• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Procedure for obtaining catalysts of formula MandCe1-xLxO2-x/2)1-yfor use in the reverse reaction of water gas displacement and partial oxidation of methane to synthesis gas by solution combustion method. The invention relates to the process for obtaining catalysts by the method of combustion in solution, to the catalysts obtained by said process and to their particular use in the reverse reaction of gas water displacement and in the partial oxidation of methane in gas of synthesis. Therefore, we understand that the present invention is situated in the area of green industry aimed at the reduction of CO2 of the planet.
    公开号:ES2674434A1
    申请号:ES201730807
    申请日:2017-06-16
    公开日:2018-06-29
    发明作者:Maria Consuelo Alvarez Galvan；Martin DAPENA OSPINA；Jose Antonio Alonso Alonso；Loreto TRONCOSO AGUILERA；Vanessa CASCOS JIMENEZ；Jose Miguel Campos Martin；Jose Luis Garcia Fierro；Horacio FALCÓN RICHENI
    申请人:Consejo Nacional de Investigaciones Cientificas y Tecnicas CONICET；Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    The invention relates to the process for obtaining catalysts by the solution combustion method, to the catalysts obtained by said process and to their particular use in the reverse reaction of displacement of water gas and in the partial oxidation of methane in gas from synthesis.
    Therefore, we understand that the present invention is located in the area of green industry aimed at reducing CO2 on the planet.
    STATE OF THE ART
    Carbon dioxide is the main source of greenhouse gases. To reduce its emissions, it is essential to gradually replace the use of fossil fuels with renewable energy sources. The current use of CO2 is limited to a few processes: the synthesis of urea, salicylic acid and polycarbonates, but this only corresponds to a small percentage of the potential CO2, useful for being transformed into chemicals and fuels. Currently, numerous efforts are being made to consider it as a resource rather than as a waste, investing in the development of new technologies that promote recycling.
    One of the most promising processes for its recovery is the production of liquid and oxygenated hydrocarbons, which have an excellent volumetric energy density, from CO2 (from thermal power plants or from combustion, pyrolysis or gasification of biomass residues, such such as agricultural, forestry, livestock, urban, etc.) and renewable H2 (which could be generated by electrolysis, thermochemical cycles, biomass gasification, reforming of alcohols and polyols, etc.). CO2 reduction with H2 is an application that provides a solution to
    Two problems: the recycling of coal and the storage of H2. This is a two-stage process, in which the first and essential is the reverse reaction of water gas displacement (Reverse Water-Gas shift, rWGS, CO2 + H2. = ;: CO + H20), which allows activating the Stable carbon dioxide molecule and transform it into a more reactive compound, carbon monoxide. The second stage would consist of the catalytic hydrogenation of CO2 / CO mixtures, to produce hydrocarbons, through the Fischer-Tropsch reaction, or methanol, by hydrogenation of CO. Methanol is a basic compound for the production of a wide variety of chemical products, such as dimethyl ether, a substitute for diesel fuel and liquefied petroleum gases (LPG) [M. Aresta,
    A. Dibenedetto, A. Angelini, Chem. Rev. (2014) 114,1709-1742) [M. D. Porosoff, B. Van, J.G. Chen, Energy Environ. Sci. (2016) 9, 62-73).
    The reverse reaction of gas displacement from water is slightly endothermic
    15 {6.Ho = 41.2 kJ / mol) and in equilibrium. This makes it favored by the use of high reaction temperatures, and close to 700-BOOcC. At temperatures below aoo, thermodynamics would favor the methanation reaction (C02 + 3 H2 ~ CH4 + H20). To achieve high conversions and favorable kinetics, the use of a catalyst that is active and stable at these high levels becomes imperative.
    20 temperatures.
    The rWGS reaction has been successfully investigated, using, among other phases,
    active, noble metals [S.S. Kim, H.H. Lee, S.C. Hong, Appl. Catal., A (2012) 423
    424, 100.) [S. S. Kim, K. H. Park, S. C. Hong, Fuel Process. Technol. (2013) 108,
    25 47), as well as nickel [B. Lu, K. Kawamoto, RSC Adv. (2012) 2, 6800. [L. Wang, S. Zhang, Y. Líu, J. Rare Earths (2008) 26, 66.) Ycobalto [L. Wang, H. Líu, Y. Chen, R. Zhang, S. Yang, Chem. Let !. (2013) 42, 682-683).
    The support plays a fundamental role in the reaction, since the existence of
    30 oxygen vacancies promotes the adsorption of carbon dioxide. Thus, a requirement of the support is that it is reducible and that it has oxygen storage capacity. One of the reducible oxides successfully used in this reaction as a support constituent is Ce02 [12,14,17], A. Goguet, F.C.
    Meunier, D. Tibiletti, J.P. Breen, R. Burch, J. Phys. Chem. B. 108 (20240-20246) (L. Wang, H. Liu, Y. Chen, R. Zhang, S. Yang, Chem. Lett. (2013) 42, 682-683).
    On the other hand, the most accepted reaction mechanism is based on the adsorption of the
    5 CO2 on an oxygen vacancy in the support, giving rise to a carbonate with an oxygen in the support network, and then desorbed as carbon monoxide and leave the oxygen vacancy occupied. Hydrogen adsorbs dissociatively on platinum and diffuses to an oxygen in the support, where it recombines, forming water vapor and creating an oxygen vacancy (W.
    10 Wang, S. Wang, X. Ma, J. Gong, Chem. Soc. Rev., 2011, Vol. 40, pages 3703 3727]. Taking into account that the most plausible reaction mechanism is bifunctional according to which both the transition metal and the oxide constituting the support have a cooperative action, it is necessary to increase the metal-support interaction, with a maximization of the contact area between these . Therefore, the
    The preparation method plays an important role in the synthesis of stable and active catalysts. Thus, the coprecipitation method, compared to the impregnation or precipitation-deposit method, gives rise to a better catalytic behavior, attributed to a greater contact between the active phase and the existing oxygen vacancies in the support [L. Wang, H. Liu, Y. Liu, Y. Chen, S. Yang, J. Rare Earths 31 (2013) 559).
    Thus, patent CN103183346, presents an invention relating to a method for synthesizing a catalyst, based on nickel and cerium, for the reverse reaction of water gas shift, in which the activation of the catalyst with pure CO2 is carried out, with high activity and stability, as well as low cost.
    In the bibliography there are other compounds also based on a metal or a metal oxide deposited on ceria doped with Gd for other uses that are not catalysts, such as a compound of the formula NiO-Ceo_9Gdo_10 2..6 that is used as an anode in solid state fuel cells and you get it by
    30 homogenization of ceria doped oxide with Gd and NiO in a ball mill ["Electrochemical characterization of Ni-CeO.9GdO.102d for SOFC anodes" Bettina Rfscha, Hengyong Tua, Andreas O. Stfrmera, Axel C. Müller and Ulrich Stimming, Solid State lonies 175 (2004) 113-117) Patent CN103418392 (A) discloses the invention of a catalyst for reverse water gas shift and preparation, by the sol-gel method, using citric acid. The catalyst consists of cobalt as the active phase and Ce02 as a support, as well as potassium as an auxiliary agent. They indicate that the prepared catalyst has high activity, good selectivity and stability for the rWGS reaction.
    However, these catalysts are of the mass type, without internal porosity. This constitutes a disadvantage since in this type of system, the dispersion of the active phases is low and it would be necessary to use a high amount of catalyst. Therefore, the synthesis of mesostructured oxides is a challenge, not only in the field of catalysis, but also in the field of fuel cells and sensors. In order to increase the dispersion of the active phase, the combustion-based catalyst synthesis method is proposed as a very interesting way, since it would form a material with high porosity, so that the amount of catalyst required would be significantly less , thus with a high thermal resistance, an essential requirement, given the high temperatures necessary to carry out the reaction.
    This combustion synthesis is an exothermic redox reaction, in which oxidation and reduction reactions occur simultaneously, between an oxidant and a fuel. Only when the oxidant and fuel are intimately mixed in a fixed ratio can combustion be started. In several cases, the heat necessary to start the reaction is generated internally. In other cases, it must be provided by an external source. The solution combustion synthesis (SCS) method, developed by Patil et al. [Patil, K.C., Mimani, T .: Solution combustion synthesis of nanoscale oxides and their composites. Mater. Phys. Mech. 4, 134-137 (2001)], is based on a self-sustaining combustion reaction (the heat released is greater than that required for the reaction and the reactions occur at high temperatures) between a fuel and an oxidant. Typically the oxidant consists of a nitrate type metallic precursor, and the fuel in glycine, urea, citric acid etc. In this type of synthesis of combustion in solution, the reagents are dissolved in water, to achieve molecular homogenization in the reaction medium. The reagent solution is preheated with an external heat source at moderate temperatures (-150-350 ° C), causing evaporation of the water; when
    a critical temperature is reached, the solution self-ignites and the temperature increases very rapidly (up to 104 oC / second) to values above 1000oC. Simultaneously, the reaction converts the mixture of precursors into materials with the desired composition and with great porosity, small particle size and a high degree of crystallinity.
    The decrease in oil reserves has increased interest in the use of natural gas as an energy resource (through the so-called "Hydrogen Economy") and as a source of chemical products. Obtaining synthesis gas (CO and hydrogen) by catalytic partial oxidation of methane (CPOM), a slightly exothermic reaction, offers an economic incentive compared to the current industrial route: steam reforming, a highly endothermic process. In addition, CPOM produces a HiCO ratio of 2, which is ideal to be used directly in the production of hydrocarbons, by the FischerTropsch synthesis, and in the synthesis of methanol, a fundamental raw material in the chemical industry (APE York, T. Xiao , and MLH Green. Topics in Catalysis Vol. 22, (2003) 345-358).
    Supported nickel metal based catalysts are active for CPOM, however they undergo further deactivation due to coke formation and sintering. If we compare its activity with that of catalysts with a noble metal (Pt, Pd, Ir, Ru or Rh) as the active phase, it is observed that the latter show greater activity and stability, however, these types of catalysts are very expensive in comparison with nickel-based ones, therefore limiting their use in industrial processes (C. Berger-Karin et al. J. Catal. 280 (2011), 116).
    In order for this process to be implemented at an industrial level, it is necessary to develop economic, active and stable catalysts, so that the deactivation phenomena decrease. Previous studies indicate that a high dispersion of the active phase is key to obtain a good catalytic behavior since coke formation is promoted by large metallic particles (J. Barbero et al., Catal. Lett. 87 (2003), 211 ) On the other hand, the use of promoters based on oxides with high ionic mobility, such as Ce02, or various lantanides, would increase reactivity and stability. (M. D. SalazarVilla panda et al. In !. J Hydrogen Energy, 34 (2009), 9723).
    The mobility of oxygen in these catalysts seems crucial to increase their reactivity in this process (B.C. Enger, R. L0deng, A Holmen, Applied Catalysis
    A: General 346 (2008) 1-27).
    On the other hand, another challenge at present is to decrease the formation of hot spots, which are the result of the combination of a high space velocity and an exothermic reaction, which would make it difficult to control the process on an industrial scale (YH Hu and E. Ruckenstein I Adv. Catal. 48 (2004) 297-345).
    DESCRIPTION OF THE INVENTION
    The present invention provides a process for obtaining a cerium oxide substituted with a lanthanide L (from La to Lu), and trio and / or scandium, in the positions of Ce. The introduction of L3 "partially replacing Ce4 + induces generation of oxygen vacancies in the crystal lattice, which are essential for the fixation of various gas molecules, as described above In addition, this invention also involves the deposition of nanoparticles of a precious or semi-precious metal selected from the groups 8, 9, 10 and 11 of the periodic table of the elements in metallic form on the surface of the cerium oxide, preferably the metal is selected from nickel, copper and platinum, which represent active centers.These cermet-type materials can be used as catalysts in various reactions.
    This procedure for obtaining or synthesis by combustion in solution gives rise to catalysts that do not require a previous stage of activation of the active phase, since the metal in the metallic state is obtained directly.
    Furthermore, the catalysts have a high activity by mass of catalyst for the reverse reaction reactions of gas displacement of water and partial oxidation of methane to synthesis gas.
    On the other hand, the synthesis method gives rise to materials with high macroporosity and nanoparticles, which increases the dispersion of the active phase_ Finally, the procedure for obtaining the present invention reduces the formation of hot spots, which would affect important in improving stability and temperature control at an industrial level.
    Therefore, in a first aspect, the present invention relates to a process for obtaining a compound of the formula:
    My (Ce1_xLx02_x / 2) 1-y where M is a metal selected from Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au or Cu, where x = 0.0 -0.4 and y = 0.001 -0 , 6, preferably y = 0.02 -0.6, Y where L is selected from a lanthanide, Y or Sc,
    characterized by comprising the following stages:
    a) dissolve in the minimum amount of water, stoichiometric amounts of Ce Nitrate, water soluble salt of a metal selected from Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au or Cu, Nitrate of L, Y or Sc
    and adding to the solution of step (a) a molar ratio of between 0.7 and 1.0 of fuel with respect to the total nitrates, b) stirring at room temperature until complete dissolution of the solution obtained in (a), and c) heating the solution obtained in (b) to a temperature of between 200 oC and
    600 oC.
    The presence of nitrates in the aqueous solution of step (a) is essential for the combustion method to work, therefore aqueous Ce and L, Y or Sc_ nitrates are used in the present process of the invention.
    Example of water soluble salts of a metal selected from Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au or Cu are nitrates, chlorides, sulfates and coordination compounds_ As precursors of platinum, nitrates can be used, as well as soluble salts of inorganic complexes (coordination compounds) such as dihydroxy tetraamin platinum (11) «NH,), Pt (OH), 'xH, O) and nitrate of tetraamin platinum (11) (Pt (NH,), (NO, ),).
    Therefore, preferably in the process of the invention, nickel nitrate (11) Ni (NO ')' 6H, ~ is used as the water-soluble Ni salt.
    Preferably, in the process of the invention, copper nitrate (11), Cu (NO,), · 6H, O is used as the water-soluble Cu 10 salt.
    Preferably, Pt salt is used in the process of the invention
    soluble in water a salt selected from dihydroxy tetraamin platinum (11)
    «NH,), Pt (OH), 'xH, O) and tetraamin platinum nitrate (11) (Pt (NH,), (NO,),).
    In another preferred embodiment of the process of the present invention, the compound of formula My (Ce1_xLx02_xl2) 1 _y that is obtained has a value of x other than O and, therefore, there will always be positions of Ce substituted by a lanthanide Y or Sc .
    That lanthanide element L is preferably selected from the following elements: La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. More preferably the lanthanide is selected from Gd and La.
    When in a preferred embodiment the lanthanide L is Gd, preferably x has a value of between 0.05 and 0.2
    When in another preferred embodiment the lanthanide L is Gd, preferably, and has a value of between 0.001 and 0.15, preferably between 0.03 and 0.15. 30
    When in a preferred embodiment the lanthanide L is La, preferably x has a value of between 0.05 and 0.2 When in another preferred embodiment the lanthanide L is La, preferably, and has a value of between 0.001 and 0.15, preferably of between 0.03 and 0.15.
    When in a preferred embodiment the lanthanide L is Sm, preferably x has a value of between 0.05 and 0.2
    When in another preferred embodiment, the Les Sm ellanthanide is preferably and has a value of between 0.001 and 0.15.
    In another preferred embodiment of the process of the present invention the fuel used in step (a) is selected from glycine, citric acid, urea; and a combination of the above. More preferably glycine is used as fuel in step (a) of the process of the invention.
    In the present invention the term "fuel" is used to carry out the synthesis by combustion in solution, so that, when the water present in the solution evaporates, the fuel ignites, reaching more than 1000 oC in the reaction medium despite applying only 300 oC to the reaction. This method causes the generation of high purity products with high macroporosity.
    In another preferred embodiment of the process of the present invention step (c) is carried out at a temperature of between 200 oC and 500 oC.
    Another aspect of the present invention relates to a compound characterized by the formula My (Ce, _xLx02_xI2) 1_ and characterized in that
    • M is a selected metal selected from Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au or Cu,
    • x = 0.0 -0.4 and y = 0.001 -0.6, preferably y = 0.02 -0.6, Y
    • L is selected from a lanthanide, Y or Sc.
    • M is Ni and
    • its formula is Niy (Ce1_xLx0 2_Kl2), _ and
    or where x = 0.0 -0.4 and y = 0.005 -0.6, preferably y = 0.02 -0.6,
    or and where L is selected from a lanthanide, I Sc.
    In another preferred embodiment of the compound of the present invention the compound is characterized in that
    In another preferred embodiment of the compound of the present invention the compound is characterized in that
    • MesCuy
    • its formula is CUy (Cel_xLx0 2_xI2) 1_y
    or where x = 0.0 -0.4 and y = 0.005 -0.6, preferably y = 0.02 -0.6,
    o and where L is selected from a lanthanide, I Sc.
    In another preferred embodiment of the compound of the present invention the compound is characterized in that
    • MesPt and
    • a compound of the formula Pty (Cel_xLx0 2.xJ2) 1.y is obtained
    or where x = 0.0 -0.4 and y = 0.001 -0.6, preferably y = 0.02 -0.6,
    or and where L is selected from a lanthanide, Y or Sc.
    On the other hand, the compound of the present invention is preferably characterized in that it has a porosity percentage of between 70% and 95% and an average pore diameter of between 0.5 iJm and 5 iJm. This porosity is a key factor in catalytic behavior because it results in a very high active surface area per unit mass of catalyst, resulting in increased catalytic activity.
    A preferred embodiment of the compound refers to a compound of formula My (Cel_xLx02_xl2) 1_y, where x is different from O, that is, in a compound there will always be Ce positions substituted by a lanthanide or by Y or by Sc.
    In a preferred embodiment of the compound the lanthanide L is selected from La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
    Preferably the lanthanide element is Gd; more preferably
    • x has a value of between 0.05 and 0.2; and
    • y has a value of between 0.001 and 0.15, even more preferably and has a
    value between 0.03 and O, 15. In another preferred embodiment of the compound the lanthanide is la; more preferably
    • x has a value of between 0.05 and 0.2; or
    • Y has a value of between 0.001 and 0.15, even more preferably and has a value of between 0.03 and 0.15.
    Preferably the lanthanide element is Sm; more preferably
    • x has a value between 0.05 and 0.2 or
    • y has a value between 0.001 and 0.15.
    Preferably the compound of the present invention has been obtained by the procedure described above.
    When the compound has the formula Niy (Cel_xlx02.xJ2) 1.y where M is Ni, x = 0.0 0.4 and y = 0.005 -0.6, preferably y = 0.02 -0.6, Y where l is selected from a lanthanide, Y or Sc, then in step (a) of the process of the present invention nickel nitrate is used.
    When the compound has the formula CUy (Cel_xl x0 2.1 12) 1.y where M is Cu, x = 0.0 0.4, yy = 0.005 -0.6 Y where l is selected from a lanthanide, Y or Sc , then in step (a) of the process of the present invention copper nitrate is used.
    When the compound has the formula pty (Cel_xl x02.xJ2) 1.y where M is Pt, x = 0.0 0.4, and y = 0.001 -0.6 Y where l is selected from a lanthanide, Y or Sc, then in step (a) of the process of the present invention dihydroxy tetra-amin-Platinum (II) is used.
    In a third aspect of the invention, this relates to the use of the compound described above, as a catalyst.
    A preferred use of the compound relates to its use as a catalyst in the reverse gas displacement reaction of water.
    In the present invention, the inverse reaction of the displacement of water gas "is understood as that reaction in which CO2 is used as a reagent together with H2 which in the presence of a catalyst produces CO and water.
    Preferably in the reverse reaction of gas displacement of water is used
    a compound of formula My (Cel.xLx0 2_xl2h.y as described above
    characterized in that x is non-zero and the lanthanide is Gd or La.
    Preferably the compound of formula Nio.l (CeO.96Gdo.040 1.9S) O.9 is used as a catalyst in the reverse reaction of gas displacement of water.
    Preferably, the compound of formula Nio., (CeO.9Gdo.l0, .9S) O.9 is used as a catalyst in the reverse reaction of gas displacement of water.
    Preferably, the compound of formula Nio.l (Ceo.gLao, 101.9S) O.9 is used as a catalyst in the reverse gas-water displacement reaction.
    Another preferred use of the compound of the present invention described above
    20 refers to its use as a catalyst in the reaction of partial oxidation of methane to synthesis gas.
    In the present invention, "partial oxidation reaction of methane to synthesis gas" is understood as that reaction that uses CH4 as a reagent that together with
    O2, in a certain proportion (CH4 / 0 2 = 2, molar), in the presence of a catalyst produces synthesis gas.
    Preferably, in the reaction of partial oxidation of methane to synthesis gas, a compound of formula My (Cel_xLx02_xI2) 1_y is used as described above, characterized in that x is different from zero and ellantanide is Gd or Sm.
    Preferably the compound of formula Nio.l (CeO.9Gdo.l0 1.9s) O.9 is used as a catalyst for the reaction of partial oxidation of methane to synthesis gas.
    The advantages of using the compounds of the present invention as a catalyst
    They are shown below, and verified in the experimental data described in the examples:
    5 • A high activity per mass of catalyst in the reactions ofreverse reaction of gas displacement of water and reaction ofpartial oxidation of methane to synthesis gas,
    • CO2 conversion is between 50% and 60%, with the highest values being close to the thermodynamic equilibrium of the reaction
    Inverse gas displacement of water for the specified reaction conditions;
    • the conversion of CH4 and yield to hydrogen obtained, are, with certain catalysts, at values close to the thermodynamic equilibrium of the reaction of partial oxidation of methane to
    Synthesis for the specified reaction conditions;
    • easy to prepare,
    • they do not need an activation stage in a reducing atmosphere,
    • nanostructured materials,
    • high macroporosity,
    20 • stable in the severe conditions in which it is carried out in the reverse reaction of displacement of water gas
    • the activity remains unchanged after 100 h duty cycles in the reverse reaction of displacement of water gas
    Throughout the description and claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components
    or steps. For those skilled in the art, other objects, advantages, and features of the invention will emerge in part from the description and in part from the practice of the invention. The following examples and figures are provided by way of
    The illustration is not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES
    Fig. 1. SEM micrograph of catalyst Nio, 04 (CeO, 9Gdo, 10 1.95) O, 96 after synthesis by the solution combustion method
    Fig. 2. Represents the percentage of CO2 conversion over the reaction time (rWGS reaction) for the catalyst Nio, 04 (CeO.9Gdo, 10 1.95) 0.96.
    Fig. 3. Distributionofsizeofporesofthecompoundsofformula
    N iO.1 (Ceo.9Gdo, 1O1.95) 0.9, Nio.l (CeO.9Lao.l0 1.95) 0.9,Nio.1 (Ceo.9NdO.1 0 1.95) 0.9and
    Nio.1 (CeO.9SmO.1 0 1.95) 0.9.
    EXAMPLES
    The invention will now be illustrated by tests carried out by the inventors, which shows the improvement in the conditions of synthesis and catalytic activity.
    Example 1
    Mix 1.051 grams of glycine, 2.606 grams of cerium nitrate (Ce (N03k 6H20), 0.229 grams of gadolinium nitrate (Gd (N03h · 6H20) in a beaker. Then add 25 mL of distilled water, to dissolve the previous compounds. The beaker with the mixture of the previous reagents is placed on a hot plate with another beaker of a larger inverted size, covering the previous one and aluminum foil at its base. plate temperature up to 300 degrees Celsius and wait a few minutes until synthesis occurs by combustion from the solution, forming a mixed oxide of cerium and gadolinium This material is called Ceo.9Gdo.l0 19S.
    Example 2
    Mix, in a beaker, 1.044 grams of glycine, 0.039 grams of nickel nitrate (Ni (N03), · 6H, O), 2.553 grams of cerium nitrate (Ce (N03 k 6H, O), 0.224 grams of gadolinium nitrate (Gd (N03k 6H, O. A
    Then 25 mL of distilled water is added, to dissolve the above compounds. The beaker with the mixture of the previous reagents is placed on a hot plate with another, larger inverted beaker covering the previous one and aluminum foil at its base. The temperature of the plate is then increased to 300 degrees Celsius and a few minutes wait until synthesis occurs by combustion in solution, forming a cermet-type material, with a micro-spongy morphology, and consisting of nickel-metal nanoparticles supported on a mixed oxide of cerium and gadolinium. This material is called (Ni) o.02 (CeO.9Gdo.1Ül.95) O.9S.
    Example 3
    Mix, in a beaker, 1.037 grams of glycine, 0.078 grams of nickel nitrate (Ni (N03h · 6H20), 2.501 grams of cerium nitrate (Ce (N03 h-6H20), 0.220 grams of nitrate of gadolinium (Gd (N03h-6H20. 25 mL of distilled water is then added to dissolve the above compounds. The beaker with the mixture of the above reagents is placed on a hot plate with another larger beaker inverted covering the and aluminum foil at its base. The temperature of the plate is then increased to 300 degrees Celsius and a few minutes wait until synthesis occurs by combustion in solution, forming a cermet-type material with a micro-spongy morphology, and made up of metallic nickel nanoparticles supported on a mixed oxide of cerium and gadolinium. This material is called (Ni) o.04 (CeO.9Gdo.l0 l.95) or.96. Its SEM micrograph (obtained by Electron Microscopy of Sweep, Scanning Electron Mi croscopy) is shown, by way of example in Figure 1.
    Example 4
    Mix, in a beaker, 1.016 grams of glycine, 0.194 grams of nickel nitrate (Ni (N03h · 6H20), 2.345 grams of cerium nitrate (Ce (NO '' '' 6H, O), 0.206 grams of gadolinium nitrate (Gd (NO ,,, · 6H, O. Then add 25 mL of distilled water, to dissolve the above compounds. Place the beaker with the mixture of the above reagents on a hot plate with another Inverted beaker of larger size covering the previous one and aluminum foil at its base. The temperature of the plate is then increased to 300 degrees Celsius and you wait a few minutes until the synthesis by combustion in solution occurs, forming a material cermet type, consisting of metallic nickel nanoparticles supported on a mixed cerium and gadolinium oxide This material is called (Ni) or., (CeO, 9GdO., O, .9S) O, 9.
    Example 5
    Mix, in a beaker, 1.016 grams of glycine, 0.194 grams of nickel nitrate (Ni (N03h "6H20), 2.345 grams of cerium nitrate (Ce (N03h" 6H20), 0.260 grams of lanthanum nitrate (La (N03h "6H20. Next, 25 mL of distilled water is added to dissolve the previous compounds. The beaker with the mixture of the previous reagents is placed on a hot plate with another larger inverted beaker covering the previous one. and aluminum foil at its base. The temperature of the plate is then increased to 300 degrees Celsius and a few minutes wait until synthesis occurs by combustion in solution, forming a cermet-type material with a micro-spongy morphology, and Consisting of metallic nickel nanoparticles supported on a mixed oxide of cerium and lanthanum This material is called (Ni) o.1 (Ceo.9Lao.10, .9s) or, 9.
    Example 6
    Mix, in a beaker, 1.0473 grams of glycine, 0.0194 grams of nickel nitrate (Ni (N03h'6HzO), 2.5793 grams of cerium nitrate (Ce (N03h "6H20), 0.2979 grams of nitrate gadolinium (Gd (N03h "6H20. Next, add 25 mL of distilled water, to dissolve the above compounds. Place the beaker with the mixture of the previous reagents on a hot plate with another beaker of larger inverted size covering the previous one and aluminum foil at its base. Next, the temperature of the plate is increased to 300 degrees Celsius and it is expected a few minutes until the synthesis by combustion in solution occurs, forming a cermet-type material, with a micro-spongy morphology , and consisting of metallic nickel nanoparticles supported on a mixed oxide of cerium and gadolinium This material is called (Ni) or, Ol (CeO, 9Gdo, 10 1.9S) O, 99 '
    5 Example 7
    Mix, in a beaker, 1.5620 grams of glycine, 0.0189 grams of copper nitrate (Cu (NO ~ h'6H20), 3.869 grams of cerium nitrate (Ce (N03h'6H20), 0, 4470 grams of gadolinium nitrate (Gd (NO ~ h'6H20. 37 ml of distilled water is then added to dissolve the above compounds. The beaker with the mixture of the previous reagents is placed on a hot plate with another beaker of a larger size inverted precipitate covering the previous one and aluminum foil at its base. The temperature of the plate is then increased to 300 degrees Celsius and you wait a few minutes
    15 until synthesis occurs by combustion in solution, forming a cermet-type material, with a micro-spongy morphology, and consisting of metallic nickel nanoparticles supported on a mixed cerium-gadolinium oxide. This material is called (CU) O, Ol (CeO, 9Gdo, 10 1.9S) O, 99 '
    20 Example 8
    1.5620 grams of glycine, 0.0297 grams of dihydroxy tetraamin platinum (11) «NHJ), Pt (OHj, 'xH, O), 3.8690 grams of cerium nitrate ( Ce (N03 h'6H20), 0.4470 grams of gadolinium nitrate (Gd (NO ~ h · 6H20. Next, 37 mL of distilled water is added to dissolve the above compounds. The glass is placed with the mixture of the above reagents on a hot plate with another larger inverted beaker covering the previous one and aluminum foil at its base. Then, increase the temperature of the plate to 300 degrees Celsius and wait a few minutes
    30 until synthesis occurs by combustion in solution, forming a cermet-type material, with a micro-spongy morphology, and consisting of nickel metal nanoparticles supported on a mixed cerium-gadolinium oxide. This material is called (CU) O, Ol (CeO.9Gdo, 10 1.9S) O, 99.
    Example 9
    The materials prepared according to the methodology described in examples 1 to 5 have been tested as catalysts in the reverse gas displacement reaction
    5 of water. These catalysts have been chosen to find the limits of use regarding the different compositions. The process has been carried out under the following reaction conditions: 300000 mLN / h · g, 700 ° C, H2JC02 = 2.10% volume of N2. The reaction temperature is increased from room temperature to the reaction temperature in the same reaction gas mixture.
    According to the results obtained (Table 1), the conversion of CO2 and catalytic stability varies depending on the nickel content. The nickel-free catalyst is the one that, after requiring an induction period of about 3 hours, increases its activity towards a stable conversion close to 26%. The other catalysts 15 present, at the beginning of the reaction, a similar conversion between 55 and 59%, but undergo different behavior throughout the reaction. Thus, the one with the lowest proportion of nickel (Ni) o.Q2 (Ceo.9Gdo., O, .9s) or.9s) deactivates slightly, reaching, after 6 hours of reaction, a conversion of around 53%, respectively . The other catalysts result in fairly stable conversions over the 6 hour reaction. According to the results obtained, a slightly higher conversion is observed for a molar ratio between nickel and mixed oxide equal to 4:96. This catalyst undergoes a slight increase in the conversion after 6 hours of reaction, and the conversion obtained is, for this reaction time, practically in thermodynamic equilibrium (which is
    25 in 59.3% for these reaction conditions). Regarding the selectivity to ca (Table 2), it is observed that it is in values higher than 96% for all the catalysts analyzed, with CH 4 being the minority compound that forms and adjusts the carbon balance.
    The catalyst consisting of nickel metal supported on ceria doped with lanthanum «Ni) or ,, (Ceo, 9Lao, 10 1.9s) or, 9) shows high activity and stability, when compared with its analogue doped with gadolinium« Ni ) or, 1 (Ceo, 9Lao "O ,, 9s) or, 9).
    . ~ Gdo. I use it." (N i) 0.04 (Ce03 GdO.l0l.n) o.n(Ni) o. l (CeO. ~ Gdo. l 0 US) 03(N i) O.l (Ceo. ~ LaO.l 0 l.'S) O.,
    With v
    Conv C02 (%) t (h)With, C02 (%)t (h)With v C02 (%)t (h)
    C02 (%)
    56.7 OR54.82OR55.2OR55.5
    57.2 0.5556.960.5055.90.5056, 3
    56.0 1.1357.151.0256.21.0156.5
    55.7 1.7357.331.5456.11.5256.7
    54.0 2.3657.452.0656.22.0556.7
    53.4 3.0257.482.6156.42.5956.8
    53.2 3.6957.543.1756.33.1456.8
    53.1 4.4057.584.3356.44.2556, 9
    52.9 5.1557.754.9256.54.8356.9
    5.94 58.626.1456.66.0057.0
    - ;
    ~ 00
    2:
    "
    "6:
    "s:
    ~ ro e
    Gl! A.
    (IJ ID 'O
    ~
    00 ID 'O O "-n
    ro
    ~
    g "
    "<;
    ro
    w
    "
    00 ro
    "
    '; n
    or
    N '
    00 <
    "
    ro
    "
    or
    ~
    ro 6:
    w
    "
    "
    ~
    ()
    O "
    'OR
    ID <O
    OR
    "
    ~
    ¡'
    'OR
    OR
    ro
    n
    n
    6:
    "
    ~ "
    , or
    "'~
    o ~
    "'~
    ~~
    , "",
    ~~
    :: io.10U ~) 0.U (N i) 0.04 (Ceo., GdO.1 OU ~) 0.'6(Ni) 0..1 (CeO., Gdo.l0 1.95) 0. '(Ni) 0.1 (Ceo.9laO.1 01.9 ~) 0. '
    leel CO (%) I (h)Seleel CO (%)I (h)Select CO (%)I (h)Select CO (%)
    98.2 OR96.6OR96.6OR96.1
    99.0 0.5598.10.5096.30.5097.3
    99.6 1.1398.41.0296.61.0197.6
    99.7 1.7398.71.5496.51.5298.5
    99.9 2.3698.92.0697.02.0598.2
    100 3.0298.92.6197.12.5998.3
    100 3.6999.33.1797.13.1498.2
    100 4.4099.34.3397.04.2598.4
    100 5.1599.24.9297.24.8398.3
    98.2 5.9499.36.1497.26.0098.7
    ~
    n
    '"
    n
    6:
    ~
    ~
    Gl
    (F)
    "
    '"
    iil
    Q.
    ~
    ~
    6 "
    S n '"
    N '
    Q.
    '"
    or
    ro
    - <
    '"
    2:
    '"
    '"
    ;; ::
    and
    <1>
    ~
    iil
    "~
    or
    il
    <1>
    ~
    ~.
    <1>
    Q.
    <1> 00
    <1>
    iD
    g
    s.
    Q.
    Q.
    '"'"
    OROR
    '"
    <5
    '; <il
    OR
    Q.
    ~
    ro '
    OR
    "
    ro
    '"
    " "6:
    ~
    ~ "
    , or
    "'~
    o ~
    "'~
    ~~
    , "",
    ~~
    Example 10
    The materials prepared according to the methodology described in Examples 6 to 8 have been tested as catalysts in the reverse gas displacement reaction of water. These catalysts have been chosen to analyze the influence of the type of active phase supported on cerium-Ianthanide mixed oxide. The process has been carried out under the following reaction conditions: 300000 mLN / h'g, 700 ° C, Hz / COz = 2.10% volume of N2. The reaction temperature is increased from room temperature to the reaction temperature in the same mixture of
    10 reaction.
    According to the results obtained (Table 3), the conversion of CO2 and selectivity to ac vary depending on the type of active phase. Thus, those based on nickel {(Ni) o.Q1 (Ceo.9Gdo.10 1.9s) o.99)) and Pt {(Pt) O.Ol (CeO.9Gdo.l0 l.9S) O.99) ) produce higher
    15 conversion of CO2 than that based on copper «CU) O.Ol (CeO.9Gdo.l0 l, 95) O.99)) 'However, that based on platinum, is somewhat less selective to carbon monoxide, forming, under these reaction conditions, a small proportion of methane.
    20 a.
    • (Pt), ,, (Ceu Gck · 0 · ...) 0 ..(Cu) c, l '(Ceo oGcJ,, 0 ,,,), ..
    Jes;). to Weatherr.0lIY. CO,~~ COWeatherkOllY. CO:~ a
    ) (%) (h »(%)(%)(h)(%)CO (%)
    17.6 0.0052.996.20.0038.3100.0
    00.0 0.5456.097.40.4745.7100.0
    00, 0 1.0955.997.00.9446.2100.0
    00, 0 1.6455.696.91.4146.5100.0
    -
    00.0 2.2356.096.91.8846.4100.0
    00.0 2.7956.096.92.3546.2100.0
    00.0 3.4155.997.02.8246.3100.0
    - <
    ~ a>
    2:
    Hey> 3 ~
    "OR
    o:; :: ro e
    a> i <l
    '"
    ¡¡¡
    " "6:
    ~
    '"
    - "tl
    or
    ro
    n
    to>
    "'"
    6; ~ "-ª".
    ~
    ~ '"a. Gl'"
    in
    - "o ~
    "O <
    to>
    Il '"
    to. 6:
    ~
    ~ a.
    ~
    OR; '"
    OR
    vo o
    N
    "
    ~ '<
    vo
    N '
    to>
    '"
    ';
    to.
    O ~
    :;and'
    ro
    I go to:
    to>
    to.to>
    OR
    ORto>
    OR"
    ID <il _ "Il
    OR
    'one'''
    or,"
    m ~
    'w
    ~ i $
    - or
    ~~
    Example 11
    The activity and stability of the catalyst have been determined.(Ni) o.04 (Ceo, 9Gdo.10, .9S) O.96, performing a durability test, for 100 hours of5 continuous reaction, for rWGS reaction. The reaction conditions areidentical to those used in Example 6. According to the results obtained, thecatalyst increases its activity to a very high CO2 conversion valueclose to thermodynamic equilibrium in the first 4 hours of reaction, for laterexperience a deactivation of less than 6% conversion in the following 4
    10 hours. Thereafter, its activity remains practically stable for 92 hours. See Figure 2.
    Example 12
    The materials (Ni) o.02 (CeO.9Gdo.l0 1.95) O.98 and (Ni) o.1 (CeO.9Gdo.l0 1.95) O.9 have been tested as catalysts in the partial oxidation reaction of methane to synthesis gas, under the following reaction conditions: 36600 mLN / h · g; 700 ° C, using a reaction mixture consisting of N2: 40%; CH4: 40% and O2: 20% (molar). Before passing the reaction gas mixture, the temperature is increased from
    At room temperature up to 700 ° C, under a nitrogen flow rate of 40 mLN / min and it is kept for 1 hour.
    The results of methane conversion and yield to hydrogen as a function of reaction time (6 hours), obtained for catalysts 25 (Ni) o.o2 (Ceo, 9Gdo.1ü, .9s) o.98 and (Ni) o .1 (Ceo.gGdo., 0 1.9s) o.9 are shown in table 4. For the catalyst with a Ni: mixed oxide molar ratio equal to 2:98, a deactivation of the catalyst is observed with the reaction time. On the contrary, for the catalyst with a mixed Ni: oxide ratio equal to 10:90, greater stability is observed, as well as CH4 conversion values and hydrogen yield.
    Top 30. The found values are very close to the thermodynamic equilibrium for these reaction conditions.
    10.1 ° 1.95) 0.98 (Ni) or 1 (Ce09GdO 10 195) 09,,,,,
    Moles H2 produced ¡mol Moles H2 produced
    t (h) CH4 conv (%)
    CH4 powered Mol CH4 powered
    1,093 one83.21,304
    0.977 282.31,316
    0.880 381.71,303
    0.897 481.41,295
    0.840 581, 11,287
    0.829 681, 01,295
    c.
    ! [
    ~
    ~
    n
    c.
    ~ ¡¡. 3rd
    "
    iil "n
    n
    c.
    6:
    OR
    "
    iil
    ~
    - "
    OR
    n
    ro
    g "
    ro
    c.
    ro
    <
    "
    ro
    ~
    6:
    "
    ORI
    •
    '<
    iil
    C.
    "
    '3
    ¡¡.
    "OR
    I
    "
    O "¡¡; <il
    OR
    iil
    n
    n
    6:
    "
    OR
    x
    to:
    n
    6:
    "
    "
    n
    0 ;.
    c.
    ro 3
    ~
    OR
    "
    <D
    ~
    '"
    c.
    ro
    ~
    "ro
    ~
    "~
    ¡¡¡
    - ;
    2:
    ...
    ; ::
    and
    ro
    ~
    ~
    ~
    ~ "
    , or
    "'~
    o ~
    "'~
    ~~
    , "",
    ~~
    Example 13
    The textural properties of the catalysts 5 Nio., (CeO.9Gdo, 101.9S) O.9, Nio., (Ceo.9Ndo., Ol.9S) O.9, Nio., (Ceo.9Smo. , O, .9s) o.9 by Hg porosimetry.
    The protocol to determine the porosity, surface area and mean pore size by mercury porosimetry was as follows: The sample was degassed at 80 10 degrees Celsius for 3 hours. A sample quantity of between 20 and 40 mg was placed in a sample holder of a mercury porosimeter (Autopore IV mercury porosimeter, Micromeritics). Then mercury intrusion porosimetry was performed, which is an adsorption technique that uses mercury as an adsorbate. Through the application of pressure, the entry of mercury in the pores of the solid is forced. The value of the volume of mercury intruded allows calculating the area, distribution by pore sizes and percentage of porosity of the material. This technique is used when the material under study has mesopores (2-50 nm) and macropores (> 50nm). The analysis conditions used were: surface tension: 484 din / cm); contact angle: 141 degrees;
    20 Maximum pressure: 60,000 psi.
    Fig. 3 shows the pore size distribution of the compounds of
    formula Nio.l (CeO.9Gdo.l0, .9s) O.9, Nio.l (CeO.9Lao.l0, .9S) O.9, Nio.l (Ceo.gNdo "O, .9S) O. 9 Y Nio., (Ceo.9Smo., O, .9s) o.9 The results are summarized in the following Table 5.
    Table 5: Shows the total pore area in m2 / g, the percentage of porosity and the
    mean pore diameter in! -1m for each of the following catalysts Nio, l (CeO, 9Gdo, 10 1.95) O, 9,
    Nio, l (Ceo, 9Ndo, 10 1.95) O, 9,
    Nio, l (CeO, 9SmO, 10 1.95) O, 9,
    Catalyst Total pore area (m'¡g) ofPorosity (%)Average pore diameter (~ m)
    Nio, l (CeO, 9Gdo, 10 1.95) O, 9 8.692.42.03
    N io, 1 (CeO, 9LaO, 1 O1.95) 0.9 8.984.10.91
    Nio, l (CeO, 9Ndo, 10 1.95) O, 9 10.495.32.96
    Nio, l (CeO, 9SmO, 10 1.95) O, 9 9.494.32.87
    权利要求:
    Claims (34)
    [1]
    1_A procedure for obtaining a compound of the formula: My (Ce1_xLx0 2_x / 2) 1 -y 5 where M is a metal selected from Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au or
    Cu,where x = 0.0 -0.4 and y = 0.001 -0.6,Y where L is selected from a lanthanide, I Sc,
    characterized by comprising the following stages:
    10 a) dissolve in the minimum amount of water, stoichiometric amounts of Ce Nitrate, water soluble salt of a metal selected from Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au or Cu, Nitrate of L, Y or Sc
    15 and add to the solution of step (a) a molar ratio of between 0.7 and 1.0 of fuel with respect to the total nitrates, b) stir at room temperature until complete dissolution of the solution obtained in (a) , and c) heating the solution obtained in (b) to a temperature of between 200 oC and
    20 600 oC
    2_The method according to claim 1, characterized in that, in step (a), nickel nitrate (11) Ni (N03) -6H20 _ is used as the water-soluble Ni salt.
    The process according to claim 1, characterized in that, in step (a), copper nitrate (11), Cu (N03 h -6H20_) is used as the water-soluble Cu salt.
    The process according to claim 1, characterized in that, in step (a), a salt selected from dihydroxy-30-tetraamin platinum (11) «NH3) 4Pt (OHk xH20) and nitrate of tetraamin platinum (11) (PI (NH,), (NO,),).
    [5]
    5. The process according to any of claims 1 to 4, characterized in that x is different from ° in the compound of formula My (Cel.xLxO ... xl2) 1. And that is obtained.
    [6]
    6. The method according to claim 5, characterized in that the lanthanide is selected from La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
    [7]
    7. The process according to any of claims 5 or 6, characterized in that the ellanthanide is Gd.
    [8]
    8. The method according to claim 7, characterized in that
    • x has a value of between 0.05 and 0.2; or
    • y has a value between 0.001 and 0.15.
    [9]
    9. The method according to any of claims 5 or 6, characterized in that the ellanthanide is La.
    [10]
    10. The method according to claim 9, characterized in that
    • x has a value of between 0.05 and 0.2; or
    • And it has a value between 0.001 and 0.15.
    [11]
    eleven. The process according to any of claims 5 or 6, characterized in that the ellanthanide is Sm.
    [12]
    12. The method according to claim 11, characterized in that
    • x has a value between 0.05 and 0.2 or
    • y has a value between 0.001 and 0.15.
    [13]
    13. The process according to any of claims 1 to 12, characterized in that the fuel used in step (a) is selected from among glycine, urea, citric acid and a combination of the above.
    [14]
    14. The method according to claim 13, characterized in that step (a) the fuel used is glycine.
    [15]
    fifteen. The process according to any of claims 1 to 14, characterized in that step (c) is carried out at a temperature of between 200 oC and 500 oC.
    [16]
    16. A compound characterized by the formula My (Ce1_xLx0 2.Kl2) '_y characterized in that
    • M is a metal selected from Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au or Cu,
    • x = 0.0 -0.4 and y = 0.001 -0.6, Y
    • L is selected from a lanthanide, Y or Sc.
    [17]
    17. The compound according to claim 16, characterized in that
    • M is Ni and
    • its formula is Niy (Ce '_xLx02.Kl2), and
    or where x = 0.0 -0.4 and y = 0.005 -0.6,
    or and where L is selected from a lanthanide, Y or Sc.
    [18]
    18. The compound according to claim 16, characterized in that
    • M is Cu and
    • its formula is CUy (Ce1_xLx02_xI2) 1_y
    or where x = 0.0 -0.4 and y = 0.005 -0.6,
    o and where L is selected from a lanthanide, I Sc.
    [19]
    19. The compound according to claim 16, characterized in that
    • MesPty
    • a compound of the formula Pty {Ce1_xLx0 2.K (2) 'is obtained.
    or where x = 0.0 -0.4 and y = 0.001 -0.6,
    or and where L is selected from a lanthanide, Y or Sc.
    [20]
    20. The compound according to any of claims 16 to 20, characterized in that it has a porosity percentage of between 70% AND 95% AND an average pore diameter of between 0.5 IJm and 5 iJrn.
    [21 ]
    twenty-one . The compound according to any of claims 16 to 20, characterized in that x is different from O.
    [22]
    22. The compound according to claim 21, characterized in that the lanthanide L is selected from La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ha, Er, Tm, Yb and Lu.
    23. The compound according to any of claims 21 or 22, characterized in that the lanthanide is Gd.
    [24]
    24. The compound according to claim 23, characterized in that
    • x has a value between 0.05 and 0.2; e 10 • Y has a value between 0.001 and O, 15.
    [25]
    25. The compound according to any of claims 21 or 22, characterized in that the lanthanide is La.
    26. The compound according to claim 25, characterized in that
    • x has a value of between 0.05 and 0.2; and
    • y has a value between 0.001 and 0.15.
    [27]
    27. The compound according to any of claims 21 or 22, characterized in that the lanthanide is Sm.
    [28]
    28. The compound according to claim 27, characterized in that
    • x has a value between 0.05 and 0.2; and
    • y has a value between 0.001 and 0.15. 25
    [29]
    29. The compound according to any of claims 16 to 28, characterized in that it is obtained according to the process of claims 1 to 15.
    [30]
    30. The compound according to claim 17, characterized in that it has been obtained by the method according to claim 2.
    [31]
    31. The compound according to claim 18, characterized in that it has been obtained by the process according to claim 3.
    [32]
    32. The compound according to claim 19, characterized in that it has been obtained by the process according to claim 4.
    [33]
    33. Use of the compound according to any of claims 16 to 32, as5 catalyst.
    [34]
    34. Use of the compound according to claim 33 as a catalyst in the reverse gas displacement reaction of water.
    35. Use of the compound according to claim 34, characterized in that x is different from zero and the ellanthanide is Gd or La.
    [36]
    36. Use according to any of claims 34 or 35, characterized in that the catalyst is Nio.l (CeO.ge.Gdo.040, .9S) O.9.
    [37]
    37. Use according to any of claims 34 or 35, characterized in that the
    catalyst is Nio, 1 (Ceo.9Gdo, 10 1.9s) o.9.
    [38]
    38. Use according to any of claims 34 or 35, characterized in that the catalyst is Nio.1 (Ceo.9Lao "O, .9s) o.9.
    [39]
    39. Use of the compound according to claim 33 as a catalyst in the reaction of partial oxidation of methane to synthesis gas.
    40. Use of the compound according to claim 39, characterized in that x is non-zero and the lanthanide is Gd or Sm.
    [41]
    41. Use of the compound according to any of claims 39 or 40, wherein the catalyst is Nio "(Ceo, 9Gdo ,, O ', 9s) or, 9
    类似技术:
    公开号 | 公开日 | 专利标题
    Sun et al.2015|Ni/Ce–Zr–O catalyst for high CO2 conversion during reverse water gas shift reaction |
    Royer et al.2014|Perovskites as substitutes of noble metals for heterogeneous catalysis: dream or reality
    Xu et al.2017|CO2 methanation over rare earth doped Ni based mesoporous catalysts with intensified low-temperature activity
    Tada et al.2014|Promotion of CO2 methanation activity and CH4 selectivity at low temperatures over Ru/CeO2/Al2O3 catalysts
    Su et al.2014|Modifying perovskite-type oxide catalyst LaNiO3 with Ce for carbon dioxide reforming of methane
    Yi et al.2019|Catalytic removal NO by CO over LaNi0. 5M0. 5O3 | perovskite oxide catalysts: tune surface chemical composition to improve N2 selectivity
    Luisetto et al.2012|Co and Ni supported on CeO2 as selective bimetallic catalyst for dry reforming of methane
    Lu et al.2017|Hydrogen production via methanol steam reforming over Ni-based catalysts: Influences of Lanthanum | addition and supports
    Tao et al.2014|Syngas production by CO2 reforming of coke oven gas over Ni/La2O3–ZrO2 catalysts
    Cao et al.2010|Autothermal reforming of methane over Rh/Ce0. 5Zr0. 5O2 catalyst: effects of the crystal structure of the supports
    Hu et al.2017|Hydrogen production by sorption-enhanced steam reforming of acetic acid over Ni/CexZr1− xO2-CaO catalysts
    Shen et al.2020|Essential role of the support for nickel-based CO2 methanation catalysts
    Erri et al.2006|Novel perovskite-based catalysts for autothermal JP-8 fuel reforming
    Iglesias et al.2017|Ni/Ce0. 95M0. 05O2− d | for methane steam reforming at mild conditions
    Sim et al.2020|Catalytic behavior of ABO3 perovskites in the oxidative coupling of methane
    Wang et al.2016|Application of Ni–Al-hydrotalcite-derived catalyst modified with Fe or Mg in CO2 methanation
    Miyamoto et al.2018|Effect of basicity of metal doped ZrO2 supports on hydrogen production reactions
    Li et al.2019|Lean methane oxidation over Co3O4/Ce0. 75Zr0. 25 catalysts at low-temperature: Synergetic effect of catalysis and electric field
    Niazi et al.2020|Cu, Mg and Co effect on nickel-ceria supported catalysts for ethanol steam reforming reaction
    Do et al.2017|Effect of acidity on the performance of a Ni-based catalyst for hydrogen production through propane steam reforming: K-AlSixOy support with different Si/Al ratios
    Kim et al.2008|Production of synthesis gas by autothermal reforming of iso-octane and toluene over metal modified Ni-based catalyst
    Wei et al.2021|Perovskite materials for highly efficient catalytic CH4 fuel reforming in solid oxide fuel cell
    Yang et al.2021|Chemical-looping reforming of methane over La-Mn-Fe-O oxygen carriers: Effect of calcination temperature
    Qi et al.2020|Hydrogen production via catalytic propane partial oxidation over Ce1-xMxNiO3-λ | towards solid oxide fuel cell | applications
    Voskanyan et al.2020|Durable ruthenium oxide/ceria catalyst with ultralarge mesopores for low-temperature CO oxidation
    同族专利:
    公开号 | 公开日
    AR110689A1|2019-04-24|
    US11253847B2|2022-02-22|
    AU2017385802A1|2019-08-08|
    CA3048958A1|2018-07-05|
    CN110267741A|2019-09-20|
    EP3586959A1|2020-01-01|
    EP3586959A4|2020-10-07|
    WO2018122439A1|2018-07-05|
    ES2674434B2|2018-12-04|
    US20200406246A1|2020-12-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20020193247A1|2001-05-18|2002-12-19|Michael Krumpelt|Autothermal hydrodesulfurizing reforming catalyst|
    CN101049566A|2007-05-23|2007-10-10|天津大学|Ni base catalyst in use for producing synthesis gas by oxidizing methane partially, and preparation method|
    WO2013135707A1|2012-03-13|2013-09-19|Bayer Intellectual Property Gmbh|Method for producing a carbon monoxide-containing gas mixture at high temperatures on mixed metal oxide catalysts comprising noble metals|
    CN103418392B|2012-05-14|2015-10-28|浙江海洋学院|A kind of Reversed Water-gas Shift Catalysts and its preparation method|
    CN103183346B|2012-12-13|2014-12-17|浙江海洋学院|Method of reverse water gas shift reaction for reverse water gas shift catalyst|
    CN103230799B|2013-04-08|2016-06-08|中国科学院广州能源研究所|A kind of Cu-Zn for reverse water-gas-shift reaction is catalyst based, its preparation method and application|
    SG2013050877A|2013-06-28|2015-01-29|Agency Science Tech & Res|Methanation catalyst|
    CN104971727B|2015-06-19|2018-07-20|南昌大学|A kind of preparation method of Ni-based catalyst for hydrogen production from methane vapor reforming|
    CN105289616A|2015-11-04|2016-02-03|上海大学|Carbon dioxide methanation catalyst O2) and preparation method thereof|
    法律状态:
    2018-06-29| BA2A| Patent application published|Ref document number: 2674434 Country of ref document: ES Kind code of ref document: A1 Effective date: 20180629 |
    2018-12-04| FG2A| Definitive protection|Ref document number: 2674434 Country of ref document: ES Kind code of ref document: B2 Effective date: 20181204 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201631709|2016-12-29|
    ESP201631709|2016-12-29|US16/474,706| US11253847B2|2016-12-29|2017-12-28|Method for producing catalysts of formula my1-y for the use thereof in the reverse water-gas shift reaction and partial oxidation of methane into synthesis gas by means of the method of combustion in solution|
    CN201780085953.4A| CN110267741A|2016-12-29|2017-12-28|Reverse water-gas-shift reaction is used for by the method production burnt in solution and methane portion oxidation is the formula M of synthesis gasy1-yCatalyst method|
    AU2017385802A| AU2017385802A1|2016-12-29|2017-12-28|Method for producing catalysts of formula My1-y|
    PCT/ES2017/070863| WO2018122439A1|2016-12-29|2017-12-28|Method for producing catalysts of formula my1-y for the use thereof in the reverse water-gas shift reaction and partial oxidation of methane into synthesis gas by means of the method of combustion in solution|
    CA3048958A| CA3048958A1|2016-12-29|2017-12-28|Method for producing catalysts of formula my1-y for the use thereof in the reverse water-gas shift reaction and partial oxidation of methane into synthesis gas by means of the method of combustion in solution|
    EP17885475.8A| EP3586959A4|2016-12-29|2017-12-28|Method for producing catalysts of formula my1-y for the use thereof in the reverse water-gas shift reaction and partial oxidation of methane into synthesis gas by means of the method of combustion in solution|
    [返回顶部]