CN1309477C - 用高纯度铁前体制备的费-托催化剂 - Google Patents
用高纯度铁前体制备的费-托催化剂 Download PDFInfo
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- CN1309477C CN1309477C CNB028292421A CN02829242A CN1309477C CN 1309477 C CN1309477 C CN 1309477C CN B028292421 A CNB028292421 A CN B028292421A CN 02829242 A CN02829242 A CN 02829242A CN 1309477 C CN1309477 C CN 1309477C
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- Prior art keywords
- catalyst
- iron
- slurry
- acid
- promoter
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000003054 catalyst Substances 0.000 title claims abstract description 135
- 239000002243 precursor Substances 0.000 title description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 45
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 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 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- -1 glycolic Chemical compound 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 229940107700 pyruvic acid Drugs 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 150000001261 hydroxy acids Chemical group 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000012692 Fe precursor Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000012798 spherical particle Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 238000005406 washing Methods 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 238000012545 processing Methods 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 101100078144 Mus musculus Msrb1 gene Proteins 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000000396 iron Nutrition 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 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 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920002274 Nalgene Polymers 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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Images
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- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/745—Iron
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
Abstract
一种包括铁和至少一种促进剂的费-托催化剂通过这样的方法制备,该方法包括制备高纯度铁前体并且在催化剂生产中使用额定数量的水。采用高纯度铁前体制备的催化剂颗粒具有基本球形的颗粒形状、相对窄的颗粒尺寸分布范围和高的表面积。
Description
发明背景
本发明是涉及一种制备用于费-托(Fischer-Tropsch)工艺的催化剂的方法和通过本发明的方法制得的催化剂。本发明的催化剂包括铁和至少一种促进剂。该催化剂通过一种包括制备高纯度铁前体并且在催化剂生产中使用额定数量的水的方法制备。采用高纯度铁前体制备的催化剂颗粒基本不含污染物并具有基本球形的颗粒形状和相对小的颗粒尺寸分布范围。
费-托合成涉及:将合成气(主要是一氧化碳和氢气的混合物)催化转化成从甲烷到重质蜡的宽范围的饱和和不饱和烃。含氧物质(oxygenate)例如醇、酮、醛和羧酸也可以通过费-托合成而合成。第一种商业费-托催化剂是基于钴的并且早在1935年在德国使用。在发展费-托合成的早期,人们对采用比钴更便宜的金属来开发催化剂产生了兴趣。铁是显而易见的选择;然而直到20世纪50年代才实现基于铁的费-托催化剂的商业应用。自从那个时期以来,基于铁的费-托催化剂已经成功地被Sasol在南非在商业规模上用于固定床、流化床和淤浆料相反应器。
基于铁的费-托催化剂的活性和选择性通过加入少量促进剂而极大地提高。传统的基于铁的费-托催化剂采用铜和I族金属例如钠、钾、铷、铯或其组合而促进。基于铁的费-托催化剂仅仅当它们已经采用氢气、一氧化碳或合成气还原时是活性的。
已经发现铜显著地降低了氧化铁的还原温度并且因此阻止了催化剂的烧结。采用I族金属例如钾的促进作用降低了氧化铁的酸性,由此降低对所不希望的甲烷的选择性并且增加了链烯烃和蜡选择性。也可以使用II族金属;然而I族金属是更有效的促进剂。也可以使用粘合剂例如SiO2和Al2O3以增加基于铁的催化剂的结构完整性和寿命;然而这些通常是酸性的并且将导致增加甲烷选择性。
已经有几种方法用于制备基于铁的费-托催化剂。由Fischer制备的最早的催化剂是用碱处理的铁屑。在高压下液体产品富含氧化的化合物,并且在较低压力下制备烃。然而通过这种方法制备的基于铁的催化剂迅速地失活。
制备基于铁的费-托催化剂的最普通方法是沉淀法。通常,铁盐例如硝酸铁的溶液用碱例如氨水或碳酸钠处理。将所得的羟基氧化铁沉淀物重复洗涤和过滤以除去在沉淀过程期间形成的盐-硝酸铵或硝酸钠。然后将洗涤的滤饼干燥并且煅烧。可以在任何时间、在干燥和煅烧步骤之前或之后采用铜和I族金属促进所沉淀的铁催化剂。最终催化剂通常由高表面积的刚玉相氧化铁(α-Fe2O3或赤铁矿)组成。
其他类型的基于铁的催化剂包括熔融铁、负载铁和烧结铁。熔融铁催化剂通过将铁矿石和一种或多种促进剂例如SiO2、Al2O3、CaO、MgO和K2O熔化而制备。所得催化剂通常主要由磁铁矿(Fe3O4)组成并且具有非常低的表面积。活性熔融铁催化剂只可以通过用氢气将氧化物还原成金属铁而获得。该还原的催化剂可以具有高达约10-15m2/g的表面积。熔融铁催化剂特征在于高的结构完整性并且因此非常适于流化床操作(Sasol);然而相对低的表面积导致费-托催化剂具有与典型的沉淀铁催化剂相比差的活性。通常通过将铁盐溶液浸渍到耐火金属氧化物例如Al2O3、SiO2、TiO2或ZrO2上而制备负载铁催化剂。可以通过初始润湿技术或者通过过度润湿接着真空干燥而进行浸渍。以铁质量计算,负载铁催化剂可以具有与沉淀铁催化剂相似的费-托活性;然而以催化剂体积计算它们通常差。负载铁催化剂不可避免地受到金属氧化物载体的酸性的损害,这增加了不希望的甲烷的选择性。
沉淀铁催化剂通常被看作是优于这里描述的其他类型铁催化剂的费-托催化剂。生产沉淀铁催化剂的主要缺陷包括高成本、该方法劳动密集和副产品对环境有害。硝酸铁是优选的沉淀铁催化剂的铁源,因为来自氯化铁或硫酸铁的氯化物和硫污染物将有害影响所得的F-T催化剂的活性。硝酸铁通过将铁金属溶于硝酸而生产,这产生了氮的氧化物,必须通过洗涤工艺回收。该必要的洗涤步骤增加了工艺的额外成本。另外,沉淀方法会导致形成非常粘和凝胶的氢氧化铁或羟基氧化铁前体。该粘的前体可能非常难以形成用于流化床应用的球形和耐磨的催化剂。
制备基于铁的费-托催化剂、减少或消除洗涤和过滤步骤并且对环境有最小发散的方法将是受欢迎的。从商业观点出发,合理的方法将是促进、形成、干燥和煅烧可商购的、具有高纯度和高表面积的氧化铁。商业的氧化铁容易获得;然而它们通常通过用盐酸或硫酸处理钢材而制备。这些氧化铁含有显著数量的包括氯化物和硫的杂质,这使得它们不能用作费-托催化剂的原材料。如现有技术中已知的,商业氧化铁(红色或黄色氧化铁)的杂质可以通过在非常高的温度下的酸洗方法减少到非常低的程度。然而由于该酸洗方法的极端条件,氧化铁的表面积通常少于10m2/g,使得氧化铁不适用于催化剂应用。
本发明概述
通过一种包括由铁金属制备高纯度氧化铁的方法制备一种包括铁和至少一种促进剂的费-托催化剂。用高纯度氧化铁制备的催化剂颗粒基本不含污染物特别是卤素、氮和硫,并且具有基本球形的颗粒形状、相对窄的颗粒尺寸分布范围和高达约100m2/g的表面积-适用于各种催化剂应用。
该方法包括:在极少数量水的存在下使铁金属与柔和的有机酸和空气反应。在本发明中水消耗的数量显著少于常规沉淀方法中使用的数量,结果在该方法中产生了极少或没有含有硫酸盐、硝酸盐或氯化物的废水。然后将所得的氧化铁浆料研磨并且加入促进剂。将该浆料喷雾干燥以形成最终催化剂。因为该方法使用铁金属,潜在的污染物例如硫和氯的程度可以通过采用干净的金属原料而保持到最低。另外,通过采用铁金属起始,没有必须通过洗涤氧化铁过滤物而除去的残余材料,因此废水的数量显著低于现有技术催化剂应用中的量。另外,因为不必重复地洗涤和过滤浆料,生产时间比现有技术催化剂制备更短。
附图简述
图1是包括氧化铁的催化剂的扫描电子显微照片的二次电子图像,放大100倍(在图像于216×280nm(8.5”× 11”纸片中产生的时候测量),该催化剂通过如实施例1中描述的现有技术沉淀方法制备;和
图2是包括氧化铁的催化剂的扫描电子显微照片的二次电子图像,放大100倍(在图像于216×280nm(8.5”× 11”)纸片中产生的时候测量),该催化剂通过根据如实施例2中描述的现有开发的方法制备。
优选实施方案的详述
本发明的催化剂目的在于用于费-托(F-T)方法。该催化剂组合物与现有技术的F-T催化剂相似并且包括铁和至少一种促进剂。然而,制备该催化剂的方法是新的并且本发明的催化剂包括较少的污染物例如硫和氯,可以比现有技术的F-T催化剂更有效地生产。
费-托方法是表面催化的聚合方法:将合成气(氢气和一氧化碳的混合物)转化成具有宽范围的链长和官能度的烃。通常,用于费-托方法的催化剂包括至少一种金属,其是有效的一氧化碳吸收剂并且有效地用于氢化反应,例如铁、钴和镍。包括铁或钴的催化剂优选用于生产一定范围的烃;基于镍的催化剂会产生大量的甲烷;取决于反应条件,基于钌的催化剂主要地产生甲烷或高熔点蜡。本发明的催化剂包括约35wt%-约70wt%的铁,基于总的催化剂重量,包括铁;在更优选实施方案中,该催化剂包括约56wt%-约70wt%的铁。
费-托催化剂,特别是铁催化剂,一般还包括至少一种促进剂,该促进剂被加入以提高催化剂的选择性或改进催化剂活性和/或选择性。然而,并不需要加入促进剂来制备具有基本球形形状和相对窄的颗粒尺寸分布的催化剂颗粒。对于基于铁的催化剂,现有技术教导铜、碱金属和碱土金属,例如钠、钾、铷、铯、镁、钙、锶、钡和其组合是有效的促进剂。其他金属可以如使用者所希望的被替换以改进催化剂性能或改进催化剂的活性和/或选择性。例如,已经采用选自下列物质的促进剂制备费-托催化剂:硼、铈、铬、铜、铱、铁、镧、锰、钼、钯、铂、铼、铑、钌、锶、钨、钒、锌、氧化钠、氧化钾、氧化铷、氧化铯、氧化镁、氧化钛、氧化锆和其他稀土金属例如钪、钇、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥和其组合。促进剂通常以比铁更小的浓度加入,并且在本发明中促进剂优选占总催化剂重量的约0.002wt%-约40wt%,更优选包括约0.01wt%-约1wt%。
费-托催化剂的物理结构也影响了催化剂活性,并且如现有技术中已知的,为了特定类型的反应器而选择合适的催化剂设计对于商业生产者而言可以转变成相对高的生产率和相对低的维护成本。催化剂的结构或机械性能,包括颗粒强度和耐磨耗性,取决于催化剂的化学稳定性并且被催化剂颗粒的尺寸和形状所影响。催化剂颗粒的形状和尺寸也可以影响例如流体分布和压力下降性能。
在本发明中,尽管催化剂组成与现有技术的费-托催化剂的组成相似,但是制备该催化剂的方法得到了基本不含污染物、具有基本球形颗粒形状、相对窄的颗粒尺寸分布范围和高表面积的催化剂。广泛地说,用于制备本发明的优选实施方案的催化剂的方法包括:采用柔和的有机酸和空气直接处理铁金属以形成氧化铁浆料,然后强烈地将该浆料研磨成小的微米尺寸,然后将一种或多种促进剂加入该浆料,然后采用齿轮喷雾器使该浆料喷雾干燥。仅仅如所需要的将水加入该方法以允许材料的混合。(如这里所使用的,术语“污染物”指现有技术中已知的有害地影响费-托催化剂性能的元素或化合物。一些普遍公认的污染物是硫和氯。)
更特别地,为了制备本发明的费-托催化剂,铁金属在大气条件下于含水介质中与柔和的有机酸反应,然后使混合物通风。铁金属可以是平均直径约1μ-约500μ的粉末、颗粒、球状、碎片或其他形式。在一个实施方案中,铁金属是平均直径约40μ-约150μ的微球体形状。另外,铁金属应该是基本不含污染物的,尽管可以存在痕量的碳、锰、镍、铜、硅和其组合。(如这里所使用的,“痕量”定义成少于所有结合的元素的约1.5wt%。)有机酸优选是含有至少一个羧酸基团、pKa在大气温度下约0.5-约6的羧酸。例如,甲酸、乙酸、乙醇酸、草酸、丙酮酸、丙二酸和丙酸可以用于反应。
伴随着搅拌将有机酸加入去离子水中以形成酸溶液。在大气温度下并且同时保持搅拌或混合,将铁金属缓慢加入酸溶液。由于铁与酸反应,反应温度增加,但加入速率应该足够低以使得温度不超过约38°(100)。我们相信当铁金属加入有机酸溶液时,铁被酸氧化并且产生氢气(H2)。氢气可以在排气口中用空气稀释到少于约4%的浓度,即在爆炸极限以下,或者其可以被送到后燃器中回收热以用于干燥或煅烧。
在铁金属混合到酸溶液中之后,将附加的氧化剂例如空气、压缩空气、氧气、过氧化氢、有机过氧化物、臭氧或其组合加入该溶液。在一个实施方案中,氧化剂是压缩空气,其通过设置在混合槽里面的不锈钢空气喷布器而强制通过溶液,然而如现有技术中已知的许多其他方式可以用来将空气起泡通过铁/酸溶液。继续该空气流并且将反应温度保持在少于约38°(100)直到基本上所有的游离铁被消耗并且形成铁浆料。该浆料被认为包括氧化铁水合物、氧化铁、氢氧化铁、羟基氧化铁或其组合。取决于铁源,总的铁消耗时间可以约24小时-约48小时,或者更长。在反应期间,浆料颜色从灰色变成褐色。一般地,颜色变化将在空气流开始之后约45分钟-约6小时变得明显。可以通过X-射线衍射图检测未反应的铁。
将铁浆料研磨成小颗粒尺寸,例如少于约40μm的中值颗粒尺寸,优选少于约10μm的颗粒尺寸。在这里存在的实施例中,使用SEPR、ER120A0.8/1.25mm瓷珠的Netzsch研磨机。然而,几种不同的研磨技术是现有技术中已知的并且可以用来代替Netzsch研磨机。
使用现有技术中已知的标准技术确定浆料中的铁含量并且将促进剂加入该浆料。加入的特定促进剂和在其中加入促进剂的浓度可以取决于应用而变化。如果促进剂作为晶体加入,该晶体可以在加入到浆料中之前溶于少量的水中。在加入促进剂之后,产品浆料应该具有约10%-约40%的固含量。
然后采用齿轮喷雾器将该浆料喷雾干燥。进口温度设定到约260℃(500),出口温度保持在约149℃(300)。优选约50μm-80μm的中值颗粒尺寸(齿轮速度约13,000rpm)。喷雾干燥后,催化剂的表面积约10m2/g-约40m2/g。然后将喷雾干燥的催化剂煅烧并且筛分以除去大颗粒。在于设定在约662的箱式炉中煅烧约4小时之后,催化剂的表面积约10m2/g-约80m2/g。喷雾干燥的催化剂具有基本球形的形状。
下列实施例阐述并解释了本发明,但不理解为从任何方面限定本发明。实施例1描述了使用常规的沉淀方法制备费-托催化剂。实施例2-8描述了使用根据本发明的最少流出物方法制备费-托催化剂。
实施例1:通过如下的现有技术沉淀方法制备费-托催化剂比较样品:
通过将约133.55kg硝酸铁溶液(7%Fe(w/w);可从ShepherdChemical,Cincinnati,OH商购获得)加到170升(45加仑)不锈钢槽中而制得约13.6kg(30磅)的氧化铁。加入去离子水直到总体积约159升(42加仑)。将硝酸铁溶液彻底混合。
然后在约890ml/分钟的进料速率下将硝酸铁溶液送入洞切口在约6.5升水平的约8升不锈钢沉淀槽。在约400ml/分钟的初始进料速率下将氨水溶液(29%w/w)基本顺流地送入沉淀槽。在沉淀容器中,合并的溶液的停留时间约5分钟。用高剪切混合器将沉淀容器中的溶液混合,调节氨水溶液进料速率以使得沉淀容器中的合并溶液的pH约10.0。形成浆料并且允许从沉淀容器上溢流到不锈钢上溢槽(容量约416升(110加仑))中,在那里其继续混合。当硝酸铁溶液被消耗时,停止氨水溶液流,在上溢槽中存在约189升(50加仑)的浆料。
该浆料通过压滤机过滤以形成滤出液,并且使用现有技术中已知的标准技术测定滤出液的电导率。用空气处理滤出液或滤饼直到坚硬。将滤饼装入容量约416升(110加仑)的不锈钢槽中并且加入约136升(36加仑)去离子水。滤饼和水彻底混合并且重复过滤过程。重复洗涤和过滤步骤直到滤出液的电导率约300μS。(这可能需要例如约7次洗涤和8次过滤。)
使用现有技术中已知的标准技术测定浆料中的铁含量,并且将促进剂加入该浆料。该浆料中每约100g的铁,加入Cu(NO3)2·21/2H2O晶体(可从Aldrich,Milwaukee,WI商购获得)或者Cu(NO3)2溶液(28%Cu,w/v(SCI设备材料)以供应约0.5g铜并且加入硝酸钾(可从Aldrich,Milwaukee,WI商购获得)以供应约0.2g K2O。如果促进剂作为晶体加入,该晶体在加入到浆料中之前可以溶于最小数量的水。
然后采用齿轮喷雾器(APV无水喷雾器)将该浆料喷雾干燥。进口温度设定到约260℃(500),出口温度保持在约149℃(300)。优选50-60μm的中值颗粒尺寸(13,000rpm)。然后在箱式炉中于约350℃(662)下将喷雾干燥的催化剂煅烧4小时。制得约9kg(20磅)催化剂。
实施例2:通过实施例1中提出的比较方法制备费-托催化剂样品,除了在洗涤和过滤步骤之后然后将约25ml硝酸加到约11.3kg(25磅)滤饼中并且彻底混合以使得滤饼随着搅拌变成流体。如所必要的可以加入水以促进混合。溶液的固含量应该在约15%-约20%。然后测定铁含量,加入促进剂,如实施例1中那样将该浆料喷雾干燥。
实施例3:通过实施例1中提出的比较方法制备费-托催化剂样品,除了在洗涤和过滤步骤之后通过SEPR、ER 120A0.8/1.25mm瓷珠的Netzsch研磨机将产品研磨成少于约2μm的中值颗粒尺寸。然后测定铁含量,加入促进剂,如实施例1中那样将该浆料喷雾干燥。
实施例4:通过实施例2中提出的比较方法制备费-托催化剂样品,除了在加入硝酸之后通过SEPR、ER 120A0.8/1.25mm瓷珠的Netzsch研磨机将产品研磨成少于约2μm的中值颗粒尺寸。
实施例5:通过在此提出的本发明方法制备费-托催化剂样品:
将不锈钢空气喷布器装入189升(50加仑)Nalgene辊筒的底部。将约136升(36加仑)去离子水和约7.5kg(16.5磅)甲酸(90%,可通过Specialty Chemical Co.LCC,Cleveland,TN,USA商购获得)加入辊筒并且彻底混合。伴随着混合将约18kg(40磅)铁粉(可从Pyron,Niagara Falls,NY,USA商购获得并且指定为产品号AC-325)加入甲酸溶液。足够缓慢地加入铁粉以将反应温度保持少于约38℃(100)。
在加入铁粉并且已经形成浆料之后使压缩空气通过喷布器。继续该空气流并且将反应温度保持在约38℃(100)直到基本所有的游离铁被消耗,或者保持约24小时。可以通过XRD检测未反应的铁。
通过SEPR、ER 120A0.8/1.25mm瓷珠的Netzsch研磨机将铁浆料研磨成少于约2μm的中值颗粒尺寸。使用现有技术中已知的标准技术测定浆料中的铁含量,并且将促进剂加入该浆料。该浆料中每约100g的铁,加入Cu(NO3)2·21/2H2O晶体(可从Aldrich,Milwaukee,WI商购获得)或者Cu(NO3)2溶液(28%Cu,w/v(SCI设备材料)以供应约0.5g铜并且加入硝酸钾(可从Aldrich,Milwaukee,WI商购获得)以供应约0.2g K2O。如果促进剂作为晶体加入,该晶体在加入到浆料中之前可以溶于最小数量的水。
然后采用齿轮喷雾器(APV无水喷雾器)将该浆料喷雾干燥。进口温度设定到约260℃(500),出口温度保持在约149(300)。优选50-60μm的中值颗粒尺寸(13,000rpm)。然后在箱式炉中于约350℃(662)下将喷雾干燥的催化剂煅烧4小时并且筛分以除去大颗粒(-150μm或-250μm)(-100或-60筛目))。制得约18.2kg(40磅)催化剂。
实施例6:通过实施例5中提出的本发明方法制备费-托催化剂样品,除了用Hoegans AB(Hoegans,瑞典)ASC-300代替铁粉AC-325,并且将通风时间增加到约48小时。
实施例8:通过实施例5中提出的本发明方法制备费-托催化剂样品,除了用乙酸代替甲酸,并且将通风时间增加到约30小时。
实施例9:通过实施例5中提出的本发明方法制备费-托催化剂样品,除了用草酸代替甲酸,并且将通风时间增加到约36小时。
实施例10:通过实施例5中提出的本发明方法制备费-托催化剂样品,除了用丙酮酸代替甲酸,并且将通风时间增加到约36小时。
实施例11:通过实施例5中提出的本发明方法制备费-托催化剂样品,除了用乙醇酸代替甲酸,并且将通风时间增加到约32小时。
实施例12:通过实施例5中提出的本发明方法制备费-托催化剂样品,除了用丙酸代替甲酸,并且将通风时间增加到约37小时。
如前所述,本发明中使用的水的数量显著地少于常规沉淀方法中使用的数量。这可以通过比较例如实施例4(沉淀方法)和实施例5(本发明方法)中使用的水的数量来说明。如表I中所示,通过实施例4的方法制备催化剂需要约2.2吨(4836磅)的水输入量。通过实施例5的方法制备催化剂需要约136kg(300磅)水或者比实施例4的方法中所使用少约16倍的水。
表I | |||||||||
实施例4 | 实施例5 | ||||||||
输入 | kg | 磅 | 摩尔数 | 磅摩尔数 | 输入 | kg | 磅 | 摩尔数 | 磅摩尔数 |
硝酸铁Fe(NO3)3 | 78.6 | 173.20 | 0.32 | 0.72 | 铁(Fe) | 18.14 | 40.00 | 0.32 | 0.72 |
氨源(NH4OH) | 32.4 | 71.56 | 0.93 | 2.04 | 甲酸(CH2O2) | 7.48 | 16.50 | 0.16 | 0.36 |
稀释水(H2O) | 379.10 | 835.77 | 21.06 | 46.43 | 水(H2O) | 135.97 | 299.77 | 7.55 | 16.65 |
洗涤水(H2O) | 1814.19 | 4000.26 | 100.81 | 222.24 | 氧气(O2) | 7.80 | 17.19 | 0.24 | 1.07 |
硝酸(HNO3) | 0.25 | 0.54 | 0.004 | 0.01 | |||||
总量 | 2304.85 | 5081.33 | 123.12 | 271.44 | 总量 | 169.40 | 373.46 | 8.27 | 18.80 |
产出 | 磅 | 按磅计的摩尔数 | 产出 | kg | 磅 | 按磅计的摩尔数 | |||
氧化铁(Fe2O3) | 25.94 | 57.19 | 0.16 | 0.72 | 氧化铁(Fe2O3) | 25.94 | 57.19 | 0.16 | 0.72 |
硝酸铵(NH4NO3) | 74.16 | 163.57 | 0.93 | 2.04 | 废水(H2O) | 0.00 | 0.00 | 0.00 | 0.00 |
废水(H2O) | 2084.19 | 4594.86 | 255.27 | 255.27 | 水蒸汽(H2O) | 135.97 | 299.77 | 7.55 | 16.65 |
水蒸汽(H2O) | 118.18 | 260.54 | 14.47 | 14.47 | 氢气(H2) | 0.33 | 0.72 | 0.17 | 0.36 |
NO2 | 2.34 | 5.17 | 0.05 | 0.11 | CO2 | 7.16 | 15.78 | 0.16 | 0.36 |
总量 | 2304.85 | 5081.33 | 270.88 | 272.62 | 总量 | 169.40 | 373.46 | 8.04 | 18.09 |
总的输入H2O用量 | 2193.59 | 4836.03 | 121.87 | 268.67 | 总的输入H2O用量 | 135.97 | 299.77 | 7.55 | 16.65 |
总的H2O输出量 | 2202.37 | 4855.40 | 122.35 | 269.40 | 总的H2O输出量 | 135.77 | 299.77 | 7.55 | 16.65 |
另外,因为本发明方法需要比沉淀方法更少的水输入到方法中,因此产生了显著更少的废水。例如,与产生2202.37kg(4855磅)废水的实施例4相比,实施例5产生了135.97kg(299.77)磅废水。而且本发明的废水更干净,即其基本不含有硫酸盐、硝酸盐或氯化物。
图1和2分别是如实施例1和6描述的那样制备的催化剂的扫描电子显微照片。如现有技术中已知的,颗粒形状可以影响催化剂的物理性能例如颗粒强度和耐磨耗性。球形颗粒会比非球形颗粒具有更大的颗粒强度和更多的耐磨耗性。颗粒尺寸可以影响催化剂性能例如流体分布和压力下降,并且为了商业操作而优选相对窄范围内的颗粒。如图2中所示,由铁粉制备的催化剂具有基本球形的形状并且具有相对窄的颗粒尺寸分布范围。通过比较,如图1中所示,通过现有技术沉淀方法制备的催化剂具有变化的形状和颗粒尺寸。
本发明的催化剂目的在于用于费-托方法并且具有与现有技术的F-T催化剂相似的组成。然而,制备该催化剂的方法使用更少的水,产生更少的废水,是更有效的,并且制得了基本不含污染物并且具有基本球形的颗粒形状和相对小的颗粒尺寸分布范围的最后产品。我们理解:催化剂的组成和特定的加工条件可以变化,而不超过本研制的范围。
Claims (12)
1.一种制备用于转化合成气的至少一种组分的催化剂的方法,所述方法包括:
a)制备含水的有机酸溶液,其中所述有机酸是含有至少一个羧酸基团、pKa在大气温度下为0.5-6的羧酸;
b)将铁金属加到所述酸溶液中;
c)将氧化剂强制通过所述酸溶液直到所述铁金属被消耗并且形成铁浆料;
d)将所述铁浆料研磨成少于2微米的中值颗粒尺寸;
e)将至少一种促进剂加到所述研磨的铁浆料中以形成产品浆料,在使得所述产品浆料的固含量为包括所述促进剂在内的10%-40%的浓度下加入所述促进剂;
f)将所述浆料喷雾干燥以形成颗粒;和
g)将所述颗粒煅烧以形成所述催化剂。
2.权利要求1的方法,其中所述有机酸选自甲酸、乙酸、乙醇酸、草酸、丙酮酸、丙二酸和丙酸,及其组合。
3.权利要求1的方法,其中所述铁金属是平均直径1μm-500μm的粉末、颗粒、球状、碎片或其他形式。
4.权利要求1的方法,其中所述促进剂选自铜、碱金属、碱土金属和其组合。
5.权利要求4的方法,其中所述碱金属选自钠、钾、铷、铯和其组合。
6.权利要求4的方法,其中所述碱金属选自镁、钙、锶、钡和其组合。
7.权利要求1的方法,其中采用齿轮喷雾器将所述浆料喷雾干燥。
8.权利要求1的方法,其中所述催化剂包括35wt%-70wt%的铁和0.002wt%-40wt%的促进剂。
9.权利要求8的方法,其中所述催化剂具有基本球形的颗粒形状和相对小的颗粒尺寸分布范围。
10.权利要求1的方法,其中所述氧化剂是空气、压缩空气、氧气、过氧化氢、有机过氧化物、臭氧和其组合。
11.一种用于转化合成气的至少一种组分的催化剂,所述催化剂根据权利要求1-10任一项的方法通过以下步骤制备:使铁源与有机酸和空气反应以形成氧化铁浆料,将一种或多种促进剂加到所述氧化铁浆料中以形成产品浆料,和将所述的产品浆料喷雾干燥并且煅烧,和所述催化剂包括35wt%-70wt%的铁和0.002wt%-40wt%的促进剂。
12.权利要求11的催化剂,进一步包括:将所述氧化铁浆料研磨成少于2μm的中值颗粒尺寸。
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US10/343,935 US7199077B2 (en) | 2002-05-15 | 2002-05-15 | Fischer-tropsch catalyst prepared with a high purity iron precursor |
PCT/US2002/015310 WO2003097236A1 (en) | 2002-05-15 | 2002-05-15 | Fischer-tropsch catalyst prepared with a high purity iron precursor |
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