TWI637909B - 錫酸矽酸鈦,其製備方法及用途 - Google Patents
錫酸矽酸鈦,其製備方法及用途 Download PDFInfo
- Publication number
- TWI637909B TWI637909B TW103113189A TW103113189A TWI637909B TW I637909 B TWI637909 B TW I637909B TW 103113189 A TW103113189 A TW 103113189A TW 103113189 A TW103113189 A TW 103113189A TW I637909 B TWI637909 B TW I637909B
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- Prior art keywords
- titanium
- patent application
- silicate
- scope
- titanium stannate
- Prior art date
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- 239000010936 titanium Substances 0.000 title claims abstract description 68
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 53
- 229940071182 stannate Drugs 0.000 title claims abstract description 52
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 125000005402 stannate group Chemical group 0.000 title claims abstract description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims description 37
- 229910052708 sodium Inorganic materials 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 9
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 239000007937 lozenge Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 230000004962 physiological condition Effects 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 238000006845 Michael addition reaction Methods 0.000 claims description 2
- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 46
- 239000000243 solution Substances 0.000 description 44
- 239000011135 tin Substances 0.000 description 41
- 239000011734 sodium Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 14
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 229910052718 tin Inorganic materials 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- -1 titanium silicates Chemical class 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 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 5
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000004760 silicates Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 235000019484 Rapeseed oil Nutrition 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910008484 TiSi Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 235000010603 pastilles Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003826 tablet Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 101100065719 Drosophila melanogaster Ets98B gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910008487 TiSn Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical class [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical compound [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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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
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- 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
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/635—0.5-1.0 ml/g
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Abstract
本發明係關於一種具有通式:Mv+ wTixSiySnzO2x+2y+2z+0.5vw之非晶形錫酸矽酸鈦,其中M為質子、銨、金屬或金屬混合物,其中v為M之為正整數的原子價,且其中x、y、z及w為莫耳比:x為1,y為0.01至99,z為0.01至99及w為0.01至50。所述錫酸矽酸鈦尤其適用於催化及吸附。
Description
本發明係關於用作催化劑及吸附劑之矽酸鹽,尤其含有諸如鈦之過渡金屬之矽酸鹽的領域。
中孔矽酸鹽材料由於其大表面積及預定直徑之孔隙,因此在如催化劑及吸附介質之許多領域中應用廣泛。此使其尤其適用於用作純化吸附劑、催化劑、催化劑載體、過濾介質、填充劑。
特定言之,美國5,508,457描述IVB族矽酸鹽,尤其矽酸鈦及矽酸鋯,其可為晶體或非晶形的。所述催化劑尤其為晶體矽酸鈦、晶體矽酸鋁鈦、非晶形矽酸鈦及相應的鋯化合物。矽酸鹽適用於(轉)酯化反應且尤其適用於固定床製程。
美國5,053,139描述可用於在通常可見於飲用水中之競爭離子存在下,自該飲用水中移除鉛之非晶形矽酸鈦及矽酸錫。
GB 212,065描述一種藉由使酸與可溶性鹽之溶液混合製備多元氧化物凝膠以生產水凝膠之方法,該可溶性鹽諸如為氧化錫、氧化鋁、氧化鎢及/或氧化鈦之酸的鈉鹽。將此方法之最終產物描述為具有超顯微孔之高孔隙度之物質。亦描述藉由混合錫酸鈉、鎢酸鈉及酸之溶液以產生水凝膠製備錫酸鎢酸鹽凝膠。但是,沒有描述使用可溶性鈦酸鹽且建議使用
之唯一鈦酸鹽為幾乎不溶於水之鈦酸鈉的實例。
雖然已存在各種矽酸鹽,但始終需要具有改良之物理性質(諸如孔徑)及改良之催化劑性質(諸如選擇性及活性)的新穎化合物用於催化及吸附應用。
為了解決前述需求中之至少一者,本發明提供一種非晶形錫酸矽酸鈦,其具有以下通式:Mv+ wTixSiySnzO2x+2y+2z+0.5vw,
其中M為質子、銨、金屬或金屬混合物中之至少一者,v為M之為正整數的原子價且其中x、y、z及w為莫耳比:x為1,y為0.01至99,z為0.01至99,及w為0.01至50。
在另一態樣中,本發明提供一種用於製備根據本發明之錫酸矽酸鈦之方法,其包含在可溶性矽酸鹽源、可溶性錫酸鹽源及可溶性鈦源之間的含水介質中之沈澱反應,藉此該錫酸矽酸鈦沈澱且分離。
在另一態樣中,本發明提供根據本發明之錫酸矽酸鈦的用途,其用作化學反應中之催化劑或催化劑載體或用作吸附劑。
圖1展示實施例2及5中獲得之產物的孔徑分佈。
根據本發明之錫酸矽酸鈦與現有矽酸鈦及矽酸錫的不同之處在於所有三種元素構成氧網路。在結構位準上,本發明化合物表示一種由互連之矽酸鹽、鈦酸鹽、及錫酸鹽多面體構成之三維氧化物網路。
因此,所有的三個原子-Si、Ti及Sn構成氧-O-鍵之網路中之一部分。在替代觀點中,據說Sn原子置換經由氧-O-鍵鍵結之Ti及Si之網路中的Ti(或Si)原子。亦據說根據本發明之化合物為鈦、錫及矽之混合氧化物。藉由與Sn陽離子進行離子交換自矽酸鈦獲得之Ti/Sn/Si化合物的區別在於錫不以陽離子形式存在於根據本發明之化合物中,而與氧原子共價結合,亦即呈錫酸鹽形式。並且,錫以Sn(IV)形式存在於根據本發明之化合物中,而通常藉由離子交換引入Sn(II)。此外術語「錫酸鹽(stannate)」特別意謂以Sn(IV)形式存在於結構中之錫。
錫酸矽酸鈦之所述結構明顯不同於藉由經錫鹽浸漬獲得之結構,其中Sn以Sn2+陽離子形式存在。在矽酸鈦(非晶形)及矽酸鈦(晶體,例如TS-1、ETS-4)中經像SnCl2之陽離子型錫化合物進行陽離子交換之實例描述於[Journal of Molecular Catalysis A:Chemical(2005),237(1-2),1-8]及[Chemical Communications(2003),(13),1500-1501]中。但是,Sn之裝載受限於可交換陽離子之量,因為錫陽離子僅微弱地與具有Si-O或Ti-O基之Ti/Si氧化物結構之表面結合。在本發明中,併入結構中之Sn之量可變化且可為極高的,諸如至少30wt.%、或至少50wt.%或甚至高達至少70wt.%。理論上,可存在於本發明之錫酸矽酸鈦中之Sn之最大量為78wt.%,以幾乎純的SnO2及痕量SiO2/TiO2進行計算。在製備本發明化合物期間,Sn不以陽離子形式而以陰離子形式添加,諸如Na2SnO3之SnO3 2-。在根據本發明之氧化
物網路中引入Sn出人意料地導致改良之物理及催化性質,如在下文中更詳細描述。
Sn原子之結構及環境可藉由不同技術測定,例如XPS、UV-可見或固態NMR。另外,藉由離子交換引入之Sn始終影響M與Sn之重量比。此意謂如通式中所用之莫耳比w及z在經離子交換引入之情況下為相互關聯的,儘管在本發明中可彼此獨立地選擇此等值。舉例而言,在離子交換期間,單個Na離子交換單個Sn離子。但在本發明中,由於Sn以錫酸鹽形式內建於氧化物結構中,因此不影響可鍵結在錫酸矽酸鈦之表面處之Na或H之量。
根據本發明之錫酸矽酸鈦以非晶形形式存在。在非晶形形式下意謂X射線非晶形,亦即其X射線粉末繞射圖案不含晶體繞射峰之固體形式。如本發明人所發現,呈非晶形形式之錫酸矽酸鈦允許在廣泛範圍內控制Ti:Si:Sn之間的莫耳比,其可繼而更好地調整材料性質且因此引起更好的催化及吸附性質。另外,非晶形形式在酯化及酯基轉移反應中具有尤其良好的催化性質。
根據本發明之錫酸矽酸鈦具有以下通式:Mv+ wTixSiySnzO2x+2y+2z+0.5vw。在此公式中,M表示H(質子)、銨、金屬或金屬混合物中之至少一種。金屬可為鹼金屬、鹼土金屬、過渡金屬或另一金屬,諸如原子價為1、2或3之金屬,在一較佳具體實例中,M為質子、銨、Na、Li、K、Cs、Ca、Mg、Sr、Ba、Fe(II)、Fe(III)、Sn(II)、Ce、La、Nb、Ni、V、W、Mo、Al、Zn、Cu、Mn中之至少一種。在一個較佳具體實例中,M為質子、銨、鹼金屬或鹼土金屬。在另一較佳具體實例中,M表示Li、
Cs、Mg、Ca、Sr、Ba、La、Nb、Fe、Ni、V、W、Mo、Al、Ce、Sn、Zn、Cu、Mn離子或此等離子之組合。
元素M具有原子價v,其為正整數。較佳地,M之原子價v為1、2、3、4、5或6。在一個較佳具體實例中,v為1、2或3。在另一較佳具體實例中,v可為5或6。值x、y、z及w為莫耳比且尤其為如下:x為1,y為0.01至99,z為0.01至99及w為0.01至50。較佳地,y在0.1-10、更佳0.2-5範圍內。較佳地,z在0.03-5、更佳0.05-1範圍內。較佳地,w在0.01-50、更佳0.1-10範圍內。如先前所提及,w及z之值可以彼此獨立之方式調整。
出人意料地,藉由在矽酸鈦結構中併入SnO2(或藉由將TiO2併入矽酸錫結構中),所得材料之物理及催化性質可經改變。
甚至更出人意料地,根據本發明之材料之孔隙體積比非晶形矽酸鈦材料典型地可見之孔隙體積:通常遠低於0.3mL/g高。舉例而言,US5053139報導介於0.03與0.25mL/g之間的孔隙體積。根據本發明之錫酸矽酸鈦具有至少0.3mL/g之孔隙體積。連同錫酸矽酸鈦材料之增加的孔隙體積一起,發現更大的平均孔隙直徑,典型地具有如由IUPAC 1994分類之中孔隙及/或大孔隙,其分別具有2-50nm及>50nm之孔隙直徑。錫酸矽酸鈦材料之典型的平均孔隙直徑值至少為40Å,更佳為至少60Å。傳統的非晶形矽酸鈦具有介於30與35Å之間的平均孔隙直徑。本發明之錫酸矽酸鈦之BET表面積為100至600,較佳為200至500m2/g。
如本文所用之BET表面積為在Micromeritics ASAP 2420上在180℃下對樣品除氣之後,藉由液氮吸附所量測且尤其藉由測定在77K及大
約0.3之P/Po下所吸附之氮氣的量且假定氮氣截面積為16.2Å2所量測之值。如本文所用,總孔隙體積為藉由使用Micromeritics ASAP 2420確定在大約1之P/Po下所吸附之液氮體積所量測之值。如本文所用,平均孔隙直徑為藉由總孔隙體積除以BET表面積及假定孔隙為圓柱形所測定之值。BJH方法可用於自實驗等溫線使用孔隙充填之開爾文(Kelvin)模型計算孔徑分佈。
本發明之錫酸矽酸鈦較佳呈粉末、錠劑、顆粒或擠出物形式,更佳呈錠劑或擠出物形式。
出人意料地,本發明者已發現根據本發明之新穎含錫材料與非晶形矽酸鈦相比具有改良之催化性質。舉例而言,與非晶形矽酸鈦相比,用作催化劑之本發明之材料對三酸甘油酯及甲醇轉化為脂肪酸甲酯更有效。並且,本發明之材料在酯化自由脂肪酸及甲醇以形成脂肪酸甲酯中更有效。
在另一態樣中,本發明提供一種用於製備本發明之錫酸矽酸鈦之方法。此方法包含在可溶性矽酸鹽、可溶性錫酸鹽及可溶性鈦源之間的含水介質中之沈澱反應,藉此該錫酸矽酸鈦沈澱且分離。作為矽酸鹽源,較佳使用可溶性矽酸鹽,諸如Na2SiO3。作為錫酸鹽源,較佳使用可溶性錫酸鹽,諸如Na2SnO3。合適之鈦源例如為鈦鹽及鈦氧鹽,諸如TiOCl2。尤其合適的為鈦(IV)化合物,諸如TiCl4、溴化鈦(IV)、氟化鈦(IV)、碘化鈦(IV)、烷醇鈦(IV)、TiO烷醇鹽,但亦可使用鈦(III)。
沈澱物以自溶液中分離(較佳地藉由過濾)之物質形式獲得。為獲得適用於催化及吸附應用之TiSiSn材料,應自物質移除水以獲得
固體產物。可在高溫下(諸如80-120℃)進行乾燥,但亦可在室溫下進行。乾燥可在空氣或氮氣流中進行。乾燥亦可在洗滌步驟之前以移除在沈澱期間所形成之鹽。
替代乾燥步驟或在乾燥步驟之後,固體材料可在例如超過200℃、較佳超過300℃、更佳超過400℃之溫度下煅燒。在較高溫度下煅燒可形成作為催化劑活性更高的材料。較佳在較高溫度下煅燒之另一原因為使用潤滑劑製備錠劑。在此情況下,潤滑劑(例如經氫化之脂肪或石墨)需要燒盡而不影響TiSiSn結構之非晶形特性。
本發明之錫酸矽酸鈦保持非晶形,甚至在450℃下煅燒之後。本發明者觀察到在氧化矽不存在之情況下,所形成之化合物為在110℃下乾燥之後已為晶體之錫酸鈦,且其亦在450℃下煅燒之後仍為晶體。未內建Si之該材料(100%TiSn,參見實施例4)在酯化及酯基轉移反應中展示相當低的活性。
根據本發明之方法可進一步包含至少一個離子交換之步驟。舉例而言,在沈澱反應之後存在於沈澱物中之至少一部分陽離子可由質子(H+)交換。質子化了之錫酸矽酸鈦可不太易於在饋料或產物流中降解及溶解。陽離子之部分(諸如Na+或K+)與H+的置換亦可具有增加催化劑之酯化活性的優點。在新鮮催化劑(亦即在將其與原料,尤其與(脂肪)酸接觸之前)中,Na或K離子之量典型地為大約5-10wt.%。此Na或K含量可藉由與H+交換降至小於3wt.%。更佳地,鈉或鉀含量藉由與H+交換降至小於1wt.%,甚至更佳地降至大約0.1至0.2wt.%。可使用其他陽離子代替H+來交換Na或K離子,諸如NH4 +、Cs+或Ca2+。離子交換之步驟可在沈
澱之後及乾燥步驟(若存在)之前,或在乾燥步驟之後(若存在)或甚至在煅燒之後進行。
同樣發現材料之熱穩定性可受離子交換影響。尤其,發現當用鈉交換質子時,經XRD量測值偵測到結晶度之煅燒溫度高得多。咸信煅燒溫度之高度對材料之BET-SA、孔隙體積及平均孔隙直徑具有影響。因此,偵測到結晶度之溫度較高意謂材料之熱穩定性增加。
在一較佳具體實例中,離子交換經選自以下之陽離子進行:質子、銨、Na、K、Li、Cs、Mg、Ca、Sr、Ba、La、Nb、Fe、Ni、V、W、Mo、Al、Ce、Sn、Zn、Cu、Mn離子及其組合。為了改良所得化合物在催化反應中之活性及/或選擇性可將陽離子引入結構中。
根據本發明之材料可用於各種應用。此材料尤其較佳用於催化反應中,諸如酯化、邁克爾(Michael)加成、酯基轉移、(環)氧化、羥基化反應。本發明之錫酸矽酸鈦較佳用作催化劑或催化劑載體,原樣或在藉由離子交換進行改質之後。本發明之材料亦可用作離子交換劑。本發明之錫酸矽酸鈦之其他用途為吸附小的無機及有機分子(例如CO2或芳族化合物)。
本發明之錫酸矽酸鈦之另一較佳用途為其用於自水溶液中吸附及移除放射性核種,較佳為Sr(尤其90Sr)或錒系元素。因此本發明之材料可用作用於處理受金屬污染之廢物流及地下水的吸附劑。
本發明之材料之另一用途為用於在生理條件下選擇性吸附及解吸附金屬,較佳為Pt(II)、Pt(IV)、Pd、Gd、Hg、Cd、Au或Ho。
本發明之材料可以粉末、錠劑、顆粒、擠出物等形式使用。
其可用作散裝材料或用在支撐物上。
現將於以下非限制性實施例中說明本發明。其中除非另外說明,否則所提及之百分比或份數意謂重量百分比或重量份。
實施例1
製備莫耳比為0.29:1:1.02:0.06之Na:Ti:Si:Sn
在含有95g脫礦水之容器中,溶解有27.6mL 30%NaOH溶液、10mL 27%Na2SiO3溶液及6.8mL 13.5wt%Na2SnO3溶液。此容器中之溶液稱為溶液A。在含有112g脫礦水之另一容器中,添加16mL 35%TiOCl2溶液。此容器中之溶液稱為溶液B。隨後,在5分鐘內伴以劇烈攪拌將溶液A添加至溶液B。在添加完全之後,使混合物繼續混合額外10分鐘。溶液之pH值應降為介於7.5與7.9之間;若需要,則用稀HCl或稀NaOH調節pH值。隨後使樣品老化超過4小時(多至4天)。漿料經過濾且在110℃下在烘箱中將剩餘物質乾燥隔夜。所得白色固體經粒化、經由425μm篩篩分、再在水中打漿且攪拌1小時。隨後,漿料經過濾,用脫礦水洗滌直至洗滌水之傳導率低於200μS/cm。所得白色材料在110℃下在烘箱中乾燥隔夜。藉由方法產生大約12.5g白色固體。
該材料為非晶形(XRD)且其中Na:Ti:Si:Sn之比為0.29:1:1.02:0.06,且孔隙體積為0.47mL/g,BET-SA=430m2/g,平均孔隙直徑=52Å。
實施例2
製備莫耳比為0.23:1:0.34:0.18之Na:Ti:Si:Sn
使用如實施例1中所述之類似程序但使用不同量之起始材
料。溶液A含有95g脫礦水、26.7mL 30%NaOH溶液、3.4mL 27%Na2SiO3溶液及20mL 13.5wt.%之Na2SnO3溶液。溶液B類似於實施例1。產生大約10.8g白色固體。
材料為非晶形(XRD)且其中Na:Ti:Si:Sn之莫耳比為0.23:1:0.34:0.18且孔隙體積為0.48mL/g。BET-SA=431m2/g,平均孔隙直徑=51Å。
實施例3
製備H+交換材料
使用如實施例1中所述之類似程序但使用不同量之起始材料。溶液A含有380g脫礦水、105mL 30%NaOH溶液、13.7mL 27%Na2SiO3溶液及80.8mL 13.5wt.%之Na2SnO3溶液。溶液B藉由將64.5mL 35%TiOCl2溶液添加至450g脫礦水中製備。隨後,在10分鐘內伴以劇烈攪拌將溶液A添加至溶液B。在添加完全之後,使混合物繼續混合額外10分鐘。溶液之pH值應降為介於7.5與7.9之間;若需要,則用稀HCl或稀NaOH調節pH值。向混合物中添加40g NaCl(視情況選用之)。隨後使樣品老化超過4小時。漿料經過濾且在110℃下在烘箱中將剩餘物質乾燥隔夜。乾燥之後,白色固體經粒化、經由425μm篩篩分、再在水中打漿且在pH 2.0(用10%HCl調節pH值)下攪拌1小時。隨後,漿料經過濾,用脫礦水洗滌直至洗滌水之傳導率低於200μS/cm。所得白色材料在110℃下在烘箱中乾燥隔夜。藉由方法產生大約40.7g白色固體。
材料為如藉由XRD所確認之非晶形,且其中Na:Ti:Si:Sn之莫耳比為0.01:1:0.34:0.16且孔隙體積為0.50mL/g。BET-SA=384m2/g,平均
孔隙直徑=55Å。
實施例4
不含Si製備
使用如實施例1中所述之類似程序但使用不同量之起始材料。溶液A含有90g脫礦水、24.3mL 30%NaOH溶液及25mL 13.5wt.%之Na2SnO3溶液。溶液B含有100g脫礦水及15mL 35%TiOCl2溶液。隨後,在5分鐘內伴以劇烈攪拌將溶液A添加至溶液B。在添加完全之後,使混合物繼續混合額外10分鐘。溶液之pH值應降為介於7.5與7.9之間;若不為此情況,則用稀HCl或稀NaOH調節pH值。向混合物中添加10g NaCl(視情況選用之)。隨後使樣品老化超過4小時(多至4天)。漿料經過濾且在110℃下在烘箱中將剩餘物質乾燥隔夜。所得白色固體經粒化、經由425μm篩篩分、再在水中打漿且在pH 2.0(用10%HCl調節pH值)下攪拌1小時。隨後,漿料經過濾,用脫礦水洗滌直至洗滌水之傳導率低於200μS/cm。所得白色材料在110℃下在烘箱中乾燥隔夜。藉由方法產生大約8.2g白色固體。
該材料為如藉由XRD所確認之晶體,且其中Na:Ti:Si:Sn之比為0.01:1:0:0.24,且孔隙體積為0.30mL/g,BET-SA=256m2/g,平均孔隙直徑=39Å。
實施例1、2、3及4之煅燒
藉由實施例1、2、3及4製備之樣品在450℃下在空氣中煅燒2小時。煅燒之後,除來自實施例4之材料仍為晶體外,所有樣品均保持非晶形。
實施例5
TiSi傳統合成
根據US-A-5053139之實施例9製得矽酸鈦粉末:兩公升1.5M氯化鈦溶液(溶液A)藉由添加569.11g TiCl4至足夠的去離子水中以形成2公升來製得。兩公升1.5M矽酸鈉溶液(溶液B)藉由將638.2g Na2SiO3.5H2O溶解於足夠的3M NaOH中以形成2公升來製得。伴以極劇烈攪拌以16立方公分/分鐘之速率將溶液B添加至溶液A。在添加完全之後,使混合物繼續混合額外15分鐘。溶液之pH值應降為介於7.5與7.9之間;若不為此情況,則用稀HCl或稀NaOH調節pH值。隨後使樣品老化2-4天。老化之後,將物質之頂部上的任何水傾析掉。樣品隨後經過濾、每公升物質用1公升去離子水洗滌、在4-6公升去離子水中再打漿、過濾且最後每公升物質在2公升水中再洗滌。
為了效率原因,樣品隨後在105℃下乾燥24小時(直至LOI低於10)。在合成程序期間從不允許物質接觸任何金屬;在整個製備過程中使用聚丙烯及玻璃實驗室器皿。
由此方法產生之固體經粒化及篩分得到小於250微米之粒子,且所得產物之鈉:鈦:矽之莫耳比為0.35:1:0.96,且孔隙體積大約為0.14mL/g,BET-SA=364m2/g,平均孔隙直徑=31Å。
圖1展示實施例2及5中獲得之產物的孔徑分佈。可見與不含Sn之化合物(實施例5)相比,Sn建構於結構中(實施例2)產生明顯更大的孔隙體積。
實施例6
藉由SnCl2改質之TiSi的陽離子交換
在玻璃燒杯中,在450mL脫礦水中將50.0g根據實施例5製備之矽酸鈦製成漿料。向此漿料中添加29.34g呈固體狀之SnCl2.2H2O。混合物之顏色自白色變成黃色。漿料之pH值自8.80變成1.60。使混合物在室溫下攪拌額外2小時。2小時之後,漿料經過濾且用脫礦水洗滌直至濾液之傳導率低於20微西門子/公分(microSiemens/cm)。微黃色的濾餅在110℃下在烘箱中乾燥隔夜產生48.2g黃色粉末。所得材料為藉由XRD確認之非晶形。
材料之Na:Ti:Si:Sn莫耳比為0.01:1:1.27:0.19。量測到之孔隙體積為0.14mL/g,BET表面積為229m2/g,平均孔隙直徑為32Å。
實施例7
錠劑製備
將實施例3之材料與石墨混合且製錠成1.5×1.5mm之大小。所得錠劑在500℃下煅燒2小時。
實施例8
在同步的酯化及酯基轉移中使用TiSi
10mL矽酸鈦錠劑由根據實施例5製備之材料製成,但其中鈉含量在pH 2.00下藉由HCl處理而降低。在過濾、洗滌及乾燥之後,材料含有0.8wt.%Na。將此材料製錠成1.5 * 1.5mm之錠劑。錠劑裝載於固定床反應器中。反應器連續饋有MeOH(1.73mL/h)及菜籽油(3.47mL/h),其中已添加5wt.%之十二烷酸。反應條件為180℃、28巴N2背壓、LHSV菜籽油0.347h-1(3.47mL/h)、LHSV MeOH 0.173h-1(1.73mL/h)。
三酸甘油酯至脂肪酸甲酯之轉化率為46%且99.1%之十二烷酸轉化成相對應的甲酯。
實施例9
在同步的酯化及酯基轉移中使用TiSiSn
自根據實施例3製備之材料製備10mL錫酸矽酸鈦錠劑。錠劑裝載於固定床反應器中。反應器連續饋有MeOH(1.73mL/h)及菜籽油(3.47mL/h),其中已添加5wt%之十二烷酸。反應條件為180℃、28巴N2背壓、LHSV菜籽油0.347h-1(3.47mL/h)、LHSV MeOH 0.173h-1(1.73mL/h)。
三酸甘油酯至脂肪酸甲酯之轉化率為60%且99.8%之十二烷酸轉化成相對應的甲酯。
Claims (19)
- 一種非晶形錫酸矽酸鈦,其具有以下通式:Mv+ wTixSiySnzO2x+2y+2z+0.5vw,其中M為質子、銨、金屬或金屬混合物中之至少一者,v為M之為正整數的原子價且其中x、y、z及w為莫耳比:x為1,y為0.01至99,z為0.01至99,及w為0.01至50。
- 如申請專利範圍第1項之錫酸矽酸鈦,其中M為質子、銨、Na、Li、K、Cs、Ca、Mg、Sr、Ba、Fe(II)、Fe(III)、Sn(II)、Ce、La、Nb、Ni、V、W、Mo、Al、Zn、Cu、Mn中之至少一者。
- 如申請專利範圍第1項或第2項之錫酸矽酸鈦,其中y在0.1至10範圍內。
- 如申請專利範圍第3項之錫酸矽酸鈦,其中y在0.2至5範圍內。
- 如申請專利範圍第3項之錫酸矽酸鈦,其中z在0.03至5範圍內。
- 如申請專利範圍第5項之錫酸矽酸鈦,其中z在0.05至1範圍內。
- 如申請專利範圍第1項之錫酸矽酸鈦,其中w在0.1至10範圍內。
- 如申請專利範圍第1項之錫酸矽酸鈦,其中該錫酸矽酸鈦具有由液氮吸附所測定之至少0.3mL/g之孔隙體積。
- 如申請專利範圍第1項之錫酸矽酸鈦,其中該錫酸矽酸鈦具有由液氮吸附所測定之至少40Å之平均孔隙直徑。
- 如申請專利範圍第1項之錫酸矽酸鈦,其呈粉末、錠劑、顆粒或擠出物形式。
- 一種製備如申請專利範圍第1項至第10項中任一項之錫酸矽酸鈦的方法,其包含在可溶性矽酸鹽源、可溶性錫酸鹽源及可溶性鈦源之間的含水介質中之沈澱反應,藉此該錫酸矽酸鈦沈澱且分離。
- 如申請專利範圍第11項之方法,其進一步包含經選自以下之陽離子進行離子交換之步驟:質子、銨、Na、Li、K、Cs、Ca、Mg、Sr、Ba、Fe(II)、Fe(III)、Sn(II)、Ce、La、Nb、Ni、V、W、Mo、Al、Zn、Cu、Mn離子及其組合。
- 如申請專利範圍第11或12項之方法,其中該錫酸矽酸鈦進一步在超過200℃之溫度下煅燒。
- 一種如申請專利範圍第1項至第10項中任一項之錫酸矽酸鈦的用途,其用作化學反應中之催化劑或催化劑載體,或用作吸附劑。
- 如申請專利範圍第14項之用途,其中該化學反應為酯化、邁克爾(Michael)加成、酯基轉移、氧化、環氧化或羥基化之反應。
- 如申請專利範圍第14項之用途,其用於自水溶液吸附及移除放射性核種。
- 如申請專利範圍第16項之用途,其用於自水溶液吸附及移除90Sr或錒系元素。
- 如申請專利範圍第14項之用途,其用於在生理條件下選擇性吸附或解吸附金屬。
- 如申請專利範圍第18項之用途,其用於在生理條件下選擇性吸附或解吸附Pt(II)、Pt(IV)、Pd、Gd、Hg、Cd、Au或Ho。
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CN107304486A (zh) * | 2016-04-25 | 2017-10-31 | 中央大学 | 非线性光学晶体及其制备方法 |
TWI585249B (zh) | 2016-04-25 | 2017-06-01 | 國立中央大學 | 非線性光學晶體及其製備方法 |
KR20180032336A (ko) * | 2016-09-22 | 2018-03-30 | 안동대학교 산학협력단 | 4가 양이온이 도입된 방사성 핵종 제거용 티타노실리케이트의 제조방법 |
WO2019006277A1 (en) * | 2017-06-29 | 2019-01-03 | Basf Se | PELLETS AND TABLETS STABLE IN WATER |
CN110152648B (zh) * | 2018-02-12 | 2022-01-04 | 中国石油化工股份有限公司 | 锡催化剂的制备方法、锡催化剂及其应用 |
ES2732747B2 (es) * | 2018-05-25 | 2020-07-02 | Consejo Superior Investigacion | Proceso catalitico para la produccion de hidrocarburos y compuestos aromaticos a partir de compuestos oxigenados presentes en mezclas acuosas |
CN110931785B (zh) * | 2019-12-11 | 2022-09-30 | 河南创力新能源科技股份有限公司 | 一种锌镍电池负极硅酸盐晶体材料的制备方法 |
CN110931786B (zh) * | 2019-12-11 | 2022-10-28 | 河南创力新能源科技股份有限公司 | 一种铁镍电池负极硅酸盐晶体材料的制备方法 |
CN113893842B (zh) * | 2021-09-24 | 2023-09-22 | 浙江工业职业技术学院 | 改性负载型氧化镁催化剂的制备方法及单甘酯生产工艺 |
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US5192519A (en) * | 1987-09-01 | 1993-03-09 | Exxon Research And Engineering Company | Substituted stannosilicates and preparation thereof |
US5508457A (en) | 1993-05-04 | 1996-04-16 | Engelhard De Meern B.V. | Esterification process |
US6074624A (en) * | 1997-04-22 | 2000-06-13 | Uop Llc | Titanostannosilicates and preparation thereof |
US5780654A (en) | 1997-04-22 | 1998-07-14 | Uop Llc | Titanostannosilicalites: epoxidation of olefins |
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AR095849A1 (es) | 2015-11-18 |
KR101773694B1 (ko) | 2017-08-31 |
MY194298A (en) | 2022-11-27 |
CA2909405A1 (en) | 2014-10-16 |
BR112015025752A2 (pt) | 2017-07-18 |
EP2984036B1 (en) | 2020-03-11 |
CN105339304B (zh) | 2018-02-13 |
KR20160006679A (ko) | 2016-01-19 |
CA2909405C (en) | 2018-11-20 |
JP6272986B2 (ja) | 2018-01-31 |
WO2014167524A1 (en) | 2014-10-16 |
US10814310B2 (en) | 2020-10-27 |
CN105339304A (zh) | 2016-02-17 |
TW201446651A (zh) | 2014-12-16 |
US20160067677A1 (en) | 2016-03-10 |
JP2016523789A (ja) | 2016-08-12 |
EP2984036A1 (en) | 2016-02-17 |
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