EP4175747A1 - Catalyseur composite d'alliage métallique/oxyde, alliage métallique/nitrure pour décomposition d'ammoniac - Google Patents

Catalyseur composite d'alliage métallique/oxyde, alliage métallique/nitrure pour décomposition d'ammoniac

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Publication number
EP4175747A1
EP4175747A1 EP20941537.1A EP20941537A EP4175747A1 EP 4175747 A1 EP4175747 A1 EP 4175747A1 EP 20941537 A EP20941537 A EP 20941537A EP 4175747 A1 EP4175747 A1 EP 4175747A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
mixture
support
liquid
ammonia
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20941537.1A
Other languages
German (de)
English (en)
Other versions
EP4175747A4 (fr
Inventor
Gang Wu
Shreya Mukherjee
Zhong Tang
Bo Lu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bettergy Corp
Research Foundation of State University of New York
Original Assignee
Bettergy Corp
Research Foundation of State University of New York
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US16/920,056 external-priority patent/US11738332B2/en
Application filed by Bettergy Corp, Research Foundation of State University of New York filed Critical Bettergy Corp
Publication of EP4175747A1 publication Critical patent/EP4175747A1/fr
Publication of EP4175747A4 publication Critical patent/EP4175747A4/fr
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/047—Decomposition of ammonia
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention is directed a series of catalysts, the method of making such catalysts and the use of such catalysts.
  • the said catalysts are made of composite metal or metal alloys or metal nanoclusters supported on perovskites, composite oxides or nitrides, or mixed oxides or mixed nitrides as the catalyst supports in the form of, but not limited to, powder, sphere, slab, pellet, or hollow cylinder.
  • Such catalysts are well positioned to be used in ammonia decomposition with almost complete conversion at temperatures below 500°C.
  • These catalysts are also well positioned to be used in ammonia decomposition with almost complete conversion at temperatures above 500°C.
  • the catalysts can also be coupled with a membrane reactor to combine reaction and separations in process that can be used in ammonia decomposition membrane reactor at various temperatures (e.g ., 100°C, 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, and higher temperatures) and pressures (e.g., 5 atm, 10 atm, 15 atm, 20 atm, 25 atm, 30 atm, 35 atm, 40 atm, 45 atm, 50 atm, and higher pressures).
  • temperatures e.g ., 100°C, 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, and higher temperatures
  • pressures e.g., 5 atm, 10 atm, 15 atm, 20 atm, 25 atm, 30 atm, 35 atm, 40 atm, 45 atm, 50 atm, and higher pressures.
  • Ammonia decomposition is a commercial process in the chemical industry and recently has become of interest as a clean, safe, and renewable source of hydrogen for fuel cell vehicles. Ammonia decomposition is endothermic. It generates two moles of products per mole of reactant.
  • the ammonia conversion rate increases with the temperature and decreases with the pressure. Since higher pressure ammonia decomposition is preferred for the compact design of the membrane reactor, conversion rate issues need to be addressed.
  • the hydrogen for fuel cells should contain no ammonia because ammonia can slowly poison proton exchange membrane fuel cells (PEMFCs) and the recovery of the PEMFC from ammonia poisoning is very slow due to the relatively slow diffusion of ammonium in the PEM. Therefore, a complete conversion of the ammonia is desirable for hydrogen generation from ammonia decomposition and an ammonia recirculation system needs to be introduced to reduce ammonia content in the fuel stream from 300 to 0 ppm.
  • PEMFCs proton exchange membrane fuel cells
  • the ammonia dissociation rate depends on the temperature, and catalyst type.
  • the reaction rate is greatly increased by operation at temperatures above 700°C.
  • High temperature operation at on-site hydrogen refueling stations is not desirable due to several reasons, including the high cost of the equipment required at that high temperature, energy costs, and catalyst stability concerns.
  • U.S. Pat. Nos. 5,055,282 and 5,976,723 and U.S. Pat. App. Pub. No. 2020/0164346 disclose ruthenium-based catalysts for cracking ammonia into hydrogen and nitrogen in a decomposition reactor.
  • the problem with Ru is that it is a noble metal which is expensive and scarcely available and its use in the decomposition of ammonia will significantly increase the cost of the hydrogen generation process.
  • US Application 20090060809A1 is based on a metallic element selected from Fe, Co, Ni and Cu by ion exchange method, supported on porous silica alumina having an Si/Al atomic ratio along with a noble metal selected from Ru, Rh, Pd, Ir and Pt in an amount of 10 ppm to 500 ppm based on the total mass of the catalyst.
  • U.S. Pat. No. 9,670,063, and U.S. Pa. App. Pub. No. 2016/0289068 A1 disclose alkali metal amides (such as NaNTb, LiNTh) and nitride-imide composite catalysts for cracking ammonia into hydrogen and nitrogen in a decomposition reactor. At 450°C and atmospheric pressure, the catalyst gives ammonia conversion of 54.9%.
  • the issue with the alkali metal amides-based catalyst is that the high activity of the catalyst during the reaction lasts only hours, which is not practical for industrial application.
  • US Patent 9,138,726 taught a copper-based catalyst comprising: a porous oxide support and a low valent copper compound mixing with the porous oxide support by an acid hydrothermal method; wherein the low valent copper compound with is Cu and C O.
  • their work is focused on production of N2 and they use a flux of O2 and NH3 mixture for low temperature combustion.
  • the present invention includes of composite metal or metal alloys or metal nanoclusters supported on perovskites, composite oxides or nitrides, or mixed oxides or mixed nitrides as the catalyst supports in the form of, but not limited to, powder, sphere, slab, pellet, or hollow cylinder.
  • Such catalysts are well positioned to be used in ammonia decomposition with almost complete conversion at temperatures below 500°C.
  • These catalysts are also well positioned to be used in ammonia decomposition with almost complete conversion at temperatures above 500°C.
  • the catalysts can also be coupled with a membrane reactor to combine reaction and separations in process that can be used in ammonia decomposition membrane reactor at various temperatures (e.g ., 100°C, 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, and higher temperatures) and pressures (e.g., 5 atm, 10 atm, 15 atm, 20 atm, 25 atm, 30 atm, 35 atm, 40 atm, 45 atm, 50 atm, and higher pressures).
  • temperatures e.g ., 100°C, 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, and higher temperatures
  • pressures e.g., 5 atm, 10 atm, 15 atm, 20 atm, 25 atm, 30 atm, 35 atm, 40 atm, 45 atm, 50 atm, and higher pressures.
  • such catalysts can promote ammonia decomposition with complete conversion at various temperatures (e.g, 100°C, 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, and higher temperatures).
  • the catalysts could also be coupled with a membrane reactor to combine reaction and separations in process that can be used in ammonia decomposition membrane reactor at various temperatures (e.g, 100°C, 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, and higher temperatures) and pressures (e.g., 5 atm, 10 atm, 15 atm, 20 atm, 25 atm, 30 atm, 35 atm, 40 atm, 45 atm, 50 atm, and higher pressures).
  • a catalyst may be used for ammonia decomposition at relatively high conversion rates at relatively low temperatures and low pressures. While persons of ordinary skill in the art will recognize that the catalysts described herein are capable of assisting in ammonia decomposition at high temperatures (e.g ., above 500°C) and pressures (e.g, above 30 atm), these catalysts are further capable of assisting in ammonia decomposition at temperatures below 500°C and below 30 atm. Due to the viability of these catalysts to assist in ammonia decomposition at relatively low temperatures and pressures, ammonia decomposition may be accomplished with greater energy efficiency, low costs, and at a greater overall conservation of resources.
  • FIG. 1 shows a high resolution transmission electron microscopy (HRTEM) image of CoNi alloy on MgSrCe04 catalyst, in accordance with various embodiments
  • FIG. 2 shows an elemental mapping of CoNi alloy on MgSrCeCri catalyst, shown in two different scale bars, in accordance with various embodiments;
  • FIG. 3 shows a XRD of monometallic Co, Ni MgSrCeCri compared to bimetallic CoNi alloy on MgSrCeCri, in accordance with various embodiments;
  • FIG. 4 shows a XRD of bimetallic CoNi on other oxides like CeSrCb, MgCeCb, MgPrCb, MgCeZrCri, MgLaSrCri, MgPrSrCri, in accordance with various embodiments; [0018] FIG.
  • FIG. 6 shows a XPS spectroscopy of 1 wt % K-CoNi-MgCeO, (a) confirming presence of Co,CoO and C03O4, (b) confirms presence of Ni, NiO and NbCri, (c) confirming presence of magnesium as MgO as well as reduced state, (d) Ce 3+ and Ce 4+ state of cerium is observed, in accordance with various embodiments; and [0020]
  • FIG. 7 shows an ammonia cracking reactor loaded with the catalyst, showing pure ammonia is being decomposed into hydrogen and nitrogen, wherein pure hydrogen is then obtained through a purification unit, in accordance with various embodiments.
  • a catalyst for ammonia decomposition may be provided.
  • the catalyst may contain bimetallic nanoclusters or an alloy.
  • the nanocluster or alloy may include at least one element (A) selected from cobalt, iron, chromium, manganese, vanadium combined with at least one element (B) selected from nickel, copper, niobium.
  • the bimetallic nanoclusters or alloy may supported on a mixed oxide or a mixed nitride or perovskite formed of at least one element from alkaline earth metal (C), including, but not limited to, magnesium, calcium, strontium or barium and at least one metal from rare earth metal (D), including, but not limited to, cerium, lanthanum, praseodymium.
  • the perovskite may alternatively be formed of at least one element (E) selected from aluminum, zirconium, molybdenum or titanium.
  • the composite catalyst may also be promoted with alkali metals such as potassium, cesium or sodium.
  • alkali metals such as potassium, cesium or sodium.
  • the chemical form of each element (A) to (D) in the catalyst (X) can be confirmed by a known method such as X-ray diffraction method (XRD). That is, the chemical form of each element (A) to (D) can be confirmed by measuring the catalyst (X).
  • Element (A) and (B) may preferably be in the form of metal clusters or metal alloys. Small amount of oxides may be detected likely due to exposure of the sample in air during measurement.
  • the element (C) and (D) may form mixed oxides or mixed nitrides where the composition of the individual elements is obtained using XPS study. Raw material used for synthesis could be salts of metal nitrate, metal acetates or metal sulfates. Metal chlorides, as precursors, may affect the catalytic activity if not completely removed.
  • the catalyst includes the elements (A) to (C), and the components are uniformly dispersed.
  • a precipitation method such as deposition precipitation or co precipitation method, may be performed for easier scalability of the synthesis technique. Any type of alkali may be used for precipitation. In an embodiment, a pH between 9 and 11 may be maintained during precipitation.
  • Solution (1) may consist of aqueous mixture of element (A), (B) and (C+D), where the molar ratio of (A) and (B) and mass ratio of (A and B) to (C+D) are accurately controlled.
  • Solution (2) consists of alkali solution with a minimum concentration of 2M. The concentration of the alkali may vary between 2M and 5M.
  • Solution (1) may be added into solution (2) at a controlled rate to prevent aggregation of the particles.
  • solution (1) may be added into solution (2) dropwise at a rate of 1 ml/min.
  • the final solution may be continuously stirred using a magnetic stirrer at a rate of 200 rpm.
  • the stirring may be stopped, and the final solution may be allowed to age for at least 4 to 12 hours.
  • the precipitate may be separated from the solution by centrifugation followed by washing with water. Washing and centrifugation steps may be repeated at least four times. After complete washing, the precipitate may be dried in a petri dish under vacuum at 60°C for 8 tol2 hours.
  • the thermal reduction may then be done for a period of 1 hour.
  • the sample may further be treated in an inert atmosphere for 1 hour to passivate the catalyst for storage and transportation.
  • the catalyst may undergo an activation process at temperatures between 500-600°C before reaction.
  • the element (A) may be in the form of metal clusters.
  • the element (A) may be a metal that forms an alloy with, or clusters with, an element (B).
  • Component (A) and (B) may be in the form of oxides.
  • the metallic alloy formation or metallic clusters is most preferable.
  • Element (A) may be selected from cobalt, iron, chromium, manganese, or vanadium but is preferable cobalt.
  • the element (B) may be at least one element selected from selected from nickel, copper, niobium.
  • the element (B) should preferably be in the form of metal clusters, or metal that forms an alloy with or clusters with an element (A).
  • Component (A) and (B) should not be in the form of nitrides or carbides, though they could be in the form of oxides.
  • the metallic alloy formation or metallic clusters is most preferable. Specific examples of the chemical form other than metallic clusters or metallic alloys are oxide or complex oxide.
  • Element (C) may be at least one element from alkaline earth metal (C), such as magnesium, calcium, strontium or barium and at least one metal from rare earth metal(D), such as cerium, lanthanum, praseodymium, or at least one element (E) selected from aluminum, zirconium, molybdenum or titanium.
  • the element (C) could be in the form of metal, or metal oxides, or metal nitrides, mixed metal oxides being most preferable.
  • at an element may be included from the group of lanthanides, which may be cerium or lanthanum or praseodymium and the mass ratio of the rare earth element may be less than 10%.
  • Examples 1 and 2 are described here to demonstrate the preparation process of the catalyst CoNi -MgSrCeCri, and catalyst 1 wt% K-CoNi-MgSrCeCri.
  • Example 1 provides a procedure of making CoNi -MgCeSrCri catalyst for ammonia decomposition.
  • solution 1 4.36 g of cobalt nitrate, 2.31 g of nickel nitrate, 1.6 g of magnesium nitrate, 0.6 g of cerium nitrate and 0.7 g of strontium nitrate are added to 100 ml water to prepare solution 1.
  • Solution 2 is prepared by adding 1 lg of potassium hydroxide in 100 ml water. The two solutions are separately prepared and stirred till all the salts completely dissolve to give a clear solution. Then, solution 1 is added to solution 2 drop wise with a rate of 1 ml/min. The mixed solution is then aged for at least 16 h, preferably 24 h. This is followed by separating the precipitates by centrifugation at 9000 rpm for 3 min followed by washing with water.
  • the centrifugation and washing is repeated at least thrice to remove all residues from the mixture. Then the mixture is dried in vacuum at 60°C for 8h. After drying, the solid residue is pulverized in a speed mixer or ball mill for 10 min. The fine powder is then thermally reduced at 600°C for lh in a stream of 10% Eb balanced by Ar. A ramping at a rate of 2°C/min is used to increase the temperature of furnace from 25°C to 600°C.
  • Example 2 provides a procedure of making potassium promoted lwt% K-CoNi - MgSrCeCri catalyst for ammonia decomposition.
  • Examples 3 to 6 are described here to demonstrate the preparation process of the catalyst CoNi-MgCeCh, catalyst 1 wt% K-CoNi-MgCeCh, catalyst Ca-CoNi-MgCeCh, and catalyst Cs-CoNi -MgCeCh.
  • Example 3 provides a procedure of making CoNi-MgCeCb catalyst for ammonia decomposition.
  • solution 1 4.36 g of cobalt nitrate, 2.31 g of nickel nitrate, 1.6g of magnesium nitrate, 0.6 g of cerium nitrate are added to 100 ml water to prepare solution 1.
  • Solution 2 is prepared by adding l lg of potassium hydroxide in 100 ml water. The two solutions are separately prepared and stirred till all the salts completely dissolve to give a clear solution. Then, solution 1 is added to solution 2 drop wise with a rate of 1 ml min 1 . The mixed solution is then aged for 8 h. This is followed by separating the precipitates by centrifugation at 8000 rpm for 5 min followed by washing with water.
  • the centrifugation and washing is repeated at least thrice to remove all residues from the mixture. Then the mixture is dried in vacuum at 60°C for 8h. After drying, the solid residue is pulverized in a speed mixer or ball mill for 10 min. The fine powder is then thermally reduced at 600°C for lh. A ramping at a rate of 2°C/min is used to increase the temperature of furnace from 25°C to 600°C.
  • Example 4 provides a procedure of making potassium promoted 1% K-CoNi- MgCeCb catalyst for ammonia decomposition.
  • the catalyst prepared in Example 3 the catalyst is dispersed in 1 wt % aqueous solution of potassium nitrate or ethanolic solution of 1 wt % of potassium nitrate. This is followed by evaporating the solvent at 80°C. Once all the solvent evaporates, the residue is pulverized in a mortar or pestle or in a speed mixer at around 2000 rpm. The fine powder is then thermally reduced again at 600°C for 1 h.
  • Example 5 provides a procedure of making calcium promoted 1% Ca-CoNi- MgSrCe04 catalyst for ammonia decomposition.
  • Example 6 provides a procedure of making cesium promoted 1% Cs-CoNi - MgCeSr04 catalyst for ammonia decomposition.
  • Examples 7-8 are described here to demonstrate the preparation process of the catalyst CoNi-MgZrCri, catalyst 1 wt% K-CoNi-MgZrCri
  • Example 7 provides a procedure of making CoNi -MgCeZrCri catalyst for ammonia decomposition.
  • solution 1 4.36 g of cobalt nitrate, 2.31 g of nickel nitrate, 1.6 g of magnesium nitrate, 0.6 g of cerium nitrate and 0.84 g of zirconium oxy-nitrate are added to 100 ml water to prepare solution 1.
  • Solution 2 is prepared by adding 1 lg of potassium hydroxide in 100 ml water. The two solutions are separately prepared and stirred till all the salts completely dissolve to give a clear solution. Then, solution 1 is added to solution 2 drop wise with a rate of 1 ml/min. The mixed solution is then aged for 8 h. This is followed by separating the precipitates by centrifugation at 8000 rpm for 5 min followed by washing with water.
  • the centrifugation and washing is repeated at least thrice to remove all residues from the mixture. Then the mixture is dried in vacuum at 60°C for 8h. After drying, the solid residue is pulverized in a speed mixer or ball mill for 10 min. The fine powder is then thermally reduced at 600°C for lh. A ramping at a rate of 2°C/min is used to increase the temperature of furnace from 25°C to 600°C.
  • Ammonia Decomposition Rate (6,000 h 1 ): 450°C-75.0%, 475°C-84.0%, 500°C-
  • Example 8 provides a procedure of making potassium promoted 1% K-CoNi- MgCeZrCri catalyst for ammonia decomposition.
  • Example 9 provides a procedure of making bimetallic nitride of Co and Ni catalyst supported on MgCeCb as a catalyst for ammonia decomposition.
  • Ammonia Decomposition Rate (6,000 h 1 ): 450°C-50.25 %, 475°C-73.50 %, 500°C-88.32%, 575 °C- 99%
  • FIG. 7 is a system for decomposing ammonia.
  • system 700 includes a tank 702, a pump 704, a heat exchanger 706, a reactor 708, and a purification unit 710.
  • liquid ammonia from ammonia tank 702 may be pumped via pump 704 into heat exchanger 706 to be vaporized and heated to the temperature range 100-200°C.
  • the gaseous ammonia then goes into the reactor 708 loaded with the catalyst and heated with a furnace for the decomposition reaction.
  • the catalyst is beneficial for at least the reason that it can decompose the ammonia at various temperatures, including, but not limited to, temperatures ranging between less than 100°C and temperatures above 1000°C and at pressures below 10 atm and above 100 atm.
  • thee ammonia may be decomposed in the reactor into hydrogen and nitrogen under the catalytic reaction.
  • the hydrogen and nitrogen mixture leaves the reactor 708 for the heat exchanger 706 to cool down, and is then purified in the purification unit 710 to obtain hydrogen.

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Abstract

La présente invention concerne une série de catalyseurs de décomposition d'ammoniac, le procédé de fabrication de tels catalyseurs et l'utilisation de tels catalyseurs. Lesdits catalyseurs sont constitués d'un métal composite ou d'alliages métalliques supportés sur des oxydes ou des nitrures composites en tant que supports de catalyseur. Les catalyseurs sont utiles dans la décomposition de l'ammoniac à diverses températures et pressions, y compris des températures inférieures à 500 °C et des pressions allant jusqu'à 30 atm.
EP20941537.1A 2020-07-02 2020-11-12 Catalyseur composite d'alliage métallique/oxyde, alliage métallique/nitrure pour décomposition d'ammoniac Pending EP4175747A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16/920,056 US11738332B2 (en) 2019-07-03 2020-07-02 Metal alloy/oxide composite catalyst for ammonia decomposition
PCT/US2020/060230 WO2022019941A1 (fr) 2019-07-03 2020-11-12 Catalyseur composite d'alliage métallique/oxyde, alliage métallique/nitrure pour décomposition d'ammoniac

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EP4175747A1 true EP4175747A1 (fr) 2023-05-10
EP4175747A4 EP4175747A4 (fr) 2024-05-01

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CN102159314B (zh) * 2008-09-17 2016-08-03 株式会社日本触媒 氨分解催化剂及其制备方法以及氨处理方法
US11738332B2 (en) * 2019-07-03 2023-08-29 Bettergy Corporation Metal alloy/oxide composite catalyst for ammonia decomposition

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