JP6153204B2 - Granulated product and production method thereof - Google Patents

Description

  The present invention relates to a granulated product and a method for producing the same. In particular, the present invention relates to a granulated product having a granular material of a porous inorganic mineral, a granular material serving as a core, and a water-soluble inorganic salt binder, and a production method.

In recent years, as a part of environmental management, soil and water quality has been actively improved and purified in order to implement environmental conservation as a preventive measure against contamination of soil and groundwater by pollutants in the applicable substances and as a measure to prevent the spread of pollution. It has been broken.
As a method of improving and purifying them, there is a method of adsorbing pollutants in applicable substances to porous inorganic minerals.

Japanese Patent No. 3369631 JP 2006-137636 A

There are various forms of the porous inorganic mineral, but if it is used as it is in the form of a granular material, clogging occurs when the water flows, resulting in a decrease in processing capacity. Therefore, it is necessary to increase the particle size of the porous inorganic mineral powder and cope with clogging when sprayed to the soil and run.
On the other hand, fine porous inorganic minerals such as zeolite have been used as adsorbents for soil improvement / purification, but cement is used as a binder for granulating them (patents) Documents 1) and those using water-soluble polymers (Patent Document 2) have been proposed.

  However, in the conventional method, the pores of the porous inorganic mineral adsorbent are covered with a binder, or the contact between the adsorbents is biased to reduce the purification processing capacity, and the adsorbent replacement frequency. It has become a problem to cause problems.

  The present invention is a porous inorganic material capable of selectively adsorbing contaminants in the application target in soil and water quality and artificially promoting the action of removing contaminants in nature. It is an object of the present invention to provide a granulated product containing a mineral powder and a method for producing the same.

  As a result of diligent studies to solve the above problems, the present inventor adsorbed by blending a granular material of a porous inorganic mineral, a granular material serving as a core, and a water-soluble inorganic salt binder, granulating and drying. The particles of porous inorganic minerals, which are agent particles, form a granulated product by point contact, and according to the formed granulated product, target pollutants in the soil and water quality can be removed without impairing the purification capacity. It was found that selective adsorption is possible. That is, this invention has the structure shown by the following [1]-[16].

[1] A granulated product comprising (A) a granular material of a porous inorganic mineral, (B) a granular material serving as a nucleus, and (C) a water-soluble inorganic salt binder.
[2] The particle diameter of the granular material of (A) porous inorganic mineral is 0.01 μm or more and 100 μm or less, and the particle diameter of the granular material serving as the core (B) is more than 0.1 mm and 2 mm or less. The granulated product according to [1], wherein
[3] The porous inorganic mineral powder (A) is at least one selected from the group consisting of iron hydroxide, clay mineral and zeolite [1] or [2] Granules described in 1.
[4] The granulated product according to [3], wherein the iron hydroxide is at least one selected from the group consisting of Schwertmannite, goethite, jarosite, and ferrihydrite.
[5] The clay mineral is a smectite consisting of montmorillonite, beidellite, nontronite, saponite, hectorite, or stevensite, mascobite, phlogopite, teniolite, biotite, margarite, clintonite, tetrasilicon mica, or sericite The structure according to [3], which is at least one selected from the group consisting of mica comprising a site and vermiculite which is an alteration mineral thereof, and amorphous silicate comprising imogolite or allophane. Grain.
[6] The granulated product according to any one of [1] to [5], wherein the granular material serving as the core (B) is porous granular activated carbon.
[7] The granulated product according to any one of [1] to [5], wherein the granular material serving as the core (B) is a porous granular zeolite.
[8] The (C) water-soluble inorganic salt binder comprises at least one water-soluble inorganic salt selected from the group consisting of potassium salt, sodium salt, calcium salt, magnesium salt, and ammonium salt. The granulated product according to any one of [1] to [7].
[9] (c1) The method further includes at least one iron compound selected from the group consisting of iron nitrate, iron sulfate, iron hydroxide, iron oxide, iron sulfate, iron oxalate, and ammonium iron sulfate. The granulated product according to any one of [1] to [8].
[10] The granulated product according to any one of [1] to [9], further comprising (D) an inorganic filler.
[11] (A) Porous inorganic mineral powder, wherein (A) porous inorganic mineral powder, (B) granular material serving as nucleus, and (C) water-soluble inorganic salt binder are mixed. 50 to 300 parts by mass (50 to 300 parts by mass) of the granular material serving as the nucleus (B) and 5 to 100 parts by mass of the water-soluble inorganic salt binder (C) with respect to 100 parts by mass of the granules. 5 to 100 parts by mass) The granulated product according to any one of [1] to [10].
[12] A method for producing a granulated product according to any one of [1] to [11],
(A) a step (α) of mixing a granular material of a porous inorganic mineral and (B) a granular material serving as a nucleus;
(C) adding an aqueous solution of a water-soluble inorganic salt binder to the mixture prepared in step (α) to form a mixture and granulated product (β);
A step (γ) of evaporating and drying water from the undried granulated product obtained in the step (β);
The manufacturing method of the granulated material characterized by comprising.
[13] The production method according to [12], wherein in the step (β) of forming the mixed and granulated product, powder (D) of inorganic filler, solution or slurry is further added.
[14] The step of forming the mixed and granulated product (β) is selected from the group consisting of rolling granulation, stirring granulation, compression granulation, extrusion granulation, fluidized bed granulation, and spray granulation. The method according to [12] or [13], which is performed using any one of the methods described above.
[15] The drying step (γ) is performed using any method selected from the group consisting of spray drying, drum drying, food dryer, and natural drying [12] to [14] ] The manufacturing method of the granulated material in any one of.
[16] The method for producing a granulated product according to any one of [12] to [15], wherein the temperature in the drying step (γ) is 120 ° C. or lower.

  ADVANTAGE OF THE INVENTION According to this invention, the granulated material containing the granular material of the porous inorganic mineral which can stably accelerate | stimulate the artificial removal action of the pollutant in nature can be provided. Thereby, the purification of the contaminants in the application target substance (for example, groundwater) can be performed without causing a bias in the contact between the adsorbents, and the load applied to the purification tool can be reduced.

It is an expansion schematic diagram which shows an example of the granulated material of this invention. It is an expansion schematic diagram which shows another example of the granulated material of this invention. It is a measurement result of the X-ray diffraction of the synthetic | combination Schwertmannite. It is a schematic diagram which shows the example of a column (arsenic simulated contamination water is passed in the direction of the arrow 12).

The granulated product of the present invention is a granulated product that is granulated by attaching a porous inorganic mineral granular material to the surface of a granular material serving as a core, with a water-soluble inorganic salt binder as an adhesive.
FIG. 1 is an enlarged schematic view showing an example of the granulated product of the present invention.
As shown in FIG. 1, the granulated product 31 of the present invention comprises (A) a porous inorganic mineral granular material, (B) a granular material serving as a nucleus, and (C) a water-soluble inorganic salt binder. . (B) The granular material used as a nucleus becomes the nucleus of the granular material of (A) porous inorganic mineral, when the granular material of (A) porous inorganic mineral adheres to the surface. (C) The water-soluble inorganic salt binder bonds (A) the porous inorganic mineral powder and (B) the granular material serving as the nucleus, and (B) the surface of the granular material serving as the nucleus (A) porous. Granules are formed by adhering powdered inorganic minerals to each other.
FIG. 2 is an enlarged schematic view showing another example of the granulated product of the present invention. As shown in FIG. 2, in addition to (C) the water-soluble inorganic salt binder, (c1) an iron compound and (D) an inorganic filler may further be contained. In that case, both (c1) the iron compound and (D) the inorganic filler may be contained, or only one of them may be contained.

  (A) The particle diameter M of the porous inorganic mineral particles is preferably 0.01 μm to 100 μm (0.01 μm or more and 100 μm or less) in average particle diameter, particularly 1.0 to 50 μm (1.0 μm or more). 50 μm or less) is more preferable from the viewpoint of adsorption efficiency. When the average particle size is not less than the above lower limit (0.01 μm), it is possible to avoid the possibility of difficulty in production and the possibility of significantly reducing the filtration rate when used in a separation and removal device such as a filter. Therefore, it is preferable. In addition, when the thickness is 100 μm or less, it is preferable because the surface of a granular material serving as a nucleus cannot be sufficiently coated or combined, and the possibility of causing molding defects can be avoided.

  (B) The average particle diameter L of the granular material serving as the nucleus is preferably in the range of 0.1 mm to 2 mm (more than 0.1 mm and 2 mm or less), particularly 0.2 to 1 mm (0). .2 mm and less than 1 mm) is more preferable from the viewpoint of granulation yield. Furthermore, it is preferable that particles having a particle diameter of 0.2 mm or less are 20% (number) or less, and particles having a particle diameter of 1 mm or more are preferably 20% (number) or less from the same point.

  The average particle diameter can be obtained by directly observing an image with a laser diffraction type particle size measuring apparatus or an electron microscope and performing statistical processing. In the measurement with the laser diffraction particle size meter, there is no significant difference between the diffraction behavior of the incident laser beam due to the aggregated particles and the diffraction behavior of the isolated primary particles, so the measured particle size exists as a single primary particle. There is no distinction between the particle size or the size of the aggregated secondary particles. Therefore, the average particle size measured by this method is an average value reflecting the average particle size of the secondary particles including the isolated primary particles that have not been agglomerated in a broad sense. It is preferable to use together with the method of observing and obtaining by statistical processing.

  The porous inorganic mineral used in the present invention is preferably at least one selected from the group consisting of iron hydroxide, clay mineral and zeolite. The granular material ((A) porous inorganic mineral granular material) used in the present invention forms a granulated material by covering the surface of the granular material as a core.

  Examples of the iron hydroxide used in the present invention include at least one selected from the group consisting of Schwertmannite, goethite, jarosite, and ferrihydrite. In particular, from the viewpoint of adsorption performance, Schwertmannite and ferrihydrite, which can obtain a granular material having a high specific surface area, are suitable.

  Examples of the clay mineral used in the present invention include montmorillonite, beidellite, nontronite, saponite, hectorite, smectites represented by stevensite, mascobite, phlogopite, teniolite, biotite, margarite, clintonite, tetrasilicon. Illustrative examples include mica such as mica and ion-exchangeable silicates such as vermiculites, imogolite, and allophane amorphous silicates, which are alteration minerals thereof. A better adsorbent can be obtained by selecting smectites, vermiculites, and amorphous silicates having high ion exchange capacity.

  The zeolite used in the present invention is not particularly limited. For example, the natrolite group represented by natrolite, gonnaldite, edding tonite, etc., the analsim group represented by analsim, leucite, yugawaralite, etc., gismondine , Gismondine Group represented by Poringite-K, Philipsite-Ca, Chabazite-Ca, Elionite-Na, Chabazite Group represented by Hojasite-Na, Mordenite, Ferrierite-Mg, Mu Structure unknowns such as mordenite group represented by Tinaite, Hulandite group represented by Hulandite-Ca, clinoptilolite-Na, Stillbite-Ca, Kouresite, etc. Examples include naturally occurring zeolites such as the minosilicate group, and synthetic zeolites such as A, L, X, Y, Na-P1, ZK-5, and ZSM-11. Synthetic zeolite having a uniform particle size, more preferably A, X, etc., which have a small difference in mass ratio between silica and alumina. It is preferable that the difference between the mass ratios of silica and alumina is not too large in order to avoid the possibility that the hydrophobicity of the surface increases and the affinity with the water-soluble binder deteriorates.

  The granular material (B) used in the present invention is not particularly limited as long as the particle diameter is satisfied, hardly soluble silica sand, inorganic particles of glass beads, finely divided clay, titanium oxide, Granules granulated with a substance selected from calcium carbonate or the like may be used.

  Since the performance as an adsorbent is further improved when a porous substance is used for the granular material (B) used in the present invention, it can be suitably used as a purifying agent. As the granular material serving as a porous core, heterogeneous non-spherical activated carbon (porous granular activated carbon) can be suitably used. There is no restriction | limiting in particular as charcoal used as the raw material, For example, what is obtained from coconut shell charcoal, coke, charcoal, coal, or resin carbonized goods etc. may be sufficient.

  Furthermore, a porous granular zeolite can be used as a granular material which becomes a porous core. There are no particular limitations on the type of zeolite used, and it is also possible to use zeolites exemplified in (A) porous inorganic mineral powders as long as they have a suitable particle size as a nucleus.

The water-soluble inorganic salt binder (C) used in the present invention is not particularly limited, but at least one of potassium salt, sodium salt, calcium salt, magnesium salt, and ammonium salt can be preferably used. The counter ion, for _{^{example, Cl -, NO 3 -?}} , SO 4 2-, CO 3 2-, HCO 3 2-, SiO 4 4, combination of anion selected from _B 4 ^{O 7-} are preferred.

  In the present invention, in addition to (C) a water-soluble inorganic salt binder, (c1) at least one iron compound selected from iron nitrate, iron sulfate, iron hydroxide, iron oxide, iron sulfate, iron oxalate, and ammonium iron sulfate Can be added. By adding an iron compound, the strength of the granulated material to be molded can be improved.

  In the present invention, in addition to (C) a water-soluble inorganic salt binder, (D) one of inorganic fillers selected from silica, potassium titanate, silicon carbide, zircon silicate, titanium oxide, zinc oxide, magnesium oxide, and aluminum oxide. More seeds can be added. (D) You may add an inorganic filler not only as a powder but as a solution or a slurry. By adding an inorganic filler, the porosity of the granulated product is increased at the same time as the drying process is shortened, and the practicality is improved.

  The blending ratio of each component constituting the granulated product of the present invention is such that, from the viewpoint of strength and the like, (B) the granular material serving as the core is 50 with respect to 100 parts by mass of the porous inorganic mineral powder. It is preferable that -300 mass parts (50-300 mass parts) and (C) water-soluble inorganic salt binder are 5-100 mass parts (5-100 mass parts). The inorganic filler (D) further added as necessary is 50 to 350 parts by mass (50 parts by mass or more and 350 parts by mass or less) with respect to 100 parts by mass of the porous inorganic mineral powder (A). Is preferably 100 to 300 parts by mass (100 to 300 parts by mass), more preferably 70 to 250 parts by mass (70 to 250 parts by mass).

  Although the water-soluble inorganic salt binder used in the present invention depends on the properties of the binder used, in general, the binder effect is manifested in as little amount as possible in order to enhance the adsorption characteristics and filterability of the resulting granulated product as much as possible. Those that do are preferred. Therefore, the content of the water-soluble inorganic salt binder is preferably 5 to 50% (5% to 50%) in the granulated product, and more preferably 10 to 30% (10% to 30%). The water-soluble inorganic salt binder is used by dissolving in a solvent such as water, but the amount can be adjusted as appropriate.

  (D) Inorganic fillers can be used for the purpose of drying the solvent used in the water-soluble inorganic salt binder and stabilizing the porosity of the granulated product, but the blending amount is (A) porous inorganic mineral The range of 50 to 350 parts by mass (50 to 350 parts by mass) is preferable, and 70 to 250 parts by mass (70 to 250 parts by mass) is more preferable with respect to 100 parts by mass of the granular material.

In this invention, the manufacturing method of the granulated material from the granular material of a porous inorganic mineral is the mixing process ((alpha)) which mixes the granular material used as (A) porous inorganic mineral, and (B) nucleus. And (C) preparing a water-soluble inorganic salt binder and water, adding to the mixture prepared in (α) to form a mixed and granulated product (β), and the undried obtained in (β) And a step (γ) of evaporating water from the granulated product and drying it.
Moreover, in this invention, the manufacturing method of the granulated material from the granular material of a porous inorganic mineral is the mixing process (A) the granular material of a porous inorganic mineral, and (B) the granular material used as a nucleus ( (α), (C) water-soluble inorganic salt binder and water, (D) powder, solution or slurry of inorganic filler are prepared and added to the mixture prepared in (α) to form a mixture and granulated product A step (β) and a step (γ) of evaporating and drying moisture from the undried granulated product obtained in (β).

In the step of adding and mixing the water-soluble inorganic salt binder aqueous solution, methods such as rolling granulation or stirring granulation, compression granulation, extrusion granulation, fluidized bed granulation, and spray granulation can be used. Specifically, a super mixer, a Henschel mixer, a ribbon mixer, a nauta mixer, a roller compactor, a Banbury mixer, a Brabender, a single or multi-screw extruder, a spray dryer, and the like can be used.
For example, if a spray dryer is used, it is also possible to perform both mixing and drying.

  The method used in the step (γ) of evaporating and drying moisture from the undried granulated product is not particularly limited. For example, natural drying, spray drying, drum drying, food dryer, hot air drying device A method such as a high-frequency drying apparatus can be used.

  The drying temperature of the undried granulated product is preferably 120 ° C. or lower so as not to cause alteration of the porous inorganic mineral, and 80 to 120 ° C. (80 ° C. to 120 ° C.) promotes evaporation of water. More preferably.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples.

  In order to identify the synthesized sample, a diffraction pattern was measured under the conditions of 40 kV and 30 mA (Cu-Kα ray) using a powder X-ray diffractometer ULTIMA-IV (manufactured by Rigaku). In order to examine the particle size of the powder sample, the used powder sample was dispersed in water or isopropyl alcohol, and the particle size distribution was measured using a laser diffraction particle size distribution measuring apparatus SLAD-7100 (manufactured by Shimadzu Corporation). In addition, using a scanning electron microscope S-5500 (manufactured by Hitachi, Ltd.), the observation was performed at an acceleration voltage of 7 kV, and the biaxial average diameter of 500 particles was measured from the observed image to obtain the average value.

[Production example]
In order to produce a porous inorganic mineral powder as an adsorbent, an iron hydroxide was prepared. First, 2 liters of a 0.02M Na ₂ SO ₄ solution was heated to 60 ° C. Solid Fe (NO ₃ ) ₂ .9H ₂ O was added thereto. Maintained at 60 ° C. for 12 minutes, further cooled and stored at pH 3. As a result, porous iron hydroxide schwertmannite was synthesized. The X-ray diffraction pattern of Schwertmannite is shown in FIG. A peak that characterizes Schwertmannite is observed in the vicinity of 2θ = 35 °. Moreover, the average particle diameter (median diameter) of the granular material was 9.8 μm.

(Evaluation of granulated product granulated from porous inorganic mineral powder)
The granulated product containing the porous inorganic mineral powder of the present invention is premised on use in soil and water, and the strength can be adjusted by changing the amount of the water-soluble inorganic salt binder. It becomes.
Moreover, in the present Example and the comparative example, the method of spraying a water-soluble inorganic salt binder was used as a method of adding a water-soluble inorganic salt binder and mixing and forming a granulated material.
It is desired that the granulated product to be manufactured satisfies the following requirements.
(A) When a water-soluble inorganic salt binder is sprayed, a granulated product containing a porous inorganic mineral powder is formed.
(B) The surface of the granular material which becomes the core when spraying the water-soluble inorganic salt binder is covered with a porous inorganic mineral powder.
(C) After a granulated product of a porous inorganic mineral is produced and dried, the porous inorganic mineral granular material and the core granular material are not separated even when touched by hand.
(D) When a granulated product of a porous inorganic mineral is put into a container containing water, bubbles are generated from the granulated product of the porous inorganic mineral under a standing condition.
In consideration of the above requirements, a granulated product of porous inorganic mineral was evaluated according to the following criteria.
A: 90% or more of the accumulated number of granules satisfies the above requirements.
(Circle): The granulated material which satisfy | fills the said requirements is 60 to 90% (60 or more and less than 90%).
(Triangle | delta): The granulated material which satisfy | fills the said requirements is 30 to 60% (more than 30 and less than 60%).
X: The granulated material which satisfy | fills the said requirements is 30% or less.

(Arsenic adsorption test)
A predetermined amount of absorbent cotton, glass beads, column material, and glass beads was packed in this order into a glass column having an inner diameter of 12 mm from the column discharge side to produce an evaluation column (FIG. 4). The column material was prepared by cutting particles of 75 μm or less of the granulated sample using a sieve. For all evaluations, the amount of porous inorganic mineral in the granulated material used for the column is converted and compared with the same amount of porous inorganic mineral.

  In the arsenic adsorption test, arsenic simulated contaminated water with an arsenic concentration of 1.06 ppm was passed through an evaluation column, and the arsenic concentration contained in the solution after passing was measured by an inductively coupled plasma mass spectrometer (ICP-MS, manufactured by PerkinElmer). ) To calculate the total amount of adsorbed arsenic.

Example 1
Schwertmannite synthesized in the production example as a granular material of a porous inorganic mineral, granular activated carbon GW48 / 100 (Kuraray Chemical Co., Ltd.) having an average particle size of 242.9 μm as a core granular material, a water-soluble inorganic salt binder aqueous solution A mixed aqueous solution of calcium chloride / iron sulfate / water = 10/1/20 (mass ratio) was prepared, and silica (average particle size 31 μm) was prepared as an inorganic filler. Next, the porous inorganic mineral powder (g) / core granular material (g) / water-soluble inorganic salt binder aqueous solution (g) / inorganic filler (g) = 2/3/3/2. Weighed as follows. Porous inorganic mineral particles / core particles / inorganic filler were put into a pan type rolling granulator and mixed while spraying a water-soluble inorganic salt binder while rotating at 60 rpm. The obtained granulated product was naturally dried, and a granulated product for evaluation was prepared by aligning the particle size with a sieve. The granulated material used in the following arsenic adsorption test was 1.86 g, and the amount of Schwermannite in the granulated material was 0.37 g. In the arsenic adsorption test, the total amount of the porous inorganic mineral constituting the granulated product used as the column material is the same as the total amount of the porous inorganic mineral filled in the column material used in Comparative Example 1. It was adjusted.
The results of the arsenic adsorption test are shown in Table 1.
Table 3 shows the evaluation results of the granulated product.
In addition, the separation of the porous inorganic mineral constituting the granulated product formed in Example 1 and the granular material serving as the nucleus was not observed for 8 hours in a state where the granulated product was allowed to stand in water.

In the arsenic adsorption test results in Table 1, the arsenic concentration is a value obtained by measuring the arsenic concentration contained in the solution after passing through the packed column. Further, the arsenic adsorption amount is calculated by calculating the total amount of arsenic adsorbed per 1 g of porous inorganic mineral Schwertmannite. By using the granulated product of the porous inorganic substance of the present invention under the condition of space velocity SV = 10, the arsenic concentration contained in the solution after passing through the column is 0.001 mg even after 72 hours have passed since the start of water flow. / L (not detected). This sufficiently satisfies the environmental standard value of 0.01 mg / L or less, and has a high arsenic removal capability. Incidentally, the amount of arsenic adsorption after 72 hours was 11.03 mg / g.
In addition, leakage of the porous inorganic substance (that is, schwertmannite) did not occur in the solution after passing through the column.

(Comparative Example 1)
An arsenic adsorption test column was prepared using the Schwertmannite granular material synthesized in Production Example 1. As a result of conducting an arsenic adsorption test under the condition of SV = 10 in the same manner as in Example 1, the porous inorganic substance (that is, Schwertmannite) gradually leaks from the column, and then clogs (water spots in the column). Occurred). As a result, 72 hours after passing water, the arsenic concentration contained in the solution after passing the column exceeded the environmental standard value of 0.01 mg / L (Table 2).

(Example 2)
Evaluation was performed in the same manner as in Example 1 except that the water-soluble inorganic salt binder and the inorganic filler were changed to the water-soluble inorganic binder FC2000 manufactured by Global Environment Research Institute. FC2000 is a mixture of a basic inorganic aqueous solution and inorganic powder containing magnesium chloride, magnesium oxide, iron sulfate, silica and the like as active ingredients. Table 3 shows the results of evaluation of the granulated product.
Moreover, the separation of the porous inorganic mineral constituting the granulated product formed in Example 2 and the granular material serving as a nucleus was not observed for 6 hours in a state where the granulated product was allowed to stand in water.

(Example 3)
Porous inorganic mineral particles, core granules, and water-soluble inorganic salt binder aqueous solution used in Example 1 were used as porous inorganic mineral powder (g) / core granules (g) / water solution. Evaluation was performed in the same manner as in Example 1 except that the aqueous inorganic salt binder solution (g) / inorganic filler (g) = 1/2/6/1. Table 3 shows the results of evaluation of the granulated product.
Moreover, in the granulated product formed in Example 3, the separation between the porous inorganic mineral constituting the granulated product and the granular material serving as the core exceeds 8 hours when left in water. I couldn't see it.

Example 4
Porous inorganic mineral particles, core granules, and water-soluble inorganic salt binder aqueous solution used in Example 1 were used as porous inorganic mineral powder (g) / core granules (g) / water solution. Evaluation was carried out in the same manner as in Example 1 except that the aqueous inorganic salt binder solution (g) / inorganic filler (g) = 2/1/3/4. Table 3 shows the results of evaluation of the granulated product.
In addition, in the granulated product formed in Example 4, the separation between the porous inorganic mineral constituting the granulated product and the granular material serving as the nucleus in a state of standing in water exceeds 8 hours. I couldn't see it.

(Example 5)
The porous inorganic mineral powder was changed to natural zeolite (clinoptlite, produced in Hokkaido) having an average particle size of 48.4 μm, and the mixing ratio with the aqueous water-soluble inorganic salt binder solution used in Example 1 was changed to porous inorganic mineral. The same as Example 1 except that the granular material (g) / particulate matter (g) / water-soluble inorganic salt binder aqueous solution (g) / inorganic filler (g) = 5/3/10/8 And evaluated. Table 3 shows the results of evaluation of the granulated product.
Further, in the granulated product formed in Example 5, the separation between the porous inorganic mineral constituting the granulated product and the granular material serving as the nucleus in a state of standing in water exceeds 8 hours. I couldn't see it.

(Example 6)
Porous inorganic mineral powder is converted to natural phlogopite (S-XF, Repco) with an average particle size of 4.4 μm, and core particles are converted to natural zeolite with an average particle size of 1.1 mm (clinoptlite, produced in Hokkaido). By changing the water-soluble inorganic salt binder aqueous solution used in Example 1 to porous inorganic mineral particles (g) / core particles (g) / water-soluble inorganic salt binder aqueous solution (g) / inorganic filler (g ) = 2/5/8/5 were measured in the same manner as in Example 1 except that they were weighed and blended. Table 3 shows the results of evaluation of the granulated product.
Moreover, in the granulated product formed in Example 6, the separation between the porous inorganic mineral constituting the granulated product and the granular material serving as the nucleus in a state of standing in water exceeds 8 hours. I couldn't see it.

(Example 7)
Schwertmannite synthesized in the production example as a granular material of a porous inorganic mineral, granular activated carbon GW48 / 100 (Kuraray Chemical Co., Ltd.) having an average particle size of 242.9 μm as a core granular material, a water-soluble inorganic salt binder aqueous solution A mixed aqueous solution of calcium chloride / water = 10/20 (mass ratio) was prepared. Next, these were weighed so that the porous inorganic mineral powder (g) / particles as core (g) / water-soluble inorganic salt binder aqueous solution (g) = 2/3/3. The porous inorganic mineral powder / core particles were put into a pan-type rolling granulator and mixed while spraying a water-soluble inorganic salt binder while rotating at 60 rpm. The obtained granulated product was naturally dried, and a granulated product for evaluation was prepared by aligning the particle size with a sieve. Table 3 shows the evaluation results of the granulated product.

  The granulated product of the present invention and the method for producing the same are related to a granulated product that can be used without deteriorating the purification treatment capacity and the frequency of replacement of the adsorbent and the method for producing the same, and can be used in the environmental purification industry, etc. There is sex.

DESCRIPTION OF SYMBOLS 5 ... Column, 5a ... Column discharge side, 7 ... Absorbent cotton, 10 ... Glass bead, 15 ... Evaluation column, 20 ... Column material (granulated material), 31, 33 ... Granulated material, (A) ... Porous inorganic mineral (B) ... powdered material as a core, (C) ... water-soluble inorganic salt binder, (c1) ... iron compound, (D) ... inorganic filler.

Claims (12)

Pollutants contaminated water and selectively adsorb and water the pollutant has been removed to a granulated product which passed through,
(A) a porous inorganic mineral powder, (B) a granular material serving as a nucleus, (C) a water-soluble inorganic salt binder, and (c1) an iron compound,
The (A) porous inorganic mineral powder is at least one selected from the group consisting of iron hydroxide, clay mineral and zeolite,
The granular material as the core (B) is at least one selected from the group consisting of silica sand, glass beads, clay, titanium oxide, calcium carbonate, activated carbon, and zeolite,
The (C) water-soluble inorganic salt binder is at least one selected from the group consisting of potassium salt, sodium salt, calcium salt, magnesium salt and ammonium salt,
The (c1) iron compound is at least one selected from the group consisting of iron nitrate, iron sulfate, iron hydroxide, iron oxide, iron oxalate and ammonium iron sulfate,
(A) The particle diameter of the porous inorganic mineral powder is 0.01 μm or more and 100 μm or less, and the particle diameter of the granular material serving as the core (B) is more than 0.1 mm and 2 mm or less. Granulated product.   The granulated product according to claim 1, wherein the iron hydroxide is at least one selected from Schbertmanite, goethite, jarosite, and ferrihydrite.   The clay mineral is composed of montmorillonite, beidellite, nontronite, saponite, hectorite, or smectite consisting of stevensite, mascobite, phlogopite, teniolite, biotite, margarite, clintonite, tetrasilicon mica, or sericite. The granulated product according to claim 1, wherein the granulated product is at least one selected from the group consisting of amorphous silicates composed of mica and its modified minerals vermiculites, imogolite, or allophane.   The granulated product according to any one of claims 1 to 3, wherein the granular material serving as the core (B) is porous granular activated carbon.   The granulated material according to any one of claims 1 to 3, wherein the granular material serving as the nucleus (B) is a porous granular zeolite.   (D) Inorganic filler is further contained, The granulated material of any one of Claims 1-5 characterized by the above-mentioned.   The blend ratio of the (A) porous inorganic mineral powder, the (B) core granule, and the (C) water-soluble inorganic salt binder is the above-mentioned (A) porous inorganic mineral powder 100. The said (B) granular material used as a nucleus is 50-300 mass parts with respect to a mass part, and the said (C) water-soluble inorganic salt binder is 5-100 mass parts. The granulated product according to any one of 1 to 6. It is a manufacturing method of the granulated material according to any one of claims 1 to 7,
(A) a step (α) of mixing a granular material of a porous inorganic mineral and (B) a granular material serving as a nucleus;
Step (β) of adding (C) a water-soluble inorganic salt binder and (c1) an aqueous solution of an iron compound to the mixture prepared in step (α) to form a mixture and granulated product,
A step (γ) of evaporating and drying water from the undried granulated product obtained in the step (β);
Comprising
The (A) porous inorganic mineral powder is at least one selected from the group consisting of iron hydroxide, clay mineral and zeolite,
The granular material as the core (B) is at least one selected from the group consisting of silica sand, glass beads, clay, titanium oxide, calcium carbonate, activated carbon, and zeolite,
The (C) water-soluble inorganic salt binder is at least one selected from the group consisting of potassium salt, sodium salt, calcium salt, magnesium salt and ammonium salt,
The (c1) iron compound is at least one selected from the group consisting of iron nitrate, iron sulfate, iron hydroxide, iron oxide, iron oxalate and ammonium iron sulfate,
(A) The particle diameter of the porous inorganic mineral powder is 0.01 μm or more and 100 μm or less, and the particle diameter of the granular material serving as the core (B) is more than 0.1 mm and 2 mm or less. A method for producing a granulated product.   The method according to claim 8, wherein in the step (β) of forming the mixed and granulated product, (D) an inorganic filler powder, solution or slurry is further added.   The mixing and granulating step (β) is any selected from the group consisting of rolling granulation, stirring granulation, compression granulation, extrusion granulation, fluidized bed granulation, and spray granulation. The production method according to claim 8 or 9, wherein the production method is performed using the method.   11. The method according to claim 8, wherein the drying step (γ) is performed using any method selected from the group consisting of spray drying, drum drying, food dryer, and natural drying. The manufacturing method of the granulated material as described in a term.   The temperature of the said drying process ((gamma)) is 120 degrees C or less, The manufacturing method of the granulated material of any one of Claims 8-11 characterized by the above-mentioned.