CN102049259A - Preparation method of cobalt-based catalyst for Fischer-Tropsch synthesis - Google Patents
Preparation method of cobalt-based catalyst for Fischer-Tropsch synthesis Download PDFInfo
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- CN102049259A CN102049259A CN2009102133488A CN200910213348A CN102049259A CN 102049259 A CN102049259 A CN 102049259A CN 2009102133488 A CN2009102133488 A CN 2009102133488A CN 200910213348 A CN200910213348 A CN 200910213348A CN 102049259 A CN102049259 A CN 102049259A
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- cobalt
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- tropsch synthesis
- fischer
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 title abstract description 21
- 239000010941 cobalt Substances 0.000 title abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 21
- 238000000352 supercritical drying Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000012153 distilled water Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000012018 catalyst precursor Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910020521 Co—Zn Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020641 Co Zr Inorganic materials 0.000 description 1
- 229910020520 Co—Zr Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of a cobalt-based catalyst for Fischer-Tropsch synthesis. The catalyst contains the following ingredients (by weight): Co: 5% to 80%, SiO2: 0% to 95%, and ZrO2: 0% to 20%. By adopting the supercritical drying method, the catalyst has high specific surface and good metal dispersion and has the characteristics of high catalytic activity, high C5+ selectivity, long lifetime and, low risk of deactivation and the like.
Description
Technical field:
The present invention relates to a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst.This catalyst can be used for Fischer-Tropsch synthesis, by the preparing hydrocarbon from synthetic gas product.
Background technology:
Be accompanied by the fast development of industrial or agricultural and traffic industry, the world increases gradually for the demand of fossil energy, and especially the degree of dependence for petroleum-based energy constantly increases, and can constantly reduce for the petroleum reserves of exploitation.Therefore, each state all actively is devoted to develop and seek new energy substitution product.Fischer-Tropsch is synthetic to be with synthesis gas (CO, H under catalyst (metallic catalysts such as Fe, Co, Ni) effect
2) be converted into the process of hydrocarbon compound, wherein lower carbon number hydrocarbons and liquid vapour, diesel oil are the synthetic focus of recent Fischer-Tropsch.Because it is a raw material with natural gas and coal, has the advantages that not rely on oil, product cleaning (N, the S constituent content is few) has caused the great attention of various countries simultaneously.Each major oil companies (as Shell, Gulf etc.) have all dropped into great amount of manpower and financial resources are carried out the exploitation and the development of fischer-tropsch synthetic catalyst.In the fischer-tropsch synthetic catalyst of report, advantage such as cobalt-base catalyst has active height, stable performance, is difficult for carbon distribution, the water gas shift reaction activity is low is the most competitive catalyst of Fischer-Tropsch building-up process.For example, U.S. Pat 5545647 has been reported a kind of manufacture method of Co based Fischer-Tropsch synthesis catalyst, be on inorganic oxide surface spraying cobalt metal active top layer, and add the power of regeneration that auxiliary agent (rhenium, zirconium, hafnium, cerium etc.) improves its reactivity and selectivity and catalyst.US P4579986 has reported a kind of Co-Zr/SiO that is used for being generated through the Fischer-Tropsch synthetic reaction by synthesis gas wax
2Catalyst is at 220 ℃, 20bar, H
2C during/CO=2
5 +(hydrocarbon compound that contains 5 and 5 above carbon atoms in the molecule) selectivity can reach more than 82%.It is the preparation method of the fischer-tropsch catalysts of carrier with oxides such as Si, Al, Zr, Sn that European patent EP 0800864 has been reported a kind of, and its active component is a metal Co, after being added into auxiliary elements such as Ti, Cu, Ru, can significantly suppress catalysqt deactivation.Chinese patent CN 1084153 discloses a kind of catalyst that is used to prepare higher hydrocarbon, and its composition comprises Co/Al
2O
3With a kind of metal promoter.CN 1785515 discloses a kind of with ZrO
2The preparation method who is used for the synthetic cobalt-base catalyst of Fischer-Tropsch for carrier.In this method, at first make mesoporous zircite by sol-gal process, the nitrate with cobalt nitrate and noble metal supports on mesoporous zircite then.The composition of catalyst (quality percentage composition) cobalt is 5～35%, and zirconia is 53～93%, and noble metal is 0～2%, and non-noble metal oxide is 0～10%.When the zirconic aperture of carrier is 12.6nm, C
12～C
18The selectivity of hydrocarbon products can reach 32%.European patent EP 1358934 discloses a kind of preparation method of Co-Zn co-precipitated catalyst, with (NH
4)
2CO
3Be precipitating reagent, with Co (NO
3)
2And Zn (NO
3)
2Precipitation, washing and filtering and roasting obtain the presoma of its Co-Zn catalyst.
Document show when catalyst precursor through the reduction after, the metallic cobalt surface area on the catalyst of unit mass is big more, the dispersiveness of cobalt is good more, then activity of such catalysts is high more, the selectivity of high-carbon hydrocarbon is also high more.Co based Fischer-Tropsch synthesis catalyst is many with immersion process for preparing in the above-mentioned document, often uses TiO
2, SiO
2, Al
2O
3In carrier, cobalt ions easily generates the difficult compound that reduces with carrier function during impregnation-calcination, does not make catalyst activity high and limited the utilization rate of cobalt.In addition, also exist the little and CH of content of metal during catalyst prepared
4Shortcomings such as selectivity height; During with the Co catalysts of general coprecipitation preparation, metal oxide particle is reunited seriously after catalyst precursor drying and the roasting, and specific area and pore volume reduce, and it is bad to cause reduction back cobalt metallic particles to disperse, activity of such catalysts and C
5 +Selectivity is low.Supercritical Drying Technology is the chemical industry new technology that development in recent years is got up, it utilizes drying medium on critical-temperature and critical pressure, gas-liquid interface disappears, surface tension has not existed, thereby eliminated in the dry run particle aggregation that pore collapse breaks that the surface tension because of water causes produces, cross the surface tension that can reduce solvent in being in the drying of catalyst, make prepared catalyst still can keep higher surface area and proper pore structure.Be applied in the fischer-tropsch synthetic catalyst preparation rarely seen domestic and international pertinent literature report with Supercritical Drying Technology.
The present invention will use the supercritical drying coprecipitation to prepare Co based Fischer-Tropsch synthesis catalyst, use the catalyst of this method preparation to have the big characteristics of cobalt content adjustable extent, and need not follow-up high-temperature process, avoided the generation of difficult reduzate, the catalyst reduction degree is higher.In fischer-tropsch reaction, this catalyst has excellent Fischer-Tropsch synthesizing activity and higher C
5 +Selectivity.Particularly, the present invention will use a kind of supercritical methanol technology dry catalyst, this preparation method can keep the catalyst precursor high-specific surface area, and can control the size of granular precursor effectively, be easy to reduction, can obtain the higher Co catalysts of decentralization after reduction, this method can maintain and be beneficial to the synthetic central hole structure of Fischer-Tropsch simultaneously.
Summary of the invention
The present invention uses the solubility salt, prepare Co based Fischer-Tropsch synthesis catalyst with coprecipitation, in catalyst preparation process, use the method for supercritical drying, reduced the influence of solvent in the dry run, make catalyst after drying, still can keep higher specific surface area and suitable central hole structure, improve the decentralization of metallic cobalt.Simultaneously, be the catalyst of activated centre and auxiliary agent with Co/Zr, can significantly reduce the selectivity of methane.This catalyst preparation process is simple, has very high activity after reducing in Fischer-Tropsch synthesis, has good higher hydrocarbon selectivity simultaneously.
Technical scheme of the present invention is as follows:
A kind of preparation method who is used for the synthetic cobalt-base catalyst of Fischer-Tropsch, it is sodium metasilicate and precipitating reagent to be dissolved in to obtain solution A in the deionized water earlier, again solubility cobalt salt when adding auxiliary agent Zr (if, then be the cobalt of solubility, zirconium salt-mixture) is dissolved in and obtains solution B in the deionized water.Stir down solution A and B are added drop-wise in 60～100 ℃ the deionized water simultaneously, obtain blue sediment.The gained sediment uses the dry cobalt that obtains of supercritical process to urge baseization agent presoma under 150～300 ℃ of conditions after distilled water fully washs, and cobalt urges baseization agent presoma promptly to get Co based Fischer-Tropsch synthesis catalyst through reduction.
Above-mentioned solubility cobalt salt is a kind of in cobalt nitrate, cobalt acetate, cobalt oxalate, the acetylacetone cobalt.
Above-mentioned solubility zirconates is a kind of in zirconium nitrate, basic zirconium chloride, the zirconium sulfate.
Above-mentioned precipitating reagent is a kind of in sodium carbonate, sodium acid carbonate, the NaOH.
Above-mentioned supercritical drying drying method is: the sediment after will washing joins in the autoclave, and the organic solvent that adds 5～50 times of amounts of sediment quality again feeds high-purity N as supercritical solvent
2Purged autoclave 30 minutes, with the air in the system of removing.Autoclave temp is risen to 150～300 ℃, kept this state 2 hours, stop heating, pressure release is used N to normal pressure
2Purge autoclave and reduce to room temperature, take out product, obtain the presoma of cobalt-base catalyst.
Used organic solvent is a kind of in absolute ethyl alcohol, acetone, isopropyl alcohol, n-butanol, ethyl acetate, cyclohexanone, normal propyl alcohol, the cyclohexane in the above-mentioned supercritical drying.
Before using, the presoma of cobalt-base catalyst of the present invention needs through reduction, reducing gas is a hydrogen, system pressure is 0.1～4MPa, preferred pressure is 0.1～2MPa, reduction temperature is 200～800 ℃, and preferred temperature is 300～600 ℃, and the recovery time is 2～30 hours, the preferred time is 4～20 hours, and air speed is 500～5000h
～1After reduction finished, system temperature was reduced to environment temperature, fed synthesis gas, carried out Fischer-Tropsch synthesis under 180～250 ℃ of temperature, system pressure 1～5MPa, and synthesis gas is the mist of carbon monoxide and hydrogen, and air speed is 100～10000ml/ (g
CataH), the ratio of its amount of substance is H
2/ CO=1/5～5/1.
The specific embodiment
The invention will be further described with following embodiment:
Embodiment 1:
Take by weighing 30.67g Co (NO
3)
26H
2O is dissolved in the 120ml deionized water; Other gets 18.95g NaSiO
39H
2O, 12.29g Na
2CO
3Water-soluble one-tenth 120ml solution.Under agitation above-mentioned two drips of solution are added to (80 ℃ of water-baths) in the 200ml distilled water, generate blue precipitation, will precipitate, add the 250ml anhydrous normal butyl alcohol again as supercritical solvent, behind the sealing device, with N with in the adding autoclave after the distilled water washing six times
2Purge after 30 minutes, autoclave temp risen to 260 ℃, keep this state after 2 hours pressure release to normal pressure, again with N
2Purged 2 hours and reduce to room temperature.Open seal cover, obtain the weight of cobalt percentage composition and be 60% cobalt Si catalyst presoma (being numbered A1).
Reference example 1:
Take by weighing 3.67g Co (NO
3)
26H
2O is dissolved in the 120ml deionized water; Other gets 18.95g NaSiO
39H
2O, 12.29g Na
2CO
3Water-soluble one-tenth 120ml solution.Under agitation hold drops and be added to (80 ℃ of water-baths) in the 200ml distilled water, generate blue precipitation above-mentioned two, will precipitate wash six times with distilled water after, put into 120 ℃ of drying in oven, obtain cobalt content equally and be load type Co/SiO of 60%
2Catalyst precursor (being numbered B1).
Embodiment 2:
Take by weighing 33.84g Co (CH
3COO)
24H
2O is dissolved in the 120ml deionized water; Other gets 9.47g NaSiO
39H
2O, 12.83gNaHCO
3Water-soluble one-tenth 120ml solution.Under agitation above-mentioned two drips of solution are added to (90 ℃ of water-baths) in the 200ml distilled water, generate blue precipitation, will precipitate with in the adding autoclave after the distilled water washing six times, adding the 250ml cyclohexane give again is supercritical solvent, behind the sealing device, with N
2Purged 30 minutes, autoclave temp risen to 260 ℃, keep this state after 2 hours pressure release to normal pressure, after this with N
2Purged 2 hours and reduce to room temperature.Open seal cover, obtain cobalt content and be 80% load C o/SiO
2Catalyst precursor (being numbered A2).
Reference example 2:
Take by weighing 33.84g Co (CH
3COO)
24H
2O is dissolved in the 120ml deionized water; Other gets 9.47g NaSiO
39H
2O, 12.83g NaHCO
3Water-soluble one-tenth 120ml solution.Under agitation above-mentioned two drips of solution are added to (90 ℃ of water-baths) in the 200ml distilled water, generate blue precipitation, will precipitate and put into 120 ℃ of drying in oven after washing six times with distilled water, obtain cobalt content equally and be load type Co/SiO of 80%
2Catalyst precursor (being numbered B2).
Embodiment 3:
Take by weighing 32.31g CoCl
26H
2O, 1.39g Zr (NO
3)
45H
2O is dissolved in the 120ml deionized water; Other gets 7.57g NaSiO
39H
2O, 15.83g Na
2CO
3Water-soluble one-tenth 120ml solution.Under agitation above-mentioned two drips of solution are added to (80 ℃ of water-baths) in the 200ml distilled water, generate blue precipitation, will precipitate with in the adding autoclave after the distilled water washing six times, adding the 250ml cyclohexane give again is supercritical solvent, behind the sealing device, with N
2Purged 30 minutes, autoclave temp risen to 260 ℃, keep this state after 2 hours pressure release to normal pressure, after this with N
2Purged 2 hours and reduce to room temperature.Open seal cover, obtain cobalt content and be 80%, ZrO
2Content is 4% load type Co/SiO
2Catalyst precursor (being numbered A3).
Reference example 3:
Take by weighing 32.31g CoCl
26H
2O, 1.39gZr (NO
3)
45H
2O is dissolved in the 120ml deionized water; Other gets 7.57g NaSiO
39H
2O, 15.83g Na
2CO
3Water-soluble one-tenth 120ml solution.Under agitation above-mentioned two drips of solution are added to (80 ℃ of water-baths) in the 200ml distilled water, generate blue precipitation, will precipitate with precipitating after the distilled water washing six times and put into 120 ℃ of drying in oven after washing with distilled water, obtain cobalt content equally and be 80%, ZrO
2Content is load type Co/SiO of 4%
2Catalyst precursor (being numbered B3).
Embodiment 4:
Take by weighing 39.52g Co (NO
3)
26H
2O, 2.79gZr (NO
3)
45H
2O is dissolved in the 120ml deionized water; Other gets 5.68gNaSiO
39H
2O, 15.83g Na
2CO
3Water-soluble one-tenth 120ml solution.Under agitation above-mentioned two drips of solution are added to (90 ℃ of water-baths) in the 200ml distilled water, generate blue precipitation, will precipitate, add the 250ml absolute ethyl alcohol again as supercritical solvent, behind the sealing device, with N with in the adding autoclave after the distilled water washing six times
2Purged 30 minutes, autoclave temp risen to 260 ℃, keep this state after 2 hours pressure release after this use N to normal pressure
2Purged 2 hours and reduce to room temperature.Open seal cover, obtain cobalt content and be 80%, ZrO
2Content is load type Co/SiO of 8%
2Catalyst precursor (being numbered A4).
With the catalyst for preparing in the foregoing description and the reference example, carry out the catalytic performance of Fischer-Tropsch synthesis after the reduction.Reduction and reaction condition are as follows:
Catalyst precursor sample is got 20～40 order sample 3g after compressing tablet, fragmentation, screening, in the fixed bed reactors of packing into, feed hydrogen, flow is 30ml/min, and temperature of reactor is risen to 500 ℃ with the speed of 1 ℃/min, keeps 4h, reduce to room temperature then, stop logical hydrogen.Change the feeding synthesis gas into, its component is H
2/ CO/N
2=64/32/4, N wherein
2Be interior mark, be used for the conversion ratio and the product selectivity of Analysis for CO, computational methods are seen document (Xiaoping Dai, Changchun Yu.Characterization and catalytic performace ofCeO
2-Co/SiO
2Catalyst for Fischer-Tropsch synthesis using nitrogen-diluted synthesis gas over a laboratoryscale reactor.Journal of Natural Gas Chemistry 17 (2008) 17-23).200 ℃ of reaction temperatures, system pressure 2.0MPa, gas flow rate 1000ml/ (g
CataH) carry out Fischer-Tropsch synthesis under.Reaction result is listed in table one.
The character of the cobalt-base catalyst of table one embodiment and reference example and Fischer-Tropsch synthesis performance.
Claims (6)
1. the preparation method of a Co based Fischer-Tropsch synthesis catalyst is characterized in that: it is sodium metasilicate and precipitating reagent to be dissolved in to obtain solution A in the deionized water earlier, solubility cobalt salt and solubility zirconates is dissolved in together obtains solution B in the deionized water again.Stir down solution A and B are added drop-wise in 60～100 ℃ the deionized water simultaneously, obtain blue sediment.The gained sediment uses supercritical drying to obtain the cobalt-base catalyst presoma under 150～300 ℃ of conditions after distilled water fully washs, and promptly gets load type cobalt-base catalyst through reduction.
2. the preparation method of Co based Fischer-Tropsch synthesis catalyst according to claim 1 is characterized in that: described solubility cobalt salt is a kind of in cobalt nitrate, cobalt acetate, cobalt oxalate, cobalt chloride, the acetylacetone cobalt.
3. the preparation method of Co based Fischer-Tropsch synthesis catalyst according to claim 1 is characterized in that: described solubility zirconates is a kind of in zirconium nitrate, basic zirconium chloride, the zirconium sulfate.
4. the preparation method of Co based Fischer-Tropsch synthesis catalyst according to claim 1 is characterized in that: described precipitating reagent is a kind of in sodium carbonate, sodium acid carbonate, the NaOH.
5. described sedimentary supercritical drying drying method of claim 1, it is characterized in that: the sediment after will washing joins in the autoclave, and the organic solvent that adds 5～50 times of amounts of sediment quality again feeds high-purity N as supercritical solvent
2Purged autoclave 30 minutes, and autoclave temp was risen to 150～300 ℃ then, kept this state 2 hours, stop heating, pressure release is to normal pressure, again with N
2Purge autoclave and reduce to room temperature, take out product, promptly get the presoma of cobalt-base catalyst.
6. sedimentary supercritical drying drying method according to claim 5 is characterized in that: described organic solvent is a kind of in absolute ethyl alcohol, acetone, isopropyl alcohol, n-butanol, ethyl acetate, cyclohexanone, normal propyl alcohol, the cyclohexane.
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| CN105214688A (en) * | 2015-10-16 | 2016-01-06 | 武汉凯迪工程技术研究总院有限公司 | A kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN106290354A (en) * | 2016-09-26 | 2017-01-04 | 湖南科技大学 | A kind of cobalt ion differentiates sodium bicarbonate and the method for sodium carbonate liquor |
| CN107456970A (en) * | 2017-07-21 | 2017-12-12 | 浙江大学 | A kind of binary or ternary metal are carried on catalyst of ground polymers and preparation method thereof and the application in chemical heat pump |
| CN107866230A (en) * | 2016-09-27 | 2018-04-03 | 中国科学院上海高等研究院 | Co catalysts and preparation method and application |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105214688A (en) * | 2015-10-16 | 2016-01-06 | 武汉凯迪工程技术研究总院有限公司 | A kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN106290354A (en) * | 2016-09-26 | 2017-01-04 | 湖南科技大学 | A kind of cobalt ion differentiates sodium bicarbonate and the method for sodium carbonate liquor |
| CN107866230A (en) * | 2016-09-27 | 2018-04-03 | 中国科学院上海高等研究院 | Co catalysts and preparation method and application |
| CN107456970A (en) * | 2017-07-21 | 2017-12-12 | 浙江大学 | A kind of binary or ternary metal are carried on catalyst of ground polymers and preparation method thereof and the application in chemical heat pump |
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