WO2009096783A1 - Process for the preparation of an aqueous colloidal precious metal suspension - Google Patents
Process for the preparation of an aqueous colloidal precious metal suspension Download PDFInfo
- Publication number
- WO2009096783A1 WO2009096783A1 PCT/NL2009/050039 NL2009050039W WO2009096783A1 WO 2009096783 A1 WO2009096783 A1 WO 2009096783A1 NL 2009050039 W NL2009050039 W NL 2009050039W WO 2009096783 A1 WO2009096783 A1 WO 2009096783A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- precious metal
- process according
- quaternary ammonium
- suspension
- catalyst
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000010970 precious metal Substances 0.000 title claims abstract description 27
- 239000000725 suspension Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- ODEHKVYXWLXRRR-UHFFFAOYSA-N hex-3-yn-1-ol Chemical compound CCC#CCCO ODEHKVYXWLXRRR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- UFLHIIWVXFIJGU-UHFFFAOYSA-N hex-3-en-1-ol Natural products CCC=CCCO UFLHIIWVXFIJGU-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 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
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229960001296 zinc oxide Drugs 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 235000019289 ammonium phosphates Nutrition 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- KMPWYEUPVWOPIM-KODHJQJWSA-N cinchonidine Chemical compound C1=CC=C2C([C@H]([C@H]3[N@]4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-KODHJQJWSA-N 0.000 description 2
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 239000010415 colloidal nanoparticle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- SGZVXLFVBKDMJH-UHFFFAOYSA-M dihydrogen phosphate;hexadecyl-(2-hydroxyethyl)-dimethylazanium Chemical compound OP(O)([O-])=O.CCCCCCCCCCCCCCCC[N+](C)(C)CCO SGZVXLFVBKDMJH-UHFFFAOYSA-M 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- 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
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Definitions
- the invention is directed to a process for the preparation of an aqueous colloidal precious metal suspension, as well as to the preparation of a supported precious metal catalyst, using the said suspension.
- Metal colloids are used as starting materials for the preparation of supported (precious) metal catalysts.
- Precious metal colloids are usually prepared by reducing a precious metal ion in an organic solvent, mostly at elevated temperature.
- the most often used method is reduction using an alcohol.
- This can either be a low boiling alcohol, such as the Ci to C4 alcohols, more in particular methanol, or high boiling solvents containing a hydroxyl group, such as ethylene glycol, or diethylene glycol mono-n-butyl ether.
- a separate stabilizer is added.
- the metal salt (ion) is mixed with the stabilizer in an alcoholic solution and refluxed for several hours.
- the high boiling materials require very high temperatures and often a protective atmosphere (nitrogen) and/or a high pH.
- colloidal nanoparticles An important use of the colloidal nanoparticles resides in the preparation of supported precious metal catalysts. Traditional methods for the preparation thereof generally yield catalysts that have small metal crystallites, but show a rather broad size distribution. It would be useful to have a process wherein the crystallite size distribution of the nanoparticles is rather narrow, thereby enabling the production of catalysts having a narrow crystallite size distribution.
- the present invention encompasses in a first embodiment a process for the preparation of an aqueous colloidal precious metal suspension, which process comprises reducing a precious metal salt in aqueous solution using a functionalised, water soluble quaternary ammonium salt in the absence of organic solvents, to form elementary nanoparticles.
- an essential element of the process of the present invention resides in the use of the specific quaternary ammonium salt, namely a functionalised quaternary ammonium salt.
- the functionalisation comprises the presence of at least one reducing group, such as — CH2OH or cyclohexenyl, preferably in combination with at least one bulky group selected from the group of C ⁇ + -alkyl, cycloalkyl, aralkyl, alkaryl or aryl groups.
- the quaternary ammonium salt can be chiral, such as a quaternised cinchonine or cinchonidine.
- Preferred quaternary ammonium salts to be used in the process of the present invention are of the formula I:
- R and R' are Ci- alkyl
- R" is Ce- and higher, more preferred Ci ⁇ -alkyl.
- the particle size of the elementary nanoparticles that are obtained by the process of the present invention is between 1 and 50, preferably between 1 and 10 nm.
- the precious metal is selected from the group of platinum, palladium, iridium, rhodium, ruthenium, rhenium, silver, gold and combinations thereof, preferably palladium.
- a palladium salt is used, more specifically Na 2 PdCl 4 .
- the process of the invention is very simple, as it suffices to combine the precious metal salt and the quaternary ammonium compound in an aqueous system, for example by mixing aqueous solutions of respectively the quaternary ammonium compound and the precious metal salt at a suitable temperature.
- Suitable temperatures are mainly determined by the reaction rate and the requirement that the compounds remain dissolved in a liquid system. Suitable temperatures for the solutions and the reaction mixture are between room temperature (20°C) and near boiling point (95°C).
- the colloidal suspension may be used as catalytic material or for the preparation thereof.
- the colloidal suspension is used to produce supported precious metal catalysts.
- This process comprises preparing an aqueous colloidal precious metal suspension in accordance with the above process according to the invention, followed by contacting the suspension with a support material and recovering the precious metal catalyst or catalyst precursor by filtration and washing, optionally after addition of an aqueous alkaline solution (NaOH and the like) or ethanol.
- the support is selected from the group of oxidic supports, such as silica, alumina, zirconia, titanium oxide and zinc-oxide, silicates, aluminates and active carbon.
- the amount of precious metal, calculated on the weight of the final catalyst is between 0.01 and 10 wt.%, preferably between 0.05 and 5 wt.% of the catalyst.
- the support may be in powder form, in the form of shaped particles, such as extrudates, or in the form of a structured material, such as a monolith.
- the colloidal suspension produced in accordance with the process of the first embodiment of the invention as well as the heterogeneous catalyst produced in accordance with the process of this third embodiment of the invention may be used generally for all reactions for which precious metal catalysts are suitable.
- Examples are the usual hydrogenation reactions, such as hydrogenation itself, hydro-isomerisation, hydro-desulfurisation and hydro- dewaxing.
- the catalyst may also have been used in dehydrogenation reactions, such as catalytic reforming.
- the catalyst is suitable for the production of 3- hexenol, which process comprises reducing 3-hexyn-l-ol in the presence of a catalyst as produced in accordance with the process above.
- This process may conveniently be carried out in slurry phase or in a fixed bed in an organic solvent and the presence of hydrogen, either in a three phase system or in a two phase system, where the hydrogen is dissolved in the organic solvent.
- Preferred conditions for a slurry phase reaction are the use of an alkanol, such as hydrous ethanol as solvent, in the presence of 1 to 20 bar of gaseous hydrogen at a temperature between room temperature and about 75°C.
- a solution of 15 g hexadecyl(2 -hydroxy ethyl) dimethylammonium dihydrogen phosphate in 1 L water is heated to 60°C.
- a solution of 0.75 g Pd (as Na2PdCl4) in 10 niL water is added in 3 minutes under vigorous stirring.
- the mixture is heated to 85°C and stirred at this temperature for 2 hours.
- the heating is stopped and the colloidal suspension, thus obtained, is stirred for an additional hour, during which it cools down to 40°C.
- a slurry of 75 g carbon powder in 750 niL water is vigorously stirred for an hour at room temperature.
- the colloidal suspension obtained according to Example 1, containing 0.75 g Pd in 1 L water is added in 40 minutes.
- the mixture is stirred for an additional 45 minutes.
- the pH of the mixture is adjusted from 2.4 to 9.3 by addition of a 10% NaOH solution in 28 minutes.
- the mixture is stirred an additional 30 minutes, while the pH is kept between 9.0 and 9.3 by addition of 10% NaOH.
- the solid supported catalyst is filtered off and washed with water until the filtrate is chlorine-free according to a precipitation test with AgNO3.
- a 250 niL stainless steel autoclave is charged with 500 mg of the catalyst produced according to Example 2 (l%Pd/C (dry weight)), 100 mL 96% ethanol, and 10 mL 3-hexyn-l-ol.
- the autoclave is closed and the mixture is heated to 30°C with stirring.
- the stirring is stopped, and the air is replaced by flushing hydrogen over the mixture.
- After flushing the autoclave is pressurised with 3 bars of hydrogen.
- the stirring is resumed (1500 rpm) and the hydrogen consumption is recorded.
- 2.0 L hydrogen is consumed the stirring is stopped, the hydrogen is vented off, and the autoclave is opened.
- Conversion and selectivity are determined by GC measurement of the crude reaction mixture. Conversion: 97%. Selectivity: >99% 3-hexenol of which 95% is the cis- isomer.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Colloid Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/863,508 US8822725B2 (en) | 2008-01-28 | 2009-01-27 | Process for the preparation of an aqueous colloidal precious metal suspension |
MX2010007883A MX2010007883A (en) | 2008-01-28 | 2009-01-27 | Process for the preparation of an aqueous colloidal precious metal suspension. |
CA 2712482 CA2712482A1 (en) | 2008-01-28 | 2009-01-27 | Process for the preparation of an aqueous colloidal precious metal suspension |
JP2010544252A JP5791901B2 (en) | 2008-01-28 | 2009-01-27 | Method for producing aqueous colloidal precious metal suspension |
RU2010136285/04A RU2491988C2 (en) | 2008-01-28 | 2009-01-27 | Method of producing aqueous suspension of noble metal colloid |
EP09706244.2A EP2249965B1 (en) | 2008-01-28 | 2009-01-27 | Process for the preparation of an aqueous colloidal precious metal suspension |
CN2009801026646A CN101925407B (en) | 2008-01-28 | 2009-01-27 | Process for preparation of aqueous colloidal precious metal suspension |
BRPI0907090-7A BRPI0907090A2 (en) | 2008-01-28 | 2009-01-27 | Process for the preparation of an aqueous colloidal precious metal suspension, for the production of a supported precious metal catalyst and for the production of 3-hexenol. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20080150726 EP2082805A1 (en) | 2008-01-28 | 2008-01-28 | Process for the preparation of an aqueous colloidal precious metal suspension |
EP08150726.1 | 2008-01-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009096783A1 true WO2009096783A1 (en) | 2009-08-06 |
Family
ID=39473834
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL2009/050039 WO2009096783A1 (en) | 2008-01-28 | 2009-01-27 | Process for the preparation of an aqueous colloidal precious metal suspension |
Country Status (10)
Country | Link |
---|---|
US (1) | US8822725B2 (en) |
EP (2) | EP2082805A1 (en) |
JP (2) | JP5791901B2 (en) |
KR (1) | KR20100123702A (en) |
CN (1) | CN101925407B (en) |
BR (1) | BRPI0907090A2 (en) |
CA (1) | CA2712482A1 (en) |
MX (1) | MX2010007883A (en) |
RU (1) | RU2491988C2 (en) |
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WO2016151453A1 (en) | 2015-03-20 | 2016-09-29 | Basf Corporation | Enhanced dispersion of edge-coated precious metal catalysts |
WO2016151454A1 (en) | 2015-03-20 | 2016-09-29 | Basf Corporation | Pt and/or pd egg-shell catalyst and use thereof |
WO2020239720A1 (en) | 2019-05-27 | 2020-12-03 | Dsm Ip Assets B.V. | Selective hydrogenation of alkynols to alkenols in the presence of a phosphorus compound |
EP3906998A1 (en) | 2020-05-05 | 2021-11-10 | BASF Corporation | Supported transition metal nanoparticle catalyst and use thereof as a hydrogenation catalyst |
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EP2082805A1 (en) * | 2008-01-28 | 2009-07-29 | Basf Se | Process for the preparation of an aqueous colloidal precious metal suspension |
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Cited By (9)
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WO2016007112A1 (en) | 2014-07-08 | 2016-01-14 | Tovaristvo Z Obmezhenou Vidpovidalnistu "Nanomedtrast" | Biocompatible colloidal solution of gold nanoparticles in non-aqueous polar solvent and method of obtaining thereof |
WO2016151453A1 (en) | 2015-03-20 | 2016-09-29 | Basf Corporation | Enhanced dispersion of edge-coated precious metal catalysts |
WO2016151454A1 (en) | 2015-03-20 | 2016-09-29 | Basf Corporation | Pt and/or pd egg-shell catalyst and use thereof |
US10232354B2 (en) | 2015-03-20 | 2019-03-19 | Basf Corporation | Enhanced dispersion of edge-coated precious metal catalysts |
US10258967B2 (en) | 2015-03-20 | 2019-04-16 | Basf Corporation | PT and/or PD egg-shell catalyst and use thereof |
WO2020239720A1 (en) | 2019-05-27 | 2020-12-03 | Dsm Ip Assets B.V. | Selective hydrogenation of alkynols to alkenols in the presence of a phosphorus compound |
WO2020239721A1 (en) | 2019-05-27 | 2020-12-03 | Dsm Ip Assets B.V. | Selective hydrogenation of alkynes to alkenes in the presence of a phosphorus compound and an organic sulphur compound |
EP3906998A1 (en) | 2020-05-05 | 2021-11-10 | BASF Corporation | Supported transition metal nanoparticle catalyst and use thereof as a hydrogenation catalyst |
WO2021224246A1 (en) | 2020-05-05 | 2021-11-11 | Basf Corporation | Supported transition metal nanoparticle catalyst and use thereof as a hydrogenation catalyst |
Also Published As
Publication number | Publication date |
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RU2491988C2 (en) | 2013-09-10 |
MX2010007883A (en) | 2010-08-10 |
CA2712482A1 (en) | 2009-08-06 |
JP2011510803A (en) | 2011-04-07 |
KR20100123702A (en) | 2010-11-24 |
EP2249965B1 (en) | 2017-08-02 |
US20110015451A1 (en) | 2011-01-20 |
RU2010136285A (en) | 2012-03-10 |
US8822725B2 (en) | 2014-09-02 |
EP2082805A1 (en) | 2009-07-29 |
JP5791901B2 (en) | 2015-10-07 |
BRPI0907090A2 (en) | 2015-07-14 |
EP2249965A1 (en) | 2010-11-17 |
CN101925407B (en) | 2013-10-23 |
CN101925407A (en) | 2010-12-22 |
JP2015227504A (en) | 2015-12-17 |
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