CN100518930C - Sintered iron catalyst for Fischer-Tropsch synthesis, preparation method and application thereof - Google Patents
Sintered iron catalyst for Fischer-Tropsch synthesis, preparation method and application thereof Download PDFInfo
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- CN100518930C CN100518930C CNB2004100247424A CN200410024742A CN100518930C CN 100518930 C CN100518930 C CN 100518930C CN B2004100247424 A CNB2004100247424 A CN B2004100247424A CN 200410024742 A CN200410024742 A CN 200410024742A CN 100518930 C CN100518930 C CN 100518930C
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000292 calcium oxide Substances 0.000 claims abstract description 5
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 230000004927 fusion Effects 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 239000003426 co-catalyst Substances 0.000 claims description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010459 dolomite Substances 0.000 claims description 6
- 229910000514 dolomite Inorganic materials 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 238000010891 electric arc Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000007500 overflow downdraw method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 239000000470 constituent Substances 0.000 description 6
- 238000013467 fragmentation Methods 0.000 description 5
- 238000006062 fragmentation reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a melting iron catalyst for Fischer-Tropsch synthesis, a preparation method thereof and applications thereof. The catalyst uses oxide of iron as a main component, alumThe invention relates to a fused-iron catalyst and it's preparing method and application. The catalyst uses ferric oxide as main component and uses alumina, potassium oxide, calcium oxide and other oxinum oxide, potassium oxide, calcium oxide and other oxide are used as auxiliary agents, the iron ratio of the catalyst is controlled between 0.20 and 1.40, and the catalyst is prepared by using a melides as auxiliary. It controls the iron of catalyst at 0.20-1.40; catalyst is prepared by fused method; the application condition of catalyst is synthetic gas [CO+H.2.] air-speed GHSV=500-3000mL/g-catting method. The application conditions of the catalyst comprise: air speed GHSV of synthetic gas [CO + H2] is from 500 to 3000 mL/g-cat/h, methane air speed GHSV is from 500 to 3000 mL/g-cat/h, CO2 a/h, mash air-speed GHSV=0-1000mL/g-cat/h, CO.2. air-speed=0-1000mL/g-cat/h; press P=1.5-6.0MPa, reacting temperature T=280-400 DEG C, H.2./CO=1.5-4.0, wherein g-cat is per gram weight of catalyst. ir speed is from 0 to 1000 mL/g-cat/h, pressure P is from 1.5 to 6.0MPa, reaction temperature T is from 280 to 400 DEG C, the ratio of H2 and CO is from 1.5 to 4.0, wherein g-cat represents the weight of catalyst per gram.
Description
Technical field
The present invention relates to catalyst, relate in particular to a kind of synthetic fused iron catalyst of Fischer-Tropsch and its production and application that is used for.
Background technology
Fischer-Tropsch is synthetic to be meant that carbon monoxide and hydrogen are converted into the reaction of hydro carbons on catalyst such as iron, cobalt and ruthenium; Wherein, fused iron catalyst is applicable to Fischer-Tropsch resultant current fluidized bed reactor, the temperature of reaction is higher, belong to the high temperature fischer-tropsch synthetic catalyst, the products such as oil distillate, low-carbon alkene, aldehyde, ketone and acid that are suitable for steaming, wherein, sulphur in the gasoline fraction/nitrogen equal size is very low, can obtain the liquid fuel of high-quality through post processing, and products such as low-carbon alkene, aldehyde, ketone and acid has very high chemical value; Synthetic cobalt of Fischer-Tropsch and ruthenium catalyst are because of the resource-constrained of cobalt, ruthenium, make the catalyst cost higher, thereby the application of limiting catalyst in the Fischer-Tropsch synthesizes industrialization, cobalt and ruthenium catalyst Fischer-Tropsch synthetic are based on long chain alkane in addition, olefin(e) centent is low, low-temperature precipitation iron catalyst product is then based on long chain alkane, and olefin(e) centent is still lower in the product.Quick and sustainable development along with China's economy, demand and day sharp increase to liquid fuel, the environmental pollution that fire coal causes also causes great concern, development coal/natural gas via synthesis gas is produced the industrial process of liquid fuel, not only can satisfy the energy demand of China significantly, thereby reduce the external dependence of energy resource supply, and be expected fundamentally solving the coal-fired problem of environmental pollution that causes.Therefore, this process of R and D realizes that the necessary catalyst of industrialization has very important strategy and realistic meaning.
Summary of the invention
Purpose of the present invention is exactly for a kind of synthetic fused iron catalyst of Fischer-Tropsch and its production and application that is used for is provided.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of synthetic fused iron catalyst of Fischer-Tropsch that is used for is characterized in that the composition of this catalyst comprises: ferric iron and two times of ferrous amount of substance ratio Fe
3+/ 2Fe
2+Be 0.20-1.40, the mass fraction 65-71% of iron; In addition, also comprise co-catalyst, it consists of: aluminium oxide 0.1-3.6g/100g Fe, potassium oxide 0.1-1.4g/100g Fe, calcium oxide 0.1-2.5g/100g Fe, other oxide〉0-5.0g/100g Fe, other oxide mainly is with dolomite (CaCO
3MgCO
3) be the magnesia of raw material.
Described other oxide also can comprise one or more in the oxide that is selected from manganese, strontium, zirconium, copper, sodium, zinc, nickel, vanadium, silicon, tungsten, titanium, lead, molybdenum, chromium.
Described iron can adopt cheap magnetic iron ore, steel slag or/and iron-oxygen scale is a raw material, and wherein slag is or/and the ferric iron of iron-oxygen scale and two times of ferrous amount of substance ratio Fe
3+/ 2Fe
2+Be 0.3-1.6.
A kind of preparation method of described fused iron catalyst, it is characterized in that, this preparation method adopts fusion method that a certain amount of co-catalyst raw material is mixed with magnetite powder and pure iron, or with a certain amount of co-catalyst raw material, magnetite powder, pure iron and carbon or graphite powder mix, or with a certain amount of co-catalyst raw material, magnetite powder and carbon or graphite powder mix, or with a certain amount of co-catalyst with steel slag or/and iron-oxygen scale mix, adopt electric arc furnaces or intermediate frequency furnace or electric smelter, through fusion, cooling, broken, ball milling and sieving technology are made, and the gained catalyst particle size is 3～500 microns; The composition of the catalyst of making at last comprises: ferric iron and two times of ferrous amount of substance ratio Fe
3+/ 2Fe
2+Be 0.20-1.40, the mass fraction 65-71% of iron; In addition, also comprise co-catalyst, it consists of: aluminium oxide 0.1-3.6g/100g Fe, potassium oxide 0.1-1.4g/100g Fe, calcium oxide 0.1-2.5g/100g Fe, other oxide〉0-5.0g/100g Fe, other oxides mainly are with dolomite (CaCO
3MgCO
3) be the magnesia of raw material.
Described smelting process is put into cooling bath with liquid melt for melt temperature is controlled at 1400～2000 ℃ when described process for cooling is the fusion end, is cooled to below 100 ℃.
Described smelting process is put into cooling bath, cool to room temperature with liquid melt for melt temperature is controlled at 1600～1800 ℃ when described process for cooling is the fusion end.
Comprise that also fragmentation, ball milling and sieving technology, gained particle size are 3～500 microns after described fusion, the process for cooling.
A kind of application that is used for the synthetic fused iron catalyst of Fischer-Tropsch is characterized in that, this catalyst is applied in the synthetic fluidized-bed reactor of Fischer-Tropsch, and the application conditions of its Fischer-Tropsch synthesis is: synthesis gas [CO+H
2] air speed GHSV=500-3000mL/g-cat/h, methane air speed GHSV=0～1000mL/g-cat/h, CO
2Air speed=0～1000mL/g-cat/h; Pressure P=1.5-6.0MPa, reaction temperature T=280-400 ℃, H
2/ CO=1.5-4.0, wherein g-cat is meant every gram catalyst weight.
Catalyst of the present invention is compared with other fischer-tropsch synthetic catalysts, has remarkable advantages:
(1) raw material sources of fused iron catalyst are in magnetic iron ore or the slag or the iron-oxygen scale of cheapness, and therefore the catalyst prod cost that makes is low, is suitable for suitability for industrialized production.
(2) olefin(e) centent is higher in the synthetic product of fused iron catalyst Fischer-Tropsch, and alkene is unusual important chemical material, and this is significant to optimizing Fischer-Tropsch synthetic.
The specific embodiment
Embodiment 1
With magnetite powder 100, iron powder 2.84, manganese oxide (MnO
2) 2.21, aluminium oxide (Al
2O
3) 0.40, potash (K
2CO
3) 0.20[or potassium nitrate (KNO
3) 0.29 or potash (K
2CO
3) 0.10 and potassium nitrate (KNO
3) 0.15], calcium oxide (CaO) 0.29[or calcium carbonate (CaCO
3) 0.52 or calcium nitrate (Ca (NO
3)
2) 0.85 or calcium carbonate (CaCO
3) 0.20 and calcium oxide (CaO) 0.18 or calcium carbonate (CaCO
3) 0.10 and calcium nitrate (Ca (NO
3)
2) 0.13 and calcium oxide (CaO) 0.19] the weight proportion mixing after, the interior fusion of switching on of the electric smelter of packing into, melt temperature (furnace temperature) is controlled at 1700 ℃, when fusion finishes liquid melt is put into cooling bath, be quickly cooled to 100 ℃, further be cooled to room temperature again, cooling back frit is through fragmentation, ball milling and screening, get catalyst prod, this catalyst prod particle size is 3～500 microns.The catalyst ultimate constituent of preparation is controlled to be: ferric iron and two times of ferrous amount of substance ratio Fe
3+/ 2Fe
2+(iron ratio) 1.40, iron (Fe) mass fraction 69.5%, manganese oxide (MnO
2) 3.0g/100g Fe, aluminium oxide (Al
2O
3) 0.6g/100g Fe, potassium oxide (K
2O) 0.2g/100g Fe, calcium oxide (CaO) 0.4g/100g Fe.At synthesis gas air speed 2500mL/g-cat/h, pressure P=2.6MPa, reaction temperature T=340 ℃, H
2/ CO=2.0, under the experiment condition of catalyst grain size 3-500 micron, the CO molar yield of this catalyst is 70.4%, methane mole selectivity is 11.3%, C
5+Hydrocarbon (five hydrocarbon that carbon atom is above) mole selectivity is 58.5%, C
3Alkene (propylene) mole selectivity 9.6%, C
4Alkene (butylene) mole selectivity 7.3%.
Embodiment 2
With magnetite powder 100, carbon 1[or graphite powder 1 or carbon and graphite powder each 0.50], manganese oxide (MnO
2) 1.8, aluminium oxide (Al
2O
3) 2.5, potash (K
2CO
3) 0.09, dolomite (MgCO
3CaCO
3) 4.7, behind the weight proportion mixing of zinc oxide (ZnO) 0.76, the interior fusion of switching on of the middle frequency furnace of packing into, melt temperature (furnace temperature) is controlled at 2000 ℃, when fusion finishes liquid melt is put into cooling bath, be quickly cooled to room temperature, cooling back frit is through fragmentation, ball milling and screening, get catalyst prod, this catalyst prod particle size is 3～500 microns.The catalyst ultimate constituent of preparation is controlled to be: Fe
3+/ 2Fe
2+(iron ratio) 0.2, iron (Fe) mass fraction 65.0%, manganese oxide (MnO
2) 2.5g/100g Fe, aluminium oxide (Al
2O
3) 3.6g/100g Fe, potassium oxide (K
2O) 0.1g/100g Fe, calcium oxide (CaO) 2.0g/100g Fe, magnesia (MgO) 1.44g/100g Fe; Zinc oxide (ZnO) 1.06g/100g Fe.Wherein, carbon that adds in the raw material or graphite powder with the volatilization of oxycarbide form, therefore, do not contain this material in the catalyst ultimate constituent when fusion.At synthesis gas air speed 500mL/g-cat/h, methane air speed=1000mL/g-cat/h, CO
2Air speed=500mL/g-cat/h, pressure P=6.0MPa, reaction temperature T=280 ℃, H
2/ CO=1.5, under the experiment condition of catalyst sample granularity 3-500 micron, the CO molar yield 93.4% of this catalyst, methane mole selectivity is 9.6%, C
5+Hydrocarbon (five hydrocarbon that carbon atom is above) selectivity is 60.2%, C
3Alkene (propylene) selectivity 10.1%, C
4Alkene (butylene) selectivity 7.2%.
Embodiment 3
With slag or/and iron-oxygen scale 100, aluminium oxide (Al
2O
3) 0.04, potassium nitrate (KNO
3) 2.09, behind the weight proportion mixing of calcium oxide (CaO) 0.05, the fusion of switching in the electric arc furnaces of packing into, melt temperature (furnace temperature) is controlled at 1400 ℃, when fusion finishes liquid melt is put into cooling bath, be quickly cooled to 100 ℃, cooling back frit is through fragmentation, ball milling and screening, get catalyst prod, this catalyst prod particle size is 3～500 microns.The catalyst ultimate constituent of preparation is controlled to be: Fe
3+/ 2Fe
2+(iron ratio) 0.60, iron (Fe) mass fraction 71%, aluminium oxide (Al
2O
3) 0.1g/100g Fe, potassium oxide (K
2O) 1.4g/100g Fe, calcium oxide (CaO) 0.1g/100g Fe, other oxide 0g/100g Fe.At synthesis gas air speed 3000mL/g-cat/h, methane air speed=800mL/g-cat/h, CO
2Air speed=1000mL/g-cat/h, pressure P=1.5MPa, reaction temperature T=400 ℃, H
2/ CO=4.0, under the experiment condition of catalyst sample granularity 3-500 micron, the CO molar yield 70.2% of this catalyst, methane mole selectivity is 12.2%, C
5+Hydrocarbon (five hydrocarbon that carbon atom is above) selectivity is 50.8%, C
3Alkene (propylene) selectivity 10.3%, C
4Alkene (butylene) selectivity 7.6%.
Embodiment 4
With magnetite powder 100, iron powder 3.57 and carbon 0.05, manganese oxide (MnO
2) 1.11, aluminium oxide (Al
2O
3) 1.06, potassium nitrate (KNO
3) 1.25, dolomite (MgCO
3CaCO
3) 5.1 and calcium oxide (CaO) 0.31[or dolomite (MgCO
3CaCO
3) 5.1 and calcium carbonate (CaCO
3) 0.55] and the weight proportion energising fusion in the electric smelter of packing into, melt temperature (furnace temperature) is controlled at 1800 ℃, when fusion finishes liquid melt is put into cooling bath, be quickly cooled to 100 ℃, further be cooled to room temperature again, cooling back frit gets catalyst prod through fragmentation, ball milling and screening, and this catalyst prod particle size is 3～500 microns.The catalyst ultimate constituent of preparation is controlled to be: Fe
3+/ 2Fe
2+(iron ratio) 0.80, iron (Fe) mass fraction 67.5%, manganese oxide (MnO
2) 1.5g/100g Fe, aluminium oxide (Al
2O
3) 1.5g/100g Fe, potassium oxide (K
2O) 0.8g/100g Fe, calcium oxide (CaO) 2.5g/100g Fe, magnesia (MgO) 1.5g/100g Fe.Wherein, carbon that adds in the raw material or graphite powder with the volatilization of oxycarbide form, therefore, do not contain this material in the catalyst ultimate constituent when fusion.At synthesis gas air speed 1500mL/g-cat/h, methane air speed=600mL/g-cat/h, CO
2Air speed=700mL/g-cat/h, pressure P=3.0MPa, reaction temperature T=360 ℃, H
2/ CO=1.8, under the experiment condition of catalyst sample granularity 3-500 micron, the CO molar yield 89.4% of this catalyst, methane mole selectivity is 10.6%, C
5+Hydrocarbon (five hydrocarbon that carbon atom is above) selectivity is 59.4%, C
3Alkene (propylene) selectivity 11.1%, C
4Alkene (butylene) selectivity 8.7%.
Claims (4)
1. one kind is used for the synthetic fused iron catalyst of Fischer-Tropsch, it is characterized in that the composition of this catalyst comprises: ferric iron and two times of ferrous amount of substance ratio Fe
3+/ 2Fe
2+Be 0.20-1.40, the mass fraction 65-71% of iron; In addition, also comprise co-catalyst, it consists of: aluminium oxide 0.1-3.6g/100g Fe, potassium oxide 0.1-1.4g/100g Fe, calcium oxide 0.1-2.5g/100g Fe, other oxide〉0-5.0g/100g Fe, other oxide mainly is with dolomite CaCO
3MgCO
3Magnesia for raw material.
2. fused iron catalyst according to claim 1 is characterized in that, described iron adopts cheap magnetic iron ore, steel slag or/and iron-oxygen scale is a raw material, and wherein slag is or/and the ferric iron of iron-oxygen scale and two times of ferrous amount of substance ratio Fe
3+/ 2Fe
2+Be 0.3-1.6.
3. the preparation method of the described fused iron catalyst of claim 1, it is characterized in that, this preparation method adopts fusion method that a certain amount of co-catalyst raw material is mixed with magnetite powder and pure iron, or with a certain amount of co-catalyst raw material, magnetite powder, pure iron and carbon or graphite powder mix, or with a certain amount of co-catalyst raw material, magnetite powder and carbon or graphite powder mix, or with a certain amount of co-catalyst with steel slag or/and iron-oxygen scale mix, adopt electric arc furnaces or intermediate frequency furnace or electric smelter, through fusion, cooling, broken, ball milling and sieving technology are made, and the gained catalyst particle size is 3～500 microns.
4. the application of the described fused iron catalyst of claim 1, it is characterized in that, this catalyst is applied in the synthetic fluidized-bed reactor of Fischer-Tropsch, the application conditions of its Fischer-Tropsch synthesis is: synthesis gas air speed GHSV=500-3000mL/g-cat/h, methane air speed GHSV=0～1000mL/g-cat/h, CO
2Air speed=0～1000mL/g-cat/h; Pressure P=1.5-6.0MPa, reaction temperature T=280 ℃-400 ℃, H
2/ CO=1.5-4.0, wherein g-cat is meant every gram catalyst weight.
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| CN103657676B (en) * | 2012-09-05 | 2016-04-13 | 中国石油化工股份有限公司 | Microspherical Fischer-Tropsch catalyst and its preparation method and application |
| CN105032441A (en) * | 2015-07-10 | 2015-11-11 | 常州市宏硕电子有限公司 | Fused-iron catalyst used for Fischer-Tropsch synthesis and preparation method thereof, and preparation process for low-carbon olefin from synthesis gas through Fischer-Tropsch synthesis |
| CN106466611B (en) * | 2015-08-21 | 2018-11-02 | 中国科学院大连化学物理研究所 | Ferrum-based catalyst, preparation method and application prepared by co-precipitation-fusion method |
| WO2017031635A1 (en) * | 2015-08-21 | 2017-03-02 | 中国科学院大连化学物理研究所 | Iron-based catalyst prepared by using coprecipitation-melting method, preparation method therefor, and application thereof |
| CN107790144B (en) * | 2016-08-30 | 2021-02-09 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method thereof |
| CN110639528A (en) * | 2019-10-30 | 2020-01-03 | 武汉容新技术有限公司 | Microsphere iron-based catalyst and preparation method and application thereof |
| CN113318772B (en) * | 2021-08-03 | 2021-11-09 | 北京三聚环保新材料股份有限公司 | Nitrided molten iron catalyst and preparation method and application thereof |
| CN114011423B (en) * | 2021-12-14 | 2023-10-20 | 上海兖矿能源科技研发有限公司 | Iron melting catalyst for preparing low-carbon olefin from synthesis gas and preparation method and application thereof |
| CN114130406A (en) * | 2021-12-14 | 2022-03-04 | 上海兖矿能源科技研发有限公司 | Molten iron catalyst for preparing high-carbon alpha olefin from synthesis gas and preparation method and application thereof |
| CN115475626B (en) * | 2022-10-04 | 2023-11-17 | 中国石油大学(华东) | Preparation method of catalyst for preparing long-chain hydrocarbon and co-producing low-carbon olefin through carbon dioxide hydrogenation |
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| FEL-XO基氨合成催化剂的制备化学. 刘化章等.高等学校化学学报，第23卷第1期. 2002 |
| FEL-XO基氨合成催化剂的制备化学. 刘化章等.高等学校化学学报，第23卷第1期. 2002 * |
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