WO2022189689A1 - Procédé d'obtention de h2, de co et/ou de gaz de synthèse à l'aide de matériaux de type pérovskite et utilisations de ces matériaux - Google Patents

Procédé d'obtention de h2, de co et/ou de gaz de synthèse à l'aide de matériaux de type pérovskite et utilisations de ces matériaux Download PDF

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WO2022189689A1
WO2022189689A1 PCT/ES2022/070134 ES2022070134W WO2022189689A1 WO 2022189689 A1 WO2022189689 A1 WO 2022189689A1 ES 2022070134 W ES2022070134 W ES 2022070134W WO 2022189689 A1 WO2022189689 A1 WO 2022189689A1
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perovskite
production
stage
metal oxide
stream
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PCT/ES2022/070134
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Spanish (es)
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María ORFILA DEL HOYO
María LINARES SERRANO
Raúl Molina Gil
Ángel Javier MARUGAN AGUADO
Juan Ángel BOTAS ECHEVARRÍA
Raúl SANZ MARTÍN
María Teresa AZCONDO SÁNCHEZ
Ulises Julio AMADOR ELIZONDO
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Universidad Rey Juan Carlos
Fundación Universitaria San Pablo-Ceu
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention belongs to the technical field of new materials for producing fuels, and more specifically to a method for obtaining hydrogen (H2), carbon monoxide (CO) and/or synthesis gas by means of thermochemical cycles based on perovskite-type materials.
  • the invention also relates to the use of these perovskite-type materials for the production of H2, CO or synthesis gas.
  • Hydrogen production at an industrial level is carried out through steam reforming, partial oxidation and autothermal reforming of hydrocarbons, gasification of coal and heavy hydrocarbons (96% of production) and electrolysis of water (4 % of production), so that the main raw materials are hydrocarbons and water (1).
  • hydrocarbons it is necessary to carry out a subsequent purification stage of the H2 obtained, while in the case of electrolysis, it is not (2).
  • thermochemical cycles Many multi-stage thermochemical cycles have been investigated (8), but two-stage thermochemical cycles based on metal oxides are the most attractive due to their simplicity and potential application on an industrial scale (9).
  • the metal oxide is thermally reduced using concentrated solar energy as a source of energy to reach the required temperature.
  • the reduced metal oxide reacts with H2O to produce H2, with CO2 to produce CO or with a mixture of H2O and CO2 to obtain H2 and CO (synthesis gas), recovering the initial metal oxide (10) .
  • thermochemical cycles can be divided into thermochemical cycles based on volatile metal oxides and non-volatile metal oxides.
  • the cycles based on volatile metal oxides are so named because during the reduction stage the reduced material is in the gas phase, like those based on the ZnO/Zn and CdO/Cd pairs (11).
  • the problem with these cycles is the operating temperatures (1500-2000°C) and the need to quench or rapidly cool the reduction products to prevent their recombination (12).
  • thermochemical cycles based on non-volatile metal oxides these in turn are divided into two groups, stoichiometric and non-stoichiometric metal oxides.
  • thermochemical cycles based on the FesCU/FeO redox couple have another disadvantage, which is the deactivation of the active material due to its sintering due to the high operating temperatures (14).
  • ferrite-type materials in which Fe atoms have been partially replaced by atoms of other metals such as Mn, Cu, Ni or Co, obtaining materials of type (Fei. x Me x )3C>4 capable of being reduced at lower temperatures.
  • the Nio ferrite . 5M no . 5Fe2C>4 is reduced from 1100°C, and subsequently decomposes water at temperatures of 800°C (13,15).
  • sintering processes are still important and hydrogen production is low (0.37%) (8,12).
  • One solution to sintering problems was to support the materials with ZrÜ2, AI 2 O 3 , Hf0 2 or T1O2, but H 2 production remains low (12).
  • thermochemical cycles based on non-stoichiometric oxides arose. These oxides have labile oxygen atoms in their structure thanks to which they are capable of undergoing high degrees of reduction at moderate temperatures. Furthermore, they have favorable oxidation thermodynamics, are stable, and exhibit rapid reduction and oxidation kinetics (17). Cerium oxide and perovskite-type materials are the most studied non-stoichiometric oxides.
  • the thermochemical cycle of cerium oxide for the production of H2 consists of a first stage in which cerium oxide IV (CeC>2) is reduced to Ce2C>3 at temperatures above 2000°C (18), to be subsequently reoxidized with water at temperatures of 400°C (19).
  • CeC>2 cerium oxide IV
  • the reduction temperature is still very high, and very different from the oxidation temperature.
  • the investigations focused on carrying out the partial reduction of CeC>2 up to CeC>2-6 at temperatures of 1500°C, to subsequently produce H2 by reaction with water (20). This material has been tested for many successive cycles demonstrating its stability (21,22).
  • the other type of non-stoichiometric oxides studied for thermochemical cycles are perovskite-type materials (17,25,26), which can have very different compositions for a wide range of oxygen non-stoichiometry.
  • this type of materials in general, the reduction takes place at temperatures between 1000 and 1400°C, while the oxidation takes place at temperatures between 600 and 800°C (17,25, 27). These materials have lower hydrogen yields than the other oxides discussed in this section.
  • the first route uses the photons of solar radiation to carry out different chemical and biological reactions (28).
  • the electrochemical route the electrical energy obtained through photovoltaic panels is used to carry out the rupture of the H2O and CO2 contained in mixtures of these gases (29).
  • thermochemical route uses solar energy to carry out different chemical reactions for the transformation of raw materials of fossil origin, H2O or CO2 into H2 and CO.
  • chemical reactions can be steam reforming of natural gas (30), gasification of carbon compounds such as coal or biomass (31), or based on the concept of hydrogen production through thermochemical cycles, the production of synthesis gas by simultaneously decomposing water and carbon dioxide in the oxidation stage.
  • thermochemical cycles have serious associated problems due to the high reduction temperatures, the lack of stability of the materials at those temperatures and/or the low production of H2 or CO.
  • the present invention solves the existing problems in the state of the art through a method of obtaining hydrogen (H 2 ), carbon monoxide (CO) and/or synthesis gas through thermochemical cycles based on perovskite-type materials, more specifically through the reaction of perovskite-type metal oxides of formula Ai- c B c Mi- g N g q 3-z (I) with water vapor and/or CO 2 .
  • the perovskite-type metal oxides of the present invention showed superior activity to that of other perovskite-type oxides found in the state of the art and operate at lower temperatures.
  • most of the perovskite-type metal oxides of the present invention have very good cyclability, that is, a good production of H 2 , CO and/or synthesis gas is obtained throughout the cycles.
  • synthesis gas in the present invention refers to a mixture of H 2 and CO.
  • thermochemical cycle in the present invention refers to a process that comprises a plurality of chemical reactions in which at least one of them is the reduction of the perovskite-type metal oxide, and at least one of them is the re-oxidation of this one, for the production of H 2 , CO and/or synthesis gas.
  • the stage of Reduction is an endothermic reaction while the H2, CO and/or synthesis gas production step is exothermic.
  • the heat required in the endothermic stage can be provided by any convenient means: electrical resistors, fuel combustion, radiation (including solar energy), or any other means suitable for producing the reaction.
  • perovskite-type metal oxide in the present invention refers to a chemical compound with the generic formula A IX B X M IY N Y 0 3-z, referred to in the present invention as Formula (I), where A represents a element of the lanthanide, alkali or alkaline earth series (according to the IUPAC Periodic Table of Elements), B represents an element of the alkali or alkaline earth series, M represents Fe or Co, N represents a transition metal or a element of the groups of block p of the Periodic Table, x and y has a value between 0 and 1, and z has a value between 0 and 0.75, so that the oxygen content of perovskite-type oxides can vary between a maximum value of 3 and a minimum of 2.25 per formula.
  • A represents a element of the lanthanide, alkali or alkaline earth series (according to the IUPAC Periodic Table of Elements)
  • B represents an element of the alkali or alkaline earth series
  • the M and N type atoms are located in the center of a more or less regular polyhedron of oxygen atoms, polyhedrons that can be octahedrons, square-based pyramids or flat-square environments depending on the oxygen content and the nature of the element M.
  • type A and B atoms occupy generally irregular environments with coordination of neighboring oxygen atoms ranging from 12 to 6.
  • the three-dimensional arrangement of type A (and B) and M (and N) atoms and oxygens can give rise to highly regular and symmetric (cubic) structures as well as highly distorted structures with low symmetry (monoclinic and triclinic symmetries).
  • the present invention provides a method for obtaining H2, CO or synthesis gas, comprising the following steps: i) heating a perovskite-type metal oxide of formula (I)
  • B represents an element of the alkali or alkaline earth series
  • M represents Fe or Co
  • N represents a transition metal or an element selected from the groups of the p block of the Periodic Table; x and y have a value between 0 and 1 ; and z has a value between 0 and 0.75; for the thermal reduction of said metal oxide in a current of air or an inert gas; and ii) reacting the reduced metal oxide obtained from step i) with a gaseous stream comprising steam and/or CO2 to obtain H2, CO or synthesis gas and re-oxidation of the metal oxide to recover the oxide metal of formula (I), in which steps i) and ii) are carried out at a temperature between 300 and 800°C and a pressure between 0.1 MPa and 20 MPa.
  • A represents La or Nd
  • B represents Ca or Sr
  • M represents Fe or Co
  • N represents Fe, Co, Ti, Mo, Sb or Al
  • x and y have a value between 0 and 1
  • z has a value between 0 and 0.75.
  • the gas stream of step i) is air.
  • the gas stream of step ii) comprises air or an inert gas, such as N2 or Ar, but not limited to these.
  • the method of obtaining the present invention comprises a first stage in which a metal oxide of the perovskite type of formula (I) is heated, as described above, and a second stage of re-oxidation of the metal oxide obtained in the previous stage and production of H2 by reaction with a current of air or inert gas (for example, N2 or Ar) saturated in water.
  • a current of air or inert gas for example, N2 or Ar
  • the method of this embodiment is characterized by an operation temperature ranging from 300 to 800°C and a working pressure in the range of 0.1 MPa to 20 MPa.
  • the gas stream fed into the reduction stage is preferably air, although an inert gas can be used, preferably N2 or Ar (but not limited to these) with a sufficient flow rate to entrain the oxygen produced during the reduction stage.
  • the stream fed into the oxidation stage (second stage) is air or any other inert carrier gas (for example N2 or Ar) saturated in steam at 50-120°C or a steam stream.
  • the method of obtaining the present invention comprises a first stage in which a metal oxide of the perovskite type of formula (I) is heated, as described above, and a second stage of re-oxidation of the metal oxide obtained in the previous stage and production of CO by reaction with a current of air or inert gas mixed with CO2 in a sufficient proportion for the reaction to take place.
  • the method of this particular embodiment is characterized by an operating temperature ranging between 300 and 800°C and a working pressure in the range of 0.1 MPa to 20 MPa.
  • the gas stream fed into the reduction stage is preferably air, although an inert gas can be used, preferably N2 or Ar (but not limited to these) with a sufficient flow rate to entrain the oxygen produced during the reduction stage. reduction, while the stream fed to the oxidation stage (second stage) is CO2 mixed with air or any other inert carrier gas (for example N2 or Ar) in a volume percentage of CO2 in the range 10-100%, preferably between 30 and 100%.
  • the method of obtaining the present invention comprises a first stage in which a metal oxide of the perovskite type of formula (I) is heated, as described above, and a second stage of re-oxidation of the metal oxide obtained in the previous stage and production of synthesis gas by reaction with a stream of inert gas (N2 or Ar) or air mixed with water vapor and CO2 in a sufficient proportion for the reaction to take place.
  • a metal oxide of the perovskite type of formula (I) is heated, as described above
  • a second stage of re-oxidation of the metal oxide obtained in the previous stage and production of synthesis gas by reaction with a stream of inert gas (N2 or Ar) or air mixed with water vapor and CO2 in a sufficient proportion for the reaction to take place a stream of inert gas (N2 or Ar) or air mixed with water vapor and CO2 in a sufficient proportion for the reaction to take place.
  • the method of this particular embodiment is characterized by an operating temperature ranging between 300 and 800°C and a working pressure in the range of 0.1 MPa to 20 MPa.
  • the gas stream fed into the reduction stage is preferably air, although an inert gas can be used, preferably N2 or Ar (but not limited to these) with a sufficient flow rate to entrain the oxygen produced during the reduction stage.
  • reduction while the stream fed to the oxidation stage (second stage) is a mixture of N2, Ar or air with CO2 in a volume percentage of CO2 in the range 10-100%, preferably between 30 and 100%. %, saturated in water vapor at 50-120°C or a mixture of a stream of water vapor and CO2 with a volume percentage of CO2 of 10-90%.
  • the present invention describes the use of a perovskite-type metal oxide of formula (I)
  • B represents an element of the alkali or alkaline earth series
  • M represents Fe or Co
  • N represents a transition metal or an element selected from the groups of the p block of the Periodic Table; x and y have a value between 0 and 1 ; and z has a value between 0 and 0.75, for the production of H2, CO or synthesis gas (CO+H2).
  • A represents La or Nd
  • B represents Ca or Sr
  • M represents Fe or Co
  • N represents Fe, Co, Ti, Mo, Sb or Al
  • x and y have a value between 0 and 1
  • z has a value between 0 and 0.75.
  • the perovskite-type metal oxide with composition Ndi / 3Sr2 / 3CoC>3- z was synthesized through different synthesis methods, which are known in the state of the art and could be used without difficulty by any expert in the field. These methods have been described without prejudice to the fact that it can be synthesized with other methods, leading to obtaining samples with identical characteristics in relation to the use that is protected in this present invention.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature. This solution was heated to around 80°C with stirring on a plate heater and citric acid was added in a stoichiometric ratio of 1 metal:3 citric acid, in this case 2.7089 g.
  • the reagent mixture was dissolved in 30 mL of distilled water at room temperature. Subsequently, 4.5735 g of glycine were dissolved in said solution.
  • This solution was used in a spray-pyrolysis system (consisting of a liquid projection system in the form of fine drops, like a nebulizer, which is projected onto a hot surface, 450°C in this case) that promotes the combustion reaction by thermal activation.
  • the powder produced in the pyrolysis was treated at 900°C for 4 hours to produce the perovskite of composition Ndi /3 Sr 2/3 Co0 3-z .
  • the following stoichiometric quantities of reagents were used: 1.3180 g of Nd 2 0 3 , 1.8740 g of Sr0 2 and 2.1605 g of CoOOH to obtain 5 g of perovskite oxide with composition Ndi /3 Sr 2/3 Co0 3 .z .
  • the mixture of the reagents was placed in a 50 mL volume zirconia grinding container with 5 mm diameter balls of the same material with a total mass of 50 g. Milling was carried out for 12 hours at 500 rpm.
  • the Ndi / 3Sr2 / 3CoC>3- z sample obtained by the conventional ceramic method, was used as perovskite-type metal oxide in the method of the present invention.
  • thermobalance During the initial heating, an air current of 100 mL/min was introduced into the thermobalance to entrain the O2 produced during the reduction stage. After completing the heating, the air stream fed to the thermobalance was replaced by a stream of pure CO2 to carry out the production of CO and the recovery of the initial perovskite.
  • Ndi / 3Sr2 / 3CoC>3- z has a stable behavior against cycles with a steady state CO production of 3038 pmol/g material ⁇ cycle, much higher than that of other perovskite-type materials. Furthermore, the reduction has been carried out at much lower temperatures (see Table 1).
  • Example 2 Evaluation of the material Ndi/3Sr 2/3 Co03-z in the production of H2
  • the production of H2 was evaluated using the Ndi / 3Sr2 / 3CoC>3- z sample, obtained by the conventional ceramic method described in example 1, as perovskite-type metal oxide in the method of the present invention.
  • 1 g of the perovskite-type metal oxide Ndi / 3Sr2 / 3CoC>3- z was introduced into a crucible of Pt/Rh 90/10 in an oven.
  • the temperature was increased to 700°C with a heating ramp of 10°C/min.
  • the furnace was fed with an air current of 50 NL/h, to transport the O2 produced in this stage to a gas analyzer. Once the temperature of 700°C was reached and the reduction finished, the air stream was saturated with water at 80°C to feed it to the reactor and carry out the perovskite oxidation stage and H2 production.
  • the perovskite-type metal oxide with composition Lai / 3Sr2 / 3CoC>3- z was synthesized through different synthesis methods, which are known in the state of the art and could be used without difficulty by any person skilled in the art. These methods have been described without prejudice to the fact that it can be synthesized with other methods, leading to obtaining samples with identical characteristics in relation to the use that is protected in this present invention.
  • the methods chosen to carry out this example were the following: conventional high temperature ceramic method, Pechini sol-gel method and solid state combustion. a) Preparation by the ceramic method The following stoichiometric amounts of metal nitrates were used: 0.6786 g of La(N0 3 ) 3 -6H 2 0, 1.3822 g of Co(N0 3 ) 2 -6H 2 0 and 0.6633 g Sr(N0 3 ) 2 to obtain 1 g of the perovskite oxide of composition Lai /3 Sr 2/3 Co0 3-z .
  • the mixture of reagents was ground and homogenized. This mixture was subjected to a first heat treatment at 800°C for 12 hours in an air oven. After grinding and homogenizing the mixture of precursors, a pellet was formed and heated at 1100°C for 72 hours with intermediate grinding every 24 hours.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature. This solution was heated to around 80°C with stirring on a hot plate and citric acid was added in a stoichiometric ratio of 1 metal:3 citric acid, in this case 2.7665 g.
  • the reagent mixture was dissolved in 10 mL of distilled water at room temperature. Subsequently, 1.5365 g of glycine were dissolved in said solution.
  • This solution was dehydrated at 60°C under vacuum for 24 hours, obtaining a solid resin that was ground. Later, it was shaped into a cylinder using a die and a hand press.
  • the ignition of the tablet was induced by contact with a flame from a lighter or gas torch.
  • the dust produced in the combustion was treated at 1100°C for 12 hours.
  • the Lai /3 Sr 2/3 Co0 3-z sample obtained by the conventional ceramic method, was used as perovskite-type metal oxide in the method of the present invention.
  • thermobalance During the initial heating, an air current of 100 mL/min was introduced into the thermobalance to entrain the 0 2 produced during the reduction stage. After heating, the air stream fed to the thermobalance was replaced by a stream of pure C0 2 to carry out the production of CO and the recovery of the initial perovskite.
  • the Lai / 3Sr2 / 3CoC>3- z does not have a stable behavior against cycles with a production of CO in the first cycle of 500 pmol/g material . However, the reduction has been carried out at much lower temperatures (see Table 1).
  • the production of H2 was evaluated using the Lai / 3Sr2 / 3CoC>3- z sample, obtained by the conventional ceramic method described in example 3, as perovskite-type metal oxide in the method of the present invention.
  • the H2 production of the first cycle is higher than that of the rest, in this case a H2 production of 225.1 pmol/g material is obtained, because the first cycle is always considered a material stabilization stage.
  • the production of H2 is stable, reaching a steady state value of 133.7 prnol /g material - cycle, similar to that found in the literature for other perovskite-type materials (see Table 2), but leading The process is carried out in isotherm at 800°C, which implies working temperatures much lower than those listed in Table 2 (1250-1400°C).
  • the perovskite-type metal oxide of composition Lai / 3Sr2 / 3Coo . 69Ugly . 3iC>3- z was synthesized through different synthesis methods, which are known in the state of the art. art and any expert in the field could use them without difficulty. These methods have been described without prejudice to the fact that it can be synthesized with other methods, leading to obtaining samples with identical characteristics in relation to the use that is protected in this present invention.
  • the mixture of reagents was ground and homogenized. Subsequently, it was subjected to a first heat treatment at 900°C for 12 hours in an air oven. After grinding and homogenizing the mixture of precursors, a pellet was formed and heated at 1350°C for 48 hours with intermediate grinding every 24 hours.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature. This solution was heated to around 80°C with stirring on a hot plate and citric acid was added in a stoichiometric ratio of 1 metal:3 citric acid, in this case 11 g. Maintaining heating and stirring, 1/10 of the initial volume of ethylene glycol (4 ml_) was added and polymerization occurred with the formation of the sol.
  • the solid mixture was allowed to cool and was ground to produce a powder which was calcined at 800°C to remove organic matter and produce an inorganic ash. Said ash was ground to homogenize it and treated at 1200°C for 24 hours.
  • the reagent mixture was dissolved in 10 mL of distilled water at room temperature. Subsequently, 3.3087 g of glycine were dissolved in said solution.
  • This solution was dehydrated at 60°C under vacuum for 24 hours, obtaining a solid resin that was ground. Later, it was shaped into a cylinder using a die and a hand press.
  • the pellet was then ignited by contact with a flame from a gas burner or torch.
  • the dust produced in the combustion was treated at 1100°C for 12 hours.
  • the Lai /3 Sr 2/3 Coo .69 Feo .3i 0 3-z sample obtained by the Pechini sol-gel method, was used as a perovskite-type metal oxide in the method of the present invention.
  • 1 g of the perovskite-type metal oxide Lai / 3Sr2 / 3Coo was introduced into a furnace . 69Ugly . 3iC>3- z using a Pt/Rh 90/10 crucible.
  • the temperature was increased to 800°C with a heating ramp of 10°C/min.
  • the furnace was fed with a stream of N2 at 50 NL/h, to transport the O2 produced in this stage to a gas analyzer. Once the temperature of 800°C was reached and the reduction was complete, the N2 stream was saturated with water at 80°C to feed it to the reactor and carry out the perovskite oxidation stage and H2 production.
  • the H2 production of the first cycle is higher than that of the rest (as explained above), obtaining in this case 514.8 pmol/g material .
  • the production of H2 is stable around 435.0 pmol/g mater ⁇ ai ⁇ cycle, this production being higher than that found in the literature for other perovskite-type materials (see Table 2), and also the process is carried out isothermally at 800°C, which implies working temperatures much lower than those listed in Table 2 (1250-1400°C).
  • the perovskite-type metal oxide with composition SrFeC>3- z was synthesized through different synthesis methods, which are known in the state of the art and could be used without difficulty by any expert in the field. These methods have been described without prejudice to the fact that it can be synthesized with other methods, leading to obtaining samples with identical characteristics in relation to the use that is protected in this present invention.
  • the following stoichiometric amounts were started: 0.4170 g Fe2C>3 and 0.7677 g of Sr(CC>3) to obtain 1 g of perovskite oxide with composition SrFeC>3- z.
  • the mixture of reagents was ground and homogenized. Subsequently, it was subjected to a first heat treatment at 900°C for 12 hours in an air oven. After grinding and homogenizing the mixture of precursors, a pellet was formed and heated at 1300°C for 48 hours, after which the oven was turned off and the sample was allowed to cool slowly.
  • the resulting sample was characterized by X-ray diffraction, obtaining a highly crystalline pure material. In this case, a material with a structure derived from tetragonal symmetry perovskite was obtained.
  • the SrFeC> 3-z compound has a structure brownmillerite in the reducing stage and a highly symmetric cubic structure in the oxidizing stage.
  • the following stoichiometric amounts of metal nitrates were used: 2.1008 g of Fe(NC> 3 ) 3 -9H 2 0 and 1.1005 g of Sr(NC> 3) 2 to obtain 1 g of perovskite oxide SrFeC>3-z composition.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature and a 0.5 M Na2(CC>3) solution was added until reaching a pH between 12 and 14, producing the quantitative coprecipitation of Fe(OH)3 and SrCC>3.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature. This solution was heated to around 80°C with stirring on a hot plate and citric acid was added in a stoichiometric ratio of 1 metal:3 citric acid, in this case 2.9971 g.
  • the following stoichiometric amounts of metal nitrates were used: 10.5040 g of Fe(N0 3 ) 3 -9F ⁇ 2 0 and 5.5025 g of Sr(NC>3)2 to obtain 5 g of perovskite oxide with composition SrFeC>3-z.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature. Subsequently, 5.4217 g of glycine were dissolved in said solution.
  • the powder obtained from the combustion induced by treatment in a microwave oven was treated at 1100°C for 12 hours to produce the perovskite of composition SrFeC> 3-z.
  • the resulting sample was characterized by X-ray diffraction, obtaining a highly crystalline pure material that corresponds to a structure derived from orthorhombic symmetry perovskite.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature. Subsequently, 5.4454 g of glycine were dissolved in said solution.
  • This solution was used in a spray-pyrolysis system that promotes the combustion reaction by thermal activation.
  • the powder obtained from the combustion was treated at 1100°C for 12 hours to produce the perovskite with composition SrFeC> 3-z.
  • the resulting sample was characterized by X-ray diffraction, obtaining a highly crystalline pure material that corresponds to a structure derived from orthorhombic symmetry perovskite.
  • the SrFeC> 3-z sample obtained by the Pechini sol-gel method, was used as perovskite-type metal oxide in the method of the present invention.
  • H2 is remarkable from the first cycle, 718.2 pmol/g material and remains stable, 714.1 pmol/g material ⁇ cycle, so that this material does not seem to need a stabilization step.
  • Its steady-state production is similar to that achieved from the beginning, being higher than that found in the literature for most of the perovskite-type state-of-the-art materials (see Table 2), but carrying out the process in isotherm at 800°C, which represents a notable decrease in the working temperature with respect to those listed in Table 2 (1250-1400°C).
  • Example 7 Evaluation of the material SrFeC> 3- z in the production of CO
  • the production of CO was evaluated using the sample of SrFeC> 3-z , obtained by the Pechini sol-gel method described in example 6, as perovskite-type metal oxide in the method of the present invention.
  • thermobalance During the initial heating, an air current of 100 mL/min was introduced into the thermobalance to entrain the O2 produced during the reduction stage. After completing the heating, the air stream fed to the thermobalance was replaced by a stream of pure CO2 to carry out the production of CO and the recovery of the initial perovskite.
  • This oxidation step was maintained for 90 min. After this time, the introduction of CO2 was stopped and air was re-introduced to carry out the reduction again. This stage lasted approximately 70 min. These changes in the gas current were carried out periodically until 16 cycles were carried out.
  • the mass variations recorded in the thermobalance correspond to the oxygen lost or gained by the material depending on whether it is in the reduction or oxidation stage. The results of this example are shown in Table 1. This material does not present a stable behavior against cycles. Although in the first cycle it presents a high production of CO, 1262 prnol/g matemi , as the cycles go by a modification of the redox process is observed.
  • Example 8 Evaluation of the material SrFeo9oMoo io0 3 - in the production of H2
  • the metal oxide type perovskite of composition SrFeo . 9oMoo .i oC>3- z was synthesized through different synthesis methods, which are known in the state of the art and could be used without difficulty by any person skilled in the art. These methods have been described without prejudice to the fact that it can be synthesized with other methods, leading to obtaining samples with identical characteristics in relation to the use that is protected in this present invention.
  • the methods chosen to carry out this example were the following: conventional high-temperature ceramic method, Pechini sol-gel method and spray-pyrolysis assisted solution combustion. a) Preparation by the ceramic method The following stoichiometric amounts were started from: 0.3677 g Fe2C>3 , 0.0737 g of M0O3 and 0.7553 g of Sr(CC>3) to obtain 1 g of the perovskite oxide of composition SrFeo.9oMoo.ioC>3-z.
  • the mixture of reagents was ground and homogenized. Subsequently, it was subjected to a first heat treatment at 900°C for 12 hours in an air oven. After grinding and homogenizing the mixture of precursors, a pellet was formed and heated at 1350°C for 48 hours, after which the oven was turned off and the sample was allowed to cool slowly.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature. This solution was heated to around 80°C with stirring on a hot plate and citric acid was added in a stoichiometric ratio of 1 metal:3 citric acid, in this case 5.8788 g.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature. Subsequently, 8.0115 g of glycine were dissolved in said solution.
  • This solution was used in a spray-pyrolysis system that promotes the combustion reaction by thermal activation.
  • the powder obtained from the combustion was treated at 1000°C for 8 hours to produce the perovskite with composition SrFeo .9 oMoo .i o0 3-z.
  • the SrFeo sample was used .
  • 9oMoo .i oC>3- z obtained by the ceramic method, as perovskite-type metal oxide in the method of the present invention.
  • H2 The production of H2 is high from the first cycle, 882.7 prnol/g matemi , and grows slightly until reaching a steady-state production of 1176.7 prnol/g matemi -cycle, which is much higher than that found in the literature for the most state-of-the-art materials of the perovskite type (see Table 2), but carrying out the process in isotherm at 800°C, which implies a notable decrease in the working temperature with respect to those collected in Table 2 ( 1250-1400°C).
  • Example 9 Evaluation of the material SrFeo9oMoo io0 3 - in the production of CO
  • the production of CO was evaluated using the SrFeo sample .
  • 9oMoo .i oC>3- z obtained by the ceramic method described in example 8, as perovskite-type metal oxide in the method of the present invention.
  • thermobalance During the initial heating, an air current of 100 mL/min was introduced into the thermobalance to entrain the O2 produced during the reduction stage. After completion of heating, the air stream fed to the thermobalance was replaced by a stream of pure CO2 to carry out the production of CO and the recovery of the initial perovskite.
  • the perovskite-type metal oxide of composition SrFeo . 9oTio .i oC>3- z was synthesized through different synthesis methods, which are known in the state of the art and could be used without difficulty by any person skilled in the art. These methods have been described without prejudice to the fact that it can be synthesized with other methods, leading to obtaining samples with identical characteristics in relation to the use that is protected in this present invention.
  • the reagent mixture was dissolved in 50 mL of distilled water at room temperature. This solution was heated to around 80°C with stirring on a hot plate and citric acid was added in a stoichiometric ratio of 1 metal:3 citric acid, in this case 6.0461 g.
  • the powder obtained from the combustion induced by treatment in a microwave oven was treated at 1000°C for 12 hours to produce the perovskite of composition SrFeo . 9oThio .i oC>3- z.
  • the SrFeo sample was used .
  • 9oTio .i oC>3- z obtained by the ceramic method, as perovskite-type metal oxide in the method of the present invention.
  • H2 The production of H2 is notable from the first cycle, 568.8 prnol/g matemi , and grows slightly until reaching a steady-state production of 719.6 prnol/g matemi -cycle, which is higher than that found in the literature for most of the state-of-the-art materials of the perovskite type (see Table 2), but carrying out the process in isotherm at 800°C, which implies a notable decrease in the working temperature with respect to those collected in Table 2 (1250 -1400°C).
  • CO production was evaluated using the SrFeo sample . 9oTio .i oC>3- z , obtained by the ceramic method described in example 10, as perovskite-type metal oxide in the method of the present invention.
  • 50 mg of the perovskite-type metal oxide SrFeo were introduced . 9oTio .i oC>3- z in a 150 pl_ alumina crucible in the thermobalance.
  • the sample was heated with a ramp of 10°C/min until reaching 800°C. This temperature was kept constant for the rest of the test.
  • an air current of 100 mL/min was introduced into the thermobalance to entrain the O2 produced during the reduction stage.
  • thermobalance After completing the heating, the air stream fed to the thermobalance was replaced by a stream of pure CO2 to carry out the production of CO and the recovery of the initial perovskite. This oxidation step was maintained for 90 min. After this time, the introduction of CO2 was stopped and air was re-introduced to carry out the reduction again. This stage lasted approximately 70 min. These changes in the gas current were carried out periodically until 16 cycles were carried out.
  • the mass variations recorded in the thermobalance correspond to the oxygen lost or gained by the material depending on whether it is in the reduction or oxidation stage. The results of this test are shown in Table 1.
  • This material has stable behavior against cycles with a steady state CO production of 1262 pmol/g material , higher than that of other perovskite-type materials. Furthermore, in this case, the reduction is carried out at much lower temperatures (see Table 1).

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Abstract

L'invention concerne un procédé d'obtention de H2, de CO et/ou de gaz de synthèse à l'aide de matériaux de type pérovskite et une utilisation de ces matériaux. La présente invention concerne un procédé d'obtention de H2, de CO et/ou de gaz de synthèse au moyen de cycles thermochimiques basés sur des matériaux de type pérovskite, plus spécifiquement par la réaction d'oxydes métalliques de type pérovskite de formule (I) : A1-xBxM1-yNyO3-z avec de la vapeur d'eau et/ou du CO2. Les oxydes métalliques de type pérovskite de la présente invention ont démontré une activité supérieure à celle d'autres oxydes de type pérovskite rencontrés dans l'état de la technique et fonctionnent à une température plus basse. En outre, ils présentent une très bonne cyclabilité, c'est-à-dire qu'une bonne production de H2, de CO et/ou de gaz de synthèse est obtenue tout au long des cycles. La présente invention concerne enfin l'utilisation de ces oxydes de formule (I) pour la production de H2, de CO ou de gaz de synthèse.
PCT/ES2022/070134 2021-03-08 2022-03-08 Procédé d'obtention de h2, de co et/ou de gaz de synthèse à l'aide de matériaux de type pérovskite et utilisations de ces matériaux WO2022189689A1 (fr)

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