CN110652991A - Molybdenum carbide/cerium oxide catalyst for ammonia synthesis and preparation method thereof - Google Patents
Molybdenum carbide/cerium oxide catalyst for ammonia synthesis and preparation method thereof Download PDFInfo
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- CN110652991A CN110652991A CN201911033520.1A CN201911033520A CN110652991A CN 110652991 A CN110652991 A CN 110652991A CN 201911033520 A CN201911033520 A CN 201911033520A CN 110652991 A CN110652991 A CN 110652991A
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- 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
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Abstract
The invention discloses a molybdenum carbide/cerium oxide catalyst for ammonia synthesis and a preparation method thereof, wherein cerium oxide is used as a carrier, a molybdenum precursor is introduced onto cerium oxide particles, and the cerium oxide particles are carbonized at high temperature in a carbon-containing mixed gas to obtain the molybdenum carbide/cerium oxide catalyst for ammonia synthesis.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a molybdenum carbide/cerium oxide catalyst for ammonia synthesis and a preparation method thereof.
Background
In the ammonia synthesis reaction, the traditional industrial iron-based catalyst must operate under the condition of high temperature and high pressure (> 15 MPa, >450 ℃) for synthesizing ammonia, and the ton energy consumption is high.
The dissociation of nitrogen-nitrogen bonds in ammonia synthesis reactions is generally considered to be a reaction rate controlling step, and molybdenum has a better nitrogen dissociation ability than iron ruthenium, and thus has been sought as an active component of ammonia synthesis catalysts. Aika et al (Molybdenum nitride and carbide catalysts for ammonia synthesis. applied catalysis A: General 219 (2001) 141-147) found that pure Molybdenum carbide has higher catalytic activity than Molybdenum nitride and is more suitable as an active component of an ammonia synthesis catalyst. However, the pure molybdenum carbide catalyst has a low specific surface area and a few pore channels, which are not favorable for the adsorption, reaction and diffusion of reactants and products on the catalyst, so the ammonia synthesis performance of the catalyst cannot be fully exerted. As an important rare earth oxide, cerium oxide has the characteristics of high thermal stability, rich and adjustable oxygen defects and unique electronic property, can be applied to multiple fields of catalysis, electrochemistry, optics and the like, and is an important carrier material and an important catalyst active component. The invention takes cerium oxide as a carrier, molybdenum carbide grows in situ on the cerium oxide, and the molybdenum carbide serving as an active component for supporting and dispersing the catalyst is utilized to prepare the molybdenum carbide-cerium oxide ammonia synthesis catalyst, wherein the ammonia synthesis reaction activity of the catalyst is equivalent to that of a cerium oxide loaded ruthenium-based catalyst, and the catalyst has good application prospect.
Disclosure of Invention
The invention aims to provide a molybdenum carbide-cerium oxide catalyst for ammonia synthesis, which has high ammonia synthesis activity, does not need to add a ruthenium active component, and has good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a Mo carbide/Ce oxide catalyst for ammonia synthesis is CeO2As a carrier, Mo2C is formed by active components; wherein the molybdenum content is 5wt.% to 75 wt.%.
The preparation method of the molybdenum carbide/cerium oxide catalyst comprises the following steps:
(1) dissolving a molybdenum precursor in an ammonia water solution to prepare a molybdenum precursor solution;
(2) introducing a molybdenum precursor solution onto cerium oxide particles to obtain a mixture of the molybdenum precursor solution and the cerium oxide particles;
(3) putting the mixture obtained in the step (2) into oxygen-containing mixed gas for heat treatment;
(4) and (4) putting the mixture after the heat treatment into carbon-containing mixed gas for high-temperature carbonization.
The precursor of the molybdenum in the step (1) is any one of ammonium molybdate and molybdic acid or a mixture of the two. The concentration of the aqueous ammonia solution is 2wt.% to 15 wt.%.
The heat treatment in the step (3) is carried out in oxygen-containing mixed gas, the treatment temperature is 30-600 ℃, the treatment time is 0.2-10 h, the volume content of oxygen in the oxygen-containing mixed gas is 3% ~ 100%, and the oxygen is specifically air or gas consisting of oxygen and 0 group inert gas.
In the carbon-containing mixed gas in the step (4), the volume content of carbon-containing gas is 10-50%, the volume content of hydrogen is 40-90%, and the balance is one or more of nitrogen and group 0 inert gas;
the carbon-containing gas is one or more of methane, ethane, propane, acetylene and propyne.
The temperature of the high-temperature carbonization in the step (4) is 300-1000 ℃, and the carbonization time is 0.5-10 h.
The invention has the following remarkable advantages:
the invention prepares the molybdenum carbide/cerium oxide catalyst by in-situ growing molybdenum carbide on cerium oxide particles. The catalyst has low preparation cost, does not need to add ruthenium active components, but has the ammonia synthesis activity equivalent to that of a ruthenium-based ammonia synthesis catalyst, thereby having better application prospect.
Drawings
FIG. 1 is an XRD pattern of a sample of the catalyst obtained in examples 1 to 3 and comparative examples 1 to 2.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1:
dissolving 4.1 g of ammonium molybdate in an ammonia solution prepared from 5 ml of deionized water and 2 ml of ammonia (28 wt.%), so as to obtain a molybdenum precursor solution; soaking 4 g of cerium oxide particles in the molybdenum precursor solution in the same volume, treating the cerium oxide particles in air (the oxygen content is about 21 percent) at 500 ℃ for 4 h, then putting the cerium oxide particles in a nitrogen-hydrogen mixed gas containing methane (the volume content of methane in the mixed gas is 15 percent, the volume content of hydrogen is 60 percent, and the rest gas is nitrogen) for carbonizing at 700 ℃ for 2 h, and cooling to obtain Mo2C/CeO2Catalyst, wherein the content of molybdenum is 35%.
Example 2:
dissolving 4.1 g of ammonium molybdate in an ammonia solution prepared from 5 ml of deionized water and 2 ml of ammonia (28 wt.%), so as to obtain a molybdenum precursor solution; 4 g of cerium oxide particles were immersed in the molybdenum precursor solution in an equal volume, and then the solution was immersed in air (containing about 21% oxygen)Treating at 50 deg.C for 1 hr, carbonizing at 500 deg.C for 6 hr in mixed gas of ethane and nitrogen (the mixed gas contains ethane 20 vol%, hydrogen 60 vol%, and nitrogen gas as the rest), and cooling to obtain Mo2C/CeO2Catalyst, wherein the content of molybdenum is 35%.
Example 3
Dissolving 3 g of ammonium molybdate in an ammonia solution prepared from 3.7 ml of deionized water and 1.5 ml of ammonia (28 wt.%), so as to obtain a molybdenum precursor solution; soaking 4 g of cerium oxide particles in the molybdenum precursor solution in the same volume, treating the prepared sample in oxygen-containing mixed gas (the volume content of oxygen in the oxygen-containing mixed gas is 10%, and the rest gas is argon) at 300 ℃ for 3 h, then putting the sample in hydrogen-argon mixed gas containing propane (the volume content of propane in the mixed gas is 30%, the volume content of hydrogen is 40%, and the rest gas is argon) for carbonization at 600 ℃ for 4 h, and cooling to obtain Mo2C/CeO2Catalyst, wherein the content of molybdenum is 28%.
Example 4
Dissolving 2 g of ammonium molybdate in an ammonia solution prepared from 2.5 ml of deionized water and 1 ml of ammonia (28 wt.%), so as to obtain a molybdenum precursor solution; soaking 4 g of cerium oxide particles in the molybdenum precursor solution in the same volume, treating the prepared sample in an oxygen-containing mixed gas (the volume content of oxygen in the oxygen-containing mixed gas is 20%, the rest gas is argon) at 450 ℃ for 6 h, then putting the sample in a hydrogen-argon mixed gas (the volume content of acetylene in the mixed gas is 30%, the volume content of hydrogen is 50%, and the rest gas is argon) containing acetylene, carbonizing the sample at 600 ℃ for 7 h, and cooling to obtain Mo2C/CeO2Catalyst, wherein the content of molybdenum is 21%.
Example 5
Dissolving 8 g of ammonium molybdate in an ammonia solution prepared from 10 ml of deionized water and 4 ml of ammonia (28 wt.%), so as to obtain a molybdenum precursor solution; soaking 4 g of cerium oxide particles in the molybdenum precursor solution in the same volume, treating the prepared sample in pure oxygen at 100 ℃ for 4 h, then putting the sample in a hydrogen-argon mixed gas containing propyne (the volume content of the propyne in the mixed gas is 10%, the volume content of hydrogen is 70%, and the rest gas is argon), carbonizing the sample at 400 ℃ for 8 h, and cooling to obtain Mo2C/CeO2Catalyst, wherein the content of molybdenum is 50%.
Comparative example 1
Dissolving 0.041 g of ammonium molybdate in an ammonia water solution prepared from 5 ml of deionized water and 2 ml of ammonia water (28 wt.%), so as to obtain a molybdenum precursor solution; soaking 4 g of cerium oxide particles in the molybdenum precursor solution in the same volume, treating the cerium oxide particles in air (the oxygen content is about 21 percent) at 500 ℃ for 4 h, then putting the cerium oxide particles in a nitrogen-hydrogen mixed gas containing methane (the volume content of methane in the mixed gas is 15 percent, the volume content of hydrogen is 60 percent, and the rest gas is nitrogen) for carbonizing at 700 ℃ for 2 h, and cooling to obtain Mo2C/CeO2Catalyst, wherein the content of molybdenum is 0.5%.
Comparative example 2
4 g of cerium nitrate hexahydrate is dissolved in 5 ml of deionized water to obtain a cerium salt solution, 4.1 g of ammonium molybdate is dissolved in 10 ml of deionized water to obtain a molybdenum precursor solution, and the cerium salt solution and the molybdenum precursor solution are mixed and dried at 100 ℃. The resulting mixture was treated at 550 ℃ for 4 h under an air atmosphere. And putting the calcined sample in a tubular reaction furnace, introducing a nitrogen-hydrogen mixed gas containing methane (the volume content of methane in the mixed gas is 15%, the volume content of hydrogen is 60%, and the rest gas is nitrogen) into the tubular reaction furnace, carbonizing the sample at 700 ℃ for 2 hours, and cooling the sample to obtain the ammonia synthesis catalyst, wherein the content of molybdenum is 58%.
Comparative example 3
Dissolving 4.1 g of ammonium molybdate in an ammonia solution prepared from 5 ml of deionized water and 2 ml of ammonia (28 wt.%), so as to obtain a molybdenum precursor solution; soaking 4 g of cerium oxide particles in the molybdenum precursor solution in the same volume, treating the solution in air (the oxygen content is about 21 percent) at 500 ℃ for 4 h, reducing the solution in nitrogen-hydrogen (the volume content of hydrogen in the nitrogen-hydrogen is 60 percent, and the rest gas is nitrogen) at 500 ℃ for 6 h, and cooling to obtain Mo/CeO2Catalyst, wherein the content of molybdenum is 35%.
Comparative example 4
Taking 4 g of cerium oxide particles, taking nitroso ruthenium nitrate as a ruthenium metal precursor, carrying out loading by an isometric immersion method, reducing for 6 h at 500 ℃ in nitrogen-hydrogen gas (the volume content of the hydrogen gas is 60 percent, and the rest gas is nitrogen gas), wherein the heating rate isThe ruthenium-based catalyst Ru/CeO with the loading of 1wt percent is obtained at the speed of 10 ℃/min2。
FIG. 1 is an XRD pattern of a sample of the catalyst obtained in examples 1 to 3 and comparative examples 1 to 2. As can be seen from the figure, the catalyst samples obtained in examples 1-3 all have the characteristic diffraction peaks of molybdenum carbide and cerium oxide, while the characteristic diffraction peaks of cerium oxide can be observed only in comparative example 1, the very weak diffraction peaks of cerium oxide can be observed only in comparative example 2, and no obvious characteristic peak of molybdenum carbide can be observed, which indicates that molybdenum carbide can be grown on the surface of cerium oxide by the method of the present invention.
The evaluation of the activity of the catalyst was carried out in a high-pressure activity test apparatus, the reactor being a fixed bed having an inner diameter of 12 mm. In the test process, 0.2 g of catalyst sample and quartz sand with the same particle size are mixed according to the volume ratio of 1:20 and are filled in an isothermal zone of a reactor. The reaction gas is a nitrogen-hydrogen mixed gas obtained by ammonia high-temperature catalytic cracking, and the ratio of hydrogen to nitrogen is 3: 1; the reaction conditions are as follows: the pressure is 1 MPa, the reaction temperature is 400 ℃, and the reaction space velocity is 3.6 multiplied by 104 cm3·g-1 h-1. The catalyst performance results are shown in table 1.
TABLE 1 comparison of Performance results for catalyst samples from example 1 ~ 3 and comparative example 1 ~ 3
As can be seen from the table, under the same conditions, the ammonia synthesis rate of the catalyst of the invention is higher than that of the cerium oxide supported molybdenum catalyst with the same loading, and is close to 1wt% of Ru/CeO2A catalyst. To prepare 1g of 1wt% Ru/CeO2The cost of ruthenium metal alone in the catalyst is as high as 13.6 yuan, in contrast to the preparation of Mo with 50% molybdenum content2C/CeO2The cost of the molybdenum metal required for the catalyst is only 1.4 yuan. Therefore, the catalyst obtained by the invention has higher catalytic activity, low preparation cost and better industrial application prospect.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A molybdenum carbide/cerium oxide catalyst for ammonia synthesis is characterized in that the catalyst is CeO2As a carrier, Mo2C is formed by active components; wherein the molybdenum content is 5wt.% to 75 wt.%.
2. A process for preparing the Mo/Ce carbide/Ce oxide catalyst used for synthesizing ammonia includes such steps as dissolving the Mo precursor in the ammonia solution to obtain Mo precursor solution, introducing it to the Ce oxide particles, heat treating, and high-temp carbonizing in the mixed gas containing carbon.
3. The method of claim 2, wherein the molybdenum precursor is one or a mixture of ammonium molybdate and molybdic acid.
4. The method of preparing a molybdenum carbide/cerium oxide catalyst according to claim 2, wherein the aqueous ammonia solution has a concentration of 2wt.% to 15 wt.%.
5. The method for preparing the molybdenum carbide/cerium oxide catalyst according to claim 2, wherein the heat treatment is performed in an oxygen-containing mixed gas at a treatment temperature of 30 to 600 ℃ for 0.2 to 10 hours;
the oxygen-containing mixed gas contains 3% ~ 100% of oxygen by volume and is specifically gas composed of air or oxygen and 0 group inert gas.
6. The method of claim 2, wherein the carbon-containing gas mixture comprises 10 to 50% by volume of carbon-containing gas, 40 to 90% by volume of hydrogen gas, and the balance of one or more of nitrogen gas and group 0 inert gas;
the carbon-containing gas is one or more of methane, ethane, propane, acetylene and propyne.
7. The method of claim 2, wherein the temperature of the high temperature carbonization is 300-1000 ℃ and the carbonization time is 0.5-10 h.
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Cited By (4)
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| CN111450843A (en) * | 2020-01-21 | 2020-07-28 | 福州大学 | High-efficiency Ru/Co limited-area ammonia synthesis catalyst and preparation method and application thereof |
| CN111468110A (en) * | 2020-04-21 | 2020-07-31 | 王永芝 | Gas-solid phase reaction double-noble metal catalyst and preparation method thereof |
| CN113058658A (en) * | 2021-03-15 | 2021-07-02 | 福州大学 | Super-hydrophobic molybdenum-loaded catalyst and preparation method and application thereof |
| CN115672365A (en) * | 2022-08-29 | 2023-02-03 | 福州大学 | High-efficiency mild synthetic ammonia catalyst and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111450843A (en) * | 2020-01-21 | 2020-07-28 | 福州大学 | High-efficiency Ru/Co limited-area ammonia synthesis catalyst and preparation method and application thereof |
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| CN113058658A (en) * | 2021-03-15 | 2021-07-02 | 福州大学 | Super-hydrophobic molybdenum-loaded catalyst and preparation method and application thereof |
| CN113058658B (en) * | 2021-03-15 | 2022-02-22 | 福州大学 | Super-hydrophobic molybdenum-loaded catalyst and preparation method and application thereof |
| CN115672365A (en) * | 2022-08-29 | 2023-02-03 | 福州大学 | High-efficiency mild synthetic ammonia catalyst and preparation method and application thereof |
| CN115672365B (en) * | 2022-08-29 | 2024-08-13 | 福州大学 | High-efficiency and mild synthetic ammonia catalyst and preparation method and application thereof |
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