CN101534944B - 富金属硅质组合物及其生产方法 - Google Patents
富金属硅质组合物及其生产方法 Download PDFInfo
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- CN101534944B CN101534944B CN2007800411100A CN200780041110A CN101534944B CN 101534944 B CN101534944 B CN 101534944B CN 2007800411100 A CN2007800411100 A CN 2007800411100A CN 200780041110 A CN200780041110 A CN 200780041110A CN 101534944 B CN101534944 B CN 101534944B
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- metal
- colloidal silica
- silica particle
- combination
- colloidal
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 87
- 239000002184 metal Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000002245 particle Substances 0.000 claims abstract description 62
- 239000008119 colloidal silica Substances 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 23
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 150000002739 metals Chemical class 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 61
- 229910052763 palladium Inorganic materials 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 19
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 16
- 239000013528 metallic particle Substances 0.000 claims description 16
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229960001422 aluminium chlorohydrate Drugs 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 238000002242 deionisation method Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- -1 chlorauride Chemical compound 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 239000004038 photonic crystal Substances 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 24
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000377 silicon dioxide Substances 0.000 abstract description 16
- 230000003993 interaction Effects 0.000 abstract description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910013500 M-O—Si Inorganic materials 0.000 abstract description 2
- 229910003849 O-Si Inorganic materials 0.000 abstract description 2
- 229910003872 O—Si Inorganic materials 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 238000000634 powder X-ray diffraction Methods 0.000 description 18
- 230000009467 reduction Effects 0.000 description 16
- 239000000084 colloidal system Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910020175 SiOH Inorganic materials 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052914 metal silicate Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 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 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- KDJOAYSYCXTQGG-UHFFFAOYSA-N disilicic acid Chemical compound O[Si](O)(O)O[Si](O)(O)O KDJOAYSYCXTQGG-UHFFFAOYSA-N 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- KDLHZDBZIXYQEI-VENIDDJXSA-N palladium-100 Chemical compound [100Pd] KDLHZDBZIXYQEI-VENIDDJXSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising 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
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- 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
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- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/049—Pillared clays
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- B01J35/23—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
公开了一种产生富金属硅质材料例如胶态二氧化硅或硅铝酸盐颗粒的改良的溶胶-凝胶法。首先将选择的金属盐加至硅酸溶液或者含有铝盐的硅酸溶液中。由于铝在二氧化硅基质中形成Al-O-Si键合,因此将其加入以改变金属载体相互作用。除了铝之外,可加入其他形成M-O-Si(M=Ti,B等)键合的金属,所述键合在用还原剂处理时不会被还原。一旦金属、硅酸和/或铝盐被混合,则通过将其加入到碱性尾料中而使其经历胶体生长。胶体一经合成,将含有金属盐的胶体颗粒原样搁置以使胶体稳定性最大化或用肼还原以产生含零价金属的胶体颗粒。由于颗粒可以容易地被喷雾干燥或与其他用于挤压成型催化剂颗粒的材料混合,因此在使用前使颗粒保持为胶体是形成催化剂材料的有效方法。
Description
技术领域
本发明一般涉及具有结合的金属颗粒(incorporated metal particle)的硅质材料和生产这种材料的工艺。更具体地,本发明涉及向硅酸溶液中加入金属盐以产生富金属硅质材料的工艺。本发明和制备具有已还原的结合的金属颗粒的胶态二氧化硅特别相关。
背景
胶体材料例如胶态二氧化硅的制备和使用是被广泛了解的。例如,具有金属涂布表面的胶态二氧化硅是被广泛了解和使用的。通常,二氧化硅胶体被首先合成。之后用金属氧化物涂布胶体。取决于金属的起始物料的特性和所用的涂布方法,这一涂布程序产生带负电荷和带正电荷的表面。含金属的二氧化硅胶体在许多领域中是有用的,例如电子工业中的化学机械抛光剂、涂料应用,以及在催化过程中作为载体材料。尽管这一多功能性,但常规型的二氧化硅胶体具有若干缺点。
液体悬浮的金属纳米颗粒在催化作用中具有若干缺点,其包括回收利用纳米颗粒催化剂的困难。将催化剂固定在载体上使得经由简单的过滤来回收利用催化剂成为可能。然而,固定的催化剂的合成(其包括用金属纳米颗粒注入载体)可能是非常耗时的。例如,钯催化的用于碳-碳键形成的反应(Heck反应)是多用途的工业合成手段。它包括用乙酸钯(II)浸渍载体(例如沉淀的二氧化硅),干燥,用氢气或其他适合的还原剂还原。
将金属结合在多孔载体上的两种众所周知的方法是浸渍(有时被称为“初湿含浸(incipient wetness)”技术)和经由溶胶-凝胶技术直接合成。浸渍包括采用固体多孔载体并将金属盐溶液加至所述载体。金属盐溶液流入(intercalate)通过多孔载体的结构并在干燥时形成表面沉积物。在还原沉积的金属盐期间,金属颗粒具有迁移至多孔载体的表面上的趋势并且必须穿过多孔结构来分散。由于较小的活性表面积,这一迁移导致烧结以及催化活性的全面下降(参见Hermans & Geus,Interaction of Nickel Ions WithSilica Supports During Deposition-Precipitation(沉积-沉淀期间镍离子与二氧化硅载体的相互作用),Stud.Surf.Sci.Catal.,1979,第113至130页)。
溶胶-凝胶技术(参见Lopez等人,Pt/SiO2 Sol-Gel Catalysts:Effects ofpH and Platinum Precursor(Pt/SiO2溶胶-凝胶催化剂:pH和钯前体的影响),J.Phys.Chem.,1993,第1671至1677页)包括将金属盐和硅烷前体例如原硅酸四乙酯(“TEOS”)混合。随着时间的过去,TEOS水解并且它的SiOH基团与金属盐相互作用。一旦SiOH基团开始缩合并形成沉淀,金属则经由封端的SiO-或SiOH基团被分散于SiO2基质中。在合成期间,溶胶-凝胶技术中的金属盐往往变得包藏在结构内。
因此,存在将金属结合至硅质胶体组合物中的改良方法的需求。具体而言,用于产生具有更均匀(homogenously)分散的金属负载(load)和在更大的pH范围内的增强的稳定性和/或其他适合的特征的基于二氧化硅的胶体或颗粒的合成方法是所需的。此外,形成这种具有窄的颗粒粒度分布的胶体是所需的。
概述
因此,本发明提供了一种制备富金属硅质材料的方法。所述方法包括将一种或多种金属的一种或多种盐与硅酸溶液混合以形成混合物。将所述混合物加至碱性尾料溶液中以形成胶态二氧化硅颗粒的悬浮液。所述胶态二氧化硅颗粒中的一种或多种包括结合的金属颗粒。在一些实施方案中,所述方法包括浓缩所述悬浮液、用还原剂还原所述结合的金属颗粒和/或进一步加工的步骤。
所述方法还可包括将硅酸钠溶液去离子以制备所述硅酸溶液。
所述方法还可包括在将一种或多种金属的一种或多种盐与所述硅酸溶液混合以形成所述混合物之前,将水合氯化铝与所述硅酸溶液混合。
在所述方法中,一种或多种金属的一种或多种盐可选自由以下组成的组:乙酸钯、氯化金、水合氯化铝、氯化铜、三硝酸铁、硝酸镍、氯化钴及其组合。
在所述方法中,所述碱性尾料溶液可包括一种或多种碱,所述碱选自由以下组成的组:氢氧化钠、氢氧化锂、氢氧化钾、氢氧化铵、伯胺、仲胺、叔胺、季铵、季化合物及其组合。
在所述方法中,可将所述混合物以控制的速率加至所述碱性尾料溶液中以将胶态二氧化硅颗粒粒度控制在从约1纳米至约250纳米,所述粒度取决于所述控制的速率。
在所述方法中,可将所述混合物以控制的速率加至所述碱性尾料溶液中以将胶态二氧化硅颗粒粒度控制在从约4纳米至约150纳米。
所述方法还可包括将所述碱性尾料溶液从约60℃加热至约90℃。
在所述方法中,所述还原剂可选自由以下组成的组:肼和氢气。
在所述方法中,所述结合的金属颗粒可基本上均匀地被分散在所述胶态二氧化硅颗粒中。
在所述方法中,对所述胶态二氧化硅颗粒或所述产物的进一步加工可包括使用一种或多种工艺,所述工艺选自由以下组成的组:超滤、去离子、加热、干燥、浓缩、表面官能化及其组合。
所述方法还可包括将所述胶态二氧化硅颗粒或所述产物用于工业应用,所述工业应用选自由以下组成的组:牙科应用、蛋白质分离、分子筛、纳米多孔膜、波导管、光子晶体、耐火应用、酒和汁液的澄清、半导体和磁盘驱动部件的化学机械平坦化、催化剂、催化剂载体、造纸中的助留剂和助滤剂、填料、表面涂料、陶瓷材料、熔模铸造黏结剂、平光剂、支撑剂、化妆品制剂以及抛光研磨剂。
本发明还提供了包括多种沉降的二氧化硅颗粒的富金属硅质组合物。所述颗粒产自硅酸溶液和一种或多种金属的一种或多种盐的混合物。以总固体为基准,从大约10重量百分比至大约50重量百分比的金属与所述胶态二氧化硅颗粒结合(associated)。
在所述富金属硅质组合物中,所述金属可以是已还原的金属。
一方面,本发明包括富金属硅质组合物,其包括多种具有从大约1纳米至大约250纳米的平均直径的胶态二氧化硅颗粒。所述颗粒产自硅酸溶液和一种或多种金属的一种或多种盐的混合物。以总固体为基准,多达大约10重量百分比的金属与所述胶态二氧化硅颗粒结合。
在所述富金属硅质组合物中,所述金属可以是已还原的金属。
在所述富金属硅质组合物中,所述富金属硅质组合物可包括与所述胶态二氧化硅颗粒结合的多种不同金属。
在所述富金属硅质组合物中,所述金属可选自由以下组成的组:碱金属、碱土金属、第一行过渡金属、第二行过渡金属、镧系元素及其组合。
在所述富金属硅质组合物中,所述金属可选自由以下组成的组:钯、铂、铁、金、铝、铜、镍、铁、钛及其组合。
在所述富金属硅质组合物中,所述胶态二氧化硅颗粒可包括紧密堆积并干燥的胶态二氧化硅颗粒。
本发明的一个优点是提供了直接将金属结合至胶体材料中的方法。
本发明的另一个优点是提供了一种形成富金属胶态二氧化硅颗粒的方法,所述颗粒具有基本上均匀分布或分散的金属颗粒和窄的颗粒粒度分布。
本发明的另一个优点是提供了一种符合成本效益并且高效率的方法,其用于配制具有金属组分的胶体材料以及在产生催化剂后用还原剂例如肼还原液态的结合的金属。
本发明的另一个优点是提供了一种符合成本效益并且高效率的方法,其用于配制具有金属组分的胶体材料以及在产生催化剂后用还原剂例如氢气还原干燥态的结合的金属。
附图简述
图1描述了5.28重量百分比的Pd(0)还原之前的PXRD图谱。
图2示例性说明了5.28重量百分比的Pd(0)还原之后的PXRD图谱。
图3展示了0.55(--)、1.10(---)和1.82(-)重量百分比的Pd(0)胶体硅铝酸盐颗粒还原之后的(111)峰的PXRD图谱。
图4是1.07重量百分比的具有Pd(0)/Au(0)=4的摩尔比的Au(0)和Pd(0)胶体硅铝酸盐颗粒的未还原(---)和已还原(-)的PXRD图谱。
详述
公开了一种产生富金属硅质材料例如胶态二氧化硅或硅铝酸盐的改良的溶胶-凝胶法。在一个实施方案中,选择的金属盐被加至硅酸溶液或者含有铝盐的硅酸溶液中。由于铝在二氧化硅基质中形成Al-O-Si键合,因此将其加入以改变金属载体相互作用。如下文所述,除了铝之外,可加入其他形成M-O-Si(M=Ti,B等)键合的金属,该键合在用还原剂处理时不会被还原。一旦金属、硅酸和/或铝盐被混合,则通过将其加入到碱性尾料中而使其经历胶体生长。将含有金属盐的胶体颗粒原样搁置以使胶体稳定性最大化或用肼还原以产生含零价金属的胶体颗粒。由于颗粒容易地被喷雾干燥或与其他用于挤压成型催化剂颗粒的材料混合,因此在使用前使颗粒保持为胶体是形成催化剂材料的有效方法。
本发明提供了一种将金属颗粒结合至硅质材料例如胶态二氧化硅或金属硅酸盐中的工艺。所述金属颗粒可包括各种金属,例如碱金属、碱土金属、第一行过渡金属、第二行过渡金属、镧系元素、类似物及其组合。在一个优选的实施方案中,所述金属包括钯、铂、铁、金、铝、铜、镍、铁、钛及其组合。在一个更优选的实施方案中,所述金属包括钯、金、铝及其组合。
所述工艺包括将金属盐例如乙酸钯加入硅酸中以产生混合物。将这一混合物引入碱性尾料溶液(下文描述)中,导致胶态二氧化硅颗粒的形成。在一个实施方案中,含钯的胶态二氧化硅颗粒接着被还原剂(例如肼或氢气)还原以形成零价的钯颗粒。此外,预期可将金属氧化物(例如氧化铝、氧化钛以及类似物)加至硅酸中以产生金属硅酸盐,该金属硅酸盐提供不同的与已还原的金属(reduced metal)的金属载体相互作用。
应理解的是,几种金属盐中的一种或多种可被用于本发明的工艺。例如,可使用混合金属诸如金和钯。在这一实例中,氯化金和乙酸钯可被加至硅酸中以形成富金属胶态二氧化硅。其他可使用的代表性的金属盐包括氯化铜、三硝酸铁(iron trinitrate)、硝酸镍、氯化钴、类似物及其组合。
本发明的胶体组合物对于凝胶化或沉淀是稳定的,并且在从总固体的大约0.1重量百分比至大约40重量百分比浓度下通常保持在胶体状态。当金属盐向金属还原时,材料在所加金属的低浓度(例如以固体为基准,多达大约2重量百分比的已还原的金属)下保持稳定。在一个实施方案中,在以固体为基准,在高于大约2重量百分比的已还原的金属浓度下发生一些沉降。在另一个实施方案中,最小的沉降发生在以固体为基准,多达大约40重量百分比的已还原的金属浓度下。
在一个实施方案中,当形成富金属硅质颗粒时,使它们经受还原剂以将结合的金属颗粒从盐形式还原为零价形式。如果金属在所述颗粒在溶液中时被还原,那么还原剂通常是肼,而如果材料在还原前已被干燥(例如,急骤干燥(flash drying)、喷雾干燥及类似方法),那么还原剂通常是氢气。
在一个实施方案中,所述方法包括制备硅酸溶液。预期可使用任何适合的方法来制备硅酸。代表性的方法包括用离子交换树脂将硅酸钠,例如原硅酸钠(Na4SiO4)、偏硅酸钠(Na2SiO3)、聚硅酸钠(Na2SiO3)n、焦硅酸钠Na6Si2O7、类似物和/或其任何组合去离子。优选地,用强酸性离子交换树脂将硅酸钠去离子以产生硅酸或酸溶胶。可选择的方法包括用熟知的法生产硅酸。
用于合成所述方法的富金属硅质材料的碱性尾料溶液起到用于形成所述材料的催化剂的作用。在可选择的实施方案中,在加入硅酸/金属盐混合物之前,将尾料溶液从大约60℃加热至大约90℃。碱性尾料溶液通常在从大约10毫克当量(″meq″)至大约200meq的范围内并且可选择地包括不同类型的碱。代表性的碱包括氢氧化钠、氢氧化锂、氢氧化钾、氢氧化铵、伯胺、仲胺、叔胺、季铵、季化合物(quaternary compound)、类似物及其组合。代表性的季化合物包括氢氧化四乙胺、氢氧化四正丁铵、氢氧化四正丙铵、氢氧化四甲铵、氢氧化NNN-三甲基-2-丁铵(NNN-trimethyl-2-butyl-ammonium hydroxide)、氢氧化NNN-三甲基-丙铵、类似物及其组合。
控制将硅酸/金属盐混合物加入碱性尾料溶液中的速率使得确定了颗粒粒度分布是本领域技术人员所熟知的。在一个优选的实施方案中,胶体颗粒具有从大约1纳米至大约250纳米的平均直径。在一个更优选的实施方案中,所述颗粒具有从大约4纳米至大约150纳米的平均直径。
预期本发明的富金属硅质材料可被用于各种工业应用。代表性的应用包括牙科应用、蛋白质分离、分子筛、纳米多孔膜、波导管、光子晶体、耐火应用、酒和汁液的澄清、半导体和磁盘驱动部件的化学机械平坦化、催化剂、催化剂载体、造纸中的助留剂和助滤剂(drainage aid)、填料、表面涂料、陶瓷材料、熔模铸造黏结剂、平光剂、支撑剂、化妆品制剂以及抛光研磨剂。这些工业应用中的某些可能在所述应用中使用前要求本发明的材料被进一步加工。可能的加工步骤包括超滤、去离子、加热、干燥、浓缩、表面官能化、类似加工及其组合。
实施例
通过参考以下的实施例可更好的理解前文,所述实施例用于示例性说明目的而不是意图限制本发明的范围。
用于以下实施例的二氧化硅源是硅酸(或酸溶胶)。硅酸通过将在57.37克去离子水中的含有25克硅酸钠(R-570)的溶液通过阳离子交换树脂来制得。尽管可使用任何适合的柱或者树脂,但是在这些实施例中,使用的是含有大约40ml DowexTM 650C强阳离子交换树脂(可从Dow ChemicalCompany获得,Midland,MI)每100克稀释的硅酸钠溶液的柱。
实施例I
将如表I中所示的乙酸钯溶于HCl(全浓度,未添加水)。在一些实施例中,将水合氯化铝在搅拌下加至硅酸中,之后添加乙酸钯/HCl混合物。硅酸/水合氯化铝/乙酸钯/HCl溶液对于凝胶化或沉淀是稳定的。
将氢氧化钠尾料在四颈圆底烧瓶中加热至大约80℃。对于0.55、1.10和1.82重量百分比(以总固体为基准)的钯金属二氧化硅胶体,在表I的每个反应中,硅酸/水合氯化铝/乙酸钯/HCl溶液被以约10ml/min的速率滴加至搅拌下的烧瓶中。对于5.28重量百分比的钯样品,唯一的制备差异是缺少水合氯化铝。混合金属的二氧化硅胶体催化剂也以1.07重量百分比的具有钯比金的摩尔比为4的总金属含量被生成。之后将这一混合的金属催化剂通过超滤浓缩至16.3%总固体。
表I
取决于乙酸钯/HCl溶液的浓度,加至硅酸或硅酸/水合氯化铝溶液后的颜色对于0.55wt% Pd(0)样品是浅黄褐色,对于5.28wt% Pd(0)样品是深褐色。所述溶液对于凝胶化或沉淀非常稳定并可在用于制备胶体颗粒前贮存数小时。将苛性碱尾料加热至80℃并将硅酸/乙酸钯或硅酸/水合氯化铝/乙酸钯溶液以10ml/min滴加以产生预期的大约10纳米的二氧化硅胶体颗粒粒度。
实施例II
随后将来自实施例I的样品原样或在用1ml的10wt%的肼的去离子水溶液还原后表征。富金属二氧化硅胶体的表征包括透射电子显微术(″TEM″)、粉末X射线衍射(″PXRD″)以及氮吸附法(nitrogen sorption)。装备有热离子钨丝的Philips(FEI)EM208S TEM(100kV)或装备有LaB6灯丝的JEOL 3010 TEM(300kV)被使用。用使用了波长的Co Kα射线的PhilipsX’Pert Pro 3040进行煅烧过的样品的PXRD。用足量的去离子水洗涤样品以除去存在的任何NaCl。用来自的Autosorb-1C进行氮吸附测量。将每个样品在300℃除气3小时。
原样(即不通过超滤进一步浓缩)使用0.55、1.10和1.82wt% Pd(0)样品,而在用肼还原前将5.28wt% Pd(0)样品浓缩至14%固体,并将1.07wt% Pd(0)和Au(0)样品浓缩至16.3%固体。5.28wt% Pd(0)还原之前的粉末X射线衍射(″PXRD″)图谱示于图1。在PXRD图谱采集之前将所述样品在通风罩中气干。所述PXRD图谱没有任何可识别的峰,所述可识别的峰包括对于Pd(0)来说应位于2θ=46.943处的100%强度的(111)峰。这表明室温干燥后在环境条件下没有发生还原。此外,没有存在的Pd(0)相位(phase)或乙酸钯相位。
图2描述了5.28wt%Pd(0)样品用肼还原后的PXRD图谱。位于2θ=46.71处的宽的Pd(0)(111)峰可见。对于来自表I中的某些样品,表II显示了用Scherer方程(t=0.9λ/(B cosθ))计算的平均Pd(0)颗粒粒度。
表II
由于在图2中除了Pd(0)没有别的钯相位存在,因此假设钯100%还原。5.28wt% Pd(0)样品是唯一在二氧化硅基质中没有使用Al2O3的样品。向二氧化硅载体加入不同的金属氧化物可以改变载体金属相互作用。这表明由于获得了非常小的Pd(0)颗粒,金属载体相互作用在本发明的直接合成技术中可能没有起到至关重要的作用。这还表明钯盐的浓度在确定颗粒粒度中起到了更关键的作用。
参照图3,描述了0.55(--)、1.10(---)和1.82(-)wt% Pd(0)材料还原之后的PXRD图谱。所述PXRD图谱显示与Pd(0)相关的(111)峰。与5.28wt% Pd(0)样品一样,具有如表II所示的通过Scherer方程确定的平均颗粒粒度的所有三个样品的峰都非常宽。与具有2.87nm的Pd(0)平均颗粒粒度的较高的1.82wt% Pd(0)样品相比,较低的0.55和1.10wt%Pd(0)样品分别具有较大的Pd(0)平均颗粒粒度,4.24nm和4.60nm。5.28wt%Pd(0)样品具有甚至比较低的Pd(0)wt%样品更小的颗粒粒度,其在经由先前已知的溶胶-凝胶合成技术的金属颗粒掺入中由PXRD通常观察不到。
图4是1.07wt%的具有Pd(0)/Au(0)=4的摩尔比的Au(0)和Pd(0)胶体硅铝酸盐颗粒的PXRD图谱(未还原(---)和已还原(-))。图3中显示的1.10wt% Pd(0)的PXRD显示出非常明显的Pd(0)(111)峰,而图4中的Au(0)和Pd(0)的1.07wt%(111)峰均未见。非常宽的PXRD峰是Au(0)和Pd(0)颗粒穿过硅铝酸盐基质的良好分散和它们的非常小的颗粒粒度的指示。
实施例III
氮吸附法被用于确定0.55、1.10和1.82wt% Pd(0)样品还原之后的的BET表面积。结果示于表III。胶体颗粒直径用式:2727/BET表面积来计算。
表III
与表面积相关的胶体颗粒粒度对于0.55wt% Pd(0)样品为12.3nm,对于1.10wt% Pd(0)样品为10.5nm和对于1.82wt% Pd(0)样品为10.8nm。所有三个样品的颗粒粒度值与预期的大约10nm的颗粒粒度良好相关。所有三个样品显示出具有相当大的滞后的IV型等温线,同时所述等温线的吸附部分给出从大约2纳米到大约30纳米的孔径分布。
应当理解的是,对本领域的技术人员来说,对此处描述的目前优选的实施方案的各种改变和变更是清楚的。可在不背离本发明精神和范围并且不减少其预期优点的情况下做出这些改变和变更。因此意在通过所附的权利要求覆盖这些改变和变更。
Claims (18)
1.一种制备富金属硅质材料的方法,所述方法包括:
a)将一种或多种金属的一种或多种盐与硅酸溶液混合以形成混合物,所述一种或多种金属的一种或多种盐选自由以下组成的组:乙酸钯、氯化金、水合氯化铝、氯化铜、三硝酸铁、硝酸镍、氯化钴及其组合;
b)将所述混合物加至碱性尾料溶液以形成胶态二氧化硅颗粒的悬浮液,其中所述胶态二氧化硅颗粒中的一种或多种包括结合的金属颗粒,其中所述结合的金属颗粒基本上均匀地被分散在所述胶态二氧化硅颗粒中,并且其中以总固体为基准,从10重量百分比至50重量百分比的金属与所述胶态二氧化硅颗粒结合;和
c)用还原剂还原所述结合的金属颗粒以形成产物,其中所述还原剂选自由以下组成的组:肼和氢气;
所述方法包括在步骤(b)中将所述混合物以控制的速率加至所述碱性尾料溶液中以将胶态二氧化硅颗粒粒度控制在从1纳米至250纳米,所述粒度取决于所述控制的速率。
2.如权利要求1所述的方法,其包括将硅酸钠溶液去离子以制备所述硅酸溶液。
3.如权利要求1所述的方法,其包括在将一种或多种金属的一种或多种盐与所述硅酸溶液混合以形成所述混合物之前,将水合氯化铝与所述硅酸溶液混合。
4.如权利要求1所述的方法,其中所述碱性尾料溶液包括一种或多种碱,所述碱选自由以下组成的组:氢氧化钠、氢氧化锂、氢氧化钾、氢氧化铵、伯胺、仲胺、叔胺、季化合物及其组合。
5.如权利要求1所述的方法,所述方法包括在步骤(b)中将所述混合物以控制的速率加至所述碱性尾料溶液中以将胶态二氧化硅颗粒粒度控制在从4纳米至150纳米。
6.如权利要求1所述的方法,其包括将所述碱性尾料溶液从60℃加热至90℃。
7.如权利要求1所述的方法,其还包括对所述胶态二氧化硅颗粒或所述产物进一步加工的步骤,其中对所述胶态二氧化硅颗粒或所述产物的进一步加工包括使用一种或多种工艺,所述工艺选自由以下组成的组:超滤、去离子、加热、干燥、浓缩、表面官能化及其组合。
8.如权利要求1所述的方法,其包括将所述胶态二氧化硅颗粒或所述产物用于工业应用,所述工业应用选自由以下组成的组:牙科应用、蛋白质分离、分子筛、纳米多孔膜、波导管、光子晶体、耐火应用、酒的澄清、半导体和磁盘驱动部件的化学机械平坦化、催化剂、催化剂载体、造纸中的助留剂和助滤剂、填料、表面涂料、陶瓷材料、熔模铸造黏结剂、平光剂、支撑剂、化妆品制剂以及抛光研磨剂。
9.如权利要求1所述的方法,其包括将所述胶态二氧化硅颗粒或所述产物用于汁液的澄清的工业应用。
10.如权利要求1所述的方法,其还包括浓缩所述悬浮液的步骤。
11.如权利要求1所述的方法,其还包括对所述胶态二氧化硅颗粒或所述产物进一步加工的步骤。
12.如权利要求4所述的方法,其中所述碱性尾料溶液包括季铵。
13.一种富金属硅质组合物,其包括多种产自硅酸溶液和一种或多种金属的一种或多种盐的混合物的沉降的胶态二氧化硅颗粒,其中以总固体为基准,从10重量百分比至50重量百分比的金属与所述胶态二氧化硅颗粒结合,并且其中结合的金属颗粒基本上均匀地被分散在所述胶态二氧化硅颗粒中,还并且其中所述金属是已还原的金属。
14.一种富金属硅质组合物,其包括多种具有从1纳米至250纳米的平均直径的胶态二氧化硅颗粒,并且所述胶态二氧化硅颗粒产自硅酸溶液和一种或多种金属的一种或多种盐的混合物,其中以总固体为基准,多达10重量百分比的金属与所述胶态二氧化硅颗粒结合,并且其中结合的金属颗粒基本上均匀地被分散在所述胶态二氧化硅颗粒中,还并且其中所述金属是已还原的金属。
15.如权利要求14所述的富金属硅质组合物,其包括与所述胶态二氧化硅颗粒结合的多种不同金属。
16.如权利要求14所述的富金属硅质组合物,其中所述金属选自由以下组成的组:碱金属、碱土金属、第一行过渡金属、第二行过渡金属、镧系元素及其组合。
17.如权利要求14所述的富金属硅质组合物,其中所述金属选自由以下组成的组:钯、铂、铁、金、铝、铜、镍、钛及其组合。
18.如权利要求14所述的富金属硅质组合物,其中所述胶态二氧化硅颗粒包括紧密堆积并干燥的胶态二氧化硅颗粒。
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CN110482559B (zh) * | 2019-09-16 | 2021-03-30 | 广东惠和硅制品有限公司 | 一种铝改性酸性硅溶胶及其制备方法和应用 |
PH12019050291A1 (en) * | 2019-11-20 | 2021-08-23 | Univ Of The Philippines Los Ba¤Os | Modified Nanostructured Silica Materials for Heavy Metal Removal from Contaminated Water and the Methods of Production Thereof |
CN111908951B (zh) * | 2020-08-14 | 2024-02-09 | 云浮市豪野材料科技有限公司 | 一种耐高温阻燃建筑复合石材的生产工艺 |
CN115212877A (zh) * | 2022-06-28 | 2022-10-21 | 深圳市添金利新材料科技有限公司 | 一种耐热性纳米催化剂及其光化学驱动制备方法 |
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- 2007-11-08 WO PCT/US2007/084095 patent/WO2008058240A2/en active Application Filing
- 2007-11-08 EP EP07864119.8A patent/EP2079546B1/en active Active
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EP2079546A4 (en) | 2012-08-29 |
JP2010509496A (ja) | 2010-03-25 |
EP2079546B1 (en) | 2020-08-12 |
CN101534944A (zh) | 2009-09-16 |
US20100074974A1 (en) | 2010-03-25 |
JP5389660B2 (ja) | 2014-01-15 |
CA2669471C (en) | 2015-03-10 |
US20080108497A1 (en) | 2008-05-08 |
EP2079546A2 (en) | 2009-07-22 |
WO2008058240A3 (en) | 2008-08-14 |
CA2669471A1 (en) | 2008-05-15 |
WO2008058240A2 (en) | 2008-05-15 |
US8003707B2 (en) | 2011-08-23 |
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