EP4175747A1 - Metal alloy/oxide, metal alloy/nitride composite catalyst for ammonia decomposition - Google Patents

Metal alloy/oxide, metal alloy/nitride composite catalyst for ammonia decomposition

Info

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)
French (fr)
Other versions
EP4175747A4 (en
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 the State University of New York
Original Assignee
Bettergy Corp
Research Foundation of the 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 the State University of New York filed Critical Bettergy Corp
Publication of EP4175747A1 publication Critical patent/EP4175747A1/en
Publication of EP4175747A4 publication Critical patent/EP4175747A4/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/83Catalysts 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06Washing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16Reducing
    • B01J37/18Reducing with gases containing free hydrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/04Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of inorganic compounds
    • C01B3/047Decomposition of ammonia
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15X-ray diffraction
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30Scanning electron microscopy; Transmission electron microscopy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/70Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/733Perovskite-type
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The present invention discloses a series of ammonia decomposition catalysts, the method of making such catalysts and the use of such catalysts. The said catalysts are made of composite metal or metal alloys supported on composite oxides or nitrides as the catalyst supports. The catalysts are useful in ammonia decomposition at various temperatures and pressures, including temperatures below 500°C and pressures up to 30 atm.

Description

METAL ALLOY/OXIDE, METAL ALLOY/NITRIDE COMPOSITE CATALYST
FOR AMMONIA DECOMPOSITION
STATEMENT REGARDING GOVERNMENT SPONSORED RESEARCH OR
DEVELOPMENT
[0001] The work described here was supported by US Department of Energy, ARPA-E (Award No. DE-AR0000817). The Federal Government may have certain rights in this work.
[0002] This invention was made with the support of the New York State Energy Research and Development Authority (NYSERDA) under Agreement Number 141102 and NYSERDA may have rights in this invention.
CROSS REFERENCE TO RELATED APPLICATIONS [0003] This application claims priority to U.S. Provisional Patent Application No. 62/870,077 filed July 3, 2019, the disclosure of which is incorporated herein in its entirety.
FIELD OF THE INVENTION
[0004] 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).
BACKGROUND OF THE INVENTION
1. Ammonia Decomposition
[0005] 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.
MU <=> 1/2M +3/2H2 (. DH°= 45.6 kJ/mol)
[0006] Thermodynamically, 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. [0007] Kinetically, 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, however, 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.
2. Ammonia Decomposition Catalysts (prior art analysis)
[0008] 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. Thus, there are catalysts which combine non-precious metal along with precious metal to reduce the use of noble metals. 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.
[0009] 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.
[0010] 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. However, their work is focused on production of N2 and they use a flux of O2 and NH3 mixture for low temperature combustion.
[0011] 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). For instance, 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).
[0012] One notable benefit to the present invention is that 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.
BRIEF SUMMARY OF THE DRAWINGS [0013] This invention may be more readily understood by reference to the following drawings wherein:
[0014] FIG. 1 shows a high resolution transmission electron microscopy (HRTEM) image of CoNi alloy on MgSrCe04 catalyst, in accordance with various embodiments;
[0015] FIG. 2 shows an elemental mapping of CoNi alloy on MgSrCeCri catalyst, shown in two different scale bars, in accordance with various embodiments;
[0016] FIG. 3 shows a XRD of monometallic Co, Ni MgSrCeCri compared to bimetallic CoNi alloy on MgSrCeCri, in accordance with various embodiments;
[0017] 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. 5 shows a XPS spectroscopy of 1 wt % K-CoNi-MgCeSrO, (a) confirms presence of Co, CoO and C03O4, (b) confirms presence of Ni, NiO and NbCri, (c) magnesium is present as MgO as well as reduced state, (d) Ce3+ and Ce4+ state of cerium is observed, and (e) strontium is also present as metal as well as metal oxide, in accordance with various embodiments;
[0019] 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) Ce3+ and Ce4+ 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.
DETAILED DESCRIPTION
[0021] In an embodiment, 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.
[0022] The composite catalyst may also be promoted with 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.
[Method for Preparing Catalyst (X)]
[0023] There are no particular restrictions on the preparation method of the catalyst (X). In an embodiment, 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.
[0024] 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.
[0025] In an embodiment, Solution (1) may be added into solution (2) at a controlled rate to prevent aggregation of the particles. For instance, 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. Upon complete mixing, the stirring may be stopped, and the final solution may be allowed to age for at least 4 to 12 hours. After aging, 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. This may be followed by thermal reduction in reducing atmosphere at temperatures ranging from 400-700°C. The ramping rate may be maintained between 2-5 °C/min. The reducing gas may be flown at a rate of 100 ml min 1. The reducing gas may be 10% Th balanced by Ar. The thermal reduction may then be done for a period of 1 hour. In an embodiment, 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.
[Element (A)]
[0026] The element (A) may be in the form of metal clusters. Alternatively, 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.
[Element (B)]
[0027] 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. However, 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)]
[0028] 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. Among the elements in (C), 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%.
Working Examples
[0029] Examples 1 and 2 are described here to demonstrate the preparation process of the catalyst CoNi -MgSrCeCri, and catalyst 1 wt% K-CoNi-MgSrCeCri.
Catalyst Preparation Example 1
[0030] Example 1 provides a procedure of making CoNi -MgCeSrCri catalyst for ammonia decomposition.
[0031] 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.
[0032] Ammonia Decomposition Rate (6000 h 1): 450°C-90.5%, 475°C-99.6%, 500°C- 100.0%
Catalyst Preparation Example 2
[0033] Example 2 provides a procedure of making potassium promoted lwt% K-CoNi - MgSrCeCri catalyst for ammonia decomposition.
[0034] Synthesis is repeated as in Example 1. After thermal reduction, the catalyst is dispersed in 1 wt % aqueous solution of potassium nitrate or ethanolic solution of 1 wt % of potassium hydroxide. 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. [0035] Ammonia Decomposition Rate (6000 h 1): 450°C-98.5%, 475°C-100.0%, 500°C- 100%
[0036] 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. Catalyst Preparation Example 3
[0037] Example 3 provides a procedure of making CoNi-MgCeCb catalyst for ammonia decomposition.
[0038] 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.
[0039] Ammonia Decomposition Rate (6,000 \ 1)A50°C-1 25 %, 475°C-94.50 %, 500°C- 100.0%
Catalyst Preparation Example 4
[0040] Example 4 provides a procedure of making potassium promoted 1% K-CoNi- MgCeCb catalyst for ammonia decomposition.
[0041] After thermal reduction 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.
[0042] Ammonia Decomposition Rate (6,000 h 1)- 450°C-81 %, 475°C-97.5 %, 500°C-99%
Catalyst Preparation Example 5
[0043] Example 5 provides a procedure of making calcium promoted 1% Ca-CoNi- MgSrCe04 catalyst for ammonia decomposition.
[0044] Synthesis is repeated as in Example 1. After thermal reduction, the catalyst is dispersed in 1 wt % aqueous solution of calcium nitrate or ethanolic solution of 1 wt. % of calcium 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.
[0045] Ammonia Decomposition Rate (6,000 h 1)-: 450°C-91.0%, 475°C-99.5%, 500°C- 100.0%
Catalyst Preparation Example 6
[0046] Example 6 provides a procedure of making cesium promoted 1% Cs-CoNi - MgCeSr04 catalyst for ammonia decomposition.
[0047] Synthesis is repeated as in Example 1. After thermal reduction the catalyst is dispersed in 1 wt % aqueous solution of cesium nitrate or ethanolic solution of 1 wt % of cesium hydroxide. 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. [0048] Ammonia Decomposition Rate (6,000 h 1): 450°C-92.3%, 475°C-99.0%, 500°C- 100.0%
[0049] Examples 7-8 are described here to demonstrate the preparation process of the catalyst CoNi-MgZrCri, catalyst 1 wt% K-CoNi-MgZrCri
Catalyst Preparation Example 7
[0050] Example 7 provides a procedure of making CoNi -MgCeZrCri catalyst for ammonia decomposition.
[0051] 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.
[0052] Ammonia Decomposition Rate (6,000 h 1): 450°C-75.0%, 475°C-84.0%, 500°C-
90.0% Catalyst Preparation Example 8
[0053] Example 8 provides a procedure of making potassium promoted 1% K-CoNi- MgCeZrCri catalyst for ammonia decomposition.
[0054] Synthesis is repeated as in Example 7. After thermal reduction the catalyst is dispersed in 1 wt % aqueous solution of potassium nitrate or ethanolic solution of 1 wt % of potassium hydroxide. 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. [0055] Ammonia Decomposition Rate (6,000 h 1): 450°C-79.0%, 475°C-89.5.0%, 500°C- 93.4%
Catalyst Preparation Example 9
[0056] Example 9 provides a procedure of making bimetallic nitride of Co and Ni catalyst supported on MgCeCb as a catalyst for ammonia decomposition.
[0057] Synthesis is repeated as in Example 3. For nitridation, thermal reduction is done in pure NEE balanced at 700 °C for 3 h.
[0058] After cooling down, the sample is tested for NEE decomposition activity.
[0059] Ammonia Decomposition Rate (6,000 h 1): 450°C-50.25 %, 475°C-73.50 %, 500°C-88.32%, 575 °C- 99%
[0060] FIG. 7 is a system for decomposing ammonia. In an embodiment, system 700 includes a tank 702, a pump 704, a heat exchanger 706, a reactor 708, and a purification unit 710. In an embodiment, 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. As noted above, 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. Thus, at various embodiments widely ranging in temperature and pressure, 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.
[0061] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration from this specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

Claims

CLAIMS We claim a catalyst for ammonia decomposition, which consists of,
1. A catalyst, comprising: a first element comprising at least one of: cobalt, iron, chromium, manganese, and vanadium; a second element comprising at least one of: nickel, copper, and niobium; a support; and a promoter; wherein the first element and the second element are combined to form at least one of a first mixture, the first mixture being at least one of: a bimetallic nanocluster; and an alloy; wherein the first mixture is supported on the support, the support comprising at least one of: a mixed oxide; a nitride; and a perovskite; wherein the promoter is an alkali metal.
2. The catalyst of claim 1, wherein the support comprises an alkaline earth metal.
3. The catalyst of claim 2, wherein the alkaline earth metal comprises at least one of magnesium, calcium, strontium, and barium.
4. The catalyst of claim 2, wherein the support further comprises a rare earth metal.
5. The catalyst of claim 4, wherein the rare earth metal comprises at least one of cerium, lanthanum, praseodymium.
6. The catalyst of claim 2, wherein the support further comprises at least one of aluminum, zirconium, molybdenum, and titanium.
7. The catalyst of claim 1, wherein the alkali metal of the promoter is at least one of potassium, cesium, sodium, lithium, and rubidium.
8. The catalyst of claim 1, wherein: the first mixture is the bimetallic nanocluster; the support is a mixed oxide comprising at least one of: an alkaline earth metal and a rare earth metal; and at least one of aluminum, zirconium, molybdenum; and titanium; wherein the alkaline earth metal comprises at least one of: magnesium, calcium, strontium, and barium; and wherein the rare earth metal comprises at least one of: cerium, lanthanum, praseodymium; and the promoter is at least one of potassium, cesium, sodium, lithium, and rubidium.
9. The catalyst of claim 1, wherein the catalyst comprises the first element and the second element at a concentration between fifteen percent and eighty -five percent by mass.
10. The catalyst of claim 1, wherein the first element and the second element form an alloy comprising cobalt.
11. A system for decomposing ammonia, comprising: a catalyst; a liquid comprising ammonia; a pump; a heat exchanger for vaporizing the liquid ammonia; a reactor; and a purification unit; wherein the liquid is contained in a container, wherein the pump is configured to receive the liquid from the container and guide the liquid to a heat exchanger, wherein the heat exchanger is configured to vaporize the liquid into a vapor and feed the vapor to a reactor, wherein the reactor comprises the catalyst and is configured to decompose the vapor into a mixture comprising hydrogen and nitrogen, and wherein the reactor is configured to guide the mixture to the heat exchanger, wherein the heat exchanger is further configured to reduce a temperature of the mixture and guide the liquid to the purification unit, and wherein the purification unit is configured to separate the hydrogen from the mixture.
12. The system of claim 11, wherein the catalyst comprises: a first element comprising at least one of: cobalt, iron, chromium, manganese, and vanadium; a second element comprising at least one of: nickel, copper, and niobium; a support; and a promoter; wherein the first element and the second element are combined to form at least one of a first mixture, the first mixture being at least one of: a bimetallic nanocluster; and an alloy; wherein the first mixture is supported on the support, the support comprising at least one of: a mixed oxide; a nitride; and a perovskite; wherein the promoter is an alkali metal.
13. The system of claim 12, wherein the heat exchanger is configured to adjust the temperature of the liquid to temperatures below 500 degrees Celsius.
14. The system of claim 12, wherein the heat exchanger is configured to adjust the temperature of the liquid to temperatures at or above 500 degrees Celsius.
15. The system of claim 11, wherein the heat exchanger is configured to adjust the temperature of the liquid to temperatures below 500 degrees Celsius.
16. The system of claim 11, wherein the heat exchanger is configured to adjust the temperature of the liquid to temperatures at or above 500 degrees Celsius.
17. A system, comprising: a liquid comprising ammonia; and a catalyst comprising: a first element comprising at least one of: cobalt, iron, chromium, manganese, and vanadium; a second element comprising at least one of: nickel, copper, and niobium; a support; and a promoter; wherein the first element and the second element are combined to form at least one of a first mixture, the first mixture being at least one of: a bimetallic nanocluster; and an alloy; wherein the first mixture is supported on the support, the support comprising at least one of: a mixed oxide; a nitride; and a perovskite; wherein the promoter is an alkali metal.
EP20941537.1A 2020-07-02 2020-11-12 METAL ALLOY/OXIDE, METAL ALLOY/NITRIDE COMPOSITE CATALYST FOR AMMONIA DECOMPOSITION Pending EP4175747A4 (en)

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 (en) 2019-07-03 2020-11-12 Metal alloy/oxide, metal alloy/nitride composite catalyst for ammonia decomposition

Publications (2)

Publication Number Publication Date
EP4175747A1 true EP4175747A1 (en) 2023-05-10
EP4175747A4 EP4175747A4 (en) 2024-05-01

Family

ID=80679492

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20941537.1A Pending EP4175747A4 (en) 2020-07-02 2020-11-12 METAL ALLOY/OXIDE, METAL ALLOY/NITRIDE COMPOSITE CATALYST FOR AMMONIA DECOMPOSITION

Country Status (3)

Country Link
EP (1) EP4175747A4 (en)
JP (1) JP2023542439A (en)
AU (2) AU2020459971A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20260022796A (en) * 2024-08-08 2026-02-20 에이치디현대오일뱅크 주식회사 Ammonia dehydrogenation catalyst, method of preparing hydrogen and air pollution prevention facility

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102159314B (en) * 2008-09-17 2016-08-03 株式会社日本触媒 Ammonia decomposition catalyzer and preparation method thereof and ammonia treatment method
US11738332B2 (en) * 2019-07-03 2023-08-29 Bettergy Corporation Metal alloy/oxide composite catalyst for ammonia decomposition

Also Published As

Publication number Publication date
AU2020459971A1 (en) 2022-02-24
JP2023542439A (en) 2023-10-10
EP4175747A4 (en) 2024-05-01
AU2024201087A1 (en) 2024-03-14
AU2024201087B2 (en) 2025-12-11

Similar Documents

Publication Publication Date Title
US11738332B2 (en) Metal alloy/oxide composite catalyst for ammonia decomposition
KR101790093B1 (en) Catalyst for manufacturing thermochemical fuel, and method for manufacturing thermochemical fuel
EP2409761B1 (en) Use of a catalyst for production of hydrogen
US7166267B2 (en) Solid solutions, applicable as catalysts, with perovskite structure comprising noble metals
JP5610408B2 (en) CeAlO3 perovskite containing transition metal
US20080219918A1 (en) Catalyst for fuel reforming and method of producing hydrogen using the same
WO2019207303A2 (en) Catalyst
US20170087537A1 (en) Mixed metal oxide catalysts for ammonia decomposition
CN101564690A (en) Preparation method of perovskite-like La*NiO* and applications
EP2658646B1 (en) Catalyst for Decomposition of Sulfur Trioxide and Hydrogen Production Process
Wang et al. Novel nano spinel-type high-entropy oxide (HEO) catalyst for hydrogen production using ethanol steam reforming
JP7515392B2 (en) CO2 methanation catalyst and its manufacturing method and method for manufacturing methane
JP2019011212A (en) Method for producing hydrogen and catalyst for producing hydrogen
JP2019155227A (en) Co2 methanation catalyst and carbon dioxide reduction method using the same
AU2024201087B2 (en) Metal alloy/oxide, metal alloy/nitride composite catalyst for ammonia decomposition
JP2010015860A (en) Reformer for fuel cell
CN116474792A (en) Catalytic material for producing hydrogen from ammonia, preparation method and application
CN116174000A (en) Preparation method and application of a low-defect perovskite-type tantalum-based oxynitride photocatalyst
JP2025126167A (en) Method of preparing catalyst for ammonia decomposition
US20180345255A1 (en) Steam reforming catalyst for hydrocarbons
KR101400889B1 (en) Carbonhydrate reforming catalyst and the method of preparation thereof
CN117545554A (en) Method for preparing a water gas shift catalyst, catalyst and method for reducing carbon monoxide content
EP3868469A1 (en) Catalyst for water gas shift reaction at middle temperature, preparation method thereof, and hydrogen preparation method using same
CN117680131B (en) Samarium-zirconium defect fluorite type nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen
JP2008229486A (en) Catalyst for producing hydrogen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220727

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20240404

RIC1 Information provided on ipc code assigned before grant

Ipc: B01J 23/78 20060101ALI20240327BHEP

Ipc: B01J 23/44 20060101ALI20240327BHEP

Ipc: B01J 21/06 20060101AFI20240327BHEP