WO2010060736A1 - Catalyseurs à base de métaux non nobles pour la décomposition de l'ammoniac et leur préparation - Google Patents

Catalyseurs à base de métaux non nobles pour la décomposition de l'ammoniac et leur préparation Download PDF

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Publication number
WO2010060736A1
WO2010060736A1 PCT/EP2009/064425 EP2009064425W WO2010060736A1 WO 2010060736 A1 WO2010060736 A1 WO 2010060736A1 EP 2009064425 W EP2009064425 W EP 2009064425W WO 2010060736 A1 WO2010060736 A1 WO 2010060736A1
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ammonia
hydrogen
catalysts
noble metals
catalyst
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PCT/EP2009/064425
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English (en)
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Claudiu Constantin Pavel
Massimiliano Comotti
Chiara Emiliani
Adriana Scaffidi
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Acta S.P.A.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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
    • 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
    • B01J23/745—Iron
    • 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
    • B01J23/75—Cobalt
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • 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
    • 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 refers to the non-noble metals based catalysts, in particular to their preparation and use for decomposition of ammonia.
  • ammonia is its availability both from degradation processes of organic waste and from direct synthesis, and its density that allows, for the same volume of gas, to contain more hydrogen than pure H 2 gas, providing an effective intermediate for hydrogen storage that does not require the drastic conditions of pressure and temperature demanded by pure hydrogen storage. Furthermore, while the large scale employment of hydrogen powered vehicles would require a drastic change in the local distribution network to adequate it to the security parameters required for the storage of such material, ammonia can be transported more easily, and in some countries such as USA it is already widely distributed to be used as fertilizer. Moreover, when new technologies for providing hydrogen from renewable sources will become available, since the efficiency of conversion process from hydrogen to ammonia is about 90 %, this technique would make an advantageous solution in terms of hydrogen storage.
  • these catalysts contains together with non-noble metals such as copper also small amounts of platinum, thus not showing its ability to perform the reforming of ammonia using only metals easily available. Furthermore, the amount of ammonia treated is very small (1 wt.% in air) and is not guaranteed the possibility to treat larger amounts as required by an internal combustion engine. Moreover in this case the reaction of ammonia decomposition has not place, but rather its oxidation in air. It is therefore evident the need of catalysts based on non-noble metals that are capable of promoting the decomposition of ammonia.
  • Figure 1 - shows conversion values as a function of temperature for decomposition of ammonia, using some of the catalysts of this invention compared to the commercial catalyst G90-B (S ⁇ d Chemie)
  • Figure. 2 - shows for some catalysts of the invention the influence of polymer loading on the support surface area and activity for ammonia decomposition at
  • the present invention relates to nanoparticled catalysts based on non-noble metals or their corresponding oxides or mixture thereof supported on a porous inorganic material obtained by a process comprising the following steps: i. preparation of the support by coating the porous inorganic material with an organic material and subsequent pyrolysis; ii. deposition onto the support of ions of the above mentioned non-noble metals by impregnation and subsequent reducing or oxidizing thermal treatment, depending on the required active metal phase metal form with the zero oxidation grade, or metal oxides or mixture thereof.
  • non-noble metals or metal oxides are selected from the first series of transition metals, preferable Fe, Co and Ni and/or their mixtures and/or alloys.
  • Said porous inorganic material is selected from metal oxides or their mixtures such as AI 2 O 3 , ZrO 2 , CeO x , MgO, MgAI 2 O 4 , La 2 O 3 , SiO 2 , Y 2 O 3 ; preferably AI 2 O 3 , ZrO 2 , CeOx, MgO or MgAI 2 O 4 (which have been proved to be some of the most active for these catalysts) eventually enriched with doping amounts of promoters such as
  • Preparation of the support able to activate and promote the catalytic activity for catalytic decomposition of ammonia consists in covering fine particles of metal oxides (the porous inorganic material) by impregnation (or combination in various forms of some metal oxides) with a nano-structured organic material comprising carbon, nitrogen and oxygen, at least two aromatic or heteroaromatic groups and at least one conjugated double bond, in order to arrange the organic coating, through intra- and intermolecular binding bond in a structure very rigid and stable.
  • R1 is chosen from the group consisting of: H and a hydrocarbon radical having from 1 to 10 carbon atoms, possible halogenated
  • R2 and R3 independently represent preferentially a electron-attractor group consisting of hydrogen, halogen, acyl, ester, carboxylic acid, formyl, nitrile, sulfonic acid, aryl groups, linear or branched alkyl groups having 1 to 15 carbon atoms possible functionalized with halogens or linked together to form one or more condensed cycles with phenyl ring and nitro groups or a polymer selected from those described in WO2004/036674A2 represented by the formula (C)
  • the coating of an inorganic support with an organic material can be done using classic impregnation methods (e.g. wet or incipient wetness) at a temperature comprised between 20 and 90 °C, according to the solvent and to the pressure used to dissolve the organic material.
  • solvent depending on the concentration and the solubility of the organic matrix, can be used for example water, alcohols, aldehydes and/or ketones or other solvents that are efficient for such purpose.
  • the solvents used in this phase of the process are water, at a pH comprised between 9 and 12, or ethanol, acetone, DMF, DMSO.
  • the ratio between the organic material and inorganic support play a fundamental role, inducing very important and substantial structural modifications in the obtained composite materials, especially related to surface area and porosity of the support (see Table 2).
  • the investigations regarding catalyst composition pointed out that the amount of organic material used to coat the inorganic support and thus the ratio between organic material and inorganic support could advantageously be varied between 0.5:1 and 2:1 in weight, but more preferably between 0.75:1 and 1.5:1 in weight.
  • wet or incipient wetness at a temperature comprised between 20 and 90 °C, according to the solvent and to the pressure.
  • a thermal treatment that requires, depending which chemical nature of the metallic particle is needed (metal with zero valence or metal oxide, or a mixture of them), a reduction with hydrogen (pure or diluted with another inert gas) or a calcination with oxygen (pure or diluted with another inert gas).
  • Such thermal treatment can be carried on at a temperature comprised between 300 and 1000 °C, obtaining a total metal loading in the final product comprised between 5 and 50 wt% of total catalyst weight.
  • the surface area of the so obtained catalyst can be comprised between 30 and 350 m 2 g "1 . Moreover, it has to be pointed out that during the thermal treatment the catalyst undergoes to structural and chemical modifications, which trigger processes devoted to increase stability of the resultant material when exposed to reaction conditions (see example 10 and Table 3).
  • the deposition process can be carried out either in one (by means of co-impregnation) or multiple steps (by means of consecutive impregnations). In the latter case, each impregnation is alternated with a thermal treatment.
  • the composite support can be firstly impregnated with an iron salt solution and then thermally treated at a temperature T 1 .
  • the resultant solid can be then impregnated with a cobalt salt solution and again thermally treated at a temperature T 2 in order to obtain the final material formulation.
  • Such thermal treatments can be either oxidative or reductive, depending on desired product.
  • Temperatures values T 1 and T 2 might be equal or different depending from the case and comprised between 300 and 1000 °C. In fact, it has been found that in some cases consecutive impregnations might drive to different nanoparticles composition and morphology (e.g. core-shell type or alloy nanoparticles), with different activities for the ammonia decomposition reaction. Catalyst stability under ammonia stream at high temperature was also found to be influenced from this aspect.
  • the precursor of said non-noble active metals can be salts such as acetates, halides, nitrates, carbonates, bicarbonates, sulfates, oxides, malonates, and analogous organic salts and their mixtures.
  • the catalyst composition can be doped with other elements which could be considered as promoters, able to increase both structural stability and catalytic activity.
  • the addition of such elements, typically belonging to the alkaline, earth- alkaline and lanthanides gruops of the periodic table, and in particular but not limited to Cs, K, Ba, Mg, Y, Ce and La, can be performed by classic impregnation methods (e.g.
  • wet or incipient wetness at a temperature comprised between 20 and 90 °C, according to the solvent and to the pressure employed.
  • the addition of such elements can be performed at any step of the catalyst preparation process, but preferably it is performed after the nanostructured support has been prepared.
  • the promoter to non noble metal(s) ratio can be varied in the range 2-0.01 taking into account the complete amount of non noble metal(s) composing the end product. After the addition of the promoter precursor the material can undergoes either to a thermal treatment (which could be either performed under oxidative or reducing atmosphere) or to an another impregnation step.
  • the precursor of said promoters can be salts such as nitrates, sulfates, bromides, carbonates, chlorides, fluorides, iodides, oxalates, hydroxides, perchlorates, and phosphates.
  • the catalysts of this inventions are useful for ammonia decomposition; thus object of the invention is a method for producing hydrogen from ammonia, said method wherein a catalyst as described above is used.
  • Catalysts of the invention as described above can be used in devices for ammonia reforming.
  • ammonia reformers comprising at least a catalyst as above described.
  • the dried material was thus pyrolyzed in argon flow at 900 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
  • 0.9 g of the composite material obtained as reported above are impregnated via incipient wetness with a aqueous solution containing 0.31 g of Iron (II) acetate in order to obtain a 10 wt %. final metal load.
  • the material is dried in oven at 70 °C and finally reduced in hydrogen flow at 500 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
  • EXAMPLE 3 Preparation of a "Catalyst C" In a 250 ml_ flask 5 g of ⁇ -AI 2 O 3 (Sasol) or alumina (Disperal 40, Sasol), 7 g of polymer (as described in WO2004/036674A2, Example 1 ), 7 g of ammonium nitrate and 150 ml_ of distilled water were added. A 30 wt% ammonia solution was added dropwise till the pH of the solution was 9. The suspension was then heated up to 50 °C and left stirring for 8 h. At this point, the solvent was removed via vacuum evaporation, and the obtained solid was dried in oven at 70 °C overnight. The dried material was thus pyrolyzed in argon flow at 900 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
  • EXAMPLE 4 Preparation of a "Catalyst D" In a 250 mL flask 5 g of alumina (Disperal 40, Sasol), 7 g of polymer (as described in WO2004/036674A2, Example 1 ), 7 g of ammonium nitrate and 150 mL of distilled water were added. A 30 wt% ammonia solution was added drop wise till the pH of the solution was 9. The suspension was then heated up to 50 °C and left stirring for 8 h. Then the solvent was removed via vacuum evaporation, and the obtained solid was dried in oven at 70 °C overnight.
  • the dried material was thus pyrolyzed in argon flow at 900 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
  • 0.8 g of the composite material obtained as reported above are impregnated via incipient wetness with a aqueous solution containing 1.44 g of Iron (III) nitrate in order to obtain a 20 wt %. final metal load.
  • the material is dried in oven at 70 °C and finally reduced in hydrogen flow at 800 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
  • EXAMPLE 7 Activity evaluation on ammonia decomposition 75 mg of Catalysts A, D and F prepared respectively as reported in Examples 1 , 4 and 6 have been placed in a quartz reactor (4 mm inner diameter) and then placed inside a tubular furnace. The furnace temperature was heated up to 600 °C (heating rate 10 °C min "1 ) under argon flow and then in hydrogen for 30 minutes. At the end of this pretreatment, pure ammonia (18.8 ml_/min) was fluxed and the catalytic activity was measured keeping the catalyst at the temperature of 600 °C, 550 °C, 500 °C, 450 °C and 400 °C for 30 minutes each.
  • EXAMPLE 9 Influence of polymer/alumina ratio on the activity of resultant catalysts It has been found that the amount of polymer used for the composite support preparation, and thus the polymer/alumina ratio, has a great influence on the composite surface area and porosity.
  • 75 mg of the catalyst was first tested following the protocol described in example 7. Successively, the temperature was raised (10 °C min "1 ) to 700 °C and the catalyst was kept at this temperature for 100 h. Then, temperature was further raised (10 °C min "1 ) to 800°C and the catalyst was kept at this temperature for 3 h.
  • EXAMPLE 1 1 Metal particle size determination.
  • Non-noble metals size and particles dispersion were determinated by
  • TEM Transmission Electron Microscopy
  • Catalyst A shows a bimodal size distribution, most of nanoparticles being characterized by a average diameter of 3 nm, but also few bigger iron clusters were observed (Table 4).

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne des catalyseurs basés sur des nanoparticules de métaux non précieux, d’oxydes ou de mélanges de ceux-ci reposant par des matériaux inorganiques, obtenus par un procédé comprenant plusieurs étapes qui peuvent être divisées en (a) la préparation du support et (b) le dépôt de la phase active. Les catalyseurs ci-décrits sont actifs dans la réaction de décomposition de l'ammoniac pour produire de l'hydrogène.
PCT/EP2009/064425 2008-11-03 2009-11-02 Catalyseurs à base de métaux non nobles pour la décomposition de l'ammoniac et leur préparation WO2010060736A1 (fr)

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ITFI2008A000210 2008-11-03
IT000210A ITFI20080210A1 (it) 2008-11-03 2008-11-03 Catalizzatori a base di metalli non nobili per la decomposizione dell'ammoniaca e loro preparazione

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Cited By (8)

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CN102161526A (zh) * 2011-03-04 2011-08-24 北京化工大学 氧化镁负载钴铁金属磁性纳米材料在降解废水中橙黄ⅱ的应用
EP2530125A1 (fr) * 2011-05-30 2012-12-05 Total SA Particules coeur/enveloppe dotées d'une activité catalytique
EP2796198A1 (fr) * 2013-04-23 2014-10-29 Danmarks Tekniske Universitet Catalyseurs pour l'oxydation sélective de l'ammoniac dans un gaz contenant de l'hydrogène
CN105289656A (zh) * 2015-11-25 2016-02-03 吉林大学 一种光催化分解水产氢固溶体催化剂及其制备方法
CN108212166A (zh) * 2018-01-16 2018-06-29 江西慧骅科技有限公司 便于拆卸实施再生的氨分解催化剂及其制备方法
WO2018229770A1 (fr) * 2017-06-15 2018-12-20 Technology Innovation Momentum Fund (Israel) Limited Partnership Catalyseurs à base de métaux de transition supportés par des lanthanides et leurs utilisations
US11478784B2 (en) 2020-02-04 2022-10-25 Saudi Arabian Oil Company Catalyst compositions for ammonia decomposition
CN115814799A (zh) * 2022-11-16 2023-03-21 武汉理工大学 非贵金属氨热解制氢催化剂及其制备方法和应用

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102161526B (zh) * 2011-03-04 2012-12-12 北京化工大学 氧化镁负载钴铁金属磁性纳米材料在降解废水中橙黄ⅱ的应用
CN102161526A (zh) * 2011-03-04 2011-08-24 北京化工大学 氧化镁负载钴铁金属磁性纳米材料在降解废水中橙黄ⅱ的应用
AU2012264715B2 (en) * 2011-05-30 2015-07-16 Total Raffinage Chimie Core-shell particles with catalytic activity
WO2012163969A1 (fr) * 2011-05-30 2012-12-06 Total Sa Particules cœur-écorce à activité catalytique
CN103649234A (zh) * 2011-05-30 2014-03-19 道达尔炼油化学公司 具有催化活性的芯-壳颗粒
EP2530125A1 (fr) * 2011-05-30 2012-12-05 Total SA Particules coeur/enveloppe dotées d'une activité catalytique
EA024839B1 (ru) * 2011-05-30 2016-10-31 Тотал Раффинаге Кимие Частицы ядро-оболочка с каталитической активностью
US9539563B2 (en) 2011-05-30 2017-01-10 Total Raffinage Chimie Core-shell particles with catalytic activity
EP2796198A1 (fr) * 2013-04-23 2014-10-29 Danmarks Tekniske Universitet Catalyseurs pour l'oxydation sélective de l'ammoniac dans un gaz contenant de l'hydrogène
CN105289656A (zh) * 2015-11-25 2016-02-03 吉林大学 一种光催化分解水产氢固溶体催化剂及其制备方法
WO2018229770A1 (fr) * 2017-06-15 2018-12-20 Technology Innovation Momentum Fund (Israel) Limited Partnership Catalyseurs à base de métaux de transition supportés par des lanthanides et leurs utilisations
CN108212166A (zh) * 2018-01-16 2018-06-29 江西慧骅科技有限公司 便于拆卸实施再生的氨分解催化剂及其制备方法
US11478784B2 (en) 2020-02-04 2022-10-25 Saudi Arabian Oil Company Catalyst compositions for ammonia decomposition
US11806700B2 (en) 2020-02-04 2023-11-07 Saudi Arabian Oil Company Catalyst compositions for ammonia decomposition
CN115814799A (zh) * 2022-11-16 2023-03-21 武汉理工大学 非贵金属氨热解制氢催化剂及其制备方法和应用

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