WO2006054718A1

WO2006054718A1 - Zeolitic composition and, utilizing the same, porous firing product and building material

Info

Publication number: WO2006054718A1
Application number: PCT/JP2005/021286
Authority: WO
Inventors: Takenori Masada; Masahiko Matsukata
Original assignee: Takenori Masada; Masahiko Matsukata
Priority date: 2004-11-19
Filing date: 2005-11-18
Publication date: 2006-05-26
Also published as: JPWO2006054718A1

Abstract

A zeolitic composition that excels in all of plasticity before firing and strength and porosity after firing; and a porous firing product obtained by firing of the composition. There is provided a porous firing product characterized in that it is obtained by firing of a zeolitic composition comprising zeolite, a plastic clay and an alkali (alkaline earth) metal compound.

Description

Specification

Zeolite-containing composition, and porous fired body and building material using the same

The present invention relates to a zeolite-containing composition excellent in mixture plasticity before firing, strength and porosity after firing, and uses such as a porous fired body and a building material using the same.

Background art

Zeolite is a generic term for microporous aluminosilicate crystals, and exhibits excellent molecular adsorption, sieving, ion exchange, and catalysis due to the negative charge possessed by micropores and their frameworks, and therefore an adsorbent. It is widely used as an environmental purification material and catalyst, etc.

[0003] A material with vitality to the properties of zeolite is usually a fired body obtained by molding and firing using a binder. There are many other conventional techniques related to such a sintered body, for example, Japanese Patent Application Laid-Open No. 2-160616, and many of them are used as adsorbents and catalysts. In order for the sintered body to exhibit excellent functions as an adsorbent and a catalyst, it has not only excellent porosity, such as specific surface area and porosity, but also has a certain strength or more in practical use. And at the same time, it is necessary to have a degree of freedom in molding that can be molded into a suitable shape according to the application.

If it is attempted to improve the porosity of the fired body by using a large amount of zeolite having excellent porosity as the main component while trying to improve the porosity of the fired body, the blending amount of the binder relatively decreases, and the fired body The strength of the On the contrary, the porosity of the sintered body can be easily improved by increasing the blending amount of NOINDA. Numerous studies have been conducted so far to improve both properties (for example, Japanese Patent Laid-Open No. 11-246282), but as described above, basically the porosity of the fired body and It is very difficult to improve the strength together. Furthermore, if the content of the zeolite as the main component is 50% by weight or more, usually, the plasticity (the degree of freedom of molding), the dispersibility and the fluidity of the raw material mixture before firing are significantly lost. Organic vine to improve its plasticity, dispersibility and fluidity Although it is sufficient to blend the daters, the cost of producing the fired body is increased, the strength is lowered, and there is a problem that the sintered body remains in the inside after firing to reduce the porosity. This improvement is the most important issue in molding of zeolite-containing fired bodies, as it is generally very difficult to secure plasticity.

From the above facts, it is extremely important to produce a zeolite-containing composition that satisfies all of plasticity before firing and strength and porosity after firing at a high level, and a fired body obtained by firing the composition. It is difficult.

Disclosure of the invention

In view of the above, according to the present invention, there is provided a zeolite-containing composition having excellent plasticity before firing, ie, high strength after molding and a high degree of freedom after firing, and a fired composition obtained by firing the composition. Intended to provide the body.

The inventors of the present invention have so far manufactured a fired body having relatively excellent strength and porosity by examining various combinations of zeolite and binder, but carefully select zeolite and a known binder. It is thought that it is impossible to obtain a zeolite-containing composition that satisfies all the above-mentioned problems, and a fired product thereof alone, and as a result of intensive studies, Zeolite is the main component and a specific binder is the essential component. By firing a zeolitic-containing composition containing the same within a predetermined temperature range, a zeolitic-containing composition and a fired body thereof which satisfy all of the above characteristics simultaneously at a high level and a level can be successfully produced, and the present invention is achieved. It came to

That is, the present invention is characterized by the matters described in the following (1) to (27).

(1) A zeolite-containing composition comprising 50 to 90% by weight of Zeolite, 5 to 49.9% by weight of a plastic clay, and 0.1 to 30% by weight of an alkaline (earth) metal compound.

(2) The zeolite-containing composition according to the above (1), wherein the alkali (earth) metal compound is thermally decomposed at 800 ° C. or less.

[0011] (3) The above-mentioned (1) or (1) or (2), wherein the plastic clay is one or more selected from the group consisting of woodblock clay, lepidome clay, kaolin, shale clay, and pottery. (2) The zeolite-containing composition according to the above.

(4) The plastic clay has an average particle diameter D of not more than the average particle diameter D of the zeolite. And the particle size ratio of the effective diameter D or less of the zeolite is 15% by weight or more.

Ten

The zeolite-containing composition according to any one of the above (1) to (3), which is characterized by the above.

(5) The alkali (earth) metal compound is an alkali (earth) metal carbonate, an alkali (earth) metal hydroxide, an alkali (earth) metal nitrate, and an alkali (earth) metal. The zeolite-containing composition according to any one of the above (1) to (4), wherein the group power of acetate is also one or two or more selected.

(6) 1 type selected from the group consisting of lithium carbonate, magnesium carbonate, calcium carbonate, basic magnesium carbonate, magnesite, limestone, and dolomite as the alkali (earth metal) metal carbonate. Or a zeolite-containing composition according to the above (5), which is a mixture or a mixture of two or more thereof.

(7) The zeolite according to (6) above, characterized in that the calcium carbonate, the limestone, and the dolomite are used as a mixture or a mixture with other alkali (earth) metal compounds. Containing composition.

(8) A group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and brucite as the alkali (earth metal) hydroxide. The zeolite-containing composition according to the above (5), which is a mixture or mixture of one or more selected or a mixture of two or more.

(9) The above alkaline (earth) metal nitrate is characterized in that it is a mixture of at least one selected from one or more selected from potassium nitrate and a group also having sodium nitrate power, or mixed milled matter. The zeolite-containing composition according to (5).

(10) The zeolite has a group power which is also selected from copper ion, silver ion and zinc ion power. One or two or more metal ions are supported on the zeolite. 9)

V, a zeolite-containing composition according to any of the preceding claims.

(11) The zeolite-containing composition according to any one of the above (1) to (10), which has a measured value of Yamanaka-type soil hardness meter in a plastic state of 14 or less.

(12) A porous fired body obtained by firing the zeolite-containing composition according to any one of the above (1) to (11) at 500 to 800 ° C.

(13) A porosity is 30% or more, and a bending strength is I MPa or more. (12) above.

(14) The specific surface area of the zeolite component contained in the fired body is at least 0.8 times the specific surface area of the zeolite component contained in the zeolite-containing composition.

Or (13).

(15) The photocatalyst particle is supported on the surface, or the photocatalyst particle is contained as a composition, The porous according to any one of the above (12) to (14), characterized in that Fired body.

(16) A Zeolite-containing composition comprising Zeolite, plastic clay, and an alkali (earth) metal compound, wherein the measured value of Yamanaka-type soil hardness meter in the plastic state is 14 or less.

And zeolite having a porosity after firing of 30% or more, a flexural strength of IMPa or more, and a specific surface area of the zeolite component of at least 0.8 times the specific surface area of the zeolite component before firing. Composition.

(17) The zeolite-containing composition as described in (16) above, wherein the content of the zeolite is 50 to 90% by weight.

(18) The plastic clay has an average particle size D which is less than or equal to the average particle size D of the zeolite.

The particle diameter ratio of 50 50 and the effective diameter D or less of the zeolite is 15% by weight or more

Ten

The zeolite-containing composition according to the above (16) or (17), characterized in that

(19) A porous fired body obtained by firing the zeolite-containing composition according to any one of the above (16) to (18) at 500 to 800 ° C.

(20) The porous fired body according to the above (19), wherein photocatalyst particles are supported on the surface, or photocatalyst particles are contained as a composition.

(21) The porous fired body according to any one of the above (12) to (15) or the above (19) or

A coated article characterized by being coated by the porous fired body according to (20).

(22) The zeolite-containing composition according to any one of (1) to (11) above, or the above (16)

A building material characterized in that the zeolite-containing composition according to any one of (1) to (18) is formed and processed by extrusion molding, press molding, or entanglement molding, and fired at 500 to 800 ° C. .

(23) The building material according to (22), which has a porosity of 30% or more and a bending strength of 3 MPa or more. (24) The building material according to (22) or (23) above, which has a volume standard water absorption of 35% or more and a flexural strength of 3 MPa or more.

(25) A zeolite-containing composition containing 50% or more of zeolite is molded, and fired at 500 to 800 ° C., and has a flexural strength of 3 MPa or more and a porosity of 30% or more or a volume standard. A building material characterized by having a water absorption rate of 35% or more.

(26) The building material according to any one of (22) to (25), wherein photocatalyst particles are supported on the surface, or photocatalyst particles are contained as a composition.

(27) A binder to be added to a porous fired body obtained by firing a porous body, the average particle diameter D being less than or equal to the average particle diameter D of the porous body, and the effective diameter of the porous body D or more

A softer comprising: a plasticizable clay having a particle size ratio of not less than 50 50 10 15 wt% or more; and an alkali (earth) metal compound.

In the prior art, in order to obtain a zeolite-containing composition excellent in all of the plasticity before calcination and the strength and porosity after calcination and the calcined product thereof, the composition of the composition was made to be the present invention. The examples go beyond, so it can be said that the present invention is a novel and very innovative invention. According to the present invention, it is possible to provide a porous fired body having excellent plasticity and strength despite the high zeolitic content. In addition, it is possible to actively use the zeolite-containing composition of the present invention and the sintered body thereof for new application fields where application is difficult because the above properties are simultaneously required at high levels. Become.

This application is accompanied by a priority claim based on the Japanese patent applications filed by the same applicant, namely, 2004-335504 (filing date: November 19, 2004), The specification of is incorporated here for reference.

Brief description of the drawings

FIG. 1 is a schematic view of a deodorizing evaluation device.

[Fig. 2] Fig. 2 is a graph showing the temporal change of ammonia concentration in the deodorization evaluation.

[FIG. 3] FIG. 3 is a graph showing the time-dependent change of acetaldehyde concentration in the deodorization evaluation.

[Fig. 4] Fig. 4 is a graph showing temporal change of acetic acid concentration in deodorization evaluation [FIG. 5] FIG. 5 is a particle size distribution curve of the lepidopteran clay and zeolite used in the present example. Best mode for carrying out the invention

The zeolite-containing composition of the present invention comprises zeolite, a plastic clay and an alkali (earth) metal compound as essential components. In the present invention, the term "alkali (earth) metal" means an alkali metal (Li, Na, K or the like) or an alkaline earth metal (Mg, Ca, Sr, Ba or the like).

[0040] Examples of the above-mentioned zeolite include the characteristics of natural zeolite such as clinopti mouth light, mordenite, A-type, X-type, Y-type, USY-type (ultrastable Y-type), silicalite, ZSM-5, and zeolite. Porous materials having silica, silica such as coal ash, wastes containing aluminum components, and synthetic zeolites such as A-type, X-type and Y-type synthesized from recycled raw materials, and are not particularly limited, but USY-type or silica It is preferable to use hydrophobic or natural zeolites such as lights because they tend to exert particularly large effects. However, it is preferable to use natural zeolite and synthetic zeolite synthesized from waste and the like from the viewpoint of cost in applications of mass consumption such as building materials and agricultural materials. The term "hydrophobic zeolite" generally refers to a material which does not have high water adsorption properties like hydrophilic zeolite and has a relatively high Si content in the zeolite component. When natural zeolite is used, it is preferable to use one having a maximum particle size of 150 m or less from the viewpoint of moldability and plasticity, and it is more preferable to use one having 100 m or less. . Further, examples of the porous body having the characteristics of the above-mentioned zeolite include a mesoporous body (mesoporous material) having a pore diameter of 2 to 50 nm and having a very narrow pore size distribution. More specifically, there are FS M-16 and MCM 41 etc.

Further, the blending amount of zeolite is not particularly limited, but in order to obtain a sintered body having excellent adsorption performance, ion exchange performance, and porosity, 50 to 90 with respect to the whole zeolite-containing composition. It is more preferable to mix | blend 60 to 80 weight% which is preferable to mix | blend weight%. In the present invention, the raw material slurry has excellent plasticity because the plastic clay and the binder containing the alkaline (earth) metal compound are further blended even when the composition contains the zeolite in an amount of more than 50% by weight. In addition, the material strength and porosity after firing can be provided. It becomes possible.

The plastic clay mainly includes clay minerals such as kaolinite, halloysite, sericite and montmorillonite in its composition. Such plastic clays have been used as clay materials for pottery for the past hundreds of years in the Tokai region such as Aichi, Gifu, Mie, particularly in the Tono region of Gifu Prefecture and the Seto Region of Aichi Prefecture. It has excellent formability, porosity and low temperature sintering. The plastic clay which can be used in the present invention is not particularly limited, but it is not particularly limited, but, for example, woodblock clay, lepidopteran clay, kaolin, shale clay, earthenware clay, red earth, blue earth, china stone, bentonite, wax stone, sepiolite, Catapulgite and the like can be mentioned, and these can be used alone or in combination of two or more. In the present invention, it is more preferable to use a moss clay which is preferred to use a woodblock clay, a moss clay, a kaolin, a shale clay, or a potash. The plastic clay is considered to be able to be fully understood by those skilled in the art from the above description, but more specifically, “Ceramics Engineering Japan, Ed. (2nd edition) [Application] Please refer to pages 581 to 585 of “Techhohodo Publishing Co., Ltd. Publication”.

Further, the above-mentioned plastic clay is preferably one whose particle size has been adjusted by a water drop. The average particle diameter D is about the same as the average particle diameter of the zeolite to be formed or the zeolite

50

It is more preferable that the average particle diameter D is less than or equal to

The 50 10 diameter ratio is more preferably 15% by weight or more. The use of a plastic clay which satisfies such conditions has an important meaning in improving the particle size distribution and the forming density of the whole composition, and in improving the strength of the fired body. In particular, when using industrial zeolite of substantially uniform diameter, in which the zeolite itself is distributed in a narrow particle size range, plasticity in which the particle diameter below the zeolite effective diameter D governing the voids in the composition is 15% by weight or more. Combine clay

Ten

Thus, the strength of the fired body is greatly improved. In the present invention, the average particle size is

The effective diameter D and the effective diameter D are respectively 5% by mass passing through the sieve with respect to 100% by weight of the sample.

50 10

It shows that 0 wt% and 10 wt% are less than the particle size.

Further, the blending amount of the plastic clay is more preferably 10 to 48% by weight, which is preferably blended in an amount of 5 to 49.9% by weight based on the whole of the zeolite containing composition.

The above-mentioned alkali (earth) metal compound is not particularly limited. Earths) Metal carbonates, hydroxides, hydrogencarbonates, acetates, sulfates, nitrates and the like may be mentioned, and they may be natural mineral raw materials comprising these alkali (earth) metal compounds. As alkali metal (earth) metal compounds, preferably, alkali (earth) metal carbonates, alkali (earth) metal hydroxides, alkali (earth) metal nitrates, and alkali (earth) metal acetates One or two or more selected.

As the above-mentioned alkali (earth) metal carbonate, lithium carbonate, magnesium carbonate, calcium carbonate, basic magnesium carbonate, magnesite, limestone, and dolomite are selected. One or more selected As the above-mentioned alkali (earths) metal hydroxides which are preferably mixtures of lithium, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and magnesium hydroxide And a brute force group selected from the group consisting of potassium nitrate, sodium nitrate, and mixtures thereof as the above alkali (earth) metal nitrate salt which is preferably a mixture of one or more selected Force is also preferred to be selected one or more!

[0047] In the case where the mixture of alkali (earth) metal compounds can be a grinding mixture that has been subjected to mechanical grinding processing and if the baking temperature of the composition can be set low by grinding There is Furthermore, the above calcium carbonate, limestone, dolomite is a mixture of calcium carbonate, limestone, or dolomite with magnesium carbonate or magnesite, which is preferably used in combination with other alkali (earth) metal compounds. Is more preferred.

Further, the fired body of the present invention is formed by firing the zeolite-containing composition of the present invention, but it is pyrolyzed at the time of firing to form a gas such as carbon dioxide or an acid oxide. The strength and porosity of the fired body tend to be improved by using an alkali (earth) metal compound which is generated. Therefore, it is preferable to select as the above-mentioned alkali (earth) metal compound, one which thermally decomposes below the actual calcination temperature. For example, when the firing temperature is 700.degree. C., it is preferable to use an alkali (earth) metal compound which thermally decomposes at a temperature of 700.degree. C. or less. In addition, since it is preferable to bake the zeolite-containing composition of the present invention at 500 to 800 ° C. to produce the fired body of the present invention as described later, basically, the alkali (earth) is basically used. It is preferable to select a metal compound that thermally decomposes at 800 ° C. or less. However, when the thermal decomposition temperature of the composition alone is higher than 800 ° C., it is 800 ° C. due to the combination with other components in the force composition. Alkali (earth) metal compounds that fall below 10% shall be treated as "thermal decomposition at 800 ° C or lower" when such a combination is made. Specifically, calcium carbonate, for example, has a thermal decomposition temperature of about 900 ° C. when it contains a silica component and other alkali (earth) metal compounds in its force composition, and that temperature Falls below 800 ° C.

Further, the above alkali metal (earth) compound is more preferably blended in an amount of 0.1 to 30% by weight to the whole of the zeolite-containing composition, more preferably 1 to 20% by weight. If the amount of the alkali (earth) metal compound is less than 0.1% by weight, the effect of the compounding tends to be insufficient, and if it exceeds 30% by weight, the proportion of zeolite or plastic clay is It tends to be lowered, and the properties tend to be biased to one of plasticity, strength and porosity, making it difficult to improve all the properties. In addition, the pH of the zeolite-containing composition of the present invention is inclined to the alkali side by the addition of an alkali metal (earth) complex, and the pH at this time is 11.5 or less. More preferably, it is 11 or less. If the fired body is produced at a pH exceeding 11.5, the properties of the zeolite in the composition may be impaired. The pH can be adjusted, for example, by using an inorganic acid compound (eg, aluminum sulfate, iron sulfate, etc.) containing an inorganic acid (eg, sulfuric acid, hydrochloric acid, nitric acid) to suppress the amount of the alkali metal (earth) complex. It is possible to carry out by a method such as blending a metal sulfate compound, hydrochloric acid complex, etc.).

The zeolite-containing composition of the present invention can obtain good plasticity by itself because it uses a binder containing the above-described plasticizable clay and an alkali (earth) metal compound. In addition, known dispersants and shaping aids such as phosphorus condensed salts such as sodium tripolyphosphate, sodium lignin sulfonate, cellulose derivative complex, curdlan, starch, polybutyl alcohol, bentonite, water glass, etc. However, this makes it possible to further improve its plasticity depending on the kind and combination of essential components.

Further, a binder containing the above-mentioned plastic clay and an alkali (earth) metal compound can impart good plasticity and excellent low-temperature sinterability to a sintered body material, and therefore other than zeolite It is also suitable as a binder material for forming a porous body.

In the zeolite-containing composition of the present invention, as components other than the above, for example, chromium And oxides of transition metals such as manganese, complex and nickel, antimony oxides, iron oxide (iron oxide), cupric oxide and other coloring materials, the properties of the fired body such as porosity, plasticity and strength are impaired. You may add, in the range which is not.

[0053] The porous fired body of the present invention is prepared by adjusting a slurry obtained by kneading the zeoliite-containing composition of the present invention having excellent plasticity, dispersibility, and fluidity with a solvent such as water to a desired viscosity, It can be obtained by molding by a molding method and baking.

The above-mentioned molding method is not particularly limited, but it is possible to carry out, for example, known molding techniques in sintered body production such as insert molding, press molding, extrusion molding, mechanical roller molding, spray drying and the like. It is possible to select an appropriate molding method according to the application etc. From the viewpoint that the strength of the molded body can be increased, it is particularly preferable that extrusion molding is preferably press molding, extrusion molding, or roll press molding. Moreover, it is preferable to adjust the viscosity (water content) of the above-mentioned slurry depending on the forming method to be applied.

The ceramic raw material mixture slurry changes its bonding state (consistency) according to the water content, and turns into various states of solid, semi-solid, plastic, and liquid. Therefore, the moisture content and consistency of the raw material mixture are appropriately determined according to the forming processing means to be applied in the forming processing process of the ceramic raw material mixture, and the flowability, dispersibility, plasticity, etc. are secured. It is extremely important.

For example, pellet-like molded articles for water treatment and gas treatment that are generally used as molded articles of zeolite-containing compositions, molded articles of honeycombs, etc., are generally from the viewpoint of molding processability. It is manufactured by a molding method, and in this case, it is desirable to adjust its water content so that the raw material mixture is in a plastic state between the plastic limit and the liquid limit. On the other hand, zeolite-containing compositions tend to narrow the range of water content generally exhibiting a plastic state and to have poor plasticity in a plastic state, and this tendency is particularly pronounced by containing Zeolite containing at least 50% by weight of zeolite. It is remarkable in the composition. In the prior art, it is widely used to add an additive such as an organic binder in order to improve this plasticity. As a result, the manufacturing cost of the fired body increases, and the strength and the porosity decrease. As mentioned above, another problem arises that Also, long time to burn off the organic ingredients Firing is required, which causes the problem of consuming a large amount of energy. Therefore, in the present invention, a binder containing plastic clay and an alkaline (earth) metal compound is used as a binder, and as a result, excellent plasticity is exhibited without using an organic binder or the like, and a sintered body excellent also. It has become possible to provide a zeolite-containing composition which also exhibits strength and porosity. The zeolite-containing composition of the present invention can be easily brought into a plastic state by adding water and kneading, and the appropriate amount of water differs depending on the type of zeolite contained, the type of binder raw material, the particle diameter and the like. In addition, with regard to the goodness or badness of plasticity in the plastic state, the measured value with a Yamanaka type soil hardness tester is one indicator, and when this measured value is 14 or less, excellent extrusion moldability can be secured. preferable.

Also, for example, in the case of using a plunging method suitable for obtaining a complex-shaped molded product, the water content of the above-mentioned slurry is relatively compounded (for example, 100 parts by weight of solid content) (60 to 80 parts by weight of water), and it is preferable to make it liquid and to give fluidity. Also, when using a press forming method suitable for obtaining a tile or a flat plate-shaped product, It is preferable to adjust the water content of water to a relatively low level to make it semisolid.

Thus, the zeolite-containing composition slurry of the present invention appropriately determines its water content and consistency according to the type of zeolite used, the raw material composition, the particle size of each component, the forming method to be applied, etc. And can be molded.

Further, the shape and size of the zeolite-containing yarn or composite of the present invention after molding can be processed into a desired shape and size depending on the application, and is not particularly limited. It can be processed into any shape such as a cam shape, a columnar shape, a plate shape or a spherical shape.

[0060] In addition, the above-mentioned slurry has the same fluidity as or more than that in the case of the above-mentioned lead molding.

(For example, in the case where about 60 to 120 parts by weight of water is applied to 100 parts by weight of solid content), it is applied to the object to be coated and fired to form the porous material of the present invention on the surface to be coated. A fired body film can be formed, which makes it possible to provide the properties of the porous fired body of the present invention at low cost to a wide variety of objects to be coated. Since the slurry used at this time is extremely excellent in fluidity and dispersibility, the viscosity can be freely prepared according to the application target and workability by properly adjusting the amount of the solvent to be blended. it can. As a method of applying this slurry, for example, the diving method, the spray method, the mouth A known means of application can be applied, such as application using a single brush or a brush, or using a coating apparatus. Furthermore, particularly high adhesion can be obtained when the object to be coated is a porous material such as pumice, perlite, and the fired body of the present invention. Furthermore, by impregnating the above-mentioned slurry with a porous body composed of an inorganic material having a heat resistance of about 800 ° C., and adhering the zeolite-containing composition of the present invention to this surface and inside, the pressure loss of fluid is small. It is possible to obtain a filter material suitable for air purification and water purification applications.

[0061] The temperature for firing is not particularly limited as long as it is a temperature at which the porosity can be sufficiently maintained without amorphizing the zeolite in the composition, but it is 800 ° C or less Is preferred. Furthermore, in order to improve the strength of the fired body, the range of 500 to 800 ° C. is preferable. Depending on the type of zeolite used, the range of 500 to 700 ° C. is preferable. For example, in the case of using a high silica type zeolite such as silicalite, the range of 500 to 800 ° C. is preferable. In the case of using a low silica type zeolite such as A type or X type, 500 to 500 It is preferable to set it as the range of 700 degreeC. In addition, it is preferable to appropriately determine the firing pattern such as the temperature rise rate and the peak temperature (firing temperature) holding time, because the optimum value varies depending on the type of essential components used, the composition, the characteristics of the intended fired body, etc. .

The porous fired body of the present invention obtained as described above preferably has a porosity of 30% or more, preferably 35% or more. In addition, its bending strength is preferably 2 MPa or more, which is preferably 1 MPa or more, and particularly preferably 3 MPa or more. Furthermore, the specific surface area of the zeolite component contained in the porous fired body of the present invention is preferably at least 0.8 times the specific surface area of the zeolite component contained in the zeolite-containing composition of the present invention. It is more preferable that it is 9 times or more. In the present invention, the “specific surface area of the zeolite component contained in the zeolite-containing composition” or the “specific surface area of the zeolite component contained in the porous fired body” means the zeolite itself contained therein In the specific surface area of the composition or its calcined product, the specific surface area of the portion contributed by zeolite (equivalent to zeolite) refers to the specific surface area of the zeolite alone, It changes depending on the content, baking conditions, binder species and their content. More specifically, the specific surface area of the zeolite component contained in the porous sintered body If the specific surface area of the binder component used is negligibly small compared to the specific surface area of the whole composition! (For example, the specific surface area of the binder component is about 3% or less of the specific surface area of the whole composition) Can be regarded as approximately the same as the specific surface area of the porous sintered body itself. On the other hand, when a plastic clay having a relatively large specific surface area such as sepiolite is used as the binder component, for example, only the binder component is separately fired under the same conditions as the porous sintered body, and the specific surface area is The specific surface area of the porous sintered body and the specific surface area of the porous sintered body can be approximately calculated. In addition, the specific surface area of the zeolite component contained in the zeolite-containing composition is expressed by the following formula

(Specific surface area of single zeolite) X (content of zeolite)

It can be calculated by Since the porous fired body of the present invention uses an inorganic binder composition and is further fired at a temperature at which the zeolite does not become amorphous, the characteristics of the contained zeolite can be sufficiently exhibited. Its porosity can be maintained at a high level. The specific surface value of the sintered body of the present invention is preferably 200 m ² Zg or more when synthetic zeolite is used. The sintered body described in the preferred and characteristic value range described above can be particularly suitably used as an adsorbent, a heat insulating material, a hygroscopic material, a humidity control material, etc. in civil engineering and construction fields where relatively high strength is required. .

The porous fired body of the present invention can be made into a fine powder fired body by a method such as spray drying or by crushing after firing, and this fine powder is dispersed together with a solvent such as alcohol or water or a binder. Can be used as a coating material. Since this coating material is obtained by dispersing the already fired one, it differs from the above-mentioned film formation by the mixture slurry before firing, and it is sufficient to heat the coated material which does not need to be fired after application. The porous fired body film of the present invention can be formed even on a low application target. On the other hand, with regard to the strength of the film, the above-mentioned fired body film formed by the mixture slurry before baking which is fired after application is superior.

The porous fired body of the present invention may further contain a functional material such as photocatalyst particles supported on the surface thereof, or a functional material as a composition. Of course, the functional substance may be supported on the surface and may be included in the composition. Functional thing By combining the qualities, it is possible to obtain a porous sintered body having a desired function in addition to excellent plasticity, porosity and strength. Examples of the functional substance include, in addition to photocatalysts, platinum, noridium, rhodium and the like which are catalyst substances used for exhaust gas purification.

When a photocatalytic function is given as a functional substance, the substance adsorbed by the porous sintered body is decomposed by the photocatalytic function, and the adsorptive capacity of the sintered body can be regenerated, so that the porous material of the present invention The quality fired body can be used for applications such as anti-soiling and anti-bacterial, and furthermore, it is possible to maintain the adsorption effect of VOC and odorous substances for a long time.

The photocatalytic particles are not particularly limited! Examples thereof include metal oxide semiconductors such as titanium oxide, zinc oxide, zinc oxide, tungsten oxide and the like, Two or more can be used simultaneously. Among them, it is preferable to use titanium oxide. In addition, those having a primary particle size of 0.01 to 0.1.m of titanium oxide are preferable because they exhibit excellent photocatalytic activity. As a method for supporting the photocatalyst particles on the surface of the porous fired body of the present invention, for example, a solution containing the photocatalyst particles or a precursor thereof (for example, titanium alkoxide, tetrabasic titanium, etc.) is used. It may be applied by a known method such as coating on the surface of the zeolite-containing composition of the present invention or the porous fired body of the present invention by spray method, deviting method or the like, drying, or drying after drying. The amount of photocatalyst particles supported on the surface of the porous sintered body is not particularly limited as long as the sintered body after supporting the photocatalyst particles exhibits photocatalytic activity which does not impair the porosity. Moreover, when mix | blending photocatalyst particle | grains as a composition, the compounding quantity will not be specifically limited if it is a range which shows a photocatalytic activity, without reducing the various characteristics of a porous sintered body.

In the zeolite according to the present invention, metal ions such as copper ions, silver ions and zinc ions may be supported by one or more kinds. By using zeolite to which metal ions are supported, it is possible to impart excellent antibacterial properties to the porous fired body of the present invention.

In addition to the photocatalytic properties and antibacterial properties described above, the porous fired body of the present invention is used in various applications in which the adsorption properties, ion exchange properties, catalytic properties, etc. that the zeolite normally has are activated. can do. For example, deodorizers, VOCs, etc., are used as vital applications of adsorption characteristics. Adsorbents for toxic substances such as quality and dioxins, hygroscopic materials, moisture control materials, water holding materials, freshness holding materials for fresh foods, waste oil treatment materials, microbial carriers, filter media for water treatment, additives for fertilizers and feeds, air purification For example, water purification materials for removing ammonia, heavy metals, radionuclide cations, etc., soil conditioners, water softeners for hard water, and the like. Examples of applications that make use of the catalytic properties include petroleum refining, purification of exhaust gases from internal combustion engines, decomposition and removal of organic chlorine compounds, and conversion of waste plastics into oils.

Further, the porous fired body of the present invention is excellent in porosity, strength, plasticity, water absorption and the like, and therefore, the application in which these characteristics are vitalized, for example, humidity control, deodorization, VOC removal, etc. Indoor environment Improving materials, building materials with water holding function and gradual release function of moisture, water retaining materials with high water retention and fertility, suitable for greening of roofs and deserts, having antibacterial function It is suitable as a material in the civil engineering and construction field, such as building materials, piping materials, and construction materials with water purification functions. Furthermore, it is applied to fields used under relatively severe conditions such as the aerospace field and the nuclear field. Is also suitable.

The building material of the present invention can be produced by molding and firing the zeolite-containing composition of the present invention, but in order to enhance its strength, the zeolite-containing composition of the present invention is extruded. It is preferable to manufacture by processing by molding, press molding, or core molding, and baking this at 500 to 800 ° C. The building material thus obtained preferably has a bending strength of 3 MPa or more and a porosity of 30% or more.

Further, for example, by using the building material of the present invention, which is particularly excellent in water retention function and water gradual release function, as an outer wall of a building, a paving block, a roofing material, etc., artificial waste heat has increased recently. The loss of natural space can significantly contribute to the suppression of the heat island phenomenon, which becomes a problem in large cities. The “JASS 7 M101 Interlocking Block Quality Standard” in the “Architectural Construction Standard Specification” of the Architectural Institute of Japan has set the flexural strength of the permeable interlocking block at 30 kgf / cm ³ or more. Therefore, such a water-retaining construction material preferably has a flexural strength of 3 MPa or more and a volume standard water absorption of 35% or more. The porous sintered body of the present invention exhibits high water absorption and absorbs water, since the zeolite is retained inside without damage. Since it is strongly adsorbed to the zeolite pores, it exhibits excellent water retention.

Thus, the zeolite-containing composition of the present invention and the porous fired body obtained by firing the same can be used by flexibly changing the application method for a wide variety of fields and applications. It is.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

Example

[0074] (Production and evaluation of fired body)

Zeolite, plastic clay, and alkali (earth) metal compounds are blended as shown in Table 1 below, 100 to 150 parts by weight of water is added to 100 parts by weight of solid content, and the mixture is kneaded for 2 to 4 hours with a pot mill. After making a mud, it is dewatered until it becomes plastic on a gypsum board (general water content is 30 to 35%), and filled in a plaster mold (cross section 10 mm, thickness 10 mm, length 70 mm), After dehydration for about 10 minutes, it was demolded and dried in a room for 1 day. Next, firing was performed under predetermined firing conditions to produce fired bodies of Examples 1 to 21.

[table 1]

Firing conditions Plasticity clay Zeolite Alkali (earth) metal compound Example Lice clay HISI V-300 O ⁵⁸² Magnesite ^ ³

1 28 t% 70 t% 2 w t%

Example Leiome clay H I S I V-3000 magnesite calcium carbonate

2 20 wt% 70 wt% 3 wt% 7 wt% Example square clay H I S I V-3000 magnesite dolomai

3 20 wt% 70 wt% 2 wt% 8 wt% Example lepidopteran clay HISI V-3000 Magnesium hydroxide lithium carbonate 4 26 wt% 70 wt% 1 wt% 3 wt% Example leopard clay HISI V- 3000 magnesite calcium carbonate 5 23 wt% 70 wt% 5t% 2 wt% Example lepidopteran clay HISI V-3000 magnesite lithium carbonate 650 wt% 5 wt% 70 wt% 10 wt% 5 wt%

5 hours Carbonation Carbonation Example Leiome clay H I S I V-3000 Magnesite

Calcium chiu 7 1 5 w t% 70 w t% 5 w t%

5 w t% 5 w t% Minoh clay clay hydroxylation example H I S I V- 3000 magnesite hydroxide potassium

24. 8 Sodium

8 70 w t% 5 w t% 0. 1 w t% w t% 0. 1 w t%

Example Leiome clay H I S I V- 3000 Sodium borate

9 25 w t% 70 w t% 5 w t%

Example lepidopteran clay HISI V-3000 potassium nitrate magnesite 10 23 t% 70 wt% 5 wt% 2 wt% Example lepidopteran clay HISI V-3000 basic magnesium carbonate 1 1 28 wt% 70 wt% 2 wt%

Example 蛙粘土粘土マグネ magnesite

1 2 1 5 w t% 80 w t% 5 w t%

Example Lectite clay monoredenite magnesite lithium carbonate 1 3 600 3⁄4 10 wt% 80 wt% 2 t% 8 wt% Example 5 h gridded soil redenite magnesite dolomite 1 4 0 t% 80 wt% 3 wt% 7 wt% Example Lepidoptera clay clinopetite mouth light ⁶ magnesite

1 5 9 w t% 90 w t% 1 w t%

Example 60 OX: Lepidoptera clay synthesis X type Zeolite ⁷ magnesite

1 6 1 hour 49 wt% 50 wt% 1 wt% Example Bindoku clay clay synthesis type X zeolite Magnesite

1 7 2 9 7 0 1,

Example Leiome clay synthesis X-type zeolite lithium carbonate

1 8 2 7 w 7 0 w t% 3 ^ t%

Example Leiothyite clay synthesis type X zeolite calcium hydroxide

1 9 2 7 w 7 0 w t% 3 -v

Example Bindoku clay clay synthesis type X zeolite light lithium hydroxide

2 0 2 7 w 7 0 w t% 3, v t%

Example Bindoku clay Synthesis X-type Zeolite Wright Magnesite Lithium carbonate

2 1 2 5 w t% 7 0 w t% 2 t% 3 w

※ 1 Made of small ceramic, special grade water-hikedame clay, average particle size less than 5 m,

※ Union Showa Co., Ltd. product name, High silica type zeolite, Specific surface area AO

※ 3 Kamijima Chemical, one star, average particle size 5.5 μπ 5

※ 4 Murakami Kogyo Co., Ltd., trade name: W 10, average particle size 3.3

※ Shin Tohoku Chemical made, mordenaite powder, average particle size 4 5 π 5

※ 6 Mitsui Metal Resources Development Co., Ltd., product name I Milite, Particle size 200 mesh or less

※ 7 Union Showa Co., Ltd. product name 1 3 X pow d er, particle size 10 m or less, specific surface area

The flexural strength, the porosity, the plasticity, the bulk specific gravity, and the specific surface area of each of the fired bodies of the above Examples 1 to 21 were measured by the methods described below. The results are shown in Table 2.

[0076] 'Bending strength: using a ORIENTICK UCT-5T, place the fired body sample on two fulcrums arranged at a span of 30 mm, apply a load of cross head speed of 0.5 mm Zmin to one central point between the fulcrums Three-point bending was performed, and the maximum load until the sintered body sample was broken was measured, and was calculated using the following equation.

Bending strength = 3WLZ2bd ²

(Wherein W: maximum load (N), L: distance between lower fulcrums (mm), b: width of test piece (m m), d: thickness of test piece (mm))

· Porosity: The fired body sample is dried at 110 ° C., the weight at constant weight is W1, and the baked body sample is put in water and boiled for 3 hours or more to completely release the air in the pores. The weight of the fired body sample is suspended in water W2 and the weight of the fired body sample is also taken out under water, and the surface is only wiped with a wet cloth and the weight after removing water drops is W3. The porosity was determined using Wl, W2, and W3 and the following equation.

Porosity = {(W3-Wl) / (W3-W2)} X 100 Water absorption rate: Calculated using the above-described method of measuring the porosity, W1 and W3 measured, and the following equation.

Water absorption rate = {(W3-Wl) / Wl} X 100

Plasticity: The plasticity of the mixture in the plastic state before firing was measured three times each using a Yamanaka type soil hardness tester, and the average value was calculated. If the indicated value of the soil hardness tester exceeds 14, molding by a general extrusion molding method becomes difficult, so the hardness tester indicated value Force S 14 or less is 〇 (good plasticity), and those exceeding 14 are X evaluated.

· Bulk specific gravity: Calculated using the following equation with the measurement methods of porosity, Wl, W2, and W3 measured in the above.

Bulk specific gravity = {W1Z (W3-W2)}

· Specific surface area: Equilibrium relative pressure (PZP) measured by gas adsorption BET method using a specific surface area measurement device (Auto Soap 1 manufactured by Yua Sionitas)

Five points were measured in the measurement range of 0. 05-0. 35 (JIS Z 8830).

[Table 2]

From Table 2, it can be seen that the fired bodies of Examples 1 to 21 are excellent in porosity and excellent in plasticity and strength despite the fact that the zeolite content is 70% by weight or more. In particular, it can be seen that the sintered body of Example 2 has excellent plasticity and strength in spite of the high proportion of the zeolite. Further, in this example, the specific surface area of the zeolite component contained in each of the sintered products using synthetic zeolite is approximately the same as the specific surface area of the sintered product since the specific surface area of the binder component used here is so small that it can be ignored. It can be seen that these values are at least 0.9 times the relative surface area of the zeolite components contained in the respective zeolite-containing compositions before firing. This result indicates that the zeolite in the composition greatly contributes to the excellent porosity of the fired body which is not amorphized by firing. For example, “the specific surface area of the zeolite component contained in the zeolite-containing composition before firing” in Examples 1 to 11 is (specific surface area of zeolite alone = 400 m ² / g) X (zeolite content = 70 wt%) = a 280 meters ² Zg.

In addition, the fired bodies of Examples 13 and 15 had water absorptions of 47. 1% and 32.8%, and volume standard water absorptions of 49.5% and 43.0%, respectively. That is, it can be seen that the fired body in the example can absorb water by 40% or more of the volume and has excellent water absorbability. The volume standard water absorption rate was calculated using the water absorption rate and the values of the volume and bulk ratio of the molded product.

(Deodorization evaluation of fired body)

The kneaded material of the composition shown in the following Table 3 is kneaded with water, formed into φ 3 mm pellets by an extrusion molding machine, and fired at 600 ° C. for 1 hour in an electric furnace at a temperature rising rate of 100 ° C. Zh. Deodorant samples were produced (Examples 22 and 23). In addition, commercially available activated carbon (Nitsubishi Chemical Co., Ltd., crushed carbon white glaze G2c) was used as a control sample (Comparative Example 1). Each of the obtained samples was sandwiched between 150 cc and 160 cc between stainless steel meshes (18 × 25 cm) to prepare a deodorizing filter. In addition, the lepidopteran clay used as the plastic clay is the same special grade hydridite clay as that used in Example 1.

[Table 3]

Deodorization evaluation was performed according to the following procedure using each deodorizing filter prepared as described above.

1) After installing two pieces of deodorizing filter in the deodorizing evaluation device shown in FIG. 1, one cigarette (mild seven) is burned, and after 5 minutes, ammonia, acetylaldehyde, acetic acid in the acrylic box The initial concentration of was measured. In FIG. 1, the capacity of the acrylic box is 250 L (56 × 56 × 80 cm), and three circulation pumps having a circulation capacity of 15 LZ min are connected to the deodorizing device via a connecting pipe of φ 12 mm.

2) Then, after operating the circulating pump connected to the deodorizing device, 15 minutes, 30 minutes, 4 The remaining concentrations of ammonia, acetaldehyde and acetic acid after 5 minutes were measured. Each gas concentration was measured by inserting Gastec NO. 3L, NO. 92L, and NO. 81L detection tubes into the connecting tubes.

3) After 45 minutes of concentration measurement, the second cigarette was burned and the same operations as in 1) and 2) above were repeated.

The results of the deodorizing evaluation of each gas component are shown in FIGS. It can be seen that the fired body of Example 22 exhibits extremely high adsorption characteristics for all gas components regardless of whether they are the first or second pipe. Further, the calcined product of Example 23 may have hydrophilic zeolite as the clinopty mouth light, and although the adsorptivity of acetaldehyde which is a VOC gas is low, the adsorptivity to ammonia and acetic acid is excellent. On the other hand, the activated carbon of Comparative Example 1 had high adsorptivity to acetaldehyde but low adsorptivity to ammonia and acetic acid.

(Evaluation of improvement of plasticity by addition of alkali (earth) metal compound)

The same plasticity evaluation as described above was performed on the mixture slurry of the composition shown in Table 4 below. In addition, the lepidopteran clay used as the plastic clay is the same special grade hydrolyzate clay as that used in Example 1.

[Table 4]

Table 4 shows that the addition of the alkali (earth) metal compound greatly improves the plasticity of the raw material mixture before firing. On the other hand, when calcium carbonate or dolomite alone is used as the alkali (earth) metal compound, it is difficult to obtain a composition having good plasticity. Its plasticity can be improved by using it in combination with iS magnesite and the like. However, when using natural zeolite with relatively good plasticity or zeolite synthesized with coal ash or the like as zeolite, a composition having good plasticity can be obtained even if calcium carbonate or dolomite is used alone. There is also a possibility.

(Evaluation of particle diameter of plastic clay and characteristics of fired body)

As plasticity clay, 20 wt% of special grade Hijime clay having an average particle diameter D of 2.4 μm was used.

50

The fired body sample of the above-mentioned Example 2 (the zeolite is HISIV-3000), and the average particle diameter D 7.1.

50

The plasticity, flexural strength, and porosity of each of the fired body samples (Example 25) prepared in the same manner as Example 2 except that IX m of clay was used. The results are shown in Table 5.

In addition, in the above Example 1 using 15 wt% of special grade Hijime clay having an average particle diameter D of 2.4 μm.

50

Sample No. 2 (Zeolite is mordenite) and a grain size of average particle diameter D 7.1 μm

50

With respect to the fired body sample (Example 26) prepared in the same manner as Example 12 except that soil was used, the plasticity, the bending strength and the porosity were measured. The results are shown in Table 5.

[Table 5]

From Table 5, the sintered body of Example 12 and Example 26 using mordenite as the zeolite showed no remarkable difference in the strength, but the experiment using HISIV-3000 as the zeolite was carried out. Comparing the fired body samples of Example 2 and Example 25, The fired body of Example 2 using the special grade hydrologically ordered clay having a grain size D of 2.4 μm is clearer

50

Show that the strength is large. FIG. 5 shows, for reference, the particle size cumulative distribution curves of the two types of Lemidoclay and various zeolites used in this example. The particle size analysis was performed using a laser diffraction type particle size distribution analyzer SALD-2000J manufactured by Shimadzu Corporation.

(Production of press-formed sintered body and photocatalytic coating)

75 wt% of Clinopetite mouth light, 20 wt% of special grade hydrolyzaceous clay, and 5 wt% of magnesite were kneaded for 4 hours with an industrial toro mill (volume It) for filter press dewatering. The moisture content of the obtained press cake was 25 wt%. Next, the press cake was dried at room temperature for 5 days and passed through a 2 mm mesh sieve to obtain granular clay having a moisture content of 13 wt% and a particle size of 2 mm under. Furthermore, this granular clay was filled into a 100 mm XI OO mm x 40 mm cast iron mold, a pressure of 50 cm ² Zg was applied by a hydraulic jack, and press molding was performed to obtain a press-molded product. The average thickness of press molding was 10.2 mm. Then, the pressed compact was dried at room temperature for 3 days, and fired at a temperature rising rate of 100 ° C. for 5 hours at a peak temperature of 600 ° C. to produce a fired body. The obtained sintered body has a bending strength of 3.5 MPa, a porosity of 41.9%, a water absorption of 30.4% (volume standard water absorption of 41.6%), and a bulk specific gravity of 1.37 g Zcm ³ and thus has good properties. I had it.

Further, a hot air low pressure coater (A BAC SG2500, manufactured by Chiron Japan Co., Ltd.) is coated on the surface of the above-mentioned sintered body with an acid titanium coating agent (a solution obtained by diluting TKC-304 50 times by Tica Co., Ltd.). ) was used to spray 0. 41gZm ^2. The sprayed coating exhibited good adhesion at normal temperature.

In addition, the composition slurry of Example 1 in which the moisture content was adjusted to 40% and 50% was applied to the surface of the above press-molded product dried for 3 days, to a thickness of about 50 m using a warm air low pressure coater. Sprayed to form a film. Then, the coated molded body was dried at room temperature for 1 day, and baked at 650 ° C. for 5 hours to obtain a baked body in which the hydrophobic zeolite composition film was well fixed to the surface. According to this method, it is possible to produce a building material which exhibits the performance such as the adsorption effect of the hydrophobic zeolite on VOC very inexpensively. Further, it was possible to apply a titanium oxide coating to this baked body with a film in the same manner as described above and to impart a photocatalytic property thereto. (Preparation of sintered body by extrusion molding method)

A predetermined amount of water is added to the composition shown in Table 6 below, and premixed with Ashizaki Iron Works Co., Ltd. product, mixer MH S-100, and further, this is subjected to kneading vacuum extrusion with Amagasaki Iron Works Ltd. product. After molding into a shape with a height of 10 mm, a width of 10 mm, and a length of 70 to LOO mm using a molding machine FM-P30, this molded body is dried at room temperature for 3 days and fired under the conditions described in Table 6. Thus, the fired bodies of Examples 27 and 28 were obtained. The flexural strength, the porosity, the bulk specific gravity, the water absorption rate, and the volume standard water absorption were determined for the obtained sintered body. The results are shown in Table 7. The clay of clay used here is made of round ceramics and has a particle diameter of 100 μm or less, and the others are the same as described above.

[Table 6]

[Table 7] Bending strength, porosity, water absorption, volume standard water absorption

Bulk specific gravity

(MP a) (%) (%) (%)

Example 27 14. 7 37. 0 1. 45 25. 4 36. 8

Example 28 14. 5 38. 2 1. 46 26. 1 38. 2

Claims

The scope of the claims

[1] Zeoraito 50 to 90 weight ^_0/0,

5 to 49.9% by weight of plastic clay,

Alkaline (earth) metal compound 0.1 to 30% by weight,

A zeolite-containing composition comprising:

[2] The zeolite-containing composition according to claim 1, wherein the alkali (earth) metal compound is thermally decomposed at 800 ° C. or less.

[3] The zeola according to claim 1 or 2, characterized in that the plastic clay is one or more selected from the group consisting of Kibushi clay, Lemoku clay, kaolin, shale clay and pottery stone. It containing composition.

[4] The plastic clay has an average particle size D of not more than the average particle size D of the zeolite and

50 50

And the particle diameter ratio of the effective diameter D or less of the zeolite is 15% by weight or more.

Ten

The zeolite-containing composition according to any one of claims 1 to 3, which is a feature of the invention.

[5] The alkali (earth) metal compound is selected from an alkali (earth) metal carbonate, an alkali (earth) metal hydroxide, an alkali (earth) metal nitrate, and an alkali (earth) metal acetate. The zeolite-containing composition according to any one of claims 1 to 4, wherein the selected group is one or more selected.

[6] One or two selected from the group consisting of lithium carbonate, magnesium carbonate, calcium carbonate, basic magnesium carbonate, magnesite, limestone, and dolomite as the alkali (earth metal) metal carbonate. The zeolite-containing composition according to claim 5, which is a mixture or a mixture of the above.

[7] The zeolite-containing composition according to claim 6, characterized in that the calcium carbonate, the limestone, and the dolomite are used as a mixture or a mixture with other alkali (earth) metal compounds. .

[8] One kind selected from the group consisting of lithium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, and brucite, as the alkali (earth) metal hydroxide. The zeolite-containing composition according to claim 5, which is a mixture or a mixture of two or more thereof.

[9] The alkali (earth) metal nitrate is preferably a mixture or mixture of one or more selected from potassium nitrate and a group selected from sodium nitrate and sodium nitrate. The zeolite-containing composition according to claim 1.

[10] The zeolite according to the present invention is characterized in that one or more metal ions selected from the group consisting of copper ions, silver ions and zinc ions are supported on the zeolite. The zeolite-containing composition according to any one of the preceding claims.

[11] The zeolite-containing composition according to any one of the items 1 to 4: LO, wherein the measured value of the Yamanaka-type soil hardness meter in the plastic state is 14 or less.

[12] A porous fired body obtained by firing the zeolite-containing composition according to any one of the items 1 to 4 at a temperature of 500 to 800 ° C.

[13] The porous sintered body according to claim 12, characterized in that the porosity is 30% or more and the bending strength is I MPa or more.

[14] The specific surface area of the zeolite component contained in the fired body is at least 0.8 times the specific surface area of the zeolite component contained in the zeolite-containing composition, according to claim 12 or 13. Porous fired body.

[15] The porous sintered body according to any one of claims 12 to 14, wherein photocatalyst particles are supported on the surface, or photocatalyst particles are contained as a composition.

[16] A zeolite-containing composition comprising zeolite, plastic clay and an alkaline (earth) metal compound,

The Yamanaka type soil hardness meter measured value in the plastic state is 14 or less,

Zeolite-containing composition characterized in that the porosity after firing is 30% or more, the bending strength is IMPa or more, and the specific surface area of the zeolite component is at least 0.8 times the specific surface area of the zeolite component before firing. object.

[17] The zeolite-containing composition according to claim 16, wherein the zeolite content is 50 to 90% by weight.

[18] The plastic clay has an average particle size D of not more than the average particle size D of the zeolite and

50 50

Ten

The zeolite-containing composition according to claim 16 or 17, which is a feature.

[19] A porous fired body obtained by firing the zeolite-containing composition according to any one of claims 16 to 18 at 500 to 800 ° C.

[20] The porous sintered body according to claim 19, characterized in that photocatalyst particles are supported on the surface, or photocatalyst particles are contained as a composition.

[21] A coated article characterized by being coated with the porous fired body according to any one of claims 12 to 15 or the porous fired body according to claim 19 or 20.

[22] Claim 1 to 1: The zeolite-containing composition according to any one of L 1 or the claim 16

A building material characterized in that the zeolite-containing composition according to any one of items 18 is formed and processed by extrusion molding, press molding, or insert molding, and is fired at 500 to 800 ° C. .

[23] The building material according to claim 22, wherein the porosity is 30% or more and the bending strength is 3 MPa or more.

[24] The building material according to claim 22 or 23, wherein a volume standard water absorption rate is 35% or more and a bending strength is 3 MPa or more.

[25] A zeolite-containing composition containing 50% or more of zeolite is molded and baked at 500 to 800 ° C., and has a flexural strength of 3 MPa or more, a porosity of 30% or more, or a volume standard water absorption rate Is 35% or more.

[26] The building material according to any one of claims 22 to 25, wherein photocatalyst particles are carried on the surface and contained or photocatalyst particles are contained as a composition.

[27] A binder to be blended into a porous fired body obtained by firing a porous body,

The average particle diameter D is equal to or less than the average particle diameter D of the porous body, and the effective diameter of the porous body

50 50

Plastic clay having a particle size ratio of not more than 15% by weight or less;

Ten

An alkaline (earth) metal compound,

Noinda characterized by including.