CN114797894A - Supported ruthenium-nickel alloy ammonia synthesis catalyst and preparation method and application thereof - Google Patents
Supported ruthenium-nickel alloy ammonia synthesis catalyst and preparation method and application thereof Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 83
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 81
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 76
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- NEGBOTVLELAPNE-UHFFFAOYSA-N [Ti].[Ce] Chemical compound [Ti].[Ce] NEGBOTVLELAPNE-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002131 composite material Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 238000011068 loading method Methods 0.000 claims abstract description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 18
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 18
- 239000012279 sodium borohydride Substances 0.000 claims description 18
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910000929 Ru alloy Inorganic materials 0.000 abstract 1
- 229910052684 Cerium Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 3
- IDIFPUPZOAXKOV-UHFFFAOYSA-N azane ruthenium Chemical compound N.[Ru] IDIFPUPZOAXKOV-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000002195 synergetic 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
- B01J23/89—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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—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 also combined with metals, or metal 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- 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
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a supported ruthenium-nickel alloy ammonia synthesis catalyst, and a preparation method and application thereof. In order to realize the close contact of metal ruthenium and nickel in the catalyst, ensure that the ammonia synthesis reaction is carried out at relatively low reaction temperature and pressure and obtain high ammonia gas generation rate, the invention takes ruthenium-nickel alloy as the active component of the catalyst and takes cerium-titanium composite oxide as a carrier. In the catalyst, the molar ratio of ruthenium and nickel atoms is 1 (0.1-0.6), and the loading capacity of ruthenium and nickel alloy on the carrier is 1-8%. The cerium-titanium atomic ratio in the cerium-titanium composite oxide is 1 (1-10). The ruthenium nickel metal atoms in the active components of the catalyst are beneficial to improving the low-temperature low-pressure ammonia synthesis activity of the catalyst, and the strong interaction between the ruthenium nickel alloy and the cerium titanium composite oxide carrier improves the stability of the catalyst. The preparation method provided by the invention is simple, has a good catalytic ammonia synthesis effect, and has an industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a supported ruthenium-nickel alloy ammonia synthesis catalyst, and a preparation method and application thereof.
Background
Ammonia (NH) 3 ) Is a basic chemical raw material related to the national civilization, and is widely applied to the fields of chemical fertilizers, environmental protection, refrigeration and the like. At the same time, NH 3 Has attracted widespread attention as an ideal energy carrier for hydrogen economy and as a future carbon-free fuel. The Haber-Bosch process in industrial nitrogen fixation requires high temperature (400-500 ℃) and high pressure (20-40 MPa). From the domestic process of preparing synthetic ammonia from coal, the consumption of raw materials, steam and equipment respectively accounts for 59%, 15% and 11% of the total cost of the synthetic ammonia. The conventional process consumes a large amount of hydrogen gas because the reaction requires operation at high temperature and high pressure, so that energy consumption is large. In the modern green chemical environment, the renewable N 2 The conversion into ammonia gas as a process for producing green energy and the reverse ammonia decomposition hydrogen production become the current research hotspots.
In order to reduce the high energy consumption required for the ammonia synthesis reaction, it is critical to develop a synthetic ammonia catalyst that has high activity and high stability under mild conditions. Ruthenium-based catalysts have excellent catalytic performance for ammonia synthesis at low temperature and low pressure, and thus have attracted extensive attention in the field of ammonia synthesis. However, ruthenium is a rare metal, and the high price is not favorable for the application and popularization of industrial tests. How to accurately construct an active site, improve the catalytic performance and improve the economy of metal ruthenium atoms is a technical problem to be solved when ruthenium-based catalysts are applied to industry.
Currently, a second metal is added to a ruthenium-based catalyst to reduce the amount of ruthenium used and improve the catalytic performance by the synergistic catalytic effect of bimetallic and metallic ruthenium. In 2006, Yang et al reported that ruthenium-based Ammonia synthesis Catalysts containing the second metals iron, cobalt, nickel, molybdenum have excellent activity (Yang, Z.; Guo, W.; Lin, J.; Liao, D.Supported Catalysts with Ru-M (M: Fe, Co, Ni, Mo) Bimetallic Active Centers for Ammonia synthesis, Chinese.J.Catal.2006,27,378- & 380). Chinese patent CN112058277A discloses a high activity catalyst for ammonia synthesis and a preparation method thereof, the catalyst for ammonia synthesis is prepared by taking ruthenium and cobalt double metals as active components, and the ammonia synthesis has high activity at low temperature and low pressure.
Ruthenium nickel catalysts have shown higher activity in ammonia synthesis reactions. However, the ruthenium-nickel-based ammonia synthesis catalyst prepared by the conventional co-impregnation method cannot ensure that metal ruthenium and metal nickel on the catalyst are completely and tightly contacted, and isolated metal ruthenium and metal nickel sites often exist, so that the catalyst cannot fully form ruthenium-nickel bimetallic active components. The invention adopts a method for directly and directionally preparing the ruthenium-nickel alloy, accurately constructs the metal ruthenium-nickel alloy to ensure that the metal ruthenium-nickel alloy has a specific active site, and improves the performance of the ruthenium-based ammonia synthesis catalyst.
Disclosure of Invention
One of the technical problems to be solved by the invention is to construct an ammonia synthesis catalyst taking ruthenium-nickel bimetallic as a catalyst active component. The second technical problem to be solved by the present invention is to provide the above catalyst preparation method, to prepare ruthenium-nickel alloy, and to realize the close contact between ruthenium and nickel. The invention also provides the application of the catalyst in ammonia synthesis reaction, so that the ammonia synthesis reaction is carried out at relatively low reaction temperature and pressure, and high ammonia gas generation rate is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
a supported ruthenium-nickel alloy ammonia synthesis catalyst takes ruthenium-nickel alloy as an active component and takes a cerium-titanium composite oxide as a carrier, and the molar ratio of ruthenium to nickel atoms in the ruthenium-nickel alloy is 1: 0.1 to 0.6, wherein the cerium-titanium atom molar ratio in the cerium-titanium composite oxide is 1: 1-10, and the loading capacity of the ruthenium-nickel alloy on the carrier is 1-8%.
A preparation method of a supported ruthenium-nickel alloy ammonia synthesis catalyst comprises the following steps:
step 1, preparing a cerium-titanium composite oxide carrier:
step 1.1, dissolving cerium nitrate and titanium sulfate in deionized water to obtain a solution, slowly dropwise adding ammonia water into the solution until the pH value reaches 10, and continuously and violently stirring to obtain a precipitate;
step 1.2, filtering, washing and drying the precipitation product obtained in the step 1.1;
step 1.3, roasting the dried product in an air atmosphere to obtain a cerium-titanium composite oxide carrier;
step 2, preparation of the supported ruthenium-nickel alloy ammonia synthesis catalyst:
step 2.1, dispersing the cerium-titanium composite oxide carrier into ethylene glycol, violently stirring, and fully dispersing the cerium-titanium composite oxide carrier to obtain a mixed solution;
2.2, continuously stirring the mixed solution obtained in the step 2.1 under the protection of nitrogen;
step 2.3, adding a sodium borohydride aqueous solution into the mixed solution obtained in the step 2.2, and continuously stirring the mixture in a nitrogen atmosphere;
step 2.4, dropwise adding an aqueous solution containing ruthenium chloride and nickel chloride into the reaction mixture obtained in the step 2.3, and continuously stirring;
and 2.5, after the reaction is finished, separating, washing and drying the obtained precipitate product in vacuum to obtain the supported ruthenium-nickel alloy ammonia synthesis catalyst.
Further, in the step 1.1, the molar ratio of the cerium nitrate to the titanium sulfate is 1: 1-10, wherein the concentration of the cerium nitrate in the solution is 0.01 mol/L.
Further, the temperature of the deionized water in the step 1.1 is 60 ℃, and the stirring time is 4 hours; the drying temperature in the step 1.2 is 110 ℃, and the drying time is 12 hours; the roasting temperature in the step 1.3 is 500-600 ℃, and the roasting time is 4-8 h.
Further, in the step 2.1, the mass fraction of the cerium-titanium composite oxide carrier in the mixed solution is 0.05-0.1%.
Further, in the step 2.2, stirring is continued for 1 hour under the protection of nitrogen at the temperature of 60-80 ℃.
Further, the mass of the sodium borohydride added in the step 2.3 is 50-80% of the mass of the cerium-titanium composite oxide carrier.
Further, in the step 2.4, the total metal content in the aqueous solution of ruthenium chloride and nickel chloride is 5% by mass, the addition amount of ruthenium-nickel atoms is 1-8% by mass of the added cerium-titanium composite oxide, and the molar ratio of ruthenium-nickel atoms is 1: 0.1 to 0.6.
Further, the drying time in the step 2.5 is 60-80 ℃ and 4-12 h.
The application of supported ruthenium-nickel alloy ammonia synthesis catalyst in ammonia synthesis catalytic reaction includes the following reaction conditions: the volume ratio of hydrogen to nitrogen of the reaction raw material gas is 3, the reaction pressure is 5MPa, the reaction temperature is 400 ℃, and the volume space velocity of the reaction gas is 10000h -1 。
Compared with the prior art, the invention has the following advantages:
in the catalyst prepared by the invention, the close contact ruthenium nickel metal atoms are beneficial to improving the low-temperature low-pressure ammonia synthesis activity of the catalyst, and the strong interaction between the ruthenium nickel alloy and the cerium titanium composite oxide carrier improves the stability of the catalyst. The preparation method provided by the invention is simple, has a good catalytic ammonia synthesis effect, and has an industrial application prospect.
Detailed Description
Example 1
A preparation method of a supported ruthenium-nickel alloy ammonia synthesis catalyst comprises the following steps:
step 1, preparing a cerium-titanium composite oxide carrier:
step 1.1, dissolving cerium nitrate and titanium sulfate in deionized water at 60 ℃ to obtain a solution, wherein the molar ratio of the cerium nitrate to the titanium sulfate is 1: 1. The concentration of the cerium nitrate in the solution is 0.01 mol/L.
And step 1.2, slowly dropwise adding ammonia water into the solution until the pH value reaches 10, and continuously and violently stirring for 4 hours to obtain a precipitated product.
Step 1.3, the precipitated product is then filtered, washed and dried at 110 ℃ for 12 h.
And step 1.4, roasting the dried product for 8 hours at 500 ℃ in an air atmosphere to obtain the cerium-titanium composite oxide carrier.
Step 2, preparation of the supported ruthenium-nickel alloy ammonia synthesis catalyst:
and 2.1, dispersing the prepared cerium-titanium composite oxide carrier into ethylene glycol, violently stirring, and fully dispersing the catalyst carrier to obtain a mixed solution, wherein the mass fraction of the catalyst carrier in the mixed solution is 0.05%.
And 2.2, continuously stirring the mixed solution obtained in the step 2.1 for 1 hour at the temperature of 60 ℃ under the protection of nitrogen.
And 2.3, adding a sodium borohydride aqueous solution into the mixed solution obtained in the step 2.2, and continuously stirring the mixture in a nitrogen atmosphere, wherein the amount of the added sodium borohydride is 50% of the mass of the cerium-titanium composite oxide carrier.
Step 2.4, dropwise adding an aqueous solution containing ruthenium chloride and nickel chloride into the reaction mixture, wherein the total metal mass content in the aqueous solution is 5%, the addition amount of ruthenium and nickel (by atomic mass) is 1% of the mass of the added cerium-titanium composite oxide, and the molar ratio of ruthenium and nickel atoms is 1: 0.1, stirring is continued.
And 2.5, after the reaction is finished, separating the obtained precipitate, washing and drying at 60 ℃ in vacuum for 12 hours to obtain the supported ruthenium-nickel alloy ammonia synthesis catalyst.
The supported ruthenium-nickel alloy ammonia synthesis catalyst prepared in the embodiment takes ruthenium-nickel alloy as an active component and takes a cerium-titanium composite oxide as a carrier, wherein the molar ratio of ruthenium to nickel atoms is 1: 0.1, the molar ratio of cerium to titanium atoms is 1:1, the loading of the ruthenium-nickel alloy on the carrier is 1 percent.
The application conditions of the supported ruthenium-nickel alloy ammonia synthesis catalyst in ammonia synthesis catalysis are as follows: the volume ratio of hydrogen to nitrogen of the reaction raw material gas is 3, the reaction pressure is 5MPa, the reaction temperature is 400 ℃, and the volume space velocity of the reaction gas is 10000h -1 . The reaction results are shown in Table 1.
Example 2
A preparation method of a supported ruthenium-nickel alloy ammonia synthesis catalyst comprises the following steps:
step 1, preparing a cerium-titanium composite oxide carrier:
step 1.1, dissolving cerium nitrate and titanium sulfate in deionized water at 60 ℃ to obtain a solution, wherein the molar ratio of the cerium nitrate to the titanium sulfate is 1: 2. The concentration of the cerium nitrate in the solution is 0.01 mol/L.
And step 1.2, slowly dropwise adding ammonia water into the solution until the pH value reaches 10, and continuously and violently stirring for 4 hours to obtain a precipitated product.
Step 1.3, the precipitated product is then filtered, washed and dried at 110 ℃ for 12 h.
And step 1.4, roasting the dried product for 6 hours at 550 ℃ in an air atmosphere to obtain the cerium-titanium composite oxide carrier.
Step 2, preparation of the supported ruthenium-nickel alloy ammonia synthesis catalyst:
and 2.1, dispersing the prepared cerium-titanium composite oxide into ethylene glycol, violently stirring, and fully dispersing a catalyst carrier to obtain a mixed solution, wherein the mass fraction of the catalyst carrier in the mixed solution is 0.06%.
And 2.2, continuously stirring the mixed solution obtained in the step 2.1 for 1 hour at the temperature of 70 ℃ under the protection of nitrogen.
And 2.3, adding the sodium borohydride aqueous solution into the mixed solution obtained in the step 2.2, and continuously stirring the mixture in the nitrogen atmosphere, wherein the amount of the added sodium borohydride is 60 percent of the mass of the cerium-titanium composite oxide carrier.
And 2.4, dropwise adding an aqueous solution containing ruthenium chloride and nickel chloride into the reaction mixture obtained in the step 2.3, wherein the total metal content in the aqueous solution is 5% by mass, the addition amount of ruthenium and nickel (by atomic mass) is 8% of the mass of the added cerium-titanium composite oxide, and the atomic ratio of ruthenium and nickel is 1:0.2, and continuously stirring.
And 2.5, after the reaction is finished, separating the obtained precipitate, washing and drying at 70 ℃ in vacuum for 8 hours to obtain the supported ruthenium-nickel alloy ammonia synthesis catalyst.
The supported ruthenium-nickel alloy ammonia synthesis catalyst prepared in the embodiment takes ruthenium-nickel alloy as an active component and takes a cerium-titanium composite oxide as a carrier, wherein the molar ratio of ruthenium to nickel atoms is 1:0.2, the molar ratio of cerium to titanium atoms is 1:2, the loading of the ruthenium-nickel alloy on the carrier is 8%.
The application conditions of the supported ruthenium-nickel alloy ammonia synthesis catalyst in ammonia synthesis catalysis are as follows: the volume ratio of hydrogen to nitrogen of the reaction raw material gas is 3, the reaction pressure is 5MPa, the reaction temperature is 400 ℃, and the volume space velocity of the reaction gas is 10000h -1 . The reaction results are shown in Table 1.
Example 3
A preparation method of a supported ruthenium-nickel alloy ammonia synthesis catalyst comprises the following steps:
step 1, preparing a cerium-titanium composite oxide carrier:
step 1.1, dissolving cerium nitrate and titanium sulfate in deionized water at 60 ℃ to obtain a mixed solution, wherein the molar ratio of the cerium nitrate to the titanium sulfate is 1: 5. The concentration of the cerium nitrate in the solution is 0.01 mol/L.
And step 1.2, slowly dropwise adding ammonia water into the solution until the pH value reaches 10, and continuously and violently stirring for 4 hours to obtain a precipitated product.
Step 1.3, followed by filtration, washing and drying of the precipitated product obtained in step 1.2 at 110 ℃ for 12 h.
And step 1.4, roasting the dried product for 4 hours at 600 ℃ in an air atmosphere to obtain the cerium-titanium composite oxide carrier.
Step 2, preparation of the supported ruthenium-nickel alloy ammonia synthesis catalyst:
and 2.1, dispersing the prepared cerium-titanium composite oxide into ethylene glycol, violently stirring, and fully dispersing a catalyst carrier to obtain a mixed solution, wherein the mass fraction of the catalyst carrier in the mixed solution is 0.08%.
And 2.2, continuously stirring the mixed solution obtained in the step 2.1 for 1 hour at the temperature of 80 ℃ under the protection of nitrogen.
And 2.3, adding a sodium borohydride aqueous solution into the mixed solution obtained in the step 2.2, and continuously stirring the mixture in a nitrogen atmosphere, wherein the amount of the added sodium borohydride is 80% of the mass of the cerium-titanium composite oxide carrier.
And 2.4, dropwise adding an aqueous solution containing ruthenium chloride and nickel chloride into the reaction mixture, wherein the mass content of total metals in the aqueous solution is 5%, the addition amount of ruthenium and nickel (calculated by the mass of atoms) is 2% of the mass of the added cerium-titanium composite oxide, and the atomic molar ratio of ruthenium and nickel is 1:0.3, and continuously stirring.
And 2.5, after the reaction is finished, separating the obtained precipitate, washing and drying at 80 ℃ in vacuum for 4 hours to obtain the supported ruthenium-nickel alloy ammonia synthesis catalyst.
The supported ruthenium-nickel alloy ammonia synthesis catalyst prepared in the embodiment takes ruthenium-nickel alloy as an active component and takes a cerium-titanium composite oxide as a carrier, wherein the molar ratio of ruthenium to nickel atoms is 1:0.3, the molar ratio of cerium to titanium atoms is 1:5, the loading of the ruthenium-nickel alloy on the carrier is 2%.
The application conditions of the supported ruthenium-nickel alloy ammonia synthesis catalyst in ammonia synthesis catalysis are as follows: the volume ratio of hydrogen to nitrogen of the reaction raw material gas is 3, the reaction pressure is 5MPa, the reaction temperature is 400 ℃, and the volume space velocity of the reaction gas is 10000h -1 . The reaction results are shown in Table 1.
Example 4
A preparation method of a supported ruthenium-nickel alloy ammonia synthesis catalyst comprises the following steps:
step 1, preparing a cerium-titanium composite oxide carrier:
step 1.1, dissolving cerium nitrate and titanium sulfate in deionized water at 60 ℃ to obtain a solution, wherein the molar ratio of the cerium nitrate to the titanium sulfate is 1: 8. The concentration of the cerium nitrate in the solution is 0.01 mol/L.
And step 1.2, slowly dropwise adding ammonia water into the solution obtained in the step 1.1 until the pH value reaches 10, and continuously and violently stirring for 4 hours to obtain a precipitated product.
Step 1.3, the precipitate is then filtered, washed and dried at 110 ℃ for 12 h.
And step 1.4, roasting the dried product for 6 hours at 550 ℃ in an air atmosphere to obtain the cerium-titanium composite oxide carrier.
Step 2, preparation of the supported ruthenium-nickel alloy ammonia synthesis catalyst:
and 2.1, dispersing the prepared cerium-titanium composite oxide into ethylene glycol, violently stirring, and fully dispersing a catalyst carrier to obtain a mixed solution, wherein the mass fraction of the catalyst carrier in the mixed solution is 0.1%.
And 2.2, continuously stirring the mixed solution obtained in the step 2.1 for 1 hour at the temperature of 80 ℃ under the protection of nitrogen.
And 2.3, adding a sodium borohydride aqueous solution into the mixed solution obtained in the step 2.2, and continuously stirring the mixture in a nitrogen atmosphere, wherein the amount of the added sodium borohydride is 80% of the mass of the cerium-titanium composite oxide carrier.
And 2.4, dropwise adding an aqueous solution containing ruthenium chloride and nickel chloride into the reaction mixture, wherein the mass content of total metals in the aqueous solution is 5%, the addition amount of ruthenium and nickel (calculated by the mass of atoms) is 5% of the mass of the added cerium-titanium composite oxide, and the atomic molar ratio of ruthenium and nickel is 1:0.5, and continuously stirring.
And 2.5, after the reaction is finished, separating the precipitate, washing and drying at 70 ℃ in vacuum for 8 hours to obtain the supported ruthenium-nickel alloy ammonia synthesis catalyst.
The supported ruthenium-nickel alloy ammonia synthesis catalyst prepared in the embodiment takes ruthenium-nickel alloy as an active component and takes a cerium-titanium composite oxide as a carrier, wherein the molar ratio of ruthenium to nickel atoms is 1:0.5, the molar ratio of cerium to titanium atoms is 1: and 8, the loading amount of the ruthenium-nickel alloy on the carrier is 5%.
The application conditions of the supported ruthenium-nickel alloy ammonia synthesis catalyst in ammonia synthesis catalysis are as follows: the volume ratio of hydrogen to nitrogen of the reaction raw material gas is 3, the reaction pressure is 5MPa, the reaction temperature is 400 ℃, and the volume space velocity of the reaction gas is 10000h -1 . The reaction results are shown in Table 1.
Example 5
A preparation method of a supported ruthenium-nickel alloy ammonia synthesis catalyst comprises the following steps:
step 1, preparing a cerium-titanium composite oxide carrier:
step 1.1, dissolving cerium nitrate and titanium sulfate in deionized water at 60 ℃ to obtain a solution, wherein the molar ratio of the cerium nitrate to the titanium sulfate is 1: 10. the concentration of the cerium nitrate in the solution is 0.01 mol/L.
And step 1.2, slowly dropwise adding ammonia water into the solution until the pH value reaches 10, and continuously and violently stirring for 4 hours to obtain a precipitated product.
Step 1.3, followed by filtration, washing and drying of the precipitate obtained in step 1.2 at 110 ℃ for 12 h.
And step 1.4, roasting the dried product for 4 hours at 600 ℃ in an air atmosphere to obtain the cerium-titanium composite oxide carrier.
Step 2, preparation of the supported ruthenium-nickel alloy ammonia synthesis catalyst:
and 2.1, dispersing the prepared cerium-titanium composite oxide into ethylene glycol, violently stirring, and fully dispersing a catalyst carrier to obtain a mixed solution, wherein the mass fraction of the catalyst carrier in the mixed solution is 0.1%.
And 2.2, continuously stirring the mixed solution obtained in the step 2.1 for 1 hour at the temperature of 60 ℃ under the protection of nitrogen.
And 2.3, adding the sodium borohydride aqueous solution into the mixed solution obtained in the step 2.2, and continuously stirring the mixture in the nitrogen atmosphere, wherein the amount of the added sodium borohydride is 60 percent of the mass of the cerium-titanium composite oxide carrier.
And 2.4, dropwise adding an aqueous solution containing ruthenium chloride and nickel chloride into the reaction mixture, wherein the mass content of total metals in the aqueous solution is 5%, the addition amount of ruthenium and nickel (calculated by the mass of atoms) is 5% of the mass of the added cerium-titanium composite oxide, and the atomic molar ratio of ruthenium and nickel is 1:0.6, and continuously stirring.
And 2.5, after the reaction is finished, separating the precipitate, washing and drying at 60 ℃ in vacuum for 12 hours to obtain the supported ruthenium-nickel alloy ammonia synthesis catalyst.
The supported ruthenium-nickel alloy ammonia synthesis catalyst prepared in the embodiment takes ruthenium-nickel alloy as an active component and takes a cerium-titanium composite oxide as a carrier, wherein the molar ratio of ruthenium to nickel atoms is 1:0.6, the molar ratio of cerium to titanium atoms is 1: the loading of ruthenium-nickel alloy on the carrier was 5%.
The application conditions of the supported ruthenium-nickel alloy ammonia synthesis catalyst in ammonia synthesis catalysis are as follows: the volume ratio of hydrogen to nitrogen of the reaction raw material gas is 3, the reaction pressure is 5MPa, the reaction temperature is 400 ℃, and the volume space velocity of the reaction gas is 10000h -1 . The reaction results are shown in Table 1.
Comparative example 1
A preparation method of a supported metal ruthenium ammonia synthesis catalyst comprises the following steps:
(1) dissolving cerium nitrate and titanium sulfate in deionized water at 60 ℃, wherein the molar ratio of the cerium nitrate to the titanium sulfate is 1: 5. The concentration of the cerium nitrate in the solution is 0.01 mol/L.
(2) To the above solution, ammonia was slowly added dropwise until the pH reached 10, and vigorous stirring was continued for 4 h.
(3) The precipitate was then filtered, washed and dried at 110 ℃ for 12 h.
(4) And roasting the dried product for 4 hours at 600 ℃ in an air atmosphere to obtain the cerium-titanium composite oxide carrier.
(5) And dispersing the prepared cerium-titanium composite oxide into ethylene glycol, and stirring vigorously to fully disperse a catalyst carrier, wherein the mass fraction of the catalyst carrier in the mixed solution is 0.06%.
(6) The mixture was stirred at 60 ℃ under nitrogen for 1 h.
(7) And adding a sodium borohydride aqueous solution into the mixed solution, and continuously stirring the mixture in a nitrogen atmosphere, wherein the amount of the added sodium borohydride is 80 percent of the mass of the cerium-titanium composite oxide carrier.
(8) Dropwise adding an aqueous solution containing ruthenium chloride into the reaction mixture, wherein the total metal mass content in the aqueous solution is 5%, and the addition amount of ruthenium (calculated by atomic mass) is 5% of the mass of the added cerium-titanium composite oxide, and continuously stirring.
(9) After the reaction is finished, separating the precipitate, washing and drying at 80 ℃ for 4h in vacuum to obtain the supported metal ruthenium ammonia synthesis catalyst.
The application conditions of the supported metal ruthenium ammonia synthesis catalyst in ammonia synthesis catalysis are as follows: the volume ratio of hydrogen to nitrogen of the reaction raw material gas is 3, the reaction pressure is 5MPa, the reaction temperature is 400 ℃, and the volume space velocity of the reaction gas is 10000h < -1 >. The reaction results are shown in Table 1.
Comparative example 2
A preparation method of a supported metal nickel ammonia synthesis catalyst comprises the following steps:
(1) dissolving cerium nitrate and titanium sulfate in deionized water at 60 ℃, wherein the molar ratio of the cerium nitrate to the titanium sulfate is 1: 5. The concentration of the cerium nitrate in the solution is 0.01 mol/L.
(2) To the above solution, ammonia was slowly added dropwise until the pH reached 10, and vigorous stirring was continued for 4 h.
(3) The precipitate was then filtered, washed and dried at 110 ℃ for 12 h.
(4) And roasting the dried product for 4 hours at 600 ℃ in an air atmosphere to obtain the cerium-titanium composite oxide carrier.
(5) Dispersing the prepared cerium-titanium composite oxide into ethylene glycol, stirring vigorously, and fully dispersing a catalyst carrier, wherein the mass fraction of the catalyst carrier in the mixed solution is 0.05-0.1%.
(6) The mixture is stirred for 1 hour under the protection of nitrogen at the temperature of 60-80 ℃.
(7) And adding a sodium borohydride aqueous solution into the mixed solution, and continuously stirring the mixture in a nitrogen atmosphere, wherein the amount of the added sodium borohydride is 80 percent of the mass of the cerium-titanium composite oxide carrier.
(8) Dropwise adding an aqueous solution containing nickel chloride into the reaction mixture, wherein the total metal mass content in the aqueous solution is 5%, and the adding amount of nickel (by atomic mass) is 5% of the added cerium-titanium composite oxide mass, and continuously stirring.
(9) After the reaction is finished, separating the precipitate, washing and drying for 4-12h at 60-80 ℃ in vacuum to obtain the supported metal nickel ammonia synthesis catalyst.
The application conditions of the supported metal nickel ammonia synthesis catalyst in ammonia synthesis catalysis are as follows: the volume ratio of hydrogen to nitrogen of the reaction raw material gas is 3, the reaction pressure is 5MPa, the reaction temperature is 400 ℃, and the volume space velocity of the reaction gas is 10000h -1 . The reaction results are shown in Table 1.
TABLE 1 evaluation results of ruthenium-nickel alloy ammonia synthesis catalyst
| Exit ammonia Rate (mol/gcath) | |
| Example 1 | 1.46 |
| Example 2 | 1.89 |
| Example 3 | 1.52 |
| Example 4 | 1.24 |
| Example 5 | 0.94 |
| Comparative example 1 | 0.56 |
| Comparative example 2 | 0.02 |
Claims (10)
1. A supported ruthenium-nickel alloy ammonia synthesis catalyst is characterized in that the catalyst takes ruthenium-nickel alloy as an active component and takes a cerium-titanium composite oxide as a carrier, and the molar ratio of ruthenium to nickel atoms in the ruthenium-nickel alloy is 1: 0.1 to 0.6, wherein the cerium-titanium atom molar ratio in the cerium-titanium composite oxide is 1: 1-10, and the loading capacity of the ruthenium-nickel alloy on the carrier is 1-8%.
2. A method for preparing the supported ruthenium-nickel alloy ammonia synthesis catalyst according to claim 1, comprising the following steps:
step 1, preparing a cerium-titanium composite oxide carrier:
step 1.1, dissolving cerium nitrate and titanium sulfate in deionized water to obtain a solution, slowly dropwise adding ammonia water into the solution until the pH value reaches 10, and continuously and violently stirring to obtain a precipitate;
step 1.2, filtering, washing and drying the precipitation product obtained in the step 1.1;
step 1.3, roasting the dried product in air atmosphere to obtain a cerium-titanium composite oxide carrier;
step 2, preparation of the supported ruthenium-nickel alloy ammonia synthesis catalyst:
step 2.1, dispersing the cerium-titanium composite oxide carrier into ethylene glycol, violently stirring, and fully dispersing the cerium-titanium composite oxide carrier to obtain a mixed solution;
2.2, continuously stirring the mixed solution obtained in the step 2.1 under the protection of nitrogen;
step 2.3, adding a sodium borohydride aqueous solution into the mixed solution obtained in the step 2.2, and continuously stirring the mixture in a nitrogen atmosphere;
step 2.4, dropwise adding an aqueous solution containing ruthenium chloride and nickel chloride into the reaction mixture in the step 2.3, and continuously stirring;
and 2.5, after the reaction is finished, separating, washing and drying the obtained precipitate product in vacuum to obtain the supported ruthenium-nickel alloy ammonia synthesis catalyst.
3. The method for preparing the supported ruthenium-nickel alloy ammonia synthesis catalyst according to claim 2, wherein the molar ratio of the cerium nitrate to the titanium sulfate in the step 1.1 is 1: 1-10, wherein the concentration of the cerium nitrate in the solution is 0.01 mol/L.
4. The preparation method of the supported ruthenium-nickel alloy ammonia synthesis catalyst according to claim 2, wherein the temperature of the deionized water in the step 1.1 is 60 ℃, and the stirring time is 4 hours; the drying temperature in the step 1.2 is 110 ℃, and the drying time is 12 hours; the roasting temperature in the step 1.3 is 500-600 ℃, and the roasting time is 4-8 h.
5. The method for preparing the supported ruthenium-nickel alloy ammonia synthesis catalyst according to claim 2, wherein the mass fraction of the cerium-titanium composite oxide carrier in the mixed solution in the step 2.1 is 0.05-0.1%.
6. The preparation method of the supported ruthenium-nickel alloy ammonia synthesis catalyst according to claim 2, wherein in the step 2.2, the stirring is continued for 1 hour under the protection of nitrogen at 60-80 ℃.
7. The preparation method of the supported ruthenium-nickel alloy ammonia synthesis catalyst according to claim 2, wherein the mass of the sodium borohydride added in the step 2.3 is 50-80% of the mass of the cerium-titanium composite oxide carrier.
8. The preparation method of the supported ruthenium-nickel alloy ammonia synthesis catalyst according to claim 2, wherein the total metal content in the aqueous solution of ruthenium chloride and nickel chloride in the step 2.4 is 5% by mass, the addition amount of ruthenium-nickel atoms is 1-8% by mass of the added cerium-titanium composite oxide, and the molar ratio of ruthenium-nickel atoms is 1: 0.1 to 0.6.
9. The preparation method of the supported ruthenium-nickel alloy ammonia synthesis catalyst according to claim 2, wherein the drying time in the step 2.5 is 60-80 ℃ and 4-12 h.
10. The application of the supported ruthenium-nickel alloy ammonia synthesis catalyst in claim 1, which is applied to ammonia synthesis catalytic reaction under the reaction conditions of: the volume ratio of hydrogen to nitrogen of the reaction raw material gas is 3, the reaction pressure is 5MPa, the reaction temperature is 400 ℃, and the volume space velocity of the reaction gas is 10000h -1 。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115779901A (en) * | 2022-12-14 | 2023-03-14 | 青岛创启新能催化科技有限公司 | Ruthenium-loaded metal oxide catalyst, preparation method and application thereof |
| CN117065765A (en) * | 2023-10-17 | 2023-11-17 | 佛山仙湖实验室 | Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011027864A1 (en) * | 2009-09-04 | 2011-03-10 | 国立大学法人北海道大学 | Photoreduction catalyst, method for synthesizing ammonia using same, and method for decreasing nitrogen oxide in water using same |
| CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
| JP2014141361A (en) * | 2013-01-22 | 2014-08-07 | Nippon Shokubai Co Ltd | Method for synthesizing ammonia |
| JP2017018907A (en) * | 2015-07-13 | 2017-01-26 | 国立大学法人 大分大学 | Composition for ammonia synthesis catalyst and method for producing the same, and method for synthesizing ammonia |
| CN106378149A (en) * | 2016-10-11 | 2017-02-08 | 湖北大学 | Preparation method and application of titanium dioxide nano tube loaded dual-metal ruthenium and nickel nano catalyst |
| CN108246300A (en) * | 2018-02-09 | 2018-07-06 | 厦门大学 | With rutile TiO2Methanation catalyst for carrier and preparation method thereof |
| CN109126782A (en) * | 2018-10-22 | 2019-01-04 | 浙江工业大学 | A kind of porous PdRu alloy catalyst and preparation method thereof for electrochemistry formated ammonia |
| CN110368933A (en) * | 2019-08-07 | 2019-10-25 | 福州大学 | It is a kind of using Ce-Ti composite oxides as ruthenium-based ammonia synthetic catalyst of carrier and preparation method thereof |
| CN110586106A (en) * | 2019-09-12 | 2019-12-20 | 中国原子能科学研究院 | Catalyst for catalytic synthesis of ammonia reaction and preparation method thereof |
-
2022
- 2022-05-09 CN CN202210502831.3A patent/CN114797894B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011027864A1 (en) * | 2009-09-04 | 2011-03-10 | 国立大学法人北海道大学 | Photoreduction catalyst, method for synthesizing ammonia using same, and method for decreasing nitrogen oxide in water using same |
| CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
| JP2014141361A (en) * | 2013-01-22 | 2014-08-07 | Nippon Shokubai Co Ltd | Method for synthesizing ammonia |
| JP2017018907A (en) * | 2015-07-13 | 2017-01-26 | 国立大学法人 大分大学 | Composition for ammonia synthesis catalyst and method for producing the same, and method for synthesizing ammonia |
| CN106378149A (en) * | 2016-10-11 | 2017-02-08 | 湖北大学 | Preparation method and application of titanium dioxide nano tube loaded dual-metal ruthenium and nickel nano catalyst |
| CN108246300A (en) * | 2018-02-09 | 2018-07-06 | 厦门大学 | With rutile TiO2Methanation catalyst for carrier and preparation method thereof |
| CN109126782A (en) * | 2018-10-22 | 2019-01-04 | 浙江工业大学 | A kind of porous PdRu alloy catalyst and preparation method thereof for electrochemistry formated ammonia |
| CN110368933A (en) * | 2019-08-07 | 2019-10-25 | 福州大学 | It is a kind of using Ce-Ti composite oxides as ruthenium-based ammonia synthetic catalyst of carrier and preparation method thereof |
| CN110586106A (en) * | 2019-09-12 | 2019-12-20 | 中国原子能科学研究院 | Catalyst for catalytic synthesis of ammonia reaction and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| GUOZHU C ET AL: "Synthesis of Ni-Ru Alloy Nanoparticles and Their High Catalytic Activity in Dehydrogenation of Ammonia Borane", 《CHEMISTRY-A EUROPEAN JOURNAL》, vol. 18, no. 25, pages 7925 - 7930, XP071835895, DOI: 10.1002/chem.201200292 * |
| 杨振威等: "具有Ru-M （M＝Fe,Co,Ni,Mo）双金属活性中心的 负载型氨合成催化剂", 《催化学报》, vol. 27, no. 5, pages 378 - 380 * |
| 杨晓龙等: "钌基氨合成催化剂作用机理及氧化物负载钌催化体系研究", 《工业催化》, vol. 18, no. 3, pages 5 - 16 * |
| 林伟忠等: "钌基氨合成催化剂研究进展", 《现代化工》, no. 7, pages 12 - 17 * |
| 赵子琦: "复合氧化物负载钌基氨合成催化剂的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 6, pages 015 - 138 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115779901A (en) * | 2022-12-14 | 2023-03-14 | 青岛创启新能催化科技有限公司 | Ruthenium-loaded metal oxide catalyst, preparation method and application thereof |
| CN115779901B (en) * | 2022-12-14 | 2024-03-29 | 青岛创启新能催化科技有限公司 | Ruthenium-loaded metal oxide catalyst, preparation method and application thereof |
| CN117065765A (en) * | 2023-10-17 | 2023-11-17 | 佛山仙湖实验室 | Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof |
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