CN103638990A - 用于制造含锡催化剂的制备方法 - Google Patents
用于制造含锡催化剂的制备方法 Download PDFInfo
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- CN103638990A CN103638990A CN201310578990.2A CN201310578990A CN103638990A CN 103638990 A CN103638990 A CN 103638990A CN 201310578990 A CN201310578990 A CN 201310578990A CN 103638990 A CN103638990 A CN 103638990A
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- Prior art keywords
- metal
- metal precursor
- carrier
- catalyst
- tin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 274
- 239000002184 metal Substances 0.000 claims abstract description 274
- 239000002243 precursor Substances 0.000 claims abstract description 185
- 238000000034 method Methods 0.000 claims abstract description 65
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001868 water Inorganic materials 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 65
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 33
- 239000012876 carrier material Substances 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- 238000007598 dipping method Methods 0.000 claims description 23
- 230000009467 reduction Effects 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 229940039748 oxalate Drugs 0.000 claims description 14
- 235000012241 calcium silicate Nutrition 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052762 osmium Inorganic materials 0.000 claims description 7
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 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
- 239000010931 gold Substances 0.000 claims description 6
- 239000011133 lead Substances 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052716 thallium Inorganic materials 0.000 claims description 6
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- FZZGRYCPJKLCHD-UHFFFAOYSA-N C(C(=O)O)(=O)O.[P] Chemical compound C(C(=O)O)(=O)O.[P] FZZGRYCPJKLCHD-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical group [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- 230000004048 modification Effects 0.000 description 35
- 238000012986 modification Methods 0.000 description 35
- 239000003795 chemical substances by application Substances 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 239000003607 modifier Substances 0.000 description 23
- 239000002253 acid Substances 0.000 description 18
- 238000005984 hydrogenation reaction Methods 0.000 description 18
- 238000005470 impregnation Methods 0.000 description 17
- 150000002739 metals Chemical class 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 229910052918 calcium silicate Inorganic materials 0.000 description 10
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 229910004762 CaSiO Inorganic materials 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000003891 oxalate salts Chemical class 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- MSMNVXKYCPHLLN-UHFFFAOYSA-N azane;oxalic acid;hydrate Chemical compound N.N.O.OC(=O)C(O)=O MSMNVXKYCPHLLN-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 238000002242 deionisation method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 241001466460 Alveolata Species 0.000 description 1
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- 241001077391 Cynea sp. Burns04 Species 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
- 229910020018 Nb Zr Inorganic materials 0.000 description 1
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- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
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- 229910052777 Praseodymium Inorganic materials 0.000 description 1
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- PXRKUDNGLSVCID-UHFFFAOYSA-R [NH4+].[NH4+].[NH4+].[NH4+].[Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PXRKUDNGLSVCID-UHFFFAOYSA-R 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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Abstract
一种制备催化剂的方法,该方法包括以下步骤:使载体与包含草酸锡、第二金属前体、增溶剂例如草酸铵和水的混合金属前体接触形成浸渍的载体,以及在有效除去至少大部分重量的水以及将来自草酸锡的锡和来自第二金属前体的第二金属还原从而形成催化剂的条件下,加热所述浸渍的载体。
Description
本申请是国际申请日为2011年1月31日、申请号为201180002011.8、发明名称为“用于制造含锡催化剂的制备方法”的发明专利申请的分案申请。
优先权要求
本申请要求2010年2月1日提交的美国申请No.12/697,781的优先权,通过引用将其全部内容和披露并入本文。
发明领域
本发明涉及制造催化剂的方法,所述催化剂可以用于例如羧酸如乙酸的加氢。更具体地,本发明涉及使用增溶剂来形成用于生产含锡加氢催化剂的混合金属前体,任选以一步载体浸渍处理。
发明背景
长期需要将乙酸转化为乙醇的经济上可行的方法,所述乙醇可以按其自身使用或随后转化为一种或多种衍生产品例如乙烯。乙烯是重要的大宗原料,因为可将其转化为聚乙烯、乙酸乙烯酯、乙酸乙酯或任何许多其它化学产品例如单体和聚合物产品。波动的天然气和原油价格促使由其按照常规生产的乙烯的成本波动。因此,当油价上升时对替代的乙烯来源的需要尤其明显。
用于还原羧酸例如乙酸和其它含羰基化合物的催化方法已得到广泛研究。文献充满了用于这类方法的催化剂、载体和操作条件的多种组合。例如,T.Yokoyama等评述了各种羧酸在金属氧化物上的还原,其中作者概述了用于多种羧酸的加氢催化剂的开发尝试中的一些。(Yokoyama,T.;Setoyama,T.“Fine chemicals throughheterogeneous catalysis.Carboxylic acids and derivatives,”2001,370-379,通过引用将其全文并入本文)。然而,用常规催化剂和载体难以获得所需的加氢产物。在一些情形中,例如,乙酸到所需加氢产物的转化率低,而在其它情形中,基于所转化乙酸的量的所需产物的选择性不合期望地低。
作为该问题的一个潜在解决方案,提出多金属如双金属催化剂用于催化乙酸加氢以形成产物例如乙醇。作为一个特定实例,在乙醇形成中利用包含锡和第二金属的双金属催化剂。这些双金属催化剂典型地通过以下形成:使多个金属前体例如锡前体和第二金属前体与合适的载体分多个接触步骤接触并且还原所述金属前体(典型地是在分开的加热步骤中),以便用两种金属浸渍所述载体。然而,这类合成方法由于需要多个浸渍步骤而是不期望和低效率的。
用于形成双金属催化剂的简化方法包括在单浸渍步骤中用多个金属前体浸渍载体,接着进行加热以将金属前体还原为它们相应的金属。然而,这类单步骤浸渍方法并不适合于所有金属前体,这是因为一些金属前体彼此不相容。锡前体例如草酸锡尤是如此,其通常具有低溶解性并且与水基金属前体不相容。
因此,需要用于形成包括锡的双金属催化剂的简化且有效的方法。
发明概述
本发明涉及用于形成在载体上包含锡和第二金属的催化剂,例如加氢催化剂的方法。本发明还涉及用于在不需要卤化的金属前体(即氯化物)的情况下形成这类催化剂的混合金属前体组合物。
在一个实施方案中,例如,本发明涉及制备催化剂的方法,该方法包括以下步骤:(a)任选通过始润浸渍技术,使载体与包含草酸锡、第二金属前体、增溶剂和水的反应产物的混合金属前体接触形成浸渍的载体;和(b)在有效除去至少大部分重量的水以及将来自草酸锡的锡和来自第二金属前体的第二金属还原且形成催化剂的条件下,将所述浸渍的载体加热到例如120℃-200℃的温度。加热步骤优选至少部分地在还原性气氛下进行。例如,加热步骤任选包括干燥步骤和还原步骤。该方法任选还包括通过将草酸锡、第二金属前体、增溶剂和水合并来形成混合金属前体的步骤。
接触步骤可以在单步骤中进行,或者如果需要,例如如果需要用衍生自第三金属前体的第三金属进一步浸渍载体,其可以分多个接触步骤中进行。在后种实施方案中,该方法还可以包括以下步骤:(c)使载体与包含第三金属的第三金属前体接触,所述第三金属不是锡且不同于第二金属;和(d)将第三金属前体还原以在载体上形成第三金属或其氧化物。步骤(c)和(d)可以在步骤(a)和(b)之前或之后进行。
期望地,甚至在相对低的温度下,例如在室温下,增溶剂如草酸铵促进草酸锡在水中溶解。因此,在一方面,在接触步骤期间,混合金属前体处于10℃-50℃,例如20℃-30℃的温度。
任选地,该方法还包括在225℃-500℃的温度下煅烧催化剂以形成煅烧的催化剂。在其它实施方案中,不需要煅烧,因为催化剂在不进行煅烧的情况下适合于在加氢方法中以大于80wt.%的选择性形成乙醇。
在另一个实施方案中,本发明涉及混合金属前体本身,其例如作为溶液。例如,在一方面,本发明涉及通过将(a)草酸锡;(b)第二金属前体;(c)增溶剂;和(d)水合并形成的混合金属前体。在再一个实施方案,本发明涉及草酸锡、第二金属草酸盐和草酸铵在水中的反应产物。
在每个这些实施方案中,增溶剂可以例如是IA族金属草酸盐、草酸铵、四烷基草酸铵或草酸磷鎓(phosphonium oxalate)。
第二金属前体(其优选是第二金属草酸盐)包含第二金属,该第二金属优选选自铂、铱、铑、钯、铜、钴、锰、铅、铬、铊、铁、锇、金、银、镉、铼、铑和钌。最优选地,第二金属是铂,第二金属前体包含草酸铂。
虽然混合金属前体中各种组分的浓度可以取决于例如最终形成的催化剂的所需组成而宽泛地变化,但是在一些示例性实施方案中,混合金属前体包含理论浓度为0.01M-0.1M的草酸锡,理论浓度为0.01M-0.1M的第二金属前体,和理论浓度为0.02M-0.32M的草酸铵。混合金属前体可以包含摩尔比大于1:1,例如大于2:1的草酸铵和草酸锡。
载体的组成可以变动,但是在一些示例性实施方案中选自铁氧化物(iron oxide)、二氧化硅、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆、氧化镁、硅酸钙、碳、石墨、高表面积石墨化碳、活性炭和它们的混合物。任选地,载体包含载体材料和载体改性剂,例如酸性载体改性剂、氧化还原型载体改性剂或碱性载体改性剂。载体的酸性或碱性特性可以有助于确定所得催化剂如何具体针对特定产品。例如,酸性载体可能倾向于促进由乙酸形成乙酸乙酯,而较碱性的载体可能倾向于促进由乙酸形成乙醇。在优选实施方案中,载体材料包含二氧化硅以及载体改性剂包含偏硅酸钙。
发明详述
引言
按照常规,难以按期望的转化率和/或乙醇选择性水平将链烷酸例如乙酸加氢产生所需产物,例如乙醇。为了获得期望的转化率和选择性,提出了双金属加氢催化剂例如铂/锡催化剂。参见例如共有美国专利No.7,863,489和美国公开No.2010/0121114,在此通过引用将其它们每一个以其全文并入本文。然而,至今为止,难以由包含锡的无卤金属前体开始制备双金属催化剂,这是由于锡前体与许多其它金属前体,特别是与水基金属前体的不相容性,其原因是锡前体例如草酸锡或乙酸锡不溶于水。
本发明涉及制备包含锡和一种或多种另外金属的双金属催化剂的有效方法。特别地,现已发现增溶剂例如草酸铵在单一混合金属前体中的存在可以促进有机锡前体例如草酸锡在水中的溶解,从而合乎期望地使它们与其它水性金属前体,例如其它金属草酸盐如草酸铂相容。
因此,在一个实施方案中,本发明涉及制备催化剂的方法,该方法包括以下步骤:(a)使载体与包含草酸锡、第二金属前体(优选第二金属草酸盐)、增溶剂例如草酸铵和水的混合金属前体接触形成浸渍的载体;和(b)在有效除去至少大部分重量的水以及将来自草酸锡的锡和来自第二金属前体的第二金属还原的条件下,加热所述浸渍的载体。虽然不作要求,但是该方法任选还包括煅烧所得催化剂以形成煅烧的催化剂组合物的步骤。
混合金属前体
如上文所示,本发明的方法涉及优选在单浸渍步骤中使用可以浸渍到载体、任选改性载体中的混合金属前体。根据本发明的实施方案,混合金属前体通过将草酸锡、第二金属前体(优选草酸铂)、增溶剂(优选草酸铵)和水合并而形成。
不受理论束缚,认为当在本发明的方法和混合金属前体中使用草酸铵和草酸铂时,草酸铵通过形成二草酸根合锡酸盐(dioxalatostannate)和其它草酸锡物质而起到促进溶解草酸锡的作用,如下面反应中所示。
2NH4 ++C2O4 2-+SnC2O4(s)→Sn(C2O4)2 2-+2NH4 +
此外,不受理论束缚,一旦将第二金属前体加入到草酸锡/草酸铵溶液中,则第二金属阳离子被锡阳离子还原形成第二金属的单质纳米颗粒。这可以由混合金属前体的颜色改变所指示。出人意料且意想不到地,草酸铵理想地起到使第二金属纳米颗粒稳定的作用。下面显示了这种反应顺序,其中第二金属前体包含草酸铂。
因此,在另一个实施方案中,本发明涉及草酸锡、第二金属前体(优选第二金属草酸盐)和草酸铵在水的反应产物。优选地,第二金属草酸盐包含草酸铂,尽管在其它方面,第二金属草酸盐可以包含选自铱、铑、钯、铜、钴、锰、铅、铬、铊、铁、锇、金、银、镉、铼和钌的第二金属。
通常,可以使用形成混合金属前体的各种组分的任意加入顺序,只要所得混合金属前体保持适合用于浸渍所需载体。在优选实施方案中,将包含水和增溶剂如草酸铵的水溶液与固体草酸锡(例如粉末形式)合并。即,将草酸铵溶解于水中,并将所得溶液加入到草酸锡中,或者可替代地,可以将固体草酸锡加入到草酸铵溶液中。然后可以将第二金属前体例如草酸铂溶解于水中并加入到草酸锡/草酸铵混合物中,或者可以将固体第二金属前体加入到草酸锡/草酸铵水溶液中。或者,可以将增溶剂在其与固体草酸锡合并之后加入到水中。在另一方面,将固体草酸锡加入到包含第二金属前体、水和增溶剂的溶液中。任选地,混合金属前体还包含第三金属前体,或另外的金属前体。通常,在形成混合金属前体时搅动混合金属前体的水性组分,尽管对此不作要求。合适的搅拌方法包括机械(搅动性)搅拌、超声波搅拌或磁力搅拌。
然而在形成时,在适合用于以单浸渍步骤浸渍载体、任选改性载体的单一水相中,所得混合金属前体有利地包含锡前体如草酸锡,和第二金属前体,优选第二金属草酸盐,从而消除用两种或更多种金属分别浸渍载体的必要性。
混合金属前体可以在各种温度下形成并且任选在室温(25℃)下形成。在一些方面,混合金属前体在20℃-80℃,例如10℃-50℃、20℃-50℃或20℃-30℃的温度下,或者在小于80℃,例如小于75℃或小于50℃的温度下形成。
除草酸锡、第二金属前体、水和增溶剂外,混合金属前体还可以包含一种或多种添加剂以调节混合金属前体的一种或多种性质。可以包括在混合金属前体中的示例性添加剂包括一种或多种溶解性调节剂、表面活性剂、酸、碱和/或非水性溶剂。
草酸锡和第二金属前体在混合金属前体中的相对理论浓度可以宽泛地变化,尽管草酸锡和第二金属前体优选以足以形成具有所需的锡与第二金属摩尔比的催化剂的量提供。当然,草酸锡和第二金属前体优选以低于它们各自饱和极限的浓度提供。通常,草酸锡和第二金属前体可以按任意量提供,只要它们保持在溶液中。例如,可以任选对混合金属前体中草酸锡和第二金属前体的浓度进行选择使得所得催化剂中存在的锡和第二金属(以及可选的任何另外金属)的总重量为0.1-25wt.%,例如0.5-15wt.%或0.75wt.%-10wt.%。就个体理论浓度而言,混合金属前体任选包含理论浓度为至少0.001M,例如至少0.01M或至少0.05M的草酸锡。就范围而言,混合金属前体任选包含理论浓度为0.001M-0.5M,例如0.01M-0.1M或0.04M-0.1M的草酸锡。混合金属前体任选包含理论浓度为至少0.001M,例如至少0.01M或至少0.05M的第二金属前体。就范围而言,混合金属前体任选包含理论浓度为0.001M-0.5M,例如0.01M-0.1M或0.04M-0.1M的第二金属前体。优选地,混合金属前体中锡与第二金属的摩尔比(不考虑相应的阴离子物质)为3:1-1:3,例如2:1-1:2或0.6:0.4-0.4:0.6。在优选实施方案中,混合金属前体包含理论浓度为0.01M-0.1M的草酸锡,理论浓度为0.01M-0.1M的第二金属前体,和理论浓度为0.02M-0.32M的草酸铵。“理论浓度”是指基于初始加入形成混合金属前体的各种组分的摩尔数和混合金属前体的总体积的计算浓度,未考虑到可能在混合的金属溶液中由草酸锡、第二金属前体和/或增溶剂中的一种或多种彼此反应所致的实际浓度的任何变化。
如上文所示,在本发明的优选实施方案中,增溶剂包含草酸盐,例如IA族草酸盐(例如草酸钠或草酸钾)、草酸铵、四烷基草酸铵或草酸磷鎓。因此,在一些方面,增溶剂可以包含季胺或膦。在优选实施方案中,增溶剂包含如上所示的草酸铵。草酸铵可以是水合形式,例如一水合草酸铵(NH4)2C2O4·H2O,尽管还可以使用无水形式。在其它实施方案中,使用除草酸铵外的增溶剂。
虽然混合金属前体中增溶剂的量可以宽泛地变化,但是增溶剂优选以足以溶解草酸锡以及在混合金属前体中形成的任何第二金属纳米颗粒的量存在。在一些示例性方面,混合金属前体包含理论浓度为至少0.01M,例如至少0.02M或至少0.1M的草酸铵。就范围而言,混合金属前体任选包含理论浓度为0.01M-0.5M,例如0.02M-0.32M或0.1M-0.22M的草酸铵。在一些示例性实施方案中,混合金属前体包含摩尔比大于1:1,例如大于2:1的草酸铵和草酸锡。
关于第二金属前体,术语“第二”所指的是表示第二金属不是锡。类似地,如果混合金属前体包含第三金属前体(或另外的金属前体),术语“第三”表示第三金属是除锡外且不同于第二金属的金属。第二金属可以宽泛地变化,只要它不是锡。在一个实施方案中,第二金属可以是IB、IIB、IIIB、IVB、VB、VIB、VIIB或VIII族过渡金属,镧系金属,锕系金属,或者IA、IIA、IIIA、IVA(除锡外)、VA或VIA族中任意族的金属。然而,优选地,第二金属选自比锡(II)具有更大电正性的任意金属,例如具有大于0.15eV的标准还原电势的任意金属。在优选实施方案中,第二金属选自铂、铱、铑、钯、铜、钴、锰、铅、铬、铊、铁、锇、金、银、镉、铼、铑和钌。任选地,第二金属选自铂、钯和钌。最优选地,第二金属是铂。第二金属前体优选包含以下金属中的一种或多种的第二金属草酸盐:铂、铱、铑、钯、铜、钴、锰、铅、铬、铊、铁、锇、金、银、镉、铼、铑和钌。可以包括在混合金属前体中的示例性第二金属前体包括但不限于氯铂酸、氯铂酸铵、胺增溶的氢氧化铂、硝酸铂、四氨合硝酸铂(platinum tetraammonium nitrate)、氯化铂、草酸铂、硝酸钯、四氨合硝酸钯(palladiumtetra ammonium nitrate)、氯化钯、草酸钯、氯化钠钯和氯化钠铂,尽管优选无卤化物的前体。最优选地,第二金属前体包含草酸铂。
在一个实施方案中,如上所示,第二金属前体是铂前体,例如草酸铂。在该实施方案中,可以将一种或多种另外的铂前体例如Pt(NH3)4(NO4)2引入到混合金属前体中。在其中催化剂意欲以高选择性用于形成乙醇的那些情形中,通常优选避免使用卤化的金属前体。
如上所示,除草酸锡和第二金属前体外,混合金属前体还可以包含一种或多种另外的金属前体。作为实例,混合金属前体还可以包含增溶形式的另外金属前体,例如溶解于水中的一种或多种金属卤化物、胺增溶的金属氢氧化物、金属硝酸盐或金属草酸盐。上文关于第二金属所提及的的金属同等地适用于任意另外金属,只要第二金属与一种或多种另外金属不相同且都不是锡。在优选方面,一种或多种另外金属(例如第三金属、第四金属等)选自铂、铱、铑、钯、铜、钴、锰、铅、铬、铊、铁、锇、金、银、镉、铼、铑和钌。对于本发明的多个实施方案,在下表1中提供了优选的三金属组合。
制造催化剂的方法
一旦形成金属前体,则优选将其浸渍到载体、任选改性载体上以形成所需的催化剂组合物。这种方法涉及使混合金属前体与载体在有效用其浸渍载体的条件下接触例如浸渍。混合金属前体的一个重要有益特征是锡组分和第二金属组分都在水相中,例如这两种金属组分不在两个分开的相中。如此,可例如在单浸渍步骤中有利地使用本发明的混合金属前体使合适的载体浸渍有锡和第二金属这二者。
典型地,将混合金属前体加入到载体中并允许该载体吸收所述金属前体。这可以通过始润浸渍技术逐滴(drop wise)地进行直到基本上实现载体的完全浸渍。或者,可以将载体逐个等分或批次地置入混合金属前体中。可以使用旋转浸渍(rotoimmersion)或其它辅助设备来实现载体和混合金属前体之间的彻底接触。另外,可以使用喷雾装置使得通过喷嘴将混合金属前体喷射到载体上,其于此被吸收。任选地,可以使用倾析、加热或减压来除去不被载体吸收的任何过量液体或者在浸渍后干燥载体。在接触步骤期间混合金属前体可以处于室温或在室温左右。在可选的实施方案中,可以通过例如US2001/0048970(在此通过引用以其全文并入本文)中所述的化学气相沉积方法使混合金属前体与载体接触。
一旦使混合金属前体接触且浸渍载体、任选改性载体,则在有效将草酸锡和第二金属前体的金属组分还原以在载体上形成单质(或氧化)锡和第二金属或第二金属氧化物的条件下加热所得浸渍的载体。加热步骤可以包含干燥步骤或还原步骤或单个整合的干燥/加热步骤。
优选地,加热步骤包含典型地在空气下的干燥步骤,其中将至少大部分重量,例如大于50wt.%、大于80wt.%或大于90wt.%的水,从所浸渍的载体除去,因此将催化剂组合物干燥。例如,可以加热到大于100℃,例如大于120℃或大于150℃的温度并持续例如1-48小时,如4-24小时或6-12小时的时段以形成干燥的催化剂。就范围而言,加热或干燥步骤优选在100-225℃,例如120℃-200℃的温度下进行。
一旦浸渍后并且优选在干燥步骤之后,则优选在还原步骤中在提高的温度下于还原性气氛下加热所浸渍的载体。在还原步骤中,将浸渍催化剂中的任何剩余的阳离子金属组分还原为它们的单质形式。在优选实施方案中,使浸渍催化剂经受包含氢气/惰性气体混合物的还原性气氛,优选在5-20mol%氢气,例如5-15mol%氢气或最优选约10mol%氢气的氢气浓度,其余为惰性气体例如氮气下进行。还原步骤的温度分布可以宽泛地变化。在优选实施方案中,还原步骤在室温下开始并逐渐斜线上升到最高还原温度,其例如可以为225℃-500℃,例如280℃-350℃,最优选约300℃。斜线上升可以按0.5℃/分钟-5℃/分钟,优选1-3℃/分钟或约2℃/分钟的速率进行。一旦达到最大温度,则优选将浸渍催化剂在最高温度保持1-12小时,例如4-8小时或约6小时。或者,将干燥的浸渍催化剂放入烘箱中并在基本上不呈斜线上升曲线的情况下加热到最高温度。
因为草酸盐在相对低的温度下分解,所以通常可在干燥和/或还原步骤期间将它们从催化剂除去。因此,使用草酸盐前体的一个优点是可以避免单独的煅烧步骤。在一些实施方案中,虽然并非必需,但是可以期望按顺序煅烧干燥的催化剂,以例如除去在最终催化剂组合物中不期望的衍生自一种或多种另外金属前体的任何其它组分。例如,如果在混合金属前体中或者在与混合金属前体分开的金属前体溶液中使用一种或多种另外前体,例如一种或多种金属硝酸盐或金属乙酸盐,则可能需要煅烧。因此,在一个实施方案中,该方法还包括煅烧载体上还原的催化组分的步骤。煅烧步骤优选包括将干燥和优选还原的催化剂加热到温度大于干燥和还原步骤中所使用的温度。例如,可以任选地将干燥和还原的催化剂加热到大于225℃,例如大于300℃、大于400℃或大于500℃的最高煅烧温度。就范围而言,最高煅烧温度任选为225℃-600℃,例如300-600℃或400℃-600℃。煅烧步骤可以进行1-12小时,例如4-8小时的时段。
在一些任选实施方案中,除混合金属前体外,使用一种或多种分开的金属前体来浸渍载体。例如,为了将比锡(II)具有更小电正性或具有小于0.15eV标准还原电势的一种或多种金属引入催化剂,这会是所需的。如果使用,分开的金属前体优选包含含有另外金属的另外金属前体,和液体载剂(carrier)例如水。一种或多种另外金属任选选自IB、IIB、IIIB、IVB、VB、VIB、VIIB或VIII族过渡金属,镧系金属,锕系金属,或者IIIA、IVA、VA或VIA族中任意族的金属。例如,一种或多种另外金属任选选自铜、铁、钴、镍、钌、铑、钯、锇、铱、铂、钛、锌、铬、钼和钨。该方法可以例如用作形成三金属催化剂例如上文表1所列出的任意那些的替代手段。
在该实施方案中,可以将分开的金属前体在加入到混合金属前体之前、之后或同时加入到载体中。如果将分开的金属前体和混合金属前体顺次加入到载体中,则优选在各浸渍步骤之间干燥并任选还原和/或煅烧载体。例如为了形成具有分层催化结构的催化剂,这种实施方案会是所期望的。例如,如果首先浸渍混合金属前体,则将载体干燥、还原并任选煅烧,接着用分开的金属前体进行浸渍,然后所得催化剂可以具有包含载体核、含有锡和第二金属(或其氧化物)的内层、和含有衍生自分开的金属前体的金属或金属氧化物的外层的分层结构。
任选地,根据本发明形成催化剂的方法还可以包括一个或多个另外步骤,例如但不限于将催化组分固载(fixing)在载体材料上,和/或洗涤该固载的催化组分。此外,一些步骤可以重复并且步骤的顺序可以不同于上文所列出的顺序(例如还原步骤可以在固载步骤之前)。
在一个实施方案中,在浸渍步骤中,对混合金属前体的体积进行选择以使其对应于载体材料孔体积的50%-150%,例如85%-110%或85%-100%。优选的是载体材料孔体积的约95%-约100%的体积。
典型地,在浸渍之前,将载体在例如100℃-150℃,优选约120℃的温度下干燥,并且成型为具有0.1-1.0mm,例如0.2-0.6mm、0.2-0.4mm或0.2-0.3mm的尺寸分布的颗粒。任选地,可以将载体压制、压碎和/或筛分成所需尺寸分布。可以使用将载体材料成型为所需尺寸分布的任何已知的方法。此外,可以按照本领域公知的方法实施固载、洗涤、还原和活化步骤。例如,这些步骤中每一个的实例公开于美国专利No.7,518,014(在此通过引用以其全文并入本文)中。
在所形成的催化剂中位于载体上的金属的结构和形态可以变化。例如,颗粒可以作为合金例如均质合金位于载体上,例如不是作为个体金属的单独颗粒。即,浸渍颗粒的结晶结构可以含有锡和第二金属分子。在一个实施方案中,将锡和第二金属如铂均匀地分布在载体上。在另一个实施方案中,金属以非分层方式位于载体上。在涉及混合金属前体和一种或多种另外金属前体的一些多步骤浸渍方法中,混合金属前体的浸渍可以产生第一金属层,而随后的浸渍步骤可以在第一层顶部产生另外的层。
催化剂的最终组成取决于在混合金属前体中或者在一种或多种分开的金属前体中所使用的草酸锡和第二金属前体的相对量以及是否使用另外金属前体。在一个实施方案中,所得催化剂包含0.1-10wt.%,例如0.3-5wt.%或0.5-3wt.%的量,或任选大于0.1wt.%,例如大于5wt.%或大于1wt.%的量的锡。该催化剂还优选包含0.1-20wt.%,例如0.3-10wt.%或0.5-5wt.%的量,或任选大于0.1wt.%,例如大于1wt.%或大于5wt.%的量的第二金属。该催化剂中锡与第二金属的摩尔比优选为10:1-1:10,例如4:1-1:4、2:1-1:2、1.5:1-1:1.5或1.1:1-1:1.1。通常,如上所论述,约1:1的锡与第二金属之比提供了氧化还原反应的所需化学计量从而形成第二金属的纳米颗粒。此外,如果第二金属是铂,提供约1:1的Sn/Pt摩尔比则现已表明获得了对乙醇形成具有高度选择性的乙酸加氢催化剂。锡和第二金属如Pt可以彼此合金化或者可以包含非合金化的金属固溶体或混合物。
通常,催化剂中存在的所有金属(如果有一些的话,包括除锡和第二金属外的另外金属)的总重量优选为0.1-25重量%,例如0.5-15重量%或0.75重量%-10重量%。在催化剂仅包含锡和第二金属时,锡优选以0.1wt.%-5wt.%,例如0.3wt.%-5wt.%的量存在,第二金属优选以0.1wt.%-10wt.%,例如0.5wt.%-5wt.%的量存在。除锡和第二金属外,如上文所论述催化剂还可以包含一种或多种另外金属。在催化剂包含另外金属(即除锡和第二金属外的金属)时,所述另外金属优选以0.1wt.%-3wt.%,例如0.2wt.%-2wt.%的量存在。就本说明书而言,除非另外指明,重量百分数是基于包括所有金属和载体在内的催化剂的总重量计。催化剂中的金属可以按一种或多种单质金属、一种或多种金属氧化物,或者这二者的组合的形式存在。就确定催化剂中金属的重量百分数而言,忽略与金属结合的任何氧的重量。
载体
通常将本发明的催化金属载于载体上和/或内。合适的载体包括特性(identity)基本上均一的材料或材料的混合物。总之,载体通常可以对待进行的反应呈惰性。载体可以由优选进行选择使得该载体每单位质量或体积具有相对高的表面积,例如多孔结构、分子筛结构、蜂窝状结构或其它合适结构的任何合适的物质组成。例如,载体可以包含二氧化硅、氧化铝、二氧化硅-氧化铝、二氧化钛、钛硅酸盐、氧化锆、锆硅酸盐、氧化铌、硅酸盐、铝硅酸盐、钛酸盐、尖晶石、碳化硅、氮化硅、碳、堇青石、滑石、斑脱土、粘土、金属、玻璃、石英、浮石、沸石、非沸石分子筛、它们的组合等。任意不同结晶形式的材料也是合适的,例如α或γ氧化铝。还可以使用含有氧化锆、锆硅酸盐和钛硅酸盐的载体材料。此外,多层载体材料也适合用于本发明。
本发明催化剂中的载体可以由具有任意各种规则或不规则形状,例如球、片、圆柱体、圆盘、环状物、星状物或其它形状的颗粒组成。载体可以具有1mm-10mm,例如3mm-9mm或3mm-8mm的尺寸例如直径、长度或宽度。优选地,颗粒最大尺寸为2mm-9mm,例如4mm-约8mm或4mm-7mm。在其它情形中,研碎(ground)或粉末载体可以是合适的。如此,载体可以具有直径为10微米-1000微米,例如10微米-700微米或180微米-450微米的规则或不规则形状。可以使用较大或较小的尺寸,以及多个颗粒尺寸的多分散集合。例如,对于流化床催化剂,优选的尺寸范围可包括10微米-200微米,例如10微米-150微米或25微米-100微米。对用于分层催化剂的前体,优选10-250微米的尺寸范围。
如通过BET(Brunauer、Emmett和Teller)方法测定的负载催化组分可用的表面积,通常可以为1m2/g-500m2/g,例如20m2/g-200m2/g或25m2/g-50m2/g。此外,对于多孔载体,载体材料的孔体积通常可以为0.1ml/g-2ml/g,例如0.4ml/g-1.2ml/g或0.5ml/g-1.0ml/g。例如10埃-5000埃,例如50埃-2000埃或100-1000埃的平均孔径大小是期望的。
在优选实施方案中,载体是选自二氧化硅、热解二氧化硅、高纯度二氧化硅、硅酸钙如偏硅酸钙以及它们的混合物的含硅载体。在其中二氧化硅用作含硅载体的情形中,有利地是确保氧化铝(其是二氧化硅的常见污染物)的量是低的,优选基于载体总重量计在1重量%以下,例如0.5重量%以下或0.3重量%以下。就此而言,优选热解二氧化硅,因为它一般以超过99.7wt.%的纯度获得。如本申请中通篇所使用的,高纯度二氧化硅是指其中酸性污染物例如氧化铝(如果有的话)以小于0.3wt.%,例如小于0.2wt.%或小于0.1wt.%的水平存在的二氧化硅。如下文所讨论,优选的载体是偏硅酸钙改性的二氧化硅。当偏硅酸钙用作载体改性剂时,关于所用二氧化硅的纯度不必十分严格,尽管氧化铝是不期望的并且将通常不是有意加入。这种二氧化硅的氧化铝含量例如可以小于10重量%,例如小于5重量%或小于3重量%。在其中载体包含2重量%-10重量%的载体改性剂的情形中,可以容许大量的酸性杂质例如氧化铝,只要它们被合适量的载体改性剂抵消。在本发明的一个实施方案中,含硅载体的表面积为至少约100m2/g,例如至少约150m2/g、至少约200m2/g或最优选至少约250m2/g。如本申请通篇所使用的,高表面积二氧化硅是指具有至少约250m2/g的表面积的二氧化硅。
合适的商业含硅载体的实例包括来自Sud Chemie的KA160,来自Saint Gobain NorPro的SS61138高表面积(HSA)二氧化硅催化剂载体,来自Degussa的Aerolyst350,以及具有1mm-25mm例如1mm-10mm颗粒尺寸和低微孔率(microporosity)的其它热解二氧化硅。Saint-Gobain NorPro SS61138二氧化硅含有约95重量%的高表面积二氧化硅;约250m2/g的表面积;12nm的中值孔径;通过压汞孔隙测量法(mercury intrusion porosimetry)测量的1.0cm3/g的总孔体积,和约352kg/m3的堆积密度。
合适的含氧化锆的载体的实例包括来自NorPro,Zirconia Sales(America),Inc.,Daichi Kigenso Kagaku Kogyo,Engelhard和Magnesium Elektron Inc(MEI)的那些。合适的氧化锆载体材料具有小于5m2/g至大于300m2/g的宽范围的表面积。优选的氧化锆载体具有20m2/g-150m2/g,例如更优选30m2/g以上和约100m2/g的表面积。在一个实施方案中,可以通过其中加热原始(virgin)载体材料的煅烧步骤来处理载体的表面。加热降低载体材料的表面积(例如煅烧)。这提供了产生具有本来可能不易于从供应商获得的比表面积的载体材料的方法。
其它合适的载体的实例包括来自Grace的钛硅酸盐例如SP18-9534(具有0.61%TiO2的二氧化硅)或来自Grace的锆硅酸盐例如SP189043(具有1.69%ZrO2的二氧化硅)。更通常地,合适的载体可以包括至多70wt.%TiO2,例如至多50wt.%TiO2或至多40wt.%TiO2;或者0.01wt.%-75wt.%TiO2,例如0.1wt.%-50wt.%TiO2或0.1wt.%-5wt.%TiO2。此外,合适的载体材料可以包括至多70wt.%ZrO2,例如至多50wt.%ZrO2或至多40wt.%ZrO2;或者0.01wt.%-75wt.%ZrO2,例如0.1wt.%-50wt.%ZrO2或0.1wt.%-5wt.%ZrO2。
在另一个实施方案中,预期使用各自具有不同特性的载体材料的组合。例如,至少两种载体材料,如具有不同特性的二氧化钛和二氧化硅,可以表现出不同的活性和选择性,如乙醇选择性,因此允许制备具有所需系列特性的催化剂。此外,在一个实施方案中,可以按如美国公开No.2005/0181940(在此通过引用以其全文并入本文)中所论述的分层构造使用多种不同的载体。已知用于产生分层载体材料的另外技术包括在美国专利No.7,518,014;6,486,370;5,935,889;和5,200,382(通过引用将它们的每一个以其全文并入本文)中所描述的那些。
载体的改性
在其中以高选择性生产基本上纯乙醇的实施方案中,通过引入载体改性剂控制载体的酸度可能是十分有利的。乙酸加氢的一种可能的副产物是乙酸乙酯。现发现,与其它加氢产物例如乙酸乙酯相比,除金属前体和所用的制备条件外,金属-载体相互作用可以对选择性例如乙醇选择性具有更强烈影响。
在一个实施方案中,载体包括降低载体材料上的酸位数量且与其它反应产物相比提高乙醇选择性的载体改性剂。载体优选包括有效抑制乙酸乙酯产生,对乙醇具有高度选择性,并且对乙酸转化为高度不期望的副产物例如甲烷、乙烷和CO2具有低选择性的载体改性剂。理想地控制载体的酸度使得小于4%,优选小于2%,最优选小于约1%的乙酸转化为乙烷。此外,载体的酸度可通过使用热解二氧化硅或高纯度二氧化硅来控制。
在一个实施方案中,载体包含偏硅酸盐例如偏硅酸钙。如果载体包含二氧化硅,则载体改性剂例如偏硅酸钙优选以有效降低或平衡由二氧化硅中任何残留的氧化铝产生的酸位的量存在。优选地,偏硅酸钙以1wt.%-10wt.%的量存在,以便确保载体的性质为基本上中性或碱性。由于偏硅酸钙倾向于具有较低的表面积,在一个实施方案中,含硅载体包括至少约10wt.%高表面积二氧化硅。
载体用载体改性剂进行改性以形成改性载体可以在金属浸渍步骤之前、之后或同时进行。在多个任选实施方案中,载体改性剂可以例如选自:(i)碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏硅酸盐,(iv)碱金属偏硅酸盐,(v)IIB族氧化物,(vi)IIB族偏硅酸盐,(vii)IIIB族氧化物,(viii)IIIB族偏硅酸盐,和(i)-(viii)的任意混合物。载体改性剂优选是碱性非挥发性稳定剂-改性剂。优选地,载体改性剂选自钠、钾、镁、钙、钪、钇和锌的氧化物和偏硅酸盐和它们的前体,以及前述的任意混合物。特别优选的载体改性剂是偏硅酸钙(CaSiO3)。优选地,将CaSiO3浸渍在载体上,优选的改性剂/载体组合是SiO2/CaSiO3。包括载体材料和载体改性剂在内的改性载体总重量基于催化剂总重量计优选为25重量%-99.9重量%,例如30重量%-97重量%或35重量%-95重量%。在一个实施方案中,载体改性剂优选以降低载体中活性酸位数量和优选确保载体表面基本上没有活性酸位的量来提供。除非上下文另外指明,其上的表面酸度或酸位数量可以通过F.Delannay编辑,“Characterization of HeterogeneousCatalysts”;Chapter III:Measurement of Acidity of Surfaces,370-404页;Marcel Dekker,Inc.,N.Y.1984中所描述的技术进行测定,通过引用将其全文并入本文。
在其它实施方案中,改性剂还可以是选自碱金属、碱土金属、过渡金属和镧系元素的金属。在其它实施方案中,改性剂选自第I族至第VI族的元素。在这些元素中,更优选钡、镁、铈、钾、钙、铌、钽、钛、钇、锶、锆、镧、镨、钒、钼和铷,稍微不太优选锆。这些元素的组合也是合适的,二元组合是优选类型的组合。例如,合适的二元组合包括Ti-Zr、Mg-Nb、Nb-Zr、Mg-Ti、Nb-Ti、Mg-Zr等。二元组合中的金属比率为10:1-1:10,例如4:1-1:4。应注意的是,认为改性或改性剂浸渍与金属浸渍是分开的。因此,涉及一个步骤例如使用本发明金属前体并且还包括载体改性的金属浸渍仍将认为是一个金属浸渍步骤。
此外,特别是如果期望对除乙醇外的加氢产物,例如乙酸乙酯具有高的选择性时,可以使用氧化还原型改性剂或酸性载体改性剂。合适的氧化还原型改性剂或酸性改性剂选自:IVb族金属氧化物、Vb族金属氧化物、VIb族金属氧化物、铁氧化物、铝氧化物和它们的混合物。这些载体改性剂是氧化还原型或酸性非挥发稳定剂-改性剂。可选的氧化还原型载体改性剂选自WO3、MoO3、Fe2O3和Cr2O3。可选的酸性载体改性剂可以选自TiO2、ZrO2、Nb2O5、Ta2O5和Al2O3。
在优选的实施方案中,载体改性剂以基于催化剂总重量计0.01wt.%-50wt.%,例如0.1wt.%-50wt.%、0.2wt.%-25wt.%、0.5wt.%-15wt.%或1wt.%-8wt.%的量存在。
在将金属前体(草酸锡和第二金属前体以及任何另外金属前体)加入到载体材料中之前通常将载体进行改性。在一个优选的实施方案中,用一种或多种改性剂水溶液(称作改性剂前体溶液)浸渍载体材料。在接触步骤期间载体材料的物理状态可以是干燥固体、浆料、溶胶-凝胶、胶体悬浮液等。
在一个实施方案中,改性剂可以包含在金属前体中。如此,改性剂可以是其水溶性盐。这些包括但不限于氯化物、其它卤化物、硝酸盐、亚硝酸盐、氢氧化物、氧化物、乳酸盐、乙酸盐(OAc)、铵和胺,优选无卤化物(例如氯化物)的盐,最优选乳酸盐、草酸盐、乙酸盐和硝酸盐。适合用于改性剂前体溶液的改性剂盐的实例包括Ba(NO3)2、Mg(NO3)2·6H2O、Ce(NO3)3·6H2O、KNO3、Ca(NO3)2·4H2O、(NH4)1.35Nb(C2O4)2.73、Ta(C2O4)2.5、Ti(CH3CH(O-)CO2NH4)2(OH)2、Y(ΝO3)3·6Η2O、ZrO(NO3)2·xH2O。
此外,可以在给定的改性剂前体溶液中使用多于一种的盐。前体溶液通常可以通过将所选择的盐,与或者不与溶解性调节剂例如酸、碱或其它溶剂一起溶解于水中来进行制备。其它非水溶剂也是合适的。
可以在单浸渍步骤中将改性剂前体溶液浸渍到载体材料上,尽管可以用具有低原子量(例如Mg)或在水中溶解度有限(例如Nb或Ba)的改性剂多次浸渍载体材料。如果使用多种改性剂,则可以同时(例如共浸渍)或相继进行浸渍,并且可以通过使用一种或多种前体溶液来浸渍载体材料。
作为一个实例,将载体改性剂例如CaSiO3加入到载体材料例如SiO2中。例如,可以通过将固体载体改性剂加入到去离子水中、接着向其加入胶体载体材料来形成载体改性剂的水性悬浮液。可以搅拌所得混合物并使用例如始润浸渍技术将其加入到另外的载体材料中,在所述始润浸渍技术中将载体改性剂加入到孔体积与载体改性剂溶液的体积相同的载体材料中。然后毛细管作用将载体改性剂吸入载体材料内的孔隙中。然后可通过干燥和煅烧去除载体改性剂溶液内的水和任何挥发性组分并使载体改性剂沉积在载体材料上来形成改性载体。干燥可以例如在50℃-300℃,例如100℃-200℃或约120℃的温度下进行任选1-24小时,例如3-15小时或6-12小时的时段。一旦形成,改性载体可以成型为具有所需尺寸分布的颗粒,例如形成平均粒径为0.2-0.4cm的颗粒。可以将载体进行挤出、造粒、压片、压制、压碎或筛分为所需尺寸分布。可使用将载体材料成型为所需尺寸分布的任何已知方法。成型的改性载体的煅烧可以例如在250℃-800℃,例如300-700℃或约500℃的温度下进行任选1-12小时,例如2-10小时、4-8小时或约6小时的时段。
本发明催化剂的一个优点是提高的催化剂活性。因此,可认识到的是,本发明的催化剂完全能够用于乙酸加氢的商业规模工业应用,特别是乙醇生产。特别地,能够实现如下这样的稳定程度:经过至少一周(168小时)、至少两周(336小时)或至少三周(504小时)的时段,催化剂活性将下降小于10%。在一个另外实施方案中,经过至少168小时、至少336小时或至少504小时的时段,催化剂活性将下降小于5%。催化剂活性还可以通过在反应器初始启动后的稳定性来测定。在启动后,典型地至多10小时、至多20小时或至多25小时后,经过至少168小时、至少336小时或至少504小时的时段,催化剂可以下降小于5%。在另外的实施方案中,在启动后,经过至少168小时、至少336小时或至少504小时的时段,催化剂可以下降小于3%。
在优选实施方案中,当催化剂载体包含高纯度二氧化硅且以偏硅酸钙作为载体改性剂时,催化剂活性可以扩大或稳定,在温度为125℃-350℃的乙酸蒸气存在下和在高于2500hr-1的空速下的商业上可行的操作的催化剂长期活性和选择性例如延长到超过4周和甚至数月。
本发明还涉及使用本发明催化剂由乙酸直接形成乙醇和/或乙酸乙酯的方法。该方法包括使乙酸和氢气与本发明催化剂接触。反应可以在足以将乙酸加氢的条件下进行。这些条件的实例论述于美国专利No.7,863,489和7,608,744(通过引用将它们每一个以其全文并入本文)中。
考虑到以下非限制性实施例,本发明的实施方案将变得更为明显。
实施例:加氢催化剂的制备
在实施例中使用以下材料:
(a)来自Heraeus的草酸铂,PtC2O4;(溶液,13.638wt.%Pt)。
(b)草酸锡(II),SnC2O4和一水合草酸铵,
(c)购自Aldrich的(NH4)2C2O4·H2O并且不进一步纯化即使用。
在使用前,在120℃于循环空气下干燥来自NorPro Saint Gobain的具有6wt.%CaSiO3的改性二氧化硅载体(HSA SS#61138,SA=250m2/g)即SiO2-CaSiO3(6)过夜。
按如下制备混合金属前体。将1.62g(11.38mmol)固体一水合草酸铵加入到50ml去离子H2O中并在室温下搅拌溶解。将0.94g(4.55mmol)草酸锡(II)加入到草酸铵溶液中。在室温下搅拌所得混合物另外10分钟从而产生略微不透明的无色溶液。使用去离子H2O将6.51g草酸铂(II)溶液(13.638wt.%Pt)稀释至18ml的总体积。然后随着搅拌将深蓝色铂溶液加入到铵/锡(II)溶液中从而产生黄褐色均匀溶液。在室温下搅拌该溶液20分钟。
使用始润浸渍技术将混合金属前体加入到具有3mm丸粒型状的改性二氧化硅载体(SiO2-CaSiO3(6))中。在室温下将该材料静置1小时,然后在旋转蒸发器中于80℃的缓慢/最低旋转浴温下抽空至干。然后在120℃于循环空气下将该材料干燥过夜。
然后使用具有10mol%H2的H2/N2混合物(在大气压下总流速为约275sccm/min)和以下温度程序将催化剂还原:
(a)以2deg/min的升温斜率从室温到300℃,
(b)在300℃下保持6小时。
(c)冷却至室温(如果在测试前于反应器中原位进行,则也可以将催化剂冷却至反应温度)。
所得催化剂按如下用于将乙酸加氢。
在室温和200psig(14bar)压力下,以GHSV~4700h-1将0.18g/min乙酸和683sccm/min H2(无N2稀释剂)给进到反应器中。该反应器含有10ml固体催化剂(1/8英寸挤出物,用3mm玻璃珠1:1v/v稀释)。反应时间为48小时。
产物流显示出乙酸的55%转化率且具有以下产物选择性:
89wt.%乙醇
6wt.%乙酸乙酯
3wt.%乙醛
2wt.%乙缩醛。
如所示,所得催化剂尤其含有锡,已知锡不具有在典型水性溶剂中溶解的能力。出人意料且意想不到地,在不使用卤化的金属前体的情况下在一步浸渍方法中使用包含水性增溶的锡和水性增溶的铂二者的混合金属前体成功地制备该催化剂。另外,所述制备不包括煅烧步骤。所述催化剂,在用于使乙酸加氢时,表现出高的转化率和对乙醇的高选择性。
可以将关于任何公开的实施方式所描述或请求保护的任何特征,以任意组合与关于任何其它公开的实施方式所描述或请求保护的任何一个或多个其它特征相组合,达到所述特征并非必须是技术上不相容的程度,并且所有这些组合是在本发明的范围以内。此外,下面所附的权利要求给出了在本发明范围内的一些非限制性特征组合,而且预期任意两个或更多个权利要求的主题的所有可能的组合,以任何可能的组合,是在本发明的范围内,条件是所述组合并非必须是技术上不相容的。
Claims (15)
1.一种制备催化剂的方法,该方法包括以下步骤:
(a)使载体与包含草酸锡、第二金属的第二金属前体、增溶剂和水的反应产物的混合金属前体接以触形成浸渍的载体;以及
(b)在有效除去至少大部分重量的水以及将来自草酸锡的锡和来自第二金属前体的第二金属还原并形成催化剂的条件下,加热所述浸渍的载体;
其中增溶剂选自草酸钠、草酸钾、草酸磷鎓及其组合。
2.权利要求1的方法,其中所述第二金属前体包括第二金属草酸盐。
3.权利要求1的方法,其中所述第二金属是铂并且第二金属前体包括草酸铂。
4.权利要求1的方法,其中所述第二金属选自铱、铑、钯、铜、钴、锰、铅、铬、铊、铁、锇、金、银、镉、铼、铑和钌。
5.权利要求1的方法,其中所述加热步骤至少部分地在还原性气氛下进行。
6.权利要求1的方法,其中所述加热步骤包括干燥步骤和还原步骤。
7.权利要求1的方法,其中所述接触包括通过始润浸渍技术进行接触。
8.权利要求1的方法,其中所述混合金属前体包含理论浓度为0.01M-0.1M的草酸锡,理论浓度为0.01M-0.1M的第二金属前体,和理论浓度为0.02M-0.32M的增溶剂。
9.权利要求1的方法,其中所述混合金属前体包含摩尔比大于1:1的增溶剂和草酸锡。
10.权利要求1的方法,其中所述混合金属前体包含在溶液中的草酸锡、第二金属前体和增溶剂。
11.权利要求1的方法,其中所述接触以单步骤进行。
12.权利要求1的方法,其中在接触步骤期间所述混合金属前体处于20℃-30℃的温度,并且其中所述加热达到120℃-200℃的温度。
13.权利要求1的方法,其中所述载体材料选自铁氧化物、二氧化硅、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆、氧化镁、硅酸钙、碳、石墨、高表面积石墨化碳、活性炭和它们的混合物。
14.权利要求1的方法,该方法还包括在225℃-500℃的温度下煅烧催化剂以形成煅烧的催化剂。
15.权利要求1的方法,该方法还包括:
(c)使载体与包含第三金属的第三金属前体接触,所述第三金属不是锡且不同于第二金属;以及
(d)将第三金属前体还原以在载体上形成第三金属或其氧化物。
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CN108358752A (zh) * | 2018-04-18 | 2018-08-03 | 肖锦 | 一种乙酸加氢制乙醇的方法 |
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US20110190117A1 (en) | 2011-08-04 |
WO2011094713A1 (en) | 2011-08-04 |
CN102421735B (zh) | 2013-12-18 |
CN103638990B (zh) | 2016-01-27 |
HK1169382A1 (zh) | 2013-01-25 |
US8569203B2 (en) | 2013-10-29 |
CN102421735A (zh) | 2012-04-18 |
US8211821B2 (en) | 2012-07-03 |
EP2531474A1 (en) | 2012-12-12 |
US20120245022A1 (en) | 2012-09-27 |
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