CN112058277A - High-activity catalyst for ammonia synthesis and preparation method thereof - Google Patents

High-activity catalyst for ammonia synthesis and preparation method thereof Download PDF

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CN112058277A
CN112058277A CN202011078355.4A CN202011078355A CN112058277A CN 112058277 A CN112058277 A CN 112058277A CN 202011078355 A CN202011078355 A CN 202011078355A CN 112058277 A CN112058277 A CN 112058277A
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ruthenium
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CN112058277B (en
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林炳裕
李春艳
江莉龙
林建新
倪军
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Fuzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • 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
    • 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
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    • 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 high-activity catalyst for ammonia synthesis and a preparation method thereof, wherein cobalt grows on a cerium oxide carrier in situ, ruthenium is introduced, and then ruthenium and cobalt double metals are used as active components to prepare the high-activity catalyst for ammonia synthesis. The catalyst obtained by the invention has higher ammonia synthesis activity and better application prospect.

Description

High-activity catalyst for ammonia synthesis and preparation method thereof
Technical Field
The invention belongs to the technical field of ammonia synthesis catalysts, and particularly relates to a high-activity catalyst for ammonia synthesis and a preparation method thereof.
Background
Ammonia is an important chemical intermediate in the production process of agricultural fertilizers, plastics, medicines, explosives and other chemicals. Ammonia is a nearly ideal hydrogen storage material due to its considerable hydrogen capacity of 17.6 wt% and its ease of condensation to a liquid state for storage or transport. At the same time, 4.3 kWh h–1High energy density and zero carbon emissions make ammonia an ideal energy carrier even as a replacement for hydrogen in future energy economies. Accordingly, the importance of ammonia in the field of new energy is becoming more and more significant, and there is a great deal of interest in developing environmentally friendly ammonia synthesis processes.
As is well known, N2Dissociation of (b) is a rate-controlled step of ammonia synthesis. Based on the volcano-type curve relationship, Ru metal having better nitrogen adsorption dissociation capability is considered as the most ideal active component of ammonia synthesis catalyst, but ruthenium-based catalyst has high cost and stability. In the volcano-type curve, the binding energy of pure Co and nitrogen species is much lower than that of Ru, which means that the adsorption energy of Co to nitrogen is small, and N is small2The energy barrier for dissociation is large, and therefore, when Co alone is used as an active metal, the ammonia synthesis activity of the catalyst is weak.
In order to prepare a high efficiency catalyst, the relationship of the catalyst to the adsorption energy of reactants and intermediates must be broken. Double active site catalysts (LiH-TM) were prepared by Chen et al (Chen, P.; Gao, W.; Wang, P. et al. Barium Hydride-Mediated Nitrogen Transfer and Hydrogenation for Ammonia Synthesis: A Case Study of cobalt Act. ACS Cat. 2017, 7 (5): 3654-3661.), and the activity of the catalyst was best when Co metal was present in the LiH-TM catalyst. The patent (CN 107376996A) reports a ruthenium-cobalt bimetallic nano-supported catalyst for ammonia borane hydrogen hydrolysis and a preparation method thereof, and the catalyst is mainly characterized in that an MIL-110 carrier is prepared by a hydrothermal synthesis method, ruthenium salt and cobalt salt are added into an MIL-110 aqueous solution, and NaBH is added finally4Obtaining a catalyst with MIL-110 as a carrier and Ru-Co as an active component, namely RuCo @ MIL-110 catalyst, wherein the molar ratio of ruthenium metal to cobalt metalThe molar ratio is 1:1, and the catalyst shows good catalytic performance in ammonia borane hydrogen hydrolysis, and has extremely high toxicity resistance and cycle stability.
In the existing preparation process of the ruthenium-cobalt bimetallic catalyst, two active metal precursors are usually mixed and added into a carrier, and the difference of the interaction between the two metals and the carrier can influence the catalytic effect of the active metals. In the ammonia synthesis catalyst using cerium oxide as a carrier, cobalt and ruthenium metals are introduced to prepare the double-activity center catalyst, so that the interaction between the metal carriers can be changed, and the synergistic effect of the double-activity centers is expected to improve the ammonia synthesis reaction performance.
Disclosure of Invention
Aiming at the defects of the existing Ru catalyst, the invention provides a high-activity catalyst for ammonia synthesis and a preparation method thereof, which can efficiently catalyze the synthesis of ammonia.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-activity catalyst for ammonia synthesis is prepared through in-situ growing Co on cerium oxide carrier, introducing Ru to form a catalyst with Ru and Co bimetal as active component; wherein, the loading amount of cobalt is 0.003-1.7 wt% and the loading amount of ruthenium is 0.1-20 wt% based on the mass of cerium oxide.
The preparation method of the high-activity catalyst comprises the following steps:
1) mixing a cobalt precursor and a cerium precursor, and dissolving the mixture in deionized water to prepare a mixed solution;
2) mixing the mixed solution obtained in the step 1) with an alkaline solution, uniformly stirring, carrying out a hydrothermal reaction for a period of time to obtain a solid solution, washing and drying the solid solution, and calcining the solid solution;
3) dipping the sample obtained in the step 2) by using a ruthenium precursor solution, and reducing to obtain the high-activity catalyst.
In the step 1), the cerium precursor is any one of cerium oxalate, cerium nitrate and cerium acetate; the cobalt precursor is any one of cobalt nitrate, cobalt oxalate and cobalt chloride; the concentration of Ce ions in the mixed solution is 0.1-0.5 mol/L.
The volume ratio of the alkaline solution to the mixed solution in the step 2) is 8:1-2: 1; the alkaline solution is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and the concentration of the alkaline solution is 6-10 mol/L.
The stirring time in the step 2) is 0.5-8 hours; the temperature of the hydrothermal reaction is 60-180 ℃ and the time is 1-36 hours; the drying temperature is 60-120 ℃, and the drying time is 0.5-18 hours; the calcining temperature is 250-600 ℃ and the time is 0.5-6 hours.
The ruthenium precursor solution in the step 3) is prepared by taking any one of ruthenium chloride, ruthenium carbonyl and ruthenium nitrosyl nitrate as a solute and taking any one or two of methanol, ethanol and water as a solvent; the concentration of Ru ions in the ruthenium precursor solution is 1 g/L-20 g/L, and the volume ratio of alcohol in the solvent is not lower than 50%.
Reducing by using a hydrogen-containing mixed gas in the step 3), wherein the volume of the hydrogen accounts for 1-100%, and the balance is argon or nitrogen; the temperature of the reduction is 150 ℃ and 600 ℃, and the time is 0.1-36 hours.
The invention has the following remarkable advantages:
in the preparation process of the ruthenium-cobalt bimetallic catalyst, cobalt grows on a cerium oxide carrier in situ, and the ruthenium precursor is introduced after washing and calcining, so that the catalyst prepared by the method has proper metal carrier interaction. With single metal supported Ru/CeO2、Co/CeO2Compared with the ruthenium-cobalt bimetallic catalyst prepared by adding the traditional bimetal together, the catalyst prepared by the invention shows better ammonia synthesis performance and has better industrial application prospect.
Drawings
FIG. 1 shows a cerium oxide support and the catalyst 0.5RuCo prepared in example 2 and comparative example 10.15/Ce、0.5Ru/CeO2Raman mapping of (a).
FIG. 2 shows the RuCo 0.5 catalyst prepared in example 2 and comparative example 10.15Ce with 0.5Ru/CeO2H of (A) to (B)2-TPD mass spectrum.
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:
2.538 g of cerium acetate and 23 mg of cobalt nitrate are mixed and dissolved in 20 mL of deionized water to form a mixed solution, and 38.4 g of NaOH is dissolved in 140 mL of distilled water to form an alkaline solution; then mixing and stirring the two solutions for 1 hour, and carrying out hydrothermal reaction for 6 hours at 160 ℃ to obtain a solid solution; after the solid solution is washed to be neutral, the solid solution is dried at 100 ℃ overnight and calcined at 400 ℃ for 1 hour, and then the obtained sample is soaked in 10 g/L ruthenium carbonyl alcohol solution for 3 hours; then in H with a hydrogen volume concentration of 10%2Reducing the mixed gas of-Ar for 4 hours at the temperature of 600 ℃ to obtain the catalyst 1RuCo0.1The amount of added ruthenium metal and cobalt metal in the catalyst was 1% and 0.1% respectively, based on the mass of cerium oxide.
Example 2:
1.736 g of cerium nitrate and 2.6 mg of cobalt chloride are mixed and dissolved in 30 mL of deionized water to form a mixed solution, and 20 g of KOH is dissolved in 60 mL of distilled water to form an alkaline solution; then mixing and stirring the two solutions for 0.5 hour, and carrying out hydrothermal reaction at 100 ℃ for 24 hours to obtain a solid solution; after the solid solution is washed to be neutral, the solid solution is dried for 2 hours at 80 ℃, calcined for 2 hours at 550 ℃, and the obtained sample is soaked for 2 hours by adopting 15 g/L of nitrosyl ruthenium nitrate alcohol solution; then pure hydrogen is used for reduction for 2 hours at 500 ℃ to obtain a catalyst 0.5RuCo0.15The amounts of added ruthenium metal and cobalt metal in the catalyst were 0.5% and 0.15%, respectively, based on the mass of cerium oxide.
Example 3:
3.472 g of cerium nitrate and 2.3 mg of cobalt nitrate are mixed and dissolved in 40mL of deionized water to form a mixed solution, and 38.4 g of NaOH is dissolved in 140 mL of distilled water to form an alkaline solution; then mixing and stirring the two solutions for 2 hours, and carrying out hydrothermal reaction for 24 hours at 100 ℃ to obtain a solid solution; washing the solid solution to neutrality, drying at 80 deg.C for 2 hr, and calcining at 550 deg.CAfter 2 hours of burning, the obtained sample is soaked for 2 hours by adopting 5 g/L ruthenium chloride alcoholic solution; then at 10% H2-3.3% N2Reducing the mixed gas of-86.7 percent Ar for 4 hours at 350 ℃ to obtain a catalyst 0.5RuCo0.05The addition amounts of ruthenium metal and cobalt metal in the catalyst were 0.5% and 0.05%, respectively, calculated on the basis of the mass of cerium oxide.
Example 4:
4.352 g of cerium oxalate and 7.5 mg of cobalt acetate are mixed and dissolved in 40mL of deionized water to form a mixed solution, and 38.4 g of KOH is dissolved in 140 mL of distilled water to form an alkaline solution; then mixing and stirring the two solutions for 2 hours, and carrying out hydrothermal reaction for 24 hours at 100 ℃ to obtain a solid solution; after the solid solution is washed to be neutral, the solid solution is dried for 2 hours at 80 ℃, and calcined for 2 hours at 550 ℃, and the obtained sample is soaked for 4 hours by adopting 5 g/L ruthenium chloride alcoholic solution; then pure hydrogen is used for reduction for 6 hours at 400 ℃ to obtain a catalyst 3RuCo1The amount of added ruthenium metal and cobalt metal in the catalyst was 3% and 1%, respectively, based on the mass of cerium oxide.
Comparative example 1:
2.538 g of cerium acetate is dissolved in 20 mL of deionized water to form a cerium acetate solution, and 38.4 g of NaOH is dissolved in 140 mL of deionized water to form an alkaline solution; then mixing and stirring the two solutions for 2 hours, and carrying out hydrothermal reaction for 24 hours at 100 ℃ to obtain a solid solution; washing the solid solution to neutrality, drying at 80 deg.C for 2 hr, calcining at 550 deg.C for 2 hr to obtain CeO2Soaking the carrier in 10 g/L ruthenium carbonyl alcohol solution for 3 hours; then in H with a hydrogen volume concentration of 10%2Reducing the mixture in an-Ar mixed gas at 550 ℃ for 4 hours to obtain a catalyst of 0.5Ru/CeO2The amount of ruthenium metal added to the catalyst was 0.5% by mass based on the mass of cerium oxide.
Comparative example 2:
dissolving 2.327g of cerium nitrate in 40mL of deionized water to form a cerium nitrate solution, and dissolving 38.4 g of NaOH in 140 mL of deionized water to form an alkaline solution; then mixing and stirring the two solutions for 2 hours, and carrying out hydrothermal reaction for 24 hours at 100 ℃ to obtain a solid solution; will be provided withWashing the solid solution to neutrality, drying at 80 deg.C for 2 hr, calcining at 500 deg.C for 2 hr to obtain CeO2Soaking the carrier in a cobaltous nitrate alcohol solution of 3g/L for 4 hours; then in H with a hydrogen volume concentration of 10%2Reducing the mixture in-Ar mixed gas at 600 ℃ for 4 hours to obtain the catalyst 0.5Co/CeO2The amount of cobalt metal added to the catalyst was 0.5% by mass based on the mass of cerium oxide.
Comparative example 3:
2.538 g of cerium acetate is dissolved in 20 mL of deionized water to form a cerium acetate solution, and 38.4 g of NaOH is dissolved in 140 mL of deionized water to form an alkaline solution; then mixing and stirring the two solutions for 2 hours, and carrying out hydrothermal reaction at 80 ℃ for 24 hours to obtain a solid solution; washing the solid solution to neutrality, drying at 80 deg.C for 2 hr, calcining at 550 deg.C for 2 hr to obtain CeO2Soaking the carrier in 5 g/L cobaltous chloride alcoholic solution for 2 hours; calcining the mixture in air at 550 ℃ for 4 hours, and soaking the mixture for 2 hours by adopting a 10 g/L ruthenium carbonyl alcohol solution; finally, H with the hydrogen volume concentration of 10 percent is used2Reducing the-Ar mixed gas at 350 ℃ for 4 hours to obtain the catalyst 0.5Ru/Co0.15/CeO2The amounts of ruthenium metal and cobalt metal added to the catalyst were 0.5% and 0.15%, respectively, based on the mass of cerium oxide.
Comparative example 4:
2.538 g of cerium acetate and 23 mg of cobalt nitrate are mixed and dissolved in 20 mL of ethanol to form a mixed solution, and 38.4 g of NaOH is dissolved in 140 mL of deionized water to form an alkaline solution; then mixing and stirring the two solutions for 1 hour, and carrying out hydrothermal reaction for 6 hours at 160 ℃ to obtain a solid solution; washing the solid solution to be neutral, drying the solid solution at 100 ℃ overnight, and calcining the solid solution at 400 ℃ for 1 hour; then the obtained sample is reduced by pure hydrogen for 6 hours at 500 ℃ to obtain the catalyst Co0.15Ce, the amount of cobalt metal added to the catalyst was 0.15% based on the mass of cerium oxide.
Comparative example 5:
1.736 g of cerium nitrate and 52 mg of cobalt chloride are mixed and dissolved in 30 mL of deionized water to form a mixed solution, and 20 g of KOH is dissolved in 60 mL of deionized waterTo form an alkaline solution; then mixing and stirring the two solutions for 0.5 hour, and carrying out hydrothermal reaction at 120 ℃ for 24 hours to obtain a solid solution; after the solid solution is washed to be neutral, the solid solution is dried for 2 hours at the temperature of 60 ℃, and calcined for 2 hours at the temperature of 500 ℃, and the obtained sample is soaked for 3 hours by adopting 15 g/L of nitrosyl ruthenium nitrate alcohol solution; then pure hydrogen is used for reduction for 2 hours at the temperature of 450 ℃ to obtain a catalyst 1RuCo3The amount of added ruthenium metal and cobalt metal in the catalyst was 1% and 3%, respectively, based on the mass of cerium oxide.
Comparative example 6:
1.736 g of cerium nitrate is dissolved in 30 mL of deionized water, 15 g/L of ruthenium nitrosyl nitrate solution is added to form a mixed solution, and 20 g of KOH is dissolved in 60 mL of distilled water to form an alkaline solution; then mixing and stirring the two solutions for 0.5 hour, and carrying out hydrothermal reaction at 100 ℃ for 24 hours to obtain a solid solution; after the solid solution is washed to be neutral, the solid solution is dried for 2 hours at 80 ℃, and calcined for 2 hours at 550 ℃, and the obtained sample is soaked for 2 hours by using a cobaltous nitrate alcohol solution of 3 g/L; then pure hydrogen is used for reduction for 2 hours at 500 ℃ to obtain a catalyst 0.15CoRu0.5The amounts of added ruthenium metal and cobalt metal in the catalyst were 0.5% and 0.15%, respectively, based on the mass of cerium oxide.
FIG. 1 shows a cerium oxide support and the catalyst 0.5RuCo prepared in example 2 and comparative example 10.15/Ce、0.5Ru/CeO2Raman mapping of (a). As can be seen from the figure, with CeO2In contrast, 0.5Ru/CeO2At 969 cm-1A new peak appeared, which could be attributed to the formation of Ru-O-Ce bonds. And 0.5Ru/CeO2In contrast, 0.5RuCo0.15/CeO2At 969 cm-1The raman peak is stronger, indicating that the addition of Co enhances the interaction of the metal support in the catalyst.
FIG. 2 shows the RuCo 0.5 catalyst prepared in example 2 and comparative example 10.15Ce and 0.5Ru/CeO2H of (A) to (B)2-TPD mass spectrum. As can be seen from the figure, the addition of Co changes the desorption path of hydrogen in the catalyst. Co introduction increases the amount of hydrogen desorbed at high temperature from the catalyst, while the amount of water desorbed decreases, indicating that Co introductionThe active sites of the catalyst for synthesizing ammonia can be increased. Therefore, the introduction of Co changes the interaction between the metal carriers, changes the adsorption property of the catalyst, and thus enhances the activity of the catalyst.
The catalysts obtained in examples 1 to 4 and comparative examples 1 to 6 were evaluated for catalytic activity in a high-pressure activity test apparatus. The reactor is a fixed bed with an inner diameter of 12 mm. During the test, 0.2 g of catalyst was mixed with quartz sand of larger particle size and packed in the isothermal zone of the 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-1The results are shown in Table 1.
TABLE 1 Ammonia Synthesis reaction rates of the catalysts
Figure DEST_PATH_IMAGE002
As can be seen from Table 1, under the conditions of the preparation method of the invention, the ammonia synthesis performance of the catalyst can be improved by adding proper cobalt; meanwhile, in the same ruthenium-cobalt adding range, the ammonia synthesis rate of the catalyst obtained in the embodiment is higher than that of ruthenium-based, cobalt-based and ruthenium-cobalt catalysts synthesized by other methods, and the catalyst has good ammonia synthesis catalytic activity and good 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 (8)

1. A method for preparing a high-activity catalyst for ammonia synthesis is characterized by comprising the following steps: the method comprises the following steps:
1) mixing a cobalt precursor and a cerium precursor, and dissolving the mixture in deionized water to prepare a mixed solution;
2) mixing the mixed solution obtained in the step 1) with an alkaline solution, uniformly stirring, carrying out a hydrothermal reaction for a period of time to obtain a solid solution, washing and drying the solid solution, and calcining the solid solution;
3) dipping the sample obtained in the step 2) by using a ruthenium precursor solution, and reducing to obtain the high-activity catalyst.
2. The method for preparing a high-activity catalyst according to claim 1, wherein: in the step 1), the cerium precursor is any one of cerium oxalate, cerium nitrate and cerium acetate; the cobalt precursor is any one of cobalt nitrate, cobalt oxalate and cobalt chloride; the concentration of Ce ions in the mixed solution is 0.1-0.5 mol/L.
3. The method for preparing a high-activity catalyst according to claim 1, wherein: the volume ratio of the alkaline solution to the mixed solution in the step 2) is 8:1-2: 1; the alkaline solution is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and the concentration of the alkaline solution is 6-10 mol/L.
4. The method for preparing a high-activity catalyst according to claim 1, wherein: the stirring time in the step 2) is 0.5-8 hours; the temperature of the hydrothermal reaction is 60-180 ℃ and the time is 1-36 hours; the drying temperature is 60-120 ℃, and the drying time is 0.5-18 hours; the calcining temperature is 250-600 ℃ and the time is 0.5-6 hours.
5. The method for preparing a high-activity catalyst according to claim 1, wherein: the ruthenium precursor solution in the step 3) is prepared by taking any one of ruthenium chloride, ruthenium carbonyl and ruthenium nitrosyl nitrate as a solute and taking any one or two of methanol, ethanol and water as a solvent; the concentration of Ru ions in the ruthenium precursor solution is 1 g/L-20 g/L, and the volume ratio of alcohol in the solvent is not lower than 50%.
6. The method for preparing a high-activity catalyst according to claim 1, wherein: reducing by using a hydrogen-containing mixed gas in the step 3), wherein the volume of the hydrogen accounts for 1-100%, and the balance is argon or nitrogen; the temperature of the reduction is 150 ℃ and 600 ℃, and the time is 0.1-36 hours.
7. The method for preparing a high-activity catalyst according to claim 1, wherein: calculated by taking the mass of cerium oxide as a reference, the loading amount of cobalt in the high-activity catalyst is 0.003-1.7 wt%, and the loading amount of ruthenium is 0.1-20 wt%.
8. A high activity catalyst for ammonia synthesis obtainable by the process according to any one of claims 1 to 7.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113181926A (en) * 2021-04-28 2021-07-30 福州大学 Ammonia synthesis catalyst of cerium oxide loaded high surface defect cobalt oxide

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789538A (en) * 1987-07-17 1988-12-06 Standard Oil Method of preparing ammonia and ammonia synthesis catalysts
JP2006055752A (en) * 2004-08-20 2006-03-02 Honda Motor Co Ltd Ammonia synthesizing catalyst
CN104936899A (en) * 2013-01-22 2015-09-23 株式会社日本触媒 Ammonia synthesis method and catalyst for ammonia synthesis
CN107008335A (en) * 2017-05-16 2017-08-04 福州大学 A kind of cerium oxide is cobalt-based ammonia synthesis catalyst of carrier and preparation method thereof
CN108579744A (en) * 2018-04-26 2018-09-28 东南大学 It is a kind of load ruthenium cerium Zirconium-base catalyst preparation and application process
CN110102295A (en) * 2019-06-06 2019-08-09 福州大学 A kind of ruthenium catalyst and preparation method thereof for synthesizing ammonia
CN111183115A (en) * 2017-09-25 2020-05-19 国立研究开发法人科学技术振兴机构 Composite oxide, metal support, and ammonia synthesis catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789538A (en) * 1987-07-17 1988-12-06 Standard Oil Method of preparing ammonia and ammonia synthesis catalysts
JP2006055752A (en) * 2004-08-20 2006-03-02 Honda Motor Co Ltd Ammonia synthesizing catalyst
CN104936899A (en) * 2013-01-22 2015-09-23 株式会社日本触媒 Ammonia synthesis method and catalyst for ammonia synthesis
CN107008335A (en) * 2017-05-16 2017-08-04 福州大学 A kind of cerium oxide is cobalt-based ammonia synthesis catalyst of carrier and preparation method thereof
CN111183115A (en) * 2017-09-25 2020-05-19 国立研究开发法人科学技术振兴机构 Composite oxide, metal support, and ammonia synthesis catalyst
CN108579744A (en) * 2018-04-26 2018-09-28 东南大学 It is a kind of load ruthenium cerium Zirconium-base catalyst preparation and application process
CN110102295A (en) * 2019-06-06 2019-08-09 福州大学 A kind of ruthenium catalyst and preparation method thereof for synthesizing ammonia

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BINGYU LIN ET AL.: ""Effect of pretreatment on ceria-supported cobalt catalyst for ammonia synthesis"", 《RSC ADVANCES》 *
BINGYU LIN ET AL.: ""Morphology Effect of Ceria on the Catalytic Performances of Ru/CeO2 Catalysts for Ammonia Synthesis"", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 *
YANG ZHENWEI ET AL.: ""Supported Catalysts with Ru–M (M = Fe, Co, Ni, Mo) Bimetallic Active Centers for Ammonia Synthesis"", 《CHINESE JOURNAL OF CATALYSIS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113181926A (en) * 2021-04-28 2021-07-30 福州大学 Ammonia synthesis catalyst of cerium oxide loaded high surface defect cobalt oxide

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