CN101827652A - 不饱和烃加氢催化剂及其制备方法 - Google Patents
不饱和烃加氢催化剂及其制备方法 Download PDFInfo
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- CN101827652A CN101827652A CN200880112183A CN200880112183A CN101827652A CN 101827652 A CN101827652 A CN 101827652A CN 200880112183 A CN200880112183 A CN 200880112183A CN 200880112183 A CN200880112183 A CN 200880112183A CN 101827652 A CN101827652 A CN 101827652A
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- Prior art keywords
- catalyst
- nickel
- hydrogenation
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- pore volume
- Prior art date
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 188
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 229930195735 unsaturated hydrocarbon Natural products 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title description 10
- 238000000034 method Methods 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 126
- 229910052759 nickel Inorganic materials 0.000 claims description 54
- 239000011148 porous material Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- 239000000395 magnesium oxide Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 9
- 239000007868 Raney catalyst Substances 0.000 claims description 8
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 29
- 238000001556 precipitation Methods 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 229910001960 metal nitrate Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- VIAPNRBXEJNZKV-UHFFFAOYSA-N nickel silicic acid Chemical compound [Ni].[Si](O)(O)(O)O VIAPNRBXEJNZKV-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 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 1
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- -1 silicon dioxide compound Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
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Abstract
本发明涉及一种不饱和烃(特别是具有宽分子量范围的芳族不饱和烃)加氢催化剂、制备该催化剂的方法和不饱和烃加氢方法。
Description
背景技术
本发明涉及一种不饱和烃(特别是具有宽分子量范围的芳烃)加氢催化剂、制备该催化剂的方法和不饱和烃加氢方法。
芳烃催化加氢是公知的。EP 0290100公开了一种用于含芳烃的烃加氢的含有5-40wt%镍的镍-θ-Al2O3成型催化剂。所应用的催化剂载体实际上没有孔小于2.0nm。催化剂的平均孔半径为7.4-10.3nm。镍的浸渍由氨性溶液来实施。
在EP 0398446中,公开了在对硫化物具有高耐受性的溶剂和白油中使芳烃加氢的催化剂体系。该催化剂在载体上分离地含有加氢组分和金属氧化物。对于金属,公开了Cu、Ni、Pt、Pd、Rh、Ru、Co或这些金属的混合物,而对于金属氧化物组分,公开了Ag、La、Sb、V、Ni、Bi、Cd、Pb、Sn、V、Ca、Sr、Ba、Co、Cu、W、Zn、Mo、Mn、Fe的氧化物或这些氧化物的混合物。催化剂载体可以由Al2O3、SiO2、Al2O3·SiO2、TiO2、ZrO2和MgO组成。
根据EP 0974637,通过组合含贵金属的载带催化剂、含金属氧化物和Ni-SiO2的催化剂,还可以达到更高的硫耐受性。因此,例如,在反应器顶部配备Pt/Pd载带的催化剂,而在其下为ZnO挤出物与Ni-SiO2挤出物的混合物。
JP 3076706描述了利用Pd载带催化剂使不饱和聚合物加氢,其中所应用的SiO2载体具有20-50nm的孔径。但是,在这种方法中,催化剂的消耗量非常高。
US 5,028,665公开了一种用于不饱和聚合物加氢的金属载带催化剂,其载体主要具有孔径>45nm的孔。催化剂使90-100%的烯烃化合物加氢,但只有<25%的芳烃加氢。Pd、Pt和Rh作为加氢活性金属描述。
在US 5,612,422中,描述了用于平均分子量为100000的聚合物加氢的金属-SiO2载带催化剂,其载体的孔体积中至少98%由孔径>60nm的孔构成。Pt和Rh作为优选的加氢活性金属提及。
对于树脂加氢,在WO 01/36093A1中公开了一种催化剂,其在SiO2(14-45wt%)、Al2O3(1-15wt%)上含有45-85%的Ni和0.25-4wt%的Fe,和其在孔径范围2-60nm内的孔体积为至少0.35ml/g。
在EP 1262234中,描述了具有低裂化倾向的芳烃加氢用催化剂,其在SiO2-MgO载体(其中MgO含量为25-50wt%)上含有0.1-2.0wt%的第8副族的贵金属。孔径>4.0nm的孔体积应该为0.3-0.6ml/g,而孔径0.7-2nm的孔体积应该为0.2-0.3ml/g。孔半径为至少200nm的孔体积应该不大于0.05ml/g。
US 6,376,622公开了用于平均分子量为40000-120000的聚合物中的烯烃和芳烃加氢的金属-SiO2载带催化剂,其中所应用的载体的表面积为30-120m2/g,其中95%的孔体积由孔径为30-100nm的孔形成,并且孔径<20nm的孔体积的比例少于4%。加氢组分为Ni、Co、Rh、Ru、Pd、Pt或它们的组合。
在US 5,149,893中,公开了用于苯加氢的Ni-或Co-铝酸钙催化剂。
这些催化剂体系对于低分子量芳烃加氢是优选的,或者主要适合于较高分子量的芳烃化合物加氢。
EP 1331033公开了用于芳族物质加氢的球形金属载体催化剂的制备方法。
DE 19909177公开了用于有机化合物的官能团加氢的载带镍催化剂,其优选具有高的锆含量。
本发明的技术问题在于提供具有较高催化活性的催化剂体系,该催化剂体系特别适合于较高和较低分子量的芳烃化合物加氢。本发明另一个目的是提供制备所述催化剂的方法和应用所述催化剂的方法。
发明内容
本发明通过提供不饱和烃加氢催化剂来解决该问题,所述催化剂为在二氧化硅(SiO2)上载带的镍催化剂,其镍含量为40-85wt%(按NiO计算),硅含量为15-60wt%(按SiO2计算),钛含量为0.5-5.0wt%(按TiO2计算),并且含有不大于0.20wt%的铁(按Fe计算),其中所述催化剂具有单峰Ni-微晶粒度分布,还原后的催化剂的平均微晶粒度为1.5-3.5nm,其中直径为1.7-300nm的孔的孔体积为至少0.60ml/g,和其中孔径≥10nm的孔的孔体积的比例为至少55%。
因此,本发明特别通过提供载带催化剂解决其技术问题,在一个优选实施方案中,所述催化剂具有硅酸镍相,并且所述催化剂的特征在于其组成、孔体积分布、微晶粒度及分布的特定组合。与常规催化剂相比,这种催化剂令人惊奇地提供明显更高的活性,并且优点在于其宽范围的可能离析物,特别是较高和较低分子量的芳烃化合物。
如果不另外说明,在本发明文中所给出的wt%值均基于催化剂总干重。在本发明的内容中,选择催化剂的各组分使其总量不超过100wt%。
本发明提供不含铁的二氧化硅上的镍加氢催化剂。在本发明的上下文中,术语不含铁指催化剂不含大量的铁,具体地,不含超过0.20wt%Fe(按Fe计算)。在更优选的实施方案中,不含铁催化剂的铁含量最大为0.1,最优选为最大0.05wt%(按Fe计算)。在特别优选的实施方案中,催化剂中没有可检测量的铁,优选完全没有铁。
在进一步优选的实施方案中,催化剂的钠含量很低,优选低手1wt%,最优选低于0.5wt%,特别是低于0.2wt%,最优选低于0.1wt%(按Na2O并相对于ROI计算)。
孔体积按BJH(Barrett,Joyner和Halenda)确定。如果不另外指出,为了确定孔体积及其所占比例,考虑直径为1.7-300nm的孔。
在特别优选的实施方案中,镍含量为40-80wt%(基于总催化剂重量按NiO计算)。
在进一步优选的实施方案中,硅含量为15-40wt%(基于总催化剂重量按SiO2计算)。
在本发明的优选实施方案中,按金属镍与总镍的比表示,本发明催化剂中镍的还原水平为52-80%。
在本发明的优选实施方案中,所述催化剂包括、特别是主要由、最优选由镍、二氧化硅、钛和一种或多种选自铝、镁、锌、铬和锆的元素(优选为其氧化物形式)组成。在优选实施方案中,除了镍和SiO2,所述催化剂包括、优选主要由、特别是由铝和钛或它们的氧化物组成。
在本发明的最优选实施方案中,催化剂的铝含量为2-10wt%(基于总催化剂重量按氧化铝Al2O3计算)。
在本发明的优选实施方案中,催化剂的镁含量为0.1-3.0wt%(基于总催化剂重量按氧化镁MgO计算)。
在本发明的优选实施方案中,催化剂的锌含量为0.1-4.0wt%(基于总催化剂重量按氧化锌ZnO计算)。
在本发明的优选实施方案中,催化剂的铬含量为0.1-0.3wt%(基于总催化剂重量按氧化铬Cr2O3计算)。
在本发明的优选实施方案中,催化剂的锆含量为0.1-3.0wt%(基于总催化剂重量按二氧化锆ZrO2计算)。
在优选实施方案中,催化剂的压实堆密度为至少0.15,优选为至少0.20,优选为至少0.25kg/dm3,最优选为0.25-0.35kg/dm3。
在进一步优选的实施方案中,BET表面积为至少150,优选为至少200,最优选为至少250m2/g。在进一步优选的实施方案中,镍金属的表面积为至少15,优选为至少20,最优选为至少23m2/g。
在特别优选的实施方案中,硅酸盐载体另外还含有一种或多种选自如下的化合物:硅酸镁、铝硅酸盐(Al2O3·SiO2)、TiO2、钛酸镍、ZrO2、锆酸镍和ZnO。在特别优选的实施方案中,催化剂包括、优选主要由、特别是由40-80wt%的镍(按NiO计算)、15-40wt%的硅(按SiO2计算)、2-10wt%的铝(按Al2O3计算)、0.5-5.0wt%的钛(按TiO2计算)和0.1-3.0wt%的镁(按MgO计算)组成,并且其中催化剂中的镍的还原水平为52-80%,其中催化剂具有单峰微晶粒度分布,还原后的催化剂的平均微晶粒度为1.5-3.5nm,和其中直径为1.7-300nm的孔的催化剂孔体积为至少0.60ml/g,并且直径≥10nm的孔的比例为至少55%。
因此,本发明具体通过提供不含铁的基于硅酸镍相的催化剂来解决其技术问题,所述催化剂包括、特别是主要由、特别是由如下物质(按元素的氧化物描述)组成:40-85wt%、优选为40-80wt%的NiO,15-60wt%、优选15-40wt%的SiO2,和0.5-5wt%的TiO2,在其中还包含至少一种选自如下的组分:2-10wt%的Al2O3、0.1-3.0wt%的ZrO2、0.1-3.0wt%的MgO、0.1-4.0wt%的ZnO和0.1-0.3wt%的Cr2O3,其中所述催化剂的镍的还原水平为52-80%,其中所述催化剂具有单峰微晶粒度分布,还原后的催化剂的平均微晶粒度为1.5-3.5nm,和其中直径为1.7-300nm的孔的催化剂孔体积为至少0.60ml/g,并且直径≥10nm的孔的比例为至少55%。本发明优选提供如上所定义的这种含镍的二氧化硅载带的催化剂,其中二氧化硅载体包含一种或多种选自如下的化合物:硅酸镁、铝硅酸盐、TiO2、钛酸镍、ZrO2、锆酸镍和ZnO,其中优选将镍与TiO2载带于硅酸镍和铝硅酸盐上。
本发明还设想了在优选实施方案中,催化剂为以粉末形式存在的催化剂,特别是用于悬浮或浆液加氢反应中。在本发明的优选实施方案中,本发明的催化剂为粉末状的催化剂,孔体积为至少0.68ml/g。在进一步优选的实施方案中,以粉末形式存在的催化剂的粒径为2-50μm,优选为2-22μm,两者的d50值均优选为4-15μm,优选为4-10μm。
在进一步优选的实施方案中,本发明的催化剂为成型或模塑催化剂,在本发明的文本中也称作成型催化剂,特别是用于固定床或流化床加氢反应中。在优选实施方案中,成型催化剂可以为例如球状、珠状、片状、丸状或挤出物形式。
在本发明的优选实施方案中,催化剂为成型催化剂,其中孔径≥10nm的孔的孔体积比例为至少65%。
本发明还提供制备上文所定义的二氧化硅上的镍催化剂的方法,其中共沉淀所述催化剂组分。
本发明还提供在二氧化硅上载带的镍催化剂的制备方法,所述方法包括使包含镍离子源和钛离子源的金属盐溶液与钠水玻璃溶液在pH为8.0-9.5、温度为70-100℃、优选为85-100℃下反应,以共沉淀催化剂材料并回收共沉淀的催化剂材料,从而得到在二氧化硅上载带的镍催化剂。
在本发明方法中应用的任何反应试剂均应基本上不含铁,从而所得催化剂将不含大于0.20wt%的铁(按Fe计)。
在特别优选的实施方案中,可以将上述溶液同时加入到沉淀容器中,也可以一个接一个地加入。
在本发明的上下文中,水玻璃是指为SiO2源的化合物。因此,在本发明的上下文中,水玻璃具体为例如水溶性碱性硅酸盐、SiO2、碱性离子与SiO2的混合物、碱性盐或氧化物、氢化硅酸盐、硅酸盐如硅酸钠等。
在本发明的上下文中,钠水玻璃溶液指包含水玻璃和钠的混合物的溶液,优选为水溶液,其中钠例如为NaOH或Na2CO3(苏打)。
在本发明的优选实施方案中,金属盐溶液包含Ni2+和TiO2+,以及Al3+、Cr3+、Mg2+、Zn2+和ZrO2+中的一种或多种。在本发明的优选实施方案中,金属盐溶液为酸性溶液。在本发明的优选实施方案中,金属盐溶液为硝酸盐溶液。
在本发明的优选实施方案中,钠水玻璃溶液包含Al(OH)- 4、TiO2、Zn和ZrO2中的一种或多种。在本发明的另一个优选实施方案中,钠水玻璃溶液为碱性溶液。
在本发明的优选实施方案中,在整个沉淀过程中,pH值保持恒定为8.0-9.5。在本发明的优选实施方案中,沉淀时间和随后的搅拌时间均为1-3小时,优选均为1.5-2.5小时,特别是均为2小时。在特别优选的实施方案中,在搅拌条件下实施沉淀。在特别优选的实施方案中,在沉淀完成时和沉淀完成后所达到的pH值≥9.0,优选≥9.1,且最大为9.5。
在优选实施方案中,本发明提供上文所规定的方法,其中在沉淀后,过滤所获得的催化剂沉淀物。在优选实施方案中,洗涤过滤后的催化剂沉淀物即所获得的滤饼,优选至Na含量<0.2wt%,优选<0.1wt%。
在本发明的优选实施方案中,优选随后干燥所述洗涤后的滤饼,例如通过闪蒸干燥、喷雾干燥或在常规干燥设备中简单干燥进行干燥。
为了制备粉末形式的催化剂,优选通过喷雾干燥处理所述滤饼。
在特别优选的实施方案中,所述干燥后的催化剂可以进行进一步处理,例如制粒,优选与粘结剂组分和/或水一起制粒。在优选实施方案中,可以干燥和煅烧所述制粒过的催化剂。
在本发明的优选实施方案中,在120-350℃的温度下,煅烧按上述方法获得的催化剂,特别是经过干燥的催化剂。在进一步优选的实施方案中,优选经过钝化催化剂步骤后,还原所述经过干燥和煅烧的催化剂。
在进一步优选的实施方案中,优选在流化床中,优选在氢气物流下,优选在300-600℃、特别是340-500℃的温度下,还原所述干燥后的催化剂。但在进一步优选的实施方案中,也可以在旋转烘箱、圆筒状旋转窑或其它合适的装置中实施还原。在进一步优选的实施方案中,例如在氮气/空气、CO2/氮气/O2或氮气/O2气氛中稳定所述经过还原的催化剂。
在本发明的特别优选的实施方案中,可以通过喷雾或闪蒸干燥催化剂沉淀物且随后进行处理、特别是经过煅烧和还原来制备所述粉末状催化剂。
在本发明另一个优选实施方案中,通过成型干燥后的沉淀产品、随后还原和稳定所述材料、随后研磨和筛分所述还原和稳定后的催化剂,以此来制备粉末形式的本发明的催化剂。
可以通过已知的成型方法来实施成型催化剂的制备。按照本发明,已经发现优选的挤出和滴落成型法是特别有利的。
本发明还提供按照上文所定义的制备方法获得的或可获得的催化剂。
本发明还提供一种应用本发明的催化剂使不饱和烃、特别是芳烃加氢的方法。
在本发明的优选实施方案中,提供不饱和烃,在合适的反应条件下使不饱和烃与至少一种本发明文本中所述的催化剂接触,和得到加氢后的烃。
适合于实施本发明的不饱和烃加氢方法的温度和压力可以由本领域的熟练技术人员确定。在一个优选实施方案中,合适的反应温度为70-350℃,优选为250-350℃。在进一步优选的实施方案中,可以应用例如1-250bar、优选为1-150bar、优选为30-140bar的氢分压。本发明的加氢方法可以在固定床反应器、流化床反应器、浆液反应器、环管反应器或类似物中实施。
优选可以按照本发明加氢的芳烃的例子有煤油、白油、芳烃溶剂或苯。
将通过如下实施例描述本发明的优点:
实施例1(本发明)
将5l水放入一个配备有搅拌器的可加热沉淀容器中,然后以酸性钛氧基硫酸盐溶液形式加入氧化钛。在搅拌条件下将溶液加热至80-90℃的温度。一旦达到温度,平行加入金属硝酸盐溶液和沉淀剂水溶液。除了镍外,金属硝酸盐溶液还含有镁、铝和铬。除了苏打(Na2CO3)外,沉淀剂溶液还含有溶解的二氧化硅化合物。在沉淀期间,使pH值保持恒定为8-8.5。沉淀时间和进一步的搅拌时间均为2小时。
镍与SiO2、Al2O3、Cr2O3、MgO和TiO2的摩尔比为1∶0.5∶0.04∶0.0085∶0.055∶0.016。
沉淀完成后,过滤所述悬浮液,并且用无碱水洗涤,直到滤饼中的Na2O含量<0.2%(以在800℃下热处理滤饼获得的烧余量(ROI)为基准)。
过滤和洗涤后,将所得到的滤饼再一次分散于水中,然后在工业喷雾干燥器中喷雾。所得到的粉末物质具有6μm的粒度。随后,将产品在350℃下煅烧2小时,钝化后,在400℃下用氢气物流还原6小时,并在氧含量为0.1-1vol%的CO2/氮气物流中在低于80℃的温度下稳定。
还原和稳定后的催化剂含有以总催化剂计约55%的镍。以金属镍与总镍比表示的镍还原水平为约70%。催化剂表现出单峰Ni-微晶粒度分布。在180℃下进一步还原的催化剂的平均镍初级粒度(即还原后的催化剂的平均微晶粒度)为约3nm。XRD光谱确认了硅酸镍相的存在。孔体积为0.73ml/g。孔径≥10nm的孔体积为0.42ml/g。
实施例2(本发明)
将15l水放入一个可加热的沉淀容器中,然后在搅拌条件下加入作为SiO2组分的硅藻土和固体TiO2(P25,Degussa Co.)。随后加入氢氧化钠水溶液(10%)。将溶液加热至85℃后,开始计量加入组合的金属硝酸盐溶液,所述金属硝酸盐溶液含有镍、铝、镁和铬离子。镍与SiO2、Al2O3、MgO、TiO2、Cr2O3和ZnO的摩尔比为1∶0.4∶0.038∶0.05∶0.016∶0.004∶0.006。
在平均温度为85℃下的沉淀时间和随后的搅拌时间均为约2小时。沉淀及随后搅拌后,pH值为约8.5。过滤和洗涤后,将所得的滤饼再一次分散,然后在工业干燥器中喷雾干燥。所得的粉末材料具有9μm的平均粒度。在350℃下在惰性气体物流中煅烧干燥的产品,然后在350℃在流化床中在氢气物流中还原2小时。经过还原后,在氮气物流中冷却,和在O2含量为0.1-1vol%的氮气/空气/CO2混合物中稳定。
还原和稳定后的催化剂含有以总催化剂计约58%的镍。以金属镍与总镍比表示的镍还原水平为约55%。催化剂表现出单峰Ni-微晶粒度分布。在180℃下进一步还原的催化剂的平均镍初级粒度(即还原后的催化剂的平均微晶粒度)为2.7nm。XRD光谱确认了硅酸镍相的存在。孔体积为0.71ml/g。孔径≥10nm的孔体积为0.40ml/g。
实施例3(本发明)
将10l水放入一个可加热的沉淀容器中,然后在搅拌条件下加入铝酸钠溶液(40g Al2O3/l溶液,100g NaOH/l)和水玻璃溶液(50gSiO2/l溶液)。将溶液加热至90-95℃后,开始计量加入硝酸镍、硝酸镁和硝酸锆的水溶液,直到pH值达到8.5。所述金属硝酸盐溶液还含有钛氧基硫酸盐溶液形式的TiO2。在pH值达到约8.5后,在90-95℃的温度下开始平行加入剩余的硝酸镍溶液和NaOH水溶液(10%)。沉淀时间为1小时,随后的搅拌时间约为2小时。
镍与SiO2、Al2O3、MgO、TiO2和ZrO2的摩尔比为1∶0.39∶0.038∶0.036∶0.016∶0.01。
按实施例1所述进一步处理催化剂。在420℃的温度下实施还原。
还原和稳定后的催化剂含有以总催化剂计约60%的镍。镍的还原水平为约80%。催化剂表现出单峰Ni-微晶粒度分布。在180℃下进一步还原的催化剂的平均镍初级粒度(即还原后的催化剂的平均微晶粒度)为约2.8nm。XRD光谱确认了硅酸镍相的存在。孔体积为0.77ml/g。孔径≥10nm的孔体积为0.51ml/g。
实施例4(本发明)
将5l水和固体TiO2(P 25,Degussa Co.)放入一个可加热的沉淀容器中,然后在搅拌条件下将悬浮液加热至90-95℃的温度。达到该温度后,平行加入组合的金属硝酸盐溶液和碱性溶液,其中所述金属硝酸盐溶液含有硝酸盐形式的镍、铝和镁,而所述碱性溶液为沉淀剂苏打和溶解SiO2化合物的水溶液。在沉淀的过程中,不断调节pH值,使其为8.0-8.3。沉淀和随后的搅拌时间均为约2小时。
镍与SiO2、Al2O3、MgO和TiO2的摩尔比为1∶0.328∶0.037∶0.053∶0.032。
沉淀完成后,过滤沉淀的悬浮液,并用纯冷凝液洗涤滤饼,直到以所取出的滤饼的重量为基准Na2O含量<0.05%为止。随后,在120-140℃的温度下干燥所述滤饼,达到烧余量(800℃下)为至少70%,然后在350-380℃下煅烧。煅烧完成后,煅烧后材料的烧余量为至少90%。接着在一个合适的装置中在氢气物流中在420-430℃的温度下还原所得产品10小时,然后在环境温度下在含O2的氮气物流中稳定。
然后在保护性气氛下在惰性气研磨机中将还原和稳定后的催化剂细细研磨。
成品粉末状催化剂含有60%的镍含量,还原水平为约80%,在180℃下进一步还原的催化剂的平均微晶粒度(即还原后的催化剂的平均微晶粒度)为约3.1nm。催化剂显示了单峰Ni-微晶粒度分布。催化剂的平均粒度为15μm,孔体积为0.70ml/g,和孔径≥10nm的孔体积为0.39ml/g。
实施例5(本发明)
将8l水和钛氧基硫酸盐放入沉淀容器中。随后,在搅拌条件下在30分钟内加入钠水玻璃溶液。在加入的过程中,加热至理想的沉淀温度90℃。达到该温度后,通过加入组合的硝酸镍、硝酸镁和硝酸铝溶液而使pH值达到约8,然后将混合物再搅拌30分钟。随后,继续沉淀过程,平行计量加入氢氧化钠溶液(150g/l)和剩余的金属硝酸盐溶液。在沉淀的过程中,温度在90℃下保持恒定。沉淀时间和随后的搅拌时间均为约1小时。镍与SiO2、Al2O3、MgO和TiO2的摩尔比为1∶0.65∶0.038∶0.05∶0.016。
然后过滤沉淀的悬浮物,并且用非常干净的冷凝液洗涤滤饼。随后,在水中再一次分散滤饼,并通过藻酸盐法制成滴状。在130℃和400℃下分别干燥和煅烧后,在氢气物流中在420℃的温度下还原模塑体。按实施例1所述实施稳定。
成品催化剂的镍含量为约52%,还原水平为约70%,在180℃下进一步还原的催化剂的平均微晶粒度(即还原后的催化剂的平均微晶粒度)为约3.2nm,并且催化剂具有2-3mm的粒度。催化剂显示了单峰Ni-微晶粒度分布。孔体积为0.70ml/g,和孔径≥10nm的孔体积为0.49ml/g。
实施例6(对比例)
将10l水放入沉淀容器中,然后在搅拌条件下加热至80℃。随后,在恒定温度80℃下,在搅拌条件下,平行加入含1.4kg镍、0.050kg MgO、0.050kg Al2O3和0.0056kg Fe的组合金属硝酸盐溶液,和含2.9kg苏打和0.345kg SiO2的苏打/水玻璃溶液。在沉淀的过程中,pH值为7.5。沉淀过程在1小时后完成。沉淀完成后,过滤悬浮液并洗涤。然后在110℃下干燥所得的滤饼,细细研磨并在350℃下煅烧。在400℃的温度下以流体相态还原后的催化剂离析材料。催化剂在氮气/空气混合物中进行稳定后,成品催化剂具有如下组成:60%的镍、18%的SiO2、2.7%的Al2O3、2%的MgO和0.3%的Fe2O3。
催化剂中,镍的还原水平为约65%,镍的初级粒径为约3.5nm。孔体积(孔径为2-60nm的孔)为0.35ml/g。孔体积为0.41ml/g,和孔径≥10nm的孔体积为0.17ml/g。
实施例7(对比例)
将10l水和实施例6中所应用且为相同组成的苏打/水玻璃溶液放入容器中,然后加热至80℃。随后,在搅拌条件下在恒定80℃的温度下加入含有1.4kg镍、0.050kg Al2O3和0.0056kg Fe的组合金属硝酸盐溶液。沉淀1小时的时间后,沉淀悬浮液的pH值为7.3。将沉淀的浆液过滤、洗涤,然后在工业喷雾干燥器中喷雾。喷雾颗粒的平均粒度为约10μm。在流体相态中实施煅烧、还原和稳定。
成品催化剂具有如下组成:62%的镍、19%的SiO2、3%的Al2O3和0.35%的Fe2O3。
催化剂中,镍的还原水平为约70%,镍的初级粒径为约3.8nm。孔体积(直径为2-60nm的孔)为0.34ml/g。孔体积为0.39ml/g。孔径≥10nm的孔的孔体积为0.13ml/g。
实施例8(对比例)
将平均粒度为10μm且堆密度为0.7kg/l的干燥和研磨后的Ni/SiO2初始材料与作为粘结剂的甲基纤维素混合,然后在试验室揉制机中通过加入冷凝水、硝酸和硅溶胶溶液而分散。基于该揉制批次的固体含量,甲基纤维素的加入量为2.5%。在揉制时间达到15分钟后,在带有切割设备的试验室挤出机中将所完成的批次物成型为3mm的圆柱形挤出物。将所获得的湿挤出物在试验室成球机(Caleva Co.,Model120,England)中进一步处理成球。然后在130℃下干燥所得到的球状材料。
如前文所述在氢气物流中在400℃下还原所述初始材料,并在标准条件下进行稳定。
成品催化剂含有约55%的镍,并且其还原水平为约75%。平均镍微晶粒度为4.5nm。催化剂表现出直径为2-4mm的宽的粒度分布。孔体积为0.30ml/g,孔径>10nm的孔的比例仅为0.02ml/g。
实施例9(对比催化剂)
下表1给出在如下比较分析中使用的本发明催化剂和对比催化剂的组成。
表1
实施例 | wt%NiO | wt%SiO2 | wt%Al2O3 | wt%TiO2 | wt%ZrO2 | wt%MgO | wt%Cr2O3 | wt%ZnO | wt%Fe2O3 |
1 | 70 | 25 | 2 | 1 | 2 | 0.2 | |||
2 | 73 | 21.8 | 2.05 | 0.9 | 1.9 | 0.15 | 0.2 | ||
3 | 75 | 20.8 | 2 | 1 | 0.4 | 1.2 | |||
4 | 73 | 18.5 | 4 | 2.3 | 2.2 | ||||
5 | 65 | 29.5 | 2.1 | 1.2 | 2.2 | ||||
6 | 78 | 16 | 3.2 | 2.3 | 0.5 | ||||
7 | 79 | 16.9 | 3.5 | 0.6 | |||||
8 | 72 | 28 | |||||||
9 | 70 | 20 | 10 |
为了进行催化剂评价,还应用了具有如下物理-化学特性的商业球形铝硅酸镍催化剂9:
表2
镍含量(wt%) | 55 |
镍的还原水平(%) | 60 |
堆密度(kg/l) | 0.95 |
平均粒径(mm) | 2.5 |
颗粒直径范围(mm) | 1.6-4.7 |
孔体积(ml/g) | 0.27 |
孔体积>10nm | 0.19 |
镍微晶粒度(nm) | 5.1 |
在固定床方法中,将按本发明制备的催化剂5和对比催化剂8和9用于芳烃加氢的催化评价中。
对于Ni载带催化剂的催化特性,应用整体流动反应器(内径为25mm)进行煤油的芳烃加氢。所加入的催化剂体积为50ml。在每一种情况中,将50ml催化剂分10份与10份SiC按体积比1∶1加入。在催化反应前,在250℃下在氢气物流(50l/hr)中重新活化催化剂4小时。作为原料,应用芳烃含量为18wt%且硫含量为1.1ppm的煤油。其它实验条件如下:
反应压力:30bar
反应温度:85℃;反应时间:40小时 100℃;反应时间:80小时
LHSV:1.3
气体-产品比:400l H2/l煤油。
结果示于表3中。
表3
催化剂 | 反应温度:85℃,ppm芳烃 | 反应温度:100℃,ppm芳烃 |
本发明的实施例5 | 1490 | 139 |
对比例8 | 2640 | 259 |
对比例9 | 3105 | 298 |
催化测量结果的比较表明本发明的催化剂具有如下优势:在高至ppm范围的芳烃加氢或降解程度方面,本发明催化剂比常规催化剂明显要更高一些。
应用Autoclave Engineers Co.的搅拌高压釜实施粉末催化剂的催化表征:将210g树脂(平均分子量:2750g)、90g Shellsol和1.8g催化剂移入高压釜,惰化后,用氢气将高压釜充压至4bar。随后将高压釜内容物加热至270℃的温度。达到该温度后,建立90bar的反应压力,然后使搅拌器投入操作。搅拌速度为每分钟2200转。在恒定的压力下,作为反应时间的函数测量氢气消耗。在反应开始后,由第10分至第30分钟之间的氢气消耗计算的平均速率(l H2/hr/g催化剂)表示活性。
催化测量的结果示于表4中。
表4
催化剂 | 加氢活性(l H2/hrg) |
本发明的实施例1 | 15.6 |
本发明的实施例2 | 16.1 |
本发明的实施例3 | 15.2 |
本发明的实施例4 | 16.0 |
实施例6(对比例) | 12.8 |
实施例7(对比例) | 13.3 |
表4中的数据清楚表明,与对比催化剂相比,本发明的催化剂具有更高的加氢活性。
Claims (14)
1.一种不饱和烃加氢催化剂,所述催化剂为在二氧化硅上载带的镍催化剂,其镍含量为40-85wt%(按NiO计算),硅含量为15-60wt%(按SiO2计算),钛含量为0.5-5.0wt%(按TiO2计算),和含有不大于0.20wt%的铁(按Fe计算),其中所述催化剂具有单峰Ni-微晶粒度分布,还原后的催化剂的平均微晶粒度为1.5-3.5nm,孔体积为至少0.60ml/g,和其中孔径≥10nm的孔的孔体积的比例为至少55%。
2.权利要求1的催化剂,其中在所述催化剂中镍的还原水平为52-80%。
3.权利要求1或2的催化剂,所述催化剂的铝含量为2-10wt%(按Al2O3计算)。
4.权利要求1-3任一项的催化剂,所述催化剂的镁含量为0.1-3.0wt%(按MgO计算)。
5.权利要求1-4任一项的催化剂,所述催化剂的锌含量为0.1-4.0wt%(按ZnO计算)。
6.权利要求1-5任一项的催化剂,所述催化剂的铬含量为0.1-0.3wt%(按Cr2O3计算)。
7.权利要求1-6任一项的催化剂,所述催化剂的锆含量为0.1-3.0wt%(按ZrO2计算)。
8.权利要求1-7任一项的催化剂,所述催化剂为粉末催化剂,其孔体积为至少0.68ml/g,或者所述催化剂为成型催化剂,其中孔径≥10nm的孔的孔体积的比例为至少65%。
9.权利要求1-8任一项的催化剂,其中所述载体含有一种或多种选自如下的化合物:硅酸镁、铝硅酸盐、TiO2、钛酸镍、二氧化锆、锆酸镍和ZnO。
10.一种制备权利要求1-9任一项的在二氧化硅上载带的镍催化剂的方法,所述方法包括使含有镍离子源和钛离子源且基本不含铁的金属盐溶液与钠水玻璃溶液在pH为8-9.5和温度为70-100℃下反应,从而共沉淀催化剂材料,和回收共沉淀的催化剂材料,以得到在二氧化硅上载带的镍催化剂,然后任选干燥、煅烧和还原所得到的催化剂。
11.权利要求10的方法,其中所述金属盐溶液包含Ni2+和TiO2+以及一种或多种选自Al3+、Cr3+、Mg2+、Zn2+和ZrO2+的离子。
12.权利要求10或11的方法,其中所述钠水玻璃溶液包含Al(OH)- 4、TiO2、ZnO或ZrO2。
13.一种不饱和烃加氢方法,其中提供不饱和烃,在合适的反应条件下与至少一种权利要求1-9任一项的催化剂接触,和得到加氢后的烃。
14.权利要求13的不饱和烃加氢方法,其中所述不饱和烃为芳烃化合物。
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CN103084180B (zh) * | 2013-02-28 | 2014-08-20 | 中国矿业大学 | 催化芳环全加氢负载型超细非晶金属镍催化剂的制备方法 |
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