WO2007085463A1 - Process for making nanostructured metal catalysts and their use in catalytic reactions. - Google Patents
Process for making nanostructured metal catalysts and their use in catalytic reactions. Download PDFInfo
- Publication number
- WO2007085463A1 WO2007085463A1 PCT/EP2007/000666 EP2007000666W WO2007085463A1 WO 2007085463 A1 WO2007085463 A1 WO 2007085463A1 EP 2007000666 W EP2007000666 W EP 2007000666W WO 2007085463 A1 WO2007085463 A1 WO 2007085463A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- reactions
- reduction reaction
- carried out
- catalysts
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 38
- 230000008569 process Effects 0.000 title claims description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 20
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 238000006722 reduction reaction Methods 0.000 claims description 32
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 8
- 230000001476 alcoholic effect Effects 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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
- 238000010485 C−C bond formation reaction Methods 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
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 238000006835 carbomethoxylation reaction Methods 0.000 claims 1
- 238000005810 carbonylation reaction Methods 0.000 claims 1
- 238000005906 dihydroxylation reaction Methods 0.000 claims 1
- 238000006459 hydrosilylation reaction Methods 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 238000006053 organic reaction Methods 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 19
- 239000002923 metal particle Substances 0.000 abstract description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 3
- 239000011943 nanocatalyst Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000003197 catalytic effect Effects 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
- 239000012467 final product Substances 0.000 description 4
- 239000007789 gas Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 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
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- -1 ethylene glycol Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229910003594 H2PtCl6.6H2O Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GCBDOTMVODVVRZ-UHFFFAOYSA-N bis(methylperoxy)methylbenzene Chemical compound COOC(OOC)C1=CC=CC=C1 GCBDOTMVODVVRZ-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000005833 cis-dihydroxylation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical group O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
-
- 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
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
-
- 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
-
- 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
- C07C29/132—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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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
- C07C5/11—Partial hydrogenation
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- 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
- C07C2523/42—Platinum
-
- 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
- C07C2523/44—Palladium
-
- 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
- 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
Definitions
- the present invention relates to a process for preparing nanostructured metal catalysts and their use in catalytic reactions.
- the present invention relates to the preparation of heterogeneous or homogeneous nanostructured metal catalysts for peculiar reactions, mainly involving the selective hydrogenation of organic substrates.
- Metal catalysts are generally employed in many catalytic reactions for the production of different organic products.
- nanostructured metal catalysts offer excellent catalytic properties and many advantages in comparison with corresponding catalysts based on metal particles with larger dimensions. Their main advantage is represented by a significant increase of the surface activity which allows to greatly improve the performances of catalytic processes where they are employed. As a consequence, different synthetic methods have been studied in order to produce nanostructured metal catalysts.
- the main known methods concern processes of electrochemical reduction of metal salts, chemical reduction of metal salts, the "metal vapors technique” and the reduction, or decomposition, of organometallic precursors.
- the electrochemical reduction of metal salts is extremely expensive for large scale applications and frequently does not allow to control the particles size.
- this process is scarcely suitable for important transition metals such as Pt, Rh, Ru and Mo, due to low solubility of their cations when employed as an anode.
- the method of the chemical reduction of the metal salts is based on the use of reducing agents such as metal hydrides or hydrogen itself, and of a stabilizing agent, generally a polymer. Otherwise, in order to avoid the eventual poisoning of the product by the reducing agent and to perform the reduction under higher control, a method of reduction in an alcohol has been proposed. Because the reduction in the presence of an alcohol generally needs high temperature to be efficient and complete, the reduction in the presence of polyols such as ethylene glycol, but mainly diethylene glycol and triethylene glycol, has been preferred. This type of process is, for instance, described in FR 2537898. Otherwise, not very often, high boiling alcohols such as n-octanol are employed, as described in WO 9604088.
- Nanosized metal catalysts can be employed in many catalytic reactions such as the selective hydrogenation of organic molecules.
- the or each metal precursor has the formula: MnXy or HxMnXy, used as that or solvated, where M is a metal cation and X is an anion selected from the group comprised of:
- the metal cation is selected from the group comprised of:
- the employed alcoholic medium can have a molecular weight below 100.
- the alcoholic solvent or co-solvent is selected from the group comprised of: — methanol;
- the alcoholic medium is selected from the group comprised of:
- the above described reduction reaction of the or each metal precursor is carried out at a pressure in the range from 10 and 150 bar, produced by an inert gas, such as, for instance, nitrogen.
- the said reduction reaction of the or each metal precursor is carried out at a pressure from 20 and 100 bar.
- the reduction of one or more metal precursors together at the same time can be carried out at a temperature from 50 to 400 0 C and preferably from 50 to 250 0 C.
- a stabilizing agent can be also employed, such as a polymer or a copolymer, for instance poly-N-vinyl-2-pyrrolidone (PVP) , polyethylenoxide, polypropylenoxide, polyacrylates, or their copolymers.
- PVP poly-N-vinyl-2-pyrrolidone
- a base and/or an inorganic or organic salt such as alkali or alkali earth hydroxides and/or their salts as acetates, oxalates, formates, amines etc. can be employed as a stabilizer.
- an inorganic or organic salt such as alkali or alkali earth hydroxides and/or their salts as acetates, oxalates, formates, amines etc.
- the polymer as stabilizing agent is not necessary.
- the nanosized catalyst mono- or poly- metallic
- an inert support such as — ⁇ ⁇ " alumina, silica, magnesia, zirconia, ceria and other metal oxides.
- the nanosized catalyst can be employed as not supported catalyst .
- the support can be directly introduced in the reactor where the reduction of the metal precursor or precursors is carried out or, otherwise, at room temperature in a successive step after the reduction reaction.
- the process of synthesis of metal nanostructured catalysts as above described allows to avoid on the one hand the use of expensive and difficult to be synthesized organometallic precursors and on the other hand the employment of high boiling solvents such as glycols and polyglycols, in particular diethylene- and triethylene- glycol, hardly removable from the final product after the reduction of the starting metal precursor.
- the nanosized metal catalyst as above described can be advantageously employed in hydrogenation, dehydrogenation, oxidation, hydroxylation, cis-dihydroxylation and in C-C bond formation reactions.
- the nanosized metal catalyst as above described can be advantageously employed in the selective hydrogenation of organic substrates, in particular in the reaction of selective hydrogenation of benzene to cyclohexene, of phenol to cyclohexanone and of benzaldehyde to benzyl alcohol.
- the nanosized ruthenium metal catalyst described in Example 1 has been prepared according the known process of the reduction in glycol , in order to have a comparison with the ruthenium catalysts described in the Examples 2-11 , prepared according to the present invention.
- TEM analysis revealed the presence of metal particles with an average diameter of 3.33 nm and with a standard deviation of 0.59 nm.
- the morphologies of the prepared catalysts have been compared with those of the commercial catalysts and of other prepared according the known process of reduction in polyols.
- the autoclave is then pressurized with 60 bar of nitrogen and the stirring started when the temperature of 200 0 C was reached; the stirring was maintained for 3 h. Then the autoclave was cooled up to room temperature and the gas discharged. Successively 1.98 g of ⁇ -A12O3 were added under stirring. The dispersion was filtered, washed with acetone and dried.
- TEM analysis revealed metal particles with an average diameter of 2.00 nm and a standard deviation of 0.28 run.
- the catalyst was synthesized analogously to that of Example 2, but using as support basic Al 2 O 3 with a surface area of 150 m 2 /g.
- the catalyst was synthesized analogously to that of Example 2, but adopting 220 0 C as reaction temperature.
- TEM analysis revealed metal particles with an average diameter of 2.05 nm and a standard deviation of 0.25 nm.
- the catalyst was synthesized analogously to that of Example 2, but using as support 1.95 g of carbon (surface area 900 m2/g) .
- Metal particles have an average diameter of 2.16 nm with a standard deviation of 0.33 nm.
- the catalyst was synthesized analogously to that of Example 2, but using as support 4.1 g of ⁇ -alumina. Metal particles have an average diameter of 2.07 nm with a standard deviation of 0.31 nm.
- the catalyst was synthesized analogously to that of Example 6, but using as a stabilizer 0.57 g of a grafted copolymer polyethyleneglycol-PVP.
- Metal particles have an average diameter of 2.03 nm with a standard deviation of 0.44 nm.
- the catalyst was synthesized analogously to that of Example 2, but using as a stabilizer 1.23 g of a grafted copolymer polyethyleneglycol-PVP.
- Metal particles have an average diameter 3.04 nm with a standard deviation 0.78 nm.
- the catalyst was synthesized analogously to that of Example 2, but ⁇ -alumina was directly introduced in the autoclave before the reduction step.
- Example 10 The catalyst was synthesized analogously to that of Example 2, but using as solvent 110 ml of isopropyl alcohol.
- the catalyst was synthesized analogously to that of Example 2, but without a stabilizing polymer and introducing in the autoclave 5.5 ml of an aqueous solution of NaOH 0. 5 M.
- the catalyst was synthesized analogously to that of Example 2, but using as a metal precursor 48 mg of RhC13.3H2O
- the catalyst was synthesized analogously to that of Example 2, but using as a metal precursor 50 mg of H 2 PtCl 6 .6H 2 O.
- Example 14
- the autoclave was then pressurized with 60 bar of nitrogen and the stirring started when the temperature of 100 0 C was reached; the stirring was maintained for 3 h. Then the autoclave was cooled up to room temperature and the gas discharged. The catalyst was filtered, washed with acetone and dried.
- the autoclave was then pressurized with 60 bar of nitrogen and the stirring started when the temperature of 80 0 C was reached; the stirring was maintained for 3 h. Then the autoclave was cooled up to room temperature and the gas discharged. The catalyst was filtered, washed with acetone and dried.
- TEM analysis revealed metal particles with an average diameter of 3.53 nm with a standard deviation of 1.24 nm.
- Example 16 0.2 ml of an aqueous solution of HAuC14 I M, 0.41 g of PVP, 3.9 g of carbon powder (Strem n.93-0601) , 70 ml of water and 30 ml of ethanol were premixed and then introduced in a 300 ml autoclave equipped with a magnetic stirrer and a manometer for pressures up to 200 bar. The autoclave was then pressurized with 60 bar of nitrogen and the stirring started when the temperature of 150 0 C was reached; the stirring was maintained for 3 h. Then the autoclave was cooled up to room temperature and the gas discharged. The catalyst was filtered, washed with acetone and dried.
- the ruthenium nanocatalysts synthesized according to the present invention besides involving a much easier preparative method, have offered better performances (in terms of yields in the target product) with respect not only to the commercial catalysts, but also to the nanosized metal catalyst 1, prepared according the reduction in glycol.
- the ruthenium based catalysts have shown a good catalytic activity also in the selective hydrogenation of phenol to cyclohexanone (Table 2) . Also in this reaction the catalysts prepared according to the present invention are better for activity and selectivity with respect to the commercial ones and to the catalyst prepared in glycol, allowing to achieve high yields in cyclohexanone. In this reaction the only formed by-product is cyclohexanol.
- the palladium catalysts prepared according to the present invention result significantly more active than the commercial ones in the hydrogenation of cyclohexene to cyclohexane (Table 3) and of benzaldehyde to benzyl alcohol (Table 4) . In this last reaction a particularly higher selectivity has been also evidenced.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a new easy, cheap and reproducible process for preparing nanostructured metal catalysts and their use in catalytic reactions. One or more metal precursors are reduced by heating in the presence of a low boiling alcohol (employed as solvent or co-solvent) under an overpressure, eventually in the presence of a stabilizing agent. A support can be directly added in the reduction step or in a successive one. The obtained catalysts present good characteristics in terms of metal particles average diameter and dimensions distribution. The said catalysts can be advantageously employed in many peculiar catalytic reactions, such as the selective hydrogenation of organic substrates. In particular, these ruthenium nanocatalysts have shown higher performances respect to commercial ones in the selective hydrogenation of benzene to cyclohexene and of phenol to cyclohexanone.
Description
TITLE
PROCESS FOR MAKING NANOSTRUCTURED METAL CATALYSTS AND THEIR USE IN CATALYTIC REACTIONS.
DESCRIPTION
Field of the invention
The present invention relates to a process for preparing nanostructured metal catalysts and their use in catalytic reactions. In particular, the present invention relates to the preparation of heterogeneous or homogeneous nanostructured metal catalysts for peculiar reactions, mainly involving the selective hydrogenation of organic substrates.
Description of the prior art Metal catalysts are generally employed in many catalytic reactions for the production of different organic products.
In particular, nanostructured metal catalysts offer excellent catalytic properties and many advantages in comparison with corresponding catalysts based on metal particles with larger dimensions. Their main advantage is represented by a significant increase of the surface activity which allows to greatly improve the performances of catalytic processes where they are employed. As a consequence, different synthetic methods have been studied in order to produce nanostructured metal catalysts.
The main known methods concern processes of electrochemical reduction of metal salts, chemical reduction of metal salts, the "metal vapors technique" and the reduction, or decomposition, of organometallic precursors.
In particular, the electrochemical reduction of metal salts is extremely expensive for large scale applications
and frequently does not allow to control the particles size. Moreover, this process is scarcely suitable for important transition metals such as Pt, Rh, Ru and Mo, due to low solubility of their cations when employed as an anode.
The method of the chemical reduction of the metal salts is based on the use of reducing agents such as metal hydrides or hydrogen itself, and of a stabilizing agent, generally a polymer. Otherwise, in order to avoid the eventual poisoning of the product by the reducing agent and to perform the reduction under higher control, a method of reduction in an alcohol has been proposed. Because the reduction in the presence of an alcohol generally needs high temperature to be efficient and complete, the reduction in the presence of polyols such as ethylene glycol, but mainly diethylene glycol and triethylene glycol, has been preferred. This type of process is, for instance, described in FR 2537898. Otherwise, not very often, high boiling alcohols such as n-octanol are employed, as described in WO 9604088. Both polyols and high molecular weight alcohols present the obvious drawback of a difficult removal from the final product and thus are not suitable for a large scale production of nanocatalysts. Another method for the production of nanostructured metal catalysts is based on the "metal vapors technology" . For this approach very expensive and rarely available reactors are necessary, thus appearing not suitable for large scale preparations. Finally, a further method for the production of nanostructured metal catalysts involves the reduction, or decomposition, of organometallic precursors. Also this type of process appears not suitable for large scale applications. This procedure, in fact, employs as
precursors organometallic derivatives which are very difficult to be synthesized and very expensive. Moreover, this process does not often enable to reach a good control of the particles sizes and their morphology. Moreover, frequently, this method is scarcely reproducible.
Nanosized metal catalysts can be employed in many catalytic reactions such as the selective hydrogenation of organic molecules.
In particular, the up to now known catalysts employed in the selective hydrogenation of benzene to cyclohexene and of phenol to cyclohexanone are not able to perform in high yield the target product and imply high costs, as when palladium based catalysts are required.
Summary of the invention It is therefore a first feature of the present invention to realize a simple and cheap process for the preparation of nanosized metal catalysts on a large scale resolving the drawbacks of the conventional methods.
It is another feature of the present invention to give a process for the preparation of nanosized metal catalysts which allows to easily separate any by-products present in the reaction mixture from the final product.
It is a further feature of the present invention to give a process for the preparation of nanosized metal catalysts which allows to obtain a final product with improved characteristics, in terms of average diameter and size distribution of the metal particles, with respect to the known nanostructured catalysts.
It is a particular feature of the present invention to produce a nanosized metal catalyst that is particularly efficient, in terms of activity and selectivity for specific catalytic reactions.
These and other features are accomplished with one exemplary process, according to the present invention,
for the preparation of nanosized metal catalysts through the reduction reaction of at least one metal precursor carried out by heating in an alcoholic solvent or co- solvent, whose main characteristic is that the above reduction is carried out under an overpressure. In this way it is possible to employ a low molecular weight alcoholic solvent which is easily removable from the target product.
In particular, the or each metal precursor has the formula: MnXy or HxMnXy, used as that or solvated, where M is a metal cation and X is an anion selected from the group comprised of:
— a halogenide
— a carboxylate — a substituted carboxylate
— a hydroxide
— a carbamate
— an aldiminate
Preferably, the metal cation is selected from the group comprised of:
— rhodium;
— ruthenium;
— rhenium;
— palladium; — platinum;
— nickel;
— copper;
— iridium;
— iron; — gold.
In particular, the employed alcoholic medium can have a molecular weight below 100.
Advantageously, the alcoholic solvent or co-solvent is selected from the group comprised of:
— methanol;
— ethanol;
— n-propanol;
— n-butanol; — n-pentanol and their isomers.
Preferably, the alcoholic medium is selected from the group comprised of:
— methanol — ethanol;
— propanol;
— isopropanol.
In particular, the above described reduction reaction of the or each metal precursor is carried out at a pressure in the range from 10 and 150 bar, produced by an inert gas, such as, for instance, nitrogen.
Preferably, the said reduction reaction of the or each metal precursor is carried out at a pressure from 20 and 100 bar. In particular, the reduction of one or more metal precursors together at the same time can be carried out at a temperature from 50 to 400 0C and preferably from 50 to 250 0C.
Advantageously, a stabilizing agent can be also employed, such as a polymer or a copolymer, for instance poly-N-vinyl-2-pyrrolidone (PVP) , polyethylenoxide, polypropylenoxide, polyacrylates, or their copolymers.
Moreover, a base and/or an inorganic or organic salt, such as alkali or alkali earth hydroxides and/or their salts as acetates, oxalates, formates, amines etc. can be employed as a stabilizer. In this case the use of the polymer as stabilizing agent is not necessary.
In particular, the nanosized catalyst, mono- or poly- metallic, can be deposited on an inert support, such as
— © ■" alumina, silica, magnesia, zirconia, ceria and other metal oxides.
Otherwise, the nanosized catalyst can be employed as not supported catalyst . Advantageously, the support can be directly introduced in the reactor where the reduction of the metal precursor or precursors is carried out or, otherwise, at room temperature in a successive step after the reduction reaction. The process of synthesis of metal nanostructured catalysts as above described allows to avoid on the one hand the use of expensive and difficult to be synthesized organometallic precursors and on the other hand the employment of high boiling solvents such as glycols and polyglycols, in particular diethylene- and triethylene- glycol, hardly removable from the final product after the reduction of the starting metal precursor.
According to another aspect of the present invention, the nanosized metal catalyst as above described can be advantageously employed in hydrogenation, dehydrogenation, oxidation, hydroxylation, cis-dihydroxylation and in C-C bond formation reactions.
In particular, the nanosized metal catalyst as above described can be advantageously employed in the selective hydrogenation of organic substrates, in particular in the reaction of selective hydrogenation of benzene to cyclohexene, of phenol to cyclohexanone and of benzaldehyde to benzyl alcohol.
The present invention will be described in further detail by the following examples 1-16; however they should not be construed as limiting the scope of the present invention.
In particular, the nanosized ruthenium metal catalyst
described in Example 1 has been prepared according the known process of the reduction in glycol , in order to have a comparison with the ruthenium catalysts described in the Examples 2-11 , prepared according to the present invention.
Example 1
123 mg of RuC13»nH2O (50.26 mg Ru) and 2.57 g of PVP were introduced under nitrogen in a 250 ml two neck round bottom flash equipped with a condenser and a magnetic stirrer. 280 ml of ethylene glycol were successively added and the resulting reaction mixture was refluxed at 198 0C by heating with a thermostatted oil bath for 3 h. At the end, after cooling, 4.17 g of γ-Al203 (surface area 110 m2/g) were added and the stirring was continued for 12 h. Then ethylene glycol was removed by evaporation at reduced pressure and the catalyst was washed with acetone and dried up to constant weight.
TEM analysis revealed the presence of metal particles with an average diameter of 3.33 nm and with a standard deviation of 0.59 nm.
In the Examples 2-16 some preparations according the present invention of the nanosized metal catalysts are described.
The morphologies of the prepared catalysts have been compared with those of the commercial catalysts and of other prepared according the known process of reduction in polyols.
Example 2
48.8 mg of RuC13»nH2O, 0.60 g of PVP and 100 ml of ethanol were introduced in a 300 ml autoclave equipped with a magnetic stirrer and a manometer for pressures up to 200 bar.
The autoclave is then pressurized with 60 bar of nitrogen and the stirring started when the temperature of
200 0C was reached; the stirring was maintained for 3 h. Then the autoclave was cooled up to room temperature and the gas discharged. Successively 1.98 g of γ-A12O3 were added under stirring. The dispersion was filtered, washed with acetone and dried.
TEM analysis revealed metal particles with an average diameter of 2.00 nm and a standard deviation of 0.28 run.
Example 3
The catalyst was synthesized analogously to that of Example 2, but using as support basic Al2O3 with a surface area of 150 m2/g.
Example 4
The catalyst was synthesized analogously to that of Example 2, but adopting 220 0C as reaction temperature. TEM analysis revealed metal particles with an average diameter of 2.05 nm and a standard deviation of 0.25 nm.
Example 5
The catalyst was synthesized analogously to that of Example 2, but using as support 1.95 g of carbon (surface area 900 m2/g) . Metal particles have an average diameter of 2.16 nm with a standard deviation of 0.33 nm.
Example 6
The catalyst was synthesized analogously to that of Example 2, but using as support 4.1 g of γ-alumina. Metal particles have an average diameter of 2.07 nm with a standard deviation of 0.31 nm.
Example 7
The catalyst was synthesized analogously to that of Example 6, but using as a stabilizer 0.57 g of a grafted copolymer polyethyleneglycol-PVP.
Metal particles have an average diameter of 2.03 nm with a standard deviation of 0.44 nm.
Example 8
The catalyst was synthesized analogously to that of
Example 2, but using as a stabilizer 1.23 g of a grafted copolymer polyethyleneglycol-PVP.
Metal particles have an average diameter 3.04 nm with a standard deviation 0.78 nm. Example 9
The catalyst was synthesized analogously to that of Example 2, but γ-alumina was directly introduced in the autoclave before the reduction step.
Example 10 The catalyst was synthesized analogously to that of Example 2, but using as solvent 110 ml of isopropyl alcohol.
Example 11
The catalyst was synthesized analogously to that of Example 2, but without a stabilizing polymer and introducing in the autoclave 5.5 ml of an aqueous solution of NaOH 0. 5 M.
Example 12
The catalyst was synthesized analogously to that of Example 2, but using as a metal precursor 48 mg of RhC13.3H2O
Example 13
The catalyst was synthesized analogously to that of Example 2, but using as a metal precursor 50 mg of H2PtCl6.6H2O. Example 14
51.7 mg di Pd (OAc) 2, 0.499 g di PVP, 4.177 g of carbon powder (Strem n.93-0601) and 100 ml of ethanol were premixed and then introduced in a 300 ml autoclave equipped with a • magnetic stirrer and a manometer for pressures up to 200 bar.
The autoclave was then pressurized with 60 bar of nitrogen and the stirring started when the temperature of 100 0C was reached; the stirring was maintained for 3 h. Then the autoclave was cooled up to room temperature and the
gas discharged. The catalyst was filtered, washed with acetone and dried.
TEM analysis revealed metal particles with an average diameter of 3.81 nm with a standard deviation of 1.22 run. Example 15
55.9 mg of Pd (OAc) 2, 0.487 g of PVP, 4.08 g of carbon powder (Strem n.93-0601) and 100 ml of methanol were premixed and then introduced in a 300 ml autoclave equipped with a magnetic stirrer and a manometer for pressures up to 200 bar.
The autoclave was then pressurized with 60 bar of nitrogen and the stirring started when the temperature of 80 0C was reached; the stirring was maintained for 3 h. Then the autoclave was cooled up to room temperature and the gas discharged. The catalyst was filtered, washed with acetone and dried.
TEM analysis revealed metal particles with an average diameter of 3.53 nm with a standard deviation of 1.24 nm.
Example 16 0.2 ml of an aqueous solution of HAuC14 I M, 0.41 g of PVP, 3.9 g of carbon powder (Strem n.93-0601) , 70 ml of water and 30 ml of ethanol were premixed and then introduced in a 300 ml autoclave equipped with a magnetic stirrer and a manometer for pressures up to 200 bar. The autoclave was then pressurized with 60 bar of nitrogen and the stirring started when the temperature of 150 0C was reached; the stirring was maintained for 3 h. Then the autoclave was cooled up to room temperature and the gas discharged. The catalyst was filtered, washed with acetone and dried.
Some examples of catalytic applications of the above described catalysts are below reported and the obtained results are compared with those reached with the commercial catalysts or with the catalysts prepared according the known
procedure of reduction in the presence of polyols.
These examples, however, should be not construed as limiting the scope of the present invention.
Selective hydrogenation reactions As an example, the same ruthenium and palladium catalysts, prepared according to the present invention, have been employed in the hydrogenation of cyclohexene to cyclohexane and in the selective hydrogenation of benzene to cyclohexene, of phenol to cyclohexanone and of benzaldehyde to benzyl alcohol comparing the performances of the catalysts prepared according to the present invention with those of some commercial ones and of the catalysts obtained according to Example 1 by reduction in glycol. As an example some results are summarized in the Tables 1-4. In the selective hydrogenation of benzene to cyclohexene and of phenol to cyclohexanone the ruthenium nanocatalysts synthesized according to the present invention, besides involving a much easier preparative method, have offered better performances (in terms of yields in the target product) with respect not only to the commercial catalysts, but also to the nanosized metal catalyst 1, prepared according the reduction in glycol.
In fact, in the benzene hydrogenation to cyclohexene this superiority is observed either working in organic medium (n-hexane) or, more suitably, in water in the presence of zinc sulfate. The only formed by-product is cyclohexane. (Table 1)
The ruthenium based catalysts have shown a good catalytic activity also in the selective hydrogenation of phenol to cyclohexanone (Table 2) . Also in this reaction the catalysts prepared according to the present invention are better for activity and selectivity with respect to the commercial ones and to the catalyst prepared in glycol,
allowing to achieve high yields in cyclohexanone. In this reaction the only formed by-product is cyclohexanol.
The palladium catalysts prepared according to the present invention result significantly more active than the commercial ones in the hydrogenation of cyclohexene to cyclohexane (Table 3) and of benzaldehyde to benzyl alcohol (Table 4) . In this last reaction a particularly higher selectivity has been also evidenced.
Table 1: Catalytic hydrogenation of benzene to cyclohexene
Runa Cat. of (mg Ru) Benzene Conv. Selectivity to Example (mol%) cyclohexene (%) 30' Ih 3h 30' Ih 3h la) 1 (5.2) 4.6 6 8 25.6 24.3
2 a, 8 (4.34) 32.9 58 8 9.3 4.2
Aldrich (3.07) 0.61
3b» 5% on C 45.5 -
Engelhard (3.7)
4 bl 62.41 - - 0.10 5% on C
5b) 1 (5.86) 2.3 - 62.6
6b) 2 (5.6) 51.4 - 36.7
7 b) 9 (3.70) 24.1 - 46.6 g b, 5 (5.11) 29.1 - 31.5
9 b. 4 (4.62) 47.3 - 31.5
10 b) 8 (5.9) 43.1 - 52.3 a) Reaction conditions: benzene (25 ml); solvent: n-hexane (20 ml); T: 100 0C; P hydrogen: 50 bar. b) Reaction conditions: benzene (25 ml); solvent: water (50 ml) with ZnSO4 (2.4 g) ; T: 160 0C; P hydrogen: 50 bar.
Table 2; Catalytic hydrogenation of phenol to cyclohexanone3'
Run Cat. of (mg Ru) Phenol Conv. Selectivity to Example: (mol%) cyclohexanone <%) 30' Ih 3h 30' Ih 3h
11 Aldrich (2.0) 33.8 75. 4 - 63.1 31 1 - 5% on C
12 1 (2.2) _ 2. 4 10. 1 86 5 78 .2
13 10 (2.5) 58.8 82. 3 _ 70.0 53 6 _
14 9 (2.3) 44.1 60. 7 _. 68.6 63 3
15 6 (2.0) 28.2 38. 4 74. 2 72.8 69 6 54 .4
16 b) 6 (2.0) 32.6 51. 1 91. 4 76.0 70. 0 46 .9
17 5 (1.8) _ 27. 9 51. 9 65. 0 48 .8
18 3 (2.1) 74.9 _ _ 54.1
19 11 (2.2) 31.5 _ 87. 2 81.7 59 .2 a)Reaction conditions:: phenol (10 g) ; solvent; cyclohexane(50 ml); T: 160 0C; P hydrogen: 50 bar. b) Water (0.46 g) has been added to the catalyst.
Table 3 - Cyclohexene hydrogenation to cyclohexane a)
Run Cat. (mg Pd) Cyclohexene conversion of Example (mol %)
Ih 2h 3h 4h 5h
20 Engelhard 2 % 0 .1 3.0 6.5 13.8 16.5 19 .1 on carbon
21 14 0 .1 10.7 19.4 27.4 35.5 42 .0
22 15 0 .1 14.1 27.9 36.8 46.2 53 .7 a)Reaction conditions: cyclohexene (5 ml); solvent: toluene (50 ml); T: 30 0C; P hydrogen: 10 bar.
Table 4 - Benzaldehyde hydrogenation to benzyl alcohol a) b)
Run Cat . (mg Pd) Benzaldehyde Selectivity of conversion (mol%) (mol %) Example 30' 60' 90' 30' 60' 90'
23 Engelhard 0 .05 22 2 38 9 58 1 42 .1 44. 4 48. 5 2 % on carbon
24 14 0 .05 28 8 65 1 91. 0 95 .0 95. 3 93. 7
25 15 0 .05 29 4 63. 6 90. 9 94 .5 96. 6 92. 1
a)Reaction conditions: benzaldehyde (0.5 ml); solvent: methanol (38 ml); T: 35 0C; P hydrogen: 1 bar. b)Selectivity to benzyl alcohol; main by-product: benzaldehyde dimethoxy acetal.
The foregoing description of a specific embodiment will so fully reveal the invention according to the conceptual point of view, so that others, by applying current knowledge, will be able to modify and/or adapt for various applications such an embodiment without further research and without parting from the invention, and it is therefore to be understood that such adaptations and modifications will have to be considered as equivalent to the specific embodiment. The means and the materials to realise the different functions described herein could have a different nature without, for this reason, departing from the field of the invention. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation.
Claims
1. Process for the preparation of nanosized metal catalysts through the reduction reaction of at least one metal precursor carried out by heating in an alcoholic solvent or co-solvent characterised in that said reduction reaction is carried out under overpressure.
2. Process, according to claim 1, wherein said or each metal precursor has the formula: MnXy or HxMnXy, used as that or solvated, where M is a metal cation and X is an anion selected from the group comprised of: a halogenide
- a carboxylate
- a substituted carboxylate - a hydroxide
- a carbamate
- an aldiminate
3. Process, according to claim 2, wherein said metal cation is selected from the group comprised of : - rhodium;
- ruthenium;
- rhenium;
- palladium;
- platinum; - nickel;
- copper;
- iridium; iron;
- gold.
4. Process, according to claim 1, wherein said alcoholic solvent or co-solvent is an alcohol with a molecular weight below 100, preferably selected from the group comprised of: - methanol;
- ethanol;
- n-propanol;
- n-butanol; n-pentanol and their isomers.
5. Process, according to claim 1, wherein said said reduction reaction of said at least one metal precursor is carried out under a pressure in the from 10 to 150 bar, using an inert gas.
6. Process, according to claim 1, wherein said reduction reaction of said at least one metal precursor is carried out under a pressure from 20 to 100 bar.
7. Process, according to claim 1, wherein said reduction reaction is carried out in an autoclave filled with an amount of inert gas corresponding to said overpressure conditions.
8. Process, according to claim 1, wherein said reduction reaction of at least one metal precursor is carried out from 50 to 400 0C , preferably from 50 to 250 0C.
9. Process, according to claim 1, wherein a stabilizing agent is also employed selected from the group comprised of:
- poly-N-vinyl-2-pyrrolidone (PVP) , polyethylenoxide, - polypropylenoxide,
- polyacrylates, copolymers thereof.
10. Process, according to claim 1, wherein a base and/or a salt is also employed.
11. Process, according to claim 1, wherein an inert support is employed where said nanosized mono- or polymetallic catalyst is dispersed.
12. Process, according to claim 11, wherein said inert support is directly introduced in the reactor where the reduction reaction is carried out.
13. Process, according to claim 11, wherein said inert support is introduced at room temperature in a successive step after said reduction reaction.
14. Reaction of selective hydrogenation of organic compounds using a nanostructured metal catalyst according to the above claims.
15. Reaction of selective hydrogenation of organic substrates, according to claim 14, wherein said reaction is selected from the group comprised of: hydrogenation of benzene to cyclohexene, - hydrogenation of phenol to cyclohexanone hydrogenation of benzaldehyde to benzyl alcohol.
16. Use of a metal nanostructured catalyst obtained in a process according to the claims from 1 to 13, for the catalysis of organic reactions selected from the group comprised of:
- dehydrogenation reactions oxidation reactions dihydroxylation reactions
- hydroxylation reactions - hydrosilylation
- carbon-carbon bond formation - carbonylation reactions
- carbomethoxylation reactions or their combinations.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT000011A ITPI20060011A1 (en) | 2006-01-26 | 2006-01-26 | PROCEDURE FOR THE PREPARATION OF NANOSTRUCTURED METALLIC CATALYZERS AND THEIR USE IN CATALYTIC REACTIONS |
ITPI2006A000011 | 2006-01-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007085463A1 true WO2007085463A1 (en) | 2007-08-02 |
Family
ID=38042856
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/000666 WO2007085463A1 (en) | 2006-01-26 | 2007-01-26 | Process for making nanostructured metal catalysts and their use in catalytic reactions. |
Country Status (2)
Country | Link |
---|---|
IT (1) | ITPI20060011A1 (en) |
WO (1) | WO2007085463A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010005859A2 (en) * | 2008-07-07 | 2010-01-14 | Albemarle Corporation | Processes for hydrogenating aromatic amines |
RU2696957C1 (en) * | 2019-05-21 | 2019-08-07 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Nanostructured catalyst for hydrogenation of aromatic hydrocarbons c6-c8 |
CN116036272A (en) * | 2023-02-08 | 2023-05-02 | 南京邮电大学 | Preparation method and application of PVP modified Ru nano-sheet |
JP7424563B2 (en) | 2020-02-03 | 2024-01-30 | 学校法人 関西大学 | Method for producing organosilicon compounds using ruthenium nanoparticle catalysts |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112452340B (en) * | 2020-11-23 | 2023-12-15 | 浙江卫星能源有限公司 | Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5759230A (en) * | 1995-11-30 | 1998-06-02 | The United States Of America As Represented By The Secretary Of The Navy | Nanostructured metallic powders and films via an alcoholic solvent process |
US6224739B1 (en) * | 1996-07-30 | 2001-05-01 | Studiengesellschaft Kohle Mbh | Process for preparing solvent-stabilized metal colloids and substrate-immobilized metal clusters |
EP1236512A1 (en) * | 2001-02-28 | 2002-09-04 | Council Of Scientific And Industrial Research | Nanosized noble metal catalyst and process for selective preparation of 1,4 butenediol |
US6833019B1 (en) * | 2003-01-31 | 2004-12-21 | The United States Of America As Represented By The Secretary Of The Navy | Microwave assisted continuous synthesis of nanocrystalline powders and coatings using the polyol process |
-
2006
- 2006-01-26 IT IT000011A patent/ITPI20060011A1/en unknown
-
2007
- 2007-01-26 WO PCT/EP2007/000666 patent/WO2007085463A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5759230A (en) * | 1995-11-30 | 1998-06-02 | The United States Of America As Represented By The Secretary Of The Navy | Nanostructured metallic powders and films via an alcoholic solvent process |
US6224739B1 (en) * | 1996-07-30 | 2001-05-01 | Studiengesellschaft Kohle Mbh | Process for preparing solvent-stabilized metal colloids and substrate-immobilized metal clusters |
EP1236512A1 (en) * | 2001-02-28 | 2002-09-04 | Council Of Scientific And Industrial Research | Nanosized noble metal catalyst and process for selective preparation of 1,4 butenediol |
US6833019B1 (en) * | 2003-01-31 | 2004-12-21 | The United States Of America As Represented By The Secretary Of The Navy | Microwave assisted continuous synthesis of nanocrystalline powders and coatings using the polyol process |
Non-Patent Citations (2)
Title |
---|
RIOUX, R.M. ET AL.: "High-surface-area catalyst design: synthesis, characterization, and reaction studies of platinum nanoparticles in mesoporous SBA-15 silica", J. PHYS. CHEM. B, vol. 109, 2005, pages 2192 - 2202, XP002438112 * |
TOSHIMA, N. ET AL.: "Catalytic activity and structural analysis of polymer-protected Au-Pd bimetallic clusters prepared by the simultaneous reduction of HAuCl4 and PdCl2", J. PHYS. CHEM., vol. 96, 1992, pages 9927 - 9933, XP002438113 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010005859A2 (en) * | 2008-07-07 | 2010-01-14 | Albemarle Corporation | Processes for hydrogenating aromatic amines |
WO2010005859A3 (en) * | 2008-07-07 | 2010-05-06 | Albemarle Corporation | Processes for hydrogenation |
RU2696957C1 (en) * | 2019-05-21 | 2019-08-07 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Nanostructured catalyst for hydrogenation of aromatic hydrocarbons c6-c8 |
JP7424563B2 (en) | 2020-02-03 | 2024-01-30 | 学校法人 関西大学 | Method for producing organosilicon compounds using ruthenium nanoparticle catalysts |
CN116036272A (en) * | 2023-02-08 | 2023-05-02 | 南京邮电大学 | Preparation method and application of PVP modified Ru nano-sheet |
Also Published As
Publication number | Publication date |
---|---|
ITPI20060011A1 (en) | 2007-07-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Pérez et al. | Highly selective palladium supported catalyst for hydrogenation of phenol in aqueous phase | |
Niu et al. | Highly efficient and recyclable ruthenium nanoparticle catalyst for semihydrogenation of alkynes | |
KR101969407B1 (en) | The Selective Hydrogenation Catalyst and Selective Hydrogenation Process using the same | |
US20140296564A1 (en) | Preparation process of nanocatalysts with (111) crystal facet exposed and process for vapour-phase co oxidative coupling to oxalate | |
CN113058644B (en) | Catalyst for catalyzing oxidative dehydrogenation and hydrogenation of organic compounds and application thereof | |
US6617477B2 (en) | Process for preparing 1,3-alkanediols from 3-hydroxyesters | |
WO2007085463A1 (en) | Process for making nanostructured metal catalysts and their use in catalytic reactions. | |
Das et al. | Influence of the metal function in the “one-pot” synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone) from acetone over palladium supported on Mg (Al) O mixed oxides catalysts | |
US20140179950A1 (en) | Method of making adipic acid using nano catalyst | |
JP2015129151A (en) | Continuous method for producing substituted cyclohexylmethanols | |
JPH03127750A (en) | Method for hydrogenation of citral | |
US20030191328A1 (en) | Method for expoxidation of hydrocarbons | |
US7169736B2 (en) | Catalyst for hydrogenation of unsaturated hydrocarbons | |
US6294696B1 (en) | Process for hydrogenating organic functions | |
CN101428226A (en) | Selective hydrogenation catalyst for fine purification of p-benzene dicarboxylic acid | |
JPS58208240A (en) | Synthesis of olefins from synthetic gas | |
CN113214146B (en) | Process for the N-alkylation of aminopyridines | |
Fan et al. | Highly efficient hydrogenation of methyl propionate to propanol over hydrous zirconia supported ruthenium | |
US9815758B2 (en) | Process of preparing 4-methyl-3-decen-5-one | |
CN112138676B (en) | Catalyst for preparing o-phenylphenol and preparation method thereof | |
KR20030036951A (en) | Process for preparing 1,3-alkanediols from 3-hydroxyester compounds | |
CN110963901A (en) | Preparation method of 3,3, 5-trimethylcyclohexanone | |
PL186931B1 (en) | Method pf obtaining carbazole | |
KR100496324B1 (en) | Process for preparing 1,3-propandiols from alkyl-3-hydroxypropionates | |
KR20020042397A (en) | Process for preparing 1,3-alkanediol from 3-hydroxyester compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 07711388 Country of ref document: EP Kind code of ref document: A1 |