TWI610718B - 經邊緣塗覆之貴金屬觸媒的增進分散性 - Google Patents
經邊緣塗覆之貴金屬觸媒的增進分散性 Download PDFInfo
- Publication number
- TWI610718B TWI610718B TW105108684A TW105108684A TWI610718B TW I610718 B TWI610718 B TW I610718B TW 105108684 A TW105108684 A TW 105108684A TW 105108684 A TW105108684 A TW 105108684A TW I610718 B TWI610718 B TW I610718B
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- Prior art keywords
- metal
- catalyst
- precious metal
- oxide
- palladium
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 239000010970 precious metal Substances 0.000 title claims description 62
- 239000006185 dispersion Substances 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 85
- 239000002184 metal Substances 0.000 claims abstract description 85
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000010931 gold Substances 0.000 claims abstract description 36
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 33
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 25
- 229910052737 gold Inorganic materials 0.000 claims abstract description 22
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 39
- 239000008139 complexing agent Substances 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 22
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 19
- 238000005259 measurement Methods 0.000 claims description 19
- 239000003381 stabilizer Substances 0.000 claims description 19
- 150000002736 metal compounds Chemical class 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- -1 borohydride Chemical compound 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 229910052914 metal silicate Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 2
- 239000000395 magnesium oxide Substances 0.000 claims 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000006698 induction Effects 0.000 claims 1
- 239000002159 nanocrystal Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 230000008569 process Effects 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- 230000009467 reduction Effects 0.000 description 21
- 238000009616 inductively coupled plasma Methods 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 16
- 239000000523 sample Substances 0.000 description 13
- 238000003917 TEM image Methods 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- ODEHKVYXWLXRRR-UHFFFAOYSA-N hex-3-yn-1-ol Chemical compound CCC#CCCO ODEHKVYXWLXRRR-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000006229 carbon black Substances 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
- 239000000084 colloidal system Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 241000283153 Cetacea Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XGNCNBYMBZPACA-UHFFFAOYSA-N [O-]P([O-])(=O)OP(=O)([O-])[O-].OCC[PH2+]CCCCCCCCCCCCCCCC.OCC[PH2+]CCCCCCCCCCCCCCCC.OCC[PH2+]CCCCCCCCCCCCCCCC.OCC[PH2+]CCCCCCCCCCCCCCCC Chemical compound [O-]P([O-])(=O)OP(=O)([O-])[O-].OCC[PH2+]CCCCCCCCCCCCCCCC.OCC[PH2+]CCCCCCCCCCCCCCCC.OCC[PH2+]CCCCCCCCCCCCCCCC.OCC[PH2+]CCCCCCCCCCCCCCCC XGNCNBYMBZPACA-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 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
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- 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
-
- B01J35/19—
-
- B01J35/23—
-
- B01J35/30—
-
- B01J35/393—
-
- B01J35/394—
-
- B01J35/397—
-
- 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
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Abstract
本發明屬於催化領域。更特定言之,本發明係關於受載型貴金屬,較佳鈀及/或金金屬觸媒,其具有高分散度及高邊緣塗覆度。本發明進一步關於一種製造此等觸媒之方法以及此等觸媒在化學反應中之用途。
Description
本發明屬於催化領域。更特定言之,本發明係關於受載型貴金屬觸媒,較佳鈀及/或金金屬觸媒,其具有高分散度及高邊緣塗覆度。本發明進一步關於一種製造此等觸媒之方法以及此等觸媒在化學反應中之用途。
許多受載型貴金屬(PM)觸媒尤其用於選擇性轉化精細化學物質,該等化學物質通常為高度官能化大分子。為最佳可獲得大分子之PM微晶,需要使大分子儘可能地位於載體之外殼中。此稱為經邊緣塗覆之金屬分佈。通常在大多數PM微晶位於載體之外殼中時達成高邊緣塗覆度。此類經邊緣塗覆之分佈具有額外優點:基質分子在其轉化之後快速離開PM微晶附近,從而使任何副反應發生減至最少。然而,製備高分散性的經邊緣塗覆之觸媒為困難的。由於僅使用載體之總表面區域之一小部分,經邊緣塗覆之觸媒一般具有低分散性。
受載型貴金屬觸媒通常藉由沈積還原法製備,其中金屬首先沈積於載體上且隨後還原。為製備高分散性觸媒,通常進行沈積沈澱製備程序,其中金屬鹽有時間擴散至載體之孔隙中。以此方式,藉由金屬分佈於載體之整個表面區域上來達成高分散性。此提供較大活性之金屬表面區域,因為所形成之金屬微晶極小,通常為約幾奈米。另一方面,對於經邊緣塗覆之觸媒的製備,金屬鹽不應過深地擴散至載體之孔隙中(亦即,對於平均尺寸為約20至100微米之載體粒子,通常為小於100nm擴散至孔隙中),但應在與載體接觸後立即沈積。此兩種方法彼此相抵觸,因此高分散之經邊緣塗覆的金屬觸媒的製備通常為此兩個因素之間的折衷。
基於膠體懸浮液之非均相觸媒的特徵為小金屬微晶尺寸,參見例如P.T.Witte,S.Boland,F.Kirby,R.van Maanen,B.F.Bleeker,D.A.M.de Winter,J.A.Post,J.W.Geus,P.H.Berben,ChemCatChem. 5(2013)582-587。本發明旨在製造具有甚至更小貴金屬粒子(微晶)尺寸之觸媒,尤其與載體之平均孔徑約為相同尺寸及/或小於該平均孔徑的奈米粒子。此外,本發明旨在製造載體之邊緣經PM微晶塗覆之觸媒。
此外,WO-A-2009/096783描述水性膠體貴金屬懸浮液之製備,該方法包含在有機溶劑不存在下使用官能化水溶性四級銨鹽在水溶液中還原貴金屬鹽,形成基本奈米粒子。雖然此已知方法產生小貴金屬粒子,仍需要具有
甚至更小貴金屬微晶之觸媒,其如上文所描述分佈。
在US-A-4 212 824中,描述如藉由ESCA(化學分析用電子光譜學)所測定具有改良之金屬分佈的鉑/碳黑載體觸媒,但在此文獻中未指定金屬分散性。此外,此文獻中所用的碳黑載體具有低表面積(亦即,20-100m2/g)。
因此,本發明之第一目標為提供一種貴金屬觸媒,尤其鈀或金金屬觸媒,其不僅為邊緣經塗覆的而且具有高金屬分散性。本發明之另一目標為提供一種製造該觸媒之方法。本發明之又一目標為提供該觸媒,使得其可用於化學反應中。
出人意料地已發現,可分別控制觸媒之邊緣塗覆及金屬分散性。因此,兩個參數可分別優化,獲得根據本發明之高度分散之經邊緣塗覆的貴金屬觸媒,尤其鈀及/或金金屬觸媒,因此滿足上文所提及之目標中的至少一者。
因此,本發明係關於一種貴金屬觸媒,其中該觸媒包含貴金屬在粉末載體上之奈米微晶,其中貴金屬為鈀及/或金金屬;其中鈀金屬觸媒包含平均尺寸為1至小於5nm之奈米微晶,且其中該觸媒之表面富集值為至少6.5至至多150;及,其中金金屬觸媒包含平均尺寸為3至小於15nm之奈米微晶,且其中該觸媒之表面富集值為至少3至至多150。
通常,本發明之鈀金屬觸媒包含平均尺寸為1至小於5nm、較佳1至4nm且更佳1.5至3nm之鈀金屬奈米微晶。
本發明之金金屬觸媒通常包含平均尺寸為3至小於15nm、較佳3至13nm且更佳5至10nm之金金屬奈米微晶。
除非另外指示,否則如本文所用之貴金屬奈米微晶之平均尺寸係以可藉由透射電子顯微鏡(TEM)確定之值計。
通常,本發明之鈀金屬觸媒之表面富集值為至少6.5,較佳至少8且更佳至少10。鈀金屬觸媒之表面富集值通常為至多150,較佳至多120且更佳至多90。
本發明之金金屬觸媒之表面富集值通常為至少3,較佳至少5且更佳至少7。金金屬觸媒之表面富集值通常為至多150,較佳至多120且更佳至多90。
出人意料地已發現,本發明之觸媒由於高金屬分散性與高邊緣塗覆之組合而具有高活性,高金屬分散性增加可供反應物使用的活性位點數以及原子在金屬奈米微晶之角或邊緣的貢獻,高邊緣塗覆導致反應物達到觸媒金屬表面之可行性改良。本發明之觸媒亦出人意料地具有高選擇性的優點,因為邊緣塗覆減小非所需副反應的可能性。本發明之觸媒的又一優點為在其用於放熱化學反應時將不發生內部熱傳遞問題,因為貴金屬主要存在於載體之表面上。因此,在化學反應期間產生的任何熱量能夠容易傳遞
至周圍反應混合物中。
表面富集值(SEV)可藉由使用X射線光電子光譜學(XPS)及感應耦合電漿(ICP)量測,尤其感應耦合電漿光學發射光譜測定法(ICP-OES)量測及下式(I)來測定:SEV=(XPS wt.%-ICP wt.%)/ICP wt.% (I)
其中XPS wt.%為根據本發明之觸媒的PM含量以重量%(wt.%)計之XPS量測值且ICP wt.%為根據本發明之觸媒的PM含量以重量%(wt.%)計之ICP量測值(亦即,ICP-OES量測值)(.XPS量測用於測定粉末載體之外殼中貴金屬之以重量%(wt.%)計的含量(亦即,距離粉末載體粒子之表面的深度通常為約0至10nm)。ICP量測(亦即,ICP-OES量測)用於測定粉末載體中以重量%(wt.%)計之貴金屬含量(亦即,體積量測值)。
貴金屬在粉末載體上之完全均勻分佈通常具有與XPS及ICP量測(亦即,ICP-OES量測)所測定之相同的貴金屬含量,且將導致表面富集值為零。在經邊緣塗覆之金屬分佈的情況下,如藉由XPS量測所測定之觸媒粉末載體之外殼中的貴金屬含量應大大高於如藉由ICP量測(亦即,ICP-OES量測)所測定之粉末載體中的貴金屬含量。XPS量測僅給出關於所量測材料之外部幾奈米(亦即,距離所量測材料之表面的深度通常為約5-10nm)的資訊之原因為雖然X射線深入穿透至材料中,所釋放之光電子將僅在其具有足夠能量逸出材料時得到量測。所釋放之光電子可經受非彈性碰撞、重組、樣品激發、以各種激發態再捕獲或捕捉於
材料內,以上所有者可減少逸出的光電子數量。此等效果呈現為隨著深度增加指數衰減,使得自表面元件偵測到的信號比自材料表面以下較深處元件偵測到的信號更強。因此,XPS量測通常僅給出關於所量測材料之外部幾奈米的資訊。
除非明確指示,否則如本文所用之觸媒之所有ICP量測值(亦即,ICP-OES量測值)為可在具有氣霧劑同心噴霧器之Thermo ScientificTM iCAPTM 7400 ICP-OES分析儀上使用自動取樣器CETAC ASX-260及通常0-25ppm校準曲線量測之值。通常使用之兩個標準系列為0ppm(空白);5、10及25ppm之元素Pd、Pt、Rh及Ru,其中各元素具有相同濃度,且其中一個系列在10wt.%硝酸水溶液(濃度為65wt.%)中且另一系列在15wt.% H3PO4/H2SO4(5:3)水溶液(H3PO4之濃度為85wt.%且H2SO4之濃度為98wt.%)中。通常,所進行之所有量測系列以標準開始,以便確定校準曲線且確保相關係數大於0.999。10ppm標準通常在一系列量測期間用作內標
除非明確指示,否則如本文所用之觸媒之所有XPS量測值為可使用單色Al Kα輻射(80W)使用Phi Versa Probe 5000光譜儀量測之值。儀器功函數經校準得到金屬金之Au 4f7/2線的84.0eV結合能(BE),且調整光譜儀分散性得到金屬銅之Cu 2p3/2線的932.6eV BE。對所有量測之樣品使用內置Phi電荷中和器系統。為使差示充電之影響減至最小,所有觸媒樣品通常相對於地面安裝及絕緣。通常,
觸媒樣品製備為雙面膠帶上之粉末薄膜。
通常以0.1×1.4mm分析區域、117eV通能及0.5eV能量步長進行觸媒樣品之XPS測量掃描分析。通常在相同分析區域上以23.5eV通能及0.1eV能量步長進行高解析度分析。每一觸媒樣品通常進行三次XPS量測。所獲得之光譜能量校正通常以C之1s信號的位置位於284.5eV結合能之方式進行。
元素豐度之定量通常藉由使用雪莉(Shirley)背景減除法及使用由上文所提及之光譜儀的製造商提供之透射函數校正及元素靈敏度因子由XPS測量光譜測定。使用下式(II)將以原子%測定之元素濃度轉化為質量(亦即,重量)%:
其中C(元素)[質量%]為元素以質量(亦即,重量%)計之濃度,C(元素)[原子%]為元素以原子%計之濃度,且M(元素)[g/mol]為元素以g/mol計之莫耳質量
本發明之觸媒通常包含以觸媒之重量計0.01至20wt.%、較佳0.1至15wt.%且最佳0.3至10wt.%量之貴金屬,尤其鈀及/或金金屬。除非另外指示,否則本文所提及之所有wt.%皆以分離且洗滌並乾燥之觸媒的重量計。
本發明之觸媒的粉末載體可選自由以下組成之群:二氧化矽、氧化鋁、氧化鋯、氧化鈦、二氧化鈰、氧
化鎂、氧化鋅、金屬矽酸鹽(例如,矽酸鈦(TiS))、金屬鋁酸鹽、沸石、碳奈米管、碳奈米纖維、石墨碳及活性碳(AC)及其組合,且較佳活性碳及/或金屬矽酸鹽,尤其矽酸鈦。
氧化載體之BET表面積通常為大於50m2/g。氧化載體之BET表面積通常為小於1000m2/g。碳基載體(諸如活性碳)之BET表面積通常為大於400m2之較高BET表面積。碳基載體(諸如活性碳)之BET表面積通常為小於3000m2/g。如本文所用之BET表面積為可在麥克默瑞提克(Micromeritics)ASAP 2420上在180℃下使樣品脫氣之後藉由測定在77K及大致0.3 P/Po下吸附的氮氣量及假定氮氣截面積為16.2Å2所量測之值。
活性碳為用於本發明之觸媒的較佳載體,因為其具有高BET表面積,在經濟上具成本效益且允許藉由僅在高溫下氧化觸媒而容易回收貴金屬。
粉末載體之平均粒度通常為0.1至500微米。如本文所定義之粉末載體之平均粒度(亦即,體積平均粒度)為如由體積粒度分佈,尤其體積平均直徑D(v0.9)測定之值,其中D(v0.9)為如下直徑:其中90%之分佈高於90%及為90%,如使用「通用」作為計算平均粒度之模型藉由Malvern MS 2000系統及取樣單元Hydro 2000G之雷射繞射所量測,對應於0.02-2000μm量測範圍。
粉末載體之微孔表面積通常為10至1100m2/g,較佳20至1000m2/g且更佳30至800m2/g。如本文所用之微孔表面積為如Applied Catalysis A:General 174(1998)
137-146中所描述可由t曲線分析測定及在液氮溫度下使用氮氣作為吸附物使用軟體程式套件在麥克默瑞提克ASAP 2040上測定之值。
通常,本發明之觸媒的粉末載體為微孔及/或中孔。
在一額外實施例中,本發明係關於一種製備根據本發明之貴金屬觸媒的方法,其中該方法包含以下步驟:- 在水溶液中藉由使該溶液與還原劑、穩定劑及配位劑接觸將貴金屬化合物還原,形成膠體貴金屬懸浮液;- 使懸浮液與粉末載體接觸;及,- 回收貴金屬觸媒。
本發明方法之優點為在第一步驟中設置貴金屬分散性。此係使用膠體方法進行,其中貴金屬化合物在水溶液中在還原劑、穩定劑及配位劑存在下還原為貴金屬微晶,形成膠體懸浮液。通常,貴金屬化合物在水溶液中與還原劑、穩定劑及配位劑接觸,尤其混合。在後續步驟中,藉由使懸浮液與載體接觸(尤其混合)將所得膠體懸浮液沈積至適合粉末載體上來設置邊緣塗覆,獲得本發明之觸媒。
貴金屬較佳為鈀及/或金金屬。
可使用的適合之貴金屬化合物包括水溶性鹽,諸如硝酸鹽、乙酸鹽、硫酸鹽、檸檬酸銨及氯化銨及其組合。較佳地,所用鹽為Na2PdCl4及/或AuCl3。
如在本發明方法中使用之還原劑及穩定劑可包
含充當還原劑及穩定劑之一種化合物或大於一種化合物。
還原劑在本發明方法中起到在水溶液中將貴金屬化合物(亦即,貴金屬離子)還原為貴金屬粒子之作用。
穩定劑在本發明方法中起到使藉由使貴金屬化合物與還原劑在水溶液中接觸形成之貴金屬粒子穩定,從而形成膠體貴金屬懸浮液的作用。根據本發明方法之使用穩定劑的優點為其防止或使貴金屬黏聚及粒子生長減至最少。
可用於根據本發明之方法的適合還原劑包括四級銨鹽、甲酸鈉、甲酸、檸檬酸鈉、檸檬酸、肼、醇(例如,通常C1-C4醇以及二醇或多元醇)、硼氫化物、甲醛、次磷酸鹽、金屬鹼化物、氫氣及其組合。
較佳地,還原劑為四級銨鹽,且更佳為官能化四級銨鹽。就此而言,官能化包含存在選自由以下組成之群的至少一個還原基團:一級醇、二級醇、環己烯基及其組合,較佳與選自由以下組成之群的至少一個龐大基團組合:C3 +烷基(亦即,C4-C20烷基)、環烷基、芳烷基、烷芳基及芳基及其組合,且其中至少一個龐大基團視情況經至少一個-OH及/或環己炔醇基官能化。另外,四級銨鹽可為對掌性的,諸如四級銨化辛可寧(cinchonine)或辛可尼丁(cinchonidine)。
最佳地,可用於本發明方法之四級銨鹽為式(III):RR'R"-N+-CH2CH2OH X- (III)
其中R、R'及R"彼此獨立地為C1烷基及高碳烷基(亦即,C4-C20烷基),其中C1烷基及高碳烷基(亦即,C4-C20烷基)視情況經至少一個-OH及/或環己炔醇基官能化,且X為Cl-、Br-、H2PO4 -、NO3 -或HSO4 -。較佳地,R及R'為C1烷基,且R"選自C3烷基及高碳烷基(亦即,C4-C20烷基),更佳C16烷基。
通常,用於根據本發明之方法中的還原劑的量為待還原之貴金屬化合物的量之至少3莫耳當量,且較佳至少5莫耳當量。通常用於本發明方法的還原劑的量為待還原之貴金屬的量之至多40莫耳當量,且較佳至多25莫耳當量。
可用於本發明方法之適合穩定劑包括四級銨鹽、供體配位體(例如,膦、胺及/或硫醚配位體)、聚合物(例如,聚(乙烯吡咯啶酮)(PVP)、聚(乙烯醇)(PVA)及/或聚(甲基乙烯基醚))、界面活性劑及其組合,較佳為四級銨鹽,且更佳為官能化四級銨鹽,其中官能化係根據如上文所描述之官能化。
通常,用於根據本發明之方法的穩定劑的量為待還原之貴金屬化合物的量之至少3莫耳當量,且較佳至少5莫耳當量。通常用於本發明方法的穩定劑的量為待還原之貴金屬化合物的量之至多25莫耳當量,且較佳至多10莫耳當量。
使用四級銨鹽作為還原劑之優點為其亦充當穩定劑,使用於根據本發明之方法的試劑數量減至最少。又一優點為大多數所描述還原劑為揮發性的或產生揮發性產
物,而四級銨鹽基本上為離子液體,無蒸氣壓且可用於生產而無還原劑(諸如低沸點有機溶劑)所需之必要的安全性要求。
配位劑在本發明方法中起到在水溶液中在還原期間與貴金屬化合物配位之作用。使用配位劑之優點為與在不使用配位劑時相比其導致所產生之貴金屬粒子的尺寸減小(亦即,較高分散性)。
可用於本發明方法之配位劑為尿素及/或氨。
可用於本發明方法的配位劑的量通常為待還原之貴金屬化合物的量之0.5或更大莫耳當量。通常用於本發明方法的配位劑的量為待還原之貴金屬化合物的量之至多25莫耳當量。較佳地,用於本發明方法的配位劑的量為待還原之貴金屬化合物的量之0.5-15莫耳當量。甚至更佳地,用於本發明方法的配位劑的量為待還原之貴金屬化合物的量之1-15莫耳當量。
可用於本發明方法之貴金屬溶液之適合濃度較佳為0.1-10g/L,更佳0.1-8g/L且甚至更佳0.2-5g/L,其中g/L係以所用PM化合物中之PM重量計。
藉由所謂的均勻沈積沈澱法使用尿素製備受載型金屬觸媒已描述於文獻中,參見例如A.C.Vermeulen,J.W.Geus,R.J.Stol及P.L.de Bruyn,J.Colloid and Interface Science 51(1975)449)。在此方法中,金屬與載體在尿素存在下混合及加熱。此導致尿素水解為CO2及NH3鹼性物質,使pH上升,且金屬物質隨後沈積至載體上。不進行鹼性物
質添加至反應混合物中,因為其使pH不均勻增加。所沈積之金屬物質在後續步驟中還原。
在本發明方法中,配位劑在沈積步驟中不添加,但在還原步驟中添加。出人意料地已發現,尿素及/或氨充當用於貴金屬化合物之還原的配位劑,其藉由金屬還原發生所需的較高溫度指示。
用於本發明方法的溶液之適合溫度通常在10℃至95℃範圍內。較佳地,在還原金金屬化合物時,用於還原步驟之溫度為10℃至50℃;或在還原鈀及/或鉑金屬化合物時,用於還原步驟之溫度為50℃至95℃。沈積步驟較佳可在10℃至50℃之溫度下進行。
亦已報導還原溫度之增加導致所形成之膠體的金屬微晶尺寸更小。(T.Teranishi,M.Miyake,Chem.Mater. 10(1998)594)。然而,不可能簡單地採用金屬化合物與穩定劑之混合物且將彼混合物加熱至高於WO-A-2009/096783中所描述之溫度,因為還原將在加熱期間發生。此外,在升溫下添加金屬化合物至穩定劑中不利地導致寬的金屬微晶粒徑分佈。
在文獻中,描述可用於調整所得金屬微晶之尺寸的幾個反應參數,諸如金屬濃度、pH及穩定劑的量,參見例如J.Turkevich,G.Kim,Science,169(1970)873。當在不使用配位劑(尤其尿素)之情況下進行鈀金屬化合物還原時,在反應參數優化之後所達成之最小可能微晶尺寸為5nm,如描述於WO-A-2009/096783中。
出人意料地已發現,使用根據本發明方法之配位劑導致具有較高分散性之貴金屬(奈米)微晶尺寸。
還原方法步驟較佳在約2至11之pH下進行。更佳地,還原步驟在還原鈀金屬化合物時在3.5至5.5之pH下進行;或在還原金金屬化合物時在8.5至10.5之pH下進行。沈積步驟較佳在4至9之pH值下進行。在必要時,可藉由添加鹼,例如鹼金屬碳酸鹽(諸如Na2CO3)或鹼金屬氫氧化物(諸如NaOH)來調節pH。
本發明之觸媒可藉由適合之分離方式,諸如過濾及/或離心來回收。通常,分離之觸媒隨後用水洗滌。可在洗滌步驟期間使用AgNO3溶液藉由指示劑測試來監測所存在的任何鹵化物(諸如氯離子)之移除。
在又一實施例中,根據本發明之貴金屬觸媒一般可用於貴金屬觸媒所適用之所有化學反應。該等反應可包括異構化、氧化、氫解(例如,加氫脫硫)、氫化/脫氫及加氫脫蠟反應。
此等反應可能宜在有機溶劑中且視情況在氫氣存在下在漿液相或固定床中進行,尤其在三相系統或兩相系統中進行氫化反應時,其中氫氣溶解於有機溶劑中。使3-己炔-1-醇氫化之漿液相反應的較佳條件為溫度高於約30℃且壓力為1-5巴H2(g)。可用於漿液相反應之典型條件為20-95℃溫度及1-10巴H2(g)壓力。
出於清楚且簡潔描述之目的,特徵在本文中描述為相同或獨立實施例之一部分,然而,應瞭解,本發明之
範疇可包括具有所有或一些所描述特徵之組合的實施例。
圖1展示所得的根據本發明之觸媒之TEM影像及存在2nm Pd金屬微晶,ICP分析確定觸媒含有0.48wt.% Pd。
圖2展示所得的根據本發明之觸媒之TEM影像及存在2nm Pd金屬微晶,ICP分析確定觸媒含有0.28wt.% Pd。
圖3展示所製備觸媒之TEM影像及存在5nm Pd金屬微晶,ICP分析確定觸媒含有0.50wt.% Pd。
圖4展示所製備觸媒之TEM影像及存在5nm Pd金屬微晶,ICP分析確定觸媒含有0.29wt.% Pd。
圖5展示根據本發明之Au觸媒之TEM影像及存在10nm Au微晶。
圖6展示所製備觸媒之TEM影像及存在20nm Au微晶。
圖7展示在3-己炔-1-醇之半氫化中使用實例1至4之觸媒的氫氣吸收(nL)與運行時間(min)。
現基於一些實例闡明本發明,該等實例不意欲限制本發明之範疇。
實例
實例1:製備由受載於活性碳_上之2nm Pd金屬微晶組成
之觸媒
使2L燒杯配備有隔板且在室溫(亦即,20-25℃)下用600mL水填充。使用頂部攪拌器,以300rpm攪拌水。一次性添加還原劑/穩定劑(30mL 30wt.% Luviquat® Mono CP(羥乙基十六烷基磷酸二銨)/水,獲自西格瑪-奧德里奇(Sigma-Aldrich))及配位劑尿素(0.30g),且攪拌混合物幾分鐘。將Pd溶液(1.58g 18.98wt.% Pd,呈Na2PdCl4形式,用60mL水稀釋)添加至混合物中歷經30min時段,在其期間溶液之pH緩慢地自5.4降至4.9。在添加Pd溶液之後,藉由添加NaOH溶液(10wt.% NaOH/水)將混合物之pH設置為5.0。將混合物加熱至95℃(pH為4.7)且在此溫度下保持兩小時,同時保持水位恆定。在冷卻之後,膠體Pd金屬懸浮液之pH為4.9。
使2L燒杯配備有隔板且用50g(乾重)活性碳粉末填充,且在室溫(亦即,20-25℃)下緩慢地添加500mL水以防止粉塵形成且形成漿液。使用頂部攪拌器,以500rpm攪拌漿液一小時,獲得均勻懸浮液。將膠體Pd金屬懸浮液添加至此懸浮液中歷經60min時段,且攪拌混合物額外一小時。過濾出所得Pd/AC觸媒,且用水洗滌直至洗滌水中不再可見Cl(使用AgNO3溶液使用指示劑測試測定)。圖1展示所得的根據本發明之觸媒之TEM影像及存在2nm Pd金屬微晶。ICP分析確定觸媒含有0.48wt.% Pd。
實例2:製備由受載於矽酸鈦上之2nm Pd金屬微晶組成之觸媒
重複實例1之反應,但膠體Pd金屬沈積於60g矽酸鈦載體上。圖2展示所得的根據本發明之觸媒之TEM影像及存在2nm Pd金屬微晶。ICP分析確定觸媒含有0.28wt.% Pd。
實例3(比較):在不使用配位劑之情況下製備由受載於活性碳上之5 nm Pd金屬微晶組成之觸媒
使2L燒杯配備有隔板且在室溫(亦即,20-25℃)下用600mL水填充。使用頂部攪拌器,以300rpm攪拌水。一次性添加還原劑/穩定劑(35mL 30wt.% Luviquat® Mono CP(羥乙基十六烷基磷酸二銨)/水,獲自西格瑪奧德里奇),且攪拌混合物幾分鐘。將Pd溶液(2.63g 18.98wt.% Pd,呈Na2PdCl4形式,用100mL水稀釋)添加至混合物中歷經30min時段,在其期間溶液之pH緩慢地自5.3降至5.0。將混合物加熱至85℃(pH為3.2),且藉由添加NaOH溶液(10wt.% NaOH/水)將pH設置為5.0。混合物在此溫度下保持兩小時,同時保持水位恆定且每隔30min將pH重新設置為5.0。在冷卻之後,膠體Pd金屬懸浮液之pH為4.9。
使2L燒杯配備有隔板且用83g(乾重)活性碳粉末填充,且在室溫(亦即,20-25℃)下緩慢地添加800mL水以防止粉塵形成且形成漿液。使用頂部攪拌器,以500rpm攪拌漿液一小時,獲得均勻懸浮液。將膠體Pd金屬懸浮液添加至此懸浮液中歷經60min時段,且攪拌混合物額外一小時。過濾出所得Pd/AC觸媒,且用水洗滌直至洗滌水中不再可見Cl(使用硝酸銀溶液使用指示劑測試測定)。圖3展示
所製備觸媒之TEM影像及存在5nm Pd金屬微晶。ICP分析確定觸媒含有0.50wt.% Pd。
實例4(比較):在不使用配位劑之情況下製備由受載於矽酸鈦上之5nm Pd金屬微晶組成之觸媒
重複實例3之反應,但膠體Pd金屬沈積於100g矽酸鈦載體上。圖4展示所製備觸媒之TEM影像及存在5nm Pd金屬微晶。ICP分析確定觸媒含有0.29wt.% Pd。
實例5:製備由受載於矽酸鈦上之10nm Au金屬微晶組成之觸媒
使600mL燒杯配備有隔板且在室溫(亦即,20-25℃)下用200mL水填充。一次性添加還原劑/穩定劑(7mL 30wt.% Luviquat® Mono CP(羥乙基十六烷基磷酸二銨)/水,獲自西格瑪-奧德里奇)及配位劑尿素(0.10g),且攪拌混合物幾分鐘。將Au溶液(0.50g 20.13wt.% Au,呈AuCl3形式,用5mL水稀釋)添加至混合物中歷經2min時段。藉由添加NaOH溶液(10wt.% NaOH/水)將混合物之pH調節至10,且保持在9.5至10持續60min。將混合物加熱至50℃,且pH保持在9.5至10之值持續另一30min。將混合物加熱至85℃,且pH保持在9.5至10之值持續另一120min,同時保持水位恆定。在冷卻之後,膠體Au金屬懸浮液之pH為約10。
使600mL燒杯配備有隔板且用20g矽酸鈦粉末填充,且在室溫(亦即,20-25℃)下緩慢地添加200mL水以防止粉塵形成且形成漿液。使用頂部攪拌器,攪拌漿液30
min,獲得均勻懸浮液。將膠體Au金屬懸浮液添加至此懸浮液中歷經90min時段,且攪拌混合物額外30min。過濾出所得Au/TiS觸媒,且用水洗滌直至洗滌水中不再可見Cl(使用硝酸銀溶液使用指示劑測試測定)。圖5展示根據本發明之Au觸媒之TEM影像及存在10nm Au微晶。
實例6(比較):在不使用配位劑之情況下製備由受載於矽酸鈦上之20nm Au金屬微晶組成之觸媒
類似於實例5進行實驗,但不使用尿素。Au之還原在50℃下已為完全的且無需進一步加熱。圖6展示所製備觸媒之TEM影像及存在20nm Au微晶。
實例7:分析觸媒
確定根據本發明之觸媒(實例1及2)之以下特性且在表1中展示。
如上文所描述獲得ICP量測值。
使用TEM量測實例1至6之上文所提及之PM微晶尺寸,其中實例1至4之PM微晶尺寸展示於下表1中。藉由首先將各觸媒分散於乙醇中及將所得分散液施加於目標載片之間產生薄膜來製備觸媒樣品。隨後使超薄碳TEM載體與各薄膜接觸。
使用在200keV下操作的Tecnai G2-F20ST機器(美國希爾斯伯勒FEI公司(FEI Company,Hillsboro,USA))研究所製備之觸媒樣品。能量色散X射線光譜學(EDXS)用於使用在Mn-Kα下之能量解析度為131eV之EDXi偵測系統(美國莫瓦EDAX(EDAX,Mahwah,USA))確定樣品之不同
位置處的化學組成。使用OlympusiTEM 5.2(Build 3554)(日本東京奧林巴斯(Olympus,Tokyo,Japan))及FEI TIA 4.1.202(美國希爾斯伯勒FEI公司)軟體套件評估影像及光譜學資料。對於PM微晶尺寸測定,使用MAG*I*CAL校準樣品(匈牙利布達佩斯泰諾琳達公司(Technoorg Linda Ltd.,Budapest,Hungary))校準顯微鏡放大率。藉由使用奧林巴斯iTEM 5.2軟體手動量測每一樣品約200PM微晶之最小直徑來確定平均PM微晶尺寸。
在如上文所描述之觸媒樣品上進行XPS量測。
使用上文所提及之式(I)確定表面富集值(SEV)。
亦對實例3與實例4之比較觸媒進行相同分析,且展示於下表1中。
除使用CO化學吸附量測Pd微晶尺寸之外,以類似方式分析以下市售之觸媒:EscatTM 1421(Pd 5wt.%/AC,還原,來自施特雷姆化學品公司(STREM Chemicals,Inc.))、EscatTM 1621(Pd 5wt.%/AC,還原,來自施特雷姆化學品公司)、EscatTM 1911(Pd 3wt.%/AC,還原,來自施特雷姆化學品公司)、EscatTM 1941(Pd 5wt.%/AC,還原,來自施特雷姆化學品公司)及EscatTM 1971(Pd 5wt.%/AC,還原,來自施特雷姆化學品公司)。此等分析之結果亦展示於下表1中。
使用來自麥克默瑞提克儀器公司(Micromeritics Instrument Corporation)之Autochem II 2920化學吸附分析儀進行上文所提及之市售觸媒之CO化學吸附量測。藉由在
105℃下乾燥觸媒隔夜以移除所吸附的水及其他揮發物來製備觸媒樣品。乾燥觸媒各自以約0.1至0.2g之量載入樣品管中。隨後在H2/Ar:15vol.%氣流(50mL/min)及10℃/min升溫速率達到200℃下預處理觸媒樣品,且在200℃溫度下保持30min。觸媒樣品隨後在He氣流(50mL/min)下冷卻至50℃。以5min)時間間隔將CO脈衝(循環體積0.39mL STP)噴射至He氣流(50mL/min)中持續6次。最後,觸媒樣品用He氣流(50mL/min)沖洗3min。使用由觸媒樣品及Autochem II 2920化學吸附分析儀之整合式軟體套件量測之資料來確定每公克PM之有效金屬表面積及PM奈米微晶平均尺寸。
如自上述結果可見,根據本發明之觸媒(實例1及2)與所分析之比較觸媒中的任一者相比具有較小Pd微晶尺寸及較高SEV值。
實例8:使用受載型鈀觸媒半氫化3-己炔-1-醇
將一定量之實例1至4之觸媒分別饋入250mL不鏽鋼高壓釜,在反應器中產生1.25mg Pd,且將3-己炔-1-
醇於96wt.%乙醇中之100g 4.5wt.%溶液添加至反應器中。封閉高壓釜,且在攪拌下將混合物加熱至30℃。停止攪拌,且藉由氫氣沖洗混合物來置換空氣。在沖洗之後,用3巴氫氣加壓高壓釜。恢復攪拌(1500rpm),且記錄氫氣消耗。90min後停止攪拌。根據H2吸收曲線以mL H2/min計算反應速率r1(半氫化)及r2(過氫化)。
圖7展示在3-己炔-1-醇之半氫化中使用實例1至4之觸媒的氫氣吸收(nL)與運行時間(min)。表2展示如由氫氣吸收確定之r1及r2值(以H2/min計)。此展示根據本發明之觸媒(實例1在活性碳上且實例2在矽酸鈦上)之所需半氫化比比較實例(分別為實例3及4)超過10%更具活性。
Claims (14)
- 一種貴金屬觸媒,其中該觸媒包含貴金屬之奈米微晶在粉末載體上,其中該貴金屬為鈀及/或金金屬;其中該鈀金屬觸媒包含具有平均尺寸為自1至小於5nm之奈米微晶,且其中該觸媒具有一表面富集值為自至少6.5至至多150;及,其中該金金屬觸媒包含具有平均尺寸為自3至小於15nm之奈米微晶,且其中該觸媒具有一表面富集值為自至少3至至多150,及,其中該表面富集值(SEV)由下式(I)決定:SEV=(XPS wt.%-ICP wt.%)/ICP wt.%; (I)其中以該觸媒之以重量%計,XPS wt.%為該貴金屬含量之X射線光電子光譜學(XPS)量測值,且ICP wt.%為該貴金屬含量之感應耦合電漿(ICP)量測值。
- 如請求項1之觸媒,其中以該觸媒之重量計,該觸媒包含介在0.01及20wt.%含量間之貴金屬。
- 如請求項1或2之觸媒,其中該鈀金屬觸媒具有至少為8之表面富集值;且其中該鈀金屬觸媒具有至多為120之表面富集值;及,其中該金金屬觸媒具有至少為5之表面富集因子;且其中該金金屬觸媒具有至多為120之表面富集值。
- 如請求項1或2之觸媒,其中該等鈀金屬奈米微晶具有介於1及4nm之平均 尺寸;及,其中該金金屬奈米微晶具有介於3及13之平均尺寸。
- 如請求項1或2之觸媒,其中該粉末載體選自由以下組成之群:二氧化矽、氧化鋁、氧化鋯、氧化鈦、二氧化鈰、氧化鎂、氧化鋅、金屬矽酸鹽、金屬鋁酸鹽、沸石、碳奈米管、碳奈米纖維、石墨碳及活性碳及其組合。
- 如請求項1或2之觸媒,其中該粉末載體之平均粒度為介於0.1及500微米。
- 一種用來製備貴金屬觸媒之方法,其中該方法包含以下步驟:在水溶液中藉由使該溶液與還原劑、穩定劑及配位劑接觸將貴金屬化合物還原,從而形成膠體貴金屬懸浮液;使該懸浮液與粉末載體接觸;及,回收該貴金屬觸媒。
- 如請求項7之方法,其中該貴金屬為鈀及/或金金屬。
- 如請求項7或8之方法,其中該還原劑係選自由以下組成之群:四級銨鹽、甲酸鈉、甲酸、檸檬酸鈉、檸檬酸、肼、C1-C4醇、二醇、多元醇、硼氫化物、甲醛、次磷酸鹽、金屬鹼化物、氫及其組合。
- 如請求項7或8之方法,其中該穩定劑選自由以下組成之群:四級銨鹽、供體配位體、聚合物、界面活性劑及其組合。
- 如請求項7或8之方法,其中該配位劑為尿素及/或氨。
- 如請求項7或8之方法,其中該載體選自由以下組成之群:二氧化矽、氧化鋁、氧化鋯、氧化鈦、二氧化鈰、氧化鎂、氧化鋅、金屬矽酸鹽、金屬鋁酸鹽、沸石、碳奈米管、碳奈米纖維、石墨碳及活性碳及其組合。
- 如請求項1或2之貴金屬觸媒,其係藉由如請求項7至12中任一項之方法獲得。
- 一種如請求項1至6或13中任一項之貴金屬觸媒的用途,其係用於氫化/脫氫、異構化、氧化、氫解或加氫脫蠟反應。
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