CN111514900B - 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
- Publication number
- CN111514900B CN111514900B CN202010456568.XA CN202010456568A CN111514900B CN 111514900 B CN111514900 B CN 111514900B CN 202010456568 A CN202010456568 A CN 202010456568A CN 111514900 B CN111514900 B CN 111514900B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- yttrium
- powder
- metal
- electrolytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 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 76
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 49
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 11
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 80
- 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 46
- 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 23
- 238000000034 method Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- 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
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 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
- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 230000000694 effects Effects 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
- 238000011161 development Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 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
- 241001417490 Sillaginidae Species 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
- 210000000795 conjunctiva Anatomy 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 229910052761 rare earth metal Inorganic materials 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
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
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: 1. baking the electrolytic cobalt powder and the metal yttrium powder; 2. smelting and casting electrolytic cobalt powder and metal yttrium powder to obtain a cobalt-yttrium alloy ingot; 3. and 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 increasingly tense, which leads to a great rise in the cost of synthetic ammonia, and the energy consumption of synthetic ammonia accounts for about 70% of the total production cost, and it is important to reduce the cost and the synthetic energy consumption, so that the development of catalysts for synthesizing ammonia with high activity at normal temperature (20-100 ℃) and normal pressure (one standard atmospheric pressure) is very important, and through many years of efforts, catalysts for synthesizing ammonia, such as Fe-K/activated carbon, ba-Ru-K/activated carbon, fe-rare earth alloy, fe-cobalt catalyst, fe-manganese catalyst, and the like, have been developed at home and abroad, and during 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, so that the production cost of synthetic ammonia at normal temperature and normal pressure is always at a high level, which is a main way of reducing the production cost of synthetic ammonia, and simultaneously has a crisis energy saving and emission reducing significance.
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 synthesized ammonia, reducing the preparation cost of the catalyst for synthesizing the ammonia and the manufacturing and maintenance cost of equipment, and further reducing the cost of the synthesized 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 easy vibration and friction formation in the process of synthesizing ammonia due to 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 cast ingot; the smelting and casting process comprises the following steps: putting electrolytic cobalt powder and 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 multiplied by 10 -2 Pa, 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; the invention melts electrolytic cobalt powder and metal yttrium powder into molten metal by controlling the smelting power, fully mixes the cobalt and yttrium molten metal by using the electromagnetic stirring function of the vacuum induction furnace, ensures that the cobalt and yttrium components in the cobalt-yttrium alloy catalyst are uniform, and continuously smelts by adjusting the smelting power, ensures that the liquid level conjunctiva of the molten metal disappears, reduces the gas content in the molten metal, improves the quality purity of a cobalt-yttrium alloy ingot, and improves the catalytic activity of the cobalt-yttrium alloy catalyst; 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: putting half of the electrolytic cobalt powder into a crucible in a vacuum induction furnace, then putting the metal yttrium powder into the crucible in the vacuum induction furnace, and then putting the rest electrolytic cobalt powder 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 cobalt with stronger activity is used as a base material of the catalyst, a 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 transition metal element cobalt has strong adsorption capacity to hydrogen at normal temperature, and can realize chemical adsorption to the hydrogen in hydrogen at normal temperature; meanwhile, cobalt is a transition metal element, and the electronic configuration is 1s 2 2s 2 2p 6 3s 2 3p 6 3d 7 4s 2 Yttrium is a third subgroup element with an electronic configuration of 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 4p 6 4d 1 5s 2 It 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 thereof 2 The anti-bonding orbital of the molecule donates an electron to N 2 Molecular dissociative chemisorption is facilitated to make N easy 2 The molecules are dissociated, thereby accelerating the synthetic ammonia reaction, and the cobalt atom acts on H through the 3d orbit 2 The reverse bond orbit of the molecular bond, thereby weakening the H-H bond and leading to H 2 The molecule is dissociated, thereby realizing the acceleration of the synthetic ammonia reaction and the dissociated N 2 Molecule and H 2 The molecule reacts to form NH 3 Thereby realizing the synthesis of ammonia, wherein, N 2 And H 2 The following reactions mainly occur on the surface of the cobalt-yttrium alloy catalyst: n is a radical of 2 +2e＝2N 1- ，N 1- +e＝N 2- ，N 2- +e＝N 3- ，H 2 ＝2H + +2e，N 3- +3H + ＝NH 3 。
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 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; the smelting and casting treatment process comprises the following steps: 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 multiplied by 10 -2 And 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 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 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, 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 multiplied by 10 -2 And 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 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 10min, stopping smelting after a liquid surface 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 oneObtaining a cobalt-yttrium alloy 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, 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 multiplied by 10 -2 And 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, 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 treatment process comprises the following steps: 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 multiplied by 10 -2 After Pa, the smelting power is increased to 110kW at a constant speed within 5min until the electrolytic cobalt powder and the metal yttrium powder are melted into molten metal, the vacuum degree in the vacuum induction furnace is kept stable during the smelting process, after the electrolytic cobalt powder and the metal yttrium powder are melted into the molten metal, the smelting power is adjusted to 100kW, and the smelting is continued for 7min, so that the molten metal is ensuredStopping smelting after the liquid surface film disappears, casting the molten metal into a steel cylinder with the inner hole diameter phi of 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.
The cobalt-yttrium alloy catalysts obtained in the embodiments 1 to 4 of the invention are respectively put into an ammonia synthesis reactor, then air and hydrogen are mixed according to the volume ratio of 1.
The cobalt yttrium alloy catalyst of the example 1 is detected to have the yield of 2.139 multiplied by 10 for synthesizing ammonia gas 2 mL/min; the yield of ammonia synthesized by the cobalt yttrium alloy catalyst of the example 2 is 1.906 multiplied by 10 2 mL/min; the yield of ammonia synthesized by the cobalt yttrium alloy catalyst of the example 3 is 1.547 multiplied by 10 2 mL/min; the yield of ammonia synthesized by the cobalt yttrium alloy catalyst of the embodiment 4 is 1.031 multiplied by 10 2 mL/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 (4)
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%; the cobalt yttrium alloy catalyst is prepared by the following steps:
step one, baking electrolytic cobalt powder and metal yttrium powder;
step two, the stepSmelting and casting the baked electrolytic cobalt powder and the baked metal yttrium powder to obtain a cobalt-yttrium alloy ingot; the smelting and casting treatment process comprises the following steps: putting electrolytic cobalt powder and 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 multiplied by 10 -2 Pa, 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.
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. The cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and pressure according to claim 1, wherein the baking process in the first step is: heating the electrolytic cobalt powder and the metal yttrium powder to 80-150 ℃, and then preserving heat for 2-5 h.
4. The cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and pressure according to claim 1, wherein the process of putting the electrolytic cobalt powder and the metal yttrium powder into the crucible of the vacuum induction furnace in the second step 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010456568.XA CN111514900B (en) | 2020-05-26 | 2020-05-26 | Cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010456568.XA CN111514900B (en) | 2020-05-26 | 2020-05-26 | Cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111514900A CN111514900A (en) | 2020-08-11 |
| CN111514900B true CN111514900B (en) | 2022-12-09 |
Family
ID=71908073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010456568.XA Active CN111514900B (en) | 2020-05-26 | 2020-05-26 | Cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111514900B (en) |
Citations (7)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010117990A2 (en) * | 2009-04-09 | 2010-10-14 | University Of Miami | Self sustained electrochemical promotion catalysts |
-
2020
- 2020-05-26 CN CN202010456568.XA patent/CN111514900B/en active Active
Patent Citations (7)
| 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 |
| 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 (1)
| Title |
|---|
| 合成氨催化剂的研究进展及展望;梁海仙等;《氮肥技术》;20081225(第06期);第7-9页，下转第30页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111514900A (en) | 2020-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ning et al. | Carbon-based materials with tunable morphology confined Ni (0) and Ni-Nx active sites: Highly efficient selective hydrogenation catalysts | |
| CN100457615C (en) | Method of removing impurities from metallurgical grade silicon to produce solar grade silicon | |
| JPH0433490B2 (en) | ||
| CN110496969B (en) | Nano tungsten powder and preparation method thereof | |
| CN110016607A (en) | A kind of preparation technology of vanadium nitride iron alloy | |
| CN109004240A (en) | A kind of preparation method of high-specific surface area iron nitrogen C catalyst | |
| CN111167443B (en) | Novel ruthenium-based catalyst and preparation method and application thereof | |
| CN111514900B (en) | Cobalt-yttrium alloy catalyst for synthesizing ammonia at normal temperature and normal pressure and preparation method thereof | |
| CN115041204B (en) | A method and application of improving catalytic degradation of reactive red 195 dye by FePC amorphous alloy | |
| CN1696076A (en) | Method for synthesizing alpha-phase silicon nitride powder by temperature-controlled combustion | |
| CN113351203A (en) | Graphene composite material ammonia synthesis catalyst, preparation method and ammonia preparation method | |
| CN112756014A (en) | Preparation method of nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst | |
| CN115025780B (en) | A kind of ternary copper powder catalyst for organosilicon monomer preparation and preparation method thereof | |
| CN115159510B (en) | Graphene heat conduction film and method for efficiently producing graphene heat conduction film | |
| CN116328816A (en) | Preparation method of monoatomic silver doped graphite phase carbon nitride catalyst | |
| CN110743572B (en) | Raney silver catalyst and preparation method and application thereof | |
| CN114457209A (en) | Process method for reducing oxygen content in prealloyed matrix powder smelting process | |
| CN111910290B (en) | A kind of cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution and its preparation method and application | |
| CN101269978B (en) | Method for Combustion Synthesis of Ultrafine Magnesium Nitride Powder | |
| CN114074186A (en) | A kind of preparation method of spherical atomized magnesium-silicon-based multi-component alloy powder and obtained alloy powder | |
| CN115852202B (en) | Sc-Sn based self-inoculated nano-grain composite material suitable for hydrolytic hydrogen production | |
| CN115475617B (en) | Preparation method and application of porous metal copper-doped disordered carbon tube material | |
| CN114604958B (en) | Method for catalytically degrading organic pollutants in wastewater by iron-based amorphous composite material | |
| CN113621864B (en) | Method for directly smelting nitrided ferrovanadium or ferrovanadium from high-temperature vanadium slag without chemical process | |
| CN108745339A (en) | A kind of NaBH4The catalyst and preparation method of fuel cell hydrogen processed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |