CN105964272B - A kind of catalyst for fischer-tropsch synthesis composition and application thereof - Google Patents
A kind of catalyst for fischer-tropsch synthesis composition and application thereof Download PDFInfo
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- CN105964272B CN105964272B CN201610215377.8A CN201610215377A CN105964272B CN 105964272 B CN105964272 B CN 105964272B CN 201610215377 A CN201610215377 A CN 201610215377A CN 105964272 B CN105964272 B CN 105964272B
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- Prior art keywords
- catalyst
- carbon monoxide
- slurry
- olefin polymeric
- added
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002002 slurry Substances 0.000 claims description 37
- 229910052707 ruthenium Inorganic materials 0.000 claims description 21
- 230000000694 effects Effects 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000036961 partial effect Effects 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 43
- 229930195733 hydrocarbon Natural products 0.000 abstract description 39
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 39
- 238000000034 method Methods 0.000 abstract description 29
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 229910017052 cobalt Inorganic materials 0.000 description 26
- 239000010941 cobalt Substances 0.000 description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 16
- 239000003502 gasoline Substances 0.000 description 16
- 230000009467 reduction Effects 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 239000002028 Biomass Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
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- 238000002309 gasification Methods 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
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- 239000000243 solution Substances 0.000 description 6
- 238000002798 spectrophotometry method Methods 0.000 description 6
- 208000019901 Anxiety disease Diseases 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
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- 238000001994 activation Methods 0.000 description 5
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- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- -1 alkene Hydrocarbon Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 241000894007 species Species 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
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- 241001133760 Acoelorraphe Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 241000237970 Conus <genus> Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000001667 episodic effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/75—Cobalt
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- 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
-
- 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
- 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
- C10G2/333—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 platinum-group
-
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Abstract
It the present invention relates to the use of Fischer-Tropsch（FT）The carbon monoxide-olefin polymeric used when reaction as the mixed gas of principal component using hydrogen and carbon monoxide by manufacturing hydro carbons and the method that hydro carbons is manufactured by above-mentioned synthesis gas using FT reactions.More particularly to comprising being carried on complex carrier TiO containing copper sulphate and FT active metals2‑SiO2‑ZrO2Carbon monoxide-olefin polymeric and the hydro carbons characterized by using above-mentioned FT synthetic catalysts manufacturing method.
Description
Technical field
The present invention relates to the use of Fischer-Tropsch (FT) reaction by using hydrogen and carbon monoxide as the mixed gas of principal component (hereinafter referred to as
For " synthesis gas ") it manufactures the carbon monoxide-olefin polymeric used when hydro carbons and hydro carbons is manufactured by above-mentioned synthesis gas using FT reactions
Method.More specifically, be related to comprising be carried on containing copper sulphate and FT active metals complex carrier carbon monoxide-olefin polymeric,
And the manufacturing method of the hydro carbons characterized by using above-mentioned FT synthetic catalysts.
Background technology
As the method by synthesis gas Synthin, Fischer-Tropsch (Fischer-Tropsch) reaction, methanol synthesis reaction etc.
It is well-known.Synthetic technology in ICL for Indirect Coal Liquefaction is by Germany scientist Frans Fischer and Hans Tropsch
In 1,923 first letter i.e. F-T names finding first and with their names, abbreviation F-T synthesis or Fiscber-Tropscb synthesis.According to
By indirect liquefaction technology, not only can from coal the common petroleums product such as extracting gasoline, diesel oil, kerosene, but also can carry
Produce a variety of high value-added products such as the high quality oil product such as Aviation Fuel, lubricating oil and alkene, paraffin.
Since Fischer and Tropsch has found to produce hydrocarbon compound on the iron catalyst of alkalization, Fischer-Tropsch
Synthetic technology just along with the fluctuation and political factor of world's crude oil price and prosperity and decline is indefinite.Fiscber-Tropscb synthesis takes the lead in Germany
Starting industrial applications, Rule chemical company in 1934 has built up First indirect liquefaction process units, and yield is 70,000 tons/year,
To nineteen forty-four, Germany shares 9 factories totally 57 ten thousand tons/year of production capacity.In the same period, Japan, France, China also have 6
Covering device is built up.FT reactions are the catalyst as active metal such as ruthenium of the iron using iron family element, cobalt, nickel, platinum family element.Separately
On the one hand, it is known that methanol synthesis reaction is carried out by Cu-series catalyst, and C2 oxygenatedchemicals (ethyl alcohol, acetaldehyde etc.) synthesis passes through rhodium
Series catalysts carry out.
Currently, Exxon-Mobil (Exxon-Mobil), British Petroleum (BP-Amoco), ConUS oil company
(ConocoPhillips) and synthetic oil company (Syntroleum) etc. is also developing the Fei of oneself-support synthesis technology, transfers the possession of
License technology, and plan to build Fischer-Tropsch synthetic natural gas liquefaction plant in the outlying region for possessing natural gas.F-T is closed
At main chemical reactions：
The main reaction of F-T synthesis：
Generate alkane：NCO+ (2n+1) H2=CnH2n+2+nH2O
Generate alkene：NCO+ (2n) H2=CnH2n+nH2O
In addition there are some side reactions, such as：
Generate methane：CO+3H2=CH4+H2O
Generate methanol：CO+2H2=CH3OH
Generate ethyl alcohol：2CO+4H2=C2H5OH+H2O
Carbon deposit reacts：2CO=C+CO2
Other than above 6 are reacted, the oxygenatedchemicals such as alcohol and aldehyde, ketone, acid, the ester of higher carbon number are also generated
Side reaction.
Fischer-Tropsch catalyst
Synthetic catalyst is mainly made of the periodic tables group VIII metal such as Co, Fe, Ni, Ru, in order to improve catalyst
Activity, stability and selectivity, will also be added some auxiliary elements, such as metal oxide or salt in addition to principal component.It is most of
Catalyst is required for carrier, such as aluminium oxide, silica, kaolin or diatomite.Only through CO+ after synthetic catalyst preparation
It is just active after H2 or H2 reduction activations.Currently, in the world using more ripe indirect liquefaction catalyst mainly have iron system and
Cobalt system two major classes, the mainly Fe-series catalyst that SASOL is used.It is used in SASOL fixed beds and paste state bed reactor
Precipitated iron catalyst uses fused iron catalyst in a fluidized bed reactor.
Only Sasol (iron, cobalt), the Shell of Fiscber-Tropscb synthesis cobalt and iron catalyst industrial applications in the world
(cobalt) two, also there are this respect patent in some also other companies, but do not hear input large-scale industrial application, only exist
It is used on pilot-plant, these companies are broadly divided into following several：Big oil company such as Exxon Mobil (cobalt),
Statoil (cobalt), BP (cobalt), Conoco (cobalt), Chevron (cobalt)；Profession do synthetic oil company such as Rentech (iron),
Syntroleum (cobalt)；Also some professions are company such as Johnson Matthey (iron, cobalt), the Albemarle of catalyst
(iron, cobalt) etc..
But current fischer-tropsch synthetic catalyst there is a problem in that：Since FT reacts, CH4Etc. lower hydrocarbons, CO2In this way
The generation of gas componant be promoted, gasoline yield reduces；Most suitable reaction problem or catalyst are not adapted to either
The relatively low easy inactivation of activity, stability is poor.
Invention content
The object of the present invention is to provide the catalyst for producing compositions of hydro carbons, can pass through reaction by synthesis gas
Obtain CO high conversion rates, gas componant generate less and aromatic series, cycloalkane, alkene, branched alkane as higher octane
It is worth the gasoline fraction of the high selectivity of ingredient.At the same time, the stability of catalyst is good, long-term non-inactivation, can efficiently by
The method that synthesis gas obtains above-mentioned gasoline fraction.
Present inventor is studied to reach above-mentioned purpose, as a result, it has been found that by using anti-containing copper sulphate and to FT
The FT synthetic catalysts of active metal species and the complex carrier with special construction are answered, can be manufactured and existing report
The method for manufacturing gasoline fraction by synthesis gas accused is generated compared to activity height, gas componant less and rich in aromatic series, cycloalkane, alkene
Hydrocarbon, branched alkane high-knock rating gasoline fraction, so as to complete the present invention.
A kind of catalyst for fischer-tropsch synthesis composition, which is characterized in that include：Make to show active gold to Fischer-Tropsch reaction
Belong to the catalyst that precursor dipping copper sulphate back loading is obtained in complex carrier, wherein the activity in the Fischer-Tropsch catalyst
Content relative to catalyst benchmark with amount of metal conversion be about 0.1~30 mass %, the complex carrier be TiO2-SiO2-
ZrO2, wherein Ti:Si:The molar ratio of Zr is 4-5：4-5：2-3, preferably 4：4：2.
The carbon monoxide-olefin polymeric, which is characterized in that active metal Co, Fe, Ru's is one or more.
The carbon monoxide-olefin polymeric, which is characterized in that the mass ratio of Ru and Co is 1：1-4.
The carbon monoxide-olefin polymeric, it is characterised in that auxiliary agent K is further included, relative to catalyst benchmark with amount of metal
Conversion is about 0.1-10%.
The complex carrier TiO2-SiO2-ZrO2Preparation process be：
(i) deionized water is added in reaction kettle a, TiO is added in stirring2, the pH values of acid control mixed liquor are added, are stirred
Mix uniformly mixed, obtained slurry A；Deionized water is added in reaction kettle b, stirring is added TiO2, is uniformly mixed, and slurry is made
Expect B；Slurry A, B are uniformly mixed, stood, slurry C is made；
(ii) Ludox is added in slurry C, is uniformly mixed, slurry D is made；
(iii) it is added in slurry D and contains zirconium solution, control temperature continues to be uniformly mixed, and slurry E is made；
(iv) granular powder will be obtained after slurry E spray drying formings, and granular powder is roasted to obtain answering for catalyst
Close carrier.
The preparation method of carbon monoxide-olefin polymeric, which is characterized in that include the following steps：
(1) complex carrier TiO is prepared2-SiO2-ZrO2；
(2) copper sulphate dispersion after being air-dried, is roasted with binder；
(3) roasting product is impregnated in the precursor solution of active metal, the complex carrier TiO is impregnated in after standing2-
SiO2-ZrO2, air drying, 120-200 DEG C roasts 2-5 hours, obtains catalyst for fischer-tropsch synthesis composition.
The binder wherein in step (2) is silicon dioxide gel；The condition of the roasting is 100-200 DEG C of roasting
1-4 hours.The active metal precursor.In solution is cobalt nitrate, ruthenic chloride, iron chloride at least one.The active metal precursor.In is molten
Liquid is preferably cobalt nitrate and ruthenic chloride.
The present invention provides the manufacturing method of hydro carbons as shown below.
A kind of manufacturing method of hydro carbons, which is characterized in that have：Using containing to Fischer-Tropsch reaction show active a kind with
On metal and copper sulphate, be carried on complex carrier TiO2-SiO2-ZrO2Fischer-Tropsch catalyst by being with hydrogen and carbon monoxide
The FT of the gas synthesis hydro carbons of principal component reacts.
The manufacturing method of hydro carbons, wherein the FT reactions are carried out at 260~350 DEG C.
It, can be efficient by fischer-tropsch reaction by synthesis gas by using the catalyst for producing composition of the hydro carbons of the present invention
Ground obtains that the CO high conversion rates of material synthesis gas, in addition gas componant generates less and aromatic series, cycloalkane, alkene, branched
The mass percent of the gasoline fraction of the high selectivity of antiknock component as alkane, product gasoline fraction can reach
85% or more.Moreover, the selectivity of catalyst is good, active higher, continuous operations 8-10 each moons, do not occur significantly inactivating mark
As can be adapted for operating with full load for 10 ton day of scale or more.
Carbon monoxide-olefin polymeric involved by present embodiment is the composition for including following substance：Contain sulfuric acid acid copper and FT
1 kind or more of the FT and complex carrier of active metal species are TiO2-SiO2-ZrO2The catalyst of synthesis.
Further include auxiliary agent K in carbon monoxide-olefin polymeric, relative to catalyst benchmark with amount of metal conversion about 0.1-10%.
Potassium is most of with K2O forms exist, and play the role of electron auxiliary agent, carbon monoxide is contributed to dissociate, increase the choosing of long chain hydrocarbons
Selecting property reduces methane selectively.
The addition of copper sulphate can reduce catalyst and be aoxidized, generally when conversion ratio is higher, the water partial pressure in reactor
Higher, when temperature is higher, this can cause catalyst to be aoxidized；Simultaneously as a small amount of sulfate ion exists to catalyst
Activity has certain benefit, it is noted that the presence of sulfate radical has facilitation rather than sulphion, sulphion is instead
It can be easy to cause catalyst poisoning, in this case, can affirm there is no benefit for catalyst higher than 5ppm.Therefore, centainly
The calcination temperature of catalyst is controlled, it is excessively high copper sulphate to be caused to decompose, catalytic action can not be played.With conventionally known method
It compares, it, can be effectively by the manufacturing method of the hydro carbons of the carbon monoxide-olefin polymeric or present embodiment of present embodiment
Manufacture high-octane gasoline fraction, not yet solved about copper sulphate detailed schematic it is bright, now in depth study in, but speculate
It is as follows：In the reaction using the carbon monoxide-olefin polymeric involved by present embodiment, closed by synthesis gas by FT synthetic catalysts
At hydro carbons contacted with carbon monoxide-olefin polymeric, can inhibit under high reaction temperature carbon atom number be 1~4 lower hydrocarbon,
CO2Such gas componant generates, can efficiently generate hydrocarbon, and carbon monoxide-olefin polymeric can effectively be made under high-temperature
With to make it possible the high-octane gasoline fraction of manufacture.
Hereinafter, to the hydro carbons of the carbon monoxide-olefin polymeric involved by the present embodiment being prepared into involved by present embodiment
Manufacturing method, used carbon monoxide-olefin polymeric involved by present embodiment hydro carbons manufacturing method, illustrate successively.
The preparation of carbon monoxide-olefin polymeric：The FT synthetic catalysts used in present embodiment contain a kind or more of FT activity
On metal species and copper sulphate load and complex carrier.
The FT active metal objects contained in FT synthetic catalysts as the carbon monoxide-olefin polymeric for constituting present embodiment
Kind, nickel, cobalt, iron, ruthenium can be enumerated.Wherein, as higher active metal species, preferably ruthenium, cobalt, the mass ratio of Ru and Co are
1：1-4.In addition, these metal species can be used alone, two or more can also be applied in combination.In addition, in catalyst further
Including auxiliary agent K, relative to catalyst benchmark with amount of metal conversion about 0.1-10%.
The copper sulphate contained in FT synthetic catalysts as the carbon monoxide-olefin polymeric for constituting present embodiment, can make
With commercially available reagent, furthermore it is also possible to use the copper sulphate manufactured by conventionally known method.By boucherizing in ruthenium
Salt, cobalt salt aqueous solution after, be dried, calcine.It is supported metal of more than two kinds as FT active metal species in sulfuric acid
Can be to prepare after the aqueous solution comprising both ruthenium salt and cobalt salt makes the aqueous solution be immersed in copper sulphate to be done when copper
Dry, calcining mode, can also be to be done after so that ruthenium saline solution and cobalt saline solution is individually immersed in copper sulphate
It is dry, calcining episodic pattern, do not provide particularly, applicant chance on copper sulphate addition can simultaneously utilize copper from
The promotion of the auxiliary agent property and sulfate radical of son, and the advantage from generating by-product, in order to realize the effect of copper sulphate, control
The content of copper sulphate is 3-15wt%, preferably 5-10wt%, more preferable 5-8wt% in catalyst, and controls catalyst preparation temperature
Degree, keeping it from can decompose and collapse.
As ruthenium salt, ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium, six ammonium of chlorination can be enumerated and close the Water-soluble Rus salt such as ruthenium.In addition,
As cobalt salt, it is preferable to use cobalt chloride, cobalt nitrate, cobalt acetate, cobaltous sulfate, cobaltous formate.In addition, about for impregnating the ruthenium supported
The solution of salt, cobalt salt may be formed as the solution of the organic solvents such as alcohol, ether, ketone other than aqueous solution.At this point, selection can
It is dissolved in the salt of various organic solvents.
The content of ruthenium in FT synthetic catalysts is scaled 0.1~3 mass % relative to catalyst benchmark with amount of metal, excellent
It is selected as 0.3~2.5 mass %, more preferably 0.5~2 mass %.The content of ruthenium is related with activated centre.The content of ruthenium is less than
When 0.1 mass %, activated centre becomes insufficient, to there is the anxiety that cannot obtain sufficient catalytic activity.On the other hand, ruthenium contains
Amount more than 3 mass % when, ruthenium cannot be fully supported on the carriers such as copper sulphate, reduced dispersion, easily cause not with carrier at
The ruthenium species of split-phase interaction generate.Therefore, catalyst cost can only be increased by supporting the ruthenium of necessity or more, and it is not preferable.
The content of cobalt in FT synthetic catalysts is scaled 5~20 mass % relative to catalyst benchmark with amount of metal, excellent
It is selected as 5~18 mass %, more preferably 5~20 mass %.When the content of cobalt is less than 3 mass %, the cobalt mistake as active metal
It is few, there is the anxiety that not can confirm that significant active rising.On the other hand, when the content of cobalt is more than 20 mass %, later drying,
Under calcination processing, FT reaction conditions, the cohesion of cobalt is easy to carry out, and has the anxiety for leading to activated centre reduction.In turn, the content mistake of cobalt
When amount, it is possible to cause the specific surface area of catalyst, pore volume to lower, and the yield of the gas componant in product is easy to increase
Add, it is not preferable.
In turn, in constituting the FT synthetic catalysts of carbon monoxide-olefin polymeric of present embodiment, in copper sulphate and FT activity
On the basis of metal species, alkali metal species can also be contained.As alkali metal species, lithium, sodium, potassium, rubidium etc. can be enumerated,
In preferably sodium, potassium.These alkali metal species can be used alone, can also two or more compound use.
For making FT synthetic catalysts also further contain alkali gold other than containing copper sulphate and FT active metal species
The method of species, is not particularly limited.For example, alkali metal species dipping can be made to support in the same manner as FT active metal species
On copper sulphate.Specifically, after for example making the aqueous solution of sodium salt, sylvite be immersed in copper sulphate, it is dried, calcines.This
Outside, it to FT active metal species and alkali metal species are supported the sequence in copper sulphate, is not particularly limited.Applicant accidentally sends out
The promotion that the auxiliary agent property and sulfate radical that can utilize copper ion simultaneously is added of existing copper sulphate, and from generating by-product
Advantage, in order to realize the effect of copper sulphate, the content for controlling copper sulphate in catalyst is 3-15wt%, preferably 5-8wt%, and is controlled
Catalyst preparation temperature processed, keeping it from can decompose and collapse.
The content of the alkali metal such as sodium, potassium in FT synthetic catalysts is preferred in terms of amount of metal conversion relative to catalyst benchmark
For 0.05~2 mass %, more preferably 0.05~1 mass %, further preferably 0.1~0.5 mass %.By set sodium,
The content of potassium inhibits the effect of the yield of gas componant to become notable more than 0.05 mass %.In addition, by being set in 2 matter
Amount % is hereinafter, can not reduce FT activity and inhibit the yield of gas componant.
After so that FT active metal species as ruthenium, cobalt is immersed in copper sulphate, it is dried, calcines.Drying at this time
Be in principle when FT active metal species dipping being supported in copper sulphate in order to evaporate the water equal solvent that has used and into
Capable, temperature is preferably 80~200 DEG C, more preferably 120~150 DEG C.It, can be with by the way that drying temperature is set in 80 DEG C or more
Promote the evaporations such as water.On the other hand, by the way that drying temperature is set in 150 DEG C hereinafter, bys can inhibiting by drastically evaporating water etc.
Caused active metal components unevenness homogenizes.
In addition, calcination temperature is preferably 150~350 DEG C, more preferably 150~300 DEG C, further preferably 100~
200℃.When calcination temperature is far more than 350 DEG C, the copper sulphate in catalyst component is decomposed into Cu oxide, and it is not preferable.This reality
The copper sulphate for applying the FT synthetic catalyst ingredients involved by mode must exist in the form of sulfate, if it is only oxide
Auxiliary agent cannot then obtain the effect of present embodiment.On the other hand, if calcination temperature is too low, it cannot achieve FT activity gold
The activation of species, it is not preferable.
It about the time of drying, calcining, must not make sweeping generalizations according to the difference for the treatment of capacity, but usually 1~10 small
When.If processing time is less than 1 hour, the evaporation of moisture is possible to become inadequate, the activation of FT active metal species
Weaken, it is not preferable.In addition, even if if processing time is more than 10 hours catalytic activity compared with 10 hours or less situations base
This does not change, so if consider workability, productivity, then preferably 10 hours or less.Wherein, the drying, calcination processing
It can carry out, or can not also be carried out under reactive atmosphere as nitrogen, helium in air, it can also be in reducing atmospheres such as hydrogen
Lower progress, without special provision.
In addition to above-mentioned dipping supports method, as the system containing copper sulphate and the FT synthetic catalysts of FT active metal species
Method is made, the aqueous slurry for preparing and including copper sulphate and FT active metal species, the method being spray-dried can be enumerated.It is right
Slurry concentration at this time, without special provision, but if slurry concentration is too low, then the precipitation that will produce, catalyst component becomes
Uneven, it is not preferable., whereas if slurry concentration is excessively high, then the conveying of slurry can become difficult, therefore select the slurry of appropriateness
Expect concentration, and active component is caused to waste.In turn, at this time to adjust the concentration of slurry, the mouldability for improving catalyst, ball
Shape turns to purpose, can also add silicon dioxide gel etc. and be used as binder.As the additive amount of binder at this time, preferably
The degree of catalytic activity reduction is not made, usually in the selection of the range of 5~20 mass %.
When obtaining FT synthetic catalysts by spray drying process, have will simultaneously contain copper sulphate, FT active metal species and
The method and then be further carried on complex carrier that Binder Composition slurry is sprayed, wherein about the air-supply in spray drying process
Temperature is preferably implemented in above-mentioned drying and calcination temperature.
Complex carrier TiO2-SiO2-ZrO2, due to having modified zirconia component in carrier, carrier can kept to stablize
Property while, improve the dispersion performance of active component, and good interaction can be carried out with copper sulphate, be conducive to target product
Flow distribution, improve gasoline fraction yield, and the compression strength and wear-resisting property of catalyst can be kept, this with common zeolite or
Person is common, and single carrier is significantly different.
And complex carrier is obtained also by fairly simple effective mixing method, or can be total to by the way that lye is added
Precipitation obtains, and the Kong Rong of carrier, ratio can be effectively adjusted by the operating parameter in control preparation process, such as temperature, pH value
Surface area and pore structure keep Active components distribution more uniform, improve the selectivity of effective product, reduce liquid hydrocarbon synthesis at
This, the zirconium component of addition can improve the bonded energy between carrier primary particle, improve the abrasion resistance properties of catalyst, extend
The service life of catalyst.
The manufacturing method of hydro carbons：The manufacturing method of the hydro carbons of present embodiment has：Use above-mentioned FT synthetic catalysts group
It closes object to be reacted by the FT of synthesis gas Synthin, if hydro carbons is made to be contacted with carbon monoxide-olefin polymeric, passes through cracking reaction, isomery
Change various reactions, the hydro carbons such as reaction to be converted.As a result, gasoline fraction increases, gasoline distribution is improved.
The FT synthetic catalysts especially used in present embodiment are even if under hot conditions as 230~350 DEG C
CO conversion ratios and C5+ selectivity (selectivity of the synthesis for the hydro carbons that carbon atom number is 5 or more) also high excellent catalyst.
The form of reactor about each reaction can enumerate fixed bed, fluid bed, suspension bed, slurry bed (slurry
Bed) etc., there is no particular limitation.
In having used the manufacturing method of hydro carbons of above-mentioned carbon monoxide-olefin polymeric, the catalyst group prepared as described above is used
Object is closed, for reaction.As an example of 1 terrace work, the manufacturing method of the hydro carbons based on fixed bed is recorded below.
When carrying out the activity rating of catalyst by fixed bed, due to there is the pressure difference generated in reactor in powder catalyst
Anxiety, therefore as the shape of catalyst, the preferably molded products such as extrusion, pearl product.As what is used in present embodiment
The size of FT synthetic catalysts, zeolite and carbon monoxide-olefin polymeric depends on the scale of reactor, but preferred as catalyst shape
Grain size is 0.5mm~5mm, more preferably 1.0mm~3mm.When grain size is 0.5mm or more, can fully it inhibit in reactor
Differential pressure rises.On the other hand, by setting grain size in 3mm hereinafter, the coefficient of efficiency of catalyst can be made to improve, so as to height
Reacted to effect.
Carbon monoxide-olefin polymeric involved by present embodiment can carry out reduction treatment (activation in advance before for reaction
Processing).
By the reduction treatment, catalyst can be activated to reaction and show desired catalytic activity.It is not carrying out
When the reduction treatment, FT active metal species are not reduced sufficiently, to show desired catalytic activity.Also original place
It is preferably 140~350 DEG C to manage temperature, more preferably 150~300 DEG C.If be less than 140 DEG C, FT active metal species not by
Fully reduction, to which sufficient reactivity cannot be obtained.
In the reduction treatment, preferably use using hydrogen as the reducibility gas of principal component.In used reproducibility gas
Can include the ingredient, such as vapor, nitrogen, rare gas etc. other than hydrogen not interfere the amount of the degree of reduction range in body.
The reduction treatment is not only influenced by above-mentioned treatment temperature, is also influenced by hydrogen partial pressure and processing time.Hydrogen partial pressure in reduction treatment
Preferably 0.1~10MPa, more preferably 0.5~6MPa, it is most preferably 0.9~3MPa.The reduction treatment time because catalytic amount,
Hydrogen ventilatory capacity etc. and it is different, it is often preferred that 0.1~72 hour, more preferably 1~48 hour, most preferably 3~48 hours.If
Processing time is less than 0.1 hour, then has the anxiety that the activation of catalyst becomes inadequate.On the other hand, although even if being surpassed
Prolonged reduction treatment in 72 hours is crossed, harmful effect will not be brought to catalyst, but does not find that catalytic performance improves, from
And lead to the problem of processing cost increase etc. it is undesirable.
It, can be to involved by the present embodiment for having carried out reduction treatment as described above in the manufacturing method of hydro carbons
Synthesis gas is passed through in carbon monoxide-olefin polymeric to carry out.
As long as used synthesis gas is mixed into it using hydrogen and carbon monoxide as principal component, not interfering the range of reaction
His ingredient is not related yet.Such as an example, the catalyst involved by present embodiment can used
Use is by synthesis gas obtained from gasification of biomass in the manufacturing method of the hydro carbons of composition.Kind as biomass at this time
Class can enumerate the agricultural aquatic resources biomass such as grain, building materials, paper pulp, agricultural, forestry, animal husbandry waste the like waste
The artificial forest such as biomass, sugarcane, palm, seaweed biomass (plantation biomass) etc..Wherein, it is preferable to use and grain
There is no the waste biomass of competition not utilized for food.Gasification process about biomass is not particularly limited.Such as conduct
The gasification process of biomass has the various methods such as direct gasification, indirect gasification, atmospheric gasification, gas-pressurized, in addition, as gas
Change stove form, it is a variety of to be divided into fixed bed, fluid bed, entrained bed etc..Using the catalyst combination involved by present embodiment
In the manufacturing method of the hydro carbons of object, it can use through biomass made of the gasification of either of which method.
As reality the hydrogen and carbon monoxide intrinsic standoff ratio range, 0.6~2.7 be it is suitable, preferably 0.8~
2.5, more preferably 1~2.3.If the intrinsic standoff ratio is less than 0.6, the tendency that the yield of the hydro carbons generated reduces can be found, separately
Outside, if the intrinsic standoff ratio is more than 2.7, the increased tendency of gas componant in the hydro carbons generated can be found.
In turn, in the manufacturing method for the hydro carbons for having used the carbon monoxide-olefin polymeric involved by present embodiment, even if closing
It is also what there is no problem at carbon dioxide coexists in gas.As the carbon dioxide coexisted in synthesis gas, even such as by oil
The carbon dioxide that the reforming reaction of product, natural gas wait until can also be used unquestionably.In addition, can be in synthesis gas
The carbon dioxide for being mixed into the other compositions for not interfering FT to react coexists.For example, it may be by the vapor weight of petroleum product etc.
Carbon dioxide containing vapor, the nitrogen being partially oxidized etc. as the substance that whole reaction is released.
On FT synthetic catalysts, if the usually H of synthesis gas2/ CO molar ratios are identical, then reaction temperature is lower, chain life
Long probability, C5+ selectivity (selectivity of the synthesis for the hydro carbons that carbon atom number is 5 or more) can become higher, and CO conversion ratios can become
It obtains lower., whereas if reaction temperature is higher, then chain growth probability and C5+ can selectively become lower, but CO conversion ratio meetings
Become higher.In addition, if H2/ CO ratios increase, then CO conversion ratios can increase, and chain growth probability and C5+ are selectively reduced, such as
Fruit H2/ CO is than low, then in contrast.About the effect that these parameters are come for FT reaction zones, size can be according to the catalysis used
Type of agent etc. and it is different.It is carried out by being carried out at the same time 1 terrace work of FT reactions and conversion reaction in same reactor
When the manufacturing method of the hydro carbons of present embodiment, reaction temperature is using 230~350 DEG C, preferably 240~310 DEG C, more preferably
250~300 DEG C.If reaction temperature is 230 DEG C or more, both FT synthetic catalysts and zeolite can be acted on effectively, can
High-octane gasoline fraction is manufactured by the generation and its cracking reaction of hydro carbons, isomerization reaction etc..In addition, by will be anti-
Temperature is answered to be set in 350 DEG C hereinafter, the undesirable gas componant on FT synthetic catalysts can be inhibited to generate, and can inhibit
The gas componant caused by the overcracking on zeolite generates.
CO conversion ratios=[(the CO molal quantitys in unstrpped gas per unit time)-is (in exit gas per unit time
CO molal quantitys)]/(the CO molal quantitys in unstrpped gas per unit time) × 100.
In embodiment below, CO analyses are by having used activated carbon (Active Carbon) (60/ in splitter
80 sieve meshes) thermal conductivity type gas-chromatography (TCD-GC) carry out.In unstrpped gas, 25 are added with used as internal standard
Synthesis gas (the H of the Ar of volume %2With the mixed gas of CO).Qualitative and quantitative analysis is by by the peak position of CO and peak face
Product is compared to progress with Ar.In addition, the composition analysis of product is to pass through hydrogen flame ion using capillary column (TC-1)
What detector gas-chromatography (FID-GC) carried out.The identification of the chemical composition of catalyst is to emit spectrophotometric analysis by ICP
What method was found out.
Specific implementation mode
The present invention will be further described in detail with reference to the specific embodiments.
Embodiment 1
Prepare complex carrier 10g：Deionized water is added in reaction kettle a, TiO is added in stirring2, add acid control mixing
The pH value of liquid, is uniformly mixed, and slurry A is made；Deionized water is added in reaction kettle b, stirring is added TiO2, is stirred
Uniformly, slurry B is made；Slurry A, B are uniformly mixed, stood, slurry C is made；Ludox is added in slurry C, is stirred
Uniformly, slurry D is made；ZrCl4 is added in slurry D, control temperature continues to be uniformly mixed, and slurry E is made；By slurry E
Granular powder is obtained after spray drying forming, and granular powder roasted to obtain the complex carrier of catalyst；
The copper sulphate for weighing 9.00g is distributed to the catalyst chemical conversion industry manufacture of 10.71g used as Binder Composition
Silicon dioxide gel (SiO2Content be 20.6%) in, after then 3 hours dry at 130 DEG C in air, in air 200
It is calcined at DEG C.Dipping is dissolved with the aqueous solution of 0.7 ruthenic chloride and places 1 hour in the calcining product of 5g.Then will
Mixed solution impregnates and complex carrier TiO2-SiO2-ZrO2, it is 3 hours dry at 100 DEG C in air, and then forged at 160 DEG C
It burns 3 hours, obtains the catalyst a1 as FT synthetic catalysts.Structural analysis is carried out by X-ray diffraction method, as a result, it has been found that urging
Copper in agent a1 maintains the state of copper sulphate.In addition, emitting the change that spectrophotometric method carries out catalyst a1 by ICP
Composition analysis is learned, as a result, it has been found that ruthenium is calculated as 3 mass % with metal conversion.
In order to confirm the activity of catalyst a1, the catalyst a1 of 6g is carried out with the silicon carbide of 100 sieve meshes of 34.6g dilute
It releases, is filled into the reaction tube that internal diameter is 10mm, with hydrogen partial pressure be 0.9MPaG, temperature is 170 DEG C, flow is 100 (STP)
Ml/ minutes (STP：Standard temperatureand pressure) it is passed through hydrogen and is restored for 3 hours.After reduction, switching
For H2The synthesis gas (Ar for including about 25 volume %) that/CO ratios are about 2, sets to temperature as 260 DEG C, stagnation pressure 0.9MPaG
It is reacted.
Comparative example 1
The addition step of copper sulphate and binder is saved, in addition to this, catalyst b is obtained similarly to Example 1, contains
The catalyst b of active component ruthenium-complex carrier.Emit the chemical composition that spectrophotometric method carries out catalyst b by ICP
Analysis, as a result, it has been found that ruthenium is calculated as 3.0 mass % with metal conversion.FT reactions are carried out by method similarly to Example 1.
The composition analysis result of the product obtained by reaction result and at this time is shown in table 1.
Embodiment 2
Active component precursors become 0.3g ruthenic chlorides and 0.4g cobalt nitrate solutions, other are identical as 1 condition of embodiment, use
Catalyst a2 implements at 270 DEG C of reaction temperature, in addition to this, is reacted with method similarly to Example 1.It will reaction
As a result the composition analysis result of the product and at this time obtained is shown in table 1.
Embodiment 3
Active component precursors become ruthenic chloride, cobalt nitrate and ferric chloride solution, living in catalyst a3 using catalyst a3
The Ru of property metal:Co:Fe mass ratioes are 1：1-4：1-3 is implemented at 280 DEG C of reaction temperature, in addition to this, with embodiment 1
Same method is reacted.The composition analysis result of the product obtained by reaction result and at this time is shown in table 1.
Embodiment 4
The process of the 4.5g copper sulphate baking mixed with binder is weighed, so that it is immersed in the water of 3.0g and is dissolved with
Cobalt nitrate Co (the NO of 3.46g3)2·6H2The aqueous solution of O is simultaneously placed 1 hour.Then, it dries 3 hours in air, at 80 DEG C,
Then use infusion process by active component and boucherizing in complex carrier TiO2-SiO2-ZrO2, and then forged at 210 DEG C
It burns 4 hours, then to obtain the catalyst a4 as FT synthetic catalysts.Structural analysis, knot are carried out by X-ray diffraction method
Fruit finds that the copper in catalyst a4 maintains the state of copper sulphate.It is catalyzed in addition, emitting spectrophotometric method by ICP
The chemical composition analysis of agent a4, as a result, it has been found that cobalt is calculated as 10.0 mass % with metal conversion.Using catalyst a4, in reduction temperature
It is to implement at 350 DEG C, in addition to this, is reacted with method similarly to Example 1.
Comparative example 2
Complex carrier is replaced using common alumina support, other conditions are same as Example 4, manufacture FT synthesis catalytics
Agent.Emit the chemical composition analysis that spectrophotometric method carries out catalyst c by ICP, as a result, it has been found that cobalt is in terms of metal conversion
For 10 mass %.
Comparative example 3
It is applicable in common zeolite ZSM-5 and replaces complex carrier, other conditions are same as Example 4, manufacture FT synthesis catalytics
Agent.Emit the chemical composition analysis that spectrophotometric method carries out catalyst d by ICP, as a result, it has been found that cobalt is in terms of metal conversion
For 10 mass %.The catalytic effect of above-mentioned catalyst is listed in table 1.
1 embodiment of table and comparative example fischer-tropsch synthetic catalyst evaluation result
According to the result of table 1 it is found that including to be carried on complex carrier containing FT active metals and copper sulphate having used
FT synthetic catalysts in the case of, and used comprising the feelings containing the different carbon monoxide-olefin polymeric of FT active metals or carrier
Condition is compared, and CO conversion ratios are very high, and the ratio of the gasoline fraction in product becomes very high, and carbon atom number is the hydrocarbon meeting of long-chain
Selectively cracking or isomerization are converted into gasoline fraction, and petrol content is high, can reach 90%.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those skilled in the art within the technical scope disclosed by the invention, can without the variation that creative work is expected or
It replaces, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Subject to fixed protection domain.
Claims (8)
1. a kind of catalyst for fischer-tropsch synthesis composition, which is characterized in that include：Make to show active metal to Fischer-Tropsch reaction
The catalyst that precursor dipping copper sulphate back loading is obtained in complex carrier, wherein the activity in the Fischer-Tropsch catalyst
The content of component is scaled 0.1~30 mass % relative to catalyst benchmark with amount of metal, and the complex carrier is TiO2-
SiO2-ZrO2, specific preparation process is：
(i) deionized water is added in reaction kettle a, TiO is added in stirring2, the pH value of acid control mixed liquor is added, is stirred
Uniformly, slurry A is made；Deionized water is added in reaction kettle b, TiO is added in stirring2, it is uniformly mixed, slurry B is made；It will
Slurry A, B are uniformly mixed, and are stood, and slurry C is made；
(ii) Ludox is added in slurry C, is uniformly mixed, slurry D is made；
(iii) it is added in slurry D and contains zirconium solution, control temperature continues to be uniformly mixed, and slurry E is made；
(iv) granular powder will be obtained after slurry E spray drying formings, and granular powder roasted to obtain the compound load of catalyst
Body.
2. carbon monoxide-olefin polymeric as described in claim 1, which is characterized in that one kind or more in active metal Co, Fe, Ru
Kind.
3. carbon monoxide-olefin polymeric as claimed in claim 2, which is characterized in that the mass ratio of Ru and Co is 1：1-4.
4. carbon monoxide-olefin polymeric as described in claim 1, which is characterized in that auxiliary agent K is further included, relative to catalyst base
Standard is scaled 0.1-2% with amount of metal.
5. carbon monoxide-olefin polymeric as claimed in claim 1 or 2, which is characterized in that Ti in complex carrier:Si:The molar ratio of Zr
It is 4：4：2.
6. carbon monoxide-olefin polymeric as claimed in claim 1 or 2, it is characterised in that be based on carbon monoxide-olefin polymeric benchmark, copper sulphate
Content is 5-8wt%.
7. application of the carbon monoxide-olefin polymeric in Fischer-Tropsch synthesis as described in claim any one of 1-6, which is characterized in that will
Carbon monoxide-olefin polymeric is filled in fixed bed reactors, and control catalytic reaction temperature is 260-350 DEG C, pressure 0.5-5MPa.
8. the use as claimed in claim 7, which is characterized in that restored before reaction, reducing condition is：Pure hydrogen atmosphere,
140~350 DEG C, hydrogen partial pressure is 0.1 ~ 10MPa, volume space velocity 500-2000h-1, the recovery time is 0.1 ~ 72 hour.
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| CN103769098A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic gas conversion catalyst, and preparation method and applications thereof |
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| CN102259003A (en) * | 2011-05-31 | 2011-11-30 | 武汉科林精细化工有限公司 | Coke-oven gas methanation catalyst and preparation method thereof |
| CN103769098A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic gas conversion catalyst, and preparation method and applications thereof |
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