CN111514900A - Cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure and preparation method thereof - Google Patents
Cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure and preparation method thereof Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910000946 Y alloy Inorganic materials 0.000 title claims abstract description 79
- VQVNCTNULYBZGL-UHFFFAOYSA-N cobalt yttrium Chemical compound [Co].[Y] VQVNCTNULYBZGL-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 50
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052751 metal Inorganic materials 0.000 claims abstract description 79
- 239000002184 metal Substances 0.000 claims abstract description 79
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000003723 Smelting Methods 0.000 claims abstract description 47
- 238000005266 casting Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000006698 induction Effects 0.000 claims description 36
- 229910052727 yttrium Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 241001062472 Stokellia anisodon Species 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002552 Fe K Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- 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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Abstract
The invention discloses a cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure, which is prepared from the following raw materials in percentage by mass: 5.0 to 30.0 percent of yttrium powder and 70.0 to 95.0 percent of cobalt powder; in addition, the invention also provides a preparation method of the cobalt-yttrium alloy catalyst, which comprises the following steps: firstly, baking electrolytic cobalt powder and metal yttrium powder; secondly, smelting and casting electrolytic cobalt powder and metal yttrium powder to obtain a cobalt-yttrium alloy ingot; and thirdly, crushing the cobalt-yttrium alloy ingot to obtain the cobalt-yttrium alloy catalyst. The invention carries out smelting treatment on the electrolytic cobalt powder and the metal yttrium powder, ensures the purity of the cobalt-yttrium alloy ingot and improves the catalytic activity of the cobalt-yttrium alloy catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation of catalysts for synthesizing ammonia, and particularly relates to a cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure and a preparation method thereof.
Background
Since the middle east oil crisis in the seventies of the last century, the world energy is becoming more and more intense, leading to a great rise in the cost of ammonia synthesis, and the energy consumption of ammonia synthesis accounts for about 70% of the total production cost, and it is critical to reduce the cost and the energy consumption thereof, so that it is very important to develop a catalyst for ammonia synthesis with high activity at normal temperature (20-100 ℃) and normal pressure (one standard atmospheric pressure), and through many years of efforts, catalysts for ammonia synthesis such as Fe-K/activated carbon, Ba-Ru-K/activated carbon, Fe-rare earth alloy, Fe-co catalyst and Fe-mn catalyst have been developed at home and abroad, and in actual use, the pressure born by an ammonia synthesis tower is about 8-30 Mpa, the reaction temperature is about 300-400 ℃, and under such high temperature and high pressure, the manufacturing and maintenance costs of the ammonia synthesis tower are quite high, therefore, the preparation of the catalyst for producing the synthetic ammonia at normal temperature and normal pressure is a main way for reducing the production cost of the synthetic ammonia, and has great significance for relieving the energy crisis, saving energy and reducing emission.
The research of yttrium as a catalyst is active internationally, and the development of yttrium as a rare metal is limited because the expensive value of yttrium as a rare metal and the amount required for industrial production cause unacceptable production users, so that a yttrium-containing catalyst doped with yttrium by using a relatively low-price catalyst as a substrate needs to be found, the yttrium-containing catalyst is characterized in that the activity at normal temperature and normal pressure is hundreds of times of that of an iron-based catalyst, and the catalyst is not sensitive to water vapor, carbon monoxide and carbon dioxide and is an ideal catalyst for synthesizing ammonia at normal temperature and normal pressure, so the research of the yttrium-containing catalyst is needed to realize the synthesis of ammonia at normal temperature and normal pressure and reduce the production cost.
Therefore, an yttrium-containing catalyst for synthesizing ammonia at normal temperature and pressure and a preparation method thereof should be provided.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and pressure, which is aimed at overcoming the defects of the prior art. The cobalt-yttrium alloy catalyst is prepared from the following raw materials in percentage by mass: 5.0 to 30.0 percent of yttrium powder and 70.0 to 95.0 percent of cobalt powder, the cobalt-yttrium alloy catalyst can directly synthesize ammonia at normal temperature and normal pressure by taking air and hydrogen as raw materials, thereby reducing the energy consumption of the synthesis ammonia, reducing the preparation cost of the catalyst for synthesizing ammonia and the manufacturing and maintenance cost of equipment, and further reducing the cost of the synthesis ammonia.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure is characterized by being prepared from the following raw materials in percentage by mass: 5.0-30.0% of yttrium powder and 70.0-95.0% of cobalt powder, wherein the mass content of cobalt in the cobalt powder is not less than 99.5%, and the mass content of yttrium in the yttrium powder is not less than 99.5%.
The invention takes cobalt as a base material, and a certain amount of yttrium is added, so that the cobalt-yttrium alloy catalyst has the optimal catalytic performance and lower cost, the defect of poor catalytic activity caused by yttrium powder lower than 5.0% is avoided, and the defect of catalyst cost increase caused by yttrium content increase but not increased catalytic activity when the yttrium powder is higher than 30.0% is avoided; the invention ensures the quality purity of the cobalt yttrium alloy catalyst and improves the catalytic performance of the cobalt yttrium alloy catalyst by ensuring the quality purity of the cobalt powder and the yttrium powder.
The cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure is characterized in that the cobalt-yttrium alloy catalyst is particles with the particle size of 2.0-3.0 mm. The invention controls the size of the cobalt yttrium alloy catalyst, so that the cobalt yttrium alloy catalyst has the advantages of large specific surface area, more active sites and convenient use, avoids the defects of small specific surface area and less active sites caused by overlarge size of the catalyst, and avoids the defect of powder generation caused by friction formed by easy vibration in the process of synthesizing ammonia caused by the undersize of the catalyst.
In addition, the invention also provides a preparation method of the cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure, which is characterized by comprising the following steps:
baking electrolytic cobalt powder and metal yttrium powder;
step two, smelting and casting the electrolytic cobalt powder and the metal yttrium powder which are baked in the step one to obtain a cobalt-yttrium alloy ingot, wherein the smelting and casting process comprises the steps of putting the electrolytic cobalt powder and the metal yttrium powder into a crucible of a vacuum induction furnace, and vacuumizing the vacuum induction furnace until the vacuum degree is less than 1.0 × 10-2Pa, uniformly increasing the smelting power to 100 kW-110 kW, regulating the smelting power to 95 kW-100 kW after smelting until the electrolytic cobalt powder and the metal yttrium powder are melted into molten metal, continuing to smelt for 5 min-10 min, stopping smelting, and pouring the molten metal into a casting mold to obtain a cobalt-yttrium alloy ingot;
and step three, crushing the cobalt-yttrium alloy ingot obtained in the step two to obtain the cobalt-yttrium alloy catalyst.
According to the invention, through baking treatment, moisture in electrolytic cobalt powder and metal yttrium powder is removed, so that the influence of water on the preparation of the catalyst is avoided, and the cobalt yttrium alloy catalyst has higher quality purity; according to the invention, the vacuum degree in the vacuum induction furnace is controlled, so that the content of gas in the vacuum induction furnace is reduced, the quality and purity of the cobalt-yttrium alloy ingot are ensured, and the catalytic activity of the cobalt-yttrium alloy catalyst is improved; according to the invention, the smelting power is controlled to melt electrolytic cobalt powder and metal yttrium powder into molten metal, the electromagnetic stirring function of the vacuum induction furnace is utilized to fully mix the molten metal of cobalt and yttrium, so that the cobalt and yttrium in the cobalt-yttrium alloy catalyst are uniform, the smelting is continued by adjusting the smelting power, the disappearance of a liquid surface film of the molten metal is ensured, the gas content in the molten metal is reduced, the quality purity of a cobalt-yttrium alloy ingot is improved, and the catalytic activity of the cobalt-yttrium alloy catalyst is improved; the cobalt-yttrium alloy catalyst of the invention can directly synthesize ammonia gas at normal temperature and normal pressure by taking air and hydrogen as raw materials, thereby reducing the energy consumption of ammonia synthesis, and reducing the preparation cost of the catalyst for ammonia synthesis and the manufacturing and maintenance cost of equipment, thereby reducing the cost of ammonia synthesis.
The method is characterized in that the baking treatment process in the step one is as follows: heating the electrolytic cobalt powder and the metal yttrium powder to 80-150 ℃, and then preserving heat for 2-5 h. According to the invention, water in the electrolytic cobalt powder and the metal yttrium powder is removed through baking treatment, the quality purity of the electrolytic cobalt powder and the metal yttrium powder is improved, the influence of water remained in the electrolytic cobalt powder and the metal yttrium powder on the smelting process is avoided, the quality purity of the cobalt yttrium alloy ingot is improved, and the catalytic activity of the cobalt yttrium alloy catalyst is improved.
The method is characterized in that the process of putting the electrolytic cobalt powder and the metal yttrium powder into the crucible of the vacuum induction furnace in the step two is as follows: half of the electrolytic cobalt powder is put into a crucible in a vacuum induction furnace, then the metal yttrium powder is put into the crucible in the vacuum induction furnace, and the rest of the electrolytic cobalt powder is put into the crucible in the vacuum induction furnace. According to the invention, by controlling the adding sequence of the electrolytic cobalt powder and the metal yttrium powder, yttrium and cobalt are uniformly mixed in the smelting process, and the catalytic activity of the cobalt-yttrium alloy catalyst is improved.
The principle of synthesizing ammonia by using the cobalt-yttrium alloy catalyst prepared by the invention is as follows: the invention takes cobalt with stronger activity as a base material of the catalyst, proper amount of yttrium is added as an alloy element, and the cobalt yttrium alloy catalyst is obtained by smelting and pouring treatment, wherein in the cobalt yttrium alloy catalyst, the adsorption capacity of transition metal cobalt to hydrogen element at normal temperature is strongThe catalyst can realize the chemical adsorption effect on hydrogen in hydrogen at normal temperature, the rare earth metal yttrium has higher adsorption capacity on nitrogen at normal temperature, and can realize the chemical adsorption effect on nitrogen in air at normal temperature, and meanwhile, the product of synthesizing ammonia by using the cobalt yttrium alloy catalyst can be directly collected without transferring generated ammonia in a high-pressure environment, so that the cobalt yttrium alloy catalyst theoretically realizes the synthesis of ammonia by using hydrogen and air at normal temperature and normal pressure; meanwhile, cobalt is a transition metal element, and the electronic configuration is 1s22s22p63s23p63d74s2Yttrium is a third subgroup element with an electronic configuration of 1s22s22p63s23p64s24p64d15s2It is understood from the above that since the atomic radius of yttrium is larger than that of cobalt, the yttrium atom in the cobalt-yttrium alloy catalyst is more shielded from the inner electrons than the cobalt atom, that is, the electrons in the 4d layer on the yttrium atom are less bound by the atomic nucleus, and according to the theory of electron donation-acceptance, when ammonia is synthesized by catalytic reaction at normal temperature and pressure using the cobalt-yttrium alloy catalyst, the yttrium atom moves to the N-orbital through the 4d orbital thereof2The reverse bond orbital of the molecule donates an electron to N2Molecular dissociative chemisorption is facilitated to make N easy2The molecules are dissociated, thereby accelerating the synthetic ammonia reaction, and the cobalt atom acts on H through the 3d orbit2The reverse bond orbit of the molecular bond, thereby weakening the H-H bond and leading to H2The molecule is dissociated, thereby realizing the acceleration of the synthetic ammonia reaction and the dissociated N2Molecule and H2The molecule reacts to form NH3Thereby realizing the synthesis of ammonia, wherein, N2And H2The following reactions mainly occur on the surface of the cobalt-yttrium alloy catalyst: n is a radical of2+2e＝2N1-，N1-+e＝N2-，N2-+e＝N3-，H2＝2H++2e，N3-+3H+＝NH3。
Compared with the prior art, the invention has the following advantages:
1. the cobalt-yttrium alloy catalyst can directly synthesize ammonia gas at normal temperature and normal pressure by only taking air and hydrogen as raw materials, and no harmful tail gas is generated in the ammonia synthesis process, so that the energy conservation and emission reduction are facilitated, the energy consumption of the ammonia synthesis is reduced, the manufacturing and maintenance cost of equipment for synthesizing ammonia is reduced, and the cost of the ammonia synthesis is reduced.
2. The cobalt-yttrium alloy catalyst of the invention integrates the active components, the auxiliary agent and the carrier into a whole by alloying the cobalt and the yttrium, and can directly synthesize ammonia at normal temperature and normal pressure without adding other substances, thereby improving the production efficiency of the synthetic ammonia, reducing the preparation cost of the catalyst for synthesizing the ammonia and further reducing the cost of the synthetic ammonia.
3. According to the invention, the cobalt-yttrium alloy catalyst has higher quality purity through baking treatment, and the components of cobalt and yttrium in the cobalt-yttrium alloy catalyst are uniform and consistent by controlling the parameters of vacuum induction melting and the adding sequence of electrolytic cobalt powder and metal yttrium powder, so that the gas content in molten metal is reduced, the quality purity of a cobalt-yttrium alloy ingot is improved, and the catalytic activity of the cobalt-yttrium alloy catalyst is improved.
4. The method is simple to operate, environment-friendly and suitable for large-scale popularization and application.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, baking 3520g of electrolytic cobalt powder with the mass content of 99.5 percent and 1480g of metal yttrium powder with the mass content of 99.5 percent; the baking treatment process comprises the following steps: heating electrolytic cobalt powder and metal yttrium powder to 150 ℃, and then preserving heat for 2 h;
step two, smelting and casting the electrolytic cobalt powder and the metal yttrium powder which are baked in the step one to obtain a cobalt-yttrium alloy cast ingot; the smelting and casting process comprises the following steps: putting half of the electrolytic cobalt powder into a crucible in a vacuum induction furnace, and putting the metal yttrium powder into the crucible in the vacuum induction furnaceThe rest of the electrolytic cobalt powder is put into a crucible in a vacuum induction furnace, and the vacuum induction furnace is vacuumized to 0.8 × 10-2And Pa, uniformly increasing the smelting power to 100kW within 5min until the electrolytic cobalt powder and the metal yttrium powder are melted into molten metal, keeping the vacuum degree in the vacuum induction furnace stable in the smelting process, adjusting the smelting power to 95kW after the electrolytic cobalt powder and the metal yttrium powder are melted into the molten metal, continuing smelting for 5min, stopping smelting after a liquid level film of the molten metal disappears, casting the molten metal into a steel cylinder with the inner hole diameter of phi 50.0mm, stopping vacuumizing after the molten metal is cooled to below 100 ℃, and discharging to obtain the cobalt-yttrium alloy ingot.
And step three, crushing the cobalt-yttrium alloy ingot obtained in the step two to obtain the granular cobalt-yttrium alloy catalyst with the grain size of 2.0-3.0 mm.
Example 2
The embodiment comprises the following steps:
step one, baking 3950g of electrolytic cobalt powder with the mass content of 99.5% and 1050g of metal yttrium powder with the mass content of 99.5%; the baking treatment process comprises the following steps: heating electrolytic cobalt powder and metal yttrium powder to 150 ℃, and then preserving heat for 2 h;
step two, smelting and casting the electrolytic cobalt powder and the metal yttrium powder which are baked in the step one to obtain a cobalt-yttrium alloy ingot, wherein the smelting and casting process comprises the steps of putting half of the electrolytic cobalt powder into a crucible in a vacuum induction furnace, putting the metal yttrium powder into the crucible in the vacuum induction furnace, putting the rest of the electrolytic cobalt powder into the crucible in the vacuum induction furnace, and vacuumizing the vacuum induction furnace to 0.8 × 10-2And Pa, uniformly increasing the smelting power to 105kW within 5min until the electrolytic cobalt powder and the metal yttrium powder are melted into molten metal, keeping the vacuum degree in the vacuum induction furnace stable during the smelting process, adjusting the smelting power to 95kW after the electrolytic cobalt powder and the metal yttrium powder are melted into the molten metal, continuing smelting for 10min, stopping smelting after a liquid level film of the molten metal disappears, casting the molten metal into a steel cylinder with the inner hole diameter of phi 50.0mm, stopping vacuumizing after the molten metal is cooled to 100 ℃, and discharging to obtain the cobalt-yttrium alloy ingot.
And step three, crushing the cobalt-yttrium alloy ingot obtained in the step two to obtain the granular cobalt-yttrium alloy catalyst with the grain size of 2.0-3.0 mm.
Example 3
The embodiment comprises the following steps:
step one, baking 4350g of electrolytic cobalt powder with the mass content of 99.5 percent and 650g of metal yttrium powder with the mass content of 99.5 percent; the baking treatment process comprises the following steps: heating electrolytic cobalt powder and metal yttrium powder to 100 ℃, and then preserving heat for 4 hours;
step two, smelting and casting the electrolytic cobalt powder and the metal yttrium powder which are baked in the step one to obtain a cobalt-yttrium alloy ingot, wherein the smelting and casting process comprises the steps of putting half of the electrolytic cobalt powder into a crucible in a vacuum induction furnace, putting the metal yttrium powder into the crucible in the vacuum induction furnace, putting the rest of the electrolytic cobalt powder into the crucible in the vacuum induction furnace, and vacuumizing the vacuum induction furnace to 0.8 × 10-2And Pa, uniformly increasing the smelting power to 110kW within 5min until the electrolytic cobalt powder and the metal yttrium powder are melted into molten metal, keeping the vacuum degree in the vacuum induction furnace stable in the smelting process, adjusting the smelting power to 98kW after the electrolytic cobalt powder and the metal yttrium powder are melted into the molten metal, continuing smelting for 7min, stopping smelting after a liquid level film of the molten metal disappears, casting the molten metal into a steel cylinder with the inner hole diameter of phi 50.0mm, stopping vacuumizing after the molten metal is cooled to 100 ℃, and discharging to obtain the cobalt-yttrium alloy ingot.
And step three, crushing the cobalt-yttrium alloy ingot obtained in the step two to obtain the granular cobalt-yttrium alloy catalyst with the grain size of 2.0-3.0 mm.
Example 4
The embodiment comprises the following steps:
step one, baking 4750g of electrolytic cobalt powder with the mass content of 99.5 percent and 250g of metal yttrium powder with the mass content of 99.5 percent; the baking treatment process comprises the following steps: heating electrolytic cobalt powder and metal yttrium powder to 80 ℃, and then preserving heat for 5 hours;
step two, the stepSmelting and casting the baked electrolytic cobalt powder and the baked metal yttrium powder to obtain a cobalt-yttrium alloy ingot, wherein the smelting and casting process comprises the steps of putting half of the electrolytic cobalt powder into a crucible in a vacuum induction furnace, putting the metal yttrium powder into the crucible in the vacuum induction furnace, putting the rest of the electrolytic cobalt powder into the crucible in the vacuum induction furnace, and vacuumizing the vacuum induction furnace to 0.9 × 10-2And Pa, uniformly increasing the smelting power to 110kW within 5min until the electrolytic cobalt powder and the metal yttrium powder are melted into molten metal, keeping the vacuum degree in the vacuum induction furnace stable in the smelting process, adjusting the smelting power to 100kW after the electrolytic cobalt powder and the metal yttrium powder are melted into the molten metal, continuing smelting for 7min, stopping smelting after a liquid level film of the molten metal disappears, casting the molten metal into a steel cylinder with the inner hole diameter of phi 50.0mm, stopping vacuumizing after the molten metal is cooled to 100 ℃, and discharging to obtain the cobalt-yttrium alloy ingot.
And step three, crushing the cobalt-yttrium alloy ingot obtained in the step two to obtain the granular cobalt-yttrium alloy catalyst with the grain size of 2.0-3.0 mm.
Respectively putting the cobalt-yttrium alloy catalysts obtained in the embodiments 1-4 of the invention into an ammonia synthesis reactor, then mixing air and hydrogen according to the volume ratio of 1:3.3, introducing the mixture into the ammonia synthesis reactor at the flow rate of 100mL/s, reacting for 30min at the temperature of 25 ℃ and under the normal temperature and pressure of one standard atmospheric pressure, and introducing the reaction product obtained after the reaction into 1000mL of distilled water.
The yield of the ammonia synthesized by the cobalt-yttrium alloy catalyst of the example 1 is 2.139 × 102mL/min, the yield of the ammonia gas synthesized by the cobalt-yttrium alloy catalyst of the example 2 is 1.906 × 102mL/min, the yield of the ammonia gas synthesized by the cobalt-yttrium alloy catalyst of the example 3 is 1.547 × 102mL/min, the yield of the ammonia gas synthesized by the cobalt-yttrium alloy catalyst of the example 4 is 1.031 × 102mL/min。
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (5)
1. The cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure is characterized by being prepared from the following raw materials in percentage by mass: 5.0-30.0% of yttrium powder and 70.0-95.0% of cobalt powder, wherein the mass content of cobalt in the cobalt powder is not less than 99.5%, and the mass content of yttrium in the yttrium powder is not less than 99.5%.
2. The cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and pressure according to claim 1, wherein the cobalt-yttrium alloy catalyst is a particle having a particle size of 2.0mm to 3.0 mm.
3. A method of preparing a cobalt yttrium alloy catalyst for ammonia synthesis according to claim 1 or 2 at ambient temperature and pressure, comprising the steps of:
baking electrolytic cobalt powder and metal yttrium powder;
step two, smelting and casting the electrolytic cobalt powder and the metal yttrium powder which are baked in the step one to obtain a cobalt-yttrium alloy ingot, wherein the smelting and casting process comprises the steps of putting the electrolytic cobalt powder and the metal yttrium powder into a crucible of a vacuum induction furnace, and vacuumizing the vacuum induction furnace until the vacuum degree is less than 1.0 × 10-2Pa, uniformly increasing the smelting power to 100 kW-110 kW, regulating the smelting power to 95 kW-100 kW after smelting until the electrolytic cobalt powder and the metal yttrium powder are melted into molten metal, continuing to smelt for 5 min-10 min, stopping smelting, and pouring the molten metal into a casting mold to obtain a cobalt-yttrium alloy ingot;
and step three, crushing the cobalt-yttrium alloy ingot obtained in the step two to obtain the cobalt-yttrium alloy catalyst.
4. The method of claim 3, wherein the baking process in step one comprises: heating the electrolytic cobalt powder and the metal yttrium powder to 80-150 ℃, and then preserving heat for 2-5 h.
5. The method of claim 3, wherein the step two of placing the electrolytic cobalt powder and the metal yttrium powder into the crucible of the vacuum induction furnace comprises the following steps: half of the electrolytic cobalt powder is put into a crucible in a vacuum induction furnace, then the metal yttrium powder is put into the crucible in the vacuum induction furnace, and the rest of the electrolytic cobalt powder is put into the crucible in the vacuum induction furnace.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888792A (en) * | 1970-06-26 | 1975-06-10 | African Explosives & Chem | Catalyst of cobalt oxide and a rare earth metal oxide and its method of preparation |
| JPS61203602A (en) * | 1985-03-07 | 1986-09-09 | Sumitomo Metal Mining Co Ltd | Preparation of rare-earth element-cobalt magnet powder for resin magnet |
| RU2007142103A (en) * | 2007-11-13 | 2009-05-20 | Институт химии твердого тела Уральского Отделения Российской Академии наук (RU) | COBALT ALLOY |
| CN102159314A (en) * | 2008-09-17 | 2011-08-17 | 株式会社日本触媒 | Catalyst for ammonia decomposition, process for producing same, and method of treating ammonia |
| US20120027670A1 (en) * | 2009-04-09 | 2012-02-02 | University Of Miami | Self sustained electrochemical promotion catalysts |
| CN105289624A (en) * | 2015-12-11 | 2016-02-03 | 赵康军 | Low-pressure synthesized ammonia catalyst and preparation method thereof |
| CN105597760A (en) * | 2015-12-18 | 2016-05-25 | 福州大学 | Cobalt catalyst for ammonia synthesis and preparation method of cobalt catalyst |
| CN109261158A (en) * | 2018-11-08 | 2019-01-25 | 烟台大学 | A kind of preparation method and application of yttrium-cobalt composite oxide catalyst |
-
2020
- 2020-05-26 CN CN202010456568.XA patent/CN111514900B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888792A (en) * | 1970-06-26 | 1975-06-10 | African Explosives & Chem | Catalyst of cobalt oxide and a rare earth metal oxide and its method of preparation |
| JPS61203602A (en) * | 1985-03-07 | 1986-09-09 | Sumitomo Metal Mining Co Ltd | Preparation of rare-earth element-cobalt magnet powder for resin magnet |
| RU2007142103A (en) * | 2007-11-13 | 2009-05-20 | Институт химии твердого тела Уральского Отделения Российской Академии наук (RU) | COBALT ALLOY |
| CN102159314A (en) * | 2008-09-17 | 2011-08-17 | 株式会社日本触媒 | Catalyst for ammonia decomposition, process for producing same, and method of treating ammonia |
| US20120027670A1 (en) * | 2009-04-09 | 2012-02-02 | University Of Miami | Self sustained electrochemical promotion catalysts |
| CN105289624A (en) * | 2015-12-11 | 2016-02-03 | 赵康军 | Low-pressure synthesized ammonia catalyst and preparation method thereof |
| CN105597760A (en) * | 2015-12-18 | 2016-05-25 | 福州大学 | Cobalt catalyst for ammonia synthesis and preparation method of cobalt catalyst |
| CN109261158A (en) * | 2018-11-08 | 2019-01-25 | 烟台大学 | A kind of preparation method and application of yttrium-cobalt composite oxide catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 梁海仙等: "合成氨催化剂的研究进展及展望", 《氮肥技术》 * |
| 车如心: "《界面与胶体化学》", 31 August 2012, 中国铁道出版社 * |
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