CN106000404B - 一种用于费托合成的碳改性二氧化硅载体负载的铁基催化剂的制备及其应用 - Google Patents
一种用于费托合成的碳改性二氧化硅载体负载的铁基催化剂的制备及其应用 Download PDFInfo
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- CN106000404B CN106000404B CN201610348097.4A CN201610348097A CN106000404B CN 106000404 B CN106000404 B CN 106000404B CN 201610348097 A CN201610348097 A CN 201610348097A CN 106000404 B CN106000404 B CN 106000404B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 30
- -1 carbon modified silica Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- 150000001336 alkenes Chemical class 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 16
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 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 claims description 4
- 238000002803 maceration Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- 239000012692 Fe precursor Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910003978 SiClx Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- ICAIHGOJRDCMHE-UHFFFAOYSA-O ammonium cyanide Chemical compound [NH4+].N#[C-] ICAIHGOJRDCMHE-UHFFFAOYSA-O 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 2
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 2
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 2
- 241000978776 Senegalia senegal Species 0.000 claims 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 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 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052635 ferrosilite Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 59
- 238000012360 testing method Methods 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 26
- 229910052681 coesite Inorganic materials 0.000 description 16
- 229910052906 cristobalite Inorganic materials 0.000 description 16
- 229910052682 stishovite Inorganic materials 0.000 description 16
- 229910052905 tridymite Inorganic materials 0.000 description 16
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000306 component Substances 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 244000215068 Acacia senegal Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- MVZXTUSAYBWAAM-UHFFFAOYSA-N iron;sulfuric acid Chemical compound [Fe].OS(O)(=O)=O MVZXTUSAYBWAAM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
-
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
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Abstract
本发明公开了一种用于费托合成的碳改性二氧化硅载体负载的铁基催化剂的制备及其应用。本发明催化剂采用碳改性的具有二级孔结构的二氧化硅作为载体,铁作为主催化剂并添加助剂。二级孔结构是由初级二氧化硅大孔结构和碳膜层改性形成的小孔结构组成。这种二级孔结构不仅有利于提高活性组分铁的分散、阻止其与二氧化硅载体形成不可还原的硅酸铁和促进铁碳化活化,且能有效抑制费托初次产品的二次加氢,获得高费托反应活性和烯烃产品选择性。此外,本发明提供的催化剂具有优异的机械强度和水热稳定性,适合浆态床和流化床费托合成;催化剂制备原料廉价,制备方法简单,重复性好,适合工业生产应用。
Description
技术领域
本发明属于合成气转化技术领域,涉及一种碳改性二氧化硅负载的铁基催化剂的制备及其在费托反应中的应用。
背景技术
烯烃,尤其是低碳烯烃(乙烯、丙烯、丁烯)是重要的化工原料,目前主要来源于石脑油裂解。基于我国富煤、少气、缺油的资源构成特点,以非石油路线合成烯烃引起越来越多的关注。而以煤基合成气直接制备烯烃具有流程短、能耗和煤耗低的优势,是目前研究的热点之一。
目前用于合成气费托合成烯烃的催化剂中,以铁基和钴基催化剂研究的较为充分。相比较钴基催化剂,铁基催化剂具有成本低、烯烃选择性高以及高温下甲烷选择性低等优势。而且由于铁基催化剂较高的逆水煤气变换活性和较好的耐硫、氯等中毒的能力,对原料组成要求低,适合煤、生物质、劣质渣油和石油沥青等含碳资源转化得到的合成气的费托反应,具有较广的应用范围。
目前关于铁基催化剂的报道多集中在沉淀铁和负载型铁基催化剂。沉淀铁催化剂尽管可获得较高的催化活性和烯烃选择性,然而催化剂机械强度较差,相比较而言,负载型催化剂的孔结构和比表面积容易通过载体的可控制备来调节,且具有很好的机械强度,适应于对传质和机械强度要求较高的浆态床和流化床费托合成。中国专利CN104549354A采用包括活性炭、无定形碳、炭黑、介孔碳、碳纳米管、石墨烯等在内的碳材料作为载体,得到了活性组分分散度很高的催化剂;专利CN103664437A采用碳化硅作为载体,负载铁和钴作为活性组分,CO单程转化率可达95%以上,且烯烃的选择性高达80%。这些负载型催化剂在费托合成烯烃中显示出了良好的催化性能。
二氧化硅载体价廉易得,具有机械强度高、易成型以及孔径和比表面积易调节等优势。传质是影响费托合成反应性能的重要因素,大孔径便于合成气进入催化剂孔道进行反应和反应产物及时扩散离开催化剂孔道,从而减少初次产品烯烃的二次加氢和氢解反应可能性,有利于提高烯烃和降低甲烷选择性。尽管大孔径有利于传质,然而大孔径载体通常具有较小的比表面积,不利于活性组分的高分散,从而降低了其利用效率。催化剂制备过程中铁容易与二氧化硅反应形成较难还原的硅酸铁,限制了铁的还原活化,导致较低的反应活性;强的铁与载体相互作用,会大大弱化助剂对铁催化性能的提升效果。碳材料往往具有较高的比表面积,有利于活性组分的高分散,而且碳材料有利于铁的碳化活化,是优异的铁基费托催化剂载体,可以获得很高的费托反应活性。活性组分和碳材料之间相互作用较弱,助剂对其催化活性、选择性的提升效果显著。碳材料还具有很好的疏水性能,具有高的水热稳定性。碳材料尽管具有较高的比表面积,然而很难合成大孔结构,不利于合成气和反应产物的有效传质,且机械强度差,不适合浆态床和流化床费托合成。基于上述技术背景,通过结合氧化物和碳材料载体的优势来开发高性能催化剂是解决费托合成反应中存在的主要问题的重要途径。
发明内容
针对现有二氧化硅负载的铁基催化剂存在的费托活性低、且活性和烯烃选择性难以提升的问题,提供一种碳改性的具有二级孔结构二氧化硅负载铁基催化剂的制备及其在费托反应中的应用。
本发明涉及一种用于合成气制烯烃的高活性、高烯烃选择性负载型铁基催化剂,其特征在于:催化剂载体为碳改性的具有二级孔结构的二氧化硅,催化剂主活性组分为铁,并添加或不添加助剂。其中二氧化硅载体的孔径为3~100nm、比表面积为2~800m2/g;碳改性的二氧化硅载体中碳的量占二氧化硅重量的0.1%~50%,优选1%~20%;催化剂中的铁含量按Fe计占催化剂重量的1%~50%,优选5%~30%;所添加的助剂为N、K、Na、Ca、Pt、Au、Mg、Pd、Rh、V、Cr、Mn、Ru、Co、Cu、Zn、Zr、Ga、Gd、Re、Mo、Nb元素中一种或两种以上,助剂含量占催化剂重量的0~20%,优选0.1%~10%。
本发明所涉及用于合成气制烯烃的高活性、高烯烃选择性负载型铁基催化剂的载体为经过碳改性的具有二级孔结构的二氧化硅,采用下述方法之一制备:
1)单次浸渍法。按照催化剂组成配比,将碳源配成溶液,以等体积或者过量体积浸渍到二氧化硅载体上,于50~120℃干燥后在150~600℃下惰性气体氛围中焙烧1~10h,焙烧空速为500~30000h-1。
2)多次浸渍法。将碳源分多次浸渍到二氧化硅载体上:重复上述单次浸渍法中的浸渍、干燥、焙烧步骤直至碳源的量达到催化剂组成配比。其中最后一次焙烧步骤的条件为150~600℃下惰性气体氛围中焙烧1~10h,其余焙烧步骤的条件为150~250℃下惰性气体氛围中焙烧1~10h;焙烧空速均为500~30000h-1。
上述碳改性的具有二级孔结构的二氧化硅载体的制备,其特征在于:碳源选自葡萄糖、蔗糖、麦芽糖、阿拉伯树胶、聚丙烯酸、P123(聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物)、聚乙烯亚胺、聚乙烯吡咯烷酮、聚苯乙烯、聚酰胺中的一种或两种以上,包括但不限于上述碳源;溶剂选自水、乙醇、丙醇、1,4-丁二醇、丙酮、甲苯、异丙醇、正己烷、对二甲苯中的一种或两种以上,包括但不限于上述溶剂。
本发明所涉及合成气制烯烃的高活性、高烯烃选择性负载型铁基催化剂,其特征在于采用下述方法之一制备:
(1)单次浸渍法。将铁前驱体、助剂按照催化剂组成配比配置成溶液,以等体积或者过量体积浸渍到上述碳改性的具有二级孔结构的二氧化硅载体上,旋转蒸发干燥后在200~600℃下惰性气体氛围中焙烧1~10h,焙烧空速为500~20000h-1。
(2)多次浸渍法。将铁前躯体和助剂分多次浸渍到上述碳改性的具有二级孔结构的二氧化硅载体上。重复上述单次浸渍中所述的浸渍、干燥和焙烧步骤直至铁前驱体和助剂的量达到催化剂组成配比。其中最后一次焙烧步骤的条件为200~600℃下惰性气体氛围中焙烧1~10h;其余焙烧步骤的条件为150~250℃下惰性气体氛围中焙烧1~10h;焙烧空速均为500~20000h-1。
上述催化剂制备过程中,铁前驱体选自硝酸铁、醋酸铁、氯化铁、柠檬酸铁铵、硫酸铁、亚铁氰化铵、硫氰酸铁、亚铁氰化钠、乙酰丙酮铁、草酸铁、亚铁氰化铁中一种或两种以上,包括但不限于上述铁前驱体源;助剂选自醋酸盐、硝酸盐、碳酸盐、乙酰丙酮盐、氯化盐、氰化盐、草酸盐、柠檬酸盐、硫氰酸盐中的一种或两种以上;惰性气体选自氮气、氩气、氦气中的一种或两种以上。
上述铁基催化剂在合成气费托反应中的应用,其特征在于反应可在固定床或流化床或浆态床反应器中进行,优选流化床、浆态床反应器;催化剂在使用前需经过还原预处理:预处理气氛为H2或CO或H2/CO;预处理温度为200~500℃;预处理时间为1~12h;预处理空速为500~20000h-1。反应条件:反应温度为150~350℃,反应压力为0.2~3MPa,反应空速为500~20000h-1。
上述合成气费托反应用的铁基催化剂的制备和应用同样适用于钴基催化剂及其费托合成。
上述铁基或钴基催化剂的制备及其应用,所用二氧化硅载体的碳改性的方法和其负载型催化剂的制备及其在费托合成中的应用,同样适用于三氧化二铝载体,三氧化二铝载体的特征在于:孔径为3~50nm、比表面积为5~800m2/g。
本发明的优点如下:
(1)本发明采用有机碳源对二氧化硅载体进行改性形成二级孔结构,即初级二氧化硅大孔结构和碳膜层在大孔内壁表面改性形成的小孔结构。碳膜层改性形成的小孔结构能大幅增加催化剂的比表面积,有利于提高活性组分的分散、阻止铁与二氧化硅形成难还原的硅酸铁和促进铁的碳化活化,从而获得高的费托反应活性;初级二氧化硅载体大孔道有利于费托反应初次产品烯烃及时扩散离开催化剂表面,抑制了烯烃的二次加氢和氢解,从而提高烯烃和降低甲烷选择性。
(2)与活性炭载体比较,这种二氧化硅改性形成的二级孔结构载体用于制备负载型铁基催化剂具有优异的机械强度和水热稳定性,特别适合浆态床和流化床费托合成。
(3)本发明所制备的催化剂机械强度高、稳定性好,催化剂制备原料廉价,制备方法简单,重复性好,适合工业生产应用。
附图说明
图1催化剂结构示意图
具体实施方式
本发明技术细节通过下述实施例做详细的说明。需要说明的是所举的实施例,其作用只是进一步说明本发明的技术特征,而不是限定本发明。同时,实施例只是给出了实现此目的的部分条件,并不意味着必须满足这些条件才可以达到此目的。为方便描述,平均孔径为10nm的二氧化硅载体记为S-10;将平均孔径为25nm的二氧化硅载体记为S-25;平均孔径为50nm的二氧化硅载体记为S-50。分为催化剂的制备及其活性测试、催化剂的制备及其稳定性测试两部分内容。
(1)催化剂的制备及其活性测试
实施例1
1)制备碳改性二氧化硅载体5C-S10。将1.189g蔗糖配成水溶液,等体积浸渍在10gSiO2(S-10)载体上,常温下浸渍10h后旋转蒸发干燥,最后于氮气氛围中450℃、4000h-1下焙烧4h,得到碳改性二氧化硅载体5C-S10。
2)制备15Fe/5C-S10催化剂。将10.821g Fe(NO3)3·9H2O配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe/5C-S10。
3)活性测试。在固定床反应器中对所制备催化剂进行活性评价。催化剂首先进行原位还原,还原条件如下:0.2MPa、纯H2、体积空速为2220h-1、350℃原位还原3h。反应条件为:H2/CO=1.0,温度为300℃,压力为1.0MPa,空速为2220h-1,活性测试时间为10h,活性测试结果取5-10h平均值,见表1。
实施例2
1)制备碳改性二氧化硅载体10C-S10。将2.378g蔗糖配成水溶液,等体积浸渍在10g SiO2(S-10)载体上,常温下浸渍10h后旋转蒸发干燥,最后于氮气氛围中450℃、4000h-1下焙烧4h,得到碳改性二氧化硅载体10C-S10。
2)制备15Fe/10C-S10催化剂。将10.821g Fe(NO3)3·9H2O配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe/10C-S10。
3)活性测试同实施例1,结果见表1。
实施例3
1)制备碳改性二氧化硅载体15C-S10。将3.567g蔗糖配成水溶液,等体积浸渍在10g SiO2(S-10)载体上,常温下浸渍10h后旋转蒸发干燥,最后于氮气氛围中450℃、4000h-1下焙烧4h,得到碳改性二氧化硅载体15C-S10。
2)制备15Fe/15C-S10催化剂。将10.821g Fe(NO3)3·9H2O配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe/15C-S10。
3)活性测试同实施例1,结果见表1。
实施例4
1)制备碳改性二氧化硅载体10C-S25。将2.378g蔗糖配成水溶液,等体积浸渍在10g SiO2(S-25)载体上,常温下浸渍10h后旋转蒸发干燥,最后于氮气氛围中450℃、4000h-1下焙烧4h,得到碳改性二氧化硅载体10C-S25。
2)制备15Fe/10C-S25催化剂。将10.821g Fe(NO3)3·9H2O配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe/10C-S25。
3)活性测试同实施例1,结果见表1。
实施例5
1)制备碳改性二氧化硅载体10C-S50。将2.378g蔗糖配成水溶液,等体积浸渍在10g SiO2(S-50)载体上,常温下浸渍10h后旋转蒸发干燥,最后于氮气氛围中450℃、4000h-1下焙烧4h,得到碳改性二氧化硅载体10C-S50。
2)制备15Fe/10C-S50催化剂。将10.821g Fe(NO3)3·9H2O配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe/10C-S50。
3)活性测试同实施例1,结果见表1。
实施例6
1)制备碳改性二氧化硅载体10C-S50,同实施例5。
2)采用二次浸渍法制备催化剂30Fe/10C-S50。①将10.821gFe(NO3)3·9H2O配成水溶液,等体积浸渍在7.0g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,在120℃下干燥12h后在氮气氛围中200℃、4000h-1下焙烧3h得到一次浸渍样品;②将10.821g Fe(NO3)3·9H2O配成水溶液,等体积浸渍在步骤①所得一次浸渍样品上。常温下浸渍1h后在80℃下负压旋转蒸发至干,120℃下干燥12h,最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂30Fe/10C-S50。
3)活性测试同实施例1,结果见表1。
实施例7
1)制备碳改性二氧化硅载体10C-S50,同实施例5。
2)制备15Fe0.4K/10C-S50催化剂。将10.821g Fe(NO3)3·9H2O、0.104g KNO3配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.4K/10C-S50。
3)活性测试同实施例1,结果见表1。
实施例8
1)制备碳改性二氧化硅载体10C-S50,同实施例5。
2)制备15Fe0.8K/10C-S50催化剂。将10.821g Fe(NO3)3·9H2O、0.208g KNO3配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.8K/10C-S50。
3)活性测试同实施例1,结果见表1。
实施例9
1)制备碳改性二氧化硅载体10C-S50,同实施例5。
2)制备15Fe0.8K0.2Cu/10C-S50催化剂。将10.821gFe(NO3)3·9H2O、0.208g KNO3、0.059g Cu(NO3)2配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.8K0.2Cu/10C-S50。
3)活性测试同实施例1,结果见表1。
实施例10
1)制备碳改性二氧化硅载体10C-S50,同实施例5。
2)制备15Fe0.2Mn/10C-S50催化剂。将10.821g Fe(NO3)3·9H2O、0.189g Mn(CH3COO)2配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.6Mn/10C-S50。
3)活性测试同实施例1,结果见表1。
实施例11
1)制备碳、氮改性二氧化硅载体10C2N-S50。将1.528g聚乙烯吡咯烷酮配成乙醇溶液,等体积浸渍在10g SiO2(S-50)载体上,常温下浸渍2h后旋转蒸发干燥,最后于N2氛围中5000h-1、400℃下焙烧2h,得到碳、氮改性二氧化硅载体10C2N-S50。
2)制备15Fe/10C2N-S50催化剂。将10.821g Fe(NO3)3·9H2O配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe/10C2N-S50。
3)活性测试同实施例1,结果见表1。
实施例12
1)制备碳、氮改性二氧化硅载体10C2N-S50,同实施例11。
2)制备15Fe0.2Cu/10C2N-S50催化剂。将Fe(NO3)3·9H2O10.821g、Cu(NO3)2 0.059g配成水溶液,等体积浸渍在8.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.2Cu/10C2N-S50。
3)活性测试同实施例1,结果见表1。
对比例1
1)制备载体未改性的负载型催化剂15Fe/S10。将10.821gFe(NO3)3·9H2O配成水溶液,等体积浸渍在8.5g SiO2(S-10)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe/S10。
2)活性测试条件同实施例1,结果见表2。
对比例2
1)制备载体未改性的负载型催化剂15Fe/S25。将10.821gFe(NO3)3·9H2O配成水溶液,等体积浸渍在8.5g SiO2(S-25)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe/S25。
3)活性测试同实施例1,结果见表2。
对比例3
1)制备载体未改性的负载型催化剂15Fe/S50。将10.821gFe(NO3)3·9H2O配成水溶液,等体积浸渍在8.5g SiO2(S-50)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe/S50。
3)活性测试同实施例1,结果见表2。
对比例4
1)采用二次浸渍法制备催化剂30Fe/S50。①将10.821gFe(NO3)3·9H2O配成水溶液,等体积浸渍在7.0g SiO2(S-50)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,在120℃下干燥12h后在氮气氛围中200℃、4000h-1下焙烧3h得到一次浸渍样品;②将10.821g Fe(NO3)3·9H2O配成水溶液,等体积浸渍在步骤①所得一次浸渍样品上。常温下浸渍1h后在80℃下负压旋转蒸发至干,120℃下干燥12h,最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂30Fe/S50。
3)活性测试同实施例1,结果见表2。
对比例5
1)制备载体未改性的负载型催化剂15Fe0.4K/S50。将10.821gFe(NO3)3·9H2O、0.104g KNO3配成水溶液,等体积浸渍在8.5g SiO2(S-50)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.4K/S50。
3)活性测试同实施例1,结果见表2。
对比例6
1)制备载体未改性的负载型催化剂15Fe0.8K/S50。将10.821gFe(NO3)3·9H2O、0.208g KNO3配成水溶液,等体积浸渍在8.5g SiO2(S-50)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.8K/S50。
3)活性测试同实施例1,结果见表2。
对比例7
1)制备载体未改性的负载型催化剂15Fe0.8K0.2Cu/S50。将10.821g Fe(NO3)3·9H2O、0.208g KNO3、0.059g Cu(NO3)2配成水溶液,等体积浸渍在8.5g SiO2(S-50)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.8K0.2Cu/S50。
3)活性测试同实施例1,结果见表2。
对比例8
1)制备载体未改性的负载型催化剂15Fe0.6Mn/S50。将10.821gFe(NO3)3·9H2O、0.189g Mn(CH3COO)2配成水溶液,等体积浸渍在8.5gSiO2(S-50)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.6Mn/S50。
3)活性测试同实施例1,结果见表2。
对比例9
1)制备载体未改性的负载型催化剂15Fe0.2Cu/S50。将10.821gFe(NO3)3·9H2O、0.059g Cu(NO3)2配成水溶液,等体积浸渍在8.5g SiO2(S-50)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂15Fe0.2Cu/S50。
3)活性测试同实施例1,结果见表2。
(2)催化剂的制备及其稳定性测试
实施例13
1)制备碳改性二氧化硅载体10C-S50,将2.378g蔗糖配成水溶液,等体积浸渍在10g SiO2(S-50)载体上,常温下浸渍10h后旋转蒸发干燥,最后于氮气氛围中450℃、4000h-1下焙烧4h,得到碳改性二氧化硅载体10C-S50。
2)制备25Fe0.8K0.2Cu/10C-S50催化剂。将18.035gFe(NO3)3·9H2O、0.208g KNO3、0.059g Cu(NO3)2配成水溶液,等体积浸渍在7.5g步骤1)所得载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂25Fe0.8K0.2Cu/10C-S50。
3)在固定床反应器中对所得催化剂进行寿命评价。还原条件如下:0.2MPa、纯H2、体积空速为2220h-1、350℃原位还原3h。反应条件为:H2/CO=1.0,温度为300℃,压力为1.0MPa,空速为3000h-1,活性测试时间为2000h,结果见表3.
对比例10
1)制备载体未改性的负载型催化剂25Fe0.8K0.2Cu/S50。将18.035g Fe(NO3)3·9H2O、0.208g KNO3、0.059g Cu(NO3)2配成水溶液,等体积浸渍在7.5g SiO2(S-50)载体上。常温下浸渍2h后在80℃下负压旋转蒸发至干,并在120℃下干燥12h。最后在氮气氛围中300℃、5000h-1下焙烧5h,制得催化剂25Fe0.8K0.2Cu/S50。
3)在固定床反应器中对所得催化剂进行寿命评价。还原条件如下:0.2MPa、纯H2、体积空速为2220h-1、350℃原位还原3h。反应条件为:H2/CO=1.0,温度为300℃,压力为1.0MPa,空速为1000h-1,活性测试时间为2000h,结果见表4.
表1碳改性载体负载催化剂在合成气转化制烯烃中的反应性能
表2对比例催化剂在合成气转化制烯烃中的反应性能
表3碳改性载体负载催化剂25Fe0.8K0.2Cu/10C-S50稳定性评价结果
反应条件为:H2/CO=1.0、温度为300℃、压力为1.0MPa、空速为3000h-1
表4对比例催化剂25Fe0.8K0.2Cu/S50稳定性评价结果
反应条件为:H2/CO=1.0、温度为300℃、压力为1.0MPa、空速为1000h-1
对比表1-4可以看出,载体经过碳改性后,催化剂的活性和烯烃选择性都有大幅度的提高。载体初级孔径大小对催化剂的活性和选择性有很大影响,孔径较大时有利于提高烯烃选择性,但不利于活性组分的分散,费托活性较低。通过助剂改善催化剂的还原性、控制链增长和促进表面中间活性物种的脱氢,可以进一步提高费托反应活性和烯烃选择性。如表3所示,对于碳改性二氧化硅负载的铁基催化剂,在反应温度为300℃时,合成气空速为3000h-1,CO的转化率可以达到80%以上,C2 =~C4 =的选择性可达45%以上,C5+的选择性低于40%,烯烷比可以达到8.6。表3和表4中催化剂2000h费托反应稳定性测试结果表明:未经碳改性的二氧化硅载体负载的铁基催化剂不但烯烃选择性低,且催化剂失活非常明显;而采用碳改性二氧化硅载体制备的铁基催化剂,不但催化活性高、烯烃选择性高,且稳定性好。
Claims (6)
1.一种合成气费托反应方法,其特征在于:所述方法是利用一种用于合成气制烯烃的高活性、高烯烃选择性负载型铁基催化剂,催化剂载体为碳改性的具有二级孔结构的二氧化硅,催化剂主活性组分为铁,并添加或不添加助剂;二氧化硅载体的孔径为 3~100nm、比表面积为2~800m2/g;碳改性的二氧化硅载体中碳的量为二氧化硅重量的0.1%~50%;催化剂中的铁含量按Fe计占催化剂重量的1%~50%;所添加的助剂为N、K、Na、Ca、 Pt、Au、Mg、Pd、Rh、V、Cr、Mn、Ru、Co、Cu、Zn、Zr、Ga、 Gd、Re、Mo、Nb元素中一种或两种以上,助剂含量占催化剂重量的0~20%;
催化剂载体为碳改性的具有二级孔结构的二氧化硅,采用下述方法之一制备:
1)单次浸渍法:按照催化剂组成配比,将碳源配成溶液,以等体积或者过量体积浸渍到二氧化硅载体上,于50~120℃干燥后 在150~600℃下惰性气体氛围中焙烧1~10h,焙烧空速为 500~30000h-1;
2)多次浸渍法:将碳源分多次浸渍到二氧化硅载体上:重复上述单次浸渍法中的浸渍、干燥、焙烧步骤直至碳源的量达到催 化剂组成配比;其中最后一次焙烧步骤的条件为150~600℃下惰性 气体氛围中焙烧1~10h,其余焙烧步骤的条件为150~250℃下惰性气体氛围中焙烧1~10h;每次的焙烧空速均为500~30000h-1;
所述合成气费托反应可在固定床或浆态床或流化床反应器中进行;催化剂在使用前需经过还原预处理:预处理气氛为H2或CO或H2/CO;预处理温度为200~500℃;预处理 时间为1~12h;预处理空速为500~20000h-1;反应条件:反应温度 为150~350℃;反应压力为0.2~3MPa;反应空速为500~20000h-1。
2.根据权利要求1所述的方法,其特征在于,碳改性的二氧化硅载体中碳的量为二氧化硅重量的1%~20%。
3.如权利要求1所述方法,其特征在于,催化剂中的铁含量按Fe计占催化剂重量的5%~30%;助剂含量占催化剂重量的0.1%~10%。
4.如权利要求1所述的方法,其特征在于:碳源选自葡萄糖、蔗糖、麦芽糖、阿拉伯树胶、聚丙烯酸、P123(聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚 物)、聚乙烯亚胺、聚乙烯吡咯烷酮、聚苯乙烯、聚酰胺中的一种或两种以上;所述碳改性的具有二级孔结构的二氧化硅载体的制备过程中浸渍的溶剂选自水、乙醇、丙醇、1,4-丁二醇、丙酮、甲苯、异丙醇、正己烷、对二甲苯中的一种或两种以上。
5.如权利要求1所述的方法,其特征在于,催化剂采用下述方法之一制备:
(1)单次浸渍法:将铁前驱体、助剂按照催化剂组成配比配置成溶液,以等体积或者过量体积浸渍到权利要求1中所述碳改性的具有二级孔结构的二氧化硅载体上,旋转蒸发干燥后在 200~600℃下惰性气体氛围中焙烧1~10h,惰性气体空速为 500~20000h-1;
(2)多次浸渍法:将铁前躯体和助剂分多次浸渍到权利要求1中所述碳改性的具有二级孔结构的二氧化硅载体上;重复上述单次浸渍中所述的浸渍、干燥和焙烧步骤直至铁前驱体和助剂的量达到催化剂组成配比;其中最后一次焙烧步骤的条件为 200~600℃下惰性气体氛围中焙烧1~10h;其余焙烧步骤的条件为150~250℃下惰性气体氛围中焙烧1~10h;焙烧空速均为 500~20000h-1。
6.如权利要求1~5任一项所述方法,其特征在于:铁前驱体选自硝酸铁、醋酸铁、氯化铁、柠檬酸铁铵、硫酸铁、亚铁氰化铵、 硫氰酸铁、亚铁氰化钠、乙酰丙酮铁、草酸铁、亚铁氰化铁中一种或两种以上;助剂选自醋酸盐、 硝酸盐、碳酸盐、乙酰丙酮盐、氯化盐、氰化盐、草酸盐、柠檬 酸盐、硫氰酸盐中的一种或两种以上;惰性气氛选自氩气、 氦气中的一种或两种。
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