JP5585821B2 - Carbon dioxide adsorptive decomposition catalyst and method for producing the same - Google Patents

Description

  The present invention relates to an adsorption / decomposition catalyst for carbon dioxide and a method for producing the same, and more specifically, an adsorption / decomposition catalyst for carbon dioxide that adsorbs carbon dioxide and decomposes by a photocatalyst excited by light including sunlight. It relates to the manufacturing method.

  In recent years, global environmental destruction due to an increase in carbon dioxide emissions has been recognized, and the reduction of such emissions has become an international issue. In addition to reducing the amount of carbon dioxide emissions, it has been recognized that recovery of the carbon dioxide emitted is also an important issue. Research has also been conducted on confining the recovered carbon dioxide in the ground or the ocean so that it is not liquefied or released into the atmosphere. However, there are concerns about the risks associated with large-scale investment and storage.

  The most desirable measure is to decompose carbon dioxide in the atmosphere into oxygen and carbon, but the conventional technique is known up to the stage of adsorbing carbon dioxide (see Patent Document 1), but decomposes. Since the technology up to the stage has not been developed, there is a problem that it does not function if the limit of the adsorption capacity is exceeded, and there is a problem that the adsorbed carbon dioxide is re-released by heating or the like. When thinking about the global environment, there is a need for technology that decomposes carbon dioxide and eliminates it.

JP 2001-300306 A

  The present invention has been made to solve the above-described conventional problems, and the object of the present invention is to absorb and decompose carbon dioxide efficiently from the atmosphere and to perform photolysis of carbon dioxide. And a manufacturing method thereof.

Adsorbing catalyst for decomposing carbon dioxide of the present invention, the porous mineral titanium dioxide is supported photocatalyst is, each of the magnetic flux density magnets are arranged opposite the pair of 2000 gauss to 5000 gauss containing an alkaline earth metal It is characterized in that it is manufactured while being kept at 350 ° C. to 550 ° C. for at least 10 minutes in the atmosphere while flowing air that has passed through the magnetic field space.

The porous mineral containing an alkaline earth metal of the carbon dioxide adsorptive decomposition catalyst of the present invention may be a porous mineral carrying a compound containing one or more of magnesium, calcium and barium as components.
The porous mineral containing an alkaline earth metal of the carbon dioxide adsorption / decomposition catalyst of the present invention is 20% to 1% or more of magnesium, calcium, and barium, with the total weight percentage of the oxide component of the raw material being 20% to It is preferable to contain 40%.
The porous mineral containing the alkaline earth metal of the carbon dioxide adsorptive decomposition catalyst of the present invention may be sepiolite.

The method for producing a carbon dioxide adsorptive decomposition catalyst according to the present invention includes an attaching step of attaching titanium dioxide to a porous mineral containing an alkaline earth metal, and firing by firing the porous mineral attached with titanium dioxide at 350 to 550 ° C. process and the fired porous minerals, while each of the magnetic flux density flowing air that has passed through the magnetic space between the magnets are oppositely disposed in pairs of 2000 gauss to 5000 gauss, 350 ° C. ~ under the atmosphere And an excitation step of holding at 550 ° C. for at least 10 minutes.
Further, the excitation process, the titanium dioxide supported on porous mineral, while flowing air, each of the magnetic flux density magnets forming a pair of 2000 gauss to 5,000 gauss passed through the magnetic space between disposed opposite In the atmosphere, the temperature may be maintained at 350 ° C. to 550 ° C. for at least 10 minutes, and subsequently cooled to at least 100 ° C. while ventilating the air that has passed through the magnetic field space.

Manufacturing method of adsorbing catalyst for decomposing carbon dioxide of the present invention, a porous mineral, organic bond of the compound and the porous minerals containing alkaline earth metals as a component decomposition temperature 450 to 800 ° C. containing an alkaline earth metal a granulation step of granulating by mixing together wood may be produced by the process ing from the granulation sintering step of firing the kneaded granules the decomposition temperature or more of the organic binder.
Here decomposition temperature organic binder 450 to 800 ° C., a polyvinyl alcohol, is used as the aqueous solution of polyvinyl alcohol 10 to 30% strength by weight, based on the weight 1 of the porous minerals, by weight of the polyvinyl alcohol is 0. It is preferably 01 to 0.08.

According to the present invention, titanium dioxide supported on a porous mineral containing an alkaline earth metal as a component becomes excited when exposed to a magnetic field atmosphere, and when exposed to light such as sunlight, the titanium dioxide is even higher. Energy is excited and carbon dioxide can be decomposed into carbon and oxygen.
The carbon dioxide adsorptive decomposition catalyst of the present invention is applied, for example, as a coating material for adhering the catalyst to the wall surface of a building made of concrete, mortar or the like, or the surface of the surface layer of the roof. On this painted surface, the carbon dioxide adsorptive decomposition catalyst adsorbs carbon dioxide discharged from factories and the general living environment by porous minerals containing alkaline earth metals as components, and uses this as light such as sunlight. Since the titanium dioxide excited by is decomposed into carbon and oxygen, the concentration of carbon dioxide in the atmosphere can be reduced.

It is a conceptual diagram of the adsorption decomposition catalyst manufacturing apparatus of the carbon dioxide of this invention. It is the schematic which shows the structure of the adsorption-decomposition catalyst manufacturing apparatus of the carbon dioxide by embodiment of this invention. It is a horizontal sectional view of the magnetic field generator of the adsorption decomposition catalyst manufacturing apparatus of the carbon dioxide by embodiment of this invention. It is a fragmentary sectional view of the carbon dioxide measuring device used for the effect check of the adsorption decomposition catalyst of carbon dioxide by an embodiment of the invention. 6 is a graph showing the carbon dioxide adsorption / decomposition catalytic effect of Sample A according to Example 1. FIG. It is a graph which shows the adsorption decomposition catalytic effect of the carbon dioxide of the samples B and C which concern on Example 2, 3. It is a graph which shows the adsorption decomposition catalytic effect of the carbon dioxide of the sample D which concerns on a comparative example.

  The present invention relates to an adsorption decomposition catalyst for carbon dioxide that is excited by light such as sunlight and decomposes carbon dioxide into carbon and oxygen. The catalyst is composed of a porous mineral containing an alkaline earth metal as a component and a photocatalyst, and the photocatalyst is polarized and excited in a magnetic field atmosphere. Polarization excitation of the photocatalyst is performed by exposing air that has passed through a magnetic field atmosphere.

  As the porous mineral containing the alkaline earth metal of the present invention as a component, a porous mineral containing a naturally occurring alkaline earth metal as a component may be used, or a naturally occurring alkaline earth metal is used as a component. The minerals contained as may be used after being processed into a porous mineral, or may be used after adding an alkaline earth metal to the porous mineral.

  Alkaline earth metals include beryllium, magnesium, calcium, strontium, barium, and radon, but those containing magnesium, calcium, and barium as components can be preferably used because of their availability.

  Sepiolite and attapulgite are known as porous minerals containing a naturally occurring alkaline earth metal as a component. Among these, sepiolite can be preferably used as a porous mineral containing the alkaline earth metal of the present invention as a component. The quality of sepiolite is not particularly limited, but those containing an alkaline earth metal content of 20 to 40% by weight in terms of an alkaline earth metal oxide can be preferably used. The shape of sepiolite is not particularly limited, but those having an average particle size of 100 to 2000 μm can be preferably used in view of production facilities. Particles of 100 μm or less are likely to become dust, and it is necessary to take measures against dust. Particles of 2000 μ or more are liable to cause clogging problems.

  As minerals containing naturally-occurring alkaline earth metals as components, sepiolite, vermiculite, talc (talc) and magnesium silicate minerals such as attapulgite, calcium minerals such as gypsum, limestone, calcite, araleite, Although barium-based minerals such as venomite and barite are known, porous minerals containing the alkaline earth metal of the present invention as a component are minerals containing these alkaline earth metals as porous minerals. Processed ones can also be used. As a method for processing a mineral containing an alkaline earth metal as a component into a porous mineral, for example, there is a method in which the mineral is baked under high temperature and high pressure, and this is returned to atmospheric pressure at once to make a porous mineral. .

Furthermore, the porous mineral containing the alkaline earth metal of the present invention as a component may be a porous mineral processed by adding an alkaline earth metal to the porous mineral. The following describes how to make a porous mineral containing as an ingredient an alkaline earth metal processed by adding an alkaline earth metal to the porous mineral.
Usable magnesium, calcium and barium compounds include calcium oxide, calcium peroxide, magnesium oxide, magnesium peroxide, magnesium aluminum oxide, barium oxide, barium peroxide and other oxides, calcium hydroxide, magnesium hydroxide, water Hydroxides such as barium oxide, calcium carbonate, magnesium carbonate, basic magnesium carbonate, carbonates such as barium carbonate, chlorides such as magnesium chloride and potassium magnesium chloride, and chloride double salts thereof, calcium fluoride, calcium silicofluoride , Fluorides such as magnesium fluoride, magnesium silicofluoride and barium fluoride, bromides such as calcium bromide, magnesium bromide and barium bromide, iodides such as calcium iodide, magnesium iodide and barium iodide, silicic acid Silicates such as lucium (water glass), magnesium silicate, barium silicate, calcium phosphate (apatite), calcium metaphosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, magnesium phosphate, magnesium hydrogen phosphate, phosphorus Phosphates such as ammonium magnesium phosphate, barium phosphate, barium hydrogen phosphate, nitrates such as calcium nitrate, magnesium nitrate, barium nitrate, calcium sulfate (gypsum), calcium thiosulfate, magnesium sulfate (key jelly), barium sulfate (heavy Crystallites), sulfates such as barium sulfite and barium thiosulfate and their sulfate double salts, chlorates such as calcium chlorate, calcium hypochlorite, barium chlorate and barium hypochlorite, calcium permanganate, Permanganates such as barium permanganate, Chromates such as calcium romate and barium chromate, calcium tungstate, tungstate such as magnesium tungstate, molybdate such as calcium molybdate, calcium cyanide, calcium thiocyanide, thiocyanide Cyanides such as barium, carbides such as calcium carbide (carbide), barium carbide, sulfides such as calcium sulfide, magnesium sulfide and barium sulfide (chicken crown), nitrides such as calcium nitride and magnesium nitride, calcium oxalate, stear Examples thereof include organic acid salts such as calcium phosphate magnesium oxalate, magnesium stearate, barium oxalate, and barium stearate.

Among these, oxides such as calcium oxide, magnesium oxide and barium oxide, and hydroxides such as calcium hydroxide, magnesium hydroxide and barium hydroxide can be preferably used, and magnesium oxide and calcium hydroxide are easy to handle. More preferably, magnesium hydroxide and barium hydroxide can be used.
A compound containing an alkaline earth metal as a component can be used alone or in combination of two or more. When two or more kinds of compounds are used in combination, the compounds containing alkaline earth metal as components may be mixed in advance and homogenized before kneading with the porous mineral, or You may add in order, mixing the compound which contains an alkaline-earth metal as a component to a porous mineral. There is no restriction | limiting in particular in the order which adds the compound which contains several alkaline-earth metal as a component.
The quality of the compound containing an alkaline earth metal as a component is not particularly limited, and those commercially available can be widely used. As for the shape, those having an average particle diameter of 45 to 500 μm can be used.

Porous minerals include silicate porous minerals such as diatomaceous earth, celite, cristobalite, aerosil and silica gel, aluminum oxide porous minerals such as activated alumina and aluminum hydroxide, vermiculite, sepiolite, talc (talc) and attapulgite Magnesium silicate based porous minerals such as acid clay, bentonite, montmorillonite, sericite (sericite), zeolite (zeolite) and clay (clay), and allophane and shirasu Tephra-based porous minerals such as balloons, pumice and pumice tuff can be listed. Among porous minerals, sepiolite, pumice, aerosil, shirasu balloon, zeolite and activated clay can be preferably used.
There is no restriction | limiting in particular in the quality of a porous mineral, The thing currently distribute | circulated in the market can be utilized widely. The shape is not particularly limited, but those having an average particle diameter of 100 to 2000 μm can be used due to the relationship of production equipment. Particles of 100 μm or less are likely to become dust, and it is necessary to take measures against dust. Particles of 2000 μ or more are liable to cause clogging problems.

  The mixing ratio of the compound containing an alkaline earth metal as a component to the porous mineral is preferably in the range of 0.1 to 0.6 as the weight of the alkaline earth metal with respect to the weight 1 of the porous mineral. It is more preferable that the total percentage in terms of oxides of magnesium, calcium and barium of the porous mineral containing the alkaline earth metal granulated and fired is 20% to 40%. If the weight ratio of the alkaline earth metal to the porous mineral is 0.1 or less, the ability to attract carbon dioxide of the alkaline earth metal may not be sufficiently exerted, and if the weight ratio is 0.6 or more, the porous mineral This reduces the amount of carbon dioxide, which may reduce the ability to adsorb carbon dioxide.

When a compound containing an alkaline earth metal as a component is added to the porous mineral, an organic binder having a decomposition temperature of 450 to 800 ° C. may be used as the binder.
As an organic binder for kneading together with a compound containing a porous mineral and an alkaline earth metal as a component, a compound containing a porous mineral and an alkaline earth metal as a component is mixed and bonded, and then fired at 450 to 800 ° C. What decomposes | disassembles in a process should just be. Organic binders include natural adhesives such as casein, latex, starch, gelatin, fibrin, acrylic resin emulsion, α-olefin resin, urethane resin emulsion ether cellulose, ethylene-vinyl acetate emulsion, epoxy resin emulsion, vinyl acetate. Synthetic adhesives such as resin emulsion, polyvinyl alcohol, and polyvinylpyrrolidone resin can be used. Of these, polyvinyl alcohol can be preferably used.

The amount of the organic binder having a decomposition temperature of 450 to 800 ° C. is based on the state of granulation formed by kneading a compound containing porous mineral and alkaline earth metal as components, and the state of the fired body after granulation firing. You can select the amount to use. If the amount of organic binder used is small, adhesion of compounds containing porous minerals and alkaline earth metals as components will be insufficient, and if the amount used is large, particles of porous mineral tend to bond together and the particle size tends to increase. There is. When polyvinyl alcohol is used as the organic binder, it is preferable to use a weight of polyvinyl alcohol of 0.01 to 0.08, more preferably 0.02 to 0.05, per weight of porous mineral. preferable. If the amount of polyvinyl alcohol used relative to the porous mineral is 0.01 or less, the adhesion of the compound containing the porous mineral and the alkaline earth metal as components becomes insufficient, and the ability of the target carbon dioxide adsorptive decomposition catalyst is There is a risk that it will not be fully utilized. In addition, when the amount of polyvinyl alcohol used for the porous mineral is 0.08 or more, the porous mineral particles are bonded to each other, the particle diameter becomes too large, and pulverization and classification are required in a later step. There is.
The concentration of the organic binder having a decomposition temperature of 450 to 800 ° C. may be selected from the dispersant and the concentration in view of the kneading state of the compound containing the porous mineral and the alkaline earth metal as components. In the case of polyvinyl alcohol, it is preferably used as an aqueous solution having a concentration of 10 to 30% by weight. If the concentration of the polyvinyl alcohol aqueous solution is 10% by weight or less, the viscosity may be low and preferable granulation may not be performed. On the other hand, if the concentration is 30% by weight or more, the viscosity becomes too high and mixing may be difficult.

There is no particular limitation on the granulation method of the compound containing the porous mineral and the alkaline earth metal as components, and the powder of the compound containing the alkaline earth metal as a component is uniformly attached around the porous mineral, and the organic binder. It suffices if it can be granulated to a size of about 0.1 to 2 mm due to the binding force.
For example, a predetermined amount of an organic binder solution is sprayed onto a compound containing a predetermined amount of porous mineral and alkaline earth metal as components in a powder mixture by a stirring granulator having an agitator that rotates horizontally on a flat bottom pan mixer A predetermined amount of each of a porous mineral, a compound containing an alkaline earth metal as a component, and an organic binder aqueous solution in a drum type rolling granulator. A method in which the mixture is mixed, granulated by stirring and mixing, a horizontal uniaxial or biaxial extrusion granulator so that each of a porous mineral, a compound containing an alkaline earth metal and an organic binder aqueous solution has a predetermined ratio. And the like, and a method of continuously taking out the granulated product. The granulation step is usually performed at room temperature in the atmosphere, but may be heated or cooled as necessary.

The granulated kneaded mixture is sent to the granulation firing step and fired in the atmosphere. The firing temperature is preferably equal to or higher than the decomposition temperature of the organic binder used, and is usually 450 ° C to 800 ° C. When the firing temperature is 450 ° C. or lower, the organic binder is not sufficiently decomposed, and the decomposition residue may remain in the porous mineral. If the firing temperature is high, it is not economical, and it takes time to cool down, which is inefficient in production. The firing time is about 5 to 30 minutes, and usually about 5 to 15 minutes. If the firing time is short, the decomposition of the organic solvent becomes insufficient, and the decomposition residue remains in the porous mineral, which may clog the pores of the porous mineral. A long firing time is uneconomical and inefficient in production.
The method for firing the granulated particles is not particularly limited as long as the necessary firing temperature and firing time can be secured. For example, general firing furnaces such as a rotary kiln, tunnel kiln, roller hearth kiln, and shuttle kiln can be used. In the case of a small amount, an experimental electric furnace can be easily used. Since the oxidation reaction of the compound containing an alkaline earth metal as a component and the thermal decomposition of the organic binder occur during the firing, the kiln used may be provided with a smoke exhausting facility.

A porous mineral containing a sepiolite or an alkaline earth metal granulated by the above method as a component has a photocatalyst attached to the surface. The method for attaching the photocatalyst will be described below.
As the photocatalyst, an oxide of titanium is known, and photocatalytic activity is recognized in titanium dioxide, titanium monoxide, and dititanium trioxide. Among them, the activity of titanium dioxide having anatase type, rutile type and brookite type in crystal form is high, and anatase type titanium dioxide has the highest photocatalytic activity. The titanium dioxide used in the present invention is preferably anatase-type titanium dioxide or amorphous (non-crystalline) titanium dioxide that changes to anatase-type titanium dioxide in the subsequent baking step. Titanium dioxide is used in the adhesion process in a state dispersed in water. Titanium dioxide dispersed in water is preferably in the form of fine particles having an average particle diameter of 10 μm or less, and colloidal titanium dioxide containing titanium dioxide nanocolloid having an average particle diameter of 1 nm to 50 nm is more preferably used.
In order to stably disperse titanium dioxide in water, acids such as hydrochloric acid and organic dispersants have been used. Recently, a colloidal anatase-type titanium dioxide dispersion containing no dispersant has also been developed. The concentration of colloidal anatase type or amorphous titanium dioxide dispersed in water is about 0.5 to 3.0% by weight, usually about 0.8 to 1.2% by weight.

As a method of attaching titanium dioxide to a porous mineral containing an alkaline earth metal as a component, there are a method of spraying a dispersion of titanium dioxide and a method of immersing in a dispersion of titanium dioxide, any one method, Or both can be selected.
The method of spraying a dispersion of titanium dioxide on a porous mineral containing an alkaline earth metal as a component includes, for example, storing a porous mineral containing an alkaline earth metal as a component in a sieve-like container and applying titanium dioxide from the top. A method of spraying the dispersed dispersion, a method of spraying a predetermined amount of titanium dioxide dispersion while mixing particles with a stirring granulator having an agitator that rotates horizontally in a flat-bottom pan mixer, and spray drying Examples thereof include a method of spray-drying a dispersion of titanium dioxide using a granulator. The amount of the dispersion of titanium dioxide to be sprayed is preferably 0.0001 to 0.1, preferably 0.01 to 0.05 as the weight of titanium dioxide with respect to the weight 1 of the porous mineral containing an alkaline earth metal as a component. More preferred.

  On the other hand, the method of immersing a porous mineral containing an alkaline earth metal as a component in a titanium dioxide dispersion is, for example, putting the porous mineral containing an alkaline earth metal as a component in a tray having a net-like bottom, There are a method of immersing the titanium dioxide dispersion in a dispersion tank, a method of putting a porous mineral containing an alkaline earth metal as a component and a dispersion of titanium dioxide in one container, and filtering after a certain time. Can be mentioned. The immersion time is about 10 seconds to 5 minutes, and usually about 1 minute to 3 minutes. If the immersion time is too short, the dispersion liquid may not enter between the particles. On the other hand, if the immersion time is too long, the dispersion enters into the pores of the porous mineral, so that it may take time to dry the next step. During the immersion, the porous mineral and titanium dioxide dispersion containing alkaline earth metal as a component is stirred, or the porous mineral containing alkaline earth metal as a component is shaken in the titanium dioxide dispersion, Immersion time can be shortened.

A porous mineral containing an alkaline earth metal having titanium dioxide attached thereto by a method of spraying a dispersion of titanium dioxide or a method of immersing in a dispersion of titanium dioxide is subjected to a drying step. The drying method includes a natural drying method and a hot air drying method, and any one method or both methods can be selected.
The natural drying method is, for example, a method in which particles attached with titanium dioxide by an immersion method are allowed to stand at room temperature in an air atmosphere and wait for evaporation of moisture. On the other hand, in the hot air drying method, for example, particles having titanium dioxide attached thereto by an immersion method are put in a shelf dryer, and hot air is circulated in an air atmosphere to evaporate moisture. Can be shortened. The above-mentioned spray drying is a method of drying with hot air while spraying a dispersion of titanium dioxide. The hot air temperature of a hot air dryer is about 30-120 degreeC, and is about 70-100 degreeC normally. At low temperatures, drying takes time, and at high temperatures, the attached titanium dioxide may peel off due to the boiling force of moisture.

The porous mineral adhered with titanium dioxide is fired to fix the titanium dioxide to the particle surface. By this firing, the dispersant used to stabilize the dispersion state of the titanium dioxide dispersion is also removed by firing. Amorphous titanium dioxide can be crystal-converted to anatase-type titanium dioxide. Below, the baking process of the porous mineral which adhered titanium dioxide is demonstrated.
350-550 degreeC is preferable and the firing temperature of this baking process has more preferable 400-500 degreeC. When the firing temperature is 350 ° C. or lower, the titanium dioxide is not sufficiently fixed, and the titanium dioxide may be peeled off. Moreover, there is a possibility that crystal conversion from amorphous titanium dioxide to anatase type titanium dioxide does not occur sufficiently. When the calcination temperature exceeds 550 ° C., the crystal form of titanium dioxide may be crystal-converted from anatase type having a high photocatalytic ability to a rutile form having a poor photocatalytic ability. Firing is usually performed in an air atmosphere, and the firing time is about 10 to 60 minutes.
There are no particular limitations on the method for firing the porous mineral to which titanium dioxide is attached, and any method can be used as long as the necessary temperature control can be performed. For example, a firing furnace such as a tunnel kiln, a roller hearth kiln, or a shuttle kiln can be used. In the case of a small amount, an experimental electric furnace can be easily used. The kiln to be used may be provided with smoke exhausting equipment.

  The titanium dioxide supported on the porous mineral is further subjected to polarization excitation by being exposed to a magnetic field atmosphere. In this excitation process, titanium dioxide is held in a magnetic field atmosphere, so that the polarization-excited titanium dioxide causes a stronger vibration in the carbon dioxide molecule and easily breaks the covalent bond between carbon and oxygen. To do. It is said that energy of 168 Kcal / mol or more is necessary to break the covalent double bond between carbon and oxygen, and the energy of the hydroxy radical that anatase-type titanium dioxide is excited by light and generated as a surface active species Is about 120 Kcal / mol, it is necessary to bring the anatase-type titanium dioxide from the ground state to the excited state in order to break the covalent bond of carbon dioxide. Below, the excitation process of titanium dioxide is demonstrated.

In order to excite polarization of titanium dioxide, titanium dioxide supported on a porous mineral may be exposed to a magnetic field atmosphere. As a method of exposing titanium dioxide supported on a porous mineral to a magnetic field atmosphere, the porous mineral is supported on the air that has passed through the magnetic field atmosphere used in the magnetic powder manufacturing apparatus disclosed in Japanese Patent Application Laid-Open No. 2006-086307. Titanium dioxide may be exposed.
Air existing in a strong magnetic field space is affected by magnetic force, and electrons and nuclei of nitrogen atoms and oxygen atoms are excited to have a spin magnetic moment. When the air that has passed through the magnetic field atmosphere has a spin magnetic moment, the air moves to a position where the porous mineral supporting titanium dioxide exists, and the energy is transmitted to the titanium dioxide, whereby the titanium dioxide is polarized and excited.
Below, the excitation process of the titanium dioxide by the exposure of the air which passed in the magnetic field atmosphere is demonstrated.

FIG. 1 shows a conceptual diagram of an apparatus for producing an adsorption decomposition catalyst for carbon dioxide according to the present invention.
The carbon dioxide adsorption / decomposition catalyst production apparatus 1 penetrates the container 2, the magnetic field generator 3, the air compressor 4, and the magnetic field generator 3 that contain porous minerals carrying titanium dioxide, and contains the porous minerals. It consists of a vent pipe 5 that connects the container 2 and the air compressor 4.
The container 2 containing the porous mineral carrying titanium dioxide is not particularly limited as long as it contains the porous mineral carrying titanium dioxide and can be exposed to the air that has passed through the magnetic field generator. A closed container to which a vent pipe 5 for introducing air that has passed through the magnetic field generator is connected is preferable. Moreover, it is preferable that the container 2 containing the porous mineral carrying titanium dioxide is provided with an exhaust port for discharging the air in the container. It is more preferable that the container containing the porous mineral carrying titanium dioxide can be heated to 350 ° C to 550 ° C. As a closed container which can be heated, for example, a general firing furnace such as a rotary kiln, a tunnel kiln, a roller hearth kiln and a shuttle kiln can be used. In the case of a small amount, an experimental atmospheric electric furnace capable of introducing gas can be easily used.

A container 2 containing a porous mineral carrying titanium dioxide and an air compressor 4 for sending out air are connected by a vent pipe 5. The vent pipe 5 is preferably provided with a magnetic field generator 3 to be described later.
The vent pipe 5 is provided with a pressure reducing valve 6 and an air flow rate adjusting valve 7, and a pressure gauge 8 may be attached to the pressure reducing valve 6. There are no particular restrictions on the types of the compressor 4, the pressure reducing valve 6, the air flow rate adjusting valve 7, and the pressure gauge 8, and a commercially available general-purpose instrument can be used as appropriate.
The material and shape of the vent pipe 5 are not particularly limited, and materials and shapes that are normally connected to the air compressor 4 can be used. The material of the normally used ventilation pipe is a stainless steel pipe, a carbon steel pipe, an alloy steel pipe or the like, and a pressure-resistant plastic air hose can also be used. The outer diameter of the vent pipe 5 is preferably 5 mm to 50 mm, and is usually about 5 mm to 20 mm.

The magnetic field generator 3 exposes air introduced into a container 2 containing a porous mineral carrying titanium dioxide to a strong magnetic field space. Air is generated in a magnetic field atmosphere created by a pair of opposed magnets. What is devised to pass is good. The magnet may be a permanent magnet, an electromagnet, or both.
When a permanent magnet is used, permanent magnets such as KS steel, MK steel, alnico magnet, ferrite magnet, samarium cobalt magnet and neodymium magnet can be used. Among these, neodymium magnets having a high magnetic flux density can be preferably used.
The shape of the magnet is not particularly limited, and a cylindrical round shape, a quadrangular prism shape, an annular ring shape, or the like can be used.
The magnetic flux density of the magnet can be 1000 gauss to 15000 gauss, preferably 2000 gauss to 5000 gauss, more preferably 3000 gauss to 5000 gauss. With a magnet of 2000 gauss or less, a sufficiently strong magnetic field cannot be created, and there is a possibility that the air that has passed cannot sufficiently excite titanium dioxide. Magnets of 5000 Gauss or more are heavy and difficult to handle, and are expensive.

The magnetic field atmosphere can be created by appropriately arranging magnets on the outer periphery of a tube through which air flows, but it is preferable to create a magnetic field atmosphere by arranging a pair of magnets each having a magnetic flux density of 2000 gauss to 5000 gauss facing each other. . The distance between the pair of magnets arranged to face each other is preferably 5 mm to 100 mm, and usually 10 m to 50 mm. When the distance between the pair of magnets is 5 mm or less, the diameter of the tube through which the air flows becomes small and the absolute amount of air exposed to the magnetic field atmosphere decreases, so that there is a possibility that the titanium dioxide is not sufficiently excited. Further, when the distance is 100 mm or more, the magnetic field is weakened, and there is a possibility that the air that has passed through cannot be sufficiently excited. The arrangement of the pair of magnets may be arranged so that the N pole and the S pole face each other, or the N pole and the N pole, and the S pole and the S pole may face each other.
There is no limitation on the number of magnets arranged to face each other in pairs, and any number of pairs may be used as long as the number is one or more, but usually 1 to 10 pairs. In the case of using a plurality of pairs of magnets, it is preferable that they are installed at a certain interval so that adjacent magnets do not contact each other. The distance between a pair of magnets and an adjacent pair of magnets is usually 10 mm to 300 mm.

The magnetic field generator 3 may be simply a pair of magnets arranged opposite to each other on the outer peripheral portion of the vent pipe 5, or alternatively, a magnetic field generator 3 connected to the vent pipe 5 is prepared separately and an intermediate portion of the vent pipe 5 is provided. You may connect to.
The distance between the magnetic field generator 3 and the container 2 containing the porous mineral carrying titanium dioxide is preferably in the range of 10 cm to 100 cm, and usually 20 to 50 cm. When the distance between the magnetic field generator 3 and the container 2 containing the porous mineral carrying titanium dioxide is 10 cm or less, the apparatus is difficult to assemble, and the magnetic field generator is susceptible to heat when the container 2 is heated. . As the distance between the magnetic field generator 3 and the container 2 containing the porous mineral carrying titanium dioxide increases, the chance that the excited air collides with other molecules during the movement increases, so The rate may increase.

When the magnetic field generation device 3 is separately prepared, the magnetic field generation device 3 includes a circular tube through which air passes, a pair of magnets disposed opposite to the outer periphery of the circular tube, and a magnet storage that stores the magnets fixedly. And a coupling portion for coupling the vent tube and the circular tube. As long as the circular pipe can be connected to the vent pipe, it does not need to be the same thickness as the vent pipe, but rather has a larger inner diameter than the vent pipe so that air is exposed to the magnetic field atmosphere for a long time in the circular pipe Is good.
The inner or outer diameter of the circular tube is usually about 5 mm to 50 mm. If the inner diameter of the circular tube is 5 mm or less, the air flow becomes fast, and there is a possibility that the passing air is not sufficiently exposed to the magnetic field atmosphere. Further, when the outer diameter is 50 mm or more, the distance between the magnets arranged opposite to each other is increased, and there is a possibility that sufficient magnetic field strength cannot be obtained. A groove or a protrusion may be provided on the inner peripheral wall of the circular tube so that air is agitated. There is no restriction | limiting in the shape of a groove | channel or processus | protrusion, For example, the some cyclic | annular processus | protrusion or dent provided in the circular pipe inner peripheral wall with the fixed space | interval may be sufficient. Further, it may be one or more spiral protrusions or depressions provided on the inner peripheral wall of the circular pipe.

The magnets arranged on the outer periphery of the circular tube are fixed by the magnet storage unit. The magnet storage unit holds the magnet and can fix the magnet in contact with the circular tube or in close proximity without contact. The magnet housing portion is not limited in its material and shape as long as it can fix the magnet to the outer peripheral portion of the circular tube, and is made of, for example, stainless steel, plastic, clay, rubber, cloth, or the like. Various shapes such as a cylindrical shape, a box shape, and a polygonal column shape can be formed.
As a coupling portion that couples the magnetic field generator 3 and the vent pipe 5, a commonly used pipe-to-tube coupling means can be used as appropriate.
The magnetic field generator 3 may combine one or two or more. When two or more magnetic field generators are combined, they can be arranged in series or in parallel with the air flow. When arranged in series, the thickness of the circular tube and the magnetic flux density of the magnet used may be changed.

  When an electromagnet is used, for example, a magnetic field generated by passing an electric current through an electromagnet coil wound around an iron core may be used, and air may be passed through the magnetic field atmosphere. The magnetic flux density, the distance to the magnet, and the exposure time for creating a magnetic field atmosphere through which air for exciting polarization of titanium dioxide is passed are the same as when a permanent magnet is used.

The air sent from the air compressor 4 is adjusted in flow rate by a pressure reducing valve 6 and an air flow rate adjusting valve 7 provided in the vent pipe 5, sent to the magnetic field generator 3, and passes through a magnetic field space created by an opposing magnet. It flows into the container 2 containing a porous mineral carrying titanium dioxide.
The speed at which the air that has passed through the magnetic field generator 3 flows into the container 2 containing the porous mineral carrying titanium dioxide is preferably 0.1 m to 5.0 m per second, and more preferably 0.5 m to 1.0 m. If it is 0.1 m or less, the absolute amount of air sent to the container containing the porous mineral carrying titanium dioxide is insufficient, so that it takes time to excite titanium dioxide. If the air sending speed is 5.0 m or more, the air may flow into the porous mineral container carrying titanium dioxide without being exposed to the magnetic field atmosphere by the magnetic field generator, and the titanium dioxide may not be sufficiently excited. In addition, there is a risk that the porous mineral carrying titanium dioxide will be scattered.

When the step of exposing the titanium dioxide to the air atmosphere that has passed through the magnetic field generator to excite polarization is performed under heating conditions, the ratio of the excited titanium dioxide can be increased. The heating temperature is preferably 350 ° C to 550 ° C, more preferably 400 to 500 ° C. If it is 350 degrees C or less, there exists a possibility that the ratio of the excited titanium dioxide cannot fully be raised. At 550 ° C. or higher, there is a risk that anatase-type titanium dioxide having a high photocatalytic activity may be crystal-converted to a rutile-type having poor activity.
The heating time is preferably 10 to 60 minutes. Usually 20 to 40 minutes. If it is less than 10 minutes, the ratio of excited titanium dioxide may not be sufficiently increased. Heating for 60 minutes or more is useless because the ratio of excited titanium dioxide cannot be increased further.
After the heating is finished, it is preferable to cool the air to 100 ° C. or lower by ventilating the air that has passed through the magnetic field generator while being stored in the container containing the porous mineral carrying titanium dioxide. When the container 2 containing the porous mineral carrying titanium dioxide is opened and rapidly cooled after the heating is finished, the titanium dioxide in the excited state passes the excitation energy to nitrogen or oxygen atoms in the atmosphere and returns to the ground state. There is a fear. Below 100 ° C., titanium dioxide can maintain an excited state.

Furthermore, it is possible to simultaneously perform the firing step of firing the porous mineral containing the alkaline earth metal to which titanium dioxide is attached and the excitation step of exciting titanium dioxide by exposing it to air that has passed through a magnetic field atmosphere. . For example, in the process of firing the porous mineral with titanium dioxide attached, air that has passed through a magnetic field atmosphere formed by a permanent magnet or electromagnet is introduced into the kiln, and the porous mineral with titanium dioxide attached is obtained. When exposed to air that has passed through a magnetic field atmosphere, the titanium dioxide is fixed to the particles by firing, and at the same time, the titanium dioxide can be brought into a polarization excited state. The firing temperature is preferably 350 to 550 ° C., more preferably 400 to 500 ° C., as in the single firing step. The firing time is about 10 to 60 minutes as in the case of the single firing step. In order to prevent the temperature in the kiln from decreasing due to the inflow of air, the air that has passed through the magnetic field atmosphere may be preheated.
After completion of the firing / excitation, it is preferable that the air passed through the magnetic field generator is ventilated while being stored in the firing furnace containing the porous mineral carrying titanium dioxide, and cooled to 100 ° C. or lower.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
<Device>
FIG. 2 shows the carbon dioxide adsorption / decomposition catalyst production apparatus 1 used in the embodiment of the present invention.
The carbon dioxide adsorption / decomposition catalyst production apparatus 1 includes an electric furnace 9, a magnetic field generator 3, an air compressor 4 (not shown), and a magnetic field generator 3 connected to an intermediate portion thereof, and the air compressor 4 and the electric furnace 9 are connected. It consisted of a vent pipe 5 to connect. The electric furnace (desktop atmosphere electric furnace TF1200-300, manufactured by Fulltech Co., Ltd.) 9 was a box-shaped electric furnace made of a heat-resistant material and had a door whose front was openable and closable. The inside size of the electric furnace 9 was 210 mm in width, 320 mm in depth, 210 mm in height, and the internal capacity was 15 liters. Below the electric furnace 9, a switch 10 for turning on and off the electric furnace, a temperature adjusting dial 11 capable of arbitrarily setting the temperature in the furnace from 300 ° C. to 1200 ° C., and a temperature display device 12 for displaying the furnace temperature are provided. An electric furnace control section 13 was provided. At the center of both side surfaces of the electric furnace 9, there are provided mounting ports 14 and 15 for attaching a vent pipe 5 for introducing gas and an exhaust pipe (not shown) for discharging gas.
A stainless steel vent pipe 5 having an outer diameter of 10 mm and an inner diameter of 8 mm is connected to the mounting opening 14 provided on the side surface of the electric furnace 9. Two magnetic field generators 3 are connected to the vent pipe 5 30 cm away from the electric furnace 9. Connected in series. A vent pipe 5 is further coupled to the tip of the magnetic field generator 3, and the vent pipe 5 is coupled to the air compressor 4. The vent pipe 5 between the air compressor 4 and the magnetic field generator 3 includes a pressure reducing valve (SS mini high pressure valve: manufactured by Yamato Sangyo Co., Ltd.) 6 and an air flow rate adjusting valve (mini adjusting valve: Nippon Swage) with a pressure gauge 8. Lock FST Co., Ltd.) 7 was provided.

FIG. 3 is a horizontal sectional view including the central portion of the cross section of the magnetic field generator 3 used in the present invention.
The magnetic field generator 3 includes a first magnetic field generator 21 and a second magnetic field generator 22 connected in series, and the vent pipe 5 communicating with the air compressor 4 is coupled to the first circular pipe 24 of the first magnetic field generator 21. It was done. The first magnetic field generator 21 includes a stainless steel first circular tube 24 having an inner diameter of 12 mm, an outer diameter of 16 mm, and a length of 155 mm, in which an annular groove 23 having a width of 5 mm and a depth of 1 mm is engraved at an interval of 5 mm on the inner peripheral wall; A stainless steel first magnet storage portion 26 having an outer diameter of 60 mm and a length of 155 mm for storing a magnet installed in close contact with the outer surface of the first circular tube 24 and four round shapes having a magnetic flux density of 4050 gauss. It consisted of neodymium magnets (diameter 3 mm, height 4 mm: manufactured by Magfine Co., Ltd.) 25a to 25d. Neodymium magnets were installed in two places so that the N pole and the S pole face each other with the first circular pipe sandwiched between the left and right outer sides of the cross section of the circular pipe. One pair of magnets and the other pair of magnets were installed so that the different poles were close to each other with an interval of 40 mm, and the space between the magnets and the space of the magnet storage tube were filled with foamable plastic. One end of the first circular tube 24 of the first magnetic field generator 21 is coupled to the vent tube 5 by a coupling member, and the other end is coupled to the second circular tube 27 of the second magnetic field generator 22. When the flow rate of the air passing through the vent pipe 5 was 1 m / s, the air passed through the first magnetic field generator in about 0.5 seconds.

The second circular tube 27 of the second magnetic field generator 22 is a stainless steel tube having an inner diameter of 41 mm, an outer diameter of 46 mm, and a length of 174 mm, and stores a magnet installed in close contact with the outer surface of the second circular tube 27. A stainless steel second magnet housing portion 29 having an outer diameter of 77 mm and a length of 150 mm and a pair of square neodymium magnets each having a magnetic flux density of 4000 gauss (length 4 mm, width 4 mm, height 3 mm: Magfine Co., Ltd.) Made) 28a, 28b. Two neodymium magnets were installed so that the N pole and the S pole face each other across the second circular pipe at the left and right positions of the cross section of the circular pipe. The space between the magnet and the magnet housing tube was filled with foamable plastic. One end of the second circular tube of the second magnetic field generator is coupled to the first circular tube 24 of the first magnetic field generator by a connecting pipe having an inner diameter of 8 mm, an outer diameter of 10 mm, and a length of 28 mm, and the other end is coupled by a coupling member. , Coupled to the vent tube 5. When the flow rate of air passing through the vent pipe 5 was 1 m / s, the air passed through the first magnetic field generator in about 5 seconds.
The air sent from the air compressor 4 is adjusted in flow rate by a pressure reducing valve 6 and an air flow rate adjusting valve 7 provided in a vent pipe 5, and a magnetic field space created by three pairs of magnets installed facing each other in the magnetic field generator 3. It was set as the structure which flows in into the electric furnace 9 through.

<Material>
Sepiolite average particle size 1mm (Mizusawa Chemical Co., Ltd .: trade name Ade Plus)
Titanium dioxide dispersion (amorphous and anatase-type mixed titanium dioxide (1% by weight dispersion) representative crystal particle size 10 nm (manufactured by Utopia Planning: trade name Iris series BX01-AB1)

<Manufacturing>
150 ml of titanium dioxide dispersion was added to 100 g of sepiolite and stirred for 5 minutes to absorb the titanium dioxide dispersion into sepiolite, and then spread over a metal net and allowed to dry naturally overnight. Sepiolite carrying titanium dioxide was placed in a ceramic tray and baked in an electric furnace (desktop atmosphere electric furnace TF1200-300, manufactured by Fulltech Co., Ltd.) 9 at 450 ° C. for 30 minutes. The power supply was turned off and left for 15 minutes until the furnace temperature dropped to 300 ° C. 50 g corresponding to half of the sepiolite carrying the baked titanium dioxide was taken out and used as a sample D for a comparative test.
The sepiolite carrying the remaining titanium dioxide was returned to the electric furnace 9, the air compressor 4 was operated, and the air that passed through the magnetic field generator 3 was allowed to flow into the electric furnace 9 at a speed of 0.8 to 1 m per second. For 30 minutes. After firing, the electric furnace 9 was shielded, cooled for 3 hours while flowing air that passed through the magnetic field generator, and then taken out from the electric furnace 9 to obtain a sample A.
The obtained sample A has magnetism, and a movement to approach the magnet was observed when the magnet was brought closer. On the other hand, in sample D, no reaction to the magnet was observed, and no magnetism was observed.

Instead of the amorphous and anatase type mixed titanium dioxide of Example 1, a 1 wt% dispersion of anatase type titanium dioxide (crystal particle diameter 10 nm: trade name Iris Series B01, manufactured by Utopia Planning Co., Ltd.) was used.
<Manufacturing>
100 ml of titanium dioxide dispersion was added to 50 g of sepiolite, stirred for 2 minutes, and then filtered to obtain sepiolite to which the titanium dioxide dispersion was adhered. Sepiolite that has absorbed titanium dioxide that has been naturally dried by spreading on a metal net is stored in a ceramic tray and baked at 450 ° C. for 30 minutes in an electric furnace (desktop atmosphere electric furnace TF1200-300, manufactured by Fulltech Co., Ltd.). . Sepiolite fired after cooling in the electric furnace was excited by polarization of titanium dioxide in the same manner as in Example 1 except that only the first magnetic field generator was used as the magnetic field generator. The obtained carbon dioxide adsorptive decomposition catalyst was designated as Sample B.

<Material>
Zeolite particle size 0.8-1.9 mm (manufactured by Nitto Flour Industry Co., Ltd .: trade name Nitto Zeolite No. 2),
Magnesium oxide average particle size 0.1 mm
Calcium hydroxide particle size 0.075-0.15mm (made by Niimi Chemical Industry Co., Ltd .: trade name, industrial slaked lime selection)
Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: trade name Gohsenol)
Titanium dioxide dispersion (amorphous titanium dioxide (1% by weight dispersion at 250 ° C.)) Particle size <50 nm (manufactured by Utopia Planning Co., Ltd .: trade name Iris series AS01)

<Manufacturing>
Zeolite particles 500 g, magnesium oxide powder 100 g, and calcium hydroxide powder 100 g were put into a 2 L flat bottom pan-type container and stirred for 5 minutes. While mixing the particles and the powder, 125 mL of a 20 wt% aqueous solution of polyvinyl alcohol was added dropwise over 20 minutes, and stirring was further continued for 10 minutes. The point at which the powder of magnesium oxide and calcium hydroxide adhered to the sepiolite particles was regarded as the end point of kneading.
The kneaded and granulated particles are stored in a ceramic tray, heated in an electric furnace (desktop atmosphere electric furnace TF1200-300, manufactured by Fulltech Co., Ltd.) from 500 ° C. to 700 ° C. for 10 minutes, and fired. Thereafter, the battery was shielded and cooled.
The cooled particles were placed in a stainless steel pass mesh tray having a bottom of 0.2 mm mesh and immersed in a titanium dioxide dispersion tank containing 1 wt% titanium dioxide dispersion. After immersion for 2 minutes, the tray was taken out of the titanium dioxide dispersion tank and air-dried overnight.
The air-dried particles were placed in a ceramic tray, and the firing step and the excitation step were performed in the same manner as in Example 2 except that only the second magnetic field generator was used as the magnetic field generator. The carbon dioxide adsorption / decomposition catalyst thus obtained was designated as Sample C.

<Evaluation method>
The evaluation method of the manufactured sample was performed as follows. FIG. 4 shows a partial cross-sectional view of the carbon dioxide measuring device 100 used for the evaluation.
The carbon dioxide measuring device 100 is obtained by processing a 60 L stainless steel open drum container 101 (diameter 796 mm, height 558 mm) into an experimental apparatus, and the top plate 102 of the drum container is freely removable. A hole was made in the center of the top plate 102 and at a position 300 mm from the center, the hole in the center was used for wiring of the ultraviolet fluorescent lamp 103, and the remaining holes were used as concentration sensor insertion holes for the carbon dioxide concentration meter 104. Two 6 W ultraviolet fluorescent lamps 103 are adjacent to each other in the center portion on the inner side of the top plate 102 so as to be lit. The wiring of the ultraviolet fluorescent lamp 103 was drawn from the hole in the center of the top plate 102 and connected to the power outlet 105. The hole through which the wiring was passed was sealed by packing so as not to leak air. A concentration sensor 106 of a carbon dioxide concentration meter (TES-1370, manufactured by Sato Corporation) was inserted into the insertion hole of the concentration sensor, and the main body of the carbon dioxide concentration meter 104 was installed outside the top plate 102. The concentration sensor 106 was installed so as to be positioned at the center of the height of the open drum container 101, and the insertion hole into which the concentration sensor 106 was inserted was sealed with packing so as not to leak air. The edge of the open portion of the body of the open drum container 101 has a body curl structure that is curved to the outside of the body, and is configured to be in close contact with the rising portion provided on the edge of the top plate. The top plate and the body were further fixed with a metal lever band (not shown).

  A sample 108 was spread as evenly and flatly as possible on a plastic circular tray 107 and placed on the bottom surface of the open drum container 101 of the carbon dioxide measuring device 100. The lid was covered with the top plate 102 and sealed tightly with a lever band. The carbon dioxide concentration meter 104 was operated with the ultraviolet fluorescent lamp 103 turned off, the carbon dioxide concentration was measured 10 minutes later, the ultraviolet fluorescent lamp 103 was turned on, and carbon dioxide was measured for 90 minutes at 5-minute intervals. .

<Evaluation test>
Carbon dioxide was measured for 30 g of each sample A, B or C according to the above method.
For sample A, after measuring carbon dioxide for 90 minutes by the above method, the ultraviolet fluorescent lamp was turned off and sample A was left in the carbon dioxide measuring device for 18 hours. The sample was taken out from the measuring apparatus and returned to the carbon dioxide measuring apparatus again, and carbon dioxide was measured for 90 minutes while the ultraviolet fluorescent lamp was turned on in the same procedure as described above.

  For sample D, first place 50 g of sample at the bottom of the drum container, cover with a top plate, and measure carbon dioxide for 90 minutes at 5 minute intervals from 10 minutes without turning on the UV fluorescent lamp. did. Thereafter, one end, the sample D in the drum container was taken out. The same sample was placed in the drum container again, sealed, and after 10 minutes, the carbon dioxide concentration was measured. Then, the ultraviolet fluorescent lamp was turned on, and measurement was performed at 5-minute intervals for 90 minutes.

<Evaluation results>
The result of having measured the adsorption decomposition catalytic effect of the carbon dioxide of sample AC obtained in Examples 1-3 and the sample D obtained as a comparative example was shown in FIGS. Sample A exposed to 500 ° C. in the air atmosphere that passed through the first and second magnetic field generators after supporting the titanium dioxide of the anatase / amorphous mixture on the sepiolite obtained in Example 1 is the light of the ultraviolet fluorescent lamp. Under irradiation, carbon dioxide in the carbon dioxide measuring device was significantly reduced, and 42% of carbon dioxide was reduced after 90 minutes.
Furthermore, after the completion of the first evaluation test, in the second test in which the sample A which was left in the carbon dioxide measuring device for 18 hours was used again and the adsorption decomposition of carbon dioxide was measured under ultraviolet fluorescent lamp irradiation, A greater reduction in carbon dioxide than in the first test and the first was seen, reducing 49% carbon dioxide in 90 minutes.
If the action of reducing the carbon dioxide of sample A is only due to the adsorption action, it is considered that sample A that was allowed to stand in the carbon dioxide measuring device for 18 hours had reached saturation in the carbon dioxide adsorption capacity. The fact that Sample A exhibited a carbon dioxide reduction effect equal to or greater than that in the first test in the second test indicates that the carbon dioxide adsorption-decomposition catalyst of the present invention is not performed only by the adsorption action.
Sample B produced in Example 2 after supporting anatase-type titanium dioxide on sepiolite and excited by air that passed through the magnetic field atmosphere of the first magnetic field generator was irradiated in the carbon dioxide measuring device under light irradiation for 90 minutes. Of 41% of carbon dioxide.
Sample C produced in Example 3 and supported by amorphous titanium dioxide on particles granulated by attaching magnesium oxide and calcium hydroxide to zeolite and excited by air that passed through the magnetic field atmosphere of the second magnetic field generator The carbon dioxide in the carbon dioxide measuring device was reduced by 30% by light irradiation of an ultraviolet fluorescent lamp for 90 minutes.

  Sample D, in which only titanium dioxide was supported on sepiolite, only reduced carbon dioxide by 8.8% in 90 minutes without irradiation with an ultraviolet fluorescent lamp. Even when Sample D was irradiated with an ultraviolet fluorescent lamp, the decrease in carbon dioxide was 9.8%, which was equivalent to the case of non-irradiation of the ultraviolet fluorescent lamp. From this result, it is considered that the decrease in carbon dioxide observed in Sample D was due to adsorption of sepiolite, and the decomposition of carbon dioxide by the photocatalyst did not occur. This result indicates that titanium dioxide needs to be excited in a magnetic field atmosphere in order for the carbon dioxide adsorption / decomposition catalyst of the present invention to act.

  ADVANTAGE OF THE INVENTION According to this invention, the adsorption-decomposition catalyst of the particulate carbon dioxide which can be utilized for general living environments including a building wall surface can be provided. When the carbon dioxide adsorption / decomposition catalyst of the present invention is coated as a surface coating material on the wall surface of a building made of concrete, mortar, or the like, or on the surface layer of a rooftop, for example, by sunlight or other light. The excited photocatalyst can decompose carbon dioxide in the atmosphere into carbon and oxygen. For this reason, the adsorption / decomposition catalyst for carbon dioxide of the present invention is suitable as a surface coating material for building walls and rooftops such as concrete and mortar.

DESCRIPTION OF SYMBOLS 1 Carbon dioxide adsorption decomposition catalyst manufacturing apparatus 2 Container which accommodates the porous mineral which carry | supported titanium dioxide 3 Magnetic field generator 4 Air compressor 5 Vent pipe 6 Pressure reducing valve 7 Air flow control valve 8 Pressure gauge 9 Electric furnace 10 Switch 11 Temperature Adjustment dial 12 Temperature display device 13 Electric furnace control unit 14, 15 Mounting port 21 First magnetic field generator 22 Second magnetic field generator 23 Groove 24 First circular tubes 25a, 25b, 25c, 25d Neodymium magnet 26 First magnet storage unit 27 Second circular tubes 28a, 28b Neodymium magnet 29 Second magnet storage unit 100 Carbon dioxide measuring device 101 Open drum container 102 Top plate 103 Ultraviolet fluorescent lamp 104 Carbon dioxide concentration meter 105 Power outlet 106 Concentration sensor 107 Circular tray 108 Sample

Claims (8)

Titanium dioxide is a photocatalyst carried on a porous minerals containing alkaline earth metals, the respective magnetic flux density and magnet pairs of 2000 gauss to 5000 gauss passed through the magnetic space between disposed opposite air A carbon dioxide adsorption / decomposition catalyst produced by maintaining at 350 ° C. to 550 ° C. for at least 10 minutes in a flowing atmosphere.   2. The carbon dioxide according to claim 1, wherein the porous mineral containing an alkaline earth metal is a porous mineral carrying a compound containing one or more of magnesium, calcium and barium as components. Adsorption cracking catalyst.   The porous mineral containing an alkaline earth metal contains one or more of magnesium, calcium and barium in an amount of 20% to 40% as a total weight percentage in terms of oxide of the alkaline earth metal. The adsorption / decomposition catalyst for carbon dioxide according to claim 1 or 2.   The carbon dioxide adsorptive decomposition catalyst according to claim 1, wherein the porous mineral containing an alkaline earth metal is sepiolite. A method for producing an adsorption cracking catalyst for carbon dioxide according to any one of claims 1 to 4,
An attachment step of attaching the titanium dioxide to a porous mineral containing the alkaline earth metal;
A firing step in which the porous mineral with the titanium dioxide attached is fired at 350 to 550 ° C. to support the titanium dioxide on the porous mineral;
The titanium dioxide supported on the porous mineral, while flowing each magnetic flux density magnets forming a pair of 2000 gauss to 5000 gauss passed through the magnetic space between disposed opposite air, under its atmosphere A method for producing a carbon dioxide adsorption / decomposition catalyst comprising an excitation step of holding at 350 ° C. to 550 ° C. for at least 10 minutes. Said excitation step, the said titanium dioxide supported on porous mineral, while flowing each magnetic flux density magnets forming a pair of 2000 gauss to 5000 gauss passed through the magnetic space between disposed opposite air 6. The step of holding at 350 ° C. to 550 ° C. in the atmosphere for at least 10 minutes, and subsequently cooling to at least 100 ° C. while ventilating the air that has passed through the magnetic field space. Of carbon dioxide adsorptive decomposition catalyst. The porous mineral containing the alkaline earth metal is
A granulation step of granulating by mixing the decomposition temperature with 450 to 800 ° C. in an organic binder and a compound with the porous minerals containing the alkaline earth metal as a component,
6. The method according to claim 5, wherein the kneaded granulated product is produced by a method comprising a granulation firing step in which the kneaded granulated product is fired at a temperature equal to or higher than the decomposition temperature of the organic binder in an air atmosphere. A method for producing an adsorption cracking catalyst. The decomposition temperature is 450 to 800 ° C. in an organic binder, a polyvinyl alcohol, is used as the aqueous solution of polyvinyl alcohol 10 to 30% strength by weight, based on the weight 1 of the porous mineral, the weight of the polyvinyl alcohol 0 carbon dioxide production method of adsorptive decomposition catalyst according to claim 7, characterized in that 0.01 to 0.08.

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