3-methylimidazolium acetate - loading and its concentration is 10 wt-%.
• Examples 10 - 17 Hydrogenation of Methylbutynol to Methylbutenol
• the reaction mixture was purged 3 times with nitrogen (pressurise to 6 bar absolute and release). Then the mixture was heated to 60 °C and purged 3 times with hydrogen (pressurise to 6 bar absolute and release).
• the mixture was pressurised to 3 bar hydrogen (absolut) and stirred at 2000 rpm. When the desired amount of hydrogen had been consumed, samples were taken and the reaction mixture was cooled to room temperature.

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• 2014
  • 2014-12-18 CN CN201480070044.XA patent/CN106660035A/zh active Pending
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