WO2018067276A1 - Procédé de production de nitrures métalliques et de carbures métalliques - Google Patents

Procédé de production de nitrures métalliques et de carbures métalliques Download PDF

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WO2018067276A1
WO2018067276A1 PCT/US2017/051054 US2017051054W WO2018067276A1 WO 2018067276 A1 WO2018067276 A1 WO 2018067276A1 US 2017051054 W US2017051054 W US 2017051054W WO 2018067276 A1 WO2018067276 A1 WO 2018067276A1
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metal
carbide
nitride
cyanometallate
iii
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PCT/US2017/051054
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English (en)
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Partha Nandi
Quddus A. NIZAMI
Christine E. Kliewer
Andrew J. STELLA
Jihad M. Dakka
Himanshu Gupta
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Exxonmobil Chemical Patents Inc.
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Priority to SG11201901826XA priority Critical patent/SG11201901826XA/en
Priority to CA3042942A priority patent/CA3042942C/fr
Priority to CN201780061701.8A priority patent/CN109790024B/zh
Priority to KR1020197009035A priority patent/KR102453050B1/ko
Priority to EP17768654.0A priority patent/EP3523240B1/fr
Priority to JP2019517957A priority patent/JP7117296B2/ja
Priority to US16/335,366 priority patent/US10974962B2/en
Publication of WO2018067276A1 publication Critical patent/WO2018067276A1/fr
Priority to ZA2019/01134A priority patent/ZA201901134B/en

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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/06Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • B01J27/25Nitrates
    • 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
    • B01J37/04Mixing
    • 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • C01B32/907Oxycarbides; Sulfocarbides; Mixture of carbides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • C01B32/914Carbides of single elements
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Definitions

  • the present invention concerns a method for producing a metal nitride and/or a metal carbide, a metal nitride and/or carbide so produced, and the use of such a metal nitride and/or carbide in catalysis. More particularly, but not exclusively, this invention concerns a method for producing metal nitrides and/or metal carbides from at least one metal oxide and at least one cyanometallate.
  • Metal nitrides and metal carbides are sought-after materials for a variety of applications.
  • metal nitrides and metal carbides are useful in catalytic hydroprocessing.
  • Alexander and Hargreaves, Chem. Soc, Rev., 2010, 39, 4388-4401 discloses that the catalytic behaviour of molybdenum- and tungsten-containing metal nitrides and carbides has been the focus of much attention because of analogy between their catalytic behaviour and that of noble metals.
  • Tungsten nitride (W2N) has been applied in hydroprocessing catalysis (J. G. Chen, Chem. Rev. 1996, 96, 1477-1498), catalytic oxidation and catalytic oxygen reduction reaction (ORR) (H.
  • transition metal carbides show an unusual combination of outstanding properties, such as high melting point, high electrical and thermal conductivities, exceptional hardness, excellent mechanical stability, and chemical stability along with high corrosion resistance under reaction conditions.
  • Tungsten nitride coating on steel can significantly reduce corrosion and wear due to its exceptional mechanical strength (Wear, 2007, 262, 655-665).
  • Tungsten nitride can also function as a useful precursor to unique kinetically stable tungsten carbide phases because transformation of tungsten nitride to carbide is topotactic (Chem. Soc. Rev., 2010, 39, 4388- 4401).
  • Metal nitrides also offer unique reactivity; for example, the prospect of lattice nitrogen of nitrides as reactive species has been shown for mixed metal nitrides such as C03M03N (S.
  • Zn3[Co(CN)6]2/polyvinylpyrrolidone nano-sphere precursors under a nitrogen atmosphere at a temperature of 600°C.
  • a method of making iron carbide is by thermal decomposition of "Prussian Blue” (Fe4[Fe(CN) ]3) (Aparicio, C, Machala, L. & Marusak, Z., J. Therm. Anal.
  • the present invention provides, according to a first aspect, a method for producing a metal nitride and/or a metal carbide, the method comprising: i) contacting at least one metal oxide comprising at least one first metal with a cyanometallate comprising at least one second metal to form a reaction mixture; and, ii) subjecting the reaction mixture to a temperature of at least 300°C for a reaction period.
  • the method is a method for producing a metal nitride.
  • the method is a method for producing a metal carbide.
  • the present inventors have surprisingly found that heating a mixture of a metal oxide and a cyanometallate to a temperature of at least 300°C provides a particularly convenient and efficient method of making a metal nitride and/or a metal carbide from readily available, relatively inexpensive precursors.
  • the process of the present invention can be used to produce metal nitrides and/or metal carbides under relatively mild reaction conditions.
  • the process of the first aspect of the present invention provides a tuneable method of making a variety of different metal nitrides and/or metal carbides, for example by the use of different metal oxide and cyanometallate precursors.
  • the present invention provides a metal nitride and/or carbide comprising: a) a first metal nitride and/or carbide selected from the list consisting of: iron nitride, iron carbide, cobalt nitride and cobalt carbide; and b) a second metal nitride and/or carbide selected from the list consisting of: tungsten nitride, tungsten carbide, rhenium nitride and rhenium carbide.
  • the metal nitride and/or metal carbide comprises tungsten nitride and at least one of iron nitride and iron carbide, for instance tungsten nitride, iron nitride and iron carbide, e. .W ⁇ 2N, Fe4N and Fe3C. It may be that such metal nitrides and/or carbides are particularly useful as catalysts, and/or can be prepared by a particularly convenient route from readily available and relatively low-cost starting materials.
  • the present invention provides a metal nitride and/or a metal carbide prepared by the method according to the first aspect of the invention, optionally wherein the metal nitride and/or metal carbide is a metal nitride and/or metal carbide according to the second aspect of the invention.
  • the present invention provides a use of the metal nitride and/or metal carbide of the second or third aspect as a catalyst. DESCRIPTION OF THE FIGURES
  • Fig. 1 shows infrared (IR) spectra of cyanometallate and metal oxide precursors and reaction mixtures following heating at various temperatures for various periods;
  • Fig. 2 shows Powder X-Ray Diffraction patterns of cyanometallate and metal oxide precursors and reaction mixtures following heating at various temperatures;
  • Fig. 3 shows a Scanning Electron Microscopy (SEM) image of the reaction product of a mixture of a cyanometallate and a metal oxide precursor subjected to a temperature of
  • FIG. 4 shows an enlarged section of the image of Fig. 3;
  • Fig. 5 shows a Transmission Electron Microscopy (TEM) image of the reaction product of a mixture of a cyanometallate and a metal oxide precursor subj ected to a temperature of 600°C for two hours.
  • TEM Transmission Electron Microscopy
  • the metal oxide comprises at least one first metal M ⁇ .
  • M ⁇ is a transition metal.
  • transition metal refers to an element in the d- or f-block of the Periodic Table of the Elements, including elements in Groups 3 to 12 of the Period Table of the Elements, and the elements of the lanthanide series and the actinide series.
  • M ⁇ may for instance be a transition metal selected from the d-block of the Periodic Table of the Elements, preferably selected from Groups 5, 6 or 7 of the Periodic Table of the Elements such as selected from the list consisting of vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium
  • Tc and rhenium (Re).
  • M ⁇ can for example be selected from the list consisting of niobium (Nb), molybdenum (Mo), tungsten (W), and rhenium (Re). It may be that when M ⁇ is Nb, Mo, W or Re, the reaction between the metal oxide and the cyanometallate proceeds particularly efficiently.
  • M ⁇ may be tungsten (W) or rhenium (Re), more particularly tungsten (W).
  • the metal oxide may comprise WO3, in particular tungstic acid, and/or Re2C>7, in particular perrhenic acid. It may be that WO3, in particular tungstic acid, and Re2C>7, in particular perrhenic acid, react readily with the cyanometallate to produce tungsten- and/or rhenium- containing metal nitrides and/or metal carbides. In a further particular embodiment, the metal oxide may comprise WO3, in particular tungstic acid.
  • the cyanometallate used in the present invention may comprise a dicyanometallate, a tetracyanometallate, a hexacyanometallate, and/or an octacyanometallate, preferably a tetracyanometallate and/or a hexacyanometallate.
  • the cyanometallate is a hexacyanometallate.
  • a dicyanometallate comprises a metal centre coordinated to two cyanide ligands
  • a tetracyanometallate comprises a metal centre coordinated to four cyanide ligands
  • a hexacyanometallate comprises a metal centre coordinated to six cyanide ligands
  • an octacyanometallate comprises a metal centre coordinated to eight cyanide ligands. It may be that tetracyanometallates and/or hexacyanometallates, for example especially hexacyanometallates, offer a particularly efficient and convenient cyanometallate precursor for use in the process of the present invention.
  • the cyanometallate comprises a dicyanometallate
  • dicyanometallate comprises copper (Cu), silver (Ag) or gold (Au).
  • the cyanometallate comprises a tetracyanometallate
  • the tetracyanometallate comprises nickel (Ni), palladium (Pd) and/or platinum (Pt).
  • the cyanometallate comprises a hexacyanometallate
  • the hexacyanometallate comprises titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), and/or cobalt (Co).
  • the cyanometallate comprises octacyanometallate
  • the octacyanometallate comprises molybdenum (Mo).
  • the cyanometallate comprises a material having the formula
  • M 3 x [M 2 (CN) y ] z wherein M 2 and M 3 are the same or different metals, in particular wherein x is an integer from 1 to 4, in particular 1 or 4, preferably y is 4 or 6, and preferably z is an integer from 1 to 3, in particular 1 or 3.
  • x is 1, z is 1, and y is 6.
  • x is
  • M 2 is a transition metal.
  • M 2 may for instance be selected from Groups 8 and 9 of the Periodic Table of the Elements, such as from the list consisting of iron (Fe) and cobalt (Co), in particular from Fe (II), Fe(III) and Co (III).
  • cyanometallate anions are of formula [Fe(II)(CN 6 )] 4" , [Fe(III)(CN) 6 ] 3" , and
  • cyanometallates comprising a wide variety of different metals as the metal M 3 , including, for example, cyanometallates in which M 3 is an alkali metal, an alkaline earth metal, a transition metal, a rare earth metal (i.e.
  • post-transition metals are metallic elements located between the transition metals and the metalloids of the Period Table of the Elements, for example including aluminium (Al), gallium (Ga), indium (In), thallium
  • M 3 may for instance be selected from the list consisting of potassium (K), iron (Fe), cobalt (Co), yttrium (Y), aluminium (Al), gallium (Ga), lanthanum (La), praseodymium (Pr), and dysprosium (Dy).
  • M 3 is K(I), Fe(III), Co(III), Y(III), Al(III), Ga(III), La(III), Pr(III) or Dy(III).
  • M 3 is a trivalent metal cation.
  • the term "trivalent metal cation” is a metal cation in the 3+ oxidation state.
  • M 3 is a transition metal.
  • M 3 may for instance be selected from Group 3, Group 8, Group 9 or the lanthanide series of the Periodic
  • M 3 may be Fe(III) or Co(III). In the present application, and M 3 may be the same or different, advantageously the same.
  • Suitable examples of cyanometallate comprise Fe4[Fe(CN) ]3, K3[Fe(CN) ], Y[Fe(CN)5],
  • the molar ratio of metal oxide to cyanometallate in contacting step i) may range from 20: 1 to 1 :20, for example from 10: 1 to 1 : 10, such as from 10: 1 to 1 :5, in particular from 10: 1 to 1 : 1. Additionally or alternatively, the molar ratio of ratio M ⁇ .M ⁇ +M 3 in contacting step i) may range from 5: 1 to 1 :5, for example from 3: 1 to 1 :3, such as from 2: 1 to 1 :2, in particular about 1 : 1. It may be that a limited molar ratio helps to avoid undue wastage of excess material.
  • the step of contacting the metal oxide with the cyanometallate to form the reaction mixture comprises forming an intimate mixture of the metal oxide and the cyanometallate. It may be that the formation of an intimate mixture of the metal oxide and the cyanometallate increases reaction efficiency and thus provides better conversion of said precursors to the desired metal nitride and/or metal carbide. Contacting of the at least one metal oxide and the cyanometallate may be conducted in the presence or absence of a solvent. If a solvent is present, it may typically be selected from water, organic solvents, and mixtures thereof, especially water.
  • water as a at least part of the solvent, or of no solvent, may offer a particularly environmentally friendly and relatively safe process for making a metal nitride and/or a metal carbide, for example through the use of less organic solvent.
  • the cyanometallate and the metal oxide may be provided in solid form and contacting step i) of forming the reaction mixture may be carried out by dry mixing the cyanometallate and the metal oxide, for example wherein the cyanometallate and the metal oxide are provided in the form of crystals or powders.
  • dry mixing' refers to a method in which the materials are mixed together substantially without the use of a solvent.
  • 'dry mixing' includes any mixing method for combining two solids without the use of a liquid solvent, and thus does not exclude, for example, the use of a solid material comprising a compound co-crystallised with a solvate. Suitable examples of dry mixing methods include milling (e.g. ball milling), as well as basic methods such as solid-solid mixing using a pestle and mortar.
  • the cyanometallate and the metal oxide may be combined in the presence of a solvent.
  • the cyanometallate used in the process of the present invention may be provided in the form of a cyanogel, wherein the cyanogel comprises a mixture of: a) the cyanometallate, and b) at least part of the solvent.
  • the term "cyanogel” means a mixture of a cyanometallate and a solvent, for example formed by combining the solvent and the cyanometallate (for example in the form of a powder), and stirring the resulting mixture. The mixing can be achieved using any suitable method, e.g. using a magnetic stirrer on a stir plate.
  • the cyanogel is in the form of a solution, gel, or solid (e.g. a solid powder or crystalline material in which the solvent is taken up in the cyanometallate by sorption). It may be that when the cyanometallate is provided in the form of a cyanogel comprising a cyanometallate and at least part of the solvent, the step of forming the reaction mixture of the metal oxide and the cyanometallate can be carried out in a particularly efficient and straightforward manner. For example, it may be that the use of a cyanogel allows an especially intimate mixture of the cyanometallate and the metal oxide to be formed in the step of forming the reaction mixture.
  • a cyanogel comprising the cyanometallate and water may offer a particularly environmentally friendly and relatively safe process for making a metal nitride and/or a metal carbide, for example through the use of less organic solvent.
  • the step of contacting the metal oxide with the cyanometallate to form the reaction mixture comprises forming an intimate mixture of the metal oxide and the cyanometallate
  • the cyanometallate is provided in the form of a cyanogel, preferably a cyanogel comprising a mixture of the cyanometallate and the solvent
  • the metal oxide is preferably provided in the form of a solid such as crystals or powder.
  • the mixing of the cyanogel and the metal oxide can be achieved using any suitable method, e.g. using ball-milling as well as a magnetic stirrer on a stir plate depending on the viscosity of the reaction mixture. Said mixing may optionally be conducted in the presence of a further amount of the solvent if the cyanogel only comprises a part thereof.
  • the process of the first aspect of the invention comprises subjecting the reaction mixture to a temperature of at least 300D C, preferably to a temperature equal to or higher than the decomposition temperature of the cyanometallate.
  • the "decomposition temperature" of a substance is the temperature at which the substance decomposes to form one or more chemically different species.
  • the reaction mixture may be subjected to a temperature of at least 400°C, such as at least 500°C, in particular at least 600°C. Suitable temperature ranges may include a temperature of from 300 to 1000°C, such as 400 to 900°C, in particular 500 to 800°C, for instance 600 to 700°C.
  • the temperature that the reaction mixture is subjected to is a balance between providing an efficient reaction speed and avoiding unwanted thermal decomposition of the nitride and/or carbide product. It may also be that the temperature that the reaction mixture is subjected to is a balance between providing an efficient reaction speed and avoiding the need for costly specialised equipment.
  • the reaction period is typically up to 48 hours, such as up to 24 hours, in particular up to 12 hours.
  • the reaction period may be from 10 minutes to 48 hours, such as from 20 minutes to 24 hours, in particular from 30 minutes to 12 hours. It may be that the reaction period is a balance between allowing enough time for a reasonable amount of the desired metal nitride and/ or metal carbide to form and preventing or reducing unwanted thermal decomposition of the desired metal nitride and/or metal carbide products and/or the metal oxide and/or cyanometallate precursors.
  • the metal nitride and/or metal carbide comprises a material selected from the list consisting of: tungsten nitride, molybdenum nitride, niobium nitride, rhenium nitride, tungsten carbide, molybdenum carbide, niobium carbide and rhenium carbide, in particular tungsten nitride or rhenium carbide.
  • the metal nitride and/or metal carbide is a metal nitride, preferably tungsten nitride, e.g. W ⁇ 2N.
  • the metal nitride and/or carbide is a metal carbide, preferably rhenium carbide.
  • the metal nitride and/or metal carbide of the third aspect of the invention may also comprise at least two different metals, such as a first metal Ml as defined in the first aspect of the present invention, in particular a first metal selected from the list consisting of W, Mo, Nb and Re, and a second metal as defined in the first aspect of the present invention, in particular a second metal selected from the list consisting of Fe and Co.
  • the metal nitride and/or metal carbide of the third aspect of the invention may comprise at least one of a) an iron nitride and/or carbide, or a cobalt nitride and/or carbide, in particular iron nitride and/or carbide; and at least one of b) a tungsten, molybdenum, niobium or rhenium nitride and/or carbide, especially tungsten nitride or rhenium carbide, in particular tungsten nitride.
  • the metal nitride and/or metal carbide of the second or third aspect of the invention comprises tungsten nitride and at least one of iron nitride and iron carbide, for instance tungsten nitride, iron nitride and iron carbide, e. .W ⁇ 2N, Fe4N and Fe3C. It may be that such metal nitrides and/or carbides are particularly useful as catalysts, and/or can be prepared by a particularly convenient route from readily available and relatively low- cost starting materials.
  • the metal nitride and/or metal carbide of the second or third aspect of the invention is typically in the form of a crystalline material or a powder.
  • the metal nitride and/or metal carbide comprises Fe4N and a Powder X-
  • the metal nitride and/or metal carbide of the present invention may be used to form (or as) a hydroprocessing catalyst.
  • a hydroprocessing catalyst may, for example, be used in a variety of different hydroprocessing applications, for example hydrocracking, hydrodenitrogenation, hydrodesulfurization, hydrofining, hydroforming, hydrogenation and/or hydrotreating.
  • the catalyst is a hydrogenation, hydrodenitrogenation and/or hydrodesulfurization catalyst.
  • tungsten nitride-containing metal nitride catalyst is particularly useful as a hydroprocessing catalyst, for example as a hydrogenation, hydrodenitrogenation and/or hydrodesulfurization catalyst.
  • the catalyst is a catalyst for hydrogenolysis of a cycloparaffin.
  • metal carbide and/or nitride of the second or third aspect of the invention may incorporate any of the features described with reference to the method of the first aspect of the invention and vice versa.
  • IR data were collected using a Vertex 80, Praying Mentis IR spectrometer in drift mode with 128 background scans, 128 sample scans, 64 good FW scans and 64 good BW scans.
  • Yttrium(III) nitrate hydrate (Y(N03)3.xH20) and potassium hexacyanoferrate(II) (K3[Fe(CN)6]) were obtained from Signma-Aldrich®.
  • a typical procedure for preparation of a mixed transition metal cyanometallate is as follows: Y(N0 3 )3.xH 2 0 (10 mmol) was added to a solution of K 3 [Fe(CN) 6 ]
  • the cyanogels used in the following examples were prepared by combining the cyanometallate and the solvent (typically Fe4[Fe(CN) ]3 and water) in a beaker and manually stirring the mixture.
  • the solvent typically Fe4[Fe(CN) ]3 and water
  • metal nitride/carbide samples produced in the following examples were obtained in the form of crystalline materials.
  • Ce/ZrC>2 ceria-zirconia
  • sulphated ZrC>2 sulphated zirconia
  • tungstated zirconia are Bronsted acidic supports obtained from commercial suppliers and used without modification.
  • H2WO4 (5 g) and Fe4[Fe(CN)6]3 (2.4 g) were combined together by solid-solid mixing using a pestle and mortar in a molar ratio of H2WO4 to Fe4[Fe(CN) ]3 of 7: 1 (giving a 1 : 1 molar ratio of W:Fe) to form an intimate solid mixture.
  • a sample (2 g) of the resulting mixture was subjected to a temperature of 600°C for one hour under a nitrogen atmosphere to form metal nitride/carbide sample XI a.
  • the infrared spectrum of sample XI a is shown as trace
  • the new material formed is believed to be largely IR inactive.
  • H2WO4 (5 g) and Fe4[Fe(CN) 6 ] 3 (2.4 g) were combined together by solid-solid mixing using a pestle and mortar in a molar ratio of H2WO4 to Fe4[Fe(CN)6]3 of 7: 1 (giving a 1 : 1 molar ratio of W:Fe) to form an intimate solid mixture.
  • a sample (2 g) of the resulting mixture was subjected to a temperature of 450°C for one hour under a nitrogen atmosphere to form metal nitride/carbide sample X3.
  • the Powder X-Ray Diffraction partem of sample X3 is shown as trace C in Fig. 2.
  • a further sample (2 g) of the mixture was subjected to a temperature of 600°C for one hour under a nitrogen atmosphere to form metal nitride/carbide sample X4.
  • the infrared spectrum of sample X4 is shown as trace B in Fig. 2.
  • a further sample (0.1 g) of the mixture was subjected to a temperature of 750°C for one hour under a nitrogen atmosphere to form metal nitride/carbide sample X5.
  • the infrared spectrum of sample X5 is shown as trace A in Fig. 2.
  • the peak indexing for tungsten nitride is indicated by the lines labelled 100, 101, 102, 220 and 201 in Fig. 2 (referenced with respect to data published in J. Mater. Chem, 2011, 21, 10761-66), showing that W2N is present in samples X3 to X5.
  • X5 also contain other metal nitrides and metal carbides such as Fe4N, C3N4, Fe3C and Fe203.
  • 2-Theta peak indexes for W2N, Fe4N and Fe3C are listed in Table 1 (the product and byproducts being identified by comparison to literature values for each individual species - W2N: Fiala, Central Research Institute, SKODA, Czechoslovakia, Private Communication (1973); Fe 4 N: Jack. Proc. R. Soc. London, Ser. A 195, 34 (1948); Fe 3 C: Konobejewski. Z. Kristallogr.,
  • the Powder X-Ray Diffraction patterns of Fig. 2 show the transformation of the metal oxide and cyanometallate precursors into the metal nitrides and carbides after heating for a relatively short amount of time at moderate temperatures.
  • H2WO4 (2.5 g) and a cyanogel comprising Fe4[Fe(CN)6]3 (1.2 g) and water (50 mL)) (giving a 1 : 1 molar ratio of W:Fe) were mixed together in a 250 mL beaker in a molar ratio of H2WO4 to Fe4[Fe(CN) ]3 of 7: 1 (giving a 1 : 1 molar ratio of W:Fe) to form an intimate mixture.
  • a sample (3 g) of the resulting mixture was subjected to a temperature of 600°C for three hour(s) under a nitrogen atmosphere to form metal nitride/carbide sample X6.
  • a Scanning Electron Microscopy (SEM) image of sample X6 was taken showing plate-like morphology (views of the SEM image are shown in Figs.3 and 4).
  • H2WO4 (2.5 g) and a cyanogel (comprising Fe4[Fe(CN)6]3 (1.2 g) and water (50 mL)) were mixed together in a 250 mL beaker in a molar ratio of H2WO4 to Fe4[Fe(CN) ]3 of 7: 1 (giving a 1 : 1 molar ratio of W:Fe) to form an intimate mixture.
  • a sample (3 g) of the resulting mixture was subjected to a temperature of 600°C for three hours under a nitrogen atmosphere to form metal nitride/carbide sample X7.
  • a Transmission Electron Microscopy image of sample X7 was taken showing no apparent phase segregation (a view of the image is shown in Fig.5).
  • H2WO4 (5 g) and Fe4[Fe(CN) 6 ] 3 (2.4 g) were combined together by solid-solid mixing using a pestle and mortar in a molar ratio of H2WO4 to Fe4[Fe(CN) ]3 of 7: 1 (giving a 1 : 1 molar ratio of W:Fe) to form an intimate solid mixture.
  • a sample (2 g) of the resulting mixture was subjected to a temperature of 350°C for one hour under a nitrogen atmosphere to form metal nitride/carbide sample X8.
  • a further sample (1 g) of the mixture was subjected to a temperature of 450°C for one hour under a nitrogen atmosphere to form metal nitride/carbide sample X9.
  • a further sample (1 g) of the mixture was subjected to a temperature of 600°C for one hour under a nitrogen atmosphere to form metal nitride/carbide sample X10.
  • a further sample (1 g) of the mixture was subjected to a temperature of 600°C for two hours under a nitrogen atmosphere to form metal nitride/carbide sample XI 1.
  • a further sample (1 g) of the mixture was subjected to a temperature of 600°C for three hours under a nitrogen atmosphere to form metal nitride/carbide sample X12.
  • X-Ray Photoelectron Spectroscopy results presented in Table 2 demonstrate the formation of metal nitride from the mixture of the metal oxide and cyanometallate precursors as the mixture is heated. It should be noted that XPS is a surface-specific technique that gives an indication of only what material is present on the surface of a relatively small fraction of a sample. Thus, it does not give an indication of the composition of the bulk material of a sample, and therefore does not provide a quantitative estimate of the completeness or otherwise of the formation of the nitride product.
  • sample X6, prepared in example 3 was tested as a catalyst in cycloparaffin hydrogenolysis according to the catalyst runs set out below.
  • Sample X6 (0.2 g) and EHC-50 (API Group II base stock comprising about 80% naphthene rings and about 20% aromatic rings) (3 g) were combined and heated to 300°C under H2 pressure (900 psig, 62 barg) in an autoclave with stirring at 600 RPM for 6 hrs. Run 2
  • Sample X6 (0.2 g), -10% Ce/Zr0 2 (0.2 g) and EHC-50 (API Group II base stock comprising about 80% cycloparaffin and about 20% aromatic rings) (3 g) were combined and heated to 300°C under H 2 pressure (900 psig, 62 barg) in an autoclave with stirring at 600 RPM for 6hrs.
  • H 2 pressure 900 psig, 62 barg
  • Sample X6 (0.2 g), sulphated Zr0 2 ( ⁇ 2.3% S) (0.2 g) and EHC-50 (API Group II base stock comprising about 80% cycloparaffin and about 20% aromatic rings) (3 g) were combined and heated to 300°C under H 2 pressure (900 psig, 62 barg) in an autoclave with stirring at 600 RPM for 6 hrs.
  • H 2 pressure 900 psig, 62 barg
  • Sample X6 (0.2 g), -15% W7Zr0 2 (0.2 g) and EHC-50 (API Group II base stock comprising about 80% cycloparaffin and about 20% aromatic rings) were combined and heated to 300°C under H 2 pressure (900 psig, 62 barg) in an autoclave with stirring at 600 RPM for 6 hrs.
  • H 2 pressure 900 psig, 62 barg
  • the invention relates to:
  • Embodiment 1 A method for producing a metal nitride and/or a metal carbide, the method comprising: i) contacting at least one metal oxide comprising at least one first metal Ml with a cyanometallate comprising at least one second metal to form a reaction mixture; and,
  • reaction mixture ii) subjecting the reaction mixture to a temperature of at least 300°C for a reaction period.
  • Embodiment 2 A method according to embodiment 1, wherein Ml is atransition metal, preferably wherein Ml is selected from Groups 5, 6 or 7 of the Periodic Table of the Elements.
  • Embodiment 3 A method according to embodiment 1 or 2, wherein M ⁇ is selected from the list consisting of: W, Re, Nb and Mo; in particular from W and Re.
  • Embodiment 4 A method according to any preceding embodiment, wherein the metal oxide comprises WO3, in particular tungstic acid; and/or wherein the metal oxide comprises
  • Embodiment 5 A method according to any preceding embodiment, wherein the cyanometallate comprises a dicyanometallate, a tetracyanometallate, a hexacyanometallate, and/or an octacyanometallate, preferably a tetracyanometallate and/or a hexacyanometallate.
  • Embodiment 6 A method according to any preceding embodiment, wherein the cyanometallate comprises a material having the formula M 3 x [M2(CN)y] z , wherein M ⁇ and
  • M 3 are the same or different metals, preferably wherein x is an integer from 1 to 4, preferably y is 4 or 6, and preferably z is an integer from 1 to 3, more preferably wherein x is 1, z is 1 and y is 6 or x is 4, z is 3 and y is 6.
  • Embodiment 7 A method according to any preceding embodiment, wherein M ⁇ is a transition metal, preferably wherein M ⁇ is selected from Groups 8 and 9 of the Periodic Table of the Elements.
  • Embodiment 8 A method according to any preceding embodiment, wherein M ⁇ is selected from the list consisting of Fe(II), Fe(III) and Co(III).
  • Embodiment 9 A method according to any one of embodiments 6 to 8, wherein M 3 is a transition metal, preferably wherein M 3 is selected from Group 3, Group 8, Group 9 or the lanthanide series of the Periodic Table of the Elements.
  • Embodiment 10 A method according to any one of embodiments 6 to 8, wherein M 3 is selected from the list consisting of K(I), Fe(III), Co(III), Y(III), Al(III), Ga(III), La(III), Pr(III) and Dy(III), preferably from the list consisting of Fe(III) and Co(III).
  • Embodiment 11 A method according to any preceding embodiment, wherein the cyanometallate comprises Fe 4 [Fe(CN) 6 ] 3 , K 3 [Fe(CN) 6 ], Y[Fe(CN) 6 ], Al[Fe(CN) 6 ],
  • Embodiment 12 A method according to any preceding embodiment, wherein the molar ratio of metal oxide to cyanometallate in contacting step i) is from 10: 1 to 1 : 10, preferably from 10: 1 to 1 :5, more preferably from 10: 1 to 1 : 1.
  • Embodiment 13 A method according to any preceding embodiment, wherein the step of contacting the metal oxide with the cyanometallate to form the reaction mixture in step i) comprises forming an intimate mixture of the metal oxide and the cyanometallate, optionally in the presence of a solvent.
  • Embodiment 14 A method according to embodiment 13, wherein the solvent is selected from water, organic solvents and their mixtures, more preferably wherein the solvent is water.
  • Embodiment 15 A method according to any preceding embodiment, wherein the cyanometallate and the metal oxide are combined in the presence of a solvent and wherein the cyanometallate is provided in the form of a cyanogel that comprises a mixture of: a) the cyanometallate, and b) at least part of the solvent.
  • Embodiment 16 A method according to any one of embodiments 1 to 13, wherein the cyanometallate and the metal oxide are provided in solid form, and wherein contacting step i) comprises combining the metal oxide with the cyanometallate using a dry mixing method, in particular ball milling.
  • Embodiment 17 A method according to any preceding embodiment, wherein the reaction mixture is subjected to a temperature of at least 400°C, such as at least 500°C, in particular at least 600°C.
  • Embodiment 18 A method according to any preceding embodiment, wherein the reaction mixture is subjected to a temperature of from 300 to 1000°C, such as 400 to 900°C, in particular 500 to 800°C.
  • Embodiment 19 A method according to any preceding embodiment, wherein the reaction period is up to 48 hours, such as up to 24 hours, in particular up to 12 hours.
  • Embodiment 20 A method according to any preceding embodiment, wherein the reaction period is from 10 minutes to 48 hours, such as from 20 minutes to 24 hours, in particular from 30 minutes to 12 hours.
  • Embodiment 21 A metal nitride and/or metal carbide comprising: a) a first metal nitride and/or carbide selected from the list consisting of: iron nitride, iron carbide, cobalt nitride and cobalt carbide; and
  • a second metal nitride and/or carbide selected from the list consisting of: tungsten nitride, tungsten carbide, rhenium nitride and rhenium carbide.
  • Embodiment 22 A metal nitride and/or metal carbide according to embodiment 21 comprising tungsten nitride and at least one of iron nitride and iron carbide.
  • Embodiment 23 A metal nitride and/or metal carbide according to embodiment 21 or embodiment 22 prepared by the method according to any one of embodiments 1 to 20.
  • Embodiment 24 A metal nitride and/or metal carbide prepared by the method according to any one of embodiments 1 to 20.
  • Embodiment 25 A metal nitride and/or metal carbide according to embodiment 24, wherein the metal nitride and/or metal carbide comprises at least two different metals, in particular: a first metal selected from the list consisting of W, Mo, Nb and Re; and a second metal M ⁇ selected from the list consisting of Fe and Co.
  • Embodiment 26 A metal nitride and/or metal carbide according to embodiment 24 or embodiment 25 comprising a material selected from the list consisting of: tungsten nitride, molybdenum nitride, niobium nitride, rhenium nitride, tungsten carbide, molybdenum carbide, niobium carbide and rhenium carbide, preferably tungsten nitride and rhenium carbide.
  • Embodiment 27 A metal nitride and/or metal carbide according to any one of embodiments 24 to 26 comprising tungsten nitride and at least one of iron nitride and iron carbide.
  • Embodiment 31 Use of the metal nitride and/or carbide of any one of embodiments 21 to 30 as a catalyst.
  • Embodiment 32 The use of embodiment 31 , wherein the catalyst is a hydroprocessing catalyst, preferably a hydrogenation, hydrodenitrogenation and/or hydrodesulfurization catalyst.
  • the catalyst is a hydroprocessing catalyst, preferably a hydrogenation, hydrodenitrogenation and/or hydrodesulfurization catalyst.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne également un procédé de production d'un nitrure métallique et/ou d'un carbure métallique, un nitrure métallique et/ou un carbure métallique éventuellement produit selon le procédé, ainsi que l'utilisation du nitrure et/ou du carbure métallique dans la catalyse, éventuellement, un hydrotraitement catalytique. Facultativement, le procédé comprend les étapes suivantes : i) mettre en contact au moins un oxyde métallique comprenant au moins un premier métal M1 avec un cyano-métallate comprenant au moins un second métal M2 pour former un mélange réactionnel; et ii) soumettre le mélange réactionnel à une température d'au moins 300°C pendant un temps de réaction. Facultativement, le nitrure métallique et/ou le carbure métallique est un nitrure métallique comprenant du nitrure de tungstène.
PCT/US2017/051054 2016-10-05 2017-09-12 Procédé de production de nitrures métalliques et de carbures métalliques WO2018067276A1 (fr)

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SG11201901826XA SG11201901826XA (en) 2016-10-05 2017-09-12 Method for producing metal nitrides and metal carbides
CA3042942A CA3042942C (fr) 2016-10-05 2017-09-12 Procede de production de nitrures metalliques et de carbures metalliques
CN201780061701.8A CN109790024B (zh) 2016-10-05 2017-09-12 制备金属氮化物和金属碳化物的方法
KR1020197009035A KR102453050B1 (ko) 2016-10-05 2017-09-12 금속 질화물 및 금속 탄화물의 제조 방법
EP17768654.0A EP3523240B1 (fr) 2016-10-05 2017-09-12 Procédé de production de nitrures et carbures métalliques
JP2019517957A JP7117296B2 (ja) 2016-10-05 2017-09-12 金属窒化物および金属炭化物を製造する方法
US16/335,366 US10974962B2 (en) 2016-10-05 2017-09-12 Method for producing metal nitrides and metal carbides
ZA2019/01134A ZA201901134B (en) 2016-10-05 2019-02-22 Method for producing metal nitrides and metal carbides

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0395746B1 (fr) * 1988-04-12 1994-06-22 United States Department Of Energy Procede de fabrication de barbes de nitrures de metaux de transition
US5443560A (en) * 1989-11-29 1995-08-22 Philip Morris Incorporated Chemical heat source comprising metal nitride, metal oxide and carbon
WO2000041404A2 (fr) 1999-01-08 2000-07-13 Trueposition, Inc. Procede puissant de demodulation pour systeme de radiolocalisation
US20070284289A1 (en) * 2006-04-17 2007-12-13 Petroleo Brasileiro S.A.-Petrobras Process to prepare mixed molded carbide and nitrite material and its application as a catalyst in hydrotreatment processes
US7390920B2 (en) * 2002-02-14 2008-06-24 Monsanto Technology Llc Oxidation catalyst and process
WO2014027096A1 (fr) * 2012-08-17 2014-02-20 Georg Vogt Procédé de production de composés de métaux de transion, composés de métaux de transition et leur utilisation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0395746B1 (fr) * 1988-04-12 1994-06-22 United States Department Of Energy Procede de fabrication de barbes de nitrures de metaux de transition
US5443560A (en) * 1989-11-29 1995-08-22 Philip Morris Incorporated Chemical heat source comprising metal nitride, metal oxide and carbon
WO2000041404A2 (fr) 1999-01-08 2000-07-13 Trueposition, Inc. Procede puissant de demodulation pour systeme de radiolocalisation
US7390920B2 (en) * 2002-02-14 2008-06-24 Monsanto Technology Llc Oxidation catalyst and process
US20070284289A1 (en) * 2006-04-17 2007-12-13 Petroleo Brasileiro S.A.-Petrobras Process to prepare mixed molded carbide and nitrite material and its application as a catalyst in hydrotreatment processes
WO2014027096A1 (fr) * 2012-08-17 2014-02-20 Georg Vogt Procédé de production de composés de métaux de transion, composés de métaux de transition et leur utilisation

Non-Patent Citations (23)

* Cited by examiner, † Cited by third party
Title
"Fe3C", KONOBEJEWSKI. Z. KRISTALLOGR., KRISTALLGEOM., KRISTALLPHYS., KRISTALLCHEM., vol. 72, 1929, pages 386
ALEXANDER; HARGREAVES, CHEM. SOC, REV., vol. 39, 2010, pages 4388 - 4401
APARICIO, C.; MACHALA, L.; MARUSAK, Z., J. THERM. ANAL. CALORIM., vol. 110, 2012, pages 661
CHEM. MATER, vol. 15, 2003, pages 2969 - 2976
CHEM. SOC. REV., vol. 39, 2010, pages 4388 - 4401
D. BRAGA; I. G. LEZAMA; H. BERGER; A. F. MORPURGO, NANO LETT., vol. 12, 2012, pages 5218 - 5223
D. MCKAY; D. H. GREGORY; J. S. J. HARGREAVES; S. M. HUNTER; X.-L. SUN, CHEM. COMMUN., 1997, pages 3051 - 3053
FE N: JACK. PROC. R. SOC. LONDON, vol. A 195, 1948, pages 34
FIALA: "Private Communication", 1973, CENTRAL RESEARCH INSTITUTE
H. J. YAN; C. G. TIAN; L. SUN; B. WANG; L. WANG; J. YIN; A. P. WU; H. G. FU, ENERGY ENVIRON. SCI., vol. 7, 2014, pages 1939 - 1949
J. G. CHEN, CHEM. REV., vol. 96, 1996, pages 1477 - 1498
J. MATER. CHEM., vol. 14, 2004, pages 228 - 232
J. MATER. CHEM., vol. 21, 2011, pages 10761 - 10766
J. S. J. HARGREAVES; D. MCKAY, J. MOL. CATAL. A: CHEM., vol. 305, 2009, pages 125 - 129
J. S. JANG; D. J. HAM; E. RAMASAMY; J. LEE; J. S. LEE, CHEM. COMMUN., vol. 46, 2010, pages 8600 - 8602
M. HUNTER; D. MCKAY; R. I. SMITH; J. S. J. HARGREAVES; D. H. GREGORY, CHEM. MATER., vol. 22, 2010, pages 2898 - 2907
MOHAMED B. ZAKARIA, RSC ADV., vol. 6, 2016, pages 10341
NANDI ET AL., ACS APPL. MATER. INTERFACES, vol. 6, 2014, pages 6606 - 6615
PHYS. CHEM. CHEM. PHYS., vol. 17, 2015, pages 17445 - 17453
WEAR, vol. 262, 2007, pages 655 - 665
WRIEDT, BULL. OF ALLOY PHASE DIAGR., vol. 10, no. 4, 1989, pages 358 - 367
XIAO ET AL., ACS NANO, vol. 8, no. 7, 2014, pages 846 - 7857
Y. LIU; W. E. MUSTAIN, ACS CATAL, vol. 1, 2011, pages 212 - 220

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