CN108654637B - Cobalt-based catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method - Google Patents

Cobalt-based catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method Download PDF

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CN108654637B
CN108654637B CN201710194717.8A CN201710194717A CN108654637B CN 108654637 B CN108654637 B CN 108654637B CN 201710194717 A CN201710194717 A CN 201710194717A CN 108654637 B CN108654637 B CN 108654637B
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catalyst
cobalt
carrier
component
carbon component
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CN108654637A (en
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郑仁垟
李明丰
夏国富
李会峰
侯朝鹏
吴玉
晋超
徐润
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—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
    • 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
    • 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

Abstract

The invention discloses a cobalt-based catalyst, a preparation method thereof and a Fischer-Tropsch synthesis method, wherein the catalyst comprises a carrier, a carbon component and a metal component, wherein the carbon component and the metal component are loaded on the carrier, the content of the carbon component is 1-30 wt%, the content of the metal component is 5-70 wt% and the balance is the carrier, wherein the element is calculated and the total amount of the catalyst is taken as a reference; wherein the carbon component or carbon component precursor in the catalyst is supported on a carrier after introducing a metallic cobalt component, the weight m of the carbon component in terms of element per gram of the catalystCThe ratio to the specific surface S of the carrier satisfies mC/S＝0.10‑4.0mg/(m2In terms of/g). Compared with the prior art, the catalyst provided by the invention has higher C while keeping higher Fischer-Tropsch reaction activity5+Selectivity and lower methane selectivity.

Description

Cobalt-based catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method
Technical Field
The invention relates to a cobalt-based catalyst, a preparation method and application thereof, and a Fischer-Tropsch synthesis method.
Background
Under the conditions that the international energy situation is rapidly fluctuated and the energy supply and demand competition is fierce at present, the method has important strategic significance for further efficiently and cleanly utilizing the coal and natural gas resources. The hydrocarbon prepared based on Fischer-Tropsch synthesis technology and other technologies has excellent performance, and can be directly used or mixed with fuel produced by low-quality crude oil for use so as to meet the increasingly rigorous requirements on environmental protection and oil performance indexes. At present, Sasol company in south Africa and Shell company in England/Netherlands master the leading Fischer-Tropsch industrialized synthetic oil technology in the world, and reactors adopted by the technology comprise a tubular fixed bed and a slurry bed. The company Sasol, at the karl's Oryx plant, is the largest slurry bed synthetic oil plant in the world, using a cobalt-based catalyst. The Pearl project which is jointly established by Shell company and Katalun domestic oil company is the natural gas synthetic oil plant with the largest world productivity at present, and the production technology is based on a cobalt-based catalyst and a tubular fixed bed reactor and has good running state.
In addition to the active component Co metal, other metals are often introduced as auxiliary agents to adjust the activity, selectivity and life of the catalyst during the preparation of the catalyst. Studies reported in the literature have shown that these metal promoters, especially noble metal promoters, have a significant effect on the activity of the fischer-tropsch synthesis reaction and on the selectivity of liquid hydrocarbons (ChemCatChem,2010,2, 1030-.
CN102909033B discloses a cobalt-based Fischer-Tropsch synthesis catalyst, which takes platinum modified alumina as a carrier and cobalt as an active component. The preparation process of the catalyst comprises the steps of respectively preparing platinum sol and aluminum sol, fully stirring the platinum sol and the aluminum sol to form gel, then drying and roasting to obtain a platinum modified alumina carrier, and finally loading an active component cobalt by adopting an impregnation method.
CN102441402B discloses a Fischer-Tropsch synthesis catalyst and application thereof, wherein the catalyst comprises a carrier, an active metal component selected from iron and/or cobalt and an auxiliary metal component selected from one or more of noble metals, wherein the active metal component is loaded on the carrier; the preparation method of the catalyst comprises the following steps: (1) carrying out impregnation reaction on the iron-containing compound and/or cobalt-containing compound solution and the carrier; (2) drying and roasting the product obtained in the step (1); (3) carrying out impregnation reaction on a solution containing at least one compound selected from noble metals and the product obtained in the step (2); (4) drying and roasting the product obtained in the step (3); wherein the solution in the step (3) contains alkali, and the molar ratio of the alkali to the noble metal is 20-200. The content of promoter metal is 0.01 to 0.3 wt.%, preferably 0.02 to 0.15 wt.%. Although the method can improve the activity of the catalyst under the condition of low metal content to a certain extent, the activity of the catalyst still needs to be further improved.
Disclosure of Invention
The invention aims to provide a catalyst with higher C5+A cobalt-based catalyst with selectivity and lower methane selectivity, a preparation method and application thereof, and a Fischer-Tropsch synthesis method. The invention provides a cobalt-based catalyst, which comprises a carrier, a carbon component and a metal component cobalt, wherein the carbon component and the metal component cobalt are loaded on the carrier, the content of the carbon component is 1-30 wt%, the content of the metal component cobalt is 5-70 wt% and the balance is the carrier, wherein the element is counted and the total amount of the catalyst is taken as a reference; wherein the carbon component or carbon component precursor in the catalyst is supported on a carrier after introducing a metallic cobalt component, the weight m of the carbon component in terms of element per gram of the catalystCThe ratio to the specific surface S of the carrier satisfies mC/S＝0.10-4.0mg/(m2/g)。
The invention also provides a preparation method of the cobalt-based catalyst, which comprises the following steps:
1) impregnating a carrier with a solution containing a cobalt compound, and then sequentially drying, roasting or not roasting, reducing and activating the impregnated carrier;
2) and (2) under a reducing or inert atmosphere, impregnating the product obtained in the step (1) with a solution containing high-boiling point organic matters, and then carrying out heat treatment to obtain the cobalt-based catalyst.
The invention also provides the cobalt-based catalyst prepared by the method, the catalyst prepared by the method and the application of the catalyst prepared by the method in Fischer-Tropsch synthesis reaction.
The invention further provides a Fischer-Tropsch synthesis method, which comprises the step of carrying out contact reaction on carbon monoxide and hydrogen and a catalyst under Fischer-Tropsch synthesis reaction conditions, wherein the catalyst is the cobalt-based catalyst.
Compared with the catalyst prepared by the prior art, the cobalt-based catalyst has obviously higher CO conversion rate and higher C when being used for Fischer-Tropsch synthesis reaction5+Selectivity and lower methane selectivity. Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a cobalt-based catalyst, which comprises a carrier, a carbon component and a metal component cobalt, wherein the carbon component and the metal component cobalt are loaded on the carrier, the content of the carbon component is 1-30 wt%, the content of the metal component cobalt is 5-70 wt% and the balance is the carrier, wherein the element is counted and the total amount of the catalyst is taken as a reference; wherein the carbon component or carbon component precursor in the catalyst is supported on a carrier after introducing a metallic cobalt component, the weight m of the carbon component in terms of element per gram of the catalystCThe ratio to the specific surface S of the carrier satisfies mC/S＝0.10-4.0mg/(m2(iv)/g); preferably, the content of the carbon component is 2-20 wt% calculated by element and based on the total amount of the catalyst, the content of the metal component cobalt is 8-50 wt%, and the balance is a carrier, wherein m is the weight of the carbon component calculated by element in each gram of the catalystCThe ratio to the specific surface S of the carrier satisfies mC/S＝0.20-2.5mg/(m2(iv)/g); further preferably, the weight m of carbon component calculated as element per gram of catalystCThe ratio to the specific surface S of the carrier satisfies mC/S＝0.50-2.0mg/(m2/g)。
According to the present invention, preferably, the metallic cobalt component is present in a reduced form before the carbon component or the carbon component precursor is supported. The carbon component precursor is a common organic matter which can be dehydrated and carbonized in the heat treatment process, and is preferably at least one of carbohydrate and polyhydroxy organic matter; wherein, the carbohydrate is at least one of sucrose, glucose, fructose, maltose and starch, the polyhydroxy organic substance is at least one of ethylene glycol, glycerol, 1, 2-propylene glycol, 1, 3-propylene glycol and polyethylene glycol, and the polyethylene glycol can be a commercial reagent, preferably the polyethylene glycol with the number average molecular weight of 190-.
The catalyst provided by the invention can also contain various assistants which do not have negative influence on the performance, preferably, the catalyst contains at least one metal assistant selected from Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y and Cu, and the content of the metal assistant is 0.01-10 wt%, preferably 0.02-8 wt%, and more preferably 0.05-5 wt% calculated by elements and based on the total weight of the catalyst.
The support for the catalyst is not particularly required in the present invention, and may be any of various catalyst supports which can be used for catalyzing the ring-opening reaction of hydrogenolysis of cycloalkanes, and the present invention is preferably one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves, and particularly preferably one or more of silica, alumina, Y-Beta and silica-alumina. The carrier can also be one or more of the carriers modified by one or more of phosphorus, silicon, fluorine and boron. The modified carrier can be obtained commercially or modified by the existing method. The inventor of the invention has found through research that when the specific surface area of the carrier in the catalyst is 50-600m2When per gram, the catalyst has lower methane selectivity while keeping higher Fischer-Tropsch synthesis reaction activity; the specific surface area of the carrier is more preferably 100-300m2/g。
According to another aspect of the present invention, there is also provided a cobalt-based catalyst preparation method comprising the steps of:
1) impregnating a carrier with a solution containing a cobalt compound, and then sequentially drying, roasting or not roasting, reducing and activating the impregnated carrier;
2) and (2) under a reducing or inert atmosphere, impregnating the product obtained in the step (1) with a solution containing high-boiling point organic matters, and then carrying out heat treatment to obtain the cobalt-based catalyst.
According to the invention, the cobalt-containing compound is preferably at least one selected from the group consisting of nitrates, acetates, sulfates, basic carbonates, chlorides of cobalt; the concentration of the solution in terms of cobalt element is preferably 50 to 1000 g/l, more preferably 100-700 g/l.
The impregnation method and conditions in steps (1) and (2) are not particularly limited in the present invention and may be the same or different, wherein the impregnation method may be various methods known to those skilled in the art, for example, an equal volume impregnation method, a supersaturated impregnation method, and preferably, the steps (1) and (2) employ an equal volume impregnation. The impregnation conditions may be conventional conditions, and the impregnation conditions of steps (1) and (2) are independently preferably: the temperature is 10-90 ℃ and the time is 0.1-10 hours; more preferably: the temperature is 15-40 ℃, and the time is 0.5-2 hours.
According to the invention, the impregnated support obtained in step (1) is first dried and further calcined or not, and then subjected to said reductive activation. The drying and firing are conventional in the art. For example, the drying conditions may be: for example, the drying conditions may be: the temperature is 40-200 ℃, preferably 80-150 ℃, and the time is 0.1-24 hours, preferably 1-12 hours; the roasting conditions may be: the temperature is 200 ℃ and 600 ℃, preferably 220 ℃ and 550 ℃, and the time is 0.1-24 hours, preferably 1-12 hours.
The reduction activation in step (1) may be carried out in a hydrogen gas or a mixed atmosphere of hydrogen and an inert gas, such as a mixed gas of hydrogen and nitrogen and/or argon, preferably in pure hydrogen. The conditions for the reduction activation are not particularly limited, and the temperature is preferably 200-500 ℃, more preferably 300-500 ℃, more preferably 350-450 ℃, and the time is preferably 1-12 hours, more preferably 1-5 hours, more preferably 2-4 hours. The pressure of the reduction may be normal pressure or increased pressure, and specifically, the partial pressure of hydrogen may be 0.1 to 4MPa, preferably 0.1 to 2 MPa. The pressure in the present invention means an absolute pressure.
The high-boiling-point organic matter in the step (2) is common organic matter with a boiling point higher than 150 ℃, and preferably, the high-boiling-point organic matter is at least one of carbohydrate and polyhydroxy organic matter; wherein, the carbohydrate is at least one of sucrose, glucose, fructose, maltose and starch, the polyhydroxy organic substance is at least one of ethylene glycol, glycerol, 1, 2-propylene glycol, 1, 3-propylene glycol and polyethylene glycol, and the polyethylene glycol can be a commercial reagent, preferably the polyethylene glycol with the number average molecular weight of 190-.
According to the present invention, the purpose of the heat treatment in step (2) is to cause the high boiling point organic matter impregnated on the support to be dehydrated and carbonized to form a carbon component supported on the support, and the atmosphere of the heat treatment is not particularly limited, and is preferably performed under oxygen-free conditions. As for the heat treatment conditions, it is preferable that: the temperature is 200-900 ℃ and the time is 0.1-24 hours, and more preferably, the temperature is 400-700 ℃ and the time is 1-12 hours.
Preferably, the solvent used in step (1) is water, and the solvent used in step (2) is at least one of water, methanol, ethanol, propanol, ethylene glycol, hexane and cyclohexane.
According to the invention, the product after the reduction activation in step (1) is preferably cooled to room temperature or the desired temperature in step (2) in a hydrogen and/or inert atmosphere, such as nitrogen and/or argon, before the impregnation in step (2) is carried out. The method also preferably comprises cooling the product after the heat treatment in the step (2) to room temperature in hydrogen or inert atmosphere, and further preferably introducing O2/N2The mixed gas with the volume ratio of 0.05-1.0% is used for 0.5-4 hours to passivate the metal active components in the mixed gas, and the catalyst which can be directly stored in the air is obtained.
According to the present invention, preferably, a step of impregnation with a solution containing a compound of a metal assistant component, the metal assistant being at least one of Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, Cu, Mn, is further included, and the step of impregnation with the solution containing a compound of a metal assistant component is performed one or more times before, during, or after the impregnation in step (1) or step (2). When the step of introducing the metal promoter is included, it is preferred to introduce it by an impregnation method comprising impregnating the support with a solution containing the metal promoter compound, followed by corresponding drying and optional calcination. If introduced in multiple portions, each impregnation is followed by a corresponding drying and optionally calcination. The impregnation, drying and calcination operations are performed under conventional conditions well known to those skilled in the art and will not be described herein. Further preferably, the solution of the compound containing the metal promoter component is used in an amount such that the metal promoter content in the final catalyst, calculated as element, is from 0.01 to 10% by weight, preferably from 0.02 to 8% by weight, further preferably from 0.05 to 5% by weight.
According to the invention, preferably, the amount of cobalt-containing compound, high-boiling point organic matter and the heat treatment conditions in step (2) are such that the carbon component content is 1-30 wt%, the metal component cobalt content is 5-70 wt%, and the balance is carrier, calculated by element and based on the total weight of the catalyst; further preferably, the content of the carbon component is 2 to 20% by weight, the content of the metal component cobalt is 8 to 50% by weight, still more preferably 10 to 30% by weight, and the balance is a carrier.
According to the invention, the carrier can be any carrier which can be used as a carrier of a Fischer-Tropsch synthesis catalyst, such as one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay and molecular sieve, preferably one or more of alumina, silica and titania. The carrier can also be one or more of the carriers modified by one or more of phosphorus, silicon, fluorine and boron. The modified carrier can be obtained commercially or modified by the existing method. The inventor of the invention discovers through research that when the specific surface area is selected to be 50-600m2A carrier having a specific surface area of 100-300m is more preferable2The catalyst obtained finally has lower methane selectivity while keeping higher Fischer-Tropsch synthesis reaction activity when the carrier is used per gram.
According to the invention, preferably, the selection of the support and the impregnation and heat treatment of step (2) are such that the weight m of the carbon component, expressed as element, is finally present per gram of catalystCThe specific surface S to the carrier satisfies mC/S＝0.1-4.0mg/(m2/g), more preferably mC/S＝0.20-2.5mg/(m2/g), more preferably mC/S＝0.50-2.0mg/(m2/g)。
The invention also provides the cobalt-based catalyst prepared by the method and application of the cobalt-based catalyst in Fischer-Tropsch synthesis reaction.
Compared with the catalyst prepared by the prior art, the cobalt-based catalyst provided by the invention has the advantages that the Fischer-Tropsch synthesis performance is obviously improved, and the catalyst has higher C5+Selectivity and lower methane selectivity. The reason for this is probably that the metallic cobalt group is introducedCarbon is introduced after the separation, and the formed surface carbon component isolates the special structure of the cobalt metal particles, so that the catalyst has relatively proper Fischer-Tropsch synthesis performance.
The invention also provides a Fischer-Tropsch synthesis method, which comprises the step of carrying out contact reaction on carbon monoxide and hydrogen and a catalyst under the Fischer-Tropsch synthesis reaction condition, wherein the catalyst is the cobalt-based catalyst.
The conditions for the contact reaction can be carried out in accordance with the prior art, for example, the molar ratio of hydrogen to carbon monoxide is from 0.5 to 2.6, preferably from 1.5 to 2.4, and more preferably from 1.8 to 2.2, the reaction pressure is from 1 to 10MPa, preferably from 1 to 4MPa, and the reaction temperature is from 150 ℃ to 300 ℃, preferably from 180 ℃ to 250 ℃.
It should be noted that the method of the present invention is suitable for both the fischer-tropsch synthesis reaction of synthesis gas and catalyst, and the fischer-tropsch synthesis reaction of directly contacting hydrogen and carbon monoxide with catalyst.
The means for contacting may be carried out in any reactor sufficient to contact react the feed gas with the catalyst under the reaction conditions, such as one or more of a fixed bed reactor, a slurry bed reactor, a fluidized bed reactor, and a bubble bed reactor.
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. In the following examples, the percentages are by weight unless otherwise specified. Wherein the ratio of converted CO to feed CO is defined as CO conversion XCOThe mole percentage of CO converted to methane to CO converted is the methane selectivity SCH4Generating C5+The mole percentage of CO in the hydrocarbon to the converted CO is C5+ selective SC5+。
Example 1
(1) Catalyst preparation and characterization
36.1 ml of cobalt nitrate and platinum tetraammine dichloride impregnation solution containing 208 g/l cobalt and 1.38 g/l platinum is prepared according to the content of metal salt required by the equal-volume impregnation method. The impregnation solution was decanted to 42.5 g SiO2Support (Fuji silicon Japan, average particle size 40-80 μm, specific surface 135m2And/g), stirring evenly and standing for 4 hours at 20 ℃, drying at 120 ℃, roasting for 4 hours at 400 ℃, and reducing for 4 hours by hydrogen at 400 ℃, wherein the pressure of the hydrogen is 0.1 MPa. Reducing to room temperature after reduction, adding 36.1 ml of 14.5 g/L sucrose aqueous solution under the condition of introducing hydrogen atmosphere, standing for 2 hours, drying at 120 ℃, and heating, dehydrating and carbonizing at 500 ℃. Cooling to room temperature, and introducing through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained is designated R1 and the characterization results are shown in Table 1, where mCS is the weight m of carbon component in each gram of catalyst calculated by element and obtained by thermogravimetric analysisCTo the specific surface S of the support.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
The fischer-tropsch synthesis reaction performance of catalyst R1 was evaluated in a fixed bed reactor. The composition of the raw material gas is H2/CO/N256%/28%/16% (volume percentage), reaction pressure 2.0MPa, reaction temperature 210 ℃. After the reaction had proceeded for 24 hours, a gas sample was taken for chromatography and calculated according to the above definition, and the results are shown in Table 2.
Comparative example 1
(1) Catalyst preparation and characterization
A comparative catalyst D1 was prepared which contained no carbon component and the remainder of the same metal component as the catalyst R1.
36.1 ml of cobalt nitrate and platinum tetraammine dichloride impregnation solution containing 208 g/l cobalt and 1.38 g/l platinum is prepared according to the content of metal salt required by the equal-volume impregnation method. The impregnation solution was decanted to 42.5 g SiO2The carrier (same as above) is stirred evenly and placed for 4 hours at the temperature of 20 ℃, then is dried at the temperature of 120 ℃, is roasted for 4 hours at the temperature of 400 ℃, and is reduced for 4 hours by hydrogen at the temperature of 400 ℃, and the pressure of the hydrogen is 0.1 MPa. Reducing, cooling to room temperature, and treating with O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as D1 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
Catalyst D1 was evaluated in the same manner and under the same evaluation conditions as in example 1, and the results are shown in Table 2.
Comparative example 2
(1) Catalyst preparation and characterization
A comparative catalyst D2, which had the same metal component as that of the catalyst R1, was prepared by co-impregnation of a carbon component compound, and the results of characterization are shown in Table 1.
36.1 ml of impregnation solution containing 208 g/l of cobalt, 1.38 g/l of platinum and 14.5 g/l of sucrose and containing cobalt nitrate, tetraammineplatinum dichloride and sucrose is prepared according to the content of metal salt required by the equal-volume impregnation method. The impregnation solution was decanted to 42.5 g SiO2The carrier (same as above) is stirred evenly and placed for 4 hours at the temperature of 20 ℃, then is dried at the temperature of 120 ℃, is roasted for 4 hours at the temperature of 400 ℃, and is reduced for 4 hours by hydrogen at the temperature of 400 ℃, and the pressure of the hydrogen is 0.1 MPa. After reduction, the temperature is continuously increased to 500 ℃, and the mixture is heated, dehydrated and carbonized. Cooling to room temperature, and introducing through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as D2 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
Catalyst D2 was evaluated in the same manner and under the same evaluation conditions as in example 1, and the results are shown in Table 2.
Comparative example 3
(1) Catalyst preparation and characterization
A comparative catalyst D3, which had the same metal component as that of the catalyst R1, was prepared by impregnation of a carbon component compound first, and the results of characterization are shown in Table 1.
36.1 ml of an impregnating solution containing 14.5 g/l of sucrose is prepared and decanted to 42.5 g of SiO2The carrier (same as above) is stirred and placed for 4 hours at 20 ℃, dried at 120 ℃, and heated, dehydrated and carbonized at 500 ℃. Cooling to room temperature, adding 36.1 ml of cobalt nitrate and platinum dichloride tetraammineplatinum impregnation solution containing 208 g/l cobalt and 1.38 g/l platinum, stirring and standing for 4 hours at 20 ℃, drying at 120 ℃, roasting for 4 hours at 400 ℃, reducing for 4 hours with 400 ℃ hydrogen, and keeping the hydrogen pressure at 0.1 MPa. Cooling to room temperature, and introducing through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as D3 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
Catalyst D3 was evaluated in the same manner and under the same evaluation conditions as in example 1, and the results are shown in Table 2.
Example 2
(1) Catalyst preparation and characterization
36.1 ml of cobalt nitrate and platinum tetraammine dichloride impregnation solution containing 208 g/l cobalt and 1.38 g/l platinum is prepared according to the content of metal salt required by the equal-volume impregnation method. The impregnation solution was decanted to 42.5 g SiO2Carrier (Qingdao ocean chemical plant, average particle size 40-80 μm, specific surface 148m2And/g), stirring evenly and standing for 4 hours at 20 ℃, drying at 120 ℃, roasting for 4 hours at 400 ℃, and reducing for 4 hours by hydrogen at 400 ℃, wherein the pressure of the hydrogen is 0.1 MPa. Reducing to room temperature after reduction, adding 36.1 ml of 15.3 g/L glucose aqueous solution under the atmosphere of hydrogen, standing for 2 hours, drying at 120 ℃, and heating at 500 ℃ for dehydration and carbonization. Cooling to room temperature, and introducing through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained is designated as R2 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
The fischer-tropsch synthesis reaction performance of catalyst R2 was evaluated in a fixed bed reactor. The composition of the raw material gas is H2/CO/N256%/28%/16% (volume percentage), reaction pressure 2.0MPa, reaction temperature 220 ℃. After the reaction had proceeded for 24 hours, a gas sample was taken for chromatography and calculated according to the above definition, and the results are shown in Table 2.
Example 3
(1) Catalyst preparation and characterization
36.1 ml of cobalt nitrate and ruthenium chloride impregnation solution containing 208 g/l cobalt and 1.38 g/l ruthenium is prepared according to the content of metal salt required by the equal-volume impregnation method. The steep was decanted to 42.5 g of gamma-Al2O3Support (Sasol alumina, average particle size 40-80 microns, specific surface 235m2And/g), stirring evenly and standing for 4 hours at 20 ℃, drying at 120 ℃, roasting for 4 hours at 450 ℃, and reducing for 4 hours by using hydrogen at 450 ℃, wherein the pressure of the hydrogen is 1.0 MPa. Reducing the temperature to room temperature, andadding 36.1 ml of 11.7 g/l aqueous solution of glycerol under the condition of introducing hydrogen, standing for 2 hours, drying at 100 ℃, and heating, dehydrating and carbonizing at 400 ℃. Cooling to room temperature, and introducing through O2/N2And passivating the mixed gas with the volume ratio of 0.5% for 1 hour, and storing the gas in a dryer for standby. The catalyst obtained is designated as R3 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
The fischer-tropsch synthesis reaction performance of catalyst R3 was evaluated in a fixed bed reactor. The composition of the raw material gas is H2/CO/N256%/28%/16% (volume percentage), reaction pressure 2.5MPa, reaction temperature 210 ℃. After the reaction had proceeded for 24 hours, a gas sample was taken for chromatography and calculated according to the above definition, and the results are shown in Table 2.
Example 4
(1) Catalyst preparation and characterization
36.1 ml of cobalt nitrate and iridium chloride impregnation solution containing 208 g/l cobalt and 0.69 g/l iridium is prepared according to the content of metal salt required by the equal-volume impregnation method. The steep was decanted to 42.5 g of gamma-Al2O3Support (Sasol alumina, average particle size 40-80 microns, specific surface 235m2And/g), stirring evenly and standing for 4 hours at 20 ℃, drying at 120 ℃, roasting for 4 hours at 350 ℃, and reducing for 4 hours by hydrogen at 350 ℃, wherein the hydrogen pressure is 0.1 MPa. Reducing to room temperature after reduction, adding 36.1 ml of 7.27 g/L sucrose aqueous solution under the condition of introducing hydrogen atmosphere, standing for 2 hours, drying at 100 ℃, and heating, dehydrating and carbonizing at 500 ℃. Cooling to room temperature, and introducing through O2/N2And passivating the mixed gas with the volume ratio of 0.5% for 2 hours, and storing the gas in a dryer for standby. The catalyst obtained is designated as R4 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
The fischer-tropsch synthesis reaction performance of catalyst R4 was evaluated in a fixed bed reactor. The composition of the raw material gas is H2/CO/N256%/28%/16% (volume percentage), reaction pressure 2.5MPa, reaction temperature 210 ℃. After 24 hours of reaction, a gas sample was taken for chromatography and calculated according to the above definition, and the results are shown in the table2。
Example 5
(1) Catalyst preparation and characterization
36.1 ml of cobalt nitrate and platinum tetraammine dichloride impregnation solution containing 208 g/l cobalt and 1.38 g/l platinum is prepared according to the content of metal salt required by the equal-volume impregnation method. The impregnation solution was decanted to 42.5 g SiO2Support (Fuji silicon Japan, average particle size 40-80 μm, specific surface 135m2And/g), stirring evenly and standing for 4 hours at 20 ℃, drying at 120 ℃, roasting for 4 hours at 400 ℃, and reducing for 4 hours by hydrogen at 400 ℃, wherein the hydrogen pressure is 0.1 MPa. Reducing to room temperature after reduction, adding 36.1 ml of 14.5 g/L sucrose aqueous solution under the atmosphere of hydrogen, standing for 2 hours, drying at 120 ℃, and heating, dehydrating and carbonizing at 300 ℃. Cooling to room temperature, and introducing through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained is designated as R5 and the characterization results are given in Table 1.
(2) Catalytic Fischer-Tropsch synthesis reaction performance of catalyst
The fischer-tropsch synthesis reaction performance of catalyst R5 was evaluated in a fixed bed reactor. The composition of the raw material gas is H2/CO/N256%/28%/16% (volume percentage), reaction pressure 2.0MPa, reaction temperature 210 ℃. After the reaction had proceeded for 24 hours, a gas sample was taken for chromatography and calculated according to the above definition, and the results are shown in Table 2.
TABLE 1
Figure BDA0001257073190000141
TABLE 2
Practice ofExample (b) Catalyst and process for preparing same XCO，％ SCH4，％ SC5+，％
1 R1 45.3 5.91 88.5
2 R2 43.2 6.02 87.7
3 R3 43.8 5.98 87.8
4 R4 42.3 6.13 87.1
5 R5 40.2 6.50 87.0
Comparative example 1 D1 34.8 7.86 85.2
Comparative example 2 D2 21.3 8.15 84.1
Comparative example 3 D3 38.2 7.85 84.9
As can be seen from the results in tables 1 and 2, the catalyst provided by the present invention has higher Fischer-Tropsch synthesis activity and C content than the catalyst prepared by the prior art and having the same metal content5+Selectivity and lower methane selectivity.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

Claims (18)

1. A cobalt-based catalyst comprising a carrier, a carbon component and a metal component, cobalt, supported on the carrier, calculated as element and based on the total amount of the catalyst,the carbon component accounts for 1-30 wt%, the metal component cobalt accounts for 5-70 wt%, and the balance is a carrier, wherein the carrier is one or more of alumina, silica, titanium oxide, magnesium oxide, zirconia, thoria, beryllium oxide, clay and a molecular sieve; wherein the carbon component or carbon component precursor in the catalyst is loaded on the carrier after the introduction of the metallic cobalt component, the metallic cobalt component is present in a reduced form before the loading of the carbon component or carbon component precursor, and the weight m of the carbon component in terms of element per gram of the catalystCThe ratio to the specific surface S of the carrier satisfies mC/S=0.10-4.0mg/(m2/g)；
The preparation method of the cobalt-based catalyst comprises the following steps:
(1) impregnating a carrier with a solution containing a cobalt compound, and then sequentially drying, roasting or not roasting, reducing and activating the impregnated carrier;
(2) and (2) under a reducing or inert atmosphere, impregnating the product obtained in the step (1) with a solution containing high-boiling point organic matters, and then carrying out heat treatment to obtain the cobalt-based catalyst.
2. The catalyst according to claim 1, wherein the content of the carbon component is 2 to 20% by weight, the content of the metal component cobalt is 8 to 50% by weight, and the balance is a carrier, calculated as element and based on the total amount of the catalyst, the weight m of the carbon component calculated as element per gram of the catalystCThe ratio to the specific surface S of the carrier satisfies mC/S=0.20-2.5mg/(m2/g)。
3. The catalyst according to claim 1 or 2, wherein the catalyst comprises at least one metal promoter selected from the group consisting of Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, Cu, in an amount of 0.01 to 10 wt% calculated on the element and based on the total weight of the catalyst.
4. The catalyst of claim 3 wherein the metal promoter is present in an amount of from 0.02 to 8 wt% on an elemental basis and based on the total weight of the catalyst.
5. The catalyst of claim 4 wherein the metal promoter is present in an amount of from 0.05 to 5 wt% on an elemental basis and based on the total weight of the catalyst.
6. The catalyst according to any one of claims 1 to 2, 4 and 5, wherein the specific surface area of the carrier is 50 to 600m2/g。
7. The catalyst according to claim 6, wherein the specific surface area of the carrier is 100-300m2/g。
8. The catalyst according to claim 1, wherein the cobalt-containing compound is at least one of nitrate, acetate, sulfate, basic carbonate and chloride of cobalt, and the solution concentration is 50-1000 g/l calculated by cobalt element.
9. The catalyst as claimed in claim 8, wherein the solution has a concentration of 100-700 g/l in terms of cobalt element.
10. The catalyst according to claim 1, wherein the impregnation conditions in step (1) and step (2) may be the same or different and are each independently selected from: the temperature is 10-90 ℃; the time is 0.1-10 hours.
11. The catalyst of claim 10, wherein the impregnation conditions of step (1) and step (2) may be the same or different and are each independently selected from: the temperature is 15-40 ℃; the time is 2-6 hours.
12. The catalyst according to claim 1, wherein the reductive activation of step (1) is carried out under a hydrogen atmosphere, and the conditions of the reductive activation include: the temperature is 200 ℃ and 500 ℃ and the time is 1-12 hours.
13. The catalyst of any one of claims 1, 8-12, wherein the high boiling point organic is at least one of a carbohydrate, a polyhydroxy organic; the carbohydrate is at least one of sucrose, glucose, fructose, maltose and starch, and the polyhydroxy organic matter is at least one of ethylene glycol, glycerol, 1, 2-propylene glycol, 1, 3-propylene glycol and polyethylene glycol.
14. The catalyst of any one of claims 1 and 8-12, wherein the heat treatment conditions of step (2) comprise: the temperature is 200 ℃ and 900 ℃ and the time is 0.1-24 hours.
15. The catalyst of any one of claims 1 and 8 to 12, wherein the method further comprises cooling the product after the reduction activation in the step (1) to room temperature or the temperature required in the step (2) under hydrogen or inert atmosphere, and then performing the impregnation in the step (2).
16. The catalyst according to any one of claims 1 and 8 to 12, wherein the method further comprises introducing O into the solid obtained in step (2)2/N2The volume ratio of the mixed gas is 0.05-1.0% for 0.5-4 hours.
17. The catalyst of claim 1, further comprising a step of impregnation with a solution containing a compound of a metal promoter component, the metal promoter being at least one of Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, Cu, the step of impregnation with a solution containing a compound of a metal promoter component being performed one or more times before, during or after the impregnation in step (1) or step (2).
18. A fischer-tropsch synthesis process comprising contacting carbon monoxide and hydrogen with a catalyst under fischer-tropsch synthesis reaction conditions, wherein the catalyst is a cobalt-based catalyst as claimed in any one of claims 1 to 17, the fischer-tropsch synthesis reaction conditions include a molar ratio of hydrogen to carbon monoxide of 0.5 to 2.6, a reaction pressure of 1 to 10MPa and a reaction temperature of 150-.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102580745A (en) * 2011-01-13 2012-07-18 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst as well as preparation and application thereof
CN102989511A (en) * 2011-09-08 2013-03-27 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst, and preparation and application thereof
CN104174398A (en) * 2014-08-19 2014-12-03 中国科学院山西煤炭化学研究所 Fischer-Tropsch synthesis cobalt-based catalyst produced by self-reduction and application thereof
WO2015183061A1 (en) * 2014-05-30 2015-12-03 한국가스공사 Method for preparing highly active fischer-tropsch catalyst
CN105772011A (en) * 2014-12-26 2016-07-20 神华集团有限责任公司 Fischer-Tropsch oil hydrofining catalyst, preparation method and application of Fischer-Tropsch oil hydrofining catalyst and Fischer-Tropsch oil hydrofining method
CN106000404A (en) * 2016-05-24 2016-10-12 江南大学 Preparation and application of carbon modified silicon dioxide carrier loaded iron-based catalyst for Fischer-Tropsch synthesis

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102580745A (en) * 2011-01-13 2012-07-18 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst as well as preparation and application thereof
CN102989511A (en) * 2011-09-08 2013-03-27 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst, and preparation and application thereof
WO2015183061A1 (en) * 2014-05-30 2015-12-03 한국가스공사 Method for preparing highly active fischer-tropsch catalyst
CN104174398A (en) * 2014-08-19 2014-12-03 中国科学院山西煤炭化学研究所 Fischer-Tropsch synthesis cobalt-based catalyst produced by self-reduction and application thereof
CN105772011A (en) * 2014-12-26 2016-07-20 神华集团有限责任公司 Fischer-Tropsch oil hydrofining catalyst, preparation method and application of Fischer-Tropsch oil hydrofining catalyst and Fischer-Tropsch oil hydrofining method
CN106000404A (en) * 2016-05-24 2016-10-12 江南大学 Preparation and application of carbon modified silicon dioxide carrier loaded iron-based catalyst for Fischer-Tropsch synthesis

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