CN109675593B - Iron-containing Fischer-Tropsch synthesis catalyst, preparation method thereof and Fischer-Tropsch synthesis reaction method - Google Patents
Iron-containing Fischer-Tropsch synthesis catalyst, preparation method thereof and Fischer-Tropsch synthesis reaction method Download PDFInfo
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
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- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention relates to the field of iron-containing Fischer-Tropsch synthesis catalysts, and discloses an iron-containing Fischer-Tropsch synthesis catalyst, and a preparation method and application thereof. The iron-containing Fischer-Tropsch synthesis catalyst comprises an inorganic component a and an organic component b wrapping the inorganic component a; the catalyst satisfies the following relationship: wb/(ρb×Wa×Ra)＝0.3～1；δ＝ρa/(ρab×Wa) -1, δ value not greater than 0.1; wherein the mass fraction of the inorganic component a is W based on the total amount of the catalystaThe mass fraction of the organic component is Wb(ii) a The water absorption of the inorganic component a is RaThe bulk density of the inorganic component a is ρaThe density of the organic component b is rhobThe bulk density of the catalyst is rhoab(ii) a The carrier is a porous heat-resistant material. The activity of the iron-containing Fischer-Tropsch synthesis catalyst can be effectively protected, the iron-containing Fischer-Tropsch synthesis catalyst can be stored in the air for a long time, and the iron-containing Fischer-Tropsch synthesis catalyst can be directly filled in a reactor for Fischer-Tropsch synthesis reaction without a pre-activation step.
Description
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis catalyst preservation, in particular to an iron-containing Fischer-Tropsch synthesis catalyst, a preparation method thereof and a Fischer-Tropsch synthesis reaction method.
Background
Along with the increasing scarcity of global petroleum resources, people pay more and more attention to environmental protection, and the preparation of clean fuels and chemicals by using coal, natural gas and the like as raw materials is paid more and more attention by people. The Fischer-Tropsch synthesis technology is one of the key technologies for clean utilization of the coal and the natural gas.
The main products of the fischer-tropsch synthesis reaction, in which synthesis gas is converted to hydrocarbons over a catalyst, include alkanes and alkenes, which are processed further to yield high quality liquid fuels and chemicals.
At present, Fischer-Tropsch synthesis catalysts with industrial application values mainly comprise two major types, namely cobalt-based catalysts and iron-based catalysts. The two types of catalysts have advantages, and different types of catalysts can be selected according to the type of reaction raw material gas, a process route, the type of a reactor and the like.
The iron-based catalyst is mostly carried out in a catalyst production plant far away from a catalytic reaction device, and the catalyst activation is usually carried out in situ on the catalytic reaction device or directly added into an activation reactor attached to the reaction device after being activated in the activation reactor. In-situ activation requires the extrusion of large amounts of reactor operation, affecting productivity and economic efficiency. In addition, the reduction activation temperature of the catalyst is estimated to be higher than the use temperature, and the direct use of the activated catalyst can reduce the material selection grade of the reactor and reduce the investment. If the activated catalyst can be directly filled and directly used, the overall benefit can be greatly improved.
Activated iron catalysts exist as carbides and are highly susceptible to deactivation upon exposure to air, so some companies encapsulate the activated catalysts in wax flakes of a specific size and then ship the wax flakes to a destination. However, the wax flake-encapsulated catalyst tends to have a large particle size and cannot be directly packed in a reactor such as a fixed bed or a microchannel for direct use.
CN103084219A discloses a reduction method of a slurry bed Fischer-Tropsch synthesis iron-based catalyst. CN103071543A discloses a reduction method of a fixed bed Fischer-Tropsch synthesis iron-based catalyst. In both methods, the iron-based catalyst is introduced into gaseous hydrocarbon or mixed gas of hydrogen and gaseous hydrocarbon to carry out reduction reaction, so that the reduction of the iron-based catalyst is realized. Gaseous hydrocarbon replaces CO as a carbon source, the crystal form of ferric oxide in the catalyst is controlled, and over carburization and over carbon deposition are effectively controlled, so that the reduced catalyst has higher activity and stability, and the selectivity of hydrocarbons from carbon 5 to carbon 30 is improved. There is no reference to how the catalyst is preserved.
Therefore, it is desirable to provide a method capable of keeping an iron-containing catalyst in the air for a long time.
Disclosure of Invention
The invention aims to solve the problem that the iron-containing Fischer-Tropsch synthesis catalyst cannot be stored in the air for a long time, and provides the iron-containing Fischer-Tropsch synthesis catalyst, a preparation method thereof and a Fischer-Tropsch synthesis reaction method.
In order to achieve the above object, the present invention provides in a first aspect an iron-containing fischer-tropsch synthesis catalyst comprising an inorganic component a and an organic component b encapsulating the inorganic component a; the catalyst satisfies the following relationship:
Wb/(ρb×Wa×Ra)＝0.3～1；δ＝ρa/(ρab×Wa) -1, δ value not greater than 0.1;
wherein the mass fraction of the inorganic component a is W based on the total amount of the catalystaThe mass fraction of the organic component is Wb(ii) a The water absorption of the inorganic component a is RaThe bulk density of the inorganic component a is ρaThe density of the organic component b is rhobThe bulk density of the catalyst is rhoab，
Wherein, the inorganic component a contains an active component, an auxiliary agent and an optional carrier; the active component is at least one of reduction state, oxide, nitride and carbide of Fe, the auxiliary agent is at least one selected from K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni and Cu, and the carrier is a porous heat-resistant material; the organic component b is a hydrocarbon compound.
Preferably, Wb/(ρb×Wa×Ra) 0.35 to 0.95, preferably Wb/(ρb×Wa×Ra)＝0.4～0.9。
Preferably, the value delta is not greater than 0.08, preferably not greater than 0.05.
Preferably, Wa25 to 95 wt.%, Wb5 to 75 wt.%, RaIs 0.2 to 3ml/g, rhoaIs 0.4 to 2g/ml, rhobIs 0.6 to 1.2g/ml, rhoabIs 0.44-2.2 g/ml.
Preferably, the inorganic component a contains an active component and an auxiliary agent, and the content of the active component in the inorganic component a is 5-95 wt%, preferably 10-90 wt%, and more preferably 20-80 wt% in terms of Fe based on the total amount of the inorganic component a; the content of the auxiliary agent in the inorganic component a is 5-95 wt%, preferably 10-90 wt%, and more preferably 20-80 wt%, calculated by metal elements.
Preferably, the inorganic component a contains an active component, an auxiliary agent and a carrier, and the content of the active component in the inorganic component a is 5-95 wt%, preferably 10-90 wt%, and more preferably 20-80 wt% in terms of Fe based on the total amount of the inorganic component a; the content of the auxiliary agent in the inorganic component a is less than 20 wt% in terms of metal elements.
Preferably, the support is selected from one or more of alumina, titania, magnesia, alumina-magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolites, activated carbon and clays.
Preferably, the support is contained in the inorganic component a in an amount of 0 to 75% by weight in terms of oxide.
Preferably, the specific surface area of the carrier is 5-600 m2A preferred concentration is 5 to 500m2A concentration of 10 to 500m2(ii)/g; the pore volume of the carrier is 0.05-3 ml/g, and the average pore diameter of the carrier is 0.3-50 nm.
Preferably, the size of the carrier ranges from 0.6mm to 1.5 cm.
Preferably, the hydrocarbon compound is selected from hydrocarbon or hydrocarbon-containing mixture with boiling point or melting point range of 45-120 ℃.
Preferably, the hydrocarbon compound contains 30 wt% or more of C20～C50More preferably 40% by weight or more of C20～C50Of (a) is a normal alkane.
In a second aspect, the present invention provides a process for the preparation of an iron-containing fischer-tropsch synthesis catalyst, the process comprising:
(1) loading an active component precursor and an auxiliary agent precursor on a carrier to obtain a catalyst precursor;
(2) activating the catalyst precursor to obtain an inorganic component a;
(3) mixing the inorganic component a with the organic component b to obtain an iron-containing Fischer-Tropsch synthesis catalyst with the inorganic component a wrapped by the organic component b;
wherein the dosage of the inorganic component a and the organic component b is such that the obtained iron-containing Fischer-Tropsch synthesis catalyst satisfies the following relationship:
Wb/(ρb×Wa×Ra)＝0.3～1；δ＝ρa/(ρab×Wa) -1, δ value not greater than 0.1;
wherein the mass fraction of the inorganic component a is W based on the total amount of the catalystaThe mass fraction of the organic component is Wb(ii) a The water absorption of the inorganic component a is RaThe bulk density of the inorganic component a is ρaThe density of the organic component b is rhobThe bulk density of the catalyst is rhoab，
The active component precursor is a compound containing Fe, the auxiliary agent precursor is a compound containing at least one of K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni and Cu, and the carrier is a porous heat-resistant material; the organic component b is a hydrocarbon compound.
Preferably, the activating treatment process comprises:
in the presence of an activating gas, heating and activating the catalyst precursor to convert the active component precursor into an active component and convert the auxiliary agent precursor into an auxiliary agent;
the active component is at least one of reduction state, oxide, nitride and carbide of Fe, and the auxiliary agent is at least one selected from K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni and Cu;
wherein the activation pressure is 0.1-2 MPa, preferably 0.2-1.8 MPa; the activation temperature is 100-800 ℃, preferably 200-600 ℃, and more preferably 250-450 ℃; the activation time is 0.5 to 72 hours, preferably 1 to 48 hours, and more preferably 2 to 36 hours; the space velocity of the activated gas is 2000-4000 h-1Preferably 2500-3500 h-1；
Wherein the activated gas is a mixed gas containing at least one of hydrogen, CO, ammonia, hydrazine and organic amine.
Preferably, the mixing in step (3) is performed by spray-depositing or dipping the organic component b on the inorganic component a; preferably, the hydrocarbon compound is selected from hydrocarbon or hydrocarbon-containing mixture with boiling point or melting point within 45-120 ℃; preferably, the hydrocarbon compound contains 30 wt% or more of C20～C50More preferably 40% by weight or more of C20～C50Of (a) is a normal alkane.
In a third aspect, the present invention provides a process for a fischer-tropsch synthesis reaction, the process comprising: the iron-containing Fischer-Tropsch synthesis catalyst provided by the invention or the iron-containing Fischer-Tropsch synthesis catalyst prepared by the method provided by the invention is mixed with CO and H under the Fischer-Tropsch synthesis reaction condition2Of (2)Carrying out Fischer-Tropsch synthesis reaction by gas contact; wherein the reaction temperature is 160-400 ℃, and preferably 190-370 ℃; the reaction pressure is 1MPa to 8MPa, preferably 1MPa to 5 MPa; h2The molar ratio of the carbon monoxide to the CO is 0.4-3, preferably 0.5-2.8, and more preferably 0.8-2.5; the volume space velocity of the synthetic gas is 500h-1～100000h-1Preferably 1000h-1～80000h-1。
Through the technical scheme, the iron-containing Fischer-Tropsch synthesis catalyst with the inorganic component a wrapped by the organic component b can effectively protect the activity of the iron-containing Fischer-Tropsch synthesis catalyst, realizes long-term storage of the iron-containing Fischer-Tropsch synthesis catalyst in air, can be directly filled in a reactor for Fischer-Tropsch synthesis reaction, and does not need a pre-activation step.
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.
The invention provides an iron-containing Fischer-Tropsch synthesis catalyst, which comprises an inorganic component a and an organic component b wrapping the inorganic component a; the catalyst satisfies the following relationship:
Wb/(ρb×Wa×Ra)＝0.3～1；δ＝ρa/(ρab×Wa) -1, δ value not greater than 0.1;
wherein the mass fraction of the inorganic component a is W based on the total amount of the catalystaThe mass fraction of the organic component is Wb(ii) a The water absorption of the inorganic component a is RaThe bulk density of the inorganic component a is ρaThe density of the organic component b is rhobThe bulk density of the catalyst is rhoab，
Wherein, the inorganic component a contains an active component, an auxiliary agent and an optional carrier; the active component is at least one of reduction state, oxide, nitride and carbide of Co, the auxiliary agent is at least one selected from K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni and Cu, and the carrier is a porous heat-resistant material; the organic component b is a hydrocarbon compound.
According to the invention, the inorganic component a is wrapped by the organic component b, so that the activity protection of the components in the inorganic component a can be provided by meeting the relation, and the good preservation of the iron-containing Fischer-Tropsch synthesis catalyst is provided.
In the present invention, preferably, Wb/(ρb×Wa×Ra) 0.35 to 0.95, preferably Wb/(ρb×Wa×Ra)＝0.4～0.9。
In the present invention, it is preferable that the value of δ be not more than 0.08, preferably not more than 0.05.
In the present invention, preferably, Wa25 to 95 wt.%, Wb5 to 75 wt.%, RaIs 0.2 to 3ml/g, rhoaIs 0.4 to 2g/ml, rhobIs 0.6 to 1.2g/ml, rhoabIs 0.44-2.2 g/ml.
In the invention, the iron-containing Fischer-Tropsch synthesis catalyst can elute the organic component b by using a gas stripping and solvent washing mode, or dissolve the inorganic component a by using inorganic acid, alkali and the like to obtain the organic component b, further analyze the content of various components in the organic component b and the inorganic component a, and various parameters in the relational expression, and determine that the iron-containing Fischer-Tropsch synthesis catalyst meets the limitation. The above parameters can also be determined by the feed of the components in the preparation process.
In the present invention, the component of the inorganic component a can maintain the desired activity state of the iron-containing Fischer-Tropsch synthesis catalyst. In one embodiment, the inorganic component a contains an active component and an auxiliary agent, and the content of the active component in the inorganic component a is 5 to 95 wt%, preferably 10 to 90 wt%, and more preferably 20 to 80 wt% in terms of Fe based on the total amount of the inorganic component a; the content of the auxiliary agent in the inorganic component a is 5-95 wt%, preferably 10-90 wt%, and more preferably 20-80 wt%, calculated by metal elements.
In another specific embodiment, the inorganic component a contains an active component, an auxiliary agent and a carrier, and the content of the active component in the inorganic component a is 5 to 95 wt%, preferably 10 to 90 wt%, and more preferably 20 to 80 wt% in terms of Fe, based on the total amount of the inorganic component a; the content of the auxiliary agent in the inorganic component a is less than 20 wt% in terms of metal elements.
In the present invention, the carrier may be a carrier conventionally used for catalysts, and preferably, the carrier is selected from one or more of alumina, titania, magnesia, alumina-magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolite, activated carbon and clay.
In the present invention, it is preferable that the content of the support in the inorganic component a is 0 to 75% by weight in terms of oxide.
In the present invention, it is preferable that the specific surface area of the carrier is 5 to 600m2A preferred concentration is 5 to 500m2A concentration of 10 to 500m2(ii)/g; the pore volume of the carrier is 0.05-3 ml/g, and the average pore diameter of the carrier is 0.3-50 nm. Can be measured by the BET nitrogen adsorption method.
In the invention, the carrier provides the application shape of the iron-containing Fischer-Tropsch synthesis catalyst and is suitable for a micro-channel reactor. For example, the support may be in the form of particles and/or spheres, and the corresponding size range may be an average particle diameter of 0.1mm to 1.5 cm; the carrier is in a cylindrical shape, a sheet shape, a strip shape, a honeycomb shape, a clover shape or a clover shape, and the corresponding sizes can include that the size of the cross section of the carrier is 0.6-10 mm, and the axial length of the carrier is 1 mm-1.5 cm; the carrier is annular, the corresponding size can include that the size of the cross section of the carrier is 0.6-10 mm, and the annular outer diameter of the carrier is 1 mm-1.5 cm.
In the present invention, the organic component b is used to provide protection to the inorganic component a, and a hydrocarbon compound capable of blocking air from contacting with the inorganic component a may be selected. The hydrocarbon compound is a hydrocarbon or a hydrocarbon-containing mixture which is solid at normal temperature, and preferably, the hydrocarbon compound is selected from hydrocarbon or hydrocarbon-containing mixture with the melting point within the range of 45-120 ℃.
Preferably, the hydrocarbon compound contains 30 wt% or more of C20～C50More preferably 40% by weight or more of C20～C50Of (a) is a normal alkane. For example, it may be Fischer-Tropsch wax, solid wax, or mixture of wax and other higher alcohol and oligomer. Higher alcohols, e.g. C12And the above alcohols, oligomers such as polyethylene glycol having an average molecular weight of 1000 to 4000. Preferably, the hydrocarbon compound is Fischer-Tropsch wax containing 40-90 wt% of C20～C90The normal paraffin of (1). Can be known substances, commercially available, such as Srarwax SX-105 manufactured by Shell company, Sasolwax-7835 manufactured by Sasol company, and Fischer-Tropsch wax manufactured by China petrochemical company, Inc.
In a second aspect, the present invention provides a process for the preparation of an iron-containing fischer-tropsch synthesis catalyst, the process comprising:
(1) loading an active component precursor and an auxiliary agent precursor on a carrier to obtain a catalyst precursor;
(2) activating the catalyst precursor to obtain an inorganic component a;
(3) mixing the inorganic component a with the organic component b to obtain an iron-containing Fischer-Tropsch synthesis catalyst with the inorganic component a wrapped by the organic component b;
wherein the dosage of the inorganic component a and the organic component b is such that the obtained iron-containing Fischer-Tropsch synthesis catalyst satisfies the following relationship:
Wb/(ρb×Wa×Ra)＝0.3～1；δ＝ρa/(ρab×Wa) -1, δ value not greater than 0.1;
wherein the mass fraction of the inorganic component a is W based on the total amount of the catalystaThe mass fraction of the organic component is Wb(ii) a The water absorption of the inorganic component a is RaThe bulk density of the inorganic component a is ρaThe density of the organic component b is rhobThe bulk density of the catalyst is rhoab，
The active component precursor is a compound containing Fe, the auxiliary agent precursor is a compound containing at least one of K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni and Cu, and the carrier is a porous heat-resistant material; the organic component b is a hydrocarbon compound.
In the method provided by the invention, the step (1) can adopt a conventional method for preparing the supported catalyst, for example, the active component precursor and the auxiliary agent precursor are dispersed on the carrier by a precipitation or impregnation method, and then are dried and calcined. The active component precursor may be an Fe-containing compound, and the auxiliary precursor may be a compound containing at least one of K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni, and Cu. In the roasting process, the active component precursor and the auxiliary agent precursor can be converted into metal oxides corresponding to the metals. And the addition amount of the active component precursor and the auxiliary agent precursor meets the composition content required by the final iron-containing Fischer-Tropsch synthesis catalyst. The precipitation may be carried out by adding a precipitating agent, such as ammonia or sodium carbonate, to the aqueous solution of the active component precursor and the auxiliary precursor, and attaching the precipitate to the carrier. The impregnation can be equal-volume impregnation of the carrier by using the aqueous solution of the active component precursor and the auxiliary agent precursor. The drying can be carried out at 80-350 ℃, preferably 100-300 ℃ for 0.001-24 h, preferably 0.001-18 h. The roasting can be carried out at 100-700 ℃, preferably 200-500 ℃ for 0.01-18 h, preferably 0.01-2 h.
In the method provided by the invention, the activation treatment is used for converting the metal oxide in the catalyst precursor into an active component required by the iron-containing catalyst. Preferably, the activating treatment process comprises:
in the presence of an activating gas, heating and activating the catalyst precursor to convert the active component precursor into an active component and convert the auxiliary agent precursor into an auxiliary agent;
the active component is at least one of reduction state, oxide, nitride and carbide of Fe, and the auxiliary agent is at least one selected from K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni and Cu;
wherein the activation pressure is 0.1-2 MPa, preferably 0.2-1.8 MPa; the activation temperature is 100-800 ℃, preferably 200-600 ℃, and more preferably 250-450 ℃; the activation time is 0.5 to 72 hours, preferably 1 to 48 hours, and more preferably 2 to 36 hours; the space velocity of the activated gas is 2000-4000 h-1Preferably 2500-3500 h-1；
Wherein the activated gas is a mixed gas containing at least one of hydrogen, CO, ammonia, hydrazine and organic amine.
In the present invention, the activating gas may have a hydrogen content of not less than 10% by volume, preferably not less than 30% by volume, and further preferably not less than 50% by volume. The reactive gas, for example, contains CO in an amount of not less than 1% by volume, preferably not less than 5% by volume, more preferably not less than 10% by volume. The active gas contains at least one of ammonia, hydrazine and organic amine, and the content of nitrogen-containing compound is not less than 1 volume ppm, preferably not less than 5 volume ppm, and more preferably not less than 10 volume ppm. The rest of the activated gas is chemically inert gas such as nitrogen, helium, argon and the like.
Specifically, the activating gas can be hydrogen gas mixture containing 20 ppm ammonia by volume, and the activation is carried out at 1.8MPa and the space velocity of 3000h-1At 400 ℃ for 4 h.
Or the activated gas is a mixed gas containing 2 volume percent of CO and 98 volume percent of hydrogen, and the activation is carried out at 0.2MPa and the space velocity of 2500h-1At 400 ℃ for 12 h.
The active component may be present in a plurality of the above-mentioned compound states, and the amount of each compound state may not be particularly limited as long as the requirement of the Fischer-Tropsch synthesis reaction can be satisfied. In order to facilitate the metering of the active component, the content of the active component can be calculated according to Fe element.
In the method provided by the invention, the organic component b is used for wrapping the inorganic component a in the step (3) to protect the active component and the auxiliary agent obtained by the activation treatment in the step (2). Preferably, the mixing in step (3) is performed by spray-depositing or dipping the organic component b on the inorganic component a; preferably, the hydrocarbon compound is selected from hydrocarbon or hydrocarbon-containing mixture with boiling point or melting point within 45-120 ℃; preferably, the hydrocarbon compound contains 30 wt% or more of C20～C50More preferably 40% by weight or more of C20～C50Of (a) is a normal alkane.
In the method provided by the present invention, the mixing of step (3) may specifically be such that an effective amount of organic component b is fused by heating and then spray-deposited on the surface of inorganic component a, provided that the catalyst relationship defined above is satisfied; or by impregnating an effective amount of organic component b onto inorganic component a; or immersing the inorganic component a into excessive organic component b, and washing with a washing agent (such as petroleum ether with a distillation range of 60-90 deg.C) for about 20s to remove excessive organic component b; or mixing organic component b with volatile solvent (such as FT synthetic light oil with distillation range of 60-90 deg.C), soaking in inorganic component a, and removing excessive volatile solvent by evaporation, reduced pressure distillation or purging. The volatile solvent can be a hydrocarbon compound or a mixture thereof which dissolves the organic component b at 20-120 ℃ and has a saturated vapor pressure of more than 0.1kPa at 20 ℃.
The mixing in step (3) is carried out without contact with air or other oxygen-containing gas. The catalyst precursor can be sealed and cooled to room temperature after the activation treatment is finished in a container for the activation treatment, and then the organic component b is directly added into the container to coat the inorganic component a.
In the method provided by the invention, the obtained iron-containing Fischer-Tropsch synthesis catalyst meets the relation, and preferably, Wb/(ρb×Wa×Ra) 0.35 to 0.95, preferably Wb/(ρb×Wa×Ra) 0.4-0.9; delta value is not largeAt 0.08, preferably not more than 0.05.
Preferably, Wa25 to 95 wt.%, Wb5 to 75 wt.%, RaIs 0.2 to 3ml/g, rhoaIs 0.4 to 2g/ml, rhobIs 0.6 to 1.2g/ml, rhoabIs 0.44-2.2 g/ml.
In the method provided by the invention, the relation that the limitation requirement on the iron-containing Fischer-Tropsch synthesis catalyst is met can be met by controlling the raw materials and the feeding amount used by each component through the steps.
In the method provided by the invention, the carrier is as described above, and preferably, the specific surface area of the carrier is 5-600 m2A preferred concentration is 5 to 500m2A concentration of 10 to 500m2(ii)/g; the pore volume of the carrier is 0.05-3 ml/g, and the average pore diameter of the carrier is 0.3-50 nm.
Preferably, the shape and size of the carrier are as described above and will not be described in detail.
In a third aspect, the present invention provides a process for a fischer-tropsch synthesis reaction, the process comprising: the iron-containing Fischer-Tropsch synthesis catalyst provided by the invention or the iron-containing Fischer-Tropsch synthesis catalyst prepared by the method provided by the invention is mixed with CO and H under the Fischer-Tropsch synthesis reaction condition2The synthesis gas is contacted to carry out Fischer-Tropsch synthesis reaction; wherein the reaction temperature is 160-400 ℃, and preferably 190-370 ℃; the reaction pressure is 1MPa to 8MPa, preferably 1MPa to 5 MPa; h2The molar ratio of the carbon monoxide to the CO is 0.4-3, preferably 0.5-2.8, and more preferably 0.8-2.5; the volume space velocity of the synthetic gas is 500h-1～100000h-1Preferably 1000h-1～80000h-1。
The present invention will be described in detail below by way of examples. In the following examples and comparative examples,
the pore structure and specific surface of the carrier were determined by the BET nitrogen adsorption method;
in the inorganic component a, the metal content is measured by an ICP method, and the carrier content is measured by a fluorescence spectrum method; bulk density was determined by GB/T6286-;
w of catalysta、WbDetermining through the feeding amount;
relation Wb/(ρb×Wa×Ra) And δ ═ ρa/(ρab×Wa) The result of-1 is determined by the actual charge.
1, medium petrochemical Fischer-Tropsch synthetic wax: melting point about 85 deg.C, density 0.81g/ml, C20～C50The content of n-alkanes of (a) was 89.1% by weight;
medium petrochemical Fischer-Tropsch synthetic wax-2: melting point about 65 deg.C, density 0.804g/ml, C20～C50The content of n-alkanes of (a) is 76.5% by weight;
3, medium petrochemical Fischer-Tropsch synthetic wax: melting point about 88 deg.C, density 0.812g/ml, C20～C50The content of n-alkanes of (a) is 65.5% by weight;
Fischer-Tropsch wax: srarwax SX-105, melting point about 100 ℃, density 0.807g/ml, C20～C50The content of n-alkanes (b) was 63.2% by weight.
Example 1
(1) Preparation of catalyst precursor
385kg of iron nitrate nonahydrate was dissolved in 500L of deionized water, and 15kg of iron nitrate nonahydrate containing 20% by weight of Al was added2O3And an alumina sol containing 20% by weight of SiO2The silica sol is subjected to parallel-flow coprecipitation, the precipitate is washed for seven times after being aged for 6 hours, 3kg of potassium phosphate is added into a filter cake, and then a proper amount of deionized water is added to form slurry with the solid content of 30%.
And then, spray-forming the slurry at the air inlet temperature of 350 ℃ and the air outlet temperature of 180 ℃, and roasting the dried sample at 750 ℃ for 2 h. The catalyst precursor was obtained, having a specific surface area of 21m2Per g, pore volume of 0.18ml/g, average pore diameter of 23 nm. Composition of catalyst precursor Fe2O3：Al2O3：SiO2: k: the weight ratio of P is 77: 3: 15: 1.65: 0.44.
(2) activation of
100g of the catalyst precursor was weighed and reduced at 320 ℃ for 12 hours under a hydrogen atmosphere containing 30 vol% CO at 0.2MPa for activation.
An inorganic component a was obtained in which the Fe content in terms of element was 78.0% by weight, and the metal content was measured by the ICP method. The content of the carrier oxide was 18.6% by weight (fluorescence spectroscopy). Denoted catalyst DC-1.
The water absorption of the inorganic component a was determined to be Ra0.66ml/g, bulk density of inorganic component a ρa0.86g/ml (GB/T6286-1986 method).
(3) Iron-containing catalyst preparation
80g of the inorganic component a were mixed with 60g of molten Fischer-Tropsch wax-2 under nitrogen and cooled to 60 ℃ and after washing with 300g of petroleum ether (distillation range 60-90 ℃) for 20s with stirring, filtered and dried at 30 ℃ overnight.
The catalyst obtained is denoted C-1, in which case Wb/(ρb*Wa*Ra) 0.7; the value of delta was 0.01.
Wherein the mass fraction of the inorganic component a is Wa73.0 wt.%, and the mass fraction of organic component b is Wb27.0% by weight, density ρ of organic component bb0.804g/ml, and the bulk density of catalyst C-1 was ρab＝1.166g/ml。
Comparative example 1
The process of example 1 was followed except that step (3) was as follows:
80g of inorganic component a were mixed with 50g of molten Fischer-Tropsch wax-2 under a nitrogen blanket and cooled to 30 ℃.
The catalyst obtained is designated DC-2. At this time Wb/(ρb*Wa*Ra) 1.18; the value of delta was 0.21.
Wherein the mass fraction of the inorganic component a (catalyst DC-1) is Wa61.5% by weight, the mass fraction of organic component b is Wb38.5% by weight, density ρ of organic component bb0.804g/ml, and the bulk density of the catalyst DC-2 is rhoab＝1.156g/ml。
Comparative example 2
The process of example 1 was followed except that step (3) was as follows:
80g of inorganic component a are mixed with 50g of molten Fischer-Tropsch wax-2 under nitrogen protection and cooled to 60 ℃, washed with 300g of petroleum ether having a distillation range of 60-90 ℃ for 120s with stirring, filtered and dried at 30 ℃ overnight.
The catalyst obtained is designated DC-3. At this time Wb/(ρb*Wa*Ra) 0.21; the value of delta was 0.005.
Wherein the mass fraction of the inorganic component a (catalyst DC-1) is Wa89.3 wt%, the mass fraction of the organic component b is Wb10.7% by weight, density ρ of organic component bb0.804g/ml, and the bulk density of the catalyst DC-3 is rhoab＝0.958g/ml。
Example 2
Catalyst evaluation a fischer-tropsch synthesis reaction was carried out in a fixed bed microreactor having a diameter of 4 mm.
The specific operation comprises the following steps: taking 0.5ml of the above catalyst in the air, diluting with 1ml of 100 μm quartz sand, and filling into a constant temperature region of a reactor, controlling the reaction pressure at 2.5MPa, the reaction temperature at 260 ℃, and the composition volume of synthesis gas as H2:CO:N244:40:16, synthesis gas space velocity of 10000h-1. The reaction is stable for 12h, and the composition of the tail gas is analyzed by using an on-line gas chromatography.
And analyzing the composition of the tail gas by utilizing an online gas chromatography.
The results are shown in Table 1.
TABLE 1
Example 3
(1) Preparation of catalyst precursor
385g of iron nitrate nonahydrate was dissolved in 500mL of deionized water, and 15g of 20 wt% Al was added2O3And an alumina sol containing 20% by weight of SiO2The silica sol and 0.1mol/L potassium carbonate solution are co-current and co-precipitated, and the precipitated and aged filter cake is extruded into a strip agent by a strip extruding machine, wherein the cross section size is 1.6mm, and the axial length is about 5 mm. After drying at 150 ℃, the sample is roasted at 550 ℃ for 2 h. A catalyst precursor is obtained. Specific surface area 46m2The pore volume is 0.34ml/g, and the average pore diameter is 16 nm. Composition of catalyst precursor Fe2O3：Al2O3：SiO2: k: the weight ratio of P is 75: 3: 15: 3.65: 0.44.
(2) activation of
100g of the catalyst precursor was weighed and reduced at 350 ℃ for 12 hours under a hydrogen atmosphere containing 30 vol% of CO at 0.2MPa for activation to obtain an inorganic component a having an Fe content of 74.0% by weight in terms of element and a metal content measured by the ICP method. The content of the carrier oxide was 26.0% by weight (fluorescence spectroscopy).
The water absorption of the inorganic component a was determined to be Ra0.66ml/g, bulk density of inorganic component a ρa0.81g/ml (GB/T6286-.
(3) Iron-containing catalyst preparation
Under the protection of nitrogen, 73g of inorganic component a is mixed with 27g of Fischer-Tropsch wax-2 and 150g of distillate petroleum ether (the distillation range is 60-90 ℃) and stirred, and the mixture is subjected to vacuum rotary evaporation at 60 ℃ to prepare free-dispersed particles.
The catalyst obtained is denoted C-3, in which case Wb/(ρb*Wa*Ra) 0.7; the value of delta was 0.01.
Wherein the mass fraction of the inorganic component a is Wa73.0 wt.%, and the mass fraction of organic component b is Wb27.0% by weight, density ρ of organic component bb0.804g/ml, catalyst C-3 bulk density of ρab＝1.099g/ml。
Storing the fresh agent of the catalyst C-3 in the air for 30 days to obtain a storage agent; the fresh agent and the storage agent are subjected to Fischer-Tropsch synthesis reaction according to the embodiment 3 respectively. CO conversion, CO of storage agent compared to C-3 freshness agent2Selectivity, methane selectivity and C5 +The selectivity did not vary by more than 1%.
Example 4
82.5g of the inorganic component a obtained in example 3 was stirred with 17.5g of Fischer-Tropsch wax-2 mixed with 150g of petroleum ether (distillation range 60-90 ℃) under nitrogen protection, and subjected to vacuum rotary evaporation at 60 ℃ to prepare freely dispersible granules.
The catalyst obtained is denoted C-4, in which case Wb/(ρb*Wa*Ra) 0.4; the value of delta was 0.001.
Wherein the mass fraction of the inorganic component a is Wa82.5 wt%, the mass fraction of the organic component b is Wb18.5% by weight, density ρ of organic component bb0.804g/ml, and the bulk density of catalyst C-4 is rhoab＝0.98g/ml。
Storing a fresh agent of the catalyst C-4 in the air for 30 days to obtain a storage agent; the fresh agent and the storage agent are subjected to Fischer-Tropsch synthesis reaction according to the embodiment 3 respectively. CO conversion, CO of storage agent compared to C-4 freshness agent2Selectivity, methane selectivity and C5 +The selectivity did not vary by more than 1%.
Example 5
(1) Preparation of catalyst precursor
165.94g of iron nitrate nonahydrate, 18.60g of zirconium nitrate pentahydrate and 10.34g of potassium nitrate were dissolved in a sufficient amount of water and dipped into 51.88g of gamma-alumina (manufactured by Changling catalyst works, clover-shaped, 2.0mm in cross-sectional dimension, 4mm in axial length, 200m in specific surface area) in 3 times2G, pore volume 0.70ml/g, average pore diameter 9.3 nm). Each impregnated sample was dried at 150 ℃ for 2 hours and then calcined at 300 ℃ for 2 hours to obtain a catalyst precursor.
(2) Activation of
50g of the procatalyst was weighed at 0.1MPa, space velocity3000h-1And activating the mixture gas of hydrogen and containing 40 volume percent of CO for 5 hours at 320 ℃ to obtain an inorganic component a, wherein the iron content, the zirconium content and the potassium content are respectively 22.94 weight percent, 4.98 weight percent and 3.96 weight percent respectively calculated by elements. The metal content was measured by ICP method. The alumina content of the carrier was 68.12 wt% (fluorescence spectroscopy).
The water absorption of the inorganic component a was determined to be Ra0.88ml/g, bulk density of inorganic component a ρa0.91g/ml (GB/T6286-.
(3) Iron-containing catalyst preparation
Under the protection of nitrogen, 63.0g of inorganic component a is mixed with 37.0g of Fischer-Tropsch wax-3 and 150ml of FT synthetic light oil (distillation range 60-90 ℃), heated to 60 ℃, fully mixed and distilled under reduced pressure until the sample is in a dispersed particle state.
Catalyst C-5 is obtained, in which case Wb/(ρb*Wa*Ra) 0.81; the value of delta was 0.04.
Wherein the mass fraction of the inorganic component a is Wa70.0 wt%, the mass fraction of the organic component b is Wb30.0% by weight, density ρ of organic component bb0.812g/ml, and the bulk density of catalyst C-5 is rhoab＝1.39g/ml。
Storing a fresh agent of the catalyst C-5 in the air for 30 days to obtain a storage agent; the fresh agent and the storage agent are subjected to Fischer-Tropsch synthesis reaction according to the embodiment 3 respectively. CO conversion, CO of the storage agent compared to the C-5 freshness agent2Selectivity, methane selectivity and C5 +The selectivity did not vary by more than 1%.
Example 6
70.0g of the inorganic component a obtained in example 5 was mixed with 30.0g of a Fischer-Tropsch wax Srarwax SX-105 and 150ml of FT synthetic light oil (distillation range 60-90 ℃ C.) under Ar gas, heated to 60 ℃ C., mixed thoroughly, and distilled under reduced pressure until the sample became dispersed particles.
Catalyst C-6 is obtained, in which case Wb/(ρb*Wa*Ra) 0.60; the value of delta was 0.01.
Wherein the mass fraction of the inorganic component aNumber Wa70.0 wt%, the mass fraction of the organic component b is Wb30.0% by weight, density ρ of organic component bb0.812g/ml, and the bulk density of catalyst C-6 is rhoab＝1.29g/ml。
Storing a fresh agent of the catalyst C-6 in the air for 30 days to obtain a storage agent; the fresh agent and the storage agent are subjected to Fischer-Tropsch synthesis reaction according to the embodiment 3 respectively. CO conversion, CO of the storage agent compared to the C-6 freshener2Selectivity, methane selectivity and C5 +The selectivity did not vary by more than 1%.
It can be seen from the results of the above examples, comparative examples and table 1 that the iron-containing catalyst provided by the present invention can be stored in the air for a long time and can be directly packed for use after 30 days of storage. The Fischer-Tropsch synthesis reaction can obtain catalytic activity equivalent to that of a fresh agent.
The catalyst DC-1 has no organic component, can not protect the activated active component and the auxiliary agent, has serious activity loss after being stored for 30 days, and can not be directly used for Fischer-Tropsch synthesis reaction. According to the conventional operation, a preactivation step is arranged in industrial production, and the complexity of the operation is increased. Catalysts DC-2 and DC-3, although treated with organic components, failed to satisfy the relationship defined in the present invention. DC-2 does not shape the reactor usable catalyst, and is not too rich in organic components. Although the DC-3 has the protection of the organic component, the protection is not sufficient, and the active component and the auxiliary agent after partial activation are deactivated, thereby still influencing the activity of the catalyst.
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 (38)
1. An iron-containing Fischer-Tropsch synthesis catalyst comprises an inorganic component a and an organic component b wrapping the inorganic component a; the catalyst satisfies the following relationship:
Wb/(ρb×Wa×Ra)=0.3～1；δ=ρa/(ρab×Wa) -1, δ value not greater than 0.1;
wherein the mass fraction of the inorganic component a is W based on the total amount of the catalystaThe mass fraction of the organic component b is Wb(ii) a The water absorption of the inorganic component a is RaThe bulk density of the inorganic component a is ρaThe density of the organic component b is rhobThe bulk density of the catalyst is rhoab，
Wherein, the inorganic component a contains an active component, an auxiliary agent and an optional carrier; the active component is at least one of reduction state, oxide, nitride and carbide of Fe, the auxiliary agent is at least one selected from K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni and Cu, and the carrier is a porous heat-resistant material; the organic component b is a hydrocarbon compound.
2. The catalyst of claim 1, wherein Wb/(ρb×Wa×Ra)=0.35～0.95。
3. The catalyst of claim 2, wherein Wb/(ρb×Wa×Ra)=0.4～0.9。
4. A catalyst as claimed in any one of claims 1 to 3, wherein the value of δ is not more than 0.08.
5. The catalyst of claim 4, wherein the delta value is not greater than 0.05.
6. The catalyst of any one of claims 1-3 and 5, wherein Wa25 to 95 wt.%, Wb5 to 75 wt.%, RaIs 0.2 to 3mL/g, rhoaIs 0.4 to 2g/mL, rhob0.6 to 1.2g/mL，ρabIs 0.44-2.2 g/mL.
7. The catalyst of claim 4, wherein Wa25 to 95 wt.%, Wb5 to 75 wt.%, RaIs 0.2 to 3mL/g, rhoaIs 0.4 to 2g/mL, rhobIs 0.6 to 1.2g/mL, rhoabIs 0.44-2.2 g/mL.
8. The catalyst according to claim 1, wherein the inorganic component a contains an active component and an auxiliary agent, and the active component is 5-95 wt% of the inorganic component a in terms of Fe based on the total amount of the inorganic component a;
the content of the auxiliary agent in the inorganic component a is 5-95 wt% in terms of metal elements.
9. The catalyst according to claim 8, wherein the active component is contained in the inorganic component a in an amount of 10 to 90 wt% in terms of Fe;
the content of the auxiliary agent in the inorganic component a is 10-90 wt% in terms of metal elements.
10. The catalyst according to claim 9, wherein the active component is contained in the inorganic component a in an amount of 20 to 80 wt% in terms of Fe;
the content of the auxiliary agent in the inorganic component a is 20-80 wt% in terms of metal elements.
11. The catalyst according to claim 1, wherein the inorganic component a contains an active component, an auxiliary agent and a carrier, and the active component is 5-95 wt% of the inorganic component a in terms of Fe based on the total amount of the inorganic component a; the content of the auxiliary agent in the inorganic component a is less than 20 wt% in terms of metal elements.
12. The catalyst according to claim 11, wherein the active component is contained in the inorganic component a in an amount of 10 to 90% by weight in terms of Fe.
13. The catalyst according to claim 12, wherein the active component is contained in the inorganic component a in an amount of 20 to 80 wt% in terms of Fe.
14. The catalyst of any one of claims 11 to 13, wherein the support is selected from one or more of alumina, titania, magnesia, alumina-magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolites, activated carbon and clays;
and/or the content of the carrier in the inorganic component a is 0-75 wt% calculated by oxide.
15. The catalyst according to claim 14, wherein the specific surface area of the carrier is 5 to 600m2(ii)/g; the pore volume of the carrier is 0.05-3 mL/g, and the average pore diameter of the carrier is 0.3-50 nm.
16. The catalyst according to claim 15, wherein the specific surface area of the carrier is 5 to 500m2/g。
17. The catalyst according to claim 16, wherein the specific surface area of the carrier is 10 to 500m2/g。
18. The catalyst of claim 14, wherein the support has a size ranging from 0.6mm to 1.5 cm.
19. The catalyst of any one of claims 15-17, wherein the support has a size in the range of 0.6mm to 1.5 cm.
20. The catalyst according to claim 1, wherein the hydrocarbon compound is selected from hydrocarbons or hydrocarbon-containing mixtures having a melting point in the range of 45 to 120 ℃.
21. The catalyst of claim 20, wherein the hydrocarbon compound contains 30 wt% or more of C20～C50Of (a) is a normal alkane.
22. The catalyst of claim 21, wherein the hydrocarbon compound contains 40% by weight or more of C20～C50Of (a) is a normal alkane.
23. A method for preparing an iron-containing fischer-tropsch synthesis catalyst, the method comprising:
(1) loading an active component precursor and an auxiliary agent precursor on a carrier to obtain a catalyst precursor;
(2) activating the catalyst precursor to obtain an inorganic component a;
(3) mixing the inorganic component a with the organic component b to obtain an iron-containing Fischer-Tropsch synthesis catalyst with the inorganic component a wrapped by the organic component b;
wherein the dosage of the inorganic component a and the organic component b is such that the obtained iron-containing Fischer-Tropsch synthesis catalyst satisfies the following relationship:
Wb/(ρb×Wa×Ra)=0.3～1；δ=ρa/(ρab×Wa) -1, δ value not greater than 0.1;
wherein the mass fraction of the inorganic component a is W based on the total amount of the catalystaThe mass fraction of the organic component b is Wb(ii) a The water absorption of the inorganic component a is RaThe bulk density of the inorganic component a is ρaThe density of the organic component b is rhobThe bulk density of the catalyst is rhoab，
The active component precursor is a compound containing Fe, the auxiliary agent precursor is a compound containing at least one of K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni and Cu, and the carrier is a porous heat-resistant material; the organic component b is a hydrocarbon compound.
24. The method of claim 23, wherein Wb/(ρb×Wa×Ra) = 0.35-0.95; delta value is not more than 0.08;
and/or, Wa25 to 95 wt.%, Wb5 to 75 wt.%, RaIs 0.2 to 3mL/g, rhoaIs 0.4 to 2g/mL, rhobIs 0.6 to 1.2g/mL, rhoabIs 0.44-2.2 g/mL.
25. The method of claim 24, wherein Wb/(ρb×Wa×Ra) = 0.4-0.9; the delta value is not more than 0.05.
26. The method of claim 23, wherein the activating process comprises:
in the presence of an activating gas, heating and activating the catalyst precursor to convert the active component precursor into an active component and convert the auxiliary agent precursor into an auxiliary agent;
the active component is at least one of reduction state, oxide, nitride and carbide of Fe, and the auxiliary agent is at least one selected from K, Ca, Na, Mg, La, Ce, Si, Al, Ti, Zr, Zn, Sn, W, P, Mn, Ni and Cu;
wherein the activation pressure is 0.1-2 MPa; the activation temperature is 100-800 ℃; the activation time is 0.5 h-72 h; the space velocity of the activated gas is 2000-4000 h-1；
Wherein the activating gas is at least one of hydrogen, CO, ammonia, hydrazine and organic amine.
27. The method according to claim 26, wherein the activation pressure is 0.2 to 1.8 MPa; the activation temperature is 200-600 ℃; the activation time is 1-48 h; the space velocity of the activated gas is 2000-4000 h-1。
28. The method of claim 27, wherein the activation temperature is 250 ℃ to 450 ℃; the activation time is 2-36 h.
29. The method as claimed in any one of claims 26 to 28, wherein the active component precursor, the auxiliary agent precursor and the carrier are used in amounts sufficient to constitute the total amount of the inorganic component a, in which the active component is contained in an amount of 5 to 95% by weight in terms of Fe, the auxiliary agent is contained in an amount of 20% by weight or less in terms of a metal element, and the carrier is contained in an amount of 0 to 75% by weight in terms of an oxide.
30. The method according to claim 23, wherein the specific surface area of the carrier is 5 to 600m2(ii)/g; the pore volume of the carrier is 0.05-3 mL/g, and the average pore diameter of the carrier is 0.3-50 nm;
and/or the size range of the carrier is 0.6 mm-1.5 cm.
31. The method according to claim 30, wherein the specific surface area of the carrier is 5 to 500m2/g。
32. The method according to claim 31, wherein the specific surface area of the carrier is 10 to 500m2/g。
33. The method according to claim 23, wherein the mixing in step (3) is performed by spray-depositing or dipping the organic component b on the inorganic component a;
and/or the hydrocarbon compound is selected from hydrocarbon or hydrocarbon-containing mixture with the boiling point or the melting point within the range of 45-120 ℃.
34. The method of claim 33, wherein the hydrocarbon compound contains 30 wt% or more of C20～C50Of (a) is a normal alkane.
35. The method of claim 34, whereinThe hydrocarbon compound contains 40 wt% or more of C20～C50Of (a) is a normal alkane.
36. A process for a fischer-tropsch synthesis reaction, the process comprising: reacting an iron-containing fischer-tropsch synthesis catalyst according to any one of claims 1 to 22 or obtainable by a process according to any one of claims 23 to 35, with a catalyst comprising CO and H under fischer-tropsch synthesis reaction conditions2The synthesis gas is contacted to carry out Fischer-Tropsch synthesis reaction; wherein the reaction temperature is 160-400 ℃; the reaction pressure is 1 MPa-8 MPa; h2The molar ratio of the carbon dioxide to the CO is 0.4-3; the volume space velocity of the synthetic gas is 500h-1～100000h-1。
37. The process of claim 36, wherein the reaction temperature is 190 ℃ to 370 ℃; the reaction pressure is 1 MPa-5 MPa; h2The molar ratio of the carbon dioxide to the CO is 0.5-2.8; the volume space velocity of the synthetic gas is 1000h-1～80000h-1。
38. The method of claim 37, wherein H is2And CO in a molar ratio of 0.8 to 2.5.
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| CN103160307A (en) * | 2011-12-14 | 2013-06-19 | Ifp新能源公司 | Method for producing hydrocarbons with continuous loading of the catalyst |
| CN106552645A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of loaded catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN107185572A (en) * | 2017-05-09 | 2017-09-22 | 中科合成油技术有限公司 | Fischer-tropsch synthetic catalyst comprising nitride carrier and its preparation method and application |
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| CN102770204A (en) * | 2010-02-26 | 2012-11-07 | 吉坤日矿日石能源株式会社 | Process for production of activated fischer-tropsch synthesis catalyst, and process for production of hydrocarbon |
| WO2012068164A2 (en) * | 2010-11-19 | 2012-05-24 | Rentech, Inc. | Protected fischer-tropsch catalyst and methods of making and using same |
| CN103160307A (en) * | 2011-12-14 | 2013-06-19 | Ifp新能源公司 | Method for producing hydrocarbons with continuous loading of the catalyst |
| CN106552645A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of loaded catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN107185572A (en) * | 2017-05-09 | 2017-09-22 | 中科合成油技术有限公司 | Fischer-tropsch synthetic catalyst comprising nitride carrier and its preparation method and application |
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