ITPI20060011A1 - PROCEDURE FOR THE PREPARATION OF NANOSTRUCTURED METALLIC CATALYZERS AND THEIR USE IN CATALYTIC REACTIONS - Google Patents
PROCEDURE FOR THE PREPARATION OF NANOSTRUCTURED METALLIC CATALYZERS AND THEIR USE IN CATALYTIC REACTIONS Download PDFInfo
- Publication number
- ITPI20060011A1 ITPI20060011A1 IT000011A ITPI20060011A ITPI20060011A1 IT PI20060011 A1 ITPI20060011 A1 IT PI20060011A1 IT 000011 A IT000011 A IT 000011A IT PI20060011 A ITPI20060011 A IT PI20060011A IT PI20060011 A1 ITPI20060011 A1 IT PI20060011A1
- Authority
- IT
- Italy
- Prior art keywords
- process according
- metal
- reduction reaction
- reactions
- nanostructured
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 46
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000006555 catalytic reaction Methods 0.000 title description 6
- 239000003054 catalyst Substances 0.000 claims description 65
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 47
- 238000006722 reduction reaction Methods 0.000 claims description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N Butanol Natural products CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010485 C−C bond formation reaction Methods 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 238000005906 dihydroxylation reaction Methods 0.000 claims 1
- 238000006053 organic reaction Methods 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000002923 metal particle Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- -1 ethylene glycol Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- 229910003591 H2PtCl6.6H20 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005833 cis-dihydroxylation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J35/23—
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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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
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- 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
- C07C5/11—Partial hydrogenation
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- C07—ORGANIC CHEMISTRY
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- 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
- C07C2523/48—Silver or gold
- C07C2523/50—Silver
Description
"PROCEDIMENTO PER LA PREPARAZIONE DI CATALIZZATORI METALLICI NANOSTRUTTURATI E LORO IMPIEGO IN REAZIONI CATALITICHE" "PROCEDURE FOR THE PREPARATION OF NANOSTRUCTURED METALLIC CATALYSTS AND THEIR USE IN CATALYTIC REACTIONS"
DESCRIZIONE DESCRIPTION
Ambito dell'invenzione Scope of the invention
La presente invenzione riguarda un procedimento per la preparazione di catalizzatori metallici nanostrutturati e loro impiego in reazioni catalitiche. The present invention relates to a process for the preparation of nanostructured metal catalysts and their use in catalytic reactions.
Inoltre, l'invenzione riguarda la preparazione di catalizzatori metallici nanostrutturati per specifiche reazioni, in particolare per reazioni di idrogenazione selettiva di composti organici. Furthermore, the invention relates to the preparation of nanostructured metal catalysts for specific reactions, in particular for selective hydrogenation reactions of organic compounds.
Descrizione della tecnica nota Description of the prior art
Come noto, i catalizzatori metallici vengono solitamente impiegati in numerose reazioni catalitiche per la produzione di svariate sostanze organiche. As is known, metal catalysts are usually used in numerous catalytic reactions for the production of various organic substances.
In particolare, i catalizzatori metallici nanostrutturati presentano eccellenti proprietà catalitiche e notevoli vantaggi rispetto ai catalizzatori di dimensioni maggiori. Tra i principali vantaggi vi sono un considerevole aumento della reattività superficiale che consente di aumentare notevolmente l'efficienza di processi catalitici nei quali essi vengono utilizzati. In particular, nanostructured metal catalysts have excellent catalytic properties and significant advantages over larger catalysts. Among the main advantages are a considerable increase in surface reactivity which allows to significantly increase the efficiency of the catalytic processes in which they are used.
Pertanto, sono state studiate diverse metodologie di sintesi allo scopo di produrre catalizzatori metallici nanostrutturati . Tra queste le principali riguardano processi di riduzione elettrochimica di sali metallici, processi di riduzione per via chimica di sali metallici, processi basati sulla tecnologia della "vaporizzazione di metalli" e di riduzione, o decomposizione, di precursori organometallici. Therefore, different synthesis methodologies have been studied in order to produce nanostructured metal catalysts. Among these, the main ones concern electrochemical reduction processes of metal salts, chemical reduction processes of metal salts, processes based on the technology of "metal vaporization" and reduction, or decomposition, of organometallic precursors.
In particolare, il processo di riduzione per via elettrochimica di sali metallici appare estremamente oneroso per applicazioni su larga scala e spesso non garantisce un controllo dimensionale. In aggiunta, tale processo risulta difficilmente applicabile per importanti metalli quali Pt, Rh, Ru e Mo a causa della bassa solubilità dei cationi quando usati come anodo. In particular, the electrochemical reduction process of metal salts appears extremely onerous for large-scale applications and often does not guarantee dimensional control. In addition, this process is difficult to apply for important metals such as Pt, Rh, Ru and Mo due to the low solubility of the cations when used as anode.
La metodologia che prevede la riduzione per via chimica di sali metallici è basata sull'impiego di agenti riducenti quali idruri metallici, o dell'idrogeno stesso, e di un agente stabilizzante, in genere un polimero. In alternativa, per evitare l'eventuale contaminazione del prodotto da parte dell'agente riducente e condurre la riduzione in maniera controllata, è stata proposta la metodologia della riduzione ad opera di un alcol. Poiché in genere la riduzione in presenza di alcoli necessita di una temperatura elevata per essere efficiente e completa, si è preferito adottare il metodo della riduzione in presenza di polioli quali glicol etilenico, ma soprattutto dietilenglicol e trietilenglicol. Un processo di questo tipo è descritto ad esempio in FR 2537898. In alternativa, molto più raramente, è riportato l'impiego di alcoli altobollenti quali l'ottanolo come descritto nel brevetto numero WO 9604088. The methodology that provides for the chemical reduction of metal salts is based on the use of reducing agents such as metal hydrides, or of the hydrogen itself, and of a stabilizing agent, generally a polymer. Alternatively, in order to avoid any contamination of the product by the reducing agent and to carry out the reduction in a controlled manner, the method of reduction by an alcohol has been proposed. Since the reduction in the presence of alcohols generally requires a high temperature to be efficient and complete, it has been preferred to adopt the reduction method in the presence of polyols such as ethylene glycol, but above all diethylene glycol and triethylene glycol. A process of this type is described for example in FR 2537898. Alternatively, much more rarely, the use of high-boiling alcohols such as octanol as described in patent number WO 9604088 is reported.
Tuttavia, sia i polioli che gli alcoli ad elevato peso molecolare presentano però l'indubbio limite di essere difficilmente allontanabili dal prodotto ottenuto, e mal si prestano ad una preparazione su larga scala. However, both polyols and high molecular weight alcohols have the undoubted limit of being difficult to remove from the product obtained, and are not suitable for large-scale preparation.
Un altro processo di produzione di catalizzatori metallici nanostrutturati adotta la tecnologia della vaporizzazione di metalli. Questo tipo di metodologia richiede l'impiego di reattori costosi e raramente disponibili e di conseguenza non appare adatta per preparazioni su larga scala. Another manufacturing process of nanostructured metal catalysts adopts metal vaporization technology. This type of methodology requires the use of expensive and rarely available reactors and consequently does not appear suitable for large-scale preparations.
Infine, un altro processo di produzione catalizzatori metallici nanostrutturati prevede la riduzione, o decomposizione, di precursori organometallici. Anche questo tipo di processo non sembra idoneo ad essere applicato su larga scala. Infatti, il processo prevede l'impiego di precursori organometallici di complessa sintesi ed elevatissimo costo. Inoltre con questa metodologia è spesso assai difficile raggiungere un efficiente controllo della dimensione e morfologia delle particelle ottenute, e spesso la riproducibilità del metodo è scarsa. Finally, another nanostructured metal catalyst production process involves the reduction, or decomposition, of organometallic precursors. Even this type of process does not seem suitable for large-scale application. In fact, the process involves the use of organometallic precursors of complex synthesis and very high cost. Moreover, with this methodology it is often very difficult to achieve an efficient control of the size and morphology of the particles obtained, and often the reproducibility of the method is poor.
Tra le possibili reazioni catalitiche in cui i catalizzatori metallici nanostrutturati possono essere impiegati vi sono le reazioni di idrogenazione selettiva di composti organici. Among the possible catalytic reactions in which nanostructured metal catalysts can be employed are the selective hydrogenation reactions of organic compounds.
In particolare, ì catalizzatori di tecnica nota utilizzati nelle reazioni di idrogenazione selettiva del benzene a cicloesene e di fenolo a cicloesanone non sono in grado di realizzare elevate rese del prodotto desiderato ed implicano costi elevati, come ad esempio nel caso di catalizzatori a base di palladio. In particular, the catalysts of the known art used in the selective hydrogenation reactions of benzene to cyclohexene and of phenol to cyclohexanone are unable to achieve high yields of the desired product and involve high costs, as for example in the case of palladium-based catalysts. .
Sintesi dell'invenzione Summary of the invention
È quindi scopo della presente invenzione fornire un procedimento per la preparazione di catalizzatori metallici nanostrutturati che sia semplice ed economicamente vantaggioso rispetto ai processi tecnica nota. It is therefore an object of the present invention to provide a process for the preparation of nanostructured metal catalysts which is simple and economically advantageous with respect to the prior art processes.
È un altro scopo della presente invenzione fornire un procedimento per la preparazione di catalizzatori metallici nanostrutturati che consenta di separare agevolmente i sottoprodotti presenti nel sito di reazione dal prodotto finale. It is another object of the present invention to provide a process for the preparation of nanostructured metal catalysts which allows to easily separate the by-products present in the reaction site from the final product.
È un ulteriore scopo della presente invenzione fornire un procedimento per la preparazione di catalizzatori metallici nanostrutturati che consenta di ottenere un prodotto finale con caratteristiche migliorate, in particolare in termini di diametro medio delle particelle metalliche e distribuzione dimensionale, rispetto ai catalizzatori nanostrutturati di tecnica nota. It is a further object of the present invention to provide a process for the preparation of nanostructured metal catalysts which allows to obtain a final product with improved characteristics, in particular in terms of average diameter of the metal particles and size distribution, with respect to the nanostructured catalysts of the known art.
È uno scopo particolare della presente invenzione fornire un catalizzatore metallico nanostrutturato particolarmente efficiente per specifiche reazioni catalitiche . It is a particular object of the present invention to provide a nanostructured metal catalyst which is particularly efficient for specific catalytic reactions.
Questi ed altri scopi sono raggiunti dal procedimento, secondo l'invenzione, per la preparazione di catalizzatori metallici nanostrutturati attraverso una reazione di riduzione di almeno un precursore metallico per riscaldamento in un solvente alcolico la cui caratteristica principale è che la suddetta reazione di riduzione viene realizzata in condizioni sovrapressione. In tal modo è possibile impiegare come solvente alcolico un alcol a basso peso molecolare, facilmente rimuovibile dal prodotto desiderato. These and other purposes are achieved by the process, according to the invention, for the preparation of nanostructured metal catalysts through a reduction reaction of at least one metal precursor by heating in an alcoholic solvent whose main characteristic is that the aforementioned reduction reaction is carried out under overpressure conditions. In this way it is possible to use as alcoholic solvent a low molecular weight alcohol, easily removable from the desired product.
In particolare, il o ciascun precursore metallico ha formula: MnXyo HxMnXy, impiegati come tali o solvatati, in cui M è un catione metallico e X è un anione scelto tra: In particular, the or each metal precursor has the formula: MnXyo HxMnXy, used as such or solvated, in which M is a metal cation and X is an anion chosen from:
<—>un alogenuro, <—> a halide,
— un carbossilato, - a carboxylate,
<—>un carbossilato sostituito, <—> a substituted carboxylate,
~ un idrossido, ~ a hydroxide,
<—>un carbammato. <—> a carbamate.
<—>un aldimminato. <—> an aldimminato.
Preferibilmente, il catione metallico è scelto tra: Preferably, the metal cation is selected from:
rodio; rhodium;
rutenio; ruthenium;
renio; rhenium;
palladio; palladium;
platino; platinum;
nichel; nickel;
rame; copper;
<—>iridio; <—> iridium;
<—>ferro . <—> iron.
In particolare, il solvente alcolico utilizzato può avere un peso molecolare inferiore a 100. In particular, the alcohol solvent used can have a molecular weight of less than 100.
Vantaggiosamente, il solvente alcolico è scelto tra: — metanolo; Advantageously, the alcoholic solvent is selected from: - methanol;
<—>etanolo; <—> ethanol;
— propanolo; - propanol;
<—>butanolo; <—> butanol;
pentanolo pentanol
e loro isomeri. and their isomers.
Preferibilmente, il solvente alcolico è scelto tra:<—>etanolo; Preferably, the alcoholic solvent is selected from: <—> ethanol;
<—>propanolo; <—> propanol;
— isopropanolo . - isopropanol.
In particolare, la suddetta reazione di riduzione del, o di ciascun, precursore metallico viene condotta ad una pressione compresa tra 10 e 150 bar, generata da un gas inerte, quale ad es.azoto. In particular, the aforesaid reduction reaction of, or of each, metal precursor is carried out at a pressure ranging from 10 to 150 bar, generated by an inert gas, such as for example nitrogen.
Preferibilmente, la suddetta reazione di riduzione del, o di ciascun, precursore metallico viene condotta ad una pressione compresa tra 20 e 100 bar. Preferably, the aforesaid reduction reaction of, or of each, metal precursor is carried out at a pressure ranging from 20 to 100 bar.
In particolare, la riduzione di uno o più precursori metallici contemporaneamente può essere condotta ad una temperatura compresa tra 50 e 400 °C e preferibilmente tra 50 e 250 °C. In particular, the reduction of one or more metal precursors at the same time can be carried out at a temperature between 50 and 400 ° C and preferably between 50 and 250 ° C.
Vantaggiosamente, è possibile impiegare, inoltre, un agente stabilizzante quale un polimero o un copolimero, ad esempio poli-N-vinil-2-pirrolidone (PVP), polietilenossìdo, polipropìlenossido, polìacrìlatì, oppure loro copolimeri. Advantageously, it is also possible to use a stabilizing agent such as a polymer or a copolymer, for example poly-N-vinyl-2-pyrrolidone (PVP), polyethylene oxide, polypropylene oxide, polyacrylates, or their copolymers.
Inoltre, è prevista la possibilità di utilizzare, come stabilizzante una base e/o un sale inorganico o organico, quale ad esempio idrossidi alcalini, alcalino terrosi e/o loro sali quali acetati, ossalati, formiati, ammine ecc. In tal caso, non è necessario l'impiego di un polimero come agente stabilizzante. In particolare, il catalizzatore nanostrutturato, mono o polimetallico, può essere disposto su un supporto inerte, ad esempio allumina, silice, carbone, magnesia, zirconia ed altri ossidi metallici. Furthermore, it is possible to use, as a stabilizer, a base and / or an inorganic or organic salt, such as for example alkaline, alkaline earth hydroxides and / or their salts such as acetates, oxalates, formates, amines, etc. In this case, it is not necessary to use a polymer as a stabilizing agent. In particular, the nanostructured catalyst, mono or polymetallic, can be arranged on an inert support, for example alumina, silica, carbon, magnesia, zirconia and other metal oxides.
Alternativamente, il catalizzatore nanostrutturato può essere impiegato come catalizzatore non supportato. Alternatively, the nanostructured catalyst can be used as an unsupported catalyst.
Vantaggiosamente, il supporto può essere introdotto direttamente nel reattore nel quale avviene la riduzione del precursore o dei precursori metallici o, in alternativa, a freddo in una fase successiva alla reazione di riduzione. Advantageously, the support can be introduced directly into the reactor in which the metal precursor or precursors are reduced or, alternatively, cold in a step subsequent to the reduction reaction.
Il procedimento di ottenimento di catalizzatori metallici nanostrutturati come sopra descritto consente di evitare da un lato l'impiego di precursori organometallici costosi e di difficile sintesi e dall'altro l'impiego di solventi altobollenti quali glicoli e poliglicoli, in particolare dietilen e trietilen glicol, difficilmente rimuovibili dal prodotto finale una volta realizzata la riduzione del precursore metallico di partenza. The process of obtaining nanostructured metal catalysts as described above allows to avoid on the one hand the use of expensive and difficult to synthesize organometallic precursors and on the other hand the use of high-boiling solvents such as glycols and polyglycols, in particular diethylene and triethylene glycol, difficult to remove from the final product once the reduction of the starting metal precursor has been achieved.
Secondo un altro aspetto dell'invenzione il catalizzatore metallico nanostrutturato come sopra descritto può essere vantaggiosamente impiegato in reazioni di idrogenazione, deidrogenazione, ossidazione, idrossilazione, cis-diidrossilazione e in reazioni di formazione del legame C-C. According to another aspect of the invention, the nanostructured metal catalyst as described above can be advantageously used in hydrogenation, dehydrogenation, oxidation, hydroxylation, cis-dihydroxylation reactions and in C-C bond formation reactions.
In particolare, il catalizzatore metallico nanostrutturato come sopra descritto può essere vantaggiosamente impiegato in reazioni di idrogenazione selettiva di composti organici, in particolare nella reazione di idrogenazione selettiva del benzene a cicloesene e in quella del fenolo a cicloesanone. In particular, the nanostructured metal catalyst as described above can be advantageously used in selective hydrogenation reactions of organic compounds, in particular in the selective hydrogenation reaction of benzene to cyclohexene and in that of phenol to cyclohexanone.
L'invenzione verrà ora descritta in modo non limitativo, attraverso i seguenti esempi da 1 a 13. The invention will now be described in a non-limiting way, through the following examples from 1 to 13.
In particolare il catalizzatore metallico nanostrutturato descritto nell'esempio 1 è stato preparato con un metodo noto di riduzione in glicol, per avere un raffronto con i catalizzatori descritti negli esempi da 2 a 13, preparati utilizzando il processo secondo la presente invenzione. In particular, the nanostructured metal catalyst described in example 1 was prepared with a known method of reduction in glycol, to have a comparison with the catalysts described in examples 2 to 13, prepared using the process according to the present invention.
Esempio 1 Example 1
In un pallone a due colli da 250 mi con refrigerante a bolle ed agitatore magnetico vengono posti in atmosfera inerte 123 mg di RuCl3-nH20 (pari a 50,26 mg di rutenio) e 2,57 g di PVP. Vengono addizionati, quindi, 280 mi di etilen glicol e la miscela di reazione viene scaldata a riflusso (198°C) con un bagno ad olio termostatato per 3 h. Al termine, dopo raffreddamento, vengono aggiunti 4,17 g di γ-Α1203(area superficiale 110 m<2>/g) e si prosegue l'agitazione per 12 h. Successivamente, allontanato 1'etilen glicol per evaporazione a pressione ridotta, il catalizzatore viene lavato con acetone e seccato fino a peso costante. 123 mg of RuCl3-nH20 (equal to 50.26 mg of ruthenium) and 2.57 g of PVP are placed in a 250 ml double-necked flask with bubble refrigerant and magnetic stirrer. 280 ml of ethylene glycol are then added and the reaction mixture is heated under reflux (198 ° C) with a thermostated oil bath for 3 h. At the end, after cooling, 4.17 g of γ-Α1203 are added (surface area 110 m <2> / g) and stirring is continued for 12 h. Subsequently, the ethylene glycol removed by evaporation under reduced pressure, the catalyst is washed with acetone and dried to constant weight.
L'analisi TEM ha evidenziato la presenza di particelle metalliche con diametro medio di 3,33 nm con una deviazione standard di 0,59 nm. TEM analysis revealed the presence of metal particles with an average diameter of 3.33 nm with a standard deviation of 0.59 nm.
Negli esempi da 2 a 13 vengono descritti alcuni procedimenti di sintesi di catalizzatori metallici nanostrutturati, secondo la presente invenzione. Le caratteristiche morfologiche dei catalizzatori ottenuti sono state quindi confrontate con quelle di si catalitici commerciali e di altri appositamente preparati secondo la metodologia nota della riduzione in polioli . Examples 2 to 13 describe some synthesis processes of nanostructured metal catalysts, according to the present invention. The morphological characteristics of the catalysts obtained were then compared with those of commercial catalytic compounds and others specially prepared according to the known method of polyol reduction.
Esempio 2 Example 2
All'interno di un'autoclave di volume di 300 mi, dotata di agitazione magnetica e di un manometro con fondo scala pari a 200 atmosfere, vengono introdotti 48,8 mg di RuCl3-nH20, 0,60 g di PVP e 100 mi di etanolo. L'autoclave viene poi pressurizzata con 60 atmosfere di azoto e, una volta riscaldata ad una temperatura di 200 °C viene dato inizio all'agitazione che viene protratta per 3 ore. Quindi, l'autoclave viene raffreddata a temperatura ambiente e degasata. Successivamente, vengono aggiunti in agitazione 1,98 g di γ-Α1203. La dispersione viene quindi filtrata, lavata con acetone ed essiccata. 48.8 mg of RuCl3-nH20, 0.60 g of PVP and 100 ml of ethanol. The autoclave is then pressurized with 60 atmospheres of nitrogen and, once heated to a temperature of 200 ° C, stirring is started which is continued for 3 hours. Then, the autoclave is cooled to room temperature and degassed. Subsequently, 1.98 g of γ-Α1203 are added under stirring. The dispersion is then filtered, washed with acetone and dried.
L'analisi TEM ha evidenziato particelle metalliche con diametro medio di 2,00 nm con una deviazione standard di 0,28 nm. TEM analysis revealed metal particles with an average diameter of 2.00 nm with a standard deviation of 0.28 nm.
Esempio 3 Example 3
Il catalizzatore viene sintetizzato in maniera del tutto analoga al catalizzatore descritto nell'esempio 2, ma impiegando come supporto AI2O3basica avente area superficiale 150 m<2>/g. The catalyst is synthesized in a completely analogous manner to the catalyst described in example 2, but using basic AI2O3 as support having a surface area of 150 m <2> / g.
Esempio 4 Example 4
Il catalizzatore viene stato sintetizzato in maniera del tutto analoga al catalizzatore descritto nell'esempio 2, ma adottando una temperatura di reazione di 220 °C. Le particelle metalliche hanno un diametro medio di 2,05 nm con una deviazione standard di 0,25 nm. The catalyst was synthesized in a completely similar way to the catalyst described in Example 2, but adopting a reaction temperature of 220 ° C. The metal particles have an average diameter of 2.05 nm with a standard deviation of 0.25 nm.
Esempio 5 Example 5
Il catalizzatore viene sintetizzato in maniera analoga al catalizzatore descritto nell'esempio 2, ma impiegando come supporto 1,95 g di carbone (con area superficiale di 900 m<2>/g). Le particelle metalliche hanno un diametro medio di 2,16 nm con una deviazione standard di 0,33 nm. The catalyst is synthesized in a similar way to the catalyst described in Example 2, but using 1.95 g of carbon as support (with a surface area of 900 m <2> / g). The metal particles have an average diameter of 2.16 nm with a standard deviation of 0.33 nm.
Esempio 6 Example 6
II catalizzatore viene sintetizzato in maniera analoga al catalizzatore descritto nell'esempio 2, ma impiegando 4,1 g di γ-allumina. Le particelle metalliche hanno un diametro medio di 2,07 nm con una deviazione standard di 0,31 nm. The catalyst is synthesized in a similar way to the catalyst described in Example 2, but using 4.1 g of γ-alumina. The metal particles have an average diameter of 2.07 nm with a standard deviation of 0.31 nm.
Esempio 7 Example 7
Il catalizzatore viene sintetizzato in maniera analoga al catalizzatore descritto nell'esempio 6, ma impiegando come agente stabilizzante 0,57 g di copolimero aggraffato polietilenglicol-PVP. The catalyst is synthesized in a similar way to the catalyst described in Example 6, but using 0.57 g of polyethylene glycol-PVP graft copolymer as stabilizing agent.
Le particelle metalliche hanno un diametro medio c 2,03 nm con una deviazione standard di 0,44 nm. The metal particles have an average diameter of 2.03 nm with a standard deviation of 0.44 nm.
Esempio 8 Example 8
Il catalizzatore viene sintetizzato in maniera analoga al catalizzatore descritto nell'esempio 2, ma impiegando come agente stabilizzante 1,23 g di un copolimero aggraffato polietilenglicol-PVP. Le particelle metalliche hanno un diametro medio di 3,04 nm con una deviazione standard di 0,78 nm. The catalyst is synthesized in a similar way to the catalyst described in Example 2, but using as stabilizing agent 1.23 g of a grafted polyethylene glycol-PVP copolymer. The metal particles have an average diameter of 3.04 nm with a standard deviation of 0.78 nm.
Esempio 9 Example 9
Il catalizzatore viene sintetizzato in maniera analoga al catalizzatore descritto nell'esempio 2, ma introducendo la γ-allumina direttamente in autoclave prima dello stadio di riduzione, anziché dopo. The catalyst is synthesized in a similar way to the catalyst described in example 2, but by introducing the γ-alumina directly into the autoclave before the reduction step, rather than after it.
Esempio 10 Example 10
Il catalizzatore viene sintetizzato in maniera analoga al catalizzatore descritto nell'esempio 2, ma usando come solvente 110 mi di alcol isopropilico. The catalyst is synthesized in a similar way to the catalyst described in Example 2, but using 110 ml of isopropyl alcohol as solvent.
Esempio 11 Example 11
Il catalizzatore viene sintetizzato in maniera analoga al catalizzatore descritto nell'esempio 2, ma in assenza di polimero ed introducendo in autoclave 5,5 mi di soluzione acquosa di NaOH 0,5 molare. The catalyst is synthesized in a similar way to the catalyst described in Example 2, but in the absence of polymer and introducing 5.5 ml of aqueous 0.5 molar NaOH solution into the autoclave.
Esempio 12 Example 12
Il catalizzatore viene sintetizzato in maniera analoga al catalizzatore descritto nell'esempio 2, ma impiegando come precursore metallico 48 mg di RhCl3.3H20 Esempio 13 The catalyst is synthesized in a similar way to the catalyst described in example 2, but using 48 mg of RhCl3.3H20 as metal precursor. Example 13
Il catalizzatore viene sintetizzato in maniera analoga al catalizzatore descritto nell'esempio 2, ma impiegando come precursore metallico 50 mg di H2PtCl6.6H20. The catalyst is synthesized in a similar way to the catalyst described in Example 2, but using 50 mg of H2PtCl6.6H20 as metal precursor.
Di seguito vengono riportati alcuni esempi di applicazioni catalitiche dei catalizzatori preparati come sopra descritto e i risultati ottenuti confrontati con catalizzatori prodotti con sistemi catalitici commerciali, o preparati attraverso la nota metodologia della riduzione in polioli. Some examples of catalytic applications of the catalysts prepared as described above are reported below and the results obtained compared with catalysts produced with commercial catalytic systems, or prepared using the known method of polyol reduction.
Reazioni di idrogenazione selettiva Selective hydrogenation reactions
A titolo di esempio alcuni dei catalizzatori a base di rutenio sintetizzati, utilizzando il procedimento secondo l'invenzione, sono stati impiegati nella reazione di idrogenazione selettiva del benzene a cicloesene e del fenolo a cicloesanone, confrontando le prestazioni dei catalizzatori preparati secondo il metodo rivendicato con quelle di alcuni catalizzatori commerciali e del catalizzatore ottenuto come descritto nell'esempio 1 mediante il metodo della riduzione in glicol. Alcuni dei risultati esemplificativi sono riassunti nelle Tabelle 1 e 2. Si può osservare che entrambe le reazioni i nanocatalizzatori sintetizzati secondo la presente invenzione, oltre ad implicare un metodo preparativo assai più semplice, hanno offerto prestazioni superiori (in termini di rese nel prodotto desiderato) non solo rispetto ai catalizzatori commerciali ma anche rispetto al catalizzatore metallico nanostrutturato 1 preparato con il metodo della riduzione in glicol. Si può osservare, infatti, che nell'idrogenazione del benzene a cicloesene tale superiorità viene osservata tanto lavorando in solvente organico (n-esano) che, più convenientemente, in acqua in presenza di solfato di zinco. L'unico sottoprodotto formato è il cicloesano. By way of example, some of the synthesized ruthenium-based catalysts, using the process according to the invention, were used in the selective hydrogenation reaction of benzene to cyclohexene and phenol to cyclohexanone, comparing the performance of the catalysts prepared according to the claimed method with those of some commercial catalysts and of the catalyst obtained as described in example 1 by the method of reduction in glycol. Some of the exemplary results are summarized in Tables 1 and 2. It can be observed that both reactions the nanocatalysts synthesized according to the present invention, in addition to implying a much simpler preparation method, offered superior performance (in terms of yields in the desired product) not only with respect to commercial catalysts but also with respect to the nanostructured metal catalyst 1 prepared with the method of reduction in glycol. It can be observed, in fact, that in the hydrogenation of benzene to cyclohexene this superiority is observed both working in organic solvent (n-hexane) and, more conveniently, in water in the presence of zinc sulphate. The only by-product formed is cyclohexane.
II catalizzatore a base di rutenio ha mostrato in particolare un'apprezzabile attività catalitica anche nella reazione di idrogenazione selettiva del fenolo a cicloesanone. Anche in questa reazione i catalizzatori preparati secondo la presente invenzione risultano superiori ai commerciali e al sistema preparato in glicol sia dal punto di vista dell'attività che della selettività, permettendo di raggiungere alte rese in cicloesanone. L'unico sottoprodotto formato in questa reazione è il cicloesanolo. The ruthenium-based catalyst in particular showed an appreciable catalytic activity also in the selective hydrogenation reaction of phenol to cyclohexanone. Also in this reaction the catalysts prepared according to the present invention are superior to the commercial ones and to the system prepared in glycol both from the point of view of activity and selectivity, allowing to reach high yields in cyclohexanone. The only by-product formed in this reaction is cyclohexanol.
Tabella 1: Idrogenazione catalitica del benzene Table 1: Catalytic hydrogenation of benzene
<a)>Condizioni di reazione: benzene 25 mi; solvente: 20 mi n-esano; T: 100 °C; P idrogeno: 50 bar. <a)> Reaction conditions: benzene 25 ml; solvent: 20 ml n-hexane; T: 100 ° C; P hydrogen: 50 bar.
<b)>Condizioni di reazione: benzene 25 mi; solvente: 50 mi acqua con 2.4 g di ZnS04; T: 160 °C; P idrogeno: 50 bar. <b)> Reaction conditions: benzene 25 ml; solvent: 50 ml of water with 2.4 g of ZnSO4; T: 160 ° C; P hydrogen: 50 bar.
Tabella 2: Idrogenazione catalitica del fenolo<31>Table 2: Catalytic hydrogenation of phenol <31>
<a)>Condizioni di reazione: fenolo 10 g; solvente: 50 cicloesano; T: 160 °C; P idrogeno: 50 bar. <a)> Reaction conditions: phenol 10 g; solvent: 50 cyclohexane; T: 160 ° C; P hydrogen: 50 bar.
<b)>Il catalizzatore è stato addizionato di 0.46 g di acqua. <b)> The catalyst was added with 0.46 g of water.
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