CN114425385A - Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof - Google Patents

Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof Download PDF

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CN114425385A
CN114425385A CN202011105872.6A CN202011105872A CN114425385A CN 114425385 A CN114425385 A CN 114425385A CN 202011105872 A CN202011105872 A CN 202011105872A CN 114425385 A CN114425385 A CN 114425385A
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catalyst
reaction
hours
roasting
temperature
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CN114425385B (en
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庞颖聪
陶跃武
李剑锋
戴毅敏
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis, and the active component of the catalyst comprises a composition represented by the following formula: fe100CoaBbOxCc(ii) a Wherein B comprises a baseOne or more of metal elements; c comprises silicon carbide and/or aluminum carbide; the value range of a is 1.0-20.0; the value range of b is 1.0-10.0; the value range of c is 50.0-500.0; x is the total number of oxygen atoms required to satisfy the valences of the elements in the formula. The specific surface area of the catalyst is 80-120m2Per g, pore volume of 0.28-0.34cm3(ii) in terms of/g. The invention has the advantages of fast reaction heat removal, difficult temperature runaway and high weight selectivity of the low-carbon olefin.

Description

Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof
Technical Field
The invention relates to a catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis, a preparation method and application thereof, and a method for preparing low-carbon olefin by using the catalyst, and belongs to the field of olefin preparation.
Background
The low-carbon olefin is generally the olefin with the carbon atom less than or equal to 4, and is an important organic chemical raw material. The low-carbon olefin represented by ethylene/propylene is a base stone and a mark in the petrochemical industry, and has great influence on national economy. With the decreasing petroleum resources and the rapid development of C1 chemistry, the traditional petroleum route for the production of lower olefins is suffering a huge impact under the current impact of middle east ethane and North American shale gas for the production of olefins, which seriously affects the competitiveness and sustainable development of the petrochemical industry. Therefore, the development of low-cost and high-efficiency low-carbon olefin production technology plays an important role in the petroleum safety strategy of oil-deficient countries. The direct production of light olefins from synthesis gas has become one of the popular research directions.
Fischer-Tropsch (Fischer-Tropsch) synthesis is a process for synthesizing hydrocarbon by utilizing synthesis gas (the main components are CO and H2) under the action of a catalyst, and is an important way for indirectly liquefying coal and natural gas. The method is invented in 1923 by German scientists Frans Fischer and Hans Tropsh, namely a process of carrying out heterogeneous catalytic hydrogenation reaction on CO on a metal catalyst to generate a mixture mainly comprising straight-chain alkane and olefin. The catalyst with industrial applicability for producing organic hydrocarbon which is not mainly C1 is a Fe series catalyst with a certain proportion of olefin and alkane in the product, and a Co series catalyst with a saturated heavy hydrocarbon as the product, and the patent CN110252358A introduces an impregnated cobalt base catalyst for producing heavy hydrocarbon by low-temperature Fischer-Tropsch synthesis. Compared with Fe, Co has higher Fischer-Tropsch activity, but is less resistant to high temperature and more afraid of carbon pollution, so Co is rarely applied to a high-temperature Fischer-Tropsch process for producing light hydrocarbons at higher temperature.
At present, the Fischer-Tropsch synthesis process for producing light hydrocarbons is carried out in a fluidized bed by adopting Fe catalysts mostly, and some reports that the Fischer-Tropsch synthesis reaction is a strong exothermic reaction and a fixed bed reactor is adopted in a laboratory stage are also provided, but because the Fischer-Tropsch synthesis reaction is a strong exothermic reaction, when the fixed bed is used, the heat in the reactor is difficult to remove, the temperature is easy to fly, the catalyst is easy to inactivate, and the technologies which try to use the fixed bed are stopped in the laboratory stage.
Disclosure of Invention
The invention aims to solve the technical problems that the Fischer-Tropsch synthesis reaction is a strong exothermic reaction, when a fixed bed is used, the reaction heat removal is difficult, the temperature runaway is easy, the catalyst is easy to inactivate, and the yield of the low-carbon olefin is low in the prior art, and provides a novel catalyst for preparing the low-carbon olefin from synthesis gas and a preparation method thereof.
In order to solve the object of the present invention, in one aspect, the present invention provides a catalyst for preparing light olefins by fischer-tropsch synthesis, wherein the active component of the catalyst comprises a composition represented by the following formula: fe100CoaBbOxCc；
Wherein, B comprises one or more of alkali metal elements, preferably one or more of lithium, sodium and potassium; c comprises silicon carbide and/or aluminum carbide;
the value range of a is 1.0-20.0, preferably 2.5-7.5; the value range of b is 1.0-10.0, preferably 2.5-7.5; the value range of c is 50.0-500.0, preferably 100.0-450.0; x is the total number of oxygen atoms required to satisfy the valences of the elements in the formula.
According to the bookIn a preferred embodiment of the invention, the specific surface area of the catalyst is from 80 to 120m2Per g, pore volume of 0.28-0.34cm3/g。
The invention also provides a preparation method of the catalyst, which comprises the following steps:
s1, obtaining a mixed solution I containing Fe salt, Co salt and alkali metal salt;
s2, obtaining a mixture II containing the mixed solution I and the carrier C;
s3, adjusting the pH value of the mixture II to 1-5 to obtain slurry III;
s4, drying the slurry III to obtain a dried material IV;
and S5, roasting the dried material IV for the first time in an air atmosphere, and then roasting for the second time in a mixed atmosphere of air and ammonia gas to obtain the catalyst.
According to a preferred embodiment of the present invention, the step S1 includes:
respectively preparing aqueous solutions of Fe salt, Co salt and alkali metal salt;
all solutions were mixed to obtain a mixed solution I.
According to a preferred embodiment of the present invention, the molar ratio of Fe, Co and alkali metal in the mixed solution I is 100: (10-20): (1-10), preferably 100:10: 5.
According to a preferred embodiment of the invention, the Fe salt is a soluble salt of Fe, preferably ferric nitrate.
According to a preferred embodiment of the invention, the Co salt is a soluble salt of Co, preferably cobalt nitrate.
According to a preferred embodiment of the present invention, the carrier C is added to the mixed solution I in the step S2, and mixed to obtain a mixture II.
According to a preferred embodiment of the invention, the support C is a nanopowder of silicon carbide and/or aluminum carbide.
According to a preferred embodiment of the present invention, the molar ratio of Fe in the support C and the mixed solution I is (0.5 to 5): 1, preferably 2: 1.
According to a preferred embodiment of the present invention, mixture II is heated to 60-100 ℃ before said step S3.
According to a preferred embodiment of the present invention, in step S3, a pH adjusting agent is added to mixture II to adjust the pH of mixture II to 1-5, thereby obtaining slurry III.
According to a preferred embodiment of the invention, the pH adjusting agent comprises ammonia and/or nitric acid.
According to a preferred embodiment of the invention, the process further comprises adjusting the solids content of slurry III to 20% to 50%, preferably 30 to 40%.
According to a preferred embodiment of the present invention, the drying process in the step S4 is a spray drying process.
According to a preferred embodiment of the invention, the temperature of the drying treatment is between 150 and 400 ℃.
According to a preferred embodiment of the present invention, the temperature of the first firing is 450 to 750 ℃, such as 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃, 620 ℃, 650 ℃, 680 ℃, 700 ℃, 720 ℃ and any value in between, preferably 500 to 700 ℃.
According to a preferred embodiment of the present invention, the first calcination is carried out for a calcination time of 0.15 to 6 hours, for example, 0.3 hour, 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours and any value therebetween, preferably 0.5 to 4 hours.
According to a preferred embodiment of the invention, the temperature of the second calcination is between 450 and 750 ℃, such as 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃, 620 ℃, 650 ℃, 680 ℃, 700 ℃, 720 ℃ and any value in between, preferably between 500 and 700 ℃.
According to a preferred embodiment of the invention, the second calcination is carried out for a calcination time of 0.5 to 8 hours, for example 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours and any value in between, preferably 1 to 6 hours.
According to a preferred embodiment of the present invention, the ratio of air and ammonia gas in the mixed atmosphere of air and ammonia gas is (10-30): 1, for example 13:1, 15:1, 18:1, 20:1, 23:1, 25: 1. 28:1 and any value in between are preferably (15-25): 1.
in another aspect, the invention provides an application of the catalyst according to the first aspect or the catalyst prepared by the preparation method according to the second aspect in preparing carbon olefins, especially an application in preparing low carbon olefins by fischer-tropsch synthesis.
In another aspect, the invention provides a method for preparing low carbon olefins by fischer-tropsch synthesis, which includes contacting synthesis gas with the catalyst according to the first aspect of the invention or the catalyst prepared by the preparation method according to the second aspect of the invention, so as to prepare low carbon olefins.
According to a preferred embodiment of the invention, the catalyst is first of all H2Reducing under atmosphere, and then contacting with synthesis gas.
According to a preferred embodiment of the invention, the temperature of the reduction treatment is between 400 and 500 ℃, preferably between 420 and 480 ℃.
According to a preferred embodiment of the invention, the time of the reduction treatment is between 2 and 20h, preferably between 5 and 15 h.
According to a preferred embodiment of the invention, the actual volume space velocity of the reduction treatment is between 300 and 1200 hours-1Preferably 500 to 1000 hours-1。
According to the invention, H2Reduction of treated H2Can be used in pure form or diluted with other inert gases2Is used in the form of (1). Those skilled in the art will know which gases are inert to the reaction, such as, but not limited to, N2, inert gases, and the like.
According to some embodiments of the invention, the synthesis gas comprises H2And CO; preferably said H2And CO in a molar ratio of 0.5 to 5.0.
According to the preferred embodiment of the invention, the reaction pressure for preparing the low-carbon olefin from the synthesis gas is 0.1-8.0MPa, and preferably 0.5-5.0 MPa.
According to the preferred embodiment of the invention, the reaction temperature for preparing the low-carbon olefin from the synthesis gas is 200-400 ℃, preferably 240-370 ℃.
According to a preferred embodiment of the invention, the synthesis gas is used to prepare oligocarbenesThe actual volume space velocity of the hydrocarbon reaction is 500-1200 h-1Preferably 800 to 1000 hours-1。
According to a preferred embodiment of the invention, the lower olefin is preferably a C2-C4 hydrocarbon containing C ═ C bonds, often denoted C2 ＝～C4 ＝。
The invention has the beneficial effects that: according to the invention, the carbide is used as a carrier, and the ammonia gas is used for carrying out surface modification on the active phases Fe and Co in the carbide, so that the particle morphology of the surface of the catalyst is changed, the change is beneficial to utilizing the high Fischer-Tropsch activity of Co and the low methane selectivity of Co, but the Co is inhibited, and the process of chain growth and chain saturation is more beneficial. When the catalyst is used for preparing low-carbon olefin by Fischer-Tropsch synthesis, the selectivity of the low-carbon olefin in the product can be improved.
Drawings
FIG. 1 is an SEM photograph of the catalyst prepared in example 1;
fig. 2 is an SEM photograph of the catalyst prepared in comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
In the following examples, C2 0～C4 0Denotes C2-C4 alkane, C2 ＝～C4 ＝Represents C2-C4 olefins.
[ example 1 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating mixture II to 80 deg.C in a water bath at 80 deg.C, using a concentration of 25 wt%Adjusting the pH value of the slurry to be 5 by using the ammonia water to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K5Ox(SiC)200. The specific surface area of the catalyst is 110m2Per g, pore volume of 0.32cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000051
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 2 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 05mol/L Fe element solution; taking 0.01mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co1K5Ox(SiC)200. The specific surface area of the catalyst is 100m2Per g, pore volume of 0.31cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000061
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (Mo)Er) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 3 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; 0.2mol of Co (NO) is taken3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co20K5Ox(SiC)200. The specific surface area of the catalyst is 105m2Per g, pore volume of 0.32cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000071
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
The catalyst load (reaction actual volume space velocity) is 1000 hoursTime of flight-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 4 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.01mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K1Ox(SiC)200. The specific surface area of the catalyst is 95m2Per g, pore volume 0.29cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000081
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 5 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.1mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K10Ox(SiC)200. The specific surface area of the catalyst is 89m2Per g, pore volume of 0.28cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000091
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 6 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of NaNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II in a water bath at 80 deg.C toAdjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% at 80 ℃ to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10Na5Ox(SiC)200. The specific surface area of the catalyst is 82m2Per g, pore volume of 0.28cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000101
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 7 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 1mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K5Ox(SiC)100. The specific surface area of the catalyst is 118m2Per g, pore volume of 0.34cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000111
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 8 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 5mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K5Ox(SiC)500. The specific surface area of the catalyst is 113m2Per g, pore volume of 0.33cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000121
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (trans)Actual volume space velocity) for 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 9 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of aluminum carbide nano powder into the mixed solution I, and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K5Ox(C3Al4)200. The specific surface area of the catalyst is 94m2Per g, pore volume 0.29cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000131
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 10 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: calcining ammonia gas at 600 deg.C for 1h under mixed atmosphere of 10 to obtain the catalystAn agent, consisting of: fe100Co10K5Ox(SiC)200. The specific surface area of the catalyst is 103m2Per g, pore volume of 0.31cm3/g
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000141
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 11 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixtureA substance II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 30 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K5Ox(SiC)200. The specific surface area of the catalyst is 97m2Per g, pore volume of 0.31cm3/g
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000151
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 12 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 40 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K5Ox(SiC)200. The specific surface area of the catalyst is 105m2Per g, pore volume of 0.32cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000161
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity))1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ example 13 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 5 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K5Ox(SiC)200. The specific surface area of the catalyst is 91m2Per g, pore volume 0.29cm3/g
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000162
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
1) Preparing a catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the slurry II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting for 1h at 600 ℃ in air atmosphere to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K5Ox(SiC)200. The specific surface area of the catalyst was 57m2Per g, pore volume of 0.17cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000171
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
specification of the reactor:
Figure BDA0002726936800000172
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
1) Preparing a catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the slurry II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying the slurry III to form a slurry, and spraying the slurry with a sprayerThe inlet temperature is 320 ℃, and the outlet temperature is 190 ℃ to obtain a drying material IV; then roasting for 2h at 600 ℃ in air atmosphere to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K5Ox(SiC)200. The specific surface area of the catalyst is 54m2Per g, pore volume of 0.17cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000181
a millimeter fluidized bed reactor;
catalyst loading: 50 g; the specific surface area of the catalyst is 100m2Per g, pore volume of 0.31cm3/g
Specification of the reactor:
Figure BDA0002726936800000182
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.005mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co0.5K5Ox(SiC)200. The specific surface area of the catalyst was 78m2G, pore volume of 0.27cm3/g
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000191
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ COMPARATIVE EXAMPLE 4 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; 0.3mol of Co (NO) is taken3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.05mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co30K5Ox(SiC)200. The specific surface area of the catalyst is 123m2Per g, pore volume of 0.35cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000201
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ COMPARATIVE EXAMPLE 5 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.005mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then roasting is carried out, firstly roasting is carried out for 1h at 600 ℃ in an air atmosphere, and then roasting is carried out in an air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K0.5Ox(SiC)200. The specific surface area of the catalyst is 126m2Per g, pore volume of 0.35cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000211
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
[ COMPARATIVE EXAMPLE 6 ]
1) Preparation of the catalyst:
taking 1mol of Fe (NO)3)3·9H2Dissolving O in water to prepare 0.5mol/L Fe element solution; taking 0.1mol of Co (NO)3)2·6H2Dissolving O in water to prepare 0.5mol/L Co element solution; 0.2mol of KNO3Dissolving the K element in water to prepare a 30 wt% K element solution; mixing the three solutions together to prepare a mixed solution I; adding 2mol of SiC nano powder into the mixed solution I and stirring to obtain a mixture II; heating the mixture II to 80 ℃ in a water bath at the temperature of 80 ℃, adjusting the pH value of the slurry to 5 by using ammonia water with the concentration of 25 wt% to obtain slurry III, and adjusting the solid content of the slurry to 35%; spray drying and forming the slurry III, wherein the inlet temperature of a spraying machine is 320 ℃, and the outlet temperature is 190 ℃ to obtain a dried material IV; then baking at 600 deg.C in air atmosphereFiring for 1h, then in air: and (2) roasting the mixture for 1h at 600 ℃ in a mixed atmosphere of ammonia gas and 20 to obtain the catalyst, wherein the catalyst comprises the following components: fe100Co10K20Ox(SiC)200. The specific surface area of the catalyst is 72m2Per g, pore volume of 0.25cm3/g。
2) Evaluation of catalyst:
the catalyst is reduced by adopting an in-situ reduction method, and the process conditions are directly switched to synthesis reaction conditions in a reactor used for reduction after the reduction is finished to start the reaction;
specification of the reactor:
Figure BDA0002726936800000221
a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure 1.0MPa
Catalyst loading (actual space velocity of reaction) 1000 hours-1
Reducing gas H2
The reduction time is 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 350 DEG C
The reaction pressure is 1.0MPa
Catalyst loading (reaction actual volume space velocity) 1100 hours-1
Raw material ratio (mol) H2/CO＝1/1
The reaction was run for 500 hours.
The results of the synthesis reaction of the prepared catalyst are shown in Table 1.
TABLE 1
Figure BDA0002726936800000231
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (11)

1. The catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis comprises the following active components: fe100CoaBbOxCc；
Wherein B comprises one or more alkali metal elements; c comprises silicon carbide and/or aluminum carbide;
the value range of a is 1.0-20.0; the value range of b is 1.0-10.0; the value range of c is 50.0-500.0; x is the total number of oxygen atoms required to satisfy the valences of the elements in the formula.
2. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 80 to 120m2Per g, pore volume of 0.28-0.34cm3/g。
3. A process for preparing the catalyst of claim 1 or 2, comprising the steps of:
s1, obtaining a mixed solution I containing Fe salt, Co salt and alkali metal salt;
s2, obtaining a mixture II containing the mixed solution I and the carrier C;
s3, adjusting the pH value of the mixture II to 1-5 to obtain slurry III;
s4, drying the slurry III to obtain a dried material IV;
and S5, roasting the dried material IV for the first time in an air atmosphere, and then roasting for the second time in a mixed atmosphere of air and ammonia gas to obtain the catalyst.
4. The preparation method according to claim 3, wherein the carrier C is added to the mixed solution I in the step S2, and mixed to obtain a mixture II; and/or carrier C is nanometer powder of silicon carbide and/or aluminum carbide.
5. The method according to claim 3 or 4, wherein the pH of mixture II is adjusted to 1 to 5 by adding a pH adjusting agent to mixture II in step S3; and/or, the pH regulator comprises ammonia and/or nitric acid.
6. The production method according to any one of claims 3 to 5, wherein the drying treatment in step S4 is a spray drying treatment; and/or the temperature of the drying treatment is 150-400 ℃.
7. The method according to any one of claims 3 to 6, wherein the temperature of the first roasting is 450 to 750 ℃, preferably 500 to 700 ℃; and/or the roasting time of the first roasting is 0.15-6h, preferably 0.5-4 h.
8. The method according to any one of claims 3 to 7, wherein the temperature of the second roasting is 450 to 750 ℃, preferably 500 to 700 ℃; and/or the roasting time of the second roasting is 0.5-8h, preferably 1-6 h; and/or the ratio of air to ammonia in the mixed atmosphere of air and ammonia is (10-30): 1, preferably (15-25): 1.
9. use of the catalyst of claim 1 or 2 or the catalyst prepared by the preparation method of any one of claims 3 to 8 for the preparation of a carbon olefin.
10. A method for preparing low carbon olefin by Fischer-Tropsch synthesis, which comprises the steps of contacting synthesis gas with the catalyst of claim 1 or 2 or the catalyst prepared by the preparation method of any one of claims 3 to 8 to prepare low carbon olefin;
preferably, the catalyst is first subjected to H2Reducing under atmosphere, and then contacting with synthesis gas; and/or the temperature of the reduction treatment is 400-500 ℃, preferably 420-480 ℃; and/or the time of the reduction treatment is 2-20h, preferably 5-15 h; and/or the actual volume space velocity of the reduction treatment is 300-1200 hours-1Preferably 500 to 1000 hours-1。
11. The method of claim 10, wherein the syngas comprises H2And CO; preferably said H2And CO in a molar ratio of 0.5 to 5.0; and/or the reaction pressure is 0.1-8.0MPa, preferably 0.5-5.0 MPa; and/or the reaction temperature is 200-400 ℃, preferably 240-370 ℃; and/or the space velocity of the reaction volume is 500-1200 hours-1Preferably 800 to 1000 hours-1。
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EP2282829A2 (en) * 2008-04-09 2011-02-16 Velocys, Inc. Process for upgrading a carbonaceous material using microchannel process technology
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