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    • 专利摘要:
    method for producing conductive mayenite powder and compound, method for producing a supported metallic catalyst, and method for synthesizing ammonia. A conductive Mayenite compound is expected to be applied to cool electron emitters, conductors, organic electron injection electrodes, thermoelectric conversion materials, thermoelectric power generation materials, suitable reducing agents, and oxidizing agents, catalysts and others. if a conductive Mayenite compound having a large specific surface area is obtained, the utility thereof in the respective applications will be remarkably increased. a powder of the conductive mayenite compound having a conduction electron density of 1015 cm-3 or more and a specific surface area of 5 m2g-1 or more will be produced by: (1) a step of forming a precursor powder subject to a mixture of a powder of the starting material and water to a hydrothermal treatment; (2) a step of forming a powder of the mayenite compound by heating and dehydrating the precursor powder; (3) a step of forming a powder of the activated mayenite compound by heating the powder of the compound in an inert gas atmosphere or in a vacuum; (4) a step for injecting electrons into the mayenite compound through a reduction treatment by mixing the powder of the activated mayenite compound with a reducing agent.
    公开号:BR112015003948A2
    申请号:R112015003948-0
    申请日:2013-08-20
    公开日:2021-08-03
    发明作者:Hideo Hosono；Michikazu Hara；Yasunori Inoue；Masaaki Kitano；Fumataka Hayashi；Toshiharu Yokoyama；Satoru Matsuishi；Yoshitake Toda
    申请人:Tokyo Institute Of Technology；Japan Science And Technology Agency；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention reports a method for producing a conductive mayenite composite powder that is suitable as electronic materials having electrical conduction properties, catalyst materials, etc. and having a large specific surface area. background
    [0002] [0002] Among the calcium aluminosilicates containing Dog, A1203 and SiO2 as components, there are substances whose mineral name is called mayenite (yenite). Compounds having the same type of crystal structure as mayenite are referred to as "mayenite compounds". Mayenite compounds have a . typical composition represented by 12CaO 7 A12 O3 (hereafter represented by “C12A7”). It has been reported that a C12A7 crystal has a specific structure in which two oxygen ions out of the 66 oxygen ions in a unit cell including two molecules are clathrated as "free oxygen" in a space of a framework formed by the crystal's skeleton ( NPL1).
    [0003] [0003] Since 2003, the inventors of the present invention have shown that the free oxygen ions include in mayenite compounds can be replaced with various types of anions. In particular, by maintaining C12A7 in a strong reducing atmosphere, all free oxygen ions can be replaced as electrons. C12A7 whose free oxygen ions are replaced with electrons may be represented by a chemical formula of [Ca24A128O64]4+(e-)4 (hereafter represented by “C12A7:e- . Substances in which anions are replaced with electrons in this manner are referred to as "electrodes", and electrodes have a characteristic of exhibiting good electron conductivity (NPL 2)
    [0004] [0004] The inventors of the present invention have found that C12A7:e- including conducting electrons at a concentration of 1 x 1019 cm-3 or more and a compound having the same kind of crystal structure as C12A7 are obtained by (A) a method which includes maintaining a single crystal isostatically pressed compact or a fine powder of C12A7 in an alkali metal vapor or an alkaline soil metal in a range of 600°C to 800°C. (B) a method that includes performing ion implantation of an inert ion into a C12A7 thin film, or (C) a method that includes casting an isostatically pressed compact of a C12A7 fine powder in a reducing atmosphere, and directly solidifying the fusion. (LPT 1).
    [0005] [0005] The inventors of the present invention have applied for patents for inventions relating to a method in which a raw material substance of a good conductive mayenite compound is melted, and the resulting melt is maintained in an atmosphere with a partial pressure of low oxygen and then subjected to cooling solidification (LPT2); and a method in which a reducing agent such as carbon, A1, or Ti being added to a powder obtained by spraying a sintered product prepared by maintaining a raw material powder at a high temperature to sinter the raw material powder in a reaction. solid phase, a pressed body molded from the powder, or a synthesized body obtained by sintering the molded body in the range of
    [0006] [0006] Invention patents reporting the following methods for producing a conductive mayenite compound have been applied for. Examples of the methods include a method in which a composite oxide film represented by 12Ca1-xSrxO7A12O3 (x = 0 to 1), the composite oxide film being obtained by cooking a raw material from a non-aqueous solution by heating in the range of 500°C to 1,500o C, being heated in the range of 700ºC to 1,500ºC to carry out a reduction treatment (LPT 6); a method in which a raw material is heated in an inert atmosphere or in a vacuum atmosphere in the range of 1200°C to 1415°C(LPT 7); a method in which a mixture of a raw material and a reducing agent with metallic A1 or metallic Ca is sintered in the range of 1200°C to 1.415°C or cast in the range of
    [0007] [0007] With respect to C12A7:e-, which has a metallic electrical conduction property, a C12A7:e- powder can be directly synthesized by mixing CaCO3 with A12O3 with A12O3 in a radius of 11:7, heating the mixture at 1300o C, heating the resulting product in a metallic atmospheric vapor Ca (NPL 3). Conductive mayenite compounds are used in electron emitters, field emission display devices, cold cathode fluorescent tubes, flat lighting devices, electron emitting materials (LPT 10), electrodes for discharge lamps (LPT 11), and the like.
    [0008] [0008] Furthermore, a patent for an invention relating to a mayenite compound in which some A1 atoms in C12A7, which is a conductive mayenite compound, are substituted with Ga or In atoms has been applied for. This mayenite compound is suitable for electrode materials that require a high temperature heat treatment, eg a plasma display panel (PDP) with protective film material, a charge injection material in an organic electroluminescent (EL) device, and the like (LPT 12).
    [0009] [0009] The inventors of the present invention have applied for patents for inventions relating to a catalyst of an ammonia synthesis reaction, the catalyst including a conductive mayenite compound and a metal such as Ru or Fe supported on the conductive mayenite compound (LPT 13) and a method of reducing carbon dioxide to carbon monoxide, by the use of a conductive mayenite compound (LPT 14). Furthermore, even C12A7 that does not have electrical conductivity has applications as a catalyst or a catalyst support. For example, it is known that a catalyst obtained by spray drying a complex solution of a raw material and subsequently calcining the resulting product in the range of 1300°C to 1400°C for two hours or more is used as a catalyst for a fractionation reaction. steam for the production of a mild olefin (LPT 15). Recently, methods for producing a support having a specifically large surface area, methods including the steps of synthesizing a precursor by a hydrothermal method or a sol gel method and subsequently heating the precursor, have been proposed (NPL 4 and NPL 5).
    [00010] [00010] It has been reported that when C12A7 is not left to default in a moisture containing atmosphere, hydroxide ions (OH-) are clathrates in a structure and are not easily removed even at high temperatures (NPL 6).
    [00011] [00011] Citation List Patent Literature LPT 1: WO2005/000741 LPT 2: WO2005/077859 LPT 3: WO2006/129675 LPT 4: WO2006/129674
    [00012] [00012] No Patent Literature NPL 1 : Von Hans Bartl und Thomas Scheller, “N. Jahbuck F. Mineralogie. Monatshefte", 35, 547-552, (1970) NPL 2: S. Matsuishi, Y. Toda, M. Miyakawa, K. Hayashi, T. Kamiya, M. Hirano, I. Tanaka, and Hosono, "Science", 301, 626-629 (2003) NPL 3: S. Matsuishi, T. Nomura, M. Hirano, K. Kodama, S. Shamoto and H. Hosono, "Chemistry of Materials", 21, 2589-2591 (2009) NPL 4: L. Gong, Z. Lin, S. Ning, J. Sun. J. Shen, Y. Torimoto, and O, Li, "Material Letters", 64, 1322-1324 (2010) NPL 5: C. Li , D. Hirabayashi and K. Suzuki, “Materials Research Bulletin”, 46, 1307-1310, (2011) NPL 6: K. Hayashi, M. Hirano and H. Hosono, “J. Phys. Chem. B", 109, 11900-11906, (2005)
    [00013] [00013] Conductive mayenite compounds are expected to be applied to cool electron emitters, conductors, organic EL electron injection electrodes, thermoelectric converting materials, reducing agents, oxidizing agents, catalysts and others.
    [00014] [00014] In known methods for the production of a conductive mayenite compound containing 1015 cm-3 or more of conducting electrons, a synthesis step at a high temperature is necessary, for example, as in a method in which the raw material is mixed with a reducing agent is heated to a high temperature of 1,200°C or more, and subjected to a reduction treatment at the same time (LPT 8) in a method in which a reduction treatment is carried out for a mayenite compound synthesized by heating to a high temperature of 1200°C or more (LPT 8).
    [00015] [00015] Accordingly, even when a raw material having a large specific surface area is used, particle sintering occurs in the steps of production and crystallization of a mayenite compound, and consequently particles having a small surface area or a block is formed. Therefore, a mayenite compound having a specific large area of at least approximately 2 m2g-1 is merely obtainable. Accordingly, a mayenite compound having a large specific surface area and containing 1015 cm-3 or more of conducting electrons and means for producing said mayenite compound are not known to date. If a mayenite compound having a specific surface area of 5 m2g-1 or more is obtained, it is believed that the usefulness of the conductive mayenite compound in the above applications will markedly increase.
    [00016] [00016] As a result of intensive studies conducted in order to achieve the above objective, the inventors of the present invention found a method for producing a conductive mayenite compound having a large specific surface area, and resulted in the complementation of the invention.
    [00017] [00017] Specifically, in existing methods, it will be necessary for a mayenite compound to be subjected to an electron injection operation by a reduction treatment at a high temperature of 1200°C or more. Accordingly, even when a raw material powder having a large specific surface area is used, a powder having a large specific surface area will not be obtained since the raw material powder is sintered by high temperature treatment. However, the inventors of the present invention have found ways to carry out an electron injection operation at a low temperature of 1100°C or less by producing a conductive mayenite composite powder having a specific surface area of 5 m2g-1 or more.
    [00018] [00018] The present invention provides a method for producing a conductive mayenite compound powder having a conduction electron concentration of 1015 cm-3 or more and a specific surface area of 5 m2g-1 or more, the method including the at least (1) a step of forming a powder precursor of a mayenite compound subjected to a mixture of a powder of raw material of the mayenite compound and water to a hydrothermal treatment, (2) a step of forming a powder of the compound mayenite by dehydrating the precursor powder by heating, (3) a step of forming a mayenite compound powder activated by heating the mayenite compound powder in an inert gas atmosphere or in a vacuum at a temperature in the range of 400°C to 1000°C for three hours or more, and (4) a step of injecting electrons into the mayenite compound by mixing the activated mayenite compound powder with a reducing agent and heating the resulting mixture at a temperature in the range of 400°C to 1,100°C to conduct a treatmentof reaction.
    [00019] [00019] In addition, the present invention provides the method for producing a powder of the conductive mayenite compound, the method further including, after steps (4), (5), a step of repeating the rapid thermal annealing process (process RTA) including temperature rise to a range of 900°C to 1,100°C.
    [00020] [00020] In the method of the present invention, the mayenite compound is typically 12 7A12O3. The reducing agent is preferably Ca or CaH2.
    [00021] [00021] The reasons why a conductive mayenite compound powder having a specific surface area of 5 m2g-1 or more can be obtained are the following two points. Firstly, by using a hydrothermal synthesis method, raw material of the mayenite compound, eg a Ca source and an A1 source in the case of C12A7, are uniformly and satisfactorily mixed, and a hydrated oxide functioning as a crystal precursor can be produced at a low temperature. By dehydrating the precursor by heating, a mayenite compound can be obtained at a lower temperature than that in solid-phase synthesis. As a result, the mayenite compound is obtained in the form of fine particles in the sub-micron order and thus having a large specific surface area. However, in a method similar to an existing method, even when a reducing agent having a high reducing performance is used, the reducing agent does not work and it will be difficult to inject a powder of the mayenite compound having said large specific surface area to the an evacuation treatment in the range of 800°C to 1000°C, adsorbed water, a surface hydroxy group, OH_ in the frame, which can be easily removed. Thus, the reducing agent can be used without deactivation. Furthermore, with the use of CaH2, which has a high reduction performance, a conductive mayenite compound powder can be obtained by conducting the reduction treatment at a low temperature (700°C to 800°C).
    [00022] [00022] Second, in the case where a rapid thermal annealing process "RTA process", is used in further reduction of a powder surface, a part of which is insulated after the reduction treatment, the temperature may be increased to high speed and then the reduction treatment can be completed before sintering and particle aggregation occurs. Accordingly, even when the reduction by heating is carried out at a relatively high temperature (900°C to
    [00023] [00023] In addition, the present invention provides a method for producing a supported metallic catalyst, the method including, by the use of an impregnation method, a physical mixing method, a thermal decomposition method, a liquid phase method, a precipitation method, or a vapor deposition method, allowing a metallic catalyst to be supported on the powder of the conductive mayenite compound produced by the above method.
    [00024] [00024] The supported metallic component that may be used is not particularly limited, but may be any one of Li, Na, K, Rb and Cs selected from the group of elements 1A; Mg, Ca, Sr, and Ba selected from element group 2A; SC, Y, lantanides, and actinides selected from the 3A element group; Ti, Zr, and Hf selected from the 4A element group; V, Nb and Ta selected from element group 5A; Vr, Mo, and W selected from element group 6A; Mn, Tc, and Re selected from the group of elements 7A; Fe, Ru and Ir selected from the group of 9 elements; Ni, Pd and Pt selected from the group of elements 10; Cu, Ag, and Au, selected from element group 11; Zn, Cd, and Hg, selected from element group 12; B, A1, Ga, In, and T1 selected from the group of 13 elements; Si, Ge, Sn and PB selected from element group 14; As, Sb, and Bi selected from element group 15; and Se and Te selected from element group 16. These components can be used in combination.
    [00025] [00025] The catalyst of the present invention can be used in various catalytic reactions such as oxidation, hydrogenation, isomerization, disproportionation, esterification, a condensation reaction, an acid base reaction, and a polymerization reaction, but the use of the catalyst is not limited to these. Among the above metallic components, transition metallic elements, are used as homogeneous/heterogeneous catalysts in various synthesis reactions. In particular, groups 6, 8 and 9 with transition metals such as Fe, Ru, Os, Co, Rh and Mo are suitable for catalysts used in the synthesis of ammonia by using a direct reaction of hydrogen and nitrogen.
    [00026] [00026] For example, Mo, W, Re, Fe, Co, Ru, Rh and Os are known as transition metals having an ammonia synthesis activity, and the catalyst can be one obtained by modifying these components with a material of electron injection, such as an alkali metal, or an alkaline soil metal. Alternatively, a combination of the above elements, a transition metal group 8 or 6B nitrate, or a Co/Mo nitrate compound could be used as the catalyst.
    [00027] [00027] In the case where a powder of the mayenite compound or porous body is used as a support, a catalyst will be obtained by mixing a powder of the mayenite compound or porous body containing 1 x 1015 cm3 or more of conducting electrons and obtained in the step above with a transition metal compound by an impregnation method or a physical mixing method, and then heating the resulting mixture to decompose the transition metal compound to a transition metal by reduction. Alternatively, for example, a transition metal compound may be deposited on a mayenite compound powder surface or porous body by a chemical vapor deposition (CDV) method, a precipitation method, or the like, and the transition metal compound it may be thermally decomposed to deposit the transition metal.
    [00028] [00028] Examples of the transition metal compound include, but are not particularly limited to, inorganic metal compounds, and organometallic complexes that are easily thermally decomposed, such as dodecacarbonyl triruthenium [Ru3(CO)12], dichlorotetrache (triphenylphosphine) ruthenium )II) , [RuC122(PPh3)4], dichlorotris (triphenylphosphine) ruthenium (II) [RuC12(PPh3)4], tri(acetylacetonate) ruthenium (III), [Ru(acac)3], ruthenocene [Ru(C5H5), chloride of ruthenium [RuC13].pentacarbonylirone [Fe(CO)5]. Iron nonacarbonyl [Fe2(CO)9], iron iodide tetracarbonyl [Fe(CO)4I2, iron chloride [FeC13], ferrocene [Fe(C5H5)2], tri-(iron(III) acetylacetonate, [Fe (acac)3], dodecarbonyltriron [De(CO)12] [Co(acac)3]. Cobalt(II) acetylacetonate [Co(acac)2, cobaltotacarbonyl [Co2(CO)8], cobaltocene [Co(Co(C5H52) ], triosmiundodecacarbonyl (Os3(CO)12], and molybdenum hexacarbonyl [Mo(CO)6].
    [00029] [00029] The following steps may be employed as the impregnation method. For example, a carbon powder is dispersed in a solution of the transition metal compound (eg, a hexane solution of a Ru carbonyl complex) and stirred. In this case, the amount of transition metal compound is approximately 0.01% to 40% by weight, preferably approximately 0.2% to 30% by weight, and more preferably 0.05% to 20% by weight relative to a backing powder. Subsequently, the resulting dispersion is heated in a flow of inert gas such as nitrogen, argon or helium or in a vacuum at 50°C to 200°C for minutes to 5 hours to evaporate the solvent, and then the powder is dried. catalyst precursor resulting from the transition metal compound is reduced. Through the above steps, a supported metal catalyst which supports, in the backing powder, a transition metal in the form of fine particles having a particle size of several nanometers to hundreds of nanometers is obtained.
    [00030] [00030] The amount of transition metal is 0.01% to 30% by weight, preferably from 0.02% to 20% by weight, and more preferably from 0.05% to
    [00031] [00031] The supported metal catalyst may be used in the form of a molded body by using a common molding technique. Specifically, examples of the supported metal catalyst shape include a granular shape, a peripheral shape, a tablet shape, a ring shape, a noodle shape, a clover leaf shape, an arch shape, and a beehive shape. . Alternatively, a suitable base could be coated with the supported metal catalyst and used.
    [00032] [00032] The present invention further provides a method for synthesizing ammonia, the method including the use of the supported metallic catalyst produced by the above method in a synthesis reaction in which nitrogen gas (N2) and hydrogen gas (H2) are allowed to react with each other to produce ammonia gas (NH3).
    [00033] [00033] Advantages and Effects of the Invention According to the method of the present invention, a powder of the conductive meienite compound that is suitable as electronic material components such as a PDP protective film material and an electrode material that requires a high heat treatment catalyst temperature or raw material that has large specific surface area can be provided by using an existing electron injection method with a reducing agent. Description of Settings
    [00034] [00034] A production method of the present invention will now be described in detail. Crystals of a mayenite compound are formed three-dimensionally by connecting frame-shaped structures (framework) each having an internal diameter of approximately 0.4 nm while dividing wall surfaces therein. In general, anions such as O2- are included within the frames of a mayenite compound. However, these anions can be replaced with conducting electrons by providing a chemical treatment. The concentration of the conducting electron in the mayenite compound is increased by increasing the annealing time.
    [00035] [00035] In mayenite compounds, electrons that are substituted for oxide ions (O2-) included in the structure of the same function as conduction electrons. In the case of C12A7, the mayenite compound is represented by a composition formula ([Ca24A128O64]4+(O2)2-x) (where 0 < x < 2). Furthermore, the concentration of the conducting electron is made to 1 x 1015 cm3 or more by replacing oxide ions with electrons. Accordingly, mayenite compounds including conducting electrons may be referred to as "conductive mayenite compounds". In the case of C12A7:e-, a theoretical maximum concentration of the conducting electrons is 2.3 x 1021 cm-3. A mayenite compound having a conductive electron concentration equal to the theoretical value can be obtained by the method described above.
    [00036] [00036] Conductive mayenite compounds generate light absorption at 2.8 ev and
    [00037] [00037] In the present invention, the term "specific surface area" refers to a value measured on the basis of an adsorption isotherm of nitrogen molecules at a temperature of liquid nitrogen (-196o C). The specific surface areas of the synthesized conductive mayenite compounds were estimated by applying the BET formula (Brunauer, Emmett and Teller) in the range of 0.05 to 0.3 of an equilibrium pressure (P/P0; where P represents a partial pressure (Pa) of an adsorption gas that is in an equilibrium state with a sample surface at –196o C, and P0 represents a vapor pressure (Pa) of the adsorption gas of the adsorption isotherm.
    [00038] [00038] <Mayenite compound synthesis > In the method of the present invention, a mayenite compound used as a starting material of a target compound is more preferably in the form of a fine powder (primary particle size: 100 nm or less) or a bulky porous body having a porous structure. When the mayenite compound is in fine particulate form, the surface area per gram increases and the gap between particles in the mesopore range (2 nm or more and 100 nm or less. A hydroxide serving as a precursor of the mayenite compound can be obtained) by a hydrothermal treatment method.
    [00039] [00039] < Method to synthesize mayenite compound using hydrothermal treatment > The hydrothermal synthesis method has been studied for a long time as a method to synthesize fine particles of inorganic oxide having a good crystal quality. A precursor compound could be loaded by loading a solvent such as water or alcohol and a raw material into a pressure-resistant container, and heating the resulting mixture to a temperature equal to or greater than the boiling point of the solvent for several hours over several days .
    [00040] [00040] Ca3A12(OH)12 which is a hydroxide serving as a precursor of a mayenite compound C12A7, which can be prepared by mixing water, calcium hydroxide, and aluminum hydroxide in a stoichiometric composition, and heating the resulting mixture, by example at 150ºC for approximately six hours. The prepared precursor is dehydrated by heating in air in a range of approximately 400°C to 1000°C. Thus, powder of the mayenite compound C12A7 having a large specific surface area (approximately 20 to 60 m2g-1) is obtained.
    [00041] [00041] < Mayenite compound pre-treatment > Mayenite compound powder having a large specific surface area and synthesized by means of the hydro-thermal treatment method retains hydroxy groups which are strongly bonded on a surface of the powder or in case of a frame skeleton. In a step that allows conducting electrons to be included, a reducing agent is consumed by the reaction with the hydroxy groups (2CaH2) + 20H -> Dog + 3H2). Therefore, it will be necessary for the surface of the powder or the interior of the scaffolding to be activated by removing the hydroxy groups as much as possible in a pretreatment step prior to the electron injection step. The specific surface area after pretreatment is decreased with increasing pretreatment temperature. In a temperature range from 400°C to 1000°C, for example, the specific surface area will change from 60 m2g-1 to 6 m2g-1.
    [00042] [00042] With respect to the pre-treatment method, heating is preferably carried out at a temperature in the range of 400°C to 1,100°C in an inert gas atmosphere or in a vacuum. The heating temperature is preferably in the range 700°C to 1000°C and more preferably in the range 900°C. When the heating temperature is below 400°C, although a powder having a large specific surface area will be obtained, a high concentration of Electron conduction cannot be obtained, since in the reduction treatment step, a reducing agent is consumed by a hydroxy group by the powder. On the other hand, when the heating temperature exceeds 1100°C, although a high concentration of conduction electron will be obtained, a powder of the mayenite compound having a large specific surface area cannot be obtained, as the powder sintering proceeds. In order to sufficiently carry out the activation, heating will preferably be conducted for three hours or more.
    [00043] [00043] < Step of allowing the conducting electron to be included in the mayenite compound by the reduction treatment > In the case where the mayenite compound powder including conducting electrons is prepared, a mayenite compound raw material powder having an equivalent chemical composition is heated in a reducing atmosphere in the range of 400°C to 1,100°C. The heating temperature is preferably in the range 700°C to 800°C. When the heating temperature is below 400°C, a reaction between an oxygen ion and a reducing agent in a frame will not proceed sufficiently, and a high conduction electron concentration cannot be obtained. On the other hand, at a heating temperature exceeding 1100o C, although high conduction electron concentration can be obtained, the specific surface area will be decreased by sintering. The treatment time will preferably be three hours or more in order to sufficiently diffuse oxygen ions and exchange oxygen ions with conducting electrons.
    [00044] [00044] Any reducing agent may be used while the reducing agent reacts with an oxygen ion in an armature in the above heating temperature range. Examples of the reducing agent that may be used include alkali metals such as Na, and Li, alkaline soil metals such as Mg, Ca, CaH2, and hydrates thereof. Calcium hydrate (CaH2) becomes Dog after reduction and remains an impurity, so the effective surface area of the conductive mayenite compound may be decreased. The higher the treatment temperature during the conduction electrons permitting step to be included, the smaller specific surface area of the mayenite compound powder subject to the step is formed. For example, in the case where a powder sample of the mayenite compound is prepared by conducting a pre-treatment at 800°C, and a sample reduction treatment being carried out in a temperature range of 600°C to 800°C, the specific surface area of the sample being changed, for example, from approximately 30 m2g-1 to 20m2g-1.
    [00045] [00045] < RTA Process > A part of a surface of the mayenite compound powder that has reacted with the reducing agent may be insulated as a result of being covered, for example, with calcium oxide. An RTA process can be used as a process for reducing the surface of the powder that has been insulated. The RTA process is an abbreviation for a rapid thermal annealing process and is known as a method to improve the crystal qualities of semiconductors. In an existing method for heating the surface of a powder, the rate of temperature rise is as low as approximately 5 to 10°C min-1, and the surface area decreases due to sintering of particles that cannot be prevented. In contrast, by using the RTA process, the crystal quality of the surface of an electrode can be improved without decreasing the surface area, and an electrical conduction property can be provided to the powder of the mayenite compound including its surface. In the case where crystallization is carried out by the RTA process, in an inert atmosphere, in a reducing atmosphere, or in a vacuum, the temperature is increased at a temperature increase rate of 30 to 60°C min-1, and the temperature being maintained as a heating temperature at 900°C to 1100°C for 5 to 15 minutes. The step of raising the temperature and the step of keeping the temperature under heating are repeated two to five times. The holding temperature is preferably in the range of 950°C to 1100°C.
    [00046] [00046] < Process for producing catalyst including conductive mayenite compound as support > A catalyst may be produced using an impregnation method, a physical mixing method, a thermal decomposition method, a liquid phase method, a precipitation method , or a method of vapor deposition, by allowing a metal catalyst such as Ru to be supported on the powder of the conductive mayenite compound produced by the method described above. In the physical mixing method, a powder of the conductive mayenite compound and a transition metal compound are mixed into a solid phase by a physical mixing method, and the transition metal compound is then reduced by heating the resulting mixture in a reducing atmosphere. as an atmosphere of hydrogen at a temperature in the range of 50°C to 600°C. Thus, a supported metallic catalyst is obtained. From the standpoint of suppressing the sintering of the supported metallic particles, prior to reduction by heating, increasing the temperature and retaining a temperature is preferably repeated several times in a vacuum.
    [00047] [00047] The impregnation method includes a step of dispersing the powder of the conductive mayenite compound in a solvent solution of the transition metal compound, a step of forming catalyst precursor compound of the transition metal compound which is dried by evaporation of a solvent from the solvent solution, and a metal catalyst formation step by reducing the transition metal compound by heating in a reducing atmosphere.
    [00048] [00048] The support powder supporting a transition metal clathrates electrons to the same degree as in the initial state, after the support step, and having a small working function in terms of support. Accordingly, support powder has a high ability to donate electrons to a transition metal. In addition, since the support has a large specific surface area, the support powder significantly accelerates the activation of nitrogen and hydrogen into a transition metal. As a result, the backing powder functions as an ammonia synthesis catalyst with a high performance when compared to the case where a conductive mayenite powder having a small specific area is used. By the use of a transition metal catalyst supported on the conductive mayenite compound powder by the use of any of these methods, ammonia can be synthesized by nitrogen and hydrogen, which are raw materials, to react with each other in the catalyst in a reactor at a reaction temperature 100°C or more and 600°C or less and at a reaction pressure of 10 kPa to 30 MPa.
    [00049] [00049] EXAMPLE 1 < Synthesis of Mayenite Compound Powder > Calcium hydroxide (Ca(OH)2) and aluminum hydroxide (A1(OH)3) were weighed so as to satisfy Ca:A1 = 12:14, and mixed . Distilled water was weighed so that the concentration of the resulting mixed powder became 10% by weight, and a total of 160 g was stirred and mixed in a planetary ball mill for four hours. The resulting mixture solution was charged into a sealed pressure-resistant container, and a heat treatment (hydro-thermal treatment) was carried out at 150ºC for six hours while agitated. The resulting precipitate was filtered off, dried, and then pulverized. Thus, approximately 20 g of a powder precursor of a mayenite compound Ca3A12(HO)12 was obtained. This precursor powder was dehydrated by heating in air at 600°C for five hours to prepare a powder of the mayenite compound as a raw material with a large specific surface area. This raw material had a specific surface area of 60 m2g-1.
    [00050] [00050] <Pre-treatment > As a pre-treatment, the powder was put into a silica glass tube, heated in a vacuum of 1 x 10-4 Pa at 900°C for five hours under evacuation, and taken out of the glass tube. The powder obtained at this stage had a specific surface area of 30 m2g-1.
    [00051] [00051] < Electron injection by reduction treatment > Subsequently, 0.4 g of CaH2 serving as a reducing agent was added relative to 3 g of the powder after pretreatment, and sufficiently mixed to prepare a mixture. A tantalum tube (Ta) was filled with the mixture. The tantalum tube (Ta) filled with the mixture was placed in a silica glass tube, and heated in a vacuum of 1 x 10-4 Pa at 700ºC for 15 hours. A conductive mayenite compound powder having a conduction electron concentration of 1.0 x 1021 cm-3 and a specific surface area of 17 m2g-1 was obtained.
    [00052] [00052] [COMPARATIVE EXAMPLE 1] < Mayenite Compound Powder Synthesis > A CaCO3 powder and an A12O3 powder were mixed so that a radius of Ca to A1 became 11:14. A total of 30 g was heated in an alumina crucible to
    [00053] [00053] < Electron injection by reduction treatment > Subsequently, 3 g of the powder prepared by the above-described synthesis method was inserted into a silica glass tube together with 0.18 g of a metallic C powder, and heated at 700°C for 15 hours , and thus generating a metallic Ca vapor atmosphere in the tube to allow metallic Ca in a vacuum state with the powder. The sample sealed in the tube in a vacuum state was taken out and crushed in a pestle. Subsequently, a silica glass tube is filled with the reground sample, and sealed under evacuation. The silica glass tube was heated at 1100ºC for two hours. Thus, a powder of the conductive mayenite compound C12A7:e- (denoted by C12A7e21) having a conduction electron concentration of 2 x 1021 cm-3 and a specific surface area of 1 m2g-1 was obtained.
    [00054] [00054] EXAMPLE 2 A powder of the mayenite compound having a large specific surface area was synthesized under the same conditions as in Example 1 except that the pretreatment was conducted at 800°C instead of the temperature of the raw material pretreatment. 900°C in Example 1. The powder obtained at this stage had a specific surface area of 40 m2 g-
    [00055] [00055] < Electron injection by reduction treatment > A powder of the mayenite compound was synthesized under the same conditions as in Example 1 except that the pretreatment was conducted at 600°C instead of the raw material pretreatment temperature of 700°C in Example 1. The concentration of the conducting electron was 1.0 x 1021 cm-3 and the specific surface area being 31 m2g-1.
    [00056] [00056] EXAMPLE 3 < Electron injection by reduction treatment > A powder of the mayenite compound was synthesized under the same conditions as in Example 1 except that the pretreatment was conducted at 600°C instead of the temperature of the raw material pretreatment. 700°C in Example 1. The concentration of the conducting electron was 0.8 x 1021 and the specific surface area being 20 m2g-1.
    [00057] [00057] EXAMPLE 4 < Pre-treatment >
    [00058] [00058] < Electron injection by reduction treatment > A powder of the mayenite compound was synthesized by conducting a reduction treatment under the same conditions as in Example 1. The concentration of the conducting electron was 1.0 x 1021 cm-3, and the specific surface area being 23 m2g-1.
    [00059] [00059] EXAMPLE 5 < Pretreatment > A powder of the mayenite compound having a large specific surface area was synthesized under the same conditions as in Example 1 except that the pretreatment was conducted at 800°C instead of the pretreatment temperature of the 900°C raw material in Example 1. The specific surface area at this stage was 40 m2g-1.
    [00060] [00060] < Electron injection by reduction treatment > A powder of the mayenite compound having a large specific surface area was synthesized under the same conditions as in Example 1 except that the pretreatment was conducted at 800°C instead of the pretreatment temperature. 900°C raw material treatment in Example 1. The conduction electron concentration was 0.4 x 1021 cm-3 and the specific surface area was 10 m2g-1.
    [00061] [00061] [COMPARATIVE EXAMPLE 2] A powder of the mayenite compound was synthesized by the same method as in Example 1. However, the pretreatment of Example 1 was not carried out, and the electron injection by the reduction treatment was also not carried out. The conduction electron concentration was zero, and the specific surface area was 60 m2g-1.
    [00062] [00062] EXAMPLE 6 < Pretreatment > An electrode was synthesized under the same conditions as in Example 1 except that the pretreatment was conducted at 1000°C instead of the raw material pretreatment temperature of 900°C in Example 1. A powder of the conductive mayenite compound having a conductive electron concentration of 1.4 x 1021 cm-1 and a specific surface area of 6 m2g-1 was obtained.
    [00063] [00063] EXAMPLE 7 < Synthesis of the mayenite compound > The Ca3A12(OH)12 prepared in Example 1 was dehydrated by heating at 800ºC for two hours in a flow of oxygen. Thus, a powder of the mayenite compound was prepared as a raw material.
    [00064] [00064] < Pre-treatment > As a pre-treatment of this raw material, the powder was put into a silica glass tube, and heated in a vacuum of 1 x 10-4 Pa at 800°C for 20 hours under evacuation.
    [00065] [00065] < Electron injection by reduction treatment > Calcium metal (Ca) was used as a reducing agent instead of CaH2 in Example 1. For 2 g of the powder after pretreatment, 0.12 g of Ca metal serving as a reducing agent was added. The resulting mixture was placed in a silica glass tube and heated in a vacuum of 1 x 10-4 Pa at 700°C for 15 hours.
    [00066] [00066] < RTA process > Furthermore, in order to activate the powder surface, a Tammann tube was filled with the powder and vacuum sealed. Subsequently, an RTA process was conducted by repeating twice in one step of increasing the temperature at a temperature increase rate of 45°Cmin-1 and then holding the temperature at 950°C for five seconds under heating. A conductive mayenite compound powder having a conducting electron concentration of 0.5 x 1021 cm-1 and a specific surface area of 19 m2g-1 was obtained.
    [00067] [00067] EXAMPLE 8 < Process RTA > A powder of the conductive mayenite compound was synthesized under the same conditions as in Example 7 except that the process RTA was conducted at a process temperature of 950°C in Example 7. A powder of the conductive mayenite compound having a conduction electron concentration of 14 m2g-1 was obtained. The synthesis and treatment conditions of Examples 1 to 8 and Comparative Examples 1 and 2 are summarized in Table 1. [Table 1] Method for Pre-Agent Condition Process synthesizing treatment of RTA raw material raw material reduction reduction Example 1 Evacuation Synthesis, CaH2 700o C Non-hydrothermal 900o C carried out Example 2 Evacuation Synthesis, CaH2 600o C Non-hydrothermal 800o C carried out Example 3 Evacuation Synthesis, CaH2 600o C Non-hydrothermal 900o C carried out Example 4 Evacuation Synthesis, CaH2 700° C Non-hydrothermal 800° C performed Example 5 Evacuation Synthesis, CaH2 800 C Non-hydrothermal 800° C performed Example 6 Evacuation Synthesis, CaH2 700° C Non-hydrothermal 1000° C performed Example 7 Evacuation Synthesis, Ca 700 C 950o C hydro-thermal 800o C
    [00068] [00068] < Ru Support in Conductive Mayenite Compound Powder > In a Pyrex glass tube (trademark) 1 g of the C12A7e- powder prepared in Example 1, the powder having an electron injection amount of 1.0 x 1021 cm- 3 and a specific surface area of 17 m2g-1, and 0.042 g of Ru3(CO)12 were put in and the glass tube was vacuum sealed. The vacuum sealed tube was subjected to a heat treatment while rotating in an electric oven using the following program.
    [00069] [00069] [40o C, increasing the temperature for 20 min. -> 40o C, holding for 60 min. -> 70o C, increasing the temperature for 120 min. -> 70o C, holding for 60 min. -> 120o C, increasing the temperature for 120 min. -> 120o C, holding for 60 min. -> 250o C, increasing the temperature for 150 min. -> 250o C, holding 120 min.] Subsequently, the vacuum-sealed tube was broken, and the resulting powder was heat treated in a hydrogen gas atmosphere (26.7 kPa) by raising the temperature to 300°C over a period of 5 hours and holding the temperature for two hours. Thus, a conductive mayenite compound powder supporting 2% by weight of Ru was obtained.
    [00070] [00070] < Ammonia synthesis reaction > A reaction in which nitrogen gas (N2) and hydrogen gas (H2) were allowed to react with each other to produce ammonia gas (NH3) was conducted. The reaction was carried out in a fixed bed flow type reactor to which a quartz glass tube filled with 0.2 g of the prepared catalyst was attached. Regarding gas flow rates, the N2 flow rate was set at 15 mLmin-1, the H2 flow rate was set at 45 mLmin-1, and the total flow rate was set at 60 mLmin-1 . The reaction was conducted at a pressure of atmospheric pressure and a reaction temperature in the range of 320°C to 400°C. A gas discharged from the flow-type reactor was bubbled into 0.005 M of an aqueous sulfuric acid solution so that the ammonia produced was dissolved in the solution. The ammonia ions produced were quantitatively determined by ion chromatography. The ammonia production rate at 340ºC was 2,388 molg-1h-1.
    [00071] [00071] [Comparative Example 3] A 2 wt% supported Ru catalyst was prepared by the same method as in Example 9 except that the C12A7e21 powder prepared in Comparative Example 1 is the powder having an electron injection amount of 2.0 x 1021 cm -3 and a specific surface area of 1 m2g-1 being used. The ammonia synthesis reaction was carried out as in example 9. The ammonia production rate at 340ºC was 1,229 molg-1h-1.
    [00072] [00072] EXAMPLE 10 A 2% w/w supported Ru catalyst was prepared by the same method as in Example 9 except that the conductive mayenite compound powder prepared in Example 2, the powder having specific surface area of 31 m2g-1 was used, The ammonia synthesis reaction was conducted as in Example 9. The ammonia production rate at 340°C was 1575 molg-1h-1.
    [00073] [00073] EXAMPLE 11 A 2% w/w supported Ru catalyst was prepared by the same method as in Example 9 except that the conductive mayenite compound powder prepared in Example 3, the powder having specific surface area of 20 m2g-1 was used, The ammonia synthesis reaction was conducted as in Example 9. The ammonia production rate at 340°C was 1,831 molg-1h-1.
    [00074] [00074] EXAMPLE 12
    [00075] [00075] EXAMPLE 13 A 2 wt% supported Ru catalyst was prepared by the same method as in Example 9 except that the conductive mayenite compound powder prepared in Example 5, the powder having specific surface area of 10 m2g-1 was used, The ammonia synthesis reaction was conducted as in Example 9. The ammonia production rate at 340°C was 1,793 molg-1h-1.
    [00076] [00076] [COMPARATIVE EXAMPLE 4] A 2 wt% supported Ru catalyst was prepared by the same method as in Example 9 except the powder of the conductive mayenite compound prepared in Example 2, the powder having specific surface area of 60 m2g -1 was used. The ammonia synthesis reaction was conducted as in Example 9. The ammonia production rate at 340°C was 895 molg-1h-1. The results of Examples 9 to 13 and Comparative Examples 3 and 4 are summarized in Table 2.
    [00077] [00077] [Table 2] Support used NH3 production rate ( molg-1h-1) Example 9 Example 1 2,388 Example 10 Example 2 1,575 Example 11 Example 3 1,831 Example 12 Example 4 1,696 Example 13 Example 5 1.793 Comparative Example 3 Example Comparative 1 1,229
    [00078] [00078] Industrial Applicability The conductive mayenite compound having a large specific surface area and produced by the method of the present invention can be used as electronic materials such as a transparent electrode and a cold emitter that has good electronic properties. In addition, the conductive mayenite compound of the present invention may be used as high-performance reducing agents, catalyst materials, etc.
    权利要求:
    Claims (9)
    [1]
    1. "METHOD FOR THE PRODUCTION OF A MAYENITE COMPOUND", comprising a step of forming a powder precursor of a mayenite compound subjected to a mixture of a powder, raw material of the mayenite compound and water for a hydrothermal treatment, a step of forming a mayenite compound powder by dehydrating the precursor powder by heating, a step of forming a mayenite compound powder activated by heating the mayenite compound powder in an inert gas atmosphere or in a vacuum at a temperature in the range of 400°C to 1,000°C for three hours or more, and a step of injecting electrons into the mayenite compound by mixing the activated mayenite compound powder with a reducing agent and heating the resulting mixture in the range of 400°C to 1,100°C, to conduct a reduction treatment, characterized by the Conductive mayenite compound powder having a conduction electron concentration of 1015 cm-3 or more and a specific surface area of 5 m2g-1 or more being obtained.
    [2]
    2. "METHOD FOR THE PRODUCTION OF A MAYENITE COMPOUND", according to claim 1, characterized in that it further comprises, after the last step, a step of repetition of a rapid thermal annealing process (RTA process) including increasing a temperature to a rate of 30 to 60oC min-1 and keeping under heating in a range of 900oC to
    1,100oC.
    [3]
    3. "METHOD FOR THE PRODUCTION OF A MAYENITE COMPOUND", according to claims 1 and 2, characterized in that the mayenite compound is 12CaO.7A12O3.
    [4]
    4. "METHOD FOR THE PRODUCTION OF A MAYENITE COMPOUND", according to claims 1 and 2, characterized in that the reducing agent is Ca or CaH2.
    [5]
    5. "METHOD FOR THE PRODUCTION OF A METALLIC BACKED CATALYST", according to claims 1 and 2, characterized in that it comprises the use of an impregnation method, a physical mixing method, a thermal decomposition method, a liquid phase method , a precipitation method, or a vapor deposition method, allowing a transition metal catalyst to be supported on the powder of the conductive mayenite compound produced by the method recited in the claims above.
    [6]
    6. "METHOD TO SYNTHETIZE AMMONIA", according to claim 5, characterized in that it comprises the use of the supported metallic catalyst produced by the method of the aforementioned claim, in a synthesis reaction in which nitrogen gas (N2) and hydrogen gas H2) are allowed to react with each other to produce ammonia gas (NH3).
    [7]
    7. "MAYENITE COMPOUND POWDER", according to claim 1, characterized in that the surface of the powder inside a skeleton of the frame is activated.
    [8]
    8. "MAYENITE COMPOUND POWDER", according to claim 1, characterized in that the mayenite compound has a conduction electron concentration of 1015 or more and a specific surface area of 5m2g-1 or more.
    [9]
    9. "METALLIC SUPPORTED CATALYST", according to claim 5, characterized in being supported by a powder of conductive mayenite compound.
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    同族专利:
    公开号 | 公开日
    EP2891627A1|2015-07-08|
    KR101940777B1|2019-01-22|
    CN106277000B|2019-01-22|
    US10124319B2|2018-11-13|
    CN104583129A|2015-04-29|
    WO2014034473A1|2014-03-06|
    CA2881788C|2020-03-24|
    RU2015111257A|2016-10-27|
    US9573822B2|2017-02-21|
    CA2881788A1|2014-03-06|
    JP6152381B2|2017-06-21|
    BR112015003948A8|2021-09-14|
    JPWO2014034473A1|2016-08-08|
    US20150239747A1|2015-08-27|
    US20170095793A1|2017-04-06|
    CN104583129B|2016-09-07|
    RU2647290C2|2018-03-15|
    KR20150051215A|2015-05-11|
    CN106277000A|2017-01-04|
    EP2891627A4|2016-06-15|
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    法律状态:
    2018-03-06| B25A| Requested transfer of rights approved|Owner name: TOKYO INSTITUTE OF TECHNOLOGY (JP) , JAPAN SCIENCE |
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-11-03| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012189371|2012-08-30|
    JP2012-189371|2012-08-30|
    PCT/JP2013/072163|WO2014034473A1|2012-08-30|2013-08-20|Method for producing conductive mayenite compound powder|
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