CN112742392B - Fischer-Tropsch synthesis catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method - Google Patents
Fischer-Tropsch synthesis catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 113
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- 239000002808 molecular sieve Substances 0.000 claims abstract description 82
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- 229910052802 copper Inorganic materials 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
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- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 9
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
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- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
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- 229910021536 Zeolite Inorganic materials 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
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- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
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- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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Abstract
The invention relates to the field of Fischer-Tropsch synthesis, in particular to a Fischer-Tropsch synthesis catalyst, a preparation method and application thereof, and a Fischer-Tropsch synthesis method. The catalyst comprises a carrier, a metal active component loaded on the carrier and an optional first metal auxiliary agent, wherein the first metal auxiliary agent is selected from at least one of transition metals; the carrier is internally provided with a through hole channel, and the ratio of the cross sectional area of the hole channel to the cross sectional area of the carrier is 0.05-25: 100, respectively; wherein the carrier contains at least one of a refractory inorganic oxide and a molecular sieve; the metal active component is Co. The Fischer-Tropsch synthesis catalyst provided by the invention is internally provided with a through pore canal, the Fischer-Tropsch synthesis activity and the C5+ hydrocarbon selectivity can be improved by adopting the Fischer-Tropsch synthesis catalyst provided by the invention, the methane selectivity is lower, and in addition, the Fischer-Tropsch synthesis catalyst provided by the invention has higher radial crushing resistance.
Description
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis, in particular to a Fischer-Tropsch synthesis catalyst, a preparation method and application thereof, and a Fischer-Tropsch synthesis method.
Background
The effect of the support on the performance of the cobalt catalyst is manifold, it has an effect on the crystallite size of the cobalt species of the catalyst, the interaction between the metal and the support, and ultimately on the F-T synthesis reaction performance and product distribution of the catalyst.
In the conventional method, alumina, especially gamma-alumina, is often used as an adsorbent or a carrier of a supported catalyst due to its superior pore structure, specific surface and heat-resistant stability. The alumina is usually prepared from hydrated alumina, such as pseudo-boehmite, by molding, drying and high-temperature roasting. The active metal component Co is loaded on the carrier, so that the Fischer-Tropsch synthesis catalyst can be obtained. However, the performance of the Fischer-Tropsch synthesis catalyst will vary greatly depending on the shape of the support. Since fischer-tropsch synthesis is a reaction where diffusion mass transfer is a significant concern, having a support with a large macroscopic external surface area and a short macroscopic diffusion distance is beneficial for increasing fischer-tropsch synthesis reaction activity and reducing methane selectivity.
However, the selection of commercial catalyst geometries and dimensions often requires a balance between multiple aspects and the properties of the catalyst. To achieve different goals, catalysts of a wide variety of morphologies are currently being developed. Usually in the form of spheres, which are commonly used for fluidized catalysts, or catalysts for which the flowability is particularly critical. The strip-shaped and fixed bed catalyst is further developed into a cylindrical strip, a trilobal strip, a quadralobe strip, other multilobal strips and deformed multilobal strips on the basis of the strip-shaped catalyst. Barrel-shaped strips, i.e. strips with holes in the cylinder, such as typical raschig rings, cross rings, pall rings, step rings, etc. Honeycomb supports, i.e., a matrix of cordierite or alumina on which regularly arranged channels are commonly used for SCR and automotive exhaust treatment, etc.
In order to improve the diffusion performance of the catalyst, a number of methods have been proposed. CN101134173A proposes a carrier and a catalyst with special shapes, wherein the special shapes are ellipsoids, and one or more grooves are arranged on the ellipsoids, so that the catalyst has large outer surface area and good mass transfer performance and can be widely usedThe method is widely used in heavy oil processing reaction. CN1859975A proposes the characteristics of a deformed trilobal stripe catalyst. CN103269798A proposes a shaped catalyst body having a bottom, a cylinder surface, a cylinder axis and at least one continuous open cylinder extending parallel to the cylinder axis, the bottom of the cylinder having at least 4 corners for a low surface support. CN105233880A proposes an inner core type cloverleaf-shaped catalyst carrier and a preparation method and application thereof. The carrier is composed of two layers, wherein the outer shell is made of porous structure material, the inner core is made of compact structure material, and the specific surface area of the inner core is less than 1m2The catalyst has high crushing strength and small diffusion effect when being used in Fischer-Tropsch synthesis catalyst. CN1064557225A proposes an oxidation catalyst of saddle-shaped carrier for use in less than 0.5m2Specific surface area per gram of support. CN101816953A proposes a catalyst carrier, which comprises: the device comprises a central hole, a convex part, a top part, a cylinder, a concave part, a groove and a body; the height of the cylinder is 3-50 mm, and the diameter is 3-50 mm.
From the aspect of utilization rate of the catalyst and active metal, the catalyst with a pore passage in the middle, such as a Raschig ring or a cross ring, has the highest utilization rate of the activity, and is in a bar shape and a spherical shape again. But the order of the strengths of the catalysts is substantially reversed. In order to balance the utilization rate and strength of the catalyst, the hollow carrier or catalyst such as a Raschig ring and a honeycomb carrier generally adopts a ceramic matrix, the strength of the ceramic matrix is high, even after the middle part is left empty, the integral strength is still high, and the strength of the ceramic matrix is not high.
The catalyst disclosed by the prior art is suitable for the conditions that the strength of the matrix is high or the specific surface area is small, and cannot be used for the conditions that the strength of the matrix is not high and the specific surface area of the carrier is large.
Disclosure of Invention
The invention aims to solve the problem that a Fischer-Tropsch synthesis catalyst in the prior art cannot give consideration to high substrate strength and high Fischer-Tropsch synthesis activity, and provides a Fischer-Tropsch synthesis catalyst, a preparation method and application thereof, and a Fischer-Tropsch synthesis method.
In order to achieve the above object, the present invention provides in a first aspect a fischer-tropsch synthesis catalyst comprising a support and, supported thereon, a metal active component and optionally a first metal promoter selected from at least one of transition metals;
the carrier is internally provided with a through hole channel, and the ratio of the cross sectional area of the hole channel to the cross sectional area of the carrier is 0.05-25: 100, respectively;
wherein the carrier contains at least one of a refractory inorganic oxide and a molecular sieve;
the metal active component is Co.
In a second aspect, the present invention provides a process for the preparation of a fischer-tropsch synthesis catalyst as described above, the process comprising:
(1) mixing a carrier precursor, water, an optional extrusion aid and an optional peptizing agent to obtain a mixture, and molding and first roasting the mixture to obtain a carrier, wherein the molding enables the interior of the carrier to have a through pore channel;
(2) and (2) impregnating the carrier obtained in the step (1) with a solution containing a metal active component precursor and an optional first metal auxiliary precursor, drying and carrying out second roasting.
In a third aspect, the invention provides a Fischer-Tropsch synthesis catalyst prepared by the preparation method.
In a fourth aspect, the invention provides the use of a fischer-tropsch synthesis catalyst as described above in a fischer-tropsch synthesis reaction.
In a fifth aspect, the invention provides a fischer-tropsch synthesis process, comprising: reacting CO and H under the condition of Fischer-Tropsch synthesis reaction2Contacting with the Fischer-Tropsch synthesis catalyst provided by the invention.
The Fischer-Tropsch synthesis catalyst provided by the invention adopts the through pore canal with the super-large pores inside, so that the carrier has an increased surface area compared with the conventional carrier, the Fischer-Tropsch synthesis activity and the C5+ hydrocarbon selectivity are further improved, and the methane selectivity is low. In addition, the Fischer-Tropsch synthesis catalyst has higher radial crushing resistance.
Drawings
FIG. 1 is a schematic diagram of the structure of the base of one embodiment of the orifice plate of the present invention.
FIG. 2 is a schematic diagram of a rack of one embodiment of the orifice plate of the present invention.
FIG. 3 is a schematic diagram of the configuration of the shaped rods of one embodiment of the orifice plate of the present invention.
FIG. 4 is a schematic cross-sectional view of a Fischer-Tropsch synthesis catalyst support ZA according to example 1 of the present invention.
FIG. 5 is a schematic cross-sectional view of the Fischer-Tropsch synthesis catalyst support, ZB, of example 2 of the present invention.
FIG. 6 is a schematic diagram of a rack of one embodiment of the orifice plate of the present invention.
Figure 7 is a schematic cross-sectional view of a fischer-tropsch synthesis catalyst support ZC according to example 3 of the present invention.
Figure 8 is a schematic cross-section of a fischer-tropsch synthesis catalyst support ZD according to example 4 of the present invention.
FIG. 9 is a schematic cross-sectional view of a Fischer-Tropsch synthesis catalyst support ZE according to example 5 of the present invention.
Fig. 10 is a schematic cross-sectional view of a fischer-tropsch synthesis catalyst carrier ZF as described in example 6 of the invention.
Fig. 11 is a schematic cross-sectional view of the fischer-tropsch synthesis catalyst support DA of comparative example 1.
Description of the reference numerals
1. Base 2, shaping hole 3, support
4. Forming rod 5, mounting hole 6 and material passing hole
7. First mounting structure 8, second mounting structure 13, head
14. Rod part
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the use of the terms of orientation such as "upper, lower, between, and middle" generally means upper, lower, between, and middle as shown in the accompanying drawings, and the use of the terms of orientation such as "inner and outer" means inner and outer with respect to the profile of the respective member itself, unless otherwise specified.
The invention provides a Fischer-Tropsch synthesis catalyst, which comprises a carrier, a metal active component loaded on the carrier and an optional first metal auxiliary agent, wherein the first metal auxiliary agent is selected from at least one of transition metals;
the carrier is internally provided with a through hole channel, and the ratio of the cross sectional area of the hole channel to the cross sectional area of the carrier is 0.05-25: 100, respectively;
wherein the carrier contains at least one of a refractory inorganic oxide and a molecular sieve;
the metal active component is Co.
The first metal additive is not Co.
In the present invention, when the ratio of the cross-sectional area of the cell to the cross-sectional area of the carrier is 0.05 to 25: the catalyst has high strength, high Fischer-Tropsch synthesis activity and high C5+ hydrocarbon selectivity at 100 ℃, and has low methane selectivity. Preferably, the ratio of the cross-sectional area of the channel to the cross-sectional area of the support is 0.1 to 20: 100, more preferably 0.2 to 9: 100, the performance of the catalyst can be further improved.
The through hole in the invention refers to a state that the carrier has unobstructed property due to the pore channel existing in the carrier, and the pore channel penetrates through the carrier.
In the present invention, the shape of the carrier is selected from a wide range, and the shape of the carrier may be various shapes conventionally used in the art, and the shape of the carrier may be regular or irregular, and is preferably regular.
Preferably, the carrier is spherical and/or in the shape of a bar, preferably a bar, more preferably a multilobal bar, more preferably a trilobe bar, a quadralobe bar or a pentalobal bar. With the preferred embodiment, the catalyst can be further improved in strength, fischer-tropsch synthesis activity and C5+ hydrocarbon selectivity, with lower methane selectivity.
The strip-shaped material is a three-dimensional structure material which is prepared by extruding or tabletting and the like, and the length of the material is not less than 50% of the diameter of the circumscribed circle.
The multi-leaf shapes mentioned in the invention refer to three-leaf shapes, four-leaf shapes, five-leaf shapes, six-leaf shapes and the like. The invention does not limit the size of each blade of the multi-blade shape and the proportion of the size of each blade to other blades, namely the multi-blade shape can be a regular multi-blade shape, an irregular multi-blade shape or a deformed multi-blade shape.
In the invention, the catalyst preferably adopts a carrier which is small in size and has through pore channels inside, and the carrier not only has high strength, but also is more beneficial to improving the utilization rate of the metal active component. Preferably, the equivalent diameter of the support is not more than 5mm, preferably from 0.05mm to 5mm, more preferably from 0.1mm to 3mm, and still more preferably from 0.5mm to 2 mm.
In the present invention, the shape of the pore passage is selected from a wide range, and may be a regular shape or an irregular shape. The cross section of the channels is the same or different (gradually increasing or gradually decreasing) along the material flow direction, and the channels include but are not limited to cones when the cross section of the channels is gradually increased along the material flow direction; in the case where the cross-section of the channel decreases progressively along the direction of flow, the channel includes, but is not limited to, an inverted cone.
In the present invention, the channels of the carrier may be channels with equal cross section or channels with non-equal cross section, preferably, the channels are channels with equal cross section, and more preferably, the channels are cylindrical and/or regular polygonal prismatic. Under the condition, the inner surface of the catalyst is more regular, the phenomenon of stress concentration caused by sharp pore walls in the pore structure is avoided, the collapse probability of the catalyst is reduced, and the catalyst has the characteristics of higher compactness and higher strength. It should be noted that, in the present invention, the circle and regular polygon also include imperfect circle and/or regular polygon.
In the present invention, the regular polygon is preferably a triangle, a square, a regular pentagon, and other regular polygons.
Further preferably, the diameter of the cylindrical shape and the diameter of the circumscribed circle of the regular polygonal pyramid shape are each independently not less than 6 μm, preferably 0.01 to 0.5mm, and further preferably 0.05 to 0.3 mm.
In the present invention, the number of the channels can be selected in a wide range, and may be 1, or 2 or more, and may be appropriately selected according to actual needs, and preferably, the number of the channels is 1 to 9, and more preferably 1 to 5.
It should be noted that if the number of the cells is 2 or more, the above-defined ratio of the cross-sectional area of the cell to the cross-sectional area of the carrier refers to the ratio of the cross-sectional area of the individual cell to the cross-sectional area of the carrier.
The specific position of the pore channel is wide in selection range, and the pore channel can penetrate through the carrier. When the number of the pore channels is one, the pore channels preferably extend along a central axis of a circumscribed circle of the cross section of the support, in which case, when the cross section of the support is circular, the pore channels extend along the central axis of the circle; when the cross section of the carrier is multi-leaf shape, the pore canal extends along the central axis of the circumcircle where the multi-leaf shape is positioned.
When the number of the pore passages is two or more, the relative arrangement position between the pore passages is not particularly limited, and preferably, the pore passages are uniformly distributed. The preferred implementation mode is more beneficial to ensuring that the stress distribution of the catalyst carrier is more balanced, and further optimizing the overall strength of the catalyst carrier. Preferably, the uniform distribution means that the distances from the pore channels to the center of a circumscribed circle where the cross section of the carrier is located are equal, more preferably, the distances between the pore channels are equal, and more preferably, the distance between the pore channels and the center of the circumscribed circle where the cross section of the carrier is located is equal to the distance between the pore channels and the edge of the carrier.
In a preferred embodiment of the present invention, the cross-section of the carrier is circular, and the pore channels extend along a central axis of the circular shape and/or are arranged at equal intervals along a circumferential direction of the central axis. The preferred embodiment enables the pore channels to be distributed evenly, effectively avoids the sudden drop of local strength caused by the arrangement of the middle pore channel structure on the catalyst carrier, and can ensure the mechanical strength of the carrier.
In another preferred embodiment of the invention, the cross-section of the support is multilobal, and the cells extend along the central axis of the circumcircle on which the multilobal vanes lie and/or along the central axis of the circumcircle on which the multilobal vanes lie. The preferred embodiment enables the pore channels to be distributed evenly, effectively avoids the sudden drop of local strength caused by the arrangement of the middle pore channel structure on the catalyst carrier, and can ensure the mechanical strength of the carrier.
In the present invention, the composition of the catalyst support may be a composition conventional in the art, and may contain at least one of a refractory inorganic oxide and a molecular sieve. If the carrier contains both the refractory inorganic oxide and the molecular sieve, the selection range of the contents of the refractory inorganic oxide and the molecular sieve is wide, and a person skilled in the art can select a suitable carrier type according to conventional technical means. Preferably, the support is a heat-resistant inorganic oxide. The refractory inorganic oxide may be a refractory inorganic oxide generally used in the art. For example, the heat-resistant inorganic oxide may be at least one selected from the group consisting of alumina, silica, titania, magnesia, zirconia, thoria and beryllia. Specific examples thereof may include, but are not limited to, alumina, silica, zirconia, titania, magnesia, thoria, beryllia, alumina-titania, alumina-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania or silica-alumina-magnesia. Preferably, the heat-resistant inorganic oxide is at least one of alumina, silica, titania and zirconia. More preferably, the heat-resistant inorganic oxide is alumina.
The alumina mentioned in the invention refers to available mAl2O3·nH2O represents a compound of its composition, wherein m and n are arbitrary numbers, and may be integers or fractions. The present invention also does not impose any limitation on the crystalline phase of the alumina.
The molecular sieve of the present invention refers to a material with regular crystal structure and pore channels, which is generally called molecular sieve or zeolite, and the molecular sieve or zeolite has a framework composed of silicon-aluminum elements, and may also contain other elements, such as: at least one of P, Ti, Ge and Ga. The invention is not limited in any way as to the composition of the elements that make up the molecular sieve.
The molecular sieve of the invention can be one type, or two or more types, or mixed crystal and twin crystal of two molecular sieves. The two molecular sieves described in the present invention refer to two different types of molecular sieves, and may be one molecular sieve, but the two molecular sieves have different properties (e.g., different silica-alumina ratios).
According to a preferred embodiment of the present invention, the molecular sieve is selected from at least one of a ZRP molecular sieve, a Y molecular sieve, a beta molecular sieve, a mordenite, a ZSM-5 molecular sieve, an MCM-41 molecular sieve, an omega molecular sieve, a ZSM-12 molecular sieve and an MCM-22 molecular sieve, such as at least one of a molecular sieve, beta and ZSM-5.
The molecular sieve of the invention can be obtained commercially or prepared by any conventional method.
In the invention, the active component comprises Co and an optional first metal promoter, namely the catalyst can contain or not contain the first metal promoter, and preferably the catalyst comprises a carrier and a metal active component and the first metal promoter which are loaded on the carrier.
According to a preferred embodiment of the present invention, the first metal additive is at least one selected from the group consisting of Ni, Fe, Cu, Ru, Rh, Re, Pd, and Pt.
The content of the metal active component and the first metal promoter in the catalyst is selected from a wide range, and preferably, the content of the metal active component is 5 to 80 wt%, more preferably 20 to 40 wt%, calculated by oxide, based on the total amount of the catalyst.
According to a preferred embodiment of the present invention, the first metal promoter is present in an amount of 0 to 40 wt.%, more preferably 0.1 to 20 wt.%, calculated as oxide, based on the total amount of catalyst. According to a preferred embodiment of the present invention, the catalyst further comprises a second metal promoter selected from at least one of alkali metals and alkaline earth metals supported on the carrier. The alkali metals include but are not limited to Li, Na, K. The alkaline earth metals include, but are not limited to, Mg, Ca. Preferably, the second metal promoter is at least one of Na, K, Mg and Ca, for example K and/or Mg.
The content of the second metal promoter is selected from a wide range, and preferably, the content of the second metal promoter is 1 to 20 wt%, more preferably 2 to 10 wt%, calculated by oxide, based on the total amount of the catalyst.
According to a preferred embodiment of the present invention, the catalyst comprises a carrier and Co, a first metal promoter and a second metal promoter supported on the carrier, the first metal promoter being selected from at least one of Ni, Fe, Cu, Ru, Rh, Re, Pd and Pt; the second metal additive is K and/or Mg; based on the total amount of the catalyst, the content of the carrier is 30-75 wt%, and the content of the metal active component (Co) is 20-40 wt% calculated by oxide; the content of the first metal additive is 0.1-20 wt%; the content of the second metal additive is 2-10 wt%. The catalyst with the optimized composition is matched with a carrier with an ultra-macroporous structure, so that the catalytic performance of the catalyst in the Fischer-Tropsch synthesis reaction is further improved.
In the present invention, when the heat-resistant inorganic oxide and the auxiliary contain the same metal element, the same metal element is counted as the auxiliary.
In a second aspect, the present invention provides a process for the preparation of a fischer-tropsch synthesis catalyst as described above, the process comprising:
(1) mixing a carrier precursor, water, an optional extrusion aid and an optional peptizing agent to obtain a mixture, and molding and first roasting the mixture to obtain a carrier, wherein the molding enables the interior of the carrier to have a through pore channel;
(2) and (2) impregnating the carrier obtained in the step (1) with a solution containing a metal active component precursor and an optional first metal auxiliary precursor, drying and carrying out second roasting.
In the present invention, the term "optional" means that it may or may not be added. In the mixing process of the step (1), the extrusion aid can be added or not added, and the peptizing agent can be added or not added.
The production method provided in the present invention, wherein the support precursor is any substance that can be converted into a support by the first firing in step (1). Specifically, the support precursor may be selected from at least one of refractory inorganic oxide, refractory inorganic oxide precursor, and molecular sieve. The heat-resistant inorganic oxide precursor is any substance that can be converted into a heat-resistant inorganic oxide by the first firing in step (1). The refractory inorganic oxide is selected as described above, and the present invention is not described herein again.
The selection of the molecular sieve is as described above and the present invention is not described herein in detail.
In the preparation method provided by the invention, the dosage of the refractory inorganic oxide and/or the refractory inorganic oxide precursor and the molecular sieve is selected in a wide range, and a person skilled in the art can select an appropriate type according to specific conditions. Preferably, the support precursor is a refractory inorganic oxide and/or a refractory inorganic oxide precursor.
In the present invention, specific examples of the precursor of the alumina may include, but are not limited to: hydrated alumina (e.g., aluminum hydroxide, pseudoboehmite), gels containing hydrated alumina, and sols containing hydrated alumina. For example, the precursor of the alumina may be a dry glue powder. The dry rubber powder may be obtained commercially (for example, from catalyst Changjingtie), or may be prepared by any conventional method, and the present invention is not particularly limited thereto.
In the present invention, the extrusion aid may be an extrusion aid conventionally used in the art, and preferably, the extrusion aid is selected from at least one of sesbania powder, cellulose and derivatives thereof, starch and derivatives thereof, ethylene glycol and diethylene glycol. The extrusion aid in the embodiment of the invention is exemplified by sesbania powder, and the invention is not limited thereto.
Wherein, the cellulose and the derivatives thereof can be one or more of cellulose ether, cellulose ester and cellulose ether ester.
Wherein, the starch and the derivatives thereof can be one or more of oxidized starch, esterified starch, carboxymethyl starch, cationic starch, hydroxyalkyl starch and multi-component starch.
According to the method provided by the invention, the selection range of the type of the peptizing agent is wide, and the peptizing agent can be at least one of inorganic acids, preferably nitric acid. The nitric acid may be introduced as dilute nitric acid.
In the present invention, it is preferable that the extrusion aid is used in an amount of 0.1 to 6 parts by weight, preferably 2 to 4 parts by weight, relative to 100 parts by weight of the carrier precursor on a dry basis.
In the present invention, the amount of the peptizing agent can be selected from a wide range and can be selected according to the means conventionally used in the art, for example, the amount of the peptizing agent can be 0.1 to 10 parts by weight, preferably 0.5 to 6 parts by weight, relative to 100 parts by weight of the carrier precursor on a dry basis.
In the present invention, the water in the mixture is used as a dispersion medium, and the amount of the water is based on the amount of the water capable of uniformly mixing the other components in the mixture.
According to the method provided by the invention, the specific manner of mixing the carrier precursor, water, the optional extrusion assistant and the optional peptizing agent is not particularly limited, and preferably, the mixing in the step (1) comprises the following steps: mixing the carrier precursor and the extrusion aid, and then adding a peptizing agent and water to obtain the mixture. In the preferred embodiment, the carrier precursor and the extrusion aid are mixed to obtain mixed powder, and then the peptizing agent and the water are added, so that the catalytic performance of the catalyst prepared from the obtained carrier can be improved.
According to the preparation method provided by the invention, the method comprises the following steps: kneading the mixture, and then performing the molding. Specifically, the mixture may be fed into a bar extruder, kneaded in the bar extruder, and extruded to obtain a molded article.
According to the preparation method provided by the invention, the molded object with the through pore channel inside is obtained through the molding. The method may be selected from a wide range of methods as long as a molded product having a through-hole in the interior can be obtained. Preferably, the forming is performed using a bar extruder comprising a perforated plate; the orifice plate includes: a base 1 (shown in figure 1) provided with a forming hole 2, a bracket 3 (shown in figure 2) provided with at least one material through hole 6 and at least one forming rod 4; the support 3 and the base 1 are arranged in an up-down overlapping mode, and the forming hole 2 is communicated with the material passing hole 6; the support 3 is further provided with at least one mounting hole 5 for a forming rod 4 to pass through, and the forming rod 4 is arranged to penetrate through the forming hole 2. In this preferred embodiment, the shaping bore 2 of the perforated plate and the shaping rod 4 extending through the shaping bore 2 together form a shaping cavity, through which the material is shaped accordingly. The preferred embodiment realizes that the carrier with the internal pore channel structure is processed and prepared by a one-step method, the operation is simple and convenient, and the Fischer-Tropsch synthesis catalyst prepared by the carrier has high strength and high Fischer-Tropsch synthesis activity and selectivity.
In the present invention, it can be understood by those skilled in the art that the molding holes 2 penetrate through the base 1, thereby obtaining a carrier having through-holes.
In the present invention, the forming rod 4 is disposed to penetrate the forming hole 2, and it is understood that the forming rod 4 has a length such that one end of the forming rod 4 is located at the end of the base 1 away from the bracket or such that one end of the forming rod 4 is located at the end of the base 1 away from the bracket.
In a preferred embodiment of the invention, the ratio of the cross-sectional area of the shaped rod 4 to the cross-sectional area of the through-shaped hole 2 corresponds to the ratio of the cross-sectional area of the duct to the cross-sectional area of the support. For example, 0.05 to 25: 100, preferably 0.1 to 20: 100, more preferably 0.2 to 9: 100. the preferred embodiment is more beneficial to the Fischer-Tropsch synthesis catalyst prepared by the method to have high strength and high Fischer-Tropsch synthesis activity.
In the present invention, it is understood that the shape of the molding holes 2 is actually the shape of the catalyst carrier to be produced. The shape of the shaping opening 2 can be selected according to the above description regarding the shape of the carrier.
In a preferred embodiment of the present invention, the cross-section of the forming hole 2 is circular or multi-lobed. The circle and the multi-lobed shape are not particularly limited and may be selected from those described above with respect to the shape of the support.
The size of the forming hole 2 is selected in a wide range, and a person skilled in the art can select the size appropriately according to the size requirement of the carrier, and the orifice plate provided by the invention is particularly suitable for preparing a small-size carrier, and preferably, the equivalent diameter of the forming hole 2 is not more than 5mm, preferably 0.05mm-5mm, further preferably 0.1mm-3mm, and more preferably 0.5mm-2 mm.
The number of the molding rods 4 is selected from a wide range, and may be 1, or two or more, and is appropriately selected according to the requirement of the number of the pore channels in the carrier, and preferably, the number of the molding rods 4 is 1 to 9, and more preferably 1 to 5. It will be appreciated that the number of shaped rods 4 matches the number of channels of the catalyst support described above.
In the present invention, the position of the molding rod corresponds to the position of the channel in the catalyst carrier, and in the above description of the position of the channel in the catalyst carrier, the skilled person knows how to arrange the molding rod. Preferably, the cross section of the molding hole 2 is circular, the molding rods 4 may extend along the central axis of the circle center of the circle, and if the number of the molding rods 4 is 2 or more, the different molding rods 4 may be disposed at equal intervals along the circumferential direction of the circle center of the circle. In a preferred embodiment of the present invention, the cross section of the shaping hole 2 is a multi-lobed shape, and the shaping rod 4 extends along a central axis of a circumscribed circle of the multi-lobed shape and/or along a central axis of a vane of the multi-lobed shape. By adopting the preferred embodiment, the opening positions of the pore structure in the catalyst carrier are designed more reasonably, so that the pore distribution is balanced, the sudden local strength drop of the catalyst carrier caused by the opening of the middle pore structure is effectively avoided, and the mechanical strength is improved.
According to an embodiment of the present invention, the forming rod 4 is detachably connected to the bracket 3 through the mounting hole 5. In the invention, the detachable connection enables the two connected parts not to move mutually during work; and when the device is stopped, the requirements of disassembly and replacement can be met.
The forming rod 4 can be arranged in various reasonable forms, for example, as shown in fig. 3, the head 13 of the forming rod 4 is installed in the installation hole 5, and the rod 14 of the forming rod extends towards the discharge hole of the forming hole to be sleeved (penetrated) in the installation hole 5 and the forming hole 2, so that the forming rod is easy to install and low in cost.
In the present invention, the number of the through holes 6 is selected from a wide range, and for example, the number may be 1 to 20, and preferably 2 to 20. Preferably, as shown in fig. 2, the plurality of through holes 6 are arranged at equal intervals in the circumferential direction of the forming rod 4. By adopting the preferred embodiment, the feeding uniformity of the periphery of the forming rod 4 is more facilitated, the periphery of the forming rod 4 is uniformly stressed, and the service life of the forming rod 4 can be prolonged. On the basis of the above, the number of the material passing holes 6 arranged in the circumferential direction of each forming rod 4 can be selected by those skilled in the art according to actual conditions. It will be appreciated that the through-flow openings 6 may be provided in any suitable manner, for example, as shown in figure 2, a plurality of through-flow openings 6 may be in communication with the mounting openings 5 or may be isolated from the mounting openings 5.
Considering that the forming rods 4 are installed on the installation holes 5 formed by the supporting structure of the bracket 3, and the supporting structure covers the distribution area of the forming holes 2, in order to ensure uniform material distribution of the raw material, and in order to simplify the processing technology of the bracket 3, the bracket 3 is preferably set to be of a uniform cross-section structure, so that the thickness of the supporting structure (referred to as the discharging direction of the forming holes) can be maximized, the extrusion effect applied when the supporting structure bears the forming holes to convey the material is enhanced, and the fixing firmness of the forming rods is improved. Preferably, the distribution area of the through holes 6 at least covers the distribution area of the forming holes 2, so that the support 3 can directly and uniformly distribute materials to the forming holes 2 of the base 1 through the through holes 6, and raw materials can enter all areas at the feeding port of the forming holes 2 at the same time. In addition, the overall outer contour of the through hole may be a multi-lobe structure having the same shape as the molding hole.
Preferably, as shown in fig. 3, the portion of the forming rod 4 extending into the forming hole 2 is provided in a uniform cross-sectional structure. The optimized implementation mode effectively ensures the stability of the processing shape of the prepared Fischer-Tropsch synthesis catalyst and is beneficial to obtaining the dense Fischer-Tropsch synthesis catalyst with high compactness and high strength.
The molding rod 4 can be formed into various reasonable shapes so as to be convenient for processing and manufacturing the Fischer-Tropsch synthesis catalyst with pore channel structures in corresponding shapes. It will be appreciated that the portions of the shaped rods 4 that extend into the shaped holes 2 correspond to the configuration of the channels in the catalyst support. Preferably, the part of the forming rod 4 extending into the forming hole 2 is provided as a cylinder. Under the condition, the prepared Fischer-Tropsch synthesis catalyst can correspondingly form a pore structure with a cylindrical structure, so that the inner surface of the Fischer-Tropsch synthesis catalyst is smoother and more regular, the phenomenon of stress concentration caused by sharp pore walls of the pore structure of the catalyst is avoided, and the probability of collapse of the Fischer-Tropsch synthesis catalyst is reduced.
Further preferably, the diameter of the cylinder is set to not less than 6 μm, preferably 0.01 to 0.5mm, further preferably 0.05 to 0.3 mm.
In another preferred case, a portion of the forming rod 4 extending into the forming hole 2 is a regular polygon. Under the condition, the prepared catalyst carrier can correspondingly form a pore channel structure with a regular polyhedral prism structure, so that the inner surface of the catalyst carrier is more regular, the stress distribution of the catalyst carrier is more balanced, and the overall strength of the catalyst carrier is further optimized.
Further preferably, the diameter of the circumscribed cylinder of the regular polygonal prism is set to be not less than 6 μm, preferably 0.01 to 0.5mm, and further preferably 0.05 to 0.3 mm.
In the invention, the regular polygonal prisms can be regular polygonal prisms such as triangular prism, quadrangular prism, pentagonal prism and the like, and the cross sections of the pore channels of the catalyst carrier correspondingly obtained are correspondingly formed into regular polygonal structures such as equilateral triangle, square, regular pentagon and the like.
In a preferred embodiment of the invention, the base 1 and the support 3 are arranged to be detachably connected. The detachable connection is such that the base 1 and the bracket 3 do not move relative to each other during operation; and when the device is stopped, the requirements of disassembly and replacement can be met. Preferably, the base 1 and the support 3 are attached to each other to avoid material leakage, for example, a first mounting structure 7 is disposed on an attaching surface of the base 1 and the support 3, and a second mounting structure 8 adapted to the first mounting structure 7 is disposed on an attaching surface of the support 3 and the base 1. For example, one of the first mounting structure 7 and the second mounting structure 8 is provided as a mounting groove, and the other is provided as a mounting protrusion adapted to the mounting groove.
In one embodiment of the present invention, the base 1 and the support 3 have the same overall outer contour. This embodiment facilitates the mounting operation.
In the present invention, the heights of the base 1 and the holder 3 are not particularly limited, and it is preferable that the ratio of the height of the base 1 to the height of the holder 3 is set to 1 (0.2 to 5).
For ease of understanding, a specific molding method is now provided, comprising: and (2) feeding the mixture obtained in the step (1) into a strip extruding machine, wherein the strip extruding machine comprises a main body and a pore plate, the main body is arranged to be capable of forming the mixture through the pore plate, the mixture enters a forming cavity formed by a forming hole 2 and a forming rod 4 through a material through hole 6 arranged on a support 3 so as to obtain a formed object with through pore channels inside, the number and the shape of the forming rods 4 correspond to the number and the shape of the pore channels, and the shape and the size of the forming hole 2 correspond to the shape and the size of the formed object.
The main body of the plodder can be a component conventionally used in the field, and the invention is not described in detail herein.
The preparation method in the present invention specifically and preferably further comprises subjecting the shaped product to first drying and then to the first firing. In the present invention, the drying conditions are not particularly limited, and examples thereof include: the temperature of the first drying can be 100-200 ℃, and the time of the first drying can be 2-12 h. The drying may be performed under normal pressure or reduced pressure, and is not particularly limited. The drying may be performed in an oxygen-containing atmosphere or in an inert atmosphere.
In the present invention, the conditions for the first firing of the shaped article are not particularly limited, and may be conventional conditions in the art. Generally, the temperature of the first roasting may be 350-; the time for the first calcination may be 1 to 10 hours, preferably 2 to 6 hours. The calcination may be carried out in an oxygen-containing atmosphere (e.g., air) or in an inert atmosphere. The inert atmosphere refers to a gas that is inactive under the drying or firing conditions, for example: nitrogen and group zero element gases (e.g., argon).
In the invention, in the step (2), the metal active component Co and the optional first metal auxiliary agent are introduced to the carrier by adopting an impregnation method. When the catalyst contains both Co and the first metal promoter, the introduction manner of both is not particularly limited, and both may be introduced together by Co-impregnation or separately by stepwise impregnation. Specifically, after the metal active component or the metal assistant is introduced, the remaining components are introduced after drying and firing. The specific operation is well known to those skilled in the art and will not be described herein.
According to a preferable mode of the present invention, the solution in the step (2) further contains a second metal promoter precursor. As mentioned above, the second metal promoter may also be co-introduced by co-impregnation with the other components, or may be introduced separately by stepwise impregnation.
The metal active component is Co, and the metal active component precursor may be a substance that can be converted into cobalt oxide by the second firing, and may be, for example, one or more of cobalt hydroxide, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, basic cobalt carbonate, cobalt formate, cobalt acetate, cobalt oxalate, and cobalt naphthenate. The cobalt nitrate is taken as an example to illustrate the embodiment of the invention, and the invention is not limited to the cobalt nitrate.
The first metal additive precursor and the second metal additive precursor may be substances that can be converted into corresponding first metal additive oxides and second metal additive oxides by second firing, respectively. The selection of the first metal promoter precursor and the second metal promoter precursor can be a precursor conventionally used in the art, such as soluble salts thereof.
The concentrations of the metal active component precursor, the first metal promoter precursor, and the second metal promoter precursor in the solution are selected based on the water absorption of the support and the target content of each component in the catalyst, and are well known to those skilled in the art.
The solvent in the solution is preferably water, more preferably deionized water.
In step (2) of the present invention, preferably, the drying temperature is 80-140 ℃ and the drying time is 1-10 hours. Preferably, the temperature of the second roasting is 350-750 ℃ and the time is 1-10 h. In the present invention, the number of times of the drying and the second firing in the step (2) may not be particularly limited, and is preferably the same as the number of times of introducing the active component by the impregnation method. The selection can be made by those skilled in the art as required, and will not be described in detail herein.
In a third aspect, the invention provides a Fischer-Tropsch synthesis catalyst prepared by the preparation method.
The structure and composition of the fischer-tropsch synthesis catalyst are identical to those of the fischer-tropsch synthesis catalyst of the first aspect and will not be described in detail herein.
In a fourth aspect, the invention provides the use of a fischer-tropsch synthesis catalyst as described above in a fischer-tropsch synthesis reaction.
In a fifth aspect, the invention provides a fischer-tropsch synthesis process, comprising: reacting CO and H under the condition of Fischer-Tropsch synthesis reaction2Is contacted with a catalyst which is a fischer-tropsch synthesis catalyst as described above.
In the present invention, the fischer-tropsch synthesis catalyst may be subjected to an activation treatment prior to use. The conditions and specific operations of the activation treatment are not particularly limited and may be carried out according to the means conventional in the art, and preferably, the activation treatment comprises: the reduction activation is carried out in the presence of hydrogen at a temperature of 120-500 ℃. The reduction activation can be carried out outside the reactor or in situ inside the reactor, and the reduction activation is converted into active substances in a metal state. The time of the activation treatment can be 1-10 h.
In the present invention, preferably, the fischer-tropsch synthesis conditions comprise: the reaction temperature is 150-300 ℃, preferably 170-250 ℃, and more preferably 190-230 ℃; the reaction pressure is 0.2-16MPa, preferably 1.0-10 MPa; the gas space velocity is 200-400000h-1Preferably 500-100000h-1More preferably 1000-50000h-1；H2The volume ratio to CO is 0.8 to 3.6, preferably 1.5 to 2.5, and more preferably 1.8 to 2.2. An inert gas, such as nitrogen, may optionally be introduced as a diluent gas during the contacting, and the volume content of nitrogen in the mixed gas may be 0 to 50 volume%.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the radial crushing strength of the carrier was measured on a crushing strength tester of model QCY-602 (manufactured by soda research, chemical engineering) according to the method specified in GB 3635-1983;
in the following examples and comparative examples, the pressure is in gauge pressure and the dry content is determined by baking the sample at 600 ℃ for 4 hours.
Example 1
This example illustrates the preparation of a support and Fischer-Tropsch catalyst according to the invention
(1) Process for producing carrier
S1, uniformly mixing 200.0g of dry rubber powder (taken from catalyst Chang Ling division, dry basis 68 wt%) and 6g of sesbania powder to obtain mixed powder, adding 2.5mL of nitric acid into 155mL of water, uniformly mixing, and adding into the mixed powder to obtain a mixture;
s2 kneading the mixture on a bar extruder for 3 times
Extruding the strip with the core trilobal pore plate, drying the extruded strip at 120 ℃ for 3 hours, and roasting the dried strip at 600 ℃ for 3 hours under the condition of introducing air to obtain the catalyst carrier ZA. The carrier is in a three-leaf strip shape, the diameter of an external circle of the cross section is 1.6mm, a through pore channel (a cylinder with the diameter of 0.1 mm) is arranged in the carrier, and the pore channel extends along the central axis of the external circle. The cross-sectional view of the catalyst support ZA is shown in fig. 4, and its radial crushing strength is shown in table 1.
The specific process of forming comprises: the molding is performed using a hole plate, the hole plate including: the device comprises a base 1 provided with forming holes 2 (as shown in figure 1, the forming holes 2 are trilobal, the diameter of an outer circle is 1.6mm), a bracket 3 provided with three material through holes 6 and a forming rod 4, wherein as shown in figure 2, 3 material through holes 6 are arranged at equal intervals along the circumferential direction of the forming rod 4; as shown in fig. 1 and 2, the bracket 3 and the base 1 are attached and stacked up and down, a first mounting structure 7 is arranged on the attaching surface of the base 1 and the bracket 3, and a second mounting structure 8 adapted to the first mounting structure 7 is arranged on the attaching surface of the bracket 3 and the base 1, so that the bracket 3 and the base 1 are detachably connected.
The bracket 3 is further provided with a mounting hole 5 for a forming rod 4 (shaped as shown in fig. 3) to pass through, and the forming rod 4 is arranged to penetrate through the forming hole 2. The profiled rod 4 extends along the central axis of the circumscribed circle on which the trilobal shape lies. The head 13 of the forming rod 4 is mounted in the mounting hole 5, and the rod 14 of the forming rod extends toward the discharge port of the forming hole to be sleeved (penetrated) in the mounting hole 5 and the forming hole 2. The portion of the molding rod 4 inserted into the molding hole is provided as a cylinder, and the diameter of the cylinder is 0.1 mm.
(2) Preparation method of Fischer-Tropsch synthesis catalyst
Cobalt nitrate (analytically pure, Beijing Yili chemical reagent factory) solution was prepared according to the cobalt oxide content of 30 wt% in the catalyst. Impregnating the carrier ZA twice by using a cobalt nitrate solution by adopting a pore saturation method, drying the carrier ZA for 3 hours at 120 ℃ after each impregnation, and roasting the carrier ZA for 3 hours at 400 ℃; obtaining the Fischer-Tropsch synthesis catalyst ZAC.
Example 2
This example illustrates the preparation of a support and Fischer-Tropsch catalyst according to the invention
(1) Process for producing carrier
According to the method of example 1, except that
The cored trilobal orifice plate is extruded, and the orifice plate is provided with 3 molding rods. The catalyst support ZB was obtained. The carrier is in a three-leaf strip shape, the diameter of an external circle of the cross section is 1.6mm, 3 through pore channels (cylindrical with the diameter of 0.1 mm) are arranged in the carrier, and the 3 pore channels respectively extend along the central axis of the external circle where the three blades are located. The schematic cross-sectional view of the catalyst carrier ZB is shown in FIG. 5, and the radial crushing strength of the catalyst carrier ZB is shown in Table 1.
The specific process of the molding is performed according to embodiment 1, except that 12 material through holes 6 are formed in the support 3, and the hole plate is provided with 3 molding rods 4, as shown in fig. 6, every 4 material through holes 6 are arranged at equal intervals along the circumferential direction of one molding rod 4; the support 3 is also provided with 3 mounting holes 5 for the molding rods 4 to pass through. The 3 forming rods 4 respectively extend along the central axis of the circumscribed circle where the three blades are located.
(2) Preparation method of Fischer-Tropsch synthesis catalyst
The Fischer-Tropsch catalyst was prepared as described in example 1, except that the support was replaced with the catalyst support ZB. Obtaining the Fischer-Tropsch synthesis catalyst ZBC.
Example 3
This example illustrates the preparation of a support and Fischer-Tropsch catalyst according to the invention
(1) Process for producing carrier
According to the method of example 2, except that
The cored trilobal orifice plate is extruded, and the orifice plate is provided with 3 molding rods. Obtaining a catalyst carrier ZC. The carrier is in a three-leaf strip shape, the diameter of an external circle of the cross section is 1.6mm, 3 through holes (a regular hexahedral prism body with the diameter of the external circle of 0.1 mm) are formed in the carrier, and the 3 holes respectively extend along the central axis of the external circle where the three blades are located. A schematic cross-sectional view of the catalyst carrier ZC is shown in FIG. 7, the radial crushing strength of the catalyst carrier ZC is shown in Table 1.
The specific process of molding was performed as in example 2, except that the 3 molding rods 4 were each in the shape of a regular hexagonal prism having a circumscribed circle diameter of 0.1 mm.
(2) Preparation method of Fischer-Tropsch synthesis catalyst
The fischer-tropsch synthesis catalyst was prepared as described in example 1, except that the support was replaced by catalyst support ZC. Obtaining the Fischer-Tropsch synthesis catalyst ZCC.
Example 4
This example illustrates the preparation of a support and Fischer-Tropsch catalyst according to the invention
(1) Process for producing carrier
According to the method of example 2, except that
The extruded strip of cored trefoil orifice plate, orifice plate are provided with 4 shaping poles (1 is the positive trilateral arris body that circumscribed circle diameter is 0.1mm, 3 is the cylinder that the diameter is 0.1 mm). Obtaining the catalyst carrier ZD. This carrier is three leaf bar-types, and the circumscribed circle diameter of cross section is 1.6mm, and the carrier is inside to have 4 pore (1 circumscribed circle diameter is the positive trilateral arris body of 0.1mm, 3 cylinders that the diameter is 0.1 mm), the central axis of the circumscribed circle of 1 positive trilateral prism pore along the trilobal extends, 3 cylinder pore extend along the central axis of the circumscribed circle at three blade place respectively. The cross-sectional view of the catalyst support ZD is shown in fig. 8, and the radial crush strength of the catalyst support ZD is shown in table 1.
(2) Preparation method of Fischer-Tropsch synthesis catalyst
The Fischer-Tropsch catalyst ZDC was prepared according to the Fischer-Tropsch catalyst preparation method described in example 1.
Example 5
This example illustrates the preparation of a support and Fischer-Tropsch catalyst according to the invention
(1) Process for producing carrier
According to the method of example 2, except that
The cored four-leaf orifice plate is extruded, and the orifice plate is provided with 4 molding rods (4 cylinders with the diameter of 0.1 mm). Obtaining the catalyst carrier ZE. The carrier is in a four-blade strip shape, the diameter of an external circle of the cross section is 1.6mm, 4 through channels (4 cylinders with the diameter of 0.1 mm) are arranged inside the carrier, and the 4 cylindrical channels respectively extend along the central axis of the external circle where the four blades are located. Catalyst carrier ZE a schematic cross-sectional view of the catalyst carrier is shown in fig. 9, and the radial crushing strength of the catalyst carrier ZE is shown in table 1.
(2) Preparation method of Fischer-Tropsch synthesis catalyst
A Fischer-Tropsch synthesis catalyst ZEC was prepared according to the Fischer-Tropsch synthesis catalyst preparation method described in example 1.
Example 6
This example illustrates the preparation of a support and Fischer-Tropsch catalyst according to the invention
(1) Process for producing carrier
According to the method of example 2, except that
The cored four-leaf-shaped orifice plate is extruded, and the orifice plate is provided with 5 forming rods (5 cylinders with the diameter of 0.1 mm). To obtain the catalyst carrier ZF. The carrier is in a four-blade strip shape, the diameter of an external circle of the cross section is 1.6mm, 5 through holes (5 cylindrical holes with the diameter of 0.1 mm) are formed in the carrier, 1 cylindrical hole extends along the central shaft of the external circle of the four-blade strip shape, and 4 cylindrical holes extend along the central shaft of the external circle where the four blades are located respectively. Catalyst carrier ZF a schematic cross-sectional view of the catalyst carrier is shown in fig. 10, and the radial crush strength of the catalyst carrier ZF is listed in table 1.
(2) Preparation method of Fischer-Tropsch synthesis catalyst
The fischer-tropsch catalyst ZFC was prepared according to the preparation method of the fischer-tropsch catalyst described in example 1.
Example 7
According to the method of example 1, except that
The cored trilobal orifice plate is extruded, and the orifice plate is provided with 1 molding rod (1 is a cylinder with the diameter of 0.2 mm). The catalyst carrier ZG is obtained. The carrier is in a trefoil strip shape, the diameter of an external circle of the cross section is 1.6mm, 1 through hole (1 cylindrical hole with the diameter of 0.2 mm) is formed in the carrier, and the cylindrical hole extends along the central axis of the external circle of the trefoil shape. The radial crushing strength of the catalyst support ZG is shown in table 1.
(2) Preparation method of Fischer-Tropsch synthesis catalyst
The Fischer-Tropsch catalyst ZGC was prepared according to the Fischer-Tropsch catalyst preparation method described in example 1.
Example 8
(1) The support was prepared according to example 1, step (1).
(2) Preparation of Fischer-Tropsch synthesis catalyst
A mixed solution of ruthenium chloride and cobalt nitrate was prepared so that the catalyst contained 0.3% by weight of Ru and 35% by weight of cobalt oxide. The carrier ZA is impregnated twice by using a mixed solution of ruthenium chloride and cobalt nitrate by adopting a pore saturation method, and after each impregnation, the carrier ZA is dried for 3 hours at 120 ℃, and then is roasted for 3 hours at 400 ℃ to obtain the Fischer-Tropsch synthesis catalyst ZHC.
Example 9
(1) The support was prepared according to example 1, step (1).
(2) Preparation of Fischer-Tropsch synthesis catalyst
A mixed solution of ruthenium chloride, cobalt nitrate and magnesium chloride was prepared with a Ru content of 0.2 wt%, a cobalt oxide content of 25 wt% and a magnesium oxide content of 5 wt% in the catalyst. And (2) impregnating the carrier ZA twice by using a mixed solution of ruthenium chloride, cobalt nitrate and magnesium chloride by adopting a pore saturation method, drying for 3 hours at 120 ℃ after each impregnation, and roasting for 3 hours at 400 ℃ to obtain the Fischer-Tropsch synthesis catalyst ZIC.
Comparative example 1
Comparative example to illustrate the preparation of a reference support and Fischer-Tropsch catalyst
(1) Process for producing carrier
A solid (without channels) catalyst support DA was obtained following the procedure of example 1, except that a conventional orifice plate was used in the molding process. The catalyst support DA had a trilobe shape, the diameter of the circumscribed circle of the cross section was 1.6mm, the schematic cross section of the catalyst support DA is shown in fig. 11, and the radial crushing strength of the catalyst support DA is shown in table 1.
(2) Preparation method of Fischer-Tropsch synthesis catalyst
The Fischer-Tropsch synthesis catalyst DAC was prepared according to the Fischer-Tropsch synthesis catalyst preparation method described in example 1.
Test example
This test example is intended to illustrate the performance of a Fischer-Tropsch synthesis catalyst
(1) Activation of Fischer-Tropsch synthesis catalyst
5ml of the Fischer-Tropsch synthesis catalysts prepared in the examples and the comparative examples were charged into a micro-reactor fixed bed reactor, and the rest was packed with silica sand. The catalyst is firstly reduced and activated by hydrogen under the pressure of 0.1MPa and the airspeed of 1000h-1And the temperature is 400 ℃ for 5 hours.
(2) Fischer-Tropsch synthesis activity evaluation of Fischer-Tropsch synthesis catalyst
The Fischer-Tropsch synthesis reaction adopts a one-pass process, the reaction temperature is 210 ℃, the reaction pressure is 2.5MPa, and the gas space velocity of the synthesis gas is 2000h-1Composition by volume of synthesis gas H2/CO/N2After 8 hours of reaction, an on-line gas sample was taken and calculated as 60/30/10.
The activity of the catalyst is expressed in terms of CO conversion and the selectivity of the fischer-tropsch catalyst is expressed in terms of methane selectivity and C5+ hydrocarbons selectivity, the results being listed in table 2.
TABLE 1
| Examples | Carrier | Radial crushing strength/(N/mm) |
| Example 1 | ZA | 25.9 |
| Example 2 | ZB | 23.8 |
| Example 3 | ZC | 24.2 |
| Example 4 | ZD | 22.9 |
| Example 5 | ZE | 23.2 |
| Example 6 | ZF | 23.7 |
| Example 7 | ZG | 24.5 |
| Comparative example 1 | DA | 26.7 |
TABLE 2
As can be seen from the results in Table 2, compared with the comparative example 1, the Fischer-Tropsch synthesis catalyst provided by the invention has obviously higher Fischer-Tropsch synthesis activity and C5+ hydrocarbon selectivity, and has lower methane selectivity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (45)
1. A Fischer-Tropsch synthesis catalyst, which is characterized by comprising a carrier, a metal active component loaded on the carrier and an optional first metal auxiliary agent, wherein the first metal auxiliary agent is at least one selected from transition metals;
the carrier is internally provided with a through hole channel, and the ratio of the cross sectional area of the hole channel to the cross sectional area of the carrier is 0.05-25: 100, respectively; the pore canal is cylindrical and/or regular polygonal prism-shaped; the diameter of the cylindrical shape and the diameter of the circumscribed circle of the regular polygonal prism shape are each independently not less than 6 μm; the cross section of the carrier is multi-leaf-shaped, and the pore canal extends along the central axis of a circumscribed circle where the multi-leaf-shaped blades are located and/or along the central axis of a circumscribed circle where the multi-leaf-shaped blades are located;
wherein the carrier contains at least one of a refractory inorganic oxide and a molecular sieve;
the metal active component is Co.
2. The fischer-tropsch synthesis catalyst of claim 1, wherein the ratio of the cross-sectional area of the channels to the cross-sectional area of the support is from 0.1 to 20: 100, respectively; and/or the diameter of the cylinder and the diameter of the circumcircle of the regular polygon prism are respectively and independently 0.01-0.5 mm.
3. The fischer-tropsch synthesis catalyst of claim 2, wherein the ratio of the cross-sectional area of the channels to the cross-sectional area of the support is from 0.2 to 9: 100, respectively;
and/or the diameter of the cylinder and the diameter of the circumcircle of the regular polygon prism are respectively and independently 0.05-0.3 mm.
4. A fischer-tropsch synthesis catalyst according to any one of claims 1 to 3, wherein the support is in the form of a multi-lobal strip;
and/or the equivalent diameter of the support is not more than 5 mm.
5. The Fischer-Tropsch synthesis catalyst of claim 4, wherein the support is in the form of a trilobe bar, a quadralobe bar or a pentalobal bar;
and/or the equivalent diameter of the carrier is 0.05mm-5 mm.
6. The Fischer-Tropsch synthesis catalyst of claim 5, wherein the equivalent diameter of the support is from 0.1mm to 3 mm.
7. The Fischer-Tropsch synthesis catalyst of claim 6, wherein the equivalent diameter of the support is from 0.5mm to 2 mm.
8. A Fischer-Tropsch synthesis catalyst according to any one of claims 1 to 3, 5 to 7, wherein the number of the channels is from 1 to 9.
9. The fischer-tropsch synthesis catalyst of claim 8, wherein the number of channels is from 1 to 5.
10. The Fischer-Tropsch synthesis catalyst of claim 4, wherein the number of channels is from 1 to 9.
11. The fischer-tropsch synthesis catalyst of claim 10, wherein the number of channels is from 1 to 5.
12. A fischer-tropsch synthesis catalyst according to any one of claims 1 to 3, 5 to 7, 9 to 11, wherein the heat-resistant inorganic oxide comprises at least one of alumina, silica, titania, magnesia, zirconia, thoria and beryllia;
and/or the molecular sieve comprises at least one of a ten-membered ring silicoaluminophosphate molecular sieve, a twelve-membered ring silicoaluminophosphate molecular sieve, a fourteen-membered ring silicoaluminophosphate molecular sieve and an eighteen-membered ring silicoaluminophosphate molecular sieve.
13. The fischer-tropsch synthesis catalyst of claim 12, wherein the refractory inorganic oxide is at least one of alumina, silica, titania and zirconia;
and/or the molecular sieve is selected from at least one of a ZRP molecular sieve, a Y molecular sieve, a beta molecular sieve, mordenite, a ZSM-5 molecular sieve, an MCM-41 molecular sieve, an omega molecular sieve, a ZSM-12 molecular sieve and an MCM-22 molecular sieve.
14. The fischer-tropsch synthesis catalyst of claim 13, wherein the molecular sieve is at least one of a Y molecular sieve, a beta molecular sieve, ZSM-5 and mordenite.
15. The Fischer-Tropsch synthesis catalyst of claim 4, wherein the refractory inorganic oxide comprises at least one of alumina, silica, titania, magnesia, zirconia, thoria, and beryllia;
and/or the molecular sieve comprises at least one of a ten-membered ring silicoaluminophosphate molecular sieve, a twelve-membered ring silicoaluminophosphate molecular sieve, a fourteen-membered ring silicoaluminophosphate molecular sieve and an eighteen-membered ring silicoaluminophosphate molecular sieve.
16. The fischer-tropsch synthesis catalyst of claim 15, wherein the heat resistant inorganic oxide is at least one of alumina, silica, titania and zirconia;
and/or the molecular sieve is selected from at least one of a ZRP molecular sieve, a Y molecular sieve, a beta molecular sieve, mordenite, a ZSM-5 molecular sieve, an MCM-41 molecular sieve, an omega molecular sieve, a ZSM-12 molecular sieve and an MCM-22 molecular sieve.
17. The fischer-tropsch synthesis catalyst of claim 16, wherein the molecular sieve is at least one of a Y molecular sieve, a beta molecular sieve, ZSM-5 and mordenite.
18. The fischer-tropsch synthesis catalyst of claim 8, wherein the refractory inorganic oxide comprises at least one of alumina, silica, titania, magnesia, zirconia, thoria and beryllia;
and/or the molecular sieve comprises at least one of a ten-membered ring silicoaluminophosphate molecular sieve, a twelve-membered ring silicoaluminophosphate molecular sieve, a fourteen-membered ring silicoaluminophosphate molecular sieve and an eighteen-membered ring silicoaluminophosphate molecular sieve.
19. The fischer-tropsch synthesis catalyst of claim 18, wherein the refractory inorganic oxide is at least one of alumina, silica, titania and zirconia;
and/or the molecular sieve is selected from at least one of a ZRP molecular sieve, a Y molecular sieve, a beta molecular sieve, mordenite, a ZSM-5 molecular sieve, an MCM-41 molecular sieve, an omega molecular sieve, a ZSM-12 molecular sieve and an MCM-22 molecular sieve.
20. The fischer-tropsch synthesis catalyst of claim 19, wherein the molecular sieve is at least one of a Y molecular sieve, a beta molecular sieve, ZSM-5 and mordenite.
21. A fischer-tropsch synthesis catalyst according to any one of claims 1 to 3, 5 to 7, 9 to 11, 13 to 20, wherein the metal active component is present in an amount of from 5 to 80 wt% calculated as oxide based on the total amount of catalyst;
and/or the first metal auxiliary agent is selected from at least one of Ni, Fe, Cu, Ru, Rh, Re, Pd and Pt;
and/or, the content of the first metal auxiliary agent is 0-40 wt% in terms of oxide based on the total amount of the catalyst.
22. A fischer-tropsch synthesis catalyst according to claim 21, wherein the metal active component is present in an amount of from 20 to 40 wt% calculated as oxide based on the total amount of catalyst;
and/or, the content of the first metal auxiliary agent is 0.1-20 wt% calculated by oxide based on the total amount of the catalyst.
23. The Fischer-Tropsch synthesis catalyst of claim 4, wherein the metal active component is present in an amount of from 5 to 80 wt%, calculated as oxide, based on the total amount of catalyst;
and/or the first metal auxiliary agent is selected from at least one of Ni, Fe, Cu, Ru, Rh, Re, Pd and Pt;
and/or, the content of the first metal auxiliary agent is 0-40 wt% in terms of oxide based on the total amount of the catalyst.
24. A fischer-tropsch synthesis catalyst according to claim 23, wherein the metal active component is present in an amount of from 20 to 40 wt% calculated as oxide based on the total amount of catalyst;
and/or, the content of the first metal auxiliary agent is 0.1-20 wt% calculated by oxide based on the total amount of the catalyst.
25. The Fischer-Tropsch synthesis catalyst of claim 8, wherein the metal active component is present in an amount of from 5 to 80 wt%, calculated as oxide, based on the total amount of catalyst;
and/or the first metal auxiliary agent is selected from at least one of Ni, Fe, Cu, Ru, Rh, Re, Pd and Pt;
and/or, the content of the first metal auxiliary agent is 0-40 wt% in terms of oxide based on the total amount of the catalyst.
26. A fischer-tropsch synthesis catalyst according to claim 25, wherein the metal active component is present in an amount of from 20 to 40 wt% calculated as oxide based on the total amount of catalyst;
and/or, the content of the first metal auxiliary agent is 0.1-20 wt% calculated by oxide based on the total amount of the catalyst.
27. A fischer-tropsch synthesis catalyst according to claim 12, wherein the metal active component is present in an amount of from 5 to 80 wt% calculated as oxide based on the total amount of catalyst;
and/or the first metal auxiliary agent is selected from at least one of Ni, Fe, Cu, Ru, Rh, Re, Pd and Pt;
and/or, the content of the first metal auxiliary agent is 0-40 wt% in terms of oxide based on the total amount of the catalyst.
28. A fischer-tropsch synthesis catalyst according to claim 27, wherein the metal active component is present in an amount of from 20 to 40 wt% calculated as oxide based on the total amount of catalyst;
and/or, the content of the first metal auxiliary agent is 0.1-20 wt% calculated by oxide based on the total amount of the catalyst.
29. A fischer-tropsch synthesis catalyst according to any one of claims 1 to 3, 5 to 7, 9 to 11, 13 to 20, 22 to 28, wherein the catalyst further comprises a second metal promoter supported on the support;
the second metal auxiliary agent is selected from at least one of alkali metal and alkaline earth metal,
and/or the content of the second metal auxiliary agent is 1-20 wt% in terms of oxide based on the total amount of the catalyst.
30. The fischer-tropsch synthesis catalyst of claim 29, wherein the second metal promoter is at least one of Na, K, Mg and Ca;
and/or, the content of the second metal auxiliary agent is 2-10 wt% calculated by oxide based on the total amount of the catalyst.
31. The Fischer-Tropsch synthesis catalyst of claim 4, wherein the catalyst further comprises a second metal promoter supported on the support;
the second metal auxiliary agent is selected from at least one of alkali metal and alkaline earth metal,
and/or the content of the second metal auxiliary agent is 1-20 wt% in terms of oxide based on the total amount of the catalyst.
32. The fischer-tropsch synthesis catalyst of claim 31, wherein the second metal promoter is at least one of Na, K, Mg and Ca;
and/or, the content of the second metal auxiliary agent is 2-10 wt% calculated by oxide based on the total amount of the catalyst.
33. The fischer-tropsch synthesis catalyst of claim 8, wherein the catalyst further comprises a second metal promoter supported on the support;
the second metal auxiliary agent is selected from at least one of alkali metal and alkaline earth metal,
and/or the content of the second metal auxiliary agent is 1-20 wt% in terms of oxide based on the total amount of the catalyst.
34. The fischer-tropsch synthesis catalyst of claim 33, wherein the second metal promoter is at least one of Na, K, Mg and Ca;
and/or, the content of the second metal auxiliary agent is 2-10 wt% calculated by oxide based on the total amount of the catalyst.
35. The fischer-tropsch synthesis catalyst of claim 12, wherein the catalyst further comprises a second metal promoter supported on the support;
the second metal auxiliary agent is selected from at least one of alkali metal and alkaline earth metal,
and/or the content of the second metal auxiliary agent is 1-20 wt% in terms of oxide based on the total amount of the catalyst.
36. The fischer-tropsch synthesis catalyst of claim 35, wherein the second metal promoter is at least one of Na, K, Mg and Ca;
and/or, the content of the second metal auxiliary agent is 2-10 wt% calculated by oxide based on the total amount of the catalyst.
37. The fischer-tropsch synthesis catalyst of claim 21, wherein the catalyst further comprises a second metal promoter supported on the support;
the second metal auxiliary agent is selected from at least one of alkali metal and alkaline earth metal,
and/or the content of the second metal auxiliary agent is 1-20 wt% in terms of oxide based on the total amount of the catalyst.
38. The fischer-tropsch synthesis catalyst of claim 37, wherein the second metal promoter is at least one of Na, K, Mg and Ca;
and/or, the content of the second metal auxiliary agent is 2-10 wt% calculated by oxide based on the total amount of the catalyst.
39. A process for the preparation of a fischer-tropsch synthesis catalyst as claimed in any one of claims 1 to 38, which process comprises:
(1) mixing a carrier precursor, water, an optional extrusion aid and an optional peptizing agent to obtain a mixture, and molding and first roasting the mixture to obtain a carrier, wherein the molding enables the interior of the carrier to have a through pore channel;
(2) and (2) impregnating the carrier obtained in the step (1) with a solution containing a metal active component precursor and an optional first metal auxiliary precursor, drying and carrying out second roasting.
40. The preparation method according to claim 39, wherein in the step (1), the extrusion aid is at least one selected from sesbania powder, cellulose and derivatives thereof, starch and derivatives thereof, ethylene glycol and diethylene glycol;
the peptizing agent is at least one of inorganic acid;
and/or, the conditions of the first calcination include: the temperature is 350-700 ℃; the time is 1-10 h.
41. The method of claim 40, wherein the peptizing agent is nitric acid;
and/or, the conditions of the first calcination include: the temperature is 450-650 ℃; the time is 2-6 h.
42. The preparation method according to claim 39, wherein in the step (2), the drying temperature is 80-140 ℃ and the drying time is 1-10 h;
and/or the temperature of the second roasting is 350-750 ℃, and the time is 1-10 h;
and/or, the solution in the step (2) also contains a second metal auxiliary agent precursor.
43. A Fischer-Tropsch synthesis catalyst, obtainable by the process of any one of claims 39 to 42.
44. Use of a fischer-tropsch synthesis catalyst as claimed in any one of claims 1 to 38 and 43 in a fischer-tropsch synthesis reaction.
45. A fischer-tropsch synthesis process, comprising: reacting CO and H under the condition of Fischer-Tropsch synthesis reaction2Contacting with a catalyst, the catalyst being a fischer-tropsch synthesis catalyst as claimed in any one of claims 1 to 38 and 43.
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| CN201911055026.5A CN112742392B (en) | 2019-10-31 | 2019-10-31 | Fischer-Tropsch synthesis catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method |
| JP2022525358A JP2022554292A (en) | 2019-10-31 | 2020-10-29 | Supported catalyst, its preparation method and its application |
| KR1020227018597A KR20220091584A (en) | 2019-10-31 | 2020-10-29 | Supported catalyst, manufacturing method thereof, and use thereof |
| US17/755,555 US20220266224A1 (en) | 2019-10-31 | 2020-10-29 | Supported catalyst, preparation method therefor and application thereof |
| CA3159650A CA3159650A1 (en) | 2019-10-31 | 2020-10-29 | Supported catalyst, preparation method therefor and application thereof |
| PCT/CN2020/124801 WO2021083270A1 (en) | 2019-10-31 | 2020-10-29 | Supported catalyst, preparation method therefor and application thereof |
| EP20881937.5A EP4052790A4 (en) | 2019-10-31 | 2020-10-29 | Supported catalyst, preparation method therefor and application thereof |
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| US7993599B2 (en) * | 2006-03-03 | 2011-08-09 | Zeropoint Clean Tech, Inc. | Method for enhancing catalyst selectivity |
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| CN205587001U (en) * | 2016-02-29 | 2016-09-21 | 武汉凯迪工程技术研究总院有限公司 | Heart -shaped column catalyst support of diplopore |
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