CN101616736A - 含有铂族金属纳米颗粒的催化剂和生产铂族金属纳米颗粒分散体系的工艺 - Google Patents
含有铂族金属纳米颗粒的催化剂和生产铂族金属纳米颗粒分散体系的工艺 Download PDFInfo
- Publication number
- CN101616736A CN101616736A CN200880005507A CN200880005507A CN101616736A CN 101616736 A CN101616736 A CN 101616736A CN 200880005507 A CN200880005507 A CN 200880005507A CN 200880005507 A CN200880005507 A CN 200880005507A CN 101616736 A CN101616736 A CN 101616736A
- Authority
- CN
- China
- Prior art keywords
- technology
- metal
- catalyst
- microemulsion
- hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000005516 engineering process Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 title claims description 17
- 239000006185 dispersion Substances 0.000 title claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title description 25
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002759 woven fabric Substances 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000002905 metal composite material Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- -1 2-ethylhexyl Chemical group 0.000 claims description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical group OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229960005137 succinic acid Drugs 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims 1
- 239000003863 metallic catalyst Substances 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 35
- 239000000203 mixture Substances 0.000 description 14
- 239000011981 lindlar catalyst Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- ZBJVLWIYKOAYQH-UHFFFAOYSA-N naphthalen-2-yl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=C(C=CC=C2)C2=C1 ZBJVLWIYKOAYQH-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYPKRALMXUUNKS-HYXAFXHYSA-N (z)-hex-2-ene Chemical compound CCC\C=C/C RYPKRALMXUUNKS-HYXAFXHYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-HWKANZROSA-N 2E-hexene Chemical compound CCC\C=C\C RYPKRALMXUUNKS-HWKANZROSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material 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
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
-
- B01J35/23—
-
- B01J35/56—
-
- B01J35/58—
-
- B01J35/617—
-
- 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
- B01J37/06—Washing
-
- 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
- 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
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
本发明涉及新颖的Pt金属族催化剂及其制备工艺,其中,制备处于烃包水系统中的Pt金属的反相微乳液,蒸发一些溶剂,加入C1C4-醇,以形成Pt金属纳米颗粒的沉淀,这可用作为规整型催化剂,例如机织织物中。
Description
本发明涉及新颖的Pt金属族催化剂及其制备工艺。更特别地,本发明涉及Pt金属族的金属的新颖纳米颗粒及其水性分散体系,涉及其上分布有此类纳米颗粒的新颖的规整型催化剂,例如,机织织物,涉及此类载体用作为催化剂的用途;以及涉及制备新颖的规整型催化剂的工艺。
由于金属纳米颗粒可用于催化,它们已吸引了特殊的关注。微乳液广泛用于制备具有窄尺寸分布的纳米颗粒,这通过在分散相中沉淀/还原金属盐来进行。从技术角度来看,使用被担载(support)的催化剂是优选的。用于经由微乳液制备被担载的催化剂的方法可在Applied Catalysis A:General 265(2004)207-219中找到。
通常,将粉末状的担载体/整体料(monolith)或担载体前体与含有纳米颗粒的微乳液混合,之后用溶剂洗,以除去过多的表面活性剂。然后将催化剂在200-600℃在空气或氢气流中煅烧2-12小时。但是,担载体浸渍(impregnation)应当以仅够填充孔体积的微乳液的量来进行,以避免溶剂过量。这在微乳液中产生了高的金属浓度,因为为保持约1wt.%的金属沉积,其在水核心中的浓度应当为约0.5M(见Catalysis Letters 64(2000)179-184)。这限制了微乳液用于制备被担载的催化剂的应用,因为水核心中金属浓度的增加导致较大的金属纳米颗粒直径(见Journal of Colloid andInterface Science 210(1999)123-129)。此外,煅烧导致金属颗粒烧结。因此,人们仍需要新的方法,来制备具有增加的金属负载的被担载的催化剂、回收和再循环液相和表面活性剂以及去除耗能量/耗时间的煅烧步骤。
因此,在一个方面,本发明涉及制备Pt族金属的纳米颗粒的工艺,其包括下述步骤:
(a)制备Pt金属在烃包水系统中的反相微乳液;
(b)将所述微乳液的溶剂的至少一部分蒸发,优选地,直到形成沉淀,更优选地,在减压下进行;
(c)向残余物中加入C1-C4-醇,优选加入甲醇,以形成Pt金属纳米颗粒的沉淀;以及,任选地,
(d)分离沉淀,将沉淀再次分散于水中,以获得Pt金属纳米颗粒的分散体系。
可通过本身已知的手段来完成Pt金属在烃包水系统中的反相微乳液的制备。例如,将选自氯化物、溴化物、碘化物、氰化物或三氟甲磺酸盐(triflate)的Pt金属盐的水溶液与氨或脂肪族胺反应,以形成Pt金属复合物溶液,此时在搅拌下,向所述水性Pt金属复合物溶液中加入还原剂的水溶液和乳化剂的烃溶液。
用于本发明的Pt金属的例子是铂,以及特别地,钯。在本发明的一种特别的实施方式中,用PdCl2与水性氨反应,以获得Pd(NH3)4Cl2的溶液。在本发明的某些实施方式中,可用有机胺代替氨来形成Pt金属复合物。
用于将Pt金属复合物还原为Pt金属单质的还原剂的例子包括肼、水合肼和硼氢化钾或硼氢化钠,特别是水合肼。烃可以是任何脂肪族的线性或带分支的链,或脂环族的烃,其在室温和大气压下是液体,并且易于蒸发,例如,己烷、环己烷、正庚烷、辛烷以及特别地异辛烷。合适地,用可以是任何类型的(即,阳离子、阴离子、非离子)表面活性剂对微乳液加以稳定。阳离子表面活性剂的例子是CTAB(十六烷基三甲基溴化铵)和CTAC(十六烷基三甲基氯化铵);示例性的阳离子表面活性剂是气溶胶OT(AOT,琥珀酸二(2-乙基己基)酯磺酸钠);用于本发明的示例性的非离子表面活性剂是Berol 02(壬基酚乙氧基化物);Berol 050(五聚乙二醇十二烷基醚PEGDE)和NP-X(聚(氧乙烯)壬基酚醚)。CTAB和CTAC适合与共表面活性剂(例如,正己醇(相对烃而言10vol.%))一起使用。优选的表面活性剂是AOT,尤其是在与异辛烷一起使用时。
在本发明工艺的步骤(a)中,对烃、表面活性剂、Pt金属复合物溶液和还原剂的混合物加以搅拌,这适合在室温下进行,直到获得透明的微乳液。水和表面活性剂的摩尔比适合在大约0.1至大约100之间,优选1至10之间,更优选为大约3。烃和水相的比例适合为大约0.1至大约100,优选为1至10。
在步骤(a)的一种实施方式中,还原剂和Pt金属复合物溶液分别单独加入烃/乳化剂混合物,搅拌,直到获得透明乳液,此时对由此获得的乳液立即进行混合,以提供反相微乳液。
在步骤(b)中,对步骤(a)中获得的反相微乳液进行蒸发,以除去基本上所有溶剂,即,烃和水。蒸发以能保留乳液稳定性以及由此保持金属纳米颗粒大小的方式进行。确保乳液稳定性的参数可能取决于所涉及的乳液的特定组分,但是蒸发通常在不超过大约100℃的温度下进行,优选不超过大约75℃,更优选不超过大约50℃。蒸发可在减压下进行。在某些实施方式中,在室温下减压进行蒸发可能是有用的。
在步骤(c)中,用C1至C4醇(包括甲醇、乙醇、丙醇、异丙醇、丁醇和异丁醇)来悬浮和洗涤步骤(b)中获得的包含金属纳米颗粒的蒸发残余物,以絮凝金属纳米颗粒,它们最终被重新分散于水中(步骤(d)),用于进一步的用途。
在另一个方面,本发明涉及下述规整型催化剂,其包含分布于其上的、可通过本文前面公开的工艺获得的Pt族的纳米颗粒;本发明还涉及制备此类规整型催化剂的工艺。
术语“规整型催化剂”(“structured catalyst”)在本文中被用于表示这样的催化剂,其中,催化剂的空间位置受到控制。规整型催化剂是本领域已知的,例如,见,Chimia 56(4),2002,159-163。规整型催化剂的例子是陶瓷载体构造和纤维结构,尤其是纤维丝机织织物。所有类型的纤维丝机织织物都可用于本发明的用途。纤维可来自有机或无机物质。例子是来自活性炭纤维、丙烯腈纤维、玻璃纤维、陶瓷纤维、金属纤维或活性炭纤维的抓绒氧化物(fleece composite oxides)的织物。特别感兴趣的是活性炭纤维。纤维丝机织织物的各纤维优选具有大约2μm至大约100μm的直径,尤其是不超过大约20μm的直径。织物适合从各纤维束构成的线织成,提供小于约1mm的机织布孔径。可对它们进行化学处理,例如用硝酸进行,以改良表面,并且它们可具有涂层,例如金属(例如Al、Ti或Pb)涂层,以改进选择性。
可通过用可由本文前面公开的工艺获得的Pt金属纳米颗粒的水性分散体系浸渍合适的规整型载体,例如陶瓷载体或机织织物,以及在可高达大约150摄氏度的温度下对经浸渍的规整型载体(例如机织织物)加以干燥,来制备根据本发明的规整型催化剂。
在另一实施方式中,本发明涉及使用具有沉积于其上的、可通过本文前面公开的工艺获得的Pt金属纳米颗粒的规整型载体(特别是机织织物)。
这种新颖的工艺允许回收微乳液的液相,并且不需要四氢呋喃;其特征在于更低的E-因子(废料/催化剂质量比,见Chemistry 3(2000)541-551)。此外,这种新颖的工艺允许以胶束水性核心中的低金属浓度获得具有更高金属负载的催化剂,并且通过避免煅烧保留纳米颗粒的单分散性。
已观察到:可根据本发明获得的催化剂的活性和选择性从第二轮起是稳定的,在重复的催化剂再利用期间,没有发生Pd浸出(leaching)。催化剂不需要运行轮次间的调整,并且在溶剂辅助氢化和无溶剂氢化方面都显示出比新鲜的Lindlar催化剂更好的催化性能。
下面通过实施例来阐述本发明。
实施例1
按照别处所述(Chen et al.,Journal of Colloid and Interface Science 210(1999),123-129),通过将PdCl2溶解于0.5N HCl溶液中,然后用氨调节至pH 8.5,来制备0.05M Pd(NH3)4Cl2溶液。使用前制备1M水合肼溶液。按照上文所述的参考文献Chen et al.,制备水与表面活性剂的摩尔比为3的含Pd纳米颗粒的微乳液。将200ml异辛烷中的0.35M AOT溶液分半。将1.88mL钯前体和还原剂溶液分别单独注射进AOT/异辛烷中,并加以搅拌,直到获得透明微乳液,立即进行混合。
在室温下对获得的反相微乳液进行1小时的搅拌。然后将其放到旋转蒸发器中,真空下于323K进行20分钟。室温下向得到的泡沫中加入甲醇,以溶解AOT和絮凝钯纳米颗粒。在8000rpm离心(20分钟)后,倾析上清液,重复洗涤。通过超声处理20分钟将沉淀重新分散于12ml水中,得到均匀黑色Pd悬浮液。
实施例2
实施例1获得的Pd悬浮液被立即用于浸渍0.5g活性炭纤维(ACF)织物。使用从Taiwan Carbon Technology Co.,Ltd.获得的Activated Carbon Fiber Fabrics AW-1101(BET比表面积为880m2/g,平均孔直径为2nm[37]),在沸腾的6.5wt.% HNO3水溶液中预处理1小时后使用。然后用蒸馏水漂洗担载体,室温下空气干燥12小时,以及在393K干燥5小时。ACF的BET比表面积是950m2/g。浸渍的担载体在393K空气干燥40分钟,接着是第二个浸渍步骤。最后,催化剂在393K干燥过夜。
通过改变悬浮液的量,来制备具有不同Pd负载(0.4÷1.2wt.%Pd)的微乳液-甲醇(ME-Met)催化剂。在浸渍步骤之间,用庚烷对一些催化剂进行重复洗涤。鉴于已知肼能促进AOT二聚化,还使用5M水合肼溶液(代替1M)来制备ME-Met催化剂。
通过混合微乳液和担载体来制备催化剂ME-Mix(“MicroEmulsion-MIXing”,微乳液-混合)。对反相微乳液进行30分钟搅拌,至形成纳米颗粒,然后将0.5g ACF浸入微乳液,搅拌1小时,接着在庚烷中重复洗涤,于393K空气干燥过夜。
像催化剂ME-Mix那样来制备催化剂ME-THF(“MicroEmulsion-TetraHydroFuran”,微乳液-四氢呋喃),但是在微乳液和担载体的混合期间逐滴加入四氢呋喃,用于去稳定。
实施例3
催化剂分析:通过原子吸收光谱(AAS),于247.6nm,用具有空气-乙炔火焰的Shimadzu AA-6650光谱仪来测定Pd的量。在空气中于970K对催化剂(新鲜的和用过的)进行3小时加热,以烧尽碳,将残余物溶解于浓缩酸(HCl∶HNO3=3∶1,按体积计)和HF水溶液的混合物中。为测定催化实验期间浸出的Pd的量,将反应混合物放到在真空下的旋转蒸发器中,然后用酸来洗涤蒸馏皿(retort)。
通过高分辨率透射电子显微镜(HRTEM),使用分辨率为0.23nm的Philips EM 430设备,以300kV来测定微乳液中的Pd颗粒大小。通过将催化剂ME-Met制备的步骤(d)中获得的水性悬浮液液滴放到铜栅网上的碳膜上以及在室温下蒸发溶剂,来制备TEM分析的样品。对栅网的不同部分加以检查。所述设备装备有能量色散型X-射线(EDX)分析仪。
图1显示了Pd纳米颗粒的TEM图像。观察到了8nm直径的单分散颗粒,这表明在催化剂制备期间没有发生凝结。水/AOT/正庚烷微乳液的蒸发显示没有导致Pd聚集。加入的甲醇溶解了AOT,并且破坏了纳米颗粒周围的表面活性剂壳,导致絮凝。由小颗粒(约2nm)构成的团块(约100nm)可容易地再分散于任何疏水溶剂中。
实施例4
在装备有加热套和氢供应系统的间歇式不锈钢反应器(150mL高压釜,Buchi AG,Uster,Switzerland)中,使用本发明的规整型催化剂进行氢化反应。将规整型的Pd/ACF催化剂放到自送料中空轴搅拌器(self-gassing hollow shaft stirrer)上固定的两块金属纱网(2x4cm)之间,见Chem.Eng.Sci.57(2002)343。对于用粉末状的Lindlar催化剂进行的反应而言,使用8-叶盘状叶片涡轮(8-blade disk turbine impeller)。在工作温度下,将装有反应混合物和催化剂并用Ar(0.8MPa)吹扫的反应器在搅拌下保持5分钟,以平衡温度。然后向反应器中充氢并加压。在反应期间,反应器中的压力保持恒定。
在303K和1.3MPa H2压力下,1500rpm的剧烈搅拌下进行典型的反应,以避免外部扩散限制。用正庚烷作为反应媒介,其100mL的总体积中含有0.5kmol/m3的1-己炔。对于溶剂辅助反应而言,底物和钯的摩尔比在20000-30000之间。在293-323K的温度和0.4-1.7MPa之间变动的氢压下研究反应动力学。
在再利用的实验中,在反应轮次之间,于室温下对催化剂进行空气干燥。在无溶剂的实验中,对101.3mL 1-己炔(对应于0.9摩尔)进行氢化。
经由采样管,定期从反应器取反应混合物样品,并通过GC加以分析。用装备有100m Petrocol DH 0.25mm毛细管柱(具有0.5μ的涂层)的Auto System XL(Perkin Elmer),在333K的炉温和280kPa的载气(He)压力下,进行GC分析。注射器和FID温度为493K。正辛烷被用作为内标。
起始反应速率r0[kmolH2·kgPd -1·s-1]被用作为催化活性的特征。相对于每初始Pd负载来计算连续轮次中的活性。对1-己烯的选择性被计算为其浓度与反应混合物中所有产物的总浓度的比例。发现了作为副产物的正己烷、顺式-2-己烯和反式-2-己烯。
表1中示出了关于ME-Met、ME-Mix和ME-THF的氢化活性和选择性的数据。
表1:不同Pd/ACF催化剂在1-己炔部分氢化中的催化性能
催化剂 | ME-Met | ME-Mix | ME-THF |
Pd负载,wt.% | 0.42 | 0.05 | 0.11 |
初始反应速率,kmolH2·kgPd -1·s-1 | 0.14 | 0.14 | 0.06 |
90%转化率时的选择性,% | 95.6 | 93.5 | 94.3 |
反应条件:正庚烷(100mL)中0.5kmol/m3 1-己炔;底物与Pd的摩尔比为20000;1.3MPa的H2压力;303K;1500rpm
实施例5
ME-Met(Pd/ACF)催化剂的再利用。与Lindlar催化剂的比较
以浸渍步骤之间没有在庚烷中洗涤的方式制备的ME-Met催化剂批次(例如1.2wt%Pd)在用同样催化剂进行的连续反应轮次期间显示出逐渐的Pd浸出。洗涤导致保留了较少的Pd含量(0.45±0.07wt.%),但是其维持了催化剂物质在担载体表面上的强烈吸附。这种情况下,在催化剂再利用的方面,观察到的浸出是可忽略的(<10%,实验误差内)。
图2显示了对于ME-Met催化剂(0.4wt%Pd)而言1-己炔转化率为90%时的选择性和初始反应速率。在反应之间没有进行对催化剂的处理。在第二轮反应中活性有一定程度降低后,其稳定在0.085±0.008kmolH2·kgPd -1·s-1,同时对1-己烯的选择性为94±1%。还发现,动力学曲线在多至6个轮次上都是相同的。这在针对第6轮的图3a和新鲜Lindlar催化剂上的曲线上显示。对Lindlar催化剂的负载加以调节,以获得与新鲜的ME-Met催化剂一样的Pd量。图3b示出了选择性对转化率的曲线。用过的ME-Met催化剂展示出比新鲜Lindlar催化剂更高的选择性,例如,在90%转化率时分别为94±1%对89±2%。用催化剂ME-Met在1.3倍短的反应时间中获得了更高的1-己烯产率(87±2%对82±3%)。更高的催化剂活性和更高的选择性可能归功于Pd大小和单分散型,因为炔加氢被认为是结构敏感型的反应。因此,开发的催化剂的活性和选择性从第二轮开始都稳定了,并且它们都优于新鲜的Lindlar催化剂。
实施例6
使用过的ME-Met催化剂上进行的无溶剂氢化
庚烷中6轮并在环境温度下干燥之后,还在无溶剂氢化中对催化剂ME-Met(0.4wt.%Pd)进行了测试。新鲜的Lindlar催化剂被用于比较。图4a显示了浓度-时间曲线,图4b显示了选择性方面的数据。和溶剂辅助反应一样,使用过的ME-Met催化剂显示出比新鲜的Lindlar催化剂更高的选择性,并且在1.2倍低的反应时间里获得了更高的1-己烯最大产率(92%对Lindlar催化剂的90%)。ME-Met催化剂(0.4wt%Pd)的总运作时间(time-on-stream)为约21小时。这令我们认为该催化剂在长期运行中是稳定的。
Claims (16)
1.制备Pt族金属的纳米颗粒和其水性分散体系的工艺,其包括下述步骤:
(a)制备Pt金属在烃包水系统中的反相微乳液;
(b)将所述微乳液的溶剂的至少一部分蒸发,优选地,直到形成沉淀,更优选地,在减压下进行;
(c)向残余物中加入C1-C4-醇,优选加入甲醇,以形成Pt金属纳米颗粒的沉淀;以及,任选地,
(d)分离所述沉淀,将所述沉淀再次分散于水中,以获得Pt金属纳米颗粒的分散体系。
2.权利要求1的工艺,其中,步骤(a)中使用的微乳液是这样制备的:将选自氯化物、溴化物、碘化物、氰化物或三氟甲磺酸盐的Pt金属盐的水溶液与氨或脂肪族胺反应,以形成Pt金属复合物溶液,在搅拌下,向所述水性Pt金属复合物溶液中加入还原剂的水溶液和乳化剂的烃溶液。
3.权利要求1或2的工艺,其中,在步骤(b)中,在对所述乳液的稳定性无害的升高的温度下进行所述微乳液的蒸发。
4.权利要求3的工艺,其中,在步骤(b)中,所述微乳液的蒸发在不超过大约100℃的温度下进行,优选不超过大约75℃,更优选不超过大约50℃。
5.权利要求1至4中任意一项所述的工艺,其中所述Pt金属是Pd。
6.权利要求2至5中任意一项所述的工艺,其中所述Pt金属盐是PdCl2。
7.权利要求2至6中任意一项所述的工艺,其中所述Pt金属复合物是Pd(NH3)4Cl2,所述还原剂是肼、水合肼或硼氢化钠(钾),优选是水合肼。
8.权利要求1至7中任意一项所述的工艺,其中所述烃是沸点为大约100℃或更低的脂肪族饱和烃。
9.权利要求8的工艺,其中所述烃是环己烷、庚烷或异辛烷,优选是异辛烷。
10.权利要求1至9中任意一项所述的工艺,其中所述乳化剂是琥珀酸二(2-乙基己基)酯磺酸钠。
11.可通过权利要求1至10中任意一项所述的工艺获得的Pt金属的纳米颗粒的水性分散体系。
12.制备处于规整型载体,例如机织织物,上的Pt金属催化剂的工艺,所述工艺包括:用可通过权利要求1至8中任意一项所述的工艺获得的Pt金属纳米颗粒的水性分散体系来浸渍此类载体,以及,在最高达大约150摄氏度的温度下对经浸渍的规整型载体加以干燥。
13.权利要求12的工艺,其中所述Pt金属是Pd。
14.规整型载体,例如,机织织物,其上沉积有可通过权利要求12的工艺获得的Pt金属纳米颗粒。
15.权利要求14的规整型载体,其中所述Pt金属是Pd。
16.权利要求14或15定义的规整型载体用作为催化剂的用途。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07003416 | 2007-02-19 | ||
EP07003416.0 | 2007-02-19 | ||
PCT/EP2008/000994 WO2008101602A2 (en) | 2007-02-19 | 2008-02-09 | Catalysts containing platinum group metal nanoparticles and process for production of dispersions of nanoparticles of platinum group metal |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101616736A true CN101616736A (zh) | 2009-12-30 |
CN101616736B CN101616736B (zh) | 2013-02-13 |
Family
ID=39643804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2008800055079A Active CN101616736B (zh) | 2007-02-19 | 2008-02-09 | 含有铂族金属纳米颗粒的催化剂和生产铂族金属纳米颗粒分散体系的工艺 |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2112955A2 (zh) |
CN (1) | CN101616736B (zh) |
WO (1) | WO2008101602A2 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109732100A (zh) * | 2019-03-11 | 2019-05-10 | 昆明理工大学 | 一种小尺寸枝状铂纳米颗粒的制备方法 |
CN113113625A (zh) * | 2021-04-14 | 2021-07-13 | 天津商业大学 | 一种高效Pt基甲醇纳米催化剂的合成方法 |
CN113406114A (zh) * | 2021-04-28 | 2021-09-17 | 中国辐射防护研究院 | 一种气溶胶中Pu、Am、U含量的联合分析方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2112955A2 (en) | 2007-02-19 | 2009-11-04 | DSM IP Assets B.V. | Catalysts containing platinum group metal nanoparticles and process for production of dispersions of nanoparticles of platinum group metal |
NL2005112C2 (en) | 2010-07-19 | 2012-01-23 | Univ Leiden | Process to prepare metal nanoparticles or metal oxide nanoparticles. |
CN105233690B (zh) * | 2014-07-11 | 2017-06-20 | 北京有色金属研究总院 | 一种载钯硅藻土复合材料的制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6110930A (en) | 1997-04-10 | 2000-08-29 | Ono Pharmaceutical Co., Ltd. | Condensed piperidine compound |
US20080003479A1 (en) * | 2006-06-29 | 2008-01-03 | Konkuk University Industrial Cooperation Corp. | Ionic polymer metal composite electrolyte for fuel cell |
US20080014355A1 (en) * | 2006-07-12 | 2008-01-17 | National Tsing Hua University | Method for Preparing a Palladium-Containing Layer |
EP2112955A2 (en) | 2007-02-19 | 2009-11-04 | DSM IP Assets B.V. | Catalysts containing platinum group metal nanoparticles and process for production of dispersions of nanoparticles of platinum group metal |
-
2008
- 2008-02-09 EP EP08707638A patent/EP2112955A2/en not_active Ceased
- 2008-02-09 CN CN2008800055079A patent/CN101616736B/zh active Active
- 2008-02-09 WO PCT/EP2008/000994 patent/WO2008101602A2/en active Application Filing
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109732100A (zh) * | 2019-03-11 | 2019-05-10 | 昆明理工大学 | 一种小尺寸枝状铂纳米颗粒的制备方法 |
CN113113625A (zh) * | 2021-04-14 | 2021-07-13 | 天津商业大学 | 一种高效Pt基甲醇纳米催化剂的合成方法 |
CN113406114A (zh) * | 2021-04-28 | 2021-09-17 | 中国辐射防护研究院 | 一种气溶胶中Pu、Am、U含量的联合分析方法 |
CN113406114B (zh) * | 2021-04-28 | 2022-10-21 | 中国辐射防护研究院 | 一种气溶胶中Pu、Am、U含量的联合分析方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2008101602A3 (en) | 2008-10-30 |
CN101616736B (zh) | 2013-02-13 |
EP2112955A2 (en) | 2009-11-04 |
WO2008101602A2 (en) | 2008-08-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101616736B (zh) | 含有铂族金属纳米颗粒的催化剂和生产铂族金属纳米颗粒分散体系的工艺 | |
CN102883809B (zh) | 制备具有沉积在载体上的贵金属纳米颗粒的催化剂的方法 | |
Liu et al. | Controlled synthesis of Pd–NiO@ SiO 2 mesoporous core–shell nanoparticles and their enhanced catalytic performance for p-chloronitrobenzene hydrogenation with H 2 | |
CN109745969A (zh) | 一种碳载超小尺寸贵金属纳米粒子催化剂及制备方法 | |
CN100398448C (zh) | 花状结构的纳米氧化铈材料及其制备方法和用途 | |
CN101157034B (zh) | 一种非晶态合金催化剂的制备方法 | |
Nasretdinova et al. | Methylviologen mediated electrochemical synthesis of catalytically active ultrasmall bimetallic PdAg nanoparticles stabilized by CTAC | |
CN102553579A (zh) | 一种高分散负载型纳米金属催化剂的制备方法 | |
Liu et al. | Architecture controlled PtNi@ mSiO 2 and Pt–NiO@ mSiO 2 mesoporous core–shell nanocatalysts for enhanced p-chloronitrobenzene hydrogenation selectivity | |
Long et al. | Construction of trace silver modified core@ shell structured Pt-Ni nanoframe@ CeO 2 for semihydrogenation of phenylacetylene | |
CN110270375B (zh) | 一种不饱和碳-碳三键选择性加氢催化剂及其制备方法 | |
CN112337462B (zh) | 一种通过硝酸蒸汽法制备的原子级分散Pd催化剂及其应用 | |
Boutonnet et al. | Microemulsion droplets to catalytically active nanoparticles. How the application of colloidal tools in catalysis aims to well designed and efficient catalysts | |
CN106881089B (zh) | 一种可控的石墨烯负载廉价ib-viiib族双金属纳米颗粒复合材料的制备方法 | |
CN108817416A (zh) | 一种Pt纳米粒子的制备方法及应用 | |
CN104801299A (zh) | 一种碳负载钌催化剂的植物还原制备方法、碳负载钌催化剂及应用 | |
CN103084174B (zh) | 一种脱除碳氧化物的甲烷化催化剂及其制备方法和应用 | |
CN108927154A (zh) | 一种金属间化合物纳米催化剂的制备方法 | |
Feng et al. | 3D-mesoporous KIT-6 supported highly dispersed Pd nanocatalyst for dodecahydro-N-ethylcarbazole dehydrogenation | |
Ma et al. | Formation of gold nanoparticles supported on carbon nanotubes by using an electroless plating method | |
CN107008478A (zh) | 一种磁性纳米催化剂的制备方法 | |
CN109174092B (zh) | 一种氧化锌/铂复合材料微球及其制备方法和应用 | |
Chen et al. | Preparation of Janus nanosheets composed of gold/palladium nanoparticles and reduced graphene oxide for highly efficient emulsion catalysis | |
CN110586081B (zh) | 钯炭催化剂及其制备方法、应用 | |
Liu et al. | Research on assembly of nano-Pd colloid and fabrication of supported Pd catalysts from the metal colloid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |