CN115475640A - Magnesium-iron-cobalt spinel structure catalyst and application thereof - Google Patents

Magnesium-iron-cobalt spinel structure catalyst and application thereof Download PDF

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CN115475640A
CN115475640A CN202211156821.5A CN202211156821A CN115475640A CN 115475640 A CN115475640 A CN 115475640A CN 202211156821 A CN202211156821 A CN 202211156821A CN 115475640 A CN115475640 A CN 115475640A
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magnesium
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CN115475640B (en
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陈海鹏
王晨玮
刘晨磊
张晓玉
王幽娇
申嘉淼
赵晨汐
王一璘
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Luoyang Normal University
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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
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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
    • 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
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • 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
    • 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
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a magnesium-iron-cobalt spinel structure catalyst and application thereof, belonging to the technical field of catalyst preparation. The magnesium-iron-cobalt spinel structure catalyst comprises the following components in parts by mass: 30 to 45 parts of magnesium iron spinel powder as a structural auxiliary agent, 30 to 35 parts of cobaltosic oxide powder as an oxidant, 20 to 25 parts of reduced iron powder as a reducing agent and 5 to 10 parts of plant ash as a hydrogenation auxiliary agent. The catalyst has low cost of raw materials and simple preparation method. For CO and CO in coal gas 2 When the components are subjected to catalytic hydrogenation, the H can be obviously improved 2 Utilization rate of the catalyst and selectivity of the low-carbon olefin.

Description

Magnesium-iron-cobalt spinel structure catalyst and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a catalyst with a magnesium-iron-cobalt spinel structure.
Background
Under the conditions of air isolation and 500-600 ℃, the coal is subjected to low-temperature dry distillation to obtain chemical products such as semicoke, tar, coal gas and the like. Wherein the CO content in the coal gas obtained by low-temperature carbonization of lignite is 5-15%, and the CO content is 5-15% 2 10% -20% of H 2 The proportion is 10% -30%. Method for enriching low-content H in coal gas by using catalyst 2 And for CO, CO 2 The method for preparing the low-carbon olefin by the catalytic hydrogenation of the equal components is an important way for improving the additional value of the low-temperature carbonization gas. Existing CO hydrogenation uses a Fischer-Tropsch synthesis route (FTS) based on an iron-based catalyst. CO 2 2 Hydrogenation requires Reverse Water Gas Shift (RWGS) prior to fischer-tropsch synthesis, i.e. the RWGS + FTS route is used. The CO and the CO in the low-temperature dry distillation coal gas 2 The catalyst has double functions of hydrogen enrichment and catalytic hydrogenation. Hydrogenation catalysts in the current market generally have low hydrogen utilization rate, poor product selectivity, high requirements on operation and equipment and low catalytic hydrogenation activity.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a magnesium-iron-cobalt spinel structure catalyst and aims to provide the application of the magnesium-iron-cobalt spinel structure catalyst to CO and CO in coal gas 2 And carrying out catalytic hydrogenation on the components. The catalyst with the magnesium-iron-cobalt spinel structure has low raw material cost and simple preparation method, and can obviously improve H 2 Utilization rate of the catalyst and selectivity of the low-carbon olefin.
In order to achieve the purpose, the invention adopts the following specific scheme:
a catalyst with a magnesium-iron-cobalt spinel structure comprises the following components in parts by mass: 30 to 45 parts of magnesium iron spinel powder, 30 to 35 parts of cobaltosic oxide powder, 20 to 25 parts of reduced iron powder and 5 to 10 parts of plant ash;
the catalyst with the magnesium-iron-cobalt spinel structure is prepared by the following steps:
1) Sequentially adding the following materials in parts by weight into a ball milling tank: 30-45 parts of magnesium iron spinel powder, 30-35 parts of cobaltosic oxide powder, 20-25 parts of reduced iron powder and 5-10 parts of plant ash; replacing air in the ball milling tank with argon, and placing the ball milling tank on a ball mill for ball milling for 5 to 10 hours to obtain powder;
2) Putting the powder obtained in the step 1) in a CO atmosphere, heating and reducing for 6 to 10 hours at the temperature of 280 to 300 ℃, and cooling to room temperature;
3) Placing the reduced powder obtained in the step 2) in a tablet machine, carrying out cold press molding under 200-250 MPa, and crushing and granulating to obtain the catalyst with the magnesium-iron-cobalt spinel structure.
As a further optimization of the scheme, the particle sizes of the magnesium iron spinel powder, the cobaltosic oxide powder and the reduced iron powder are all below 200 meshes.
As a further optimization of the scheme, the main shaft rotating speed of the ball mill in the step 1) is 600 revolutions per minute.
As a further optimization of the above scheme, the CO reduction pressure in step 2) is 1.0 MPa.
The invention also provides application of the catalyst with the magnesium-iron-cobalt spinel structure in low-temperature carbonization coal gas catalytic hydrogenation upgrading.
The beneficial effects of the invention are mainly expressed as follows: in the raw material composition of the catalyst with the magnesium-iron-cobalt spinel structure, magnesium-iron spinel powder is used as a structural auxiliary agent, cobaltosic oxide powder is used as an oxidizing agent, reduced iron powder is used as a reducing agent, and plant ash is used as a hydrogenation auxiliary agent. The CoFe component is obtained by chemically reducing cobaltosic oxide powder by reduced iron powder under the action of high-energy mechanical force. Heating and reducing the mixture in CO atmosphere to obtain the product containing CoFe and Co 2 C、Fe 5 C 2 And K 2 CO 3 Is a powder material of a main active component. The granular catalyst with the magnesium-iron-cobalt spinel structure is obtained through cold press molding, crushing and granulation. The invention utilizes the principle of mechanochemical action to reduce the particle size of the cobaltosic oxide powder and obtain the pre-reduction product CoFe. Magnesium iron spinelThe stone powder is used as a structural assistant to effectively improve the active components CoFe and Co 2 C、Fe 5 C 2 And K 2 CO 3 The catalytic stability of (3). When the catalyst is used for hydro-conversion of the lean hydrogen gas, the CoFe component is used for H 2 Adsorption and activation of H 2 The utilization ratio of (2). Co 2 C and Fe 5 C 2 The component is used as CO and CO 2 Activation and hydrogenation of, K 2 CO 3 The components are used as an auxiliary agent to improve the selectivity of the low-carbon olefin.
Detailed Description
The technical scheme of the invention will be clearly and completely described in the following by combining the embodiment of the invention.
Example 1
A magnesium-iron-cobalt spinel structure catalyst for quality improvement by catalytic hydrogenation of low-temperature dry distillation coal gas is composed of the following components in parts by mass: 30 parts of magnesium iron spinel powder, 35 parts of cobaltosic oxide powder, 25 parts of reduced iron powder and 10 parts of plant ash powder.
The particle sizes of the magnesium iron spinel powder, the cobaltosic oxide powder and the reduced iron powder are all below 200 meshes.
A magnesium-iron-cobalt spinel structure catalyst for catalytic hydrogenation upgrading of low-temperature dry distillation coal gas comprises the following preparation steps:
1) Sequentially adding the following materials in parts by weight into a ball milling tank: 30 parts of magnesium iron spinel powder, 35 parts of cobaltosic oxide powder, 25 parts of reduced iron powder and 10 parts of plant ash powder, replacing air in a ball milling tank with argon, placing the ball milling tank on a ball mill for ball milling for 5 hours, wherein the rotating speed of a main shaft of the ball mill is 600 revolutions per minute, and obtaining powder;
2) Placing the powder obtained in the step 1) in a CO atmosphere of 1.0 MPa, heating and reducing for 6 hours at 280 ℃, and cooling to room temperature;
putting the powder obtained in the step 2) into a tablet press, cold-pressing and molding under 250 MPa, and crushing and granulating to obtain the catalyst with the magnesium-iron-cobalt spinel structure.
The following tests were carried out on a catalyst product of magnesium-iron-cobalt spinel structure:
loading a catalyst of magnesium-iron-cobalt spinel structure into a continuously operating fixed bedIntroducing pretreated low-temperature dry distillation coal gas (wherein the content of CO is 10%, and CO is introduced into the reactor) 2 15% of H 2 30% by weight). Reacting under the pressure of 1.5 MPa and the temperature of 320 ℃. The selectivity of the hydrogenated low-carbon olefin is 52.3 percent by gas chromatography, and the CO content is measured 2 The conversion was 31.2% and the CO conversion was 12.2%.
Comparative example 1
The difference from the example 1 is that the plant ash powder is not added, and the addition amount of other raw materials is not changed.
The particle size of the raw materials added and the method of preparing the catalyst were the same as in example 1.
The hydrogenation method for the low-temperature dry distillation coal gas is the same as that of the example 1. The selectivity of the hydrogenated low-carbon olefin was 20.1% as determined by gas chromatography, and CO was 2 The conversion was 28.4% and the CO conversion was 7.6%.
Example 2
A magnesium-iron-cobalt spinel structure catalyst for catalytic hydrogenation upgrading of low-temperature dry distillation coal gas is composed of the following components in parts by mass: 40 parts of magnesium iron spinel powder, 30 parts of cobaltosic oxide powder, 25 parts of reduced iron powder and 5 parts of plant ash powder.
The granularity of the magnesium iron spinel powder, the granularity of the cobaltosic oxide powder and the granularity of the reduced iron powder are all below 200 meshes.
A magnesium-iron-cobalt spinel structure catalyst for catalytic hydrogenation upgrading of low-temperature dry distillation coal gas comprises the following preparation steps:
1) Sequentially adding the following materials in parts by weight into a ball milling tank: 40 parts of magnesium iron spinel powder, 30 parts of cobaltosic oxide powder, 25 parts of reduced iron powder and 5 parts of plant ash powder, replacing air in a ball milling tank with argon, placing the ball milling tank on a ball mill for ball milling for 8 hours, wherein the rotating speed of a main shaft of the ball mill is 600 revolutions per minute, and obtaining powder;
2) Placing the powder obtained in the step 1) in a CO atmosphere of 1.0 MPa, heating and reducing for 8 hours at 300 ℃, and cooling to room temperature;
putting the powder obtained in the step 2) into a tablet press, cold-pressing and molding under 200 MPa, and crushing and granulating to obtain the catalyst with the magnesium-iron-cobalt spinel structure.
The following tests were carried out on a catalyst product of magnesium-iron-cobalt spinel structure:
loading Mg-Fe-Co spinel catalyst into a continuously operated fixed bed reactor, introducing desulfurized low-temperature dry distillation coal gas (wherein CO accounts for 10%, and CO accounts for 10%) 2 15% of H 2 30% by weight). Reacting under the pressure of 1.5 MPa and the temperature of 320 ℃. The selectivity of the hydrogenated low-carbon olefin is 50.5 percent by gas chromatography, and the CO content is measured 2 The conversion was 32.1% and the CO conversion was 13.1%.
Comparative example 2
The difference from example 2 is that the addition amount of reduced iron powder was not changed and the other raw materials were not changed.
The particle size of the added raw materials and the catalyst preparation method were the same as in example 2.
The hydrogenation method for the low-temperature dry distillation coal gas is the same as that of the example 2. The selectivity of the hydrogenated low-carbon olefin is 5.2 percent by gas chromatography, and the content of CO is measured 2 The conversion was 13.4% and the CO conversion was 3.6%.
Example 3
A magnesium-iron-cobalt spinel structure catalyst for catalytic hydrogenation upgrading of low-temperature dry distillation coal gas is composed of the following components in parts by mass: 35 parts of magnesium iron spinel powder, 35 parts of cobaltosic oxide powder, 20 parts of reduced iron powder and 10 parts of plant ash powder.
The particle sizes of the magnesium iron spinel powder, the cobaltosic oxide powder and the reduced iron powder are all below 200 meshes.
A magnesium-iron-cobalt spinel structure catalyst for catalytic hydrogenation upgrading of low-temperature dry distillation coal gas comprises the following preparation steps:
1) Sequentially adding the following materials in parts by weight into a ball milling tank: 35 parts of magnesium iron spinel powder, 35 parts of cobaltosic oxide powder, 20 parts of reduced iron powder and 10 parts of plant ash powder, replacing air in a ball milling tank with argon, placing the ball milling tank on a ball mill for ball milling for 5 hours, wherein the rotating speed of a main shaft of the ball mill is 600 revolutions per minute, and obtaining powder;
2) Placing the powder obtained in the step 1) in a CO atmosphere of 1.0 MPa, heating and reducing for 6 hours at 280 ℃, and cooling to room temperature;
putting the powder obtained in the step 2) into a tablet press, cold-pressing and molding under 250 MPa, and crushing and granulating to obtain the catalyst with the magnesium-iron-cobalt spinel structure.
The following tests were carried out on a catalyst product of magnesium-iron-cobalt spinel structure:
loading Mg-Fe-Co spinel catalyst into a continuously operated fixed bed reactor, introducing pretreated low-temperature dry distillation coal gas (wherein CO accounts for 10%, and CO accounts for 10% 2 15% of H 2 30% by weight). The reaction is carried out under the pressure of 1.5 MPa and the temperature of 320 ℃. The selectivity of the hydrogenated low-carbon olefin is 51.6 percent by gas chromatography, and the content of CO is measured 2 The conversion was 30.1% and the CO conversion was 12.6%.
Comparative example 3
The difference from the example 3 is that the cobaltosic oxide powder is not added, and the addition amount of other raw materials is not changed.
The particle size of the added raw materials and the catalyst preparation method were the same as in example 3.
The hydrogenation method for the low-temperature dry distillation coal gas is the same as that of the example 3. The selectivity of the hydrogenated low-carbon olefin is 16.3 percent by gas chromatography, and the content of CO is measured 2 The conversion was 15.34% and the CO conversion was 2.6%.
Example 4
A magnesium-iron-cobalt spinel structure catalyst for quality improvement by catalytic hydrogenation of low-temperature dry distillation coal gas is composed of the following components in parts by mass: 45 parts of magnesium iron spinel powder, 30 parts of cobaltosic oxide powder, 20 parts of reduced iron powder and 5 parts of plant ash powder.
The particle sizes of the magnesium iron spinel powder, the cobaltosic oxide powder and the reduced iron powder are all below 200 meshes.
A magnesium-iron-cobalt spinel structure catalyst for catalytic hydrogenation upgrading of low-temperature dry distillation coal gas comprises the following preparation steps:
1) Sequentially adding the following materials in parts by weight into a ball milling tank: 45 parts of magnesium iron spinel powder, 30 parts of cobaltosic oxide powder, 20 parts of reduced iron powder and 5 parts of plant ash powder, replacing air in a ball milling tank with argon, placing the ball milling tank on a ball mill for ball milling for 8 hours, and enabling the rotating speed of a main shaft of the ball mill to be 600 revolutions per minute to obtain powder;
2) Placing the powder obtained in the step 1) in a CO atmosphere of 1.0 MPa, heating and reducing for 8 hours at 300 ℃, and cooling to room temperature;
putting the powder obtained in the step 2) into a tablet press, cold-pressing and molding under 200 MPa, and crushing and granulating to obtain the catalyst with the magnesium-iron-cobalt spinel structure.
The following tests were carried out on a catalyst product of magnesium-iron-cobalt spinel structure:
loading Mg-Fe-Co spinel structure catalyst into a continuously operated fixed bed reactor, and introducing desulfurized low-temperature dry distillation coal gas (wherein the content of CO is 10%, and CO is 2 15% of H 2 30% by weight). Reacting under the pressure of 1.5 MPa and the temperature of 320 ℃. The selectivity of the hydrogenated low-carbon olefin is 50.9 percent by gas chromatography, and the content of CO is measured 2 The conversion was 30.6% and the CO conversion was 11.3%.
Comparative example 4
The difference from the example 4 is that the pleonaste powder is not added, and the addition amount of other raw materials is not changed.
The particle size of the added raw materials and the catalyst preparation method were the same as in example 4.
The hydrogenation method for the low-temperature dry distillation coal gas is the same as that of the example 4. The selectivity of the hydrogenated low-carbon olefin is 21.2 percent by gas chromatography, and the CO content is measured 2 The conversion was 23.4% and the CO conversion was 7.6%.
Comparative example 5
The difference from the example 4 is that quartz powder is used as a structural assistant instead of magnesium iron spinel powder, and other raw materials are not changed.
The particle size of the added raw materials and the catalyst preparation method were the same as in example 4.
The hydrogenation method for the low-temperature dry distillation coal gas is the same as that of the example 4. The selectivity of the hydrogenated low-carbon olefin is 45.6 percent by gas chromatography, and the content of CO is measured 2 The conversion was 27.4% and the CO conversion was 10.6%.
Comparative example 6
The difference from example 4 is that the powdered cobaltosic oxide is replaced by powdered ferric oxide powder as the oxidant, and the other raw materials are unchanged.
The particle size of the added raw materials and the catalyst preparation method were the same as in example 4.
The hydrogenation method for the low-temperature dry distillation coal gas is the same as that of the example 4. The selectivity of the hydrogenated low-carbon olefin is 43.4 percent by gas chromatography, and the CO content is measured 2 The conversion was 22.4% and the CO conversion was 8.6%.
Comparative example 7
The difference from example 4 is that magnesium powder was used as a reducing agent instead of reduced iron powder, and the other raw materials were not changed.
The particle size of the raw materials added and the method for preparing the catalyst were the same as in example 4.
The hydrogenation method for the low-temperature carbonization gas was the same as in example 4. The selectivity of the hydrogenated low-carbon olefin is 23.2 percent by gas chromatography, and the content of CO is measured 2 The conversion was 20.1% and the CO conversion was 4.8%.
Comparative example 8
The difference from the example 4 is that the plant ash is replaced by the alkali ash to be used as the hydrogenation auxiliary agent, and other raw materials are not changed.
The particle size of the raw materials added and the method for preparing the catalyst were the same as in example 4.
The hydrogenation method for the low-temperature dry distillation coal gas is the same as that of the example 4. The selectivity of the hydrogenated low-carbon olefin was 41.2% as determined by gas chromatography, and CO was measured 2 The conversion was 25.4% and the CO conversion was 9.6%.
It should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, which is defined by the appended claims. It will be apparent to those skilled in the art that certain insubstantial modifications and adaptations of the present invention can be made without departing from the spirit and scope of the invention.

Claims (5)

1. A catalyst with a magnesium-iron-cobalt spinel structure is characterized in that: the paint comprises the following components in parts by mass: 30 to 45 parts of magnesium iron spinel powder, 30 to 35 parts of cobaltosic oxide powder, 20 to 25 parts of reduced iron powder and 5 to 10 parts of plant ash;
the catalyst with the magnesium-iron-cobalt spinel structure is prepared by the following steps:
1) Sequentially adding the following materials in parts by weight into a ball milling tank: 30-45 parts of magnesium iron spinel powder, 30-35 parts of cobaltosic oxide powder, 20-25 parts of reduced iron powder and 5-10 parts of plant ash; replacing air in a ball milling tank with argon, and placing the ball milling tank on a ball mill for ball milling for 5 to 10 hours to obtain powder;
2) Putting the powder obtained in the step 1) in a CO atmosphere, heating and reducing for 6 to 10 hours at the temperature of 280 to 300 ℃, and cooling to room temperature;
3) Putting the reduced powder obtained in the step 2) into a tablet machine, cold-pressing and molding under 200-250 MPa, and crushing and granulating to obtain the catalyst with the magnesium-iron-cobalt spinel structure.
2. The catalyst of magnesium iron cobalt spinel structure of claim 1, characterized in that: the particle sizes of the magnesium iron spinel powder, the cobaltosic oxide powder and the reduced iron powder are all below 200 meshes.
3. The magnesium-iron-cobalt spinel structure catalyst of claim 1, wherein: the main shaft rotating speed of the ball mill in the step 1) is 600 revolutions per minute.
4. The catalyst of magnesium iron cobalt spinel structure of claim 1, characterized in that: the CO reduction pressure in step 2) was 1.0 MPa.
5. The application of the catalyst with a magnesium-iron-cobalt spinel structure according to any one of claims 1 to 4 in the aspect of catalytic hydrogenation upgrading of low-temperature dry distillation coal gas.
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US20090152500A1 (en) * 2007-12-17 2009-06-18 Chao Chen Iron-Based Water Gas Shift Catalyst
CN103230808A (en) * 2013-05-25 2013-08-07 南昌航空大学 Method for preparing Pt-C3N4-TiO2 three-component visible light photocatalyst
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