TW202406852A - 穩定化的氧化鋅材料 - Google Patents
穩定化的氧化鋅材料 Download PDFInfo
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- TW202406852A TW202406852A TW112115494A TW112115494A TW202406852A TW 202406852 A TW202406852 A TW 202406852A TW 112115494 A TW112115494 A TW 112115494A TW 112115494 A TW112115494 A TW 112115494A TW 202406852 A TW202406852 A TW 202406852A
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- Prior art keywords
- silicon
- zinc oxide
- modified zinc
- range
- oxide material
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 57
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 79
- 239000011787 zinc oxide Substances 0.000 title claims description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000008188 pellet Substances 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- 239000008187 granular material Substances 0.000 claims abstract description 11
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 44
- 239000003463 adsorbent Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 8
- -1 aluminum compound Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 150000003752 zinc compounds Chemical class 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 7
- 239000011872 intimate mixture Substances 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 238000005481 NMR spectroscopy Methods 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 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
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 150000003464 sulfur compounds Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 7
- 239000002594 sorbent Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000004110 Zinc silicate Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 2
- 235000019352 zinc silicate Nutrition 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920004459 Kel-F® PCTFE Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000995 aerosol-assisted chemical vapour deposition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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Abstract
本發明提供經矽改性之氧化鋅材料,其中該經矽改性之氧化鋅材料(i)具有至少50 m
2/g之BET表面積,(ii)具有0.001至0.5:1之範圍內之Si:Zn原子比率及(iii)係呈選自粒料、擠出物或顆粒之成型單元或單片擔體上之洗塗層之形式。該經矽改性之氧化鋅材料具有改良之抗熱燒結性且可用作觸媒或吸附劑材料。
Description
本發明係關於穩定化的氧化鋅材料,特定言之經矽改性之氧化鋅材料,其可用於觸媒或吸附劑中。
氧化鋅為有用的觸媒材料且已用於甲醇合成及費托(Fischer-Tropsch)觸媒中作為催化活性金屬(其通常各自為銅或鈷)之擔體材料。EP0261867 A1揭示使用矽酸鋅觸媒用於甲醇脫氫。氧化鋅亦已用作吸附材料用於自天然氣及煉油廠烴移除硫化氫。於此等用途中,已發現氧化鋅之表面積為其有效性之重要因素。然而,此等材料於使用中可遭受熱燒結,藉此氧化鋅微晶聚結,從而減少其表面積,此對材料之性能有影響。
申請者已出人意料地發現藉由沉澱製備之經矽改性之氧化鋅材料具有提高之熱穩定性。
因此,本發明提供經矽改性之氧化鋅材料,其適合於觸媒或吸附劑材料中使用,其中該經矽改性之氧化鋅材料(i)具有至少50 m
2/g之BET表面積,(ii)具有0.001至0.5:1之範圍內之Si:Zn原子比率及(iii)係呈選自粒料、擠出物或顆粒之成型單元或單片擔體上之洗塗層之形式。
本發明進一步提供包含經矽改性之氧化鋅材料之觸媒或吸附劑材料,製備該經矽改性之氧化鋅材料及觸媒或吸附劑材料之方法,及使用該觸媒或吸附劑材料之製程。
已知經矽摻雜之氧化鋅材料用於製備透明導電薄膜。例如,此等材料述於Darr, J. A.等人,
Si-doped zinc oxide transparent conducting oxides; nanoparticle optimisation, scale-up and thin film deposition, J. Mater. Chem. C, (2017), 5, 8796;Potter, D. B.等人,
Transparent conducting oxide thin films of Si doped ZnO prepared by aerosol assisted CVD. RSC Adv. 7 (2017)及Luo, J. T.等人,
The electrical, optical and magnetic properties of Si doped ZnO films. Appl. Surf. Sci. 258, 2177 2181 (2012)中。於此類材料中,引入矽以增加材料之相對載荷密度,其中小心控制摻雜劑含量以最佳化導電性。該等材料用作透明薄膜及因此材料之熱穩定性及表面積非重要因素。此外,本發明提供呈成型微粒形式之觸媒或吸附劑,其不透明,且其中該等導電性質不相關。
增加之穩定性所提供之優點包括觸媒或吸附劑穩定性提高、更長觸媒或吸附劑壽命、觸媒或吸附劑體積減小及製程效率提高之潛力。
「吸附劑」包括吸附劑及吸收劑。
經矽改性之氧化鋅材料可為鋅及矽之任何混合氧化物。矽可以與氧化鋅之混合氧化物存在,但是較佳地將矽併入氧化鋅晶格中。Si:Zn原子比率係於0.001至0.5:1之範圍內,但是較佳地於0.01至0.1:1之範圍內。以SiO
2表示之經矽改性之氧化鋅材料之Si含量可為至多約10重量%。適宜穩定化的氧化鋅材料可具有0.019:1、0.021、0.037、0.044:1或0.083:1之Si:Zn原子比率。
經矽改性之氧化鋅可僅由Si及Zn之氧化物組成。然而,若所需,則可存在其他氧化物以調適觸媒或吸附劑材料之物理性質。例如,可以水合形式存在之氧化鋁可以材料之至多約20重量%之量存在。
材料中之金屬氧化物含量在無損失之基礎上適宜測定,以移除由殘留碳酸鹽化合物及水分之量之差異引起的可變性。在無損失基礎上測定氧化矽含量之特別適宜方法為將材料於空氣中加熱至900℃持續2小時以在量測氧化物含量之前移除揮發物。材料之矽含量可使用任何適宜元素分析技術,諸如使用已知技術之X-射線熒光光譜法(XRF)測定。
經矽改性之氧化鋅材料係呈選自粒料、擠出物或顆粒之成型單元之形式,或經矽改性之氧化鋅可作為單片擔體上之洗塗層施覆。
該等粒料、擠出物或顆粒較佳地具有1至25 mm之範圍內之長度及寬度,其中縱橫比(最長尺寸除以最短尺寸) ≤ 4。當用作觸媒或吸附劑容器中之成型單元之固定床時,粒料及擠出物可有用地具有兩個或更多個圍繞其外周之凹槽、溝槽或凸起以提高幾何表面積及減少壓降。此外,粒料可具有一或多個通孔以進一步提高幾何表面積及減少壓降。
單片擔體為包含複數個平行通道之擠出形狀或結構。單片可含有藉由薄壁限定及分離之幾十個、幾百個或甚至幾千個平行通道或通孔,諸如呈蜂窩結構。通道可為正方形、六角形、圓形或其他形狀。孔密度可為30至200個/cm
2,及分離壁可為0.05至1.0 mm厚。單片可具有10至100 cm之範圍內之寬度或橫截面及10至100 cm之範圍內之長度。與用於隨機填裝之固定床中之粒料、顆粒及擠出物相比,製程流體經該固定床通過,單片係設置於容器中使得製程流體被引導穿過通道。橫截面中之開口空間可為前面積之70至87%,因此對穿過孔之氣體流動之抗性低,其最小化迫使氣體穿過結構所消耗之能量。經矽改性之氧化鋅作為塗層施覆在單片擔體表面上。
不同成型方法對成型物品之表面積、多孔性及孔隙結構具有影響及繼而此通常對吸附特性及體積密度具有影響。因此,呈經模製粒料之形式之成型單元之床可展示相對寬的吸收前沿,然而經造粒聚結物之床可具有窄得多吸收前沿:此使能更接近理論吸收容量。換言之,聚結物一般具有較粒料或擠出組合物更低體積密度。
該成型單元較佳地為粒料,因為此提供製備高強度材料之能力。因此,該經矽改性之氧化鋅可經受造粒,視情況於預壓縮粉末後,其可改善造粒製程。粒料可適宜為圓柱形粒料。圓柱形粒料可具有2.5至10 mm,較佳地3至10 mm之範圍內之直徑及0.5至2.0之範圍內之縱橫比(長度/直徑)。或者,該成型單元可呈環之形式。於特別適宜實施例中,該成型單元係呈圓柱體之形式,該圓柱體具有兩個或更多個,較佳地3至7個沿著其長度運行之溝槽。
期望地製備粒料,特定言之具有平坦或圓頂端之圓柱形粒料,其粒料密度在1.8至2.4 g/cm
3,較佳地1.9至2.3 g/cm
3之範圍內。粒料密度可容易藉由自粒料尺寸計算體積及量測其重量來測定。隨著密度增加,成型單元之間隙體積減少,其繼而降低反應氣體之穿透性。因此,針對密度> 2.4 g/cm
3,反應性可低於最佳。針對密度< 1.8 g/cm
3,抗壓強度可不足夠用於長期使用。
該經矽改性之氧化鋅材料之BET表面積為至少50 m
2/g,及較佳地≥ 55 m
2/g,更佳地≥ 60 m
2/g,最佳地≥ 65 m
2/g。可達成至多約130 m
2/g之BET表面積。BET表面積藉由氮物理吸附使用確立方法(諸如ASTM方法D 3663-03)測定。BET表面積在經壓碎粒料上適宜測定。未成型粉末之BET表面積更高,及可於60至150 m
2/g範圍內。據信,此極高BET表面積部分由於製備方法而產生並提供高度分散觸媒及高容量吸附劑之穩定擔體。
該經矽改性之氧化鋅可具有於約-60 ppm至-80 ppm之範圍內之一或多個
29Si固態核磁共振(SSNMR)信號,參考針對在-91.2 ppm處之高嶺石。
該經矽改性之氧化鋅可具有10 nm或更少,較佳地8 nm或更少之微晶尺寸,如藉由XRD所測定。
該經矽改性之氧化鋅可藉由可溶性鋅前體使用沉澱方法之沉澱產生。因此,本發明包括一種製備經矽改性之氧化鋅材料之方法,其包括以下步驟:
(i)於水性介質中形成包含鋅化合物之沉澱物及二氧化矽之密切混合物,其中該二氧化矽由可溶性矽酸鹽或膠體二氧化矽提供,
(ii)將該密切混合物回收、洗滌及乾燥以形成經乾燥之組合物,及
(iii)藉由煅燒並藉由造粒、擠出或製粒使該經乾燥之組合物成型來形成成型單元,或藉由將該經乾燥之組合物或經煅燒之組合物作為洗塗層施覆至單片擔體。
該可溶性鋅前體可為任何適宜可溶性鋅鹽,但是較佳地為硝酸鋅,使得沉澱之副產物可容易藉由煅燒移除。
該矽可衍生自氧化矽溶膠,或自水溶性矽化合物,諸如鹼金屬矽酸鹽,例如,矽酸鉀。亦可使用有機矽酸鹽,包括烷基矽酸鹽,諸如四甲基正矽酸鹽及四乙基正矽酸鹽。二氧化矽使氧化鋅微晶在使用期間穩定對抗熱燒結及從而與不使用二氧化矽之觸媒或吸附劑相比提高觸媒或吸附劑中之氧化鋅之長期活性。
沉澱物可藉由使含有一或多種可溶性鋅化合物之酸性水性溶液與水性鹼性沉澱劑溶液混合來製備。該鹼性沉澱劑可為鹼金屬碳酸鹽、鹼金屬氫氧化物或其混合物。該鹼性沉澱劑較佳地包括鹼金屬碳酸鹽。可使用鉀或鈉沉澱劑,但是鉀沉澱劑係較佳,因為其較鈉更容易藉由洗滌自經沉澱之組合物移除。鹼性沉澱劑與酸性溶液中之鋅化合物之反應引起含鋅沉澱物之沉澱。沉澱可在10至80℃之範圍內之溫度下進行,但是較佳地在升高之溫度下(即,40至80℃,更佳地50至80℃,尤其60至80℃之範圍內)進行,因為發現此產生小微晶,該等微晶於煅燒後提供更高表面積。
可將酸性及鹼性溶液一個接一個添加至沉澱容器中,但是較佳地同時添加至沉澱容器中使得沉澱容器之pH維持在6與9之間,較佳地6與8之間,之後將所得共沉澱漿液較佳地於單獨老化容器中在10至80℃之範圍,較佳地40至80℃,更佳地50至80℃,尤其60至80℃之範圍內之溫度下老化,以形成鋅之結晶羥基碳酸鹽化合物。沉澱漿液之老化可以分批或半連續程序進行,藉此將經沉澱材料之水性漿液保持於一或多個攪拌容器中持續選定時間段。沉澱物於液體中之懸浮可僅藉由攪拌,攪拌動力取決於粒子沉降之傾向及黏度。或者,沉澱漿液可於脈衝流動反應器中老化,如WO2008/047166中所述,其以引用的方式併入本文中。可選擇共沉澱漿液之反應及後處理條件以產生例如紅鋅礦(ZnO)或矽鋅礦(Zn
2SiO
4)型之明確結晶化合物,其可藉由X-射線繞射(XRD)測定。
若使用氧化矽溶膠作為二氧化矽來源,則可將其添加至酸性金屬溶液中及/或添加至沉澱容器及/或老化容器中。特別適宜氧化矽溶膠包括具有10至20 nm之範圍內之粒度之膠體分散二氧化矽的水性分散液。分散液之pH可為< 7,較佳地於2至4之範圍內。溶膠中之二氧化矽濃度可為100至400 g/公升。此等溶膠以商品名Nissan Chemicals Snowtex-O及Grace Ludox HAS可得。
若使用水溶性矽酸鹽(諸如鹼金屬矽酸鹽)作為二氧化矽來源,則可將其添加至鹼性沉澱劑溶液及/或沉澱容器及/或老化容器中。適宜鹼金屬矽酸鹽為可溶性矽酸鈉及可溶性矽酸鉀。此等鹼性矽酸鹽可以商品名PQ Corporation Kasil
TM1、PQ Corporation Kasolv
TM16、Zaclon LLC Zacsil
TM18或Evonik Zeopol
TM可得。在鹼金屬矽酸鹽用作二氧化矽來源之情況下,鹼金屬矽酸鹽中之鹼金屬較佳地匹配沉澱劑溶液中之鹼金屬,因為此改善大規模洗滌、回收及廢物溶液之再加工。鹼金屬矽酸鹽溶液中之SiO
2之量可於15至35重量%之範圍內。
若有機矽酸鹽(諸如式Si(OR)
4之烷基矽酸鹽,其中R = C1至C4烷基)用作二氧化矽來源,則因為當與水接觸時,其將水解,所以較佳地一旦於沉澱及/或老化容器中形成,就將其直接添加至沉澱物中。
若所需,則氧化鋁溶膠亦可視情況包含於沉澱中。氧化鋁溶膠為氫氧化鋁(包括水鋁石及僞水鋁石)之水性膠體分散液。分散液之pH可適宜地<7,較佳地於3至4之範圍內。可將氧化鋁溶膠適宜添加至沉澱容器中。可將氧化鋁溶膠與酸性金屬溶液或鹼性沉澱劑溶液分開添加至沉澱容器中。氧化鋁溶膠係市售或可藉由已知方法製備。溶膠中之氧化鋁濃度可為30至200 g/公升。特別適宜氧化鋁溶膠包括膠體分散之水鋁石的分散液,當分散時,具有5至200 nm,較佳地5至100 nm,更佳地5至50 nm之範圍內之D50平均粒度。此等溶膠係市售。
除了氧化鋁溶膠或替代地,若所需,則可將可溶性鋁化合物(諸如硝酸鋁或鋁酸鈉)添加至沉澱容器中。例如,硝酸鋁可包含於酸性水性含鋅溶液中,而鋁酸鈉可包含於鹼性沉澱劑溶液中。
若所需,則選自Fe、Co、K、Cs、Mg、Ti、V、Cr、Mn、Mo或Ni之金屬之一或多種可溶性化合物可包含於酸性水性含鋅溶液或鹼性沉澱劑溶液中。
於沉澱及老化後,該密切混合物(例如)藉由使用已知方法(諸如過濾、傾析或離心)分離母液來回收,並洗滌以移除殘留之可溶性鹽。
在回收之前,密切混合物之洗滌可使用習知設備(諸如板式及框式壓濾機)例如藉由將混合物於無鹽水中再漿化一或多次或藉由使用Artisan增稠器或Shiver增稠器動態錯流過濾來進行。針對某些觸媒,諸如甲醇合成觸媒,回收及經乾燥之混合物之鹼金屬含量應期望地降低至低於0.2重量%,較佳地低於0.1重量%,在無損失基礎上以經乾燥材料上之各自鹼金屬氧化物計算,因為鹼金屬可對觸媒之性能有害。將回收密切混合物乾燥以形成經乾燥之組合物。乾燥可包括將潮濕混合物歷時延長時間段以離散階段或連續加熱直至達到最大溫度。乾燥步驟可在90至150℃,較佳地90至130℃之範圍內之溫度下在空氣或惰性氣體下使用習知乾燥設備,諸如於烘箱、旋轉乾燥器、噴霧乾燥器或相似設備中進行。若所需,則可包含乾燥步驟作為煅燒步驟之第一部分。
該經乾燥之組合物通常呈粉末之形式。平均粒度(如由篩分粒級,即,重量平均粒度所測定)可於10至1000 μm (微米)之範圍內。
該經乾燥之組合物可包含一或多種鋅、二氧化矽及視情況氧化鋁之羥基碳酸鹽,其可呈水合形式。
該經乾燥之組合物可經煅燒及成型以形成觸媒或吸附劑材料。該經乾燥之組合物可經煅燒(即,加熱)以在成型之前將沉澱之鋅化合物轉化成氧化鋅或較不佳地,該經乾燥之組合物可在煅燒之前形成成型單元。此後者方法較不佳,因為對成型單元之煅燒一般降低其強度及使其更難以控制粒料密度。因此,經煅燒產品較佳地呈粉末形式,然後使其成型以形成粒料、擠出物或顆粒。
煅燒可在225至450℃,較佳地250至400℃,更佳地275至350℃之範圍內之溫度下進行。更低溫度提供更低穩定性,然而更高溫度可減少初始表面積。煅燒可在空氣或惰性氣體(諸如氮氣)下進行,但是空氣或另一不含氧氣體係較佳。
粒料、擠出物或顆粒係自粉末化組合物形成。成型單元之成型可藉由造粒、擠出或製粒。因此,成型可包括以下步驟:(i)將粉末化材料,視情況與造粒助劑(諸如石墨、硬脂酸鋁或硬脂酸鎂)進料至造粒模具中,(ii)將粉末壓縮以形成成型單元。或者,擠出物可藉由迫使自粉末化組合物與水及擠出助劑形成之糊劑透過模具,接著將自模具萌出之材料切割成短長度形成。或者,顆粒可藉由將粉末組合物與不足以形成漿液或糊劑之少量液體(諸如水)混合,及然後引起組合物於製粒機中聚結成大致球形顆粒形成。所添加之液體之量將取決於組分之多孔性及潤濕性,但是可為0.1至0.5 ml/g混合物。可使用水性或非水性液體,但是水係較佳。適宜造粒、擠出及製粒裝置係市售。
或者,經乾燥之組合物或經煅燒之組合物可呈單片擔體之洗塗層施覆。洗塗層可自經乾燥或經煅燒之經矽改性之氧化鋅粉末使用已知方法,例如藉由將該粉末分散於水性介質中以形成漿液,然後藉由將單片擔體用該漿液浸漬或噴霧而將該漿液施覆至單片擔體以形成經塗覆單片,接著將經塗覆單片乾燥及視情況煅燒來製備。
該經矽改性之氧化鋅可用作觸媒擔體。因此,本發明包括包含支持催化活性金屬或金屬化合物之經矽改性之氧化鋅的觸媒。催化活性金屬或金屬化合物可浸漬入成型觸媒擔體及/或在成型觸媒擔體上沉積。催化活性金屬可為Na、K、Mg、Ca、Ba、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Sn、Sb、La、Hf、W、Re、Ir、Pt、Au、Pb或Ce中之一或多者或其化合物。
觸媒可使用確立浸漬或沉積方法製造。
於一些實施例中,該觸媒包括已浸漬入或沉積至經矽改性之氧化鋅之一或多種過渡金屬(諸如鎳、銅、鈷或鐵)及/或貴金屬(諸如鉑、鈀、銠、釔或釕)。
此等觸媒中之過渡金屬及貴金屬含量可為至多85重量%,但是較佳地於1至60重量%之範圍內。
含有催化活性金屬或金屬化合物之觸媒可經受各種處理,諸如煅燒以形成金屬氧化物,利用含有氫氣及/或一氧化碳之氣體物流還原以將金屬氧化物還原成元素形式或例如利用硫化氫硫化以形成金屬硫化物,及致使其於使用中活性。後處理可場外或原位,即,在使用其之反應器中安裝之前或之後進行。
根據本發明製備之觸媒可應用於任何非均相催化製程,但是較佳地應用於固定床製程,更佳地使用氣態反應物之固定床製程。因此,催化製程包括使反應物混合物,較佳地氣態反應物混合物與觸媒在實現催化反應之條件下接觸。催化製程可選自加氫處理,包括加氫脫硫、氫化、蒸汽重組(包括預先重組、催化蒸汽重組、自熱重組及二次重組)及用於離子之直接還原、催化部分氧化、水-氣轉換(包括等溫轉換)、酸轉換、低溫轉換、中間溫度轉換、中溫轉換及高溫轉換反應、甲烷化、藉由費托反應之烴合成、甲醇合成、氨水合成、氨水氧化及氧化氮分解反應之重組製程。較佳氣態反應物包括氫氣,例如包含氫氣及二氧化碳及一氧化碳中之一或多者之合成氣體。
該經矽改性之氧化鋅可用作吸附劑,或用作吸附劑之組分,或吸附劑前體。該經矽改性之氧化鋅吸附劑可用於捕獲來自製程流體(諸如天然氣)之硫化合物,諸如硫化氫。視情況經鹼金屬化合物處理之經矽改性之氧化鋅吸附劑可用於捕獲來自製程流體(諸如煉油廠物流)之氯化物,諸如氯化氫。於利用硫化合物(諸如硫化氫或元素硫)處理後之經矽改性之氧化鋅可用於捕獲來自經污染氣體或液體流體物流之重金屬(諸如汞及砷)。
於一些實施例中,該吸附劑可包含浸漬入或沉積至經矽改性之氧化鋅之一或多種鹼金屬、鹼土金屬或過渡金屬(諸如鎳、銅、鈷或鐵)。
於實例中,XRD係使用壓製至X-射線透明樣品架及裝載至Bruker D8 Advance粉末繞射儀中之經精細研磨樣品進行。該儀器係以巴拉格-佈倫塔諾(Bragg-Brentano) (反射)模式使用在40 kV及40 mA下操作之銅X-射線管與0.2 mm Ni濾波器操作以移除CuKβ線。繞射圖通常在10至130° 2θ範圍利用0.02°步長及1秒/步收集。相識別係使用Bruker Eva v4.2.1軟體及ICDD PDF4+結構資料庫完成。Pawley擬合(Bruker Topas v4.2)係用於計算基於該(等)選定相之已知反射之模型。微晶尺寸量測係基於假設各向同性峰加寬之積分寬度法。
於實例中,BET表面積係於乾燥後在碎砂(0.6至1.0 mm之粒子)上藉由使用Micromeritics 2420 ASAP物理吸附分析儀之氮氣物理吸附根據ASTM方法D 3663-03;表面積之標準試驗測定。氮氣係用作吸附質及在液氮溫度(77K)下進行量測。取氮氣分子之橫截面積為16.2Å
2。在分析之前藉由在最佳溫度下用乾燥氮氣淨化最少1小時將樣品除氣。在0.05至0.20 P/Po (包含端值)之相對壓力區域內獲得五個相對壓力/體積數據對。各點之平衡時間為10秒。
於實例中,固態
29Si SSNMR光譜係以9.4T (400 MHz)之靜態磁場強度在Bruker Advance Neo控制台上使用TopSpin 4.0軟體獲取。使用大口徑Bruker 4mm BB/1H WVT MAS探針,調整至79.51 MHz及參考在-91.2 ppm處之高嶺石。將粉末化樣品填裝至具有Kel-F蓋之氧化鋯MAS轉子。
實例 1 :製備經矽改性之氧化鋅具有0.004:1之Si:Zn原子比率之經矽改性之氧化鋅樣品係藉由含有所需量之二氧化矽溶膠之硝酸鋅溶液與碳酸鉀溶液在6.3至6.8之pH及65至70℃之溫度下之沉澱來製備。將所得沉澱物在65至70℃下老化至多2小時,過濾,用去礦物質水洗滌,乾燥及於空氣中在300℃下煅燒6小時。將所得粉末壓實成粒料,隨後將其壓碎成適用於測試之砂粒子。
實例 2具有原子比率Si:Zn:0.019:1之經矽改性之氧化鋅樣品觸媒係如實例1中所述製備。
實例 3具有原子比率Si:Zn:0.044:1之經矽改性之氧化鋅樣品觸媒係如實例1中所述製備。
實例 4具有原子比率Si:Zn:0.083:1之經矽改性之氧化鋅樣品觸媒係如實例1中所述製備。
比較例 1氧化鋅樣品係藉由將硝酸鋅溶液與碳酸鉀溶液在6.3至6.8之pH及65至70℃之溫度下之沉澱來製備。不包含矽化合物。將所得沉澱物在65至70℃下老化2小時,過濾,用去礦物質水洗滌,乾燥及於空氣中在300℃下煅燒6小時。將所得粉末壓實成粒料,隨後將其壓碎成適用於測試之砂粒子。
實例 5 :穩定性測試。將來自實例1至4及比較例1之造粒材料各者壓碎及過篩成0.6至1.0 mm之粒度級。老化實驗使用裝載至高壓反應器系統中之新製樣品及用含有合成氣之物流處理。此等實驗係在305℃及85巴(bar)下利用具有以下近似組成之流動合成氣體進料進行330小時:77.8體積% H
2,3.7體積% CO,4.4體積% CO
2,2.6體積% H
2O及3.2體積% CH
3OH。於老化後,排放樣品及使用粉末X-射線繞射(XRD)、
29Si固態核磁共振(SSNMR)及BET表面積量測表徵。
各種樣品之微晶尺寸(均以新製狀態及於老化後)係使用XRD譜線變寬分析使用以下討論之方法評價。所獲得之結果於表1中闡述及於圖1中顯示,該圖1顯示新製樣品及老化樣品二者之針對Si:Zn原子比率繪製之微晶尺寸。針對未經改性之ZnO樣品,由於所述老化處理,微晶尺寸自10 nm增加至26 nm。然而,在添加Si下,發現觀察到之燒結程度急劇減少。在所評價之負載範圍內,抗燒結性隨著負載增加而改善,使得在所測試之最高負載下,當將新製樣品與老化樣品相比時,觀察到微晶尺寸之極小變化。
除了微晶尺寸量測,表面積亦使用BET方法量測。此等結果列於表1中,與對應XRD數據一起。表面積量測再次顯示,經Si改性樣品顯著更高之抗燒結性,其中穩定性隨著負載增加而改善,與XRD數據良好一致。
經老化之0.019:1 Si:ZnO樣品(實例2)之對應
29Si SSNMR光譜示於圖2中。在-66 ppm處觀察到信號,與Si原子併入ZnO晶格中形成矽酸鋅物質一致。
表1:
*兩次量測之平均值
樣品 | Si:Zn原子比率 | XRD域尺寸新製(nm) | XRD域尺寸老化(nm) | BET新製(m 2/g) | BET老化(m 2/g) |
實例1 | 0.004 | 10.0 | 14.6 | 53 | 27 |
實例2 | 0.019 | 7.5 | 10.0 | 70 | 47 |
實例3 | 0.044 | 6.4 | 7.6 | 70 | 59 |
實例4 | 0.083 | 5.4 | 5.7 | 71 | 62 |
比較例1 * | - | 10.3 | 26.2 | 43 | 16 |
實例 6具有0.021:1之Si:Zn原子比率之經矽改性之氧化鋅樣品係藉由硝酸鋅溶液與含有所需量之矽酸鈉之碳酸鈉溶液在6.3至6.9之pH及65至70℃之溫度下之沉澱來製備。將所得沉澱物在65至70℃下老化多至2小時,過濾,用去礦物質水洗滌,乾燥及於空氣中在300℃下煅燒6小時。將所得粉末壓實成粒料,隨後將其壓碎成適用於測試之砂粒子。
實例 7具有原子比率Si:Zn:0.037:1之經矽改性之氧化鋅樣品觸媒係如實例6中所述製備。
實例 8 :穩定性測試。將來自實例6及7及比較例1之經造粒材料壓碎及過篩成0.6至1.0 mm之粒度級。老化實驗使用裝載至高壓反應器系統中之新製樣品及用含有合成氣之物流處理。此等實驗係在220℃及27.5巴下利用具有以下近似組成之流動合成氣進料進行330小時:36.7體積% H
2,2.6體積% CO,10.6體積% CO
2,33.3體積% H
2O及其餘為N
2。於老化後,排放樣品及使用粉末X-射線繞射(XRD)表徵。
各種樣品之微晶尺寸(均以新製狀態及於老化後)係使用XRD譜線變寬分析使用以上討論之方法評價。所獲得之結果於表2中闡述。針對未經改性之ZnO樣品,由於所述老化處理,微晶尺寸自10 nm增加至23 nm。然而,在添加Si下,材料於老化處理後能保留小得多的微晶尺寸。在所評價之負載範圍內,抗燒結性再次隨著負載增加而改善。
表2:
樣品 | Si:Zn原子比率 | XRD域尺寸新製(nm) | XRD域尺寸老化(nm) |
實例6 | 0.021 | 5.5 | 10 |
實例7 | 0.037 | 4.0 | 7.4 |
比較例1 | - | 10.3 | 22.6 |
現參考下列實例及參考圖1及圖2進一步描述本發明。
圖1為描述針對Si:Zn原子比率繪製之經矽改性之氧化鋅在老化之前及之後之微晶尺寸的圖;及
圖2為根據本發明之經矽改性之氧化鋅之
29Si NMR光譜的描述。
Claims (25)
- 一種適合於觸媒或吸附劑材料中使用之經矽改性之氧化鋅材料,其中該經矽改性之氧化鋅材料(i)具有至少50 m 2/g之BET表面積,(ii)具有0.001至0.5:1之範圍內之Si:Zn原子比率及(iii)係呈選自粒料、擠出物或顆粒之成型單元或單片擔體上之洗塗層之形式。
- 如請求項1之經矽改性之氧化鋅材料,其中該Si:Zn原子比率係於0.01至0.1:1之範圍內。
- 如請求項1或請求項2之經矽改性之氧化鋅材料,其中表示為SiO 2之該Si含量為至多10重量%。
- 如請求項1至3中任一項之經矽改性之氧化鋅材料,其中該矽經併入該氧化鋅晶格中。
- 如請求項1至4中任一項之經矽改性之氧化鋅材料,其進一步包含量為該材料之至多20重量%之氧化鋁或水合氧化鋁。
- 如請求項1至5中任一項之經矽改性之氧化鋅材料,其中該粒料、擠出物或顆粒具有各在1至25 mm之範圍內之長度及寬度,其中縱橫比≤ 4。
- 如請求項1至5中任一項之呈單片擔體上之洗塗層之形式的經矽改性之氧化鋅材料,其中該單片擔體具有各在10至100 cm之範圍內之長度及寬度。
- 如請求項1至7中任一項之經矽改性之氧化鋅材料,其中該BET表面積≥ 55 m 2/g,較佳地≥ 60 m 2/g,更佳地≥ 65 m 2/g。
- 如請求項1至8中任一項之經矽改性之氧化鋅材料,其具有於約-60 ppm至-80 ppm之範圍內的一或多個 29Si固態核磁共振(SSNMR)信號,參考針對在-91.2 ppm處之高嶺石。
- 一種製備如請求項1至9中任一項之經矽改性之氧化鋅材料的方法,其包括以下步驟: (i)於水性介質中形成包含鋅化合物之沉澱物及二氧化矽之密切混合物,其中該二氧化矽由可溶性矽酸鹽或膠體二氧化矽提供, (ii)將該密切混合物回收、洗滌及乾燥以形成經乾燥之組合物,及 (iii)藉由煅燒及藉由造粒、擠出或製粒使該經乾燥之組合物成型來形成成型單元,或藉由將該經乾燥之組合物或經煅燒之組合物作為洗塗層施覆至單片擔體。
- 如請求項10之方法,其中該鋅化合物之沉澱物及二氧化矽藉由將含有鋅化合物之酸性水性溶液與水性鹼性沉澱劑溶液於沉澱容器中混合來製備。
- 如請求項11之方法,其中該鋅化合物為硝酸鋅及該鹼性沉澱劑包括鹼金屬碳酸鹽。
- 如請求項11或請求項12之方法,其中該沉澱在40至80℃,較佳地50至80℃,尤其60至80℃之範圍內之溫度下進行。
- 如請求項11至13中任一項之方法,其中將該沉澱物於單獨老化容器中在10至80℃之範圍內,較佳地40至80℃,更佳地50至80℃,尤其60至80℃之範圍內之溫度下老化。
- 如請求項10至14中任一項之方法,其中該二氧化矽衍生自氧化矽溶膠及/或水溶性矽化合物(諸如鹼金屬矽酸鹽)或有機矽酸鹽。
- 如請求項11或請求項14之方法,其中將氧化矽溶膠添加至該酸性水性溶液中及/或添加至該沉澱容器及/或該老化容器中。
- 如請求項11或請求項14之方法,其中將鹼金屬矽酸鹽添加至該鹼性沉澱劑溶液中及/或至該沉澱容器及/或老化容器中。
- 如請求項11至17中任一項之方法,其中將氧化鋁溶膠或可溶性鋁化合物添加至該沉澱容器中。
- 如請求項10至18中任一項之方法,其中該乾燥步驟係在90至150℃之範圍內之溫度下進行。
- 如請求項10至19中任一項之方法,其中該煅燒係在225至450℃,較佳地250至400℃,更佳地275至350℃之範圍內之溫度下進行。
- 如請求項10至20中任一項之方法,其中該煅燒係在藉由造粒、擠出或製粒成型之前進行。
- 一種觸媒,其包含如請求項1至9中任一項或如請求項10至21中任一項製備之經矽改性之氧化鋅,其支持催化活性金屬或金屬化合物。
- 一種使用如請求項22之觸媒之催化方法。
- 一種吸附劑或吸附劑前體,其包含如請求項1至9中任一項或如請求項10至21中任一項製備之經矽改性之氧化鋅。
- 一種使用如請求項24之吸附劑或吸附劑前體的吸附劑方法,其用以捕獲來自製程流體之硫化合物或氯化合物或捕獲來自經污染氣體或液體流體物流之重金屬。
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JP2506589B2 (ja) * | 1991-08-24 | 1996-06-12 | 工業技術院長 | 排ガス中の窒素酸化物の除去方法 |
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