CN109647427B - Iron-based catalyst for producing low-carbon olefin by synthesis gas one-step method - Google Patents
Iron-based catalyst for producing low-carbon olefin by synthesis gas one-step method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 17
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 8
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007921 spray Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000009718 spray deposition Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 40
- 230000009467 reduction Effects 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 238000003756 stirring Methods 0.000 description 24
- 239000011572 manganese Substances 0.000 description 20
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 18
- 239000011777 magnesium Substances 0.000 description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 16
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000011268 mixed slurry Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- -1 carbon hydrocarbon Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an iron-based catalyst for producing low-carbon olefin by a synthesis gas one-step method, which mainly solves the problem of low selectivity of the low-carbon olefin in the prior art, and the iron-based catalyst for producing the low-carbon olefin by the synthesis gas one-step method comprises a carrier and an active component, wherein the active component contains a composition with the following chemical formula in atomic ratio: fe100MnaCobMgcQfOxThe technical scheme that Q comprises at least one element selected from lanthanide elements better solves the problem, and can be used for industrial production of synthesizing low-carbon olefin by fluidized bed synthesis gas.
Description
Technical Field
The invention relates to an iron-based catalyst for producing low-carbon olefin by a synthesis gas one-step method.
Background
The method for converting synthesis gas into hydrocarbons by the action of catalyst is invented by Frans Fischer and Hans Tropsch, German scientists, and is called F-T synthesis for short in 1923, namely the process that CO is subjected to heterogeneous catalytic hydrogenation reaction on a metal catalyst to generate a mixture mainly comprising straight-chain alkane and olefin. Research and development are carried out in the last 20 th century in germany, and industrialization is realized in 1936, and the two-war aftermath is closed because the economy cannot compete with the petroleum industry; south Africa has abundant coal resources, but oil resources are scarce, and are limited by international socioeconomic and political sanctions for a long time, so that the south Africa is forced to develop the coal-to-oil industrial technology, and a first coal-based F-T synthetic oil plant (Sasol-1) with the production capacity of 25-40 ten thousand tons of products per year is built in 1955.
The two global oil crises in 1973 and 1979 caused the price of crude oil in the world to fall and rise greatly, and the F-T synthesis technology re-aroused interest in industrialized countries based on the consideration of strategic technical reserves. In 1980 and 1982, Sasol company in south Africa built and produced two coal-based synthetic oil plants in succession. However, the great reduction of the oil price in the world in 1986 postpones the large-scale industrialization process of the F-T synthesis technology in other countries.
Since the 90 s of the twentieth century, petroleum resources have been in shortage and deterioration, and the exploratory reserves of coal and natural gas have been increasing, so that F-T synthesis technology has attracted much attention again. At present, the main raw materials of the low-carbon olefins in the world are petroleum hydrocarbons, wherein naphtha accounts for most of the raw materials, and alkane, hydrogenated diesel oil, part of heavy oil and the like are also used. Natural gas or light petroleum fractions are mostly used as raw materials at home and abroad, low-carbon olefin is produced by adopting a steam cracking process in an ethylene combination device, the steam cracking is a high-energy consumption device in petrochemical industry, and the steam cracking completely depends on non-renewable petroleum resources, so that alternative resources are urgently needed to be searched along with the gradual shortage of the petroleum resources. Therefore, the research work of preparing olefin by replacing petroleum with other resources is gradually emphasized, and some famous petroleum companies and scientific research institutes in the world perform the research and obtain good results.
Over the course of decades, fischer-tropsch catalysts have also developed in a great deal, and typically comprise the following components: active metals (transition metals of group VIII), oxide supports or structural assistants (SiO)2,Al2O3Etc.), chemical assistants (alkali metal oxides, transition metals) and noble metal assistants (Ru, Re, etc.). Fe produces a large amount of olefins and oxygen-containing compounds, Ru and Co produce mainly long-chain saturated hydrocarbons, and Ni produces mainly methane. Because of the loss of carbonyl compounds easily formed during Ni pressurization reaction and serious methanation, and the expensive Ru and Rh equivalents, the currently commonly used catalysts are divided into two categories from the aspect of active components: iron-based catalysts and cobalt-based catalysts. The selectivity of the cocatalyst has great influence on the selectivity of the low-carbon olefin, the improvement of the selectivity of the low-carbon olefin is mainly realized by the cocatalyst, and the selection and addition technology of the cocatalyst is one of key technologies for developing excellent catalysts.
The F-T synthesis reactors are further classified into fixed bed reactors, fluidized bed reactors and slurry bed reactors according to the difference in the catalysts used and the difference in the target products. The fixed bed reactor has complex structure, high price, difficult heat removal and lower productivity of the whole device. The slurry bed is characterized by low reaction temperature, easy control, low conversion rate, most of products of high carbon hydrocarbon and difficult liquid-solid separation of slurry in the reactor. The fluidized bed reactor has the characteristics of higher temperature, higher conversion rate, no difficulty of liquid-solid separation and mostly low-carbon hydrocarbon as a product; the lower construction and operating costs, while the lower pressure differential saves a lot of compression costs and facilitates the removal of the heat evolved during the reaction, while the longer run is possible due to the lower gas line speed and less wear problems.
The iron catalyst has many advantages, such as obtaining low-carbon olefin with high selectivity and preparing gasoline with high octane value, and the iron catalyst also has the characteristics of wide operating condition and large product adjustability. The preparation method of the iron-based catalyst mainly comprises three methods: the precipitation method (precipitation catalyst) comprises the steps of preparing a mixed solution according to a certain proportion by using Fe and auxiliary agents such as Mg, Co, K and the like, heating to boil, adding a precipitator, stirring, filtering and washing. Adding water into the obtained filter cake for repulping, adding a certain amount of potassium silicate, drying, carrying out extrusion forming, then, grinding and screening; sintering process (sintering catalyst); oxide mixing method (molten iron catalyst) using mill scale or magnetite powder as raw material and adding Al as auxiliary agent2O3MgO, MgO and the like are fed into an electric arc furnace at 1500 ℃ for melting, and the outflow melt is subjected to casting, cooling and multistage crushing.
At present, the iron-based catalyst is used for directly synthesizing low-carbon olefin by F-T in a fixed bed, for example, the patent CN1040397C mentions an iron-based catalyst for Fischer-Tropsch synthesis of low-carbon olefin, and the selectivity of the low-carbon olefin can be as high as 69%. However, the fixed bed reactor has a complex structure, high price, difficult heat removal and low productivity of the whole device. The fluidized bed reactor has the characteristics of higher temperature, higher conversion rate, no difficulty of liquid-solid separation and mostly low-carbon hydrocarbon as a product; the lower construction and operating costs, while the lower pressure differential saves a lot of compression costs and facilitates the removal of the heat evolved during the reaction, while the longer run is possible due to the lower gas line speed and less wear problems. Most of the prior reports on the application of the catalyst to the fluidized bed F-T synthesis are molten iron type catalysts, for example, a molten iron type catalyst for the F-T synthesis is mentioned in patent CN 1704161A; however, the existing fluidized bed F-T synthesis has the problems of insufficiently concentrated products and insufficiently high selectivity of low-carbon olefins.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low selectivity of low-carbon olefin in the prior art, and provides an iron-based catalyst for producing low-carbon olefin by one-step method of synthesis gas, which has the characteristic of high selectivity of low-carbon olefin.
The second technical problem to be solved by the present invention is the application of the above catalyst.
The third technical problem to be solved by the invention is a preparation method of the catalyst.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
the iron-based catalyst for producing the low-carbon olefin by the synthesis gas one-step method comprises a carrier and an active component, wherein the active component contains a composition with the following chemical formula in atomic ratio:
Fe100MnaCobMgcQfOx；
q comprises at least one element selected from the lanthanide series;
the value range of a is 5.0-60.0;
the value range of b is 5.0-60.0;
the value range of c is 1.0-30.0;
the value range of f is 0.9-40.0;
x is the total number of oxygen atoms required to satisfy the valences of the elements in the catalyst.
In the above technical solution, the support is not particularly limited, and those commonly used in the art may be used, for example, but not limited to, including at least one of alumina, silica and titania.
In the above technical solution, the amount of the carrier is not particularly limited, and those skilled in the art can reasonably select the carrier without creative efforts, for example, but not limited to, the amount of the carrier is 30 to 70% by weight of the catalyst.
In the above technical solution, Q preferably further includes at least one of IA elements, and the presence of both lanthanide and alkali metal elements is beneficial to improving the selectivity of the low-carbon olefin. At this time Fe100MnaCobMgcQfOxMay be further expressed as Fe100MnaCobMgcAdLeOxWherein A is at least one of IA elements, L is at least one of lanthanide elements, d ranges from 1.0 to 30.0, and e ranges from 0.1 to 10.0.
In the technical scheme, the value range of a is preferably 10.0-50.0. Such as, but not limited to, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, and the like.
In the technical scheme, the value range of b is preferably 10.0-50.0. Such as, but not limited to, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, and the like.
In the technical scheme, the value range of c is preferably 5.0-25.0. Such as, but not limited to, 10.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, and the like.
In the technical scheme, the value range of d is preferably 2.0-25.0. Such as, but not limited to, 3.0, 4.0, 5.0, 8.0, 10.0, 15.0, 20.0, and the like.
In the technical scheme, the value range of e is preferably 1.0-8.0. Such as but not limited to 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, and so forth.
In the above technical solution, the IA element is selected from at least one of Li, Na, K and Cs; more preferably, the IA element includes at least two of Li, K and Cs at the same time, and when the two elements, such as Li and K, Li and Cs, K and Cs, have synergistic effect in improving the selectivity of the lower olefins. The atomic ratio between the two elements is not particularly limited, but is not limited to 0.1 to 10, wherein more specific atomic ratios may be 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, and the like.
In the above technical solution, the lanthanide includes Ce.
The catalyst of the invention can be reduced or not reduced before being used for the reaction of producing the low-carbon olefin by the synthesis gas one-step method, but is preferably reduced. When reducing, the reducing conditions are not particularly limited and can be reasonably selected by the person skilled in the art, for example but not limited to the reducing conditions of the catalyst prepared according to the invention: the pressure is 0.05-5 MPa, preferably 0.1-4 MPa; the reducing gas can be hydrogen, carbon monoxide or synthesis gas, and when the reducing gas is synthesis gas, H thereof2The mol ratio of/CO is 0.1-6.0, preferably 0.2-6.0; the load of reducing gas is 100-8000 hours-1Preferably 500 to 6000 hours-1(ii) a The reduction temperature is 200-600 ℃, preferably 220-500 ℃; the reduction time is 1 to 100 hours, preferably 6 to 72 hours.
For comparison, the reduction conditions used for the catalyst prepared in the embodiment of the present invention are:
to solve the second technical problem, the technical solution of the present invention is as follows:
the application of the catalyst in the technical scheme of one of the technical problems in the reaction for producing the low-carbon olefin by the synthesis gas one-step method.
The technical key of the present invention is the choice of catalyst, which can be reasonably selected by those skilled in the art for the process conditions of a specific application without inventive effort, such as but not limited to:
in the presence of the catalyst in any of the technical schemes of the technical problems, the synthesis gas reacts to generate the low-carbon olefin.
As known to those skilled in the art, lower olefins are C2-C4 olefins, more specifically ethylene, propylene and butylene or mixtures thereof. The butene includes butene-1, butene-2, isobutene and butadiene.
The reaction temperature can be 200-600 ℃, preferably 220-500 ℃;
the pressure of the reaction can be 0.5-10MPa, preferably 1-8 MPa; (ii) a
H in synthesis gas2The mol ratio of/CO can be 0.1-5.0, preferably 0.5-3.0;
the volume space velocity of the synthetic gas can be 100-8000 hours-1Preferably 500 to 6000 hours-1More preferably 2000 to 6000 hours-1。
For the sake of comparability, the evaluation conditions of the catalyst used in the embodiment of the present invention were as follows:
phi 38 mm fluidized bed reactor
In order to solve the third technical problem of the invention, the technical scheme of the invention is as follows:
the preparation method of the catalyst in any one of the technical schemes of the technical problems comprises the following process steps:
obtaining slurry comprising a catalyst carrier and active component elements, wherein the pH value of the slurry is 1-6;
feeding the slurry into a spray dryer for spray forming;
and (4) roasting.
When the active component contains both lanthanide and alkali metal elements, the preparation method of the catalyst preferably comprises the following process steps:
obtaining an aqueous solution comprising metallic elements other than alkali metals in the composition;
adding sol of a carrier with required amount into the aqueous solution, adding an alkali metal hydroxide solution, and adjusting the pH value to 1-6 by using an acid-base regulator to obtain slurry;
feeding the slurry into a spray dryer for spray forming;
and (4) roasting.
In the technical scheme, the roasting temperature is preferably 400-1000 ℃, and more preferably 450-800 ℃.
In the above technical scheme, the roasting time is preferably 0.15 to 10 hours, and more preferably 0.5 to 8 hours.
The process conditions for spray drying and shaping are not particularly limited and can be appropriately selected by those skilled in the art and can achieve comparable technical effects. For example, but not limited to, the inlet temperature of the spray can be 200-380 ℃, the outlet temperature can be 100-230 ℃, the spray drying is carried out to form microspheres, and finally the microspheres are roasted to prepare the catalyst.
In order to facilitate comparison, the spray drying conditions adopted by the specific embodiment of the invention are as follows:
the inlet temperature is 300 ℃,
the exit temperature was 200 ℃.
In the above technical scheme, the soluble ferric salt can be ferric nitrate or ferric sulfate.
In the above technical scheme, the soluble compounds of Mn, Co, Mg and lanthanoid can be nitrates and salts decomposable into oxides.
In the above-mentioned embodiment, although the atmosphere for firing is not particularly limited, an oxidizing atmosphere or an inert atmosphere is preferable, and an air atmosphere is more preferable from the economical viewpoint.
In the present invention, unless otherwise specified, the pressure including the reaction pressure means a gauge pressure.
The catalyst is used, and the reaction temperature is 200-600 ℃, the reaction pressure is 0.5-10MPa, and the catalyst load is 100-8000 hours-1Raw material ratio (mol) H2The F-T synthesis reaction is carried out under the condition that the ratio of/CO (0.1-5.0): 1, the CO conversion rate can reach 91.3%, the selectivity of low-carbon olefin in a reaction product can reach 71.2%, and a better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
1. Catalyst preparation
360.10 g of ferric nitrate (Fe (NO)3)3·9H2O), dissolving with 500g of water to obtain a material I, and taking 19.20 g of cerium nitrate (Ce (NO)3)3·6H2O) is dissolved in 100g of water under heating to obtain a material II, 125.0 g of 50% manganese nitrate (Mn (NO)3)2) 51.40 g of cobalt nitrate (Co (NO)3)2·6H2O), 33.90 g of magnesium nitrate (Mg (NO)3)2·6H2O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.
Materials I and III were mixed, 312.50 g of a 40 wt% silica sol material was added under stirring, 50g of an aqueous solution containing 7.17 g of KOH was then added, the pH of the slurry was adjusted with 27 wt% ammonia water so that the pH of the mixed slurry became 6.0, and the slurry was subjected to microspherical molding in a spray dryer under specific spray drying conditions of 300 ℃ at the inlet and 200 ℃ at the outlet of a spray machine. Finally, the catalyst is calcined in a rotary calcining furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm) for 2.0 hours at 500 ℃ in an air atmosphere, and the prepared catalyst comprises the following components:
50% by weight Fe100Mn40Co20Mg15K12Ce5Ox+ 50% by weight of SiO2
2. Reduction and evaluation of the catalyst
The prepared catalyst is carried out under the reduction conditions:
reduction was carried out and then the Fischer-Tropsch synthesis reaction was carried out under the following conditions:
phi 38 mm fluidized bed reactor
The experimental results of the synthesis reaction are shown in table 1.
[ example 2 ]
1. Catalyst preparation
370.10 g of ferric nitrate (Fe (NO)3)3·9H2O), dissolving with 500g of water to obtain a material I, and taking 19.70 g of cerium nitrate (Ce (NO)3)3·6H2O) was dissolved in 100g of water under heating to obtain a material II, 128.50 g of 50% manganese nitrate (Mn (NO)3)2) 52.80 g cobalt nitrate (Co (NO)3)2·6H2O), 34.90 g of magnesium nitrate (Mg (NO)3)2·6H2O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.
Materials I and III were mixed, 312.50 g of a 40 wt% silica sol material was added under stirring, 50g of an aqueous solution containing 7.45 g of LiOH was then added, the pH of the slurry was adjusted with 27 wt% ammonia water so that the pH of the mixed slurry became 6.0, and the slurry obtained after sufficient stirring was subjected to microspherical molding in a spray dryer under specific spray drying conditions of 300 ℃ at the inlet temperature and 200 ℃ at the outlet temperature of a spray machine. Finally, the catalyst is calcined in a rotary calcining furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm) for 2.0 hours at 500 ℃ in an air atmosphere, and the prepared catalyst comprises the following components:
50% by weight Fe100Mn40Co20Mg15Li12Ce5Ox+ 50% by weight of SiO2
2. Reduction and evaluation of the catalyst
The prepared catalyst is carried out under the reduction conditions:
reduction was carried out and then the Fischer-Tropsch synthesis reaction was carried out under the following conditions:
phi 38 mm fluidized bed reactor
The experimental results of the synthesis reaction are shown in table 1.
[ example 3 ]
1. Catalyst preparation
333.80 g of ferric nitrate (Fe (NO)3)3·9H2O), dissolving with 500g of water to obtain a material I, taking 17.80 g of cerium nitrate (Ce (NO)3)3·6H2O) was dissolved in 100g of water under heating to obtain a material II, 115.90 g of 50% manganese nitrate (Mn (NO)3)2) 47.60 g of cobalt nitrate (Co (NO)3)2·6H2O), 31.50 g magnesium nitrate (Mg (NO)3)2·6H2O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.
Materials I and III were mixed, 312.50 g of a 40 wt% silica sol material was added under stirring, 50g of an aqueous solution containing 19.40 g of CsOH was then added, the pH of the slurry was adjusted with 27 wt% aqueous ammonia so that the pH of the mixed slurry became 6.0, and the slurry obtained after sufficient stirring was subjected to microspherical molding in a spray dryer under specific spray drying conditions of 300 ℃ at the inlet temperature and 200 ℃ at the outlet temperature of a spray machine. Finally, the catalyst is calcined in a rotary calcining furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm) for 2.0 hours at 500 ℃ in an air atmosphere, and the prepared catalyst comprises the following components:
50% by weight Fe100Mn40Co20Mg15Cs12Ce5Ox+ 50% by weight of SiO2
2. Reduction and evaluation of the catalyst
The prepared catalyst is carried out under the reduction conditions:
reduction was carried out and then the Fischer-Tropsch synthesis reaction was carried out under the following conditions:
phi 38 mm fluidized bed reactor
The experimental results of the synthesis reaction are shown in table 1.
[ example 4 ]
1. Catalyst preparation
365.00 g of ferric nitrate (Fe (NO)3)3·9H2O), dissolving with 500g of water to obtain a material I, and taking 19.40 g of cerium nitrate (Ce (NO)3)3·6H2O) was dissolved in 100g of water under heating to obtain a material II, 126.70 g of 50% manganese nitrate (Mn (NO)3)2) 52.10 g of cobalt nitrate (Co (NO)3)2·6H2O), 34.40 g magnesium nitrate (Mg (NO)3)2·6H2O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.
Materials I, II and III are mixed, 312.50 g of 40 wt% silica sol material is added under stirring, 50g of aqueous solution containing 4.30 g of NaOH is then added, the pH value of the slurry is adjusted by 27 wt% ammonia water to make the pH value of the mixed slurry 6.0, and the slurry prepared after full stirring is subjected to microspherical molding in a spray dryer, wherein the specific spray drying conditions are that the inlet temperature of a sprayer is 300 ℃ and the outlet temperature is 200 ℃. Finally, the catalyst is calcined in a rotary calcining furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm) for 2.0 hours at 500 ℃ in an air atmosphere, and the prepared catalyst comprises the following components:
50% by weight Fe100Mn40Co20Mg15Na12Ce5Ox+ 50% by weight of SiO2
2. Reduction and evaluation of the catalyst
The prepared catalyst is carried out under the reduction conditions:
reduction was carried out and then the Fischer-Tropsch synthesis reaction was carried out under the following conditions:
phi 38 mm fluidized bed reactor
The experimental results of the synthesis reaction are shown in table 1.
[ example 5 ]
1. Catalyst preparation
365.00 g of ferric nitrate (Fe (NO)3)3·9H2O), dissolving with 500g of water to obtain a material I, and taking 19.40 g of cerium nitrate (Ce (NO)3)3·6H2O) was dissolved in 100g of water under heating to obtain a material II, 126.70 g of 50% manganese nitrate (Mn (NO)3)2) 52.10 g of cobalt nitrate (Co (NO)3)2·6H2O), 34.40 g magnesium nitrate (Mg (NO)3)2·6H2O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.
Materials I, II and III were mixed, 312.50 g of 40 wt% silica sol material was added under stirring, 50g of an aqueous solution containing 3.67 g of LiOH and 3.63 g of KOH was added, the pH of the slurry was adjusted with 27 wt% aqueous ammonia so that the pH of the mixed slurry became 6.0, and the slurry obtained after sufficient stirring was subjected to microspherical molding in a spray dryer under conditions of an inlet temperature of 300 ℃ and an outlet temperature of 200 ℃ with a sprayer. Finally, the catalyst is calcined in a rotary calcining furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm) for 2.0 hours at 500 ℃ in an air atmosphere, and the prepared catalyst comprises the following components:
50% by weight Fe100Mn40Co20Mg15Li6K6Ce5Ox+ 50% by weight of SiO2
2. Reduction and evaluation of the catalyst
The prepared catalyst is carried out under the reduction conditions:
reduction was carried out and then the Fischer-Tropsch synthesis reaction was carried out under the following conditions:
phi 38 mm fluidized bed reactor
The experimental results of the synthesis reaction are shown in table 1.
[ example 6 ]
1. Catalyst preparation
351.00 g of ferric nitrate (Fe (NO)3)3·9H2O), dissolving with 500g of water to obtain a material I, and taking 18.70 g of cerium nitrate (Ce (NO)3)3·6H2O) was dissolved in 100g of water under heating to obtain a material II, 121.90 g of 50% manganese nitrate (Mn (NO)3)2) 50.10 g of cobalt nitrate (Co (NO)3)2·6H2O), 33.10 g magnesium nitrate (Mg (NO)3)2·6H2O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.
Materials I and III were mixed, 312.50 g of a 40 wt% silica sol material was added under stirring, 50g of an aqueous solution containing 3.53 g of LiOH and 10.01 g of CsOH was added, the pH of the slurry was adjusted to 6.0 with 27 wt% aqueous ammonia, and the slurry obtained after sufficient stirring was subjected to microspherical molding in a spray dryer under conditions of 300 ℃ at the inlet and 200 ℃ at the outlet of a sprayer. Finally, the catalyst is calcined in a rotary calcining furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm) for 2.0 hours at 500 ℃ in an air atmosphere, and the prepared catalyst comprises the following components:
50% by weight Fe100Mn40Co20Mg15Li6Cs6Ce5Ox+ 50% by weight of SiO2
2. Reduction and evaluation of the catalyst
The prepared catalyst is carried out under the reduction conditions:
reduction was carried out and then the Fischer-Tropsch synthesis reaction was carried out under the following conditions:
phi 38 mm fluidized bed reactor
The experimental results of the synthesis reaction are shown in table 1.
[ example 7 ]
1. Catalyst preparation
346.40 g of ferric nitrate (Fe (NO)3)3·9H2O), dissolving with 500g of water to obtain a material I, and taking 18.40 g of cerium nitrate (Ce (NO)3)3·6H2O) was dissolved in 100g of water under heating to obtain a material II, 120.30 g of 50% manganese nitrate (Mn (NO)3)2) 49.40 g of cobalt nitrate (Co (NO)3)2·6H2O), 32.60 g magnesium nitrate (Mg (NO)3)2·6H2O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.
Materials I, II and III were mixed, 312.50 g of a 40 wt% silica sol material was added under stirring, 50g of an aqueous solution containing 3.45 g of KOH and 9.88 g of CsOH was added, the pH of the slurry was adjusted to 6.0 with 27 wt% aqueous ammonia, and the slurry obtained after sufficient stirring was subjected to microspherical molding in a spray dryer under conditions of 300 ℃ at the inlet and 200 ℃ at the outlet of a sprayer. Finally, the catalyst is calcined in a rotary calcining furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm) for 2.0 hours at 500 ℃ in an air atmosphere, and the prepared catalyst comprises the following components:
50% by weight Fe100Mn40Co20Mg15K6Cs6Ce5Ox+ 50% by weight of SiO2
2. Reduction and evaluation of the catalyst
The prepared catalyst is carried out under the reduction conditions:
reduction was carried out and then the Fischer-Tropsch synthesis reaction was carried out under the following conditions:
phi 38 mm fluidized bed reactor
The experimental results of the synthesis reaction are shown in table 1.
[ example 8 ]
1. Catalyst preparation
354.00 g of ferric nitrate (Fe (NO)3)3·9H2O), dissolving with 500g of water to obtain a material I, and taking 18.80 g of cerium nitrate (Ce (NO)3)3·6H2O) was dissolved in 100g of water under heating to obtain a material II, 122.90 g of 50% manganese nitrate (Mn (NO)3)2) 50.50 g of cobalt nitrate (Co (NO)3)2·6H2O), 33.40 g magnesium nitrate (Mg (NO)3)2·6H2O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.
Materials I, II and III were mixed, 312.50 g of a 40 wt% silica sol material was added under stirring, 50g of an aqueous solution containing 2.35 g of KOH, 2.37 g of LiOH and 6.73 g of CsOH was added, the pH of the slurry was adjusted with 27 wt% aqueous ammonia so that the pH of the mixed slurry became 6.0, and the slurry obtained after sufficient stirring was subjected to microspherical molding in a spray dryer under conditions of an inlet temperature of 300 ℃ and an outlet temperature of 200 ℃ in a sprayer. Finally, the catalyst is calcined in a rotary calcining furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm) for 2.0 hours at 500 ℃ in an air atmosphere, and the prepared catalyst comprises the following components:
50% by weight Fe100Mn40Co20Mg15Li4K4Cs4Ce5Ox+ 50% by weight of SiO2
2. Reduction and evaluation of the catalyst
The prepared catalyst is carried out under the reduction conditions:
reduction was carried out and then the Fischer-Tropsch synthesis reaction was carried out under the following conditions:
phi 38 mm fluidized bed reactor
The experimental results of the synthesis reaction are shown in table 1.
TABLE 1
Claims (8)
1. The iron-based catalyst for producing the low-carbon olefin by the synthesis gas one-step method comprises a carrier and an active component, wherein the active component contains a composition with the following chemical formula in atomic ratio:
Fe100MnaCobMgcAdLeOx；
the value range of a is 5.0-60.0;
the value range of b is 5.0-60.0;
the value range of c is 1.0-30.0;
the value range of d is 1.0-30.0;
the value range of e is 0.1-10.0;
wherein A simultaneously contains Li, K and Cs;
wherein L is at least one of lanthanide elements, and at least comprises Ce element; x is the total number of oxygen atoms required to satisfy the valences of the elements in the catalyst.
2. The catalyst according to claim 1, wherein the carrier comprises at least one selected from the group consisting of silica, alumina and titania.
3. The catalyst of claim 1, wherein a is in the range of 10.0 to 50.0.
4. The catalyst of claim 1, wherein b is in the range of 10.0 to 50.0.
5. The catalyst of claim 1, wherein c is selected from the range of 5.0 to 25.0.
6. The catalyst of claim 1, wherein the catalyst is reduced before being used in the reaction of producing low-carbon olefin by using synthesis gas one-step method.
7. The application of the catalyst in the claim 1 in the reaction of producing low-carbon olefin by a synthesis gas one-step method;
the reaction pressure is 0.5-10 MPa.
8. A process for preparing the catalyst of claim 1, comprising the process steps of:
obtaining slurry comprising a catalyst carrier and active component elements, wherein the pH value of the slurry is 1-6;
feeding the slurry into a spray dryer for spray forming;
and (4) roasting.
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| CN104148106A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by using synthesis gas and preparation method of catalyst |
| CN104549296A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from microspherical synthesis gas, as well as preparation method thereof |
| CN105363464A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Catalyst for directly preparing light hydrocarbon through synthesis gas and preparation method of catalyst |
| CN105435803A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst |
| CN106582662A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Load-type catalyst, preparing method and application thereof, and method of using synthesis gas to prepare low-carbon olefin |
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| CN104148106A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by using synthesis gas and preparation method of catalyst |
| CN104549296A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from microspherical synthesis gas, as well as preparation method thereof |
| CN105363464A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Catalyst for directly preparing light hydrocarbon through synthesis gas and preparation method of catalyst |
| CN105435803A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst |
| CN106582662A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Load-type catalyst, preparing method and application thereof, and method of using synthesis gas to prepare low-carbon olefin |
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