• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    Magnetic support and system as transporters of O2 and CO2 . The present invention relates to a magnetically stable support, structurally and chemically at high temperatures in oxidizing and reducing atmospheres, and which shows and maintains magnetic properties at room temperature, of general formula (Mnx Fe 1-x)3 O4, which has a spinel-like crystalline structure, and the general formula system (Mnx Fe1-x Mand)3 O4 + 5/FA formed by that support and an active phase . The present invention also relates to the methods of obtaining said support and said magnetic system, as well as its uses in processes in which said system needs to be separated from other materials after its use in industrial processes with oxidizing and/or reducing atmospheres . The present invention is included within the industrial and energy sector in processes aimed at mitigating climate change. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2724726A1
    申请号:ES201830222
    申请日:2018-03-07
    公开日:2019-09-13
    发明作者:Elorza Juan Adanez；Diego Poza Luis Francisco De；Labiano Francisco García；Sanz Pilar Gayan；Secades Alberto Abad；Pantoja María Teresa Izquierdo；Vicen María Abian；Vega Raúl Pérez
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    [0001]
    [0002] MAGNETIC SUPPORT AND SYSTEM AS TRANSPORTERS OF OR And CO 2
    [0003]
    [0004] The present invention relates to a magnetically stable support, structurally and chemically at high temperatures in oxidizing and reducing atmospheres, and which shows and maintains magnetic properties at room temperature, of general formula (MnxFe1-x) 3O4, which has a spinel-like crystalline structure , and to the general formula system (MnxFe1_xMy) 3O4 + 5 / FA formed by said support and an active phase. The present invention also relates to the methods of obtaining said support and said magnetic system, as well as its uses in processes in which said system needs to be separated from other materials after its use in industrial processes with oxidizing and / or reducing atmospheres . The present invention is included within the industrial and energy sector in processes aimed at mitigating climate change.
    [0005]
    [0006] STATE OF THE TECHNIQUE
    [0007]
    [0008] There are various industrial processes in which a particulate material must be separated from other materials after use in conditions where a metal oxide can be oxidized and / or reduced. The magnetic properties of certain materials can be used for this purpose. Preferably, this invention describes materials for use as a support for particulate material that maintain magnetic properties after use in the industrial process.
    [0009]
    [0010] Combustion technologies with oxygen transporters or in English, Chemical Looping Combustion (CLC), are suitable for the concentration and separation of CO2 in the combustion of fossil fuels due to its low cost and energy penalty. There are different variants of this technology such as combustion with solid oxygen transporters, combustion with solid oxygen transporters with gas oxygen generation or CLOU, of its acronym in English, the production of oxygen generated with solid oxygen transporters or CLAS, of its acronym in English, assisted combustion with solid oxygen transporters or OCAC, its acronym in English, the generation of hydrogen by reforming processes with solid oxygen carriers or CLR, the generation of hydrogen by gasification processes with solid oxygen carriers or CLG.
    [0011]
    [0012] In addition, other CO2 separation and concentration technologies have been developed by high temperature sorbents, such as the combustion process with CO2 capture with solid sorbents (or calcium-looping, CaL), preferably with calcium sorbents, although other types of sorbents can be used.
    [0013]
    [0014] Preferably, in these systems two interconnected reactors are needed but isolated from each other by the reaction atmosphere. Particles of a solid that act as an oxygen transporter or CO2 sorbent circulating between the reactors are also needed. Therefore in these processes, solids undergo a high number of cycles in reducing, oxidizing or both environments (redox processes). In general, these solids are simple metal oxides or a combination of two metal oxides, of metals such as Ni, Cu, Fe, Mn and / or Co, for the transport of oxygen, or of metals such as Ca, Mg or Li for the transport of CO 2 , supported in an inert.
    [0015]
    [0016] When solid fuels are used in a combustion process, the fuel ashes must be continuously extracted from the reactor where the fuel is fed to prevent its accumulation. In the Chemical Looping (CL) processes described above, these ashes are mixed with the carrier particles that are circulating between the process reactors, and therefore a certain amount of the conveyor will be extracted along with the fuel ashes. If the transporter particles are continuously extracted from the process, it will be necessary, to maintain the required inventory of them in the process, to feed them continuously back to the system. To reduce the costs of raw materials related to the particles of transporter, it would be convenient if the extracted particles were reintroduced to the process, thus reducing the amount of fresh particles needed. However, to carry out this reuse it is necessary to separate them from the ashes of the fuel with which they are mixed. This selective separation (ashes-transporter) can be done by different physical or chemical processes (buoyancy, density, magnetism). Of all of them, magnetic separation is a cheap technique, easy to implement and known at the industrial level.
    [0017] Likewise, CO2 sorbents can be mixed with ashes of a solid fuel used in limestone calcination processes, preferably for use in cement production.
    [0018]
    [0019] To carry out a magnetic separation of the conveyor from the ashes of the fuel or other type of particles, it is required that the transporter particles be magnetic after their use in the high temperature process with oxidizing and / or reducing environments. If the conveyor maintains the magnetic property at room temperature, the separation process can be carried out by reducing the process costs.
    [0020]
    [0021] It is known the magnetic property that iron oxides in the reduced state of Fe3O4 have at room temperature, however not in oxidized states such as FeO or Fe2O3. Therefore, the addition of small amounts of iron to the transporters of the CL process is not an adequate solution since, by going through oxidizing and / or reducing environments, they will not maintain their magnetic properties. If, after use in the process, the material is found as Fe2O3, a previous stage of reduction with H2 at high temperature (300-400 ° C) can be carried out to reduce the hematite, Fe2O3 to magnetite, Fe3O4, to generate magnetic properties and can then separate the solid. However, this adds one more stage to the separation process, not without a high cost for the consumption of H2 and equipment.
    [0022]
    [0023] Other compounds with magnetic properties that can be used as transporters are the mixed oxides of Fe and Mn. These metals can form mixed compounds in the spinel form (MnxFe1-x) 3O4 (Novák P. Contribution of octahedrally co-ordinated Mn3 + ion to magnetic torque. Czechoslovak Journal of Physics 1971; 21: 1198-1212 and Bakare PP, Gupta MP, Date SK, Sinha APB. Structural, magnetic and Mossbauer studies on MnxFe3-xO4 (0 <x <1). Proceedings of the Indian Academy of Sciences - Chemical Sciences 1984; 93: 1349-1359). In addition to the spinel, in oxidized form they can form the bixbyite (MnxFe 1- x) 2 O 3 phase, and in reduced form form the mannan-wustite compound (MnxFe1-x) O. Only the spinel has magnetic properties, so it is important that it be maintained in that phase. In addition to Fe-Mn compounds, the addition of other cations that improve the magnetic properties of these compounds, such as by example the addition of Ti4 + ([Mostafa NY, Hessien MM, Shaltout AA. Hydrothermal synthesis and characterizations of Ti substituted Mn-ferrites. Journal of Alloys and Compounds 2012; 529: 29-33] and [Abián et al. in "Titanium substituted manganeseferrite as an oxygen carrier with permanent magnetic properties for Chemical looping combustion of solid fuels ", Fuel 195 (2017) 38-48]), to mixtures of Mn-Fe for use as oxygen transporters with magnetic properties in CLC processes for separation of the conveyor from the ashes of the process.
    [0024]
    [0025] In all these works (Abián et al. Already mentioned and R. Pérez-Vega, et al. Development of (Mn0,77Fe0, 2 3) 2O3 particles as an oxygen carrier for coal combustion with CO2 capture via in-situ gasification chemical looping combustion (iG-CLC) aided by oxygen uncoupling (CLOU), In Fuel Processing Technology, Volume 164, 2017, Pages 69-79), the materials developed undergo rapid reductions and oxidations of their spinel phase (magnetic form) during stages a high temperature of CLC processes, so they would not maintain their stable magnetic properties after use in the process.
    [0026]
    [0027] Therefore, it is necessary to develop magnetically stable oxygen transport materials or CO2 sorbents throughout the temperature range in which processes with oxidizing and / or reducing atmospheres at high temperature take place, such as CLC, CLOU and CaL through use of magnetic supports that are also inert to the redox reactions that take place in these processes.
    [0028]
    [0029] DESCRIPTION OF THE INVENTION
    [0030]
    [0031] The invention relates to a support with magnetic properties that is structurally and chemically stable at high temperatures in oxidizing and reducing atmospheres. Said support has general formula (MnxFe1-xMy) 3O4 + 5 and spinel-like crystalline structure; It has undergone doping with metals (M) selected from Ti, Mg, Ca and Si, which are introduced into the cationic vacancies of the spinel structure.
    [0032]
    [0033] In said support an active phase (FA) can be sustained giving rise to a magnetically stable system, structurally and chemically at high temperatures in oxidizing and reducing atmospheres, where said FA is preferably at least one Ni oxide, at least one Cu oxide. , at least one oxide of Fe, at least one oxide of Mn or at least one Co oxide), for the transport of oxygen in CLC processes, or alkali metal or alkaline earth oxides, preferably Li oxide, Ca oxide, or Mg oxide for the transport of CO2 in CaL processes , resulting in a general formula (MnxFe1-xMy) 3O4 + 5 / FA.
    [0034]
    [0035] Thus, the magnetically stable support of the present invention has the following advantages over other supports:
    [0036] • the support exhibits magnetic behavior, in particular ferrimagnetism (FM) and improved relative permeabilities with respect to undoped supports, or with other doping ranges, allowing the conveyor to be recovered from the ashes removed at the end of the combustion processes.
    [0037]
    [0038] Similarly, the system formed by the magnetic support plus the active phase, (MnxFe1_xMy) 3O4 + 5 / FA, has the following advantages over other oxygen or CO 2 transporters:
    [0039] • the active phase FA that carries the O2 or CO2 does not react with the magnetic support of the invention.
    [0040] • the support maintains both its crystalline structure and magnetic properties, after multiple redox cycles in processes in oxidizing and / or reducing atmospheres.
    [0041]
    [0042] Thanks to its magnetic properties, said magnetic support can be recovered, as well as the active phase FA used and adhered to it, by applying a magnetic field to separate it from the ashes / residues of combustion or other components, without great expense of energy, thus being able to reuse in the following cycles to be carried out.
    [0043]
    [0044] In a first aspect, the present invention relates to a magnetically stable support at a temperature lower than its Curie temperature (from here "the support of the invention"), characterized by the general formula (MnxFe1_xMy) 3O4 + 5
    [0045] where M is selected from Ti, Mg, Ca and Si;
    [0046] x has a value between 0.1 and 0.75; and
    [0047] and has a value between 0.01 and 0.06; Y
    [0048] 5 has a value between 0.03 and 0.36;
    [0049] and where said support at least has a spinel-like crystalline structure.
    [0050] In the present invention, "support" is understood as any substance on which an active phase FA is deposited, wherein said FA is preferably a metal oxide, and where said support is inert to the oxidation and / or reduction processes described in the present invention, as well as being inert to react chemically with said FA.
    [0051]
    [0052] In the present invention the supports used are materials that have at least spinel, iron and manganese crystalline structure, and doped with another cation that can be Ti, Mg, Ca and Si, such that when subjected to different reactive atmospheres, for example, at a high temperature oxidation atmosphere, the spinel material is not oxidized to a material with a bixbyite crystalline structure, resulting in inert and therefore maintaining its magnetic properties. And on the other hand, if the support of the present invention is subjected to a reducing atmosphere, the spinel material is not reduced to a phase of structure type mangano-wüstita.
    [0053]
    [0054] In a preferred embodiment of the invention, the magnetically stable support is characterized in that x has a value between 0.33 and 0.66.
    [0055]
    [0056] In another preferred embodiment of the support of the invention, and has a value between 0.01 and 0.04.
    [0057]
    [0058] In another preferred embodiment of the present invention, the magnetically stable support is characterized in that M is Ti.
    [0059]
    [0060] In another preferred embodiment of the magnetically stable support, M is Ti and x = 0.5 and y = 0.01.
    [0061]
    [0062] In a more preferred embodiment, the magnetically stable support is characterized in that it has a general formula (MnxFe1-xMy) 3O 4 +5 where M is Ti, where x is 0.5, and is 0.01 and 5 is 0.09, with formula (Mn0.5Fe0.5Ti0.01) 3O409.
    [0063]
    [0064] Another aspect of the invention relates to a magnetically stable system (from here "the system of the invention") characterized by the general formula (MnxFe1-xMy) 3O4 + 5 / FA, where (MnxFe1_xMy) 3O4 + 5 is the support of the invention and is in a weight percentage of between 40% and 85% with respect to the final system; Y
    [0065] • where the active phase FA is an active phase in the form of particles selected from
    [0066] ■ a Ca oxide, Li oxide, Mg oxide, or
    [0067] ■ at least one Cu oxide, at least one Mn oxide, at least one Fe oxide, at least one Co oxide or at least one Ni oxide,
    [0068]
    [0069] or where said particles have a size between 1 pm and 20 pm,
    [0070] or where said active phase FA is supported on a support; and where said active phase FA is in a weight percentage of between 15% and 60% with respect to the final system.
    [0071]
    [0072] In a preferred embodiment of the present invention, the magnetically stable support has a weight percentage of between 60% and 80% with respect to the system and the active phase FA a weight percentage of between 20% and 40% with respect to the system.
    [0073]
    [0074] In the present invention, "active phase (FA)" means any substance capable of transporting oxygen or CO2. The active phase FA carrying oxygen is capable of accepting oxygen from the air to be transferred to a fuel during a total or partial combustion process. The most commonly used active FA phase for oxygen transport is at least one transition metal oxide such as Ni, Cu, Fe, Mn and Co. In order for an active FA phase to be used for oxygen transport it must have a series of characteristics such as high rates of reduction and oxidation, low tendency to carbon deposition during its reduction and a high capacity of regeneration, and this during a high number of redox cycles of operation.The active phase FA that carries CO2 is able to accept CO2 from a gas stream where this gas is found along with other gases to selectively separate it from the gas mixture The active phase FA for transport of C O 2 most commonly used is CaO, which preferably accepts CO 2 after reacting with it through a reaction called carbonation. In addition to CaO, other oxides such as MgO and Li2O can also be used as active phase FA for transporting CO 2 . For an active phase FA to be used for the transport of CO 2 it must have a series of characteristics such as high absorption rates and desorption of CO2, commonly known as carbonation and calcination reactions, maintained during a high number of cycles of operation.
    [0075]
    [0076] In the present invention, "support or support" is understood as the action of depositing a material, which in this case is the active phase FA, on the magnetically stable support and that both materials, FA and support, are closely related and / or agglutinated so that the mechanical or physical properties of one can be exploited by the other The methods used to support are spray-drying or spray drying, mass mixing, compaction, granulation, extrusion, briquetting, pelletizing, and sintering.
    [0077]
    [0078] In another more preferred embodiment, the magnetically stable system is characterized in that it has a general formula (MnxFe1-xMy) 3O4 + 5 / FA where M is Ti.
    [0079]
    [0080] In another more preferred embodiment, the magnetically stable system is characterized in that the active phase FA is Ca oxide.
    [0081]
    [0082] In another more preferred embodiment, the magnetically stable system is characterized in that the active phase FA is a Cu oxide.
    [0083]
    [0084] In another even more preferred embodiment, the magnetically stable system is characterized in that it has a general formula (MnxFe1_xMy) 3O4 + 5 / FA where M is Ti, x = 0.5 ey = 0.01, with formula (Mn0.5Fe05Ti001) 3O4. 09 / FA, and where FA is at least one simple metal oxide, preferably Cu, Mn, Fe, Co or Ni oxide. The support used in this even more preferred embodiment, (Mn0.5Fe0.5Ti0.01) 3O409, has an optimal value in terms of susceptibility and inerticity. (see table 1)
    [0085]
    [0086] In another even more preferred embodiment, the magnetically stable system is characterized in that it has a general formula (MnxFe1_xMy) 3O4 + 5 / FA where M is Ti, x = 0.5 ey = 0.01, with formula (Mn05Fe05Ti001) 3O4.09 / FA, and where FA comprises an oxide of Ca, Mg or Li, and preferably an oxide of Ca. The support used in this even more preferred embodiment, (Mn05Fe05Ti001) 3O4.09, has an optimum value in terms of susceptibility and inerticity ( see table 1).
    [0087]
    [0088] In the present invention, "inerticity" means the percentage by weight of material, support in this patent, which does not react with reactive gases in atmospheres reducing or oxidizing.
    [0089]
    [0090] Another aspect of the invention is the method of obtaining the support of the present invention of the general formula (MnxFe1_xMy) 3O4 + 5 and wherein said process comprises the following steps:
    [0091] a) mix the stoichiometric amounts of Mn3O4 and Fe2O3 with respect to the final support weight;
    [0092] b) adding at least one compound selected from a titanium oxide precursor, a magnesium oxide precursor, a calcium oxide precursor, a silicon oxide precursor, a silicon oxide precursor onto the mixture obtained in step (a) titanium, magnesium oxide, calcium oxide or silicon oxide, in a weight percentage of between 1% and 6% with respect to the final support weight. c) heat treating the mixture obtained in step (b) at a temperature between 1300 ° C and 1400 ° C for a period of time between 2 hours and 10 hours; Y
    [0093] d) grind the calcined product obtained in step (c) to obtain a particle size between 2 and 10 pm.
    [0094]
    [0095] In a preferred embodiment of the process for obtaining the support of the present invention, the mixing of stage (a) and milling of stage d) is carried out in one of the following: planetary mill, crusher and mortar.
    [0096]
    [0097] In a preferred embodiment of the process for obtaining the support of the present invention, the mixing of step (a) is carried out in a planetary mill.
    [0098]
    [0099] In another preferred embodiment of the method of obtaining the system, step (c) is carried out in muffle or other oven system at a temperature between 1340 ° C and 1360 ° C and for a period of time between 5.5 hours and 6.5 hours.
    [0100]
    [0101] Another aspect of the invention is a method of obtaining the magnetically stable system characterized in that in addition to the previous stages of obtaining the support it comprises the following steps:
    [0102] a) mix the stoichiometric amounts of Mn3O4 and Fe2O3 with respect to the final support weight;
    [0103] b) adding at least one compound selected from a titanium oxide precursor, a magnesium oxide precursor, a calcium oxide precursor, a silicon oxide precursor, a silicon oxide precursor onto the mixture obtained in step (a) titanium, magnesium oxide, calcium oxide or silicon oxide, in a weight percentage of between 1% and 6% with respect to the final support weight. c) heat treating the mixture obtained in step (b) at a temperature between 1300 ° C and 1400 ° C for a period of time between 2 hours and 10 hours;
    [0104] d) grind the calcined product obtained in step (c) until a particle size of between 2 and 10 pm is obtained;
    [0105] e) mixing and agglomerating the product obtained in step (d) with active phase FA; Y
    [0106] f) grind the product obtained in step (e) and / or select the particles of size between 100 pm and 300 pm.
    [0107]
    [0108] In a preferred embodiment of the method of obtaining the system of the present invention, the mixing of step (a) is carried out in one of the following: planetary mill, crusher and mortar.
    [0109]
    [0110] In a preferred embodiment of the method of obtaining the system of the present invention, the mixing of step (a) is carried out in a planetary mill.
    [0111]
    [0112] In another preferred embodiment of the method of obtaining the system, step (c) is carried out in muffle or other oven system at a temperature between 1340 ° C and 1360 ° C and for a period of time between 5.5 hours and 6.5 hours.
    [0113]
    [0114] In a preferred embodiment of the method of obtaining the magnetically stable system, the step (e) of mixing and agglomeration is carried out by a method selected from the following list: "spray-drying" or spray drying, mass mixing, compaction, granulation, extrusion, briquetting, pelletizing, or sintering
    [0115]
    [0116] In a more preferred embodiment of the method of obtaining the magnetically stable system, the mixing stage (e) is performed by granulation.
    [0117] In the present invention, "granulation" is understood as any operation that aims to agglomerate finely divided substances such as dusts by means of adding binder substances. One of the most used methods is the fluidized bed, which is based on the fact that a gas at a faster speed than the dust settling speed can suspend it in the air.
    [0118]
    [0119] When mixing and agglomerating the product with the active phase FA is done by mass mixing, compaction, briquetting, extrusion, pelletization or sintering it is necessary to perform stage (f) in a planetary or ball mill.
    [0120] When the mixing and agglomeration of the product with the active phase FA is done by granulation or "spray drying" the grinding stage is not necessary, only selection.
    [0121]
    [0122] Another aspect of the invention relates to the use of the support of the invention as a support for an active phase. In a preferred embodiment the active phase is a metal oxide of Ca, Li, or Mg, for the transport of CO2 or is at least one Cu oxide, at least one Mn oxide, at least one Fe oxide, at least one Co oxide or at least one Ni oxide, for oxygen transport.
    [0123]
    [0124] In the present invention, "oxygen transporter" is understood as any substance capable of accepting oxygen from the air and transferring it to the fuel during a total or partial combustion process. In the present invention these conveyors are at least one simple metal oxides of Ni, Cu, Fe, Mn and Co, being necessary to have high rates of reduction and oxidation, high mechanical resistance to limit their breakage and attrition, not showing signs of agglomeration , low tendency to carbon deposition during its reduction and a high regeneration capacity, since they must withstand a large number of operating cycles. Frequently, these conveyors are used in conjunction with a support. In such a way that the metal oxide gives the system the ability to transport oxygen to the fuel and, on the other hand, the support confers the mechanical resistance to the system to be used for many cycles. If the support had invariable magnetic properties after use in the process, it could be used to recover the support / transport system from the losses in the solid waste generated in such processes.
    [0125] In the present invention, "carbon dioxide transporter" is understood as any substance capable of accepting carbon dioxide from the medium by carbonation or calcination and yielding it after calcination. In the present invention the carbon dioxide transporters are calcium oxide, lithium oxide and magnesium oxide.
    [0126]
    [0127] Another aspect of the invention relates to the use of the system of present invention as carrier of CO2.
    [0128]
    [0129] Preferably it refers to using the system of the present invention in reactions with CO2 capture by carbonatation cycles / calcination.
    [0130]
    [0131] Another aspect of the invention relates to the use of the system of the present invention as an oxygen transporter. Preferably it refers to the use of the system of the invention in combustion reactions with oxygen transporters or in combustion reactions with solid oxygen transporters with generation of gaseous oxygen.
    [0132]
    [0133] In the present invention, "combustion process with oxygen transporters" is understood as any method in which an oxygen transfer from the air to the fuel takes place by means of an oxygen transporter, preferably in the form of metallic oxide, which circulates between two reactors interconnected with each other, one in which a reduction occurs and the other in which oxidation occurs, and the fuel does not contact the air at any time. The combustion can be total or partial.
    [0134]
    [0135] In the present invention, "combustion process with solid oxygen carriers with generation of gaseous oxygen generation" is understood as any procedure derived from a combustion process with oxygen carriers, in which there are also two interconnected reactors, one in which produces a reduction and another in which oxidation occurs, and in which the oxygen transporter has the ability to release O 2 after decomposition at high temperatures. So that the solid fuel (for example coal) that reacts with the oxygen released by the metal oxide generating CO 2 and H 2 O vapor is fed directly into the reduction reactor. Oxidation the oxygen carrier is regenerated with air leaving it ready to start a new cycle.
    [0136]
    [0137] In the present invention, "combustion process with CO2 capture with solid sorbents (CaL)" means any procedure in which there is a CO2 capture by means of carbonation / calcination cycles based on a CO2 acceptor, preferably the reaction of CaO with the CO2 present in a gas stream, and in the inverse reaction of calcination of CaCO 3 in a second reactor, in a concentrated atmosphere of CO 2 .
    [0138]
    [0139] In the present invention, "Curie temperature (TCurie)" is understood as the temperature above which a body with magnetic properties (Km> 1) loses its magnetism, showing a relative permeability similar to that of vacuum (Km = 1 ).
    [0140]
    [0141] In the present invention, "normalized speed index" is understood as the parameter that measures the reactivity of an oxygen transporter. This can be calculated using the formula:
    [0142]
    [0143]
    [0144]
    [0145] where ra represents the loss of normalized mass or mass conversion of the oxygen transporter during the reduction with 15 vol% of gas or during oxidation with 10 vol% O2. These values were set as reference values to compare normalized speed indices between different oxygen transporters.
    [0146]
    [0147] In the present invention, "thermogravimetric analysis or TGA" is understood as the analysis technique that consists in measuring the variation of the mass of a solid substance as a function of the change in temperature and / or time at the passage of a gas stream
    [0148]
    [0149] In the present invention, "precursor" means compounds such as nitrates, acetates, carbonates, sulfates of the corresponding cations, which in the reaction medium will be transformed into the corresponding oxide of said cations. In this invention the precursors are: titanium nitrate, magnesium nitrate, calcium nitrate or silicon nitrate, or titanium acetate, magnesium acetate, calcium acetate or silicon acetate, or titanium sulfate, magnesium sulfate, calcium sulfate or silicon sulfate.
    [0150]
    [0151] In the present invention, "relative permeability (Km)" means the proportion of the internal magnetization with respect to an applied magnetic field. If the material does not respond to the magnetization of the applied field, the relative permeability will be 1. If the material is magnetized in response to the applied external magnetic field, the relative permeability will be positive with a value greater than one.
    [0152]
    [0153] Throughout the description and the 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 be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0154]
    [0155] BRIEF DESCRIPTION OF THE FIGURES
    [0156]
    [0157] Figure 1 shows the mass variation of (Mn05Fe05Ti001) 3O4.09 over time during three consecutive redox cycles of N2-air at 950 ° C performed in TGA.
    [0158]
    [0159] Figure 2 shows the mass variation of (Mn05Fe05Ti001) 3O4.09 over time during three consecutive redox cycles of H2-air at 950 ° C performed in TGA
    [0160]
    [0161] EXAMPLES
    [0162]
    [0163] The invention will now be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the product of the invention.
    [0164]
    [0165] Example 1: magnetically stable support of formula (Mn0.5Fe0.5Ti0.01) 3O4.09. The powdered metal oxides in mass ratio of Mn3O4 (Strem Chemical Inc.), Fe2O3 (Panreac Prs.) And TiO2 (Panreac Prs.) 48.5: 50.0: 1.5 are first mixed in a planetary mill. Briquettes are obtained in the form of a pressure tablet in a hydraulic press. The mixture is calcined at 1350 ° C in air for 6 h and the briquettes are milled to size 10. ^ M.
    [0166] These particles are characterized physically and chemically, as shown in Table 1. The particles obtained are characterized by X-ray diffraction to know the crystalline phases that compose them. Also, a measure of relative permeability is performed to assess its initial magnetism. Subsequently, the particles are exposed to several redox cycles in thermogravimetric analysis (TGA) to obtain the reactivity of the material prepared against O 2 (thermodynamic conditions that allow spinel oxidation) and H 2 (as a gas with high reducing power). Finally, the measurement of the relative permeability of the particles subjected to different reactant atmospheres is performed on the one hand to an oxidizing atmosphere in air-N2 cycles, and on the other hand to a reducing atmosphere in H2-air cycles, to evaluate the magnetism in the materials after being exposed to these atmospheres.
    [0167]
    [0168] The spinel phase was composed of the following crystalline phases with general formula (MnxFe1-x) O4: Mn2FeO4 and Mn3Fe3O8.
    [0169]
    [0170] During its heat treatment, the spinel phase does not oxidize, allowing the material to retain magnetism at room temperature.
    [0171]
    [0172] The relative permeability value (Km), which is the proportion of the internal magnetization with respect to an applied magnetic field and which is calculated after a measurement on a Bartington Instruments MS3 susceptibility meter for the particles obtained in the described procedure and which have not been exposed to any reactant atmosphere, it turned out to be 9.9.
    [0173]
    [0174] The Km value for particles exposed to an oxidizing atmosphere (after 3 redox N2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, turned out to be 8.8.
    [0175]
    [0176] The Km value for particles exposed to a reducing atmosphere (after 3 H2-air redox cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was found to be 5.2.
    [0177]
    [0178] In particular, under oxidation conditions, after performing 3 redox cycles in reduction TGA with N2 and oxidation in air at 950 ° C (thermodynamic conditions that allow spinel oxidation), as shown in Figure 1, only 11.7% of the spinel phase is able to oxidize to form bixbyite, the rest behaving inert (88.3%), which allows The material still has magnetic properties at room temperature, with a relative permeability value of Km = 8.8.
    [0179]
    [0180] And in conditions of reduction, after performing 3 redox cycles in reduction TGA with H2 and oxidation in air at 950 ° C (thermodynamic conditions that allow spinel reduction), as shown in Figure 2, only 53, 2% of the spinel phase is able to reduce to the mangano-wüstita phase, the rest behaving inert (46.8%), which allows the material to continue to possess magnetic properties at room temperature, with a relative permeability value of Km = 5.2.
    [0181] The observed decreases in relative permeability after use in oxidizing and reducing atmospheres are directly related to the inerticity of the support to the reaction gases.
    [0182]
    [0183] Example 2: magnetically stable support of formula (Mn0, i7Fe0.83Ti0.04) 3O4.21. The powdered metal oxides in mass ratio of Mn3O4 (Strem Chemical Inc.), Fe2O3 (Panreac Prs.) And TiO2 (Panreac Prs.) 16.0: 80.5: 3.5 are first mixed in a planetary grind. Briquettes are obtained in the form of a pressure tablet in a hydraulic press. The mixture is calcined at 1350 ° C in air for 6 h and the briquettes are ground to size 10 p, m.
    [0184]
    [0185] These particles are characterized physically and chemically, as shown in Table 1. The particles obtained are characterized by X-ray diffraction to know the crystalline phases that compose them. Also, an initial magnetism measurement is performed. Subsequently, the particles are exposed to several redox cycles in thermogravimetric analysis (TGA) to obtain the reactivity of the material prepared against O 2 (thermodynamic conditions that allow spinel oxidation) and H2 (as a gas with high reducing power). Finally, the measurement of the relative permeability of the particles subjected to different reactant atmospheres is carried out on the one hand to an oxidizing atmosphere of N2-air, and on the other hand to a reducing atmosphere of H2-air, to evaluate the magnetism in the materials after being exposed to these atmospheres.
    [0186] The spinel phase was composed of the following crystalline phases with general formula (MnxFe1-x) O4: MnFe2O4 and Mn2FeO4.
    [0187]
    [0188] During its heat treatment, the spinel phase does not oxidize, allowing the material to retain magnetism at room temperature.
    [0189]
    [0190] The relative permeability value (Km), which is the proportion of the internal magnetization with respect to an applied magnetic field and which is calculated after a measurement on a Bartington Instruments MS3 susceptibility meter for the particles obtained in the described procedure and which have not been exposed to any reactant atmosphere, it turned out to be 4.9.
    [0191]
    [0192] The Km value for the particles exposed to an oxidizing atmosphere (after 3 redox N2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was 4.5.
    [0193]
    [0194] The Km value for particles exposed to a reducing atmosphere (after 3 redox H2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was 3.2.
    [0195]
    [0196] In particular, under oxidation conditions, after performing 3 redox cycles in reduction TGA with N2 and oxidation in air at 950 ° C (thermodynamic conditions that allow spinel oxidation) only 10.2% of the spinel phase It is capable of oxidizing itself to oxidize to form bixbyite, the rest behaving in an inert manner (89.8%), which allows the material to continue to possess magnetism at room temperature, with a value of Km = 4.5.
    [0197]
    [0198] And in conditions of reduction, after performing 3 redox cycles in reduction TGA with H2 and oxidation in air at 950 ° C (thermodynamic conditions that allow the spinel to be reduced) only 43.7% of the spinel phase is capable If reduced to the Mangano-Wüstita phase, the rest behaving inert (56.3%), which allows the material to retain magnetism at room temperature, with a value of Km = 3.2.
    [0199] Example 3: magnetically stable support of formula (Mn0.33Fe0.67Ti0.04) 3O4.21. The powdered metal oxides in mass ratio of Mn3O4 (Strem Chemical Inc.), Fe2O3 (Panreac Prs.) And TiO2 (Panreac Prs.) 31.0: 65.5: 3.5 are first mixed in a planetary mill. Briquettes are obtained in the form of a pressure tablet in a hydraulic press. The mixture is calcined at 1350 ° C in air for 6 h and the briquettes are milled to size 10. ^ M.
    [0200]
    [0201] These particles are characterized physically and chemically, as shown in Table 1. The particles obtained are characterized by X-ray diffraction to know the crystalline phases that compose them. Also, a measure of relative permeability is performed to assess its initial magnetism. Subsequently, the particles are exposed to several redox cycles in thermogravimetric analysis (TGA) to obtain the reactivity of the material prepared against O2 (thermodynamic conditions that allow spinel oxidation) and H2 (as a gas with high power reducer). Finally, the measurement of the relative permeability of the particles subjected to different reactant atmospheres is carried out on the one hand to an oxidizing atmosphere of N2-air, and on the other hand to a reducing atmosphere of H2-air, to evaluate the magnetism in the materials after being exposed to these atmospheres.
    [0202]
    [0203] The spinel phase was composed of the following crystalline phases with general formula (MnxFe1-x) O4: Mn2FeO4, Mn3Fe3O8 and Mn1.58Fe1.42O4.
    [0204]
    [0205] During its heat treatment, the spinel phase does not oxidize, allowing the material to retain magnetism at room temperature.
    [0206]
    [0207] The relative permeability value (Km), which is the proportion of the internal magnetization with respect to an applied magnetic field and which is calculated after a measurement on a Bartington Instruments MS3 susceptibility meter for the particles obtained in the described procedure and which have not been exposed to any reactant atmosphere, it turned out to be 9.1.
    [0208]
    [0209] The Km value for the particles exposed to an oxidizing atmosphere (after 3 redox N2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was found to be 8.1.
    [0210] The Km value for particles exposed to a reducing atmosphere (after 3 redox H2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was 5.4.
    [0211]
    [0212] In particular, under oxidation conditions, after carrying out 3 redox cycles in reduction TGA with N2 and oxidation in air at 950 ° C (thermodynamic conditions that allow the spinel oxidation) only 12.6% of the spinel phase It is able to oxidize to form bixbyite, the rest behaving in an inert manner (87.4%), which allows the material to continue to possess magnetism at room temperature, with a value of Km = 8.1.
    [0213]
    [0214] And under conditions of reduction, after performing 3 redox cycles in reduction TGA with H2 and oxidation in air at 950 ° C (thermodynamic conditions that allow the spinel to be reduced) only 46.1% of the spinel phase is capable If reduced to the Mangano-Wüstita phase, the rest behaving in an inert manner (53.9%), which allows the material to continue to have magnetism at room temperature, with a value of Km = 5.4.
    [0215]
    [0216] Example 4: magnetically stable support of formula (Mn0.5Fe0.5Ti0.04) 3O4.21. The powdered metal oxides in mass ratio of Mn3O4 (Strem Chemical Inc.), Fe2O3 (Panreac Prs.) And TiO2 (Panreac Prs.) 47.0: 49.5: 3.5 are first mixed in a planetary mill. Briquettes are obtained in the form of a pressure tablet in a hydraulic press. The mixture is calcined at 1350 ° C in air for 6 h and the briquettes are ground to size 10 p, m.
    [0217]
    [0218] These particles are characterized physically and chemically, as shown in Table 1. The particles obtained are characterized by X-ray diffraction to know the crystalline phases that compose them. Also, a measure of relative permeability is performed to assess its initial magnetism. Subsequently, the particles are exposed to several redox cycles in thermogravimetric analysis (TGA) to obtain the reactivity of the material prepared against O 2 (thermodynamic conditions that allow spinel oxidation) and H2 (as a gas with high reducing power). Finally, the measurement of the relative permeability of the particles subjected to different reactant atmospheres is performed on the one hand to an oxidizing atmosphere of N2-air, and on the other hand to a reducing atmosphere of H2-air, to evaluate the magnetism in the materials after being exposed to these atmospheres.
    [0219]
    [0220] During its heat treatment, the spinel phase does not oxidize, allowing the material to continue to possess magnetism at room temperature.
    [0221]
    [0222] The relative permeability value (Km), which is the proportion of the internal magnetization with respect to an applied magnetic field and which is calculated after a measurement on a Bartington Instruments MS3 susceptibility meter for the particles obtained in the described procedure and which have not been exposed to any reactant atmosphere, it turned out to be 9.3.
    [0223]
    [0224] The Km value for particles exposed to an oxidizing atmosphere (after 3 redox N2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was 7.2.
    [0225]
    [0226] The spinel phase was composed of the following crystalline phases with general formula (MnxFe1-x) O4: Mn2FeO4 and Mn3Fe3O8.
    [0227]
    [0228] The Km value for particles exposed to a reducing atmosphere (after 3 H2-air redox cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was found to be 5.1.
    [0229]
    [0230] In particular, under oxidation conditions, after performing 3 redox cycles in reduction TGA with N2 and oxidation in air at 950 ° C (thermodynamic conditions that allow spinel oxidation) only 25.6% of the spinel phase It is able to oxidize to form bixbyite, the rest behaving inert (74.4%), which allows the material to continue to possess magnetism at room temperature, with a value of Km = 7.2.
    [0231]
    [0232] And in conditions of reduction, after performing 3 redox cycles in reduction TGA with H2 and oxidation in air at 950 ° C (thermodynamic conditions that allow the spinel to be reduced) only 50.7% of the spinel phase is capable If reduced to the Mangano-Wüstita phase, the rest behaving in an inert manner (49.3%), which allows the material to continue to have magnetism at room temperature, with a value of Km = 5.1.
    [0233] Example 5: magnetically stable support of formula (Mn0.66Fe0.34Ti0.04) 3O4.21. The powdered metal oxides in mass ratio of Mn3O4 (Strem Chemical Inc.), Fe2O3 (Panreac Prs.) And TiO2 (Panreac Prs.) 62.5: 34.0: 3.5 are first mixed in a planetary grind. Briquettes are obtained in the form of a pressure tablet in a hydraulic press. The mixture is calcined at 1350 ° C in air for 6 h and the briquettes are milled to size 10. ^ M.
    [0234]
    [0235] These particles are characterized physically and chemically, as shown in Table 1. The particles obtained are characterized by X-ray diffraction to know the crystalline phases that compose them. Also, a measure of relative permeability is performed to assess its initial magnetism. Subsequently, the particles are exposed to several redox cycles in thermogravimetric analysis (TGA) to obtain the reactivity of the material prepared against O2 (thermodynamic conditions that allow spinel oxidation) and H2 (as a gas with high power reducer). Finally, the measurement of the relative permeability of the particles subjected to different reactant atmospheres is carried out on the one hand to an oxidizing atmosphere of N2-air, and on the other hand to a reducing atmosphere of H2-air, to evaluate the magnetism in the materials after being exposed to these atmospheres.
    [0236]
    [0237] The spinel phase was composed of the following crystalline phases with general formula (MnxFe1-x) O4: Mn2FeO4 and Mn15,8Fe1,42O4.
    [0238]
    [0239] During its heat treatment, the spinel phase does not oxidize, allowing the material to continue to possess magnetism at room temperature.
    [0240]
    [0241] The relative permeability value (Km), which is the proportion of the internal magnetization with respect to an applied magnetic field and which is calculated after a measurement on a Bartington Instruments MS3 susceptibility meter for the particles obtained in the described procedure and which have not been exposed to any reactant atmosphere, it turned out to be 8.9.
    [0242]
    [0243] The Km value for the particles exposed to an oxidizing atmosphere (after 3 redox N2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was 6.9.
    [0244] The Km value for particles exposed to a reducing atmosphere (after 3 H2-air redox cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was found to be 4.3.
    [0245]
    [0246] In particular, under oxidation conditions, after performing 3 redox cycles in reduction TGA with N2 and oxidation in air at 950 ° C (thermodynamic conditions that allow spinel oxidation) only 24.8% of the spinel phase It is capable of oxidizing itself to oxidize to form bixbyite, the rest behaving in an inert manner (75.2%), which allows the material to continue to possess magnetism at room temperature, with a value of Km = 6.9.
    [0247]
    [0248] And in conditions of reduction, after performing 3 redox cycles in TGA reduction with H2 and oxidation in air at 950 ° C (thermodynamic conditions that allow the spinel to be reduced) only 58.6% of the spinel phase is capable If reduced to the Mangano-Wüstita phase, the rest behaving in an inert manner (41.4%), which allows the material to continue to have magnetism at room temperature, with a value of Km = 4.3.
    [0249]
    [0250] Example 6: magnetically stable support of formula (Mno, 5 Fe0, 5 Tio, or 3 ) 3 O4, i 5 . The powdered metal oxides in mass ratio of Mn3O4 (Strem Chemical Inc.), Fe2O3 (Panreac Prs.) And TiO2 (Panreac Prs.) 48.0: 49.5: 2.5 are first mixed in a planetary mill. Briquettes are obtained in the form of a pressure tablet in a hydraulic press. The mixture is calcined at 1350 ° C in air for 6 h and the briquettes are ground to size 10 p, m.
    [0251]
    [0252] These particles are characterized physically and chemically, as shown in Table 1. The particles obtained are characterized by X-ray diffraction to know the crystalline phases that compose them. Also, a measure of relative permeability is performed to assess its initial magnetism. Subsequently, the particles are exposed to several redox cycles in thermogravimetric analysis (TGA) to obtain the reactivity of the material prepared against O 2 (thermodynamic conditions that allow spinel oxidation) and H2 (as a gas with high reducing power). Finally, the measurement of the relative permeability of the particles subjected to different reactant atmospheres is performed on the one hand to a oxidizing atmosphere of N2-air, and on the other hand to a reducing atmosphere of H2-air, to evaluate the magnetism in the materials after being exposed to these atmospheres.
    [0253]
    [0254] The spinel phase was composed of the following crystalline phases with general formula (MnxFe1-x) O4: Mn2FeO4 and Mn3Fe3O8.
    [0255]
    [0256] During its heat treatment, the spinel phase does not oxidize, allowing the material to continue to possess magnetism at room temperature.
    [0257]
    [0258] The relative permeability value (Km), which is the proportion of the internal magnetization with respect to an applied magnetic field and which is calculated after a measurement on a Bartington Instruments MS3 susceptibility meter for the particles obtained in the described procedure and which have not been exposed to any reactant atmosphere, it turned out to be 9.3.
    [0259]
    [0260] The Km value for particles exposed to an oxidizing atmosphere (after 3 redox N2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was 7.7.
    [0261]
    [0262] The Km value for particles exposed to a reducing atmosphere (after 3 redox H2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was found to be 4.9.
    [0263]
    [0264] In particular, under oxidation conditions, after performing 3 redox cycles in reduction TGA with N2 and oxidation in air at 950 ° C (thermodynamic conditions that allow spinel oxidation) only 19.4% of the spinel phase It is capable of oxidizing to form bixbyite, the rest behaving in an inert manner (80.6%), which allows the material to continue to possess magnetism at room temperature, with a value of Km = 7.7.
    [0265]
    [0266] And in conditions of reduction, after the completion of 3 redox cycles in reduction TGA with H2 and oxidation in air at 950 ° C (thermodynamic conditions that allow the spinel to be reduced) only 52.4% of the spinel phase is capable if reduced to the mangano-wüstita phase, the rest behaving in an inert manner (47.6%), which allows the material to continue to possess magnetism at room temperature, with a value of Km = 4.9.
    [0267]
    [0268] Example 7: magnetically stable support of formula (Mn0, 5 Ugly, 5 Tio, or 5 ) 3 O4, 3 . The powdered metal oxides in mass ratio of Mn3O4 (Strem Chemical Inc.), Fe2O3 (Panreac Prs.) And TiO2 (Panreac Prs.) 48.0: 49.5: 5.0 are first mixed in a planetary mill. Briquettes are obtained in the form of a pressure tablet in a hydraulic press. The mixture is calcined at 1350 ° C in air for 6 h and the briquettes are ground to size 10 p, m.
    [0269]
    [0270] These particles are characterized physically and chemically, as shown in Table 1. The particles obtained are characterized by X-ray diffraction to know the crystalline phases that compose them. Also, a measure of relative permeability is performed to assess its initial magnetism. Subsequently, the particles are exposed to several redox cycles in thermogravimetric analysis (TGA) to obtain the reactivity of the material prepared against O2 (thermodynamic conditions that allow spinel oxidation) and H2 (as a gas with high power reducer). Finally, the measurement of the relative permeability of the particles subjected to different reactant atmospheres is carried out on the one hand to an oxidizing atmosphere of N2-air, and on the other hand to a reducing atmosphere of H2-air, to evaluate the magnetism in the materials after being exposed to these atmospheres.
    [0271]
    [0272] The spinel phase was composed of the following crystalline phases with general formula (MnxFe1-x) O4: Mn2FeO4 and Mn3Fe3O8.
    [0273]
    [0274] During its heat treatment, the spinel phase does not oxidize, allowing the material to continue to possess magnetism at room temperature.
    [0275]
    [0276] The relative permeability value (Km), which is the proportion of the internal magnetization with respect to an applied magnetic field and which is calculated after a measurement on a Bartington Instruments MS3 susceptibility meter for the particles obtained in the described procedure and which have not been exposed to any reactant atmosphere, it turned out to be 9.1.
    [0277]
    [0278] The Km value for particles exposed to an oxidizing atmosphere (after 3 N2-air redox cycles), calculated after measurement on a Bartington MS3 susceptibility meter Instruments, turned out to be 7.1.
    [0279]
    [0280] The Km value for particles exposed to a reducing atmosphere (after 3 redox H2-air cycles), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was found to be 4.9.
    [0281]
    [0282] In particular, under oxidation conditions, after carrying out 3 redox cycles in reduction TGA with N2 and oxidation in air at 950 ° C (thermodynamic conditions that allow spinel oxidation) only 24.5% of the spinel phase It is able to oxidize to form bixbyite, the rest behaving inert (75.5%), which allows the material to continue to possess magnetism at room temperature, with a value of Km = 7.1.
    [0283]
    [0284] And in conditions of reduction, after performing 3 redox cycles in reduction TGA with H2 and oxidation in air at 950 ° C (thermodynamic conditions that allow the spinel to be reduced) only 51.3% of the spinel phase is capable If reduced to the Mangano-Wüstita phase, the rest behaving in an inert manner (48.7%), which allows the material to continue to have magnetism at room temperature, with a value of Km = 4.9.
    [0285]
    [0286] Example 8. Obtaining the magnetically stable system of formula (Mno, 5Feo, 5Tio, oi) 3O4.09 / CuO
    [0287]
    [0288] Exemplary embodiment of joining the support with an active phase (FA) by granulation to prepare a copper-based oxygen transporter for a combustion process with oxygen transporters.
    [0289]
    [0290] 1000 g of oxygen transporter were prepared, for this the following steps were carried out:
    [0291]
    [0292] First, 300 g CuO (Panreac with particle size less than 10 pm) and 700 g of (Mn0.5Fe0.5Ti0.01) 3O409 (according to embodiment example number 1, with particle size less than 10 are mixed) pm) in mill with 190 steel balls for 10 min.
    [0293]
    [0294] Next, a suspension is prepared with 300 g of water, 12 g of PEO (polyethylene oxide), 3.4 g of Targon®, 11.7 g of Darvan®, 9.6 g of Dolapix® and added to Mix the (Mn0.5Fe0.5Ti0.01) 3O409 prepared in step 1.
    [0295]
    [0296] The prepared suspension is subjected to a fluidized bed granulation step at 80 ° C. The particles obtained in the granulation are screened with a sieve from 100 to 300 pm. The particles collected with the appropriate size between 100 and 300 pm are calcined at 1000 ° C for a time of 2 h in an air flask, with a heating ramp of 10 ° C / min to reach said temperature.
    [0297]
    [0298] Example 9. Use of the system (Mn0.5Fe0.5Ti0.01) 3O409 / CuO in a combustion process with oxygen transporters (CLC).
    [0299]
    [0300] On the support material formulated as (Mn05Fe05Ti001) 3O4.09 an active FA phase consisting of CuO with a ratio of 30% by weight with respect to the total mass has been supported. After the preparation of a material as an oxygen transporter for a CLC process (see Example 8: preparation of an oxygen transporter (FA support) by granulation), a physical-chemical characterization of it is carried out to evaluate the inerticity of the gas support reaction in a CLC process, the behavior (reactivity) of the oxygen transporter in a CLC process and its magnetism.
    [0301]
    [0302] The crystalline structure of the magnetically stable system was characterized by X-ray diffraction to know the crystalline phases that make up said system. First, a measure of relative permeability was performed with the particles not subjected to any reactive process to assess their initial magnetism. Subsequently, the particles are exposed to several redox cycles in thermogravimetric analysis (TGA) to obtain the reactivity of the oxygen transporters to the redox reactions of the CLC process using air and H2. In addition, the inerticity of the support to said reactions was evaluated.
    [0303]
    [0304] The oxygen transporter was composed of the following crystalline phases: CuO, Mn2FeO4 and Mn3Fe3O8. The CuO being the active phase FA and the modified spinel-like phases, (MnxFe1.x) 3O4, the constituents of the support. It must be said that they are the same as those initially described in the support without FA binding (see Table 1).
    [0305]
    [0306] As for the characterization in TGA, the behavior of the oxygen transporter in conjunction with the support during its reaction in a CLC process has been evaluated, by determining its reactivity by reaction with different gases. It is determined that in an oxidizing atmosphere the oxygen transfer rate per kg of oxygen transporter is 1,910 "3 kg O2 / s kg. This value is higher than that measured for support without FA (see Table 1: 1.2 10" 5 kg O2 / s kg). Likewise, an oxygen transfer rate of the oxygen transporter of 4.2 10 "3 kg O2 / s kg was measured in a reducing atmosphere, much higher than that measured for the support material without FA (see Table 1: 1.010" 3 kg O2 / s kg).
    [0307]
    [0308] The normalized speed value calculated for this oxygen transporter against H2 and O2 was 25.1% / min and 11.1% / min respectively. These values are similar to those calculated with other oxygen transporters already evaluated in the literature, which demonstrates the suitability of this material for use as an oxygen transporter in a CLC process.
    [0309]
    [0310] As for the characterization of the inerticity of the support made in TGA, after the realization of 3 redox cycles of reduction with N2 and oxidation in air at 950 ° C (thermodynamic conditions that allow the oxidation of the spinel phase), at a At the same reaction time of 10 minutes, similar to that used for the supports of Table 1, the support is capable of oxidizing to bixbyite phase only 10% of the total amount of support, the rest behaving inert (90%). After carrying out 3 redox cycles in TGA reduction with H2 and oxidation in air at 950 ° C (thermodynamic conditions that allow the spinel phase to be reduced), 52% of the support was able to be reduced to the mangano-wüstita phase, with the rest inert (48%). These inerticity values to the redox reactions of the CLC process allow the oxygen transporter to maintain its magnetic properties after use in the process.
    [0311]
    [0312] The value of the relative permeability (Km) for the particles obtained from the system without reaction, calculated after the measurement on an MS3 susceptibility meter from Bartington Instruments, was found to be 7.3. The Km value for oxygen transporter particles exposed to an oxidizing atmosphere (after 3 redox cycles in TGA), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was found to be 6.5. The Km value for particles exposed to a reducing atmosphere (after 3 redox cycles in TGA), calculated after measurement on a Bartington Instruments MS3 susceptibility meter, was 4.5.
    [0313]
    [0314] These relative permeability values (Km) obtained demonstrate that the oxygen transporter maintains magnetic properties both in oxidizing and reducing atmospheres, and therefore allows its magnetic separation of a mixture of solids.
    [0315]
    [0316] Example 10. Comparative example with the closest examples of the prior art.
    [0317]
    [0318] Comparative example: The closest examples of the prior art of similar compounds designed for use as oxygen transporters have been synthesized. These are: Mn28FeTi7, Mn55FeTi7, Mn66FeTi7, which corresponds to chemical formulas (Mn0 „, 2n <8, Fe 0„, 7.2T in 0, n0v7) * 3 „O 4.45, (v M ^ 0.5„ 5 F e 0.4, 5 JL 0.077L * 3 OR 4.45 yy (vMn „0.66 Fe„ 0 „, 3„ 4Tin 0, n0.4) * „3O, 4 ^ respectively.
    [0319] The most similar materials found in the literature with magnetic properties are those shown in Table 2.
    [0320] A characterization of the materials has been carried out by X-ray diffraction, relative permeability measurements and chemical reactivity measurements after several redox cycles in a thermogravimetric analysis unit (TGA), analogously to what has been done previously. All data obtained after characterization are presented in Table 2.
    [0321]
    [0322] These materials are less inert for use as a support and less magnetic than those prepared in this patent.
    [0323]
    [0324] More specifically, the material (Mn0.28Fe0.72Ti0.07) 3O4.45 is formed the spinel phase by the following crystalline phases Mn2FeO4, and Mn103Fe197O4 The relative permeability value (Km), for particles that have not been exposed to no reactant atmosphere turned out to be 5.8. Under oxidation conditions, after performing 3 redox cycles in TGA air-N2, 85.0% behaves inertly, which allows the material to present magnetism at room temperature, with a value of Km = 5.1 .
    [0325]
    [0326] And in conditions of reduction, after the realization of 3 redox cycles in TGA of reduction H2-air, it behaves inertly by 50%, which allows the material to present magnetism at room temperature, with a value of Km = 3, Four.
    [0327]
    [0328] Likewise, the material (Mn0.55Fe0.45Ti0.07) 3O4.45 is formed the spinel phase by the following crystalline phases Mn2FeO4, and Mn3Fe3O8 The value of the relative permeability (Km), for particles that have not been exposed to no reactant atmosphere turned out to be 8.3. Under oxidation conditions, after performing 3 redox cycles in TGA air-N2, 65.0% behaves inertly, which allows the material to present magnetism at room temperature, with a value of Km = 5.7 .
    [0329] And in conditions of reduction, after the realization of 3 redox cycles in TGA of reduction H2-air, it behaves inertly by 23%, which allows the material to present magnetism at room temperature, with a value of Km = 1, 9.
    [0330]
    [0331] Finally, the material (Mn066Fe034Ti007) 3O4,45 is formed the spinel phase by the following crystalline phases Mn2FeO4, and Mn158Fe142O4 The relative permeability value (Km), for particles that have not been exposed to any reactant atmosphere, turned out to be of 7.8. Under oxidation conditions, after performing 3 redox cycles in TGA air-N2, 68.0% behaves inertly, which allows that the material present magnetism at room temperature, with a value of Km = 5.6.
    [0332] And in conditions of reduction, after the realization of 3 redox cycles in TGA of reduction H2-air, it behaves inertly by 20%, which allows the material to present magnetism at room temperature, with a value of Km = 1, 8.
    [0333]

    权利要求:
    Claims (16)
    [1]
    1. A magnetically stable support at a temperature lower than its Curie temperature, characterized by the general formula (MnxFe1_xMy) 3O4 + 5
    where M is selected from Ti, Mg, Ca or Si;
    x has a value between 0.1 and 0.75; and
    and has a value between 0.01 and 0.06; Y
    5 has a value between 0.03 and 0.36
    and where said support at least has a spinel-like crystalline structure.
    [2]
    2. The support according to claim 1, wherein x has a value between 0.33 and 0.66.
    [3]
    3. The support according to any of claims 1 or 2, wherein and has a value between 0.01 and 0.04.
    [4]
    4. The support according to any of claims 1 to 3, wherein M is Ti.
    [5]
    5. The support according to claim 4, wherein x = 0.5 and y = 0.01.
    [6]
    6. The support according to claim 1, wherein M is Ti, where x is 0.5, and is 0.01 and 5 is 0.09, with final formula (Mn0.5Fe0.5Ti0.01) 3O409
    [7]
    7. A magnetically stable system characterized by the general formula (MnxFe1_xMy) 3O4 + 5 / FA where (MnxFe1_xMy) 3O4 + 5 is the support according to any one of claims 1 to 6 and is in a weight percentage of between 40% and 85% with respect to the final system; Y
    • where the active phase FA is an active phase in the form of particles selected from
    ■ a Ca oxide, Li oxide, Mg oxide, or
    ■ at least one Cu oxide, at least one Mn oxide, at least one Fe oxide, at least one Co oxide or at least one Ni oxide,
    or where said particles have a size between 1 pm and 20 pm,
    or where said active phase FA is supported on a support; Y or where said active phase FA is in a weight percentage of between 15% and 60% with respect to the final system.
    [8]
    8. The system according to claim 7, characterized in that the active phase FA is Ca oxide.
    [9]
    9. The system according to claim 7, characterized in that the active phase FA comprises at least one Cu oxide.
    [10]
    10. A method of obtaining the support according to claims 1 to 6, characterized in that it comprises the following steps:
    a) mix the stoichiometric amounts of Mn3O4 and Fe2O3 with respect to the final support weight;
    b) adding at least one compound selected from a titanium oxide precursor, a magnesium oxide precursor, a calcium oxide precursor, a silicon oxide precursor, a silicon oxide precursor onto the mixture obtained in step (a) titanium, magnesium oxide or silicon oxide, in a weight percentage of between 1% and 6% with respect to the final support weight;
    c) thermally treating the product obtained in step (b) at a temperature between 1300 ° C and 1400 ° C for a period of time between 2 hours and 10 hours; Y
    d) grind the calcined product obtained in step (c) to obtain a particle size between 2 pm and 10 pm.
    [11]
    11. The method of obtaining the magnetically stable system according to claims 7 to 9, characterized in that it comprises steps (a) to (d) of the method described in claim 10 and the following steps:
    e) mixing and agglomerating the product obtained in step (d) with an active phase FA;
    f) grind the product obtained in step (e) and / or select the particles of size between 100 pm and 300 pm.
    [12]
    12. Use of the support according to any of claims 1 to 6, as a support for an active phase.
    [13]
    13. Use of the system according to any of claims 7 or 8 as a carbon dioxide transporter.
    [14]
    14. Use of the system according to claim 13 in reactions with CO2 capture by carbonation / calcination cycles.
    [15]
    15. Use of the system according to any of claims 7 or 9 as an oxygen transporter.
    [16]
    16. Use of the system according to claim 15 in combustion reactions with oxygen transporters or in combustion reactions with solid oxygen transporters with generation of gaseous oxygen.
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    同族专利:
    公开号 | 公开日
    WO2019170944A1|2019-09-12|
    ES2724726B2|2020-03-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2018043177A|2016-09-13|2018-03-22|田中貴金属工業株式会社|Catalyst composition for exhaust purification and catalyst for exhaust purification|
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    ES201830222A|ES2724726B2|2018-03-07|2018-03-07|MAGNETIC SUPPORT AND SYSTEM AS O2 AND CO2 CONVEYORS|ES201830222A| ES2724726B2|2018-03-07|2018-03-07|MAGNETIC SUPPORT AND SYSTEM AS O2 AND CO2 CONVEYORS|
    PCT/ES2019/070122| WO2019170944A1|2018-03-07|2019-02-28|Magnetic system and support as o2 and co2 transporters|
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