JPH10258228A - Granular sintered body and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To purify water by granular sintered material having necessary hardness and strength by a method wherein adsorptive inorganic raw material fine powder is made granular, sintered within a specific temperature range, continuous pierced macro pore of a specific diameter is formed in an outer skin part, a pore gap of a specific diameter is formed in a sintered body core part, and a capsule structure is provided wherein respective activated raw material particles are gently bonded to each other. SOLUTION: One or more kinds of inorganic raw material having adsorptive activity such as natural minerals being micro crystalline porous material with dehydration by heating of granite porphyry or the like, activated alumina, etc., are made powdery, mixed uniformly, and dipped in iron chloride aqueous solution. Thereafter, they are dried. One or more kinds of carbon raw materials of starch or the like are mixed by blending in plastic clay raw material, soluble alkali salt aqueous solution of sodium silicates are added at outer percentage, which is formed by granulation, dried, and burned within a temperature range of 700-1000 deg.C under a reducing atmosphere to obtain a capsule structure wherein a continuous pierced macro pore of 0.5[μm] or over diameter is provided in a skin part of hard glass material layer of sintered material, a pore gap of 5-100μm is provided in a sintered material core part, and respective activated raw material particles are gently bonded to each other. It has necessary hardness and strength, and can be purified in water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention mainly relates to granulating inorganic active minerals used for the purpose of water purification,
When used as a granular sintered body, especially when it is impacted, washed and regenerated by forced water flow like a 24 hour bath purifier, the purifier must have hardness and strength not to be powdered. This is to remove by adsorption. Further, the present invention relates to a granular sintered body for purifying water by sterilizing hot water in a 24-hour bath, which has been problematic because sterilization is insufficient to date.

[0002]

2. Description of the Related Art Zeolite mineral which is a fused silicate mineral,
For example, Otani stone or feldspar genus barite, which is a tectoaluminosilicate mineral, has long been known as an [active stone] having adsorption activity. The adsorption capacity of these raw materials is due to the physical structure and the ion-exchange properties of the constituent components that contain a large amount of micropores and macropores in the crystal structure.
Each of these minerals has a high activity in the temperature range from immediately after dehydration of the crystallization water to the transformation of the crystal structure.
The change from [° C.] to amorphous begins to occur,
At [° C.], it becomes cristobalite and loses its specific pore structure. Feldspar minerals such as malite are originally amorphous, but crystal water dehydrates by 800 ° C.
When the temperature exceeds 00 [° C.], crystallization gradually progresses to mullite (3Al ₂ O ₃ 2SiO ₂ ) and quartz (SiO ₂ ).
A calcined product at 800 to 900 [° C.] has the highest adsorption activity.

[0003]

However, a temperature of at least 1100 [° C.] is required to obtain a hard granular material as the object of the present invention. In order to make these raw materials into granules having sufficient hardness at a low temperature of about 800 ° C, the content of active stone should be reduced, and frit or glass that melts at a low temperature and a small amount of clay should be added. However, in order to sinter these compositions, a large amount of a glass phase is generated, the pore structure is destroyed, and the adsorption function is inevitably reduced. As a prior art relating to this type of technology, JP-A-5-105548 discloses a composition coexisting with an adsorbent having a zeolite diameter and barley stone, etc., in a range higher than the transformation temperature of the mineral component and lower than the softening melting temperature. Although the conditions for baking are specified,
Oya stone baked at 1000 [° C] has low strength,
In addition, the function as an adsorbent is reduced, and has a high far-infrared radiation characteristic. In addition, Japanese Unexamined Patent Publication
Japanese Patent No. 210169 discloses an adsorbent for cristobalite mineral similar to barley stone, but 900 [° C.]
Since the above heating changes the crystal structure, it is 400 [° C.]
The temperature range of 900 ° C. is claimed. According to recent newspaper information, a mixture of granulated zeolite, active rock and the like can be seen as a soil conditioner, but the strength properties for the purpose of use are low. It is an object of the present invention that the temperature range in which various active materials are brought into a sintered grain state is 700 [° C.] to 1000 [° C.], which is the highest active function.
Focusing on the low temperature, hardness and strength conditions, which cannot be reached in the range of the prior art, the invention was invented on the basis of the expression of a capsule structure that is generally popular as a medicinal tablet. . In particular, an object of the present invention is water purification, in which the granular material is always in water, absorbs water, adsorbs harmful substances, and is regenerated while periodically forcing a water stream to give a collision impact. It is necessary that the macropores for water to enter and exit communicate from the surface layer to the core, and have the required hardness and strength. Furthermore, the conventional technique alone cannot almost always sterilize a so-called 24-hour bath, which causes a problem of bacterial infection. Recently, the sales of 24-hour baths have been drastically reduced. Solving this and restoring sales is also an important issue of the present invention.

[0004]

According to the method for producing a double structure of a tablet for medicine, a core is granulated in advance, and the outer skin is coated to form a multilayer structure. In the case of, in the process of drying and baking, about 5%
A change in volume such as 10% shrinkage occurs, and if there is a large difference in the degree of sintering between the outer shell and the core, cracks are generated or deformed. In particular, the vitreous portion that becomes the outer shell causes sintering shrinkage of about 10%, but the core material is hardly changed in volume in a temperature range of 700 ° C. to 1000 ° C. It is.
Therefore, it is extremely difficult to integrate a ceramic sintered body having a vitreous and hard outer skin and a loosely bonded core into a composite body. In the present invention, a technical point is a means for improving these conditions.

That is, the first feature of the granular sintered body of the present invention is that a fine powder of an inorganic material having an adsorption activity is formed into a granular form and fired in a temperature range of 700 to 1000 ° C. In particular, the outer shell of the sintered body is wrapped with a hard vitreous layer having macropores continuously penetrating with a diameter of 0.5 (μm) or more, and the sintered body core is
The active material particles have pores having a diameter of 5 to 100 [μm] and have a capsule structure in which each active material particle is loosely bonded.

A second feature is that one or more of the inorganic raw materials having an adsorption activity is converted into powder having a particle size of 250 [μm] or less, and immersed in an iron chloride aqueous solution having a solution concentration of 3 to 5 [%]. The dried product is 60 to 95 by weight.
[%], And 0 to 20 [% by weight]
5 to 20% by weight of at least one selected from carbon materials such as starch, urea, phenolic resins and the like, which are carbonized by heating, charcoal, activated carbon, coke, etc.
And adjusted to a total of 100% by weight. To the mixed composition, sodium silicate, sodium phosphate, silica gel, and an aqueous solution of a soluble alkali salt of alumina sol were further added. After granulation and drying, 700
Sintering in a temperature range of 1 to 1000 ° C. and in a reducing atmosphere containing 5% or more of CO.

[0007] Next, the third feature is that the inorganic raw material having the adsorptive activity is a zeolite mineral, maltite, a natural mineral which becomes a microcrystalline porous body by heating and dehydration,
It is a mixture of one or more selected from artificially produced activated alumina and synthetic zeolites, and is a raw material of the granular sintered body of the present invention.

A fourth feature of the granular sintered body of the present invention is that the zeolite mineral is powdered to 250 [μm] or less, and then silver nitrate, an aqueous solution of silver chloride of silver chloride, copper chloride, copper sulfate, or the like. Ag ions or Cu ions are adsorbed or ion-exchanged by immersion in an aqueous solution of iron ore as dry powder, and barite, natural minerals that become microcrystalline porous material by heating and dehydration, artificially A mixture of at least one raw material selected from the produced activated alumina and synthetic zeolites and a dry powder treated with an aqueous solution of iron chloride in a total of 60 to 90% by weight; From 0 to 20% by weight, and from 5 to 20 at least one selected from carbon raw materials such as starch, urea, phenolic resins, carbonaceous materials carbonized by heating, charcoal, activated carbon and coke. % By weight) and a total of 100%, and an aqueous solution of a soluble alkali salt such as sodium silicate, sodium phosphate, sodium aluminate, silica gel, alumina sol, etc. is added to the mixed composition. After mixing uniformly, granulating and drying, 700 to 1
It is fired in a reducing atmosphere containing 5% or more of CO in a temperature range of 000 ° C.

Furthermore, the method of the present invention for producing a granular sintered body is characterized by zeolite minerals, maltstones, natural minerals that become microcrystalline porous bodies by heating and dehydration, and artificially produced active substances. Alumina, synthetic zeolites, at least one selected from inorganic raw materials having adsorptive activity to powder with a particle size of 250 [μm] or less, uniformly mixed,
After being immersed in an aqueous solution of iron chloride having a solution concentration of 3 to 5%, the dried material is contained in a weight ratio of 60 to 95%, and the plastic clay material is 0 to 20% by weight, starch, urea, One or more selected from carbon materials such as phenolic resins, carbonaceous materials carbonized by heating, charcoal, activated carbon, and coke are blended in the range of 5 to 20% by weight, and the whole is 100% by weight. Sodium silicate, sodium phosphate, silica gel, aqueous solution of soluble alkali salts of alumina sols were added to the mixed composition, granulated, molded, dried, and then coke, graphite Is placed in a refractory box containing carbonaceous powders and a reducing atmosphere containing 5% or more of CO.
Firing at a temperature in the range of 00 ° C. to 100 ° C.

Further, the configuration of the present invention will be specifically described. In the compounding raw material as set forth in the claim, 5% to 2% of a carbonaceous raw material such as starch, urea, phenolic resin, charcoal, activated carbon, coke, etc., together with an active mineral serving as a main raw material.
The addition in the range of 0 [%] has the function of forming pores in the outer vitreous material, which will be described later, and also causes the carbonaceous material to oxidize and burn during the firing process to greatly reduce the volume. Even if the ratio affects the composition of the core portion, it can absorb a large amount of compressive stress, and can leave a necessary pore. Further, sodium silicate, sodium phosphate, sodium aluminate, and silica gel added after mixing of the composition are all aqueous solutions of soluble alkali salts, and are heated and formed into steam in the process of drying and firing after granulation. It was confirmed by experiments that when the ions were released to the outside, the alkali ions moved together with the water vapor to the outer skin portion, and were concentrated and fixed on the surface layer. The choice of the aqueous solution of the alkaline salt is selected depending on the required quality such as the chemical composition of the main raw material, an appropriate firing temperature, and the required thickness of the outer shell. In addition, carbonaceous materials act as a molding aid in forming granules of starch, urea, phenolic resin and the like, and emit CO, C during firing.
Carbon materials such as charcoal, coke, and activated rock that play a role such as formation of pores in the outer glass layer due to generation of O ₂ gas and bonding as a carbide of the core do not work as a forming aid, but the former carbonaceous material. CO, CO for a long time at high temperature side
The release of ₂ occurs, forming carbides.

[0011] The adsorptive active material is in the form of a powder in an amount of 3% to
5% iron chloride (FeCl ₂ ) aqueous solution, iron ions are adsorbed on the surface, and then dried and compounded. The loose binding of the active material particles in the core is due to the carbon and carbide. Although formed, in this reaction, it was discovered that the presence of a small amount of iron ions promoted carbon fixation. As described above, each composition raw material functions according to the purpose of the present invention, and the formation of the continuous permeable macropores formed in the outer vitreous layer will be further described. As described above, the granular material in which the alkali ions are concentrated in the surface layer is heated to 700 [° C.] and becomes sodium silicate or sodium aluminate. Those having a low alkali content such as sodium phosphate are melted and vitrification starts. Those with low alkali content such as silica gel are mainly amorphous SiO
_The sintering of only the surface layer is started by the reaction between ₂ and the active material composition, but is adopted in a temperature range of 900 ° C. to 1000 ° C.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS These vitrifications start at 700 ° C. at low temperatures, but the release of water of crystallization does not end from the inside of the granules, and CO, CO ₂
Since a glass phase is formed while the generation of porosity continues, macropores penetrate. In the case where the carbon material is coke or the like, gas is still generated even at 1000 ° C., but it can be controlled by setting the firing atmosphere to a reducing property of CO of 5% or more, and at the core portion, Creates a connective tissue as a carbon bond or carbon material, leaving the necessary carbon. If the content of the carbon substance is 5% or less, the degree of bonding of the core is too low, and if it exceeds 20%, glassy carbon or the like is formed and the affinity with water deteriorates.

A fourth aspect of the present invention is a granular sintered body having an antibacterial or bactericidal function, and in particular, a mixing treatment while adsorbing antibacterial ions such as zeolitic raw materials, Ag ions and Cu ions among the adsorbing active materials. Ag and C
It is expected that the salts of u will be heated to release volatile components and then reduced to exhibit an effective action. According to the fourth aspect, if the granulated product is not heated uniformly in the furnace, the glass skin has an uneven thickness, and cracks and the like are likely to occur. In addition, the molded body is filled in a box, and if the glass skins adhere to each other, they are welded together to improve defects, such as increasing the number of defective products.High heat transfer coefficient and poor glass wetting with glass The solution was achieved by embedding in a powder such as coke. It is also convenient for controlling the reduction conditions.

Embodiment 1 Raw materials Oya stone (zeolite) and barley stone (produced in China) were crushed to 250 [μm] or less as active natural materials, and activated alumina 20 [μm] or less was used as an artificial raw material. 2. Pretreatment The used raw material was immersed in a 3% aqueous solution of FeCl ₂ for 5 minutes and then dried.

[0015]

[Table 1]

1 kg of each sample was produced at the above mixing ratio, and a pan-type granulator was used to form spherical granules in a range of 5 mm to 10 mm. ] For 1 hour, and further dried at 100 ° C. to 120 ° C. for 1 hour. After the dried material is buried in a fire-resistant box together with glass-fight powder (flakes having a particle size of 1 mm to 2 mm),
In a gas furnace in a reducing atmosphere with CO of 5% to 6%,
The temperature was raised to 850 ° C. ± 10 ° C. at a rate of temperature rise of 5 ° C./min, and then held for one hour for firing.

[0017]

[Table 2]

Each physical property test was performed in the following manner. (A) Impact powdering amount Sample granules 200 [gr] water 250 [gr] 500
1 ml with an amplitude of 40 mm
The solution is treated with a shaker at 30 [times / minute] for 90 minutes, the liquid is filtered, and the amount of powder is measured with an analytical balance. The requirement for a 24-hour bath is <0.1 [gr]. (B) Methylene blue adsorption rate 20 [gr] of methylene blue 40 [mg / l] solution,
A sample ball 10 [gr] is put in a bottle, and the decrease in concentration is measured with the passage of time. About 4 [%] adsorption of a current product for a bath for 24 hours in 8 hours. ], The mouth of a bottle containing 10 [gr] of sample balls is sealed with Saran wrap, and the chlorine concentration is measured with a 0.1 [%] solution of ortho-tolidine over time. %] Adsorption (d) Ammonia adsorption rate Take 1 [mg / l] of ammonia water and 50 [ml], put 10 [gr] of sample balls, seal the bottle mouth with Saran wrap, and establish the ammonia amount over time. Measured with a Riken pack set 50% of the current product for a 24-hour bath in 4 hours-60%
〔%〕adsorption

[0019]

【The invention's effect】

1) The above-mentioned embodiment has a vitreous skin at only one end, and has a very low impact powdering amount, but has a high absorption rate, and water to be purified easily flows from the surface to the core. The present invention has achieved the object of the present invention, in which the constituent material (active material) of the core portion exhibits a high adsorption rate without impairing the respective adsorption activities, and is suitable for this kind of application. As a material, it has excellent properties that are unique and can be widely used for applications such as a water treatment agent or a modification treatment for the purpose of antibacterial property and bactericidal property. 2) As a prominent example, the conventional technology up to the present stage has a revolutionary effect in the purification and sterilization of so-called 24-hour bath water in which many illnesses due to bacteria are occurring.

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[Procedure amendment]

[Submission date] March 27, 1997

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 4

[Correction method] Change

[Correction contents]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] Claim 5

[Correction method] Change

[Correction contents]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

A second characteristic is that one or more of the inorganic raw materials having an adsorption activity is converted into powder having a particle size of 250 [μm] or less and immersed in an aqueous solution of iron chloride having a solution concentration of 3 to 5 [%]. The dried product is 60 to 9 by weight.
5% [%] and 0 to 20% by weight of a plastic clay material, selected from carbon materials such as starch, urea, phenolic resins, carbonaceous materials carbonized by heating, charcoal, activated carbon, and coke more, from 5 were compounded in a range of 20 [wt%], the whole was adjusted to be 100 [% by weight], a mixed composition, further outside split, sodium silicate, sodium phosphate, silica zone And an aqueous solution of a soluble alkali salt of alumina sol, and then granulated and dried.
That is, firing is performed in a reducing atmosphere containing 5% or more of CO in a temperature range of 00 to 1000 ° C.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

[0008] Furthermore, the same applies to the fourth aspect of the granular sintered body of the present invention.
The feature of this is that after the zeolite mineral is turned into a powder of 250 [μm] or less, it is immersed in a silver salt aqueous solution of silver nitrate silver chloride or copper chloride, copper sulfate or an aqueous solution to adsorb Ag ions or Cu ions. Or one selected from dry powder of ion-exchanged product, barley stone, natural minerals that become microcrystalline porous material by heating and dehydration, activated alumina artificially produced, and synthetic zeolite A total of 60 to 90% by weight of a mixture of the above raw materials and a dry powder treated with an aqueous iron chloride solution, 0 to 20% by weight of a plastic clay raw material, starch urea, phenolic resins One or more carbon materials selected from carbonaceous materials, charcoal, activated carbon, coke, and the like, which are carbonized by heating, are blended in an amount of 5 to 20% by weight and a total of 100%. The mixed composition, further outer percentage, sodium silicate, sodium phosphate, sodium aluminate, silica zone <br/> Le, by adding soluble alkaline salt solution, such as alumina sol was uniformly mixed granulated molding and dried Later, 700 to 10
It is fired in a reducing atmosphere containing 5% or more of CO in a temperature range of 00 ° C.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

Further, the method of the present invention for producing a granular sintered body is characterized by zeolite minerals, maltstones, natural minerals that become microcrystalline porous bodies by heating and dehydration, and artificially produced active substances. Alumina, synthetic zeolites, at least one selected from inorganic raw materials having adsorptive activity are powdered with a particle size of 250 [μm] or less, and uniformly mixed,
After being immersed in an aqueous solution of iron chloride having a solution concentration of 3 to 5%, the dried material is contained in a weight ratio of 60 to 95%, and the plastic clay soil raw material is 0 to 20% by weight, starch,
One or more selected from carbon materials such as urea, phenolic resins, carbonaceous materials carbonized by heating, charcoal, activated carbon, and coke are blended in a range of 5 to 20% by weight, and the whole is 100% by weight. %] become so adjusted, with further outer split the mixed composition, sodium silicate, sodium phosphate, silica zo le, alumina sol such, by adding soluble alkaline salt solution of granulation, molding, drying, and then , Coke, graphite, etc., placed in a refractory sheath containing carbonaceous powder, and fired in a reducing atmosphere containing 5% or more of CO in a temperature range of 700 ° C to 1000 ° C. It is.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

[0010] Further, the configuration of the present invention will be specifically described. In the blended raw material as set forth in the claim, a raw material of carbonaceous material such as starch, urea, phenolic resin and charcoal, activated carbon and coke is 5% to 2% together with an active mineral as a main raw material.
The addition in the range of 0 [%] has the role of forming pores in the outer vitreous material, which will be described later, and also causes the carbonaceous material to oxidize and burn during the firing process to greatly reduce the volume. Even if the ratio affects the composition of the core portion, it can absorb a large compressive stress and leave pores that need to be maintained. Moreover, sodium silicate added after mixing of the composition, sodium phosphate, sodium aluminate, silica zone le are both alkaline salt solution of a soluble, in the process of drying and baking after granule, it is heated, water vapor As a result, it was confirmed by experiments that when the ions were released to the outside, the alkali ions moved together with the water vapor to the outer skin portion, and were concentrated and fixed on the surface layer. The selection of these alkali salts depends on the required quality, such as the chemical composition of the main raw material, the appropriate firing temperature, and the required thickness of the outer shell. In addition, carbonaceous materials, such as starch, urea, and phenolic resin, act as molding aids when producing granulated compacts, and generate CO and CO ₂ gas during firing to form pores in the outer glass layer and to form carbides in the core. carbon materials such as charcoal which acts such as binding, coke, active rock, but does not act as a molding aid, the former, carbonaceous material also long time at a high temperature side CO, the release of CO ₂ take place, forming a carbide I do.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

Each physical property test was conducted in the following manner. (A) Impact powdering amount Sample granules 200 [gr] water 250 [gr] 500
1 ml with an amplitude of 40 [mm]
The mixture was treated with a shaker at 30 [times / minute] for 90 minutes, the liquid was filtered, and the amount of powder was measured with an analytical balance. The demand for a 24-hour bath is <0.1 [gr]. (B) Methylene blue adsorption rate 20 [gr] of methylene blue 40 [mg / l] solution,
A sample ball (10 gr) was placed in a bottle, and the decrease in concentration was measured over time. Conventional product for bath for 24 hours _ About 40 [%] adsorption in 8 hours. (C) Adsorption Rate of Free Chlorine The mouth of a bottle containing 10 [gr] of water in 50 [ml] of water was sealed with Saran wrap, and the chlorine concentration was measured with a 0.1 [%] solution of ortho-tolidine over time. Conventional product for bath for 24 hours _ About 60 [%] adsorption in 2 hours. (D) Ammonia adsorption rate Take 1 [mg / l] of ammonia water and 50 [ml], put 10 [gr] of sample balls, seal the mouth of the bottle with Saran wrap, and adjust the amount of ammonia with the passage of time. Measured in sets. Prior art product for 24-hour bath
50% to 60% adsorption in 4 hours.

Claims (5)

[Claims] 1. A fine powder of an inorganic raw material having an adsorption activity is formed into a granular form,
A granular sintered body fired in the temperature range of [° C.], in particular, the outer shell portion of the sintered body is a hard vitreous layer having continuous macropores having a diameter of 0.5 [μm] or more. The granular sintered body is characterized in that the core part of the sintered body has a pore having a diameter of 5 to 100 [μm] and has a capsule structure in which each active material particle is loosely bonded. body. 2. One or more inorganic raw materials having adsorptive activity are converted into powder having a particle size of 250 [μm] or less, immersed in an aqueous solution of iron chloride having a solution concentration of 3 to 5 [%], and dried to obtain a powder by weight ratio. The plastic clay raw material containing 60 to 95% is selected from 0 to 20% by weight, and carbon materials such as starch, urea, and phenolic resin, which are carbonized by heating, and charcoal, activated carbon, and coke. At least 5 to 20% by weight.
Then, sodium silicate, sodium phosphate, silica gel, and an aqueous solution of a soluble alkali salt of alumina sol were added to the mixed composition, and the mixture was granulated and dried. A granular sintered body characterized in that it is fired in a temperature range of 1 to 1000 ° C. and in a reducing atmosphere containing 5% or more of CO. 3. The inorganic raw material having the adsorptive activity is selected from the group consisting of zeolite minerals, barley stones, natural minerals that become microcrystalline porous bodies by heat dehydration, artificially produced activated alumina, and synthetic zeolites. 3. The granular sintered body according to claim 1, which is a mixture of one or more selected materials. 4. A powder of a zeolite mineral having a particle size of 250 μm or less is immersed in an aqueous solution of silver nitrate or silver chloride, or an aqueous solution of copper chloride or copper sulfate to adsorb Ag ions or Cu ions. Or ion-exchanged dry powder and barley stone, natural minerals that become microcrystalline porous material by heating and dehydration, artificially produced activated alumina, and synthetic zeolites. A mixture of at least one raw material and a dry powder treated with an aqueous solution of iron chloride is 60 to 90% by weight in total, 0 to 20% by weight of a plastic clay raw material, starch urea, phenol Of at least one selected from the group consisting of carbonaceous materials, carbonaceous materials that can be carbonized by heating, charcoal, activated carbon, and coke, and a total of 5 to 20% by weight.
[%], Add aqueous sodium salt solution such as sodium silicate, sodium phosphate, sodium aluminate, silica gel, alumina sol, etc. to the mixed composition and mix uniformly. A granular sintered body characterized in that after being formed and dried, it is fired in a reducing atmosphere containing 5% or more of CO in a temperature range of 700 to 1000 ° C. 5. A material selected from the group consisting of zeolite minerals, barley stones, natural minerals that become microcrystalline porous bodies by heating and dehydration, artificially produced activated alumina, synthetic zeolites, and inorganic raw materials having adsorption activity. More than one
Powder having a particle size of 50 [μm] or less, uniformly mixed and immersed in an aqueous solution of iron chloride having a solution concentration of 3 to 5 [%],
The dried product contains 60 to 95% by weight,
0 to 20% by weight of a plastic clay material, starch, urea,
A phenolic resin, carbonaceous material carbonized by heating, charcoal, activated carbon, at least one selected from carbon materials such as coke, in a range of 5 to 20% by weight,
The total composition was adjusted to 100% by weight, and the mixed composition was further divided into sodium silicate, sodium phosphate,
Add an aqueous solution of a soluble alkali salt of silica gel and alumina sol, granulate, mold and dry. Then, place in a refractory box containing carbonaceous powder of coke and graphite,
In a reducing atmosphere containing O 5% or more, 700
A method for producing a granular sintered body, characterized by firing in a temperature range of [° C] to 100 [° C].