JP2020019701A - Amorphous composition, water granulated molten matter, water granulated molten matter-containing composition, and fertilizer - Google Patents

Abstract

To provide a composition in which an elution rate of silicic acid is large and which is effective as fertilizer.SOLUTION: An amorphous composition of this invention includes: MgO, SiO, CaO, and POas chemical composition, and an alumina component of 1.2 mass% or more, in which the molar ratio on the molar basis of the sum of the CaO and MgO to the sum of the SiOand PO, that is (CaO+MgO)/(SiO+PO), is 1.20-1.35 and the particle diameter is 0.5 mm or less; or MgO, SiO, CaO, and POas chemical composition, and an alumina component of 1.2 mass% or more, in which the molar ratio on the molar basis of the sum of the CaO and MgO to the sum of the SiOand PO, that is (CaO+MgO)/(SiO+PO), is 1.35-1.45 and the particle diameter is 0.15-0.5 mm.SELECTED DRAWING: None

Description

  The present invention relates to an amorphous composition, a crushed melt, a composition containing a crushed melt, and a fertilizer.

Silicic acid fertilizers useful for rice cultivation include siliceous (calcium silicate) and potassium silicate fertilizers. Silica is produced from slag as a raw material, and is a soil modifier mainly composed of SiO ₂ , CaO, and Al ₂ O ₃ and mainly for replenishing alkali content and silicic acid. However, silica has a hydrochloric acid-soluble silicic acid content of more than 30% by mass, but the elution amount is extremely reduced in a region of about 5 to 7 which is close to the actual soil pH, and is very efficient as a silicic acid source. Is a bad material.

  Therefore, even when actually used, fertilizer must be applied in a large amount of 200 kg per field 10a, and the labor required for it has become a heavy burden on farmers. Keikal is a material that does not contain any of the three elements of fertilizers, so it is common to use it by mixing it with other fertilizers. Is being done. Yorin is known to have a high dissolution property in the pH range near the neutrality of the silicic acid contained in it, and it is recognized that it is a phosphoric acid fertilizer and a siliceous source at the same time. Have been.

  It is said that the potassium silicate fertilizer has a higher leaching property than silicic acid, but is inferior to yorin at pH 5 to 7 and is not sufficient. Potassium silicate fertilizers are often fertilized in a mixture with iodine, as in the case of silicate, where again, iodine serves as a source of siliceous material.

  The potassium component generally facilitates vitrification of the composition and improves the dissolution of siliceous substances, but on the other hand, (1) the resulting product is expensive because the potassium raw material is expensive, and (2) sufficient It is uneconomical to increase the potassium content in order to ensure a high silica dissolution property. (3) Potassium is a strong alkali, which erodes furnace materials of manufacturing equipment. If added, the viscosity of the melt will increase, making it difficult to operate, and if the temperature is raised to lower it, potash will be volatilized.

On the other hand, it is known that the silicic acid component contained in yorin has a high dissolution property and a high plant absorbability. As is commercially available, the amount of SiO ₂ contained in phosphorus is about 20 to 25% by mass, but it is known that the elution rate decreases as the content of silicic acid increases. That is, a test example in which silica was added to a general raw material mixture of fused phosphorus fertilizer, heated, melted and quenched, and the dissolution property of silicic acid into a 2% citric acid aqueous solution was measured (Industrial Chemistry Magazine Vol. 60, 1109). P. 1957) states that the dissolution rate of silicic acid into a 2% citric acid aqueous solution (initial pH is about 2) reaches a peak at about 30% by mass.

Therefore, Patent Document 1 proposes an inorganic composition containing 30% by mass or more of SiO ₂ having a high elution property especially at pH = 5 to 7 of actual soil, and mixing with phosphorus manure before application by adding phosphorus. It is not necessary to provide materials mainly containing silicic acid, phosphorus and alkali, and it can be easily manufactured using ordinary phosphorus manufacturing equipment, and can be manufactured at low cost because it does not contain potassium. Proposal of siliceous fertilizer and soil modifying material used for crops that require silicic acid in the soil such as rice and rice.

JP 2000-34185 A

  The fertilizer of Patent Literature 1 is useful as a crop in which silicic acid in soil works usefully, particularly as a soil-making material or fertilizer for rice action.

Until now, serpentinite has been mainly used as the MgO source and the SiO ₂ source. Serpentine has been widely used as a fertilizer raw material because of its excellent MgO and SiO ₂ supply capacity, but it has become difficult to obtain it and alternative materials have been required. When you try to employ other ingredients as MgO and SiO ₂ source alternative to serpentinite, there or to inhibit the supply of the MgO and SiO ₂ by many other impurity components or cause an increase in cost.

Then, the present inventors examined components that inhibit the supply of SiO ₂ , and as a result, found that when a large amount of the alumina component was contained, this gelled and inhibited the elution of SiO ₂ . Therefore, it is expected that the use of a material having a small amount of alumina component is effective. However, such a material is actually more expensive than serpentine and has a cost problem.
For example, it is possible to use a magnesite ore or the like as the MgO source, but it becomes difficult to provide inexpensive fertilizer as imported raw materials soar.

  In view of the above situation, the present inventors have dared to use a material having a high alumina content and control the composition and particle size of the material, and thereby demonstrate the same effectiveness as using serpentine. I found it. That is, the present invention is as follows.

[1] An amorphous composition containing MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components and containing an alumina component in an amount of 1.2% by mass or more. the total molar ratio of said CaO and MgO to the sum of ₂ and _{P 2 O 5 [(CaO +} MgO) / (SiO 2 + P 2 O 5)] is 1.20 to 1.35, the particle diameter is 0.5mm An amorphous composition comprising:
[2] An amorphous composition containing MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components, and containing 1.2% by mass or more of an alumina component. the total molar ratio of said CaO and MgO to the sum of ₂ and _{P 2 O 5 [(CaO +} MgO) / (SiO 2 + P 2 O 5)] is 1.35 to 1.45, the particle diameter is 0.15mm An amorphous composition that is 0.5 mm.
[3] The amorphous composition according to [1] or [2], wherein the MgO and SiO ₂ sources include ferronickel slag.
[4] The amorphous composition according to any one of [1] to [3], wherein a dissolution rate of silicic acid is 75% or more.
[5] A granulated melt containing the amorphous composition according to any one of [1] to [4].
[6] A composition comprising the crushed molten substance according to [5].
[7] A fertilizer comprising the crushed molten substance according to [5] or the composition containing the crushed molten substance according to [6].
[8] An amorphous composition containing MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components and containing an alumina component in an amount of 1.2% by mass or more. Particles of the amorphous composition having a molar ratio [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] of the total of CaO and MgO to the total of ₂ and P ₂ O ₅ of 1.20 to 1.35 An amorphous composition having a silica elution rate of 75% or more when the diameter is adjusted to 0.5 mm or less.
[9] An amorphous composition containing MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components and containing an alumina component in an amount of 1.2% by mass or more. ₂ and a molar ratio of the combination of the said CaO and MgO to the total of _{P 2 O 5 [(CaO +} MgO) / (SiO 2 + P 2 O 5)] particle of amorphous composition is 1.35 to 1.45 An amorphous composition having a silica elution rate of 75% or more when the diameter is adjusted to 0.15 mm to 0.5 mm.

  ADVANTAGE OF THE INVENTION According to this invention, the dissolution rate of a silicic acid is large and it can provide the amorphous composition effective as a fertilizer.

  Hereinafter, each embodiment (this embodiment) of the amorphous composition, the crushed molten substance, the composition containing the crushed molten substance, and the fertilizer of the present invention will be described in detail.

[1. Amorphous composition, crushed melt, crushed melt-containing composition]
The amorphous composition according to the present embodiment is preferably a granulated melt. The value of each chemical component of the amorphous composition is preferably calculated as an MgO equivalent, a SiO ₂ equivalent, a P ₂ O ₅ equivalent, a CaO equivalent, or an Al ₂ O ₃ equivalent.
The crushed molten product according to the present embodiment includes, for example, a configuration of the following first amorphous composition or second amorphous composition.

The first amorphous composition contains MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components, contains 1.2% by mass or more of an alumina component, and contains SiO ₂ and P ₂ O molar ratio of the combination of CaO and MgO to the sum of _{5 [(CaO + MgO) /} (SiO 2 + P 2 O 5)] is 1.20 to 1.35, the particle size is 0.5mm or less .

Further, the second amorphous composition is a molten granulated product containing MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components and containing an alumina component in an amount of 1.2% by mass or more. when converted, the molar ratio of the sum of the CaO and MgO to the sum of SiO ₂ and _{P 2 O 5 [(CaO +} MgO) / (SiO 2 + P 2 O 5)] is 1.35 to 1.45, the particle It is a granulated melt having a diameter of 0.15 mm to 0.5 mm.

The “chemical components” are those obtained by converting Mg, Si, Ca, and P into oxides of MgO, SiO ₂ , CaO, and P ₂ O ₅ , respectively. For example, the fertilizer analysis method (Ministry of Agriculture, Forestry and Fisheries, Agriculture) Environmental Technology Research Institute method). The actual product can be confirmed by, for example, X-ray fluorescence diffraction (XRF).

Both the first amorphous composition and the second amorphous composition contain an alumina component (Al ₂ O ₃ ) of 1.2% by mass or more. The alumina component is derived from the raw material to be used. When the alumina component is contained in an amount of 1.2% by mass or more, elution of an effective component such as SiO ₂ is hindered, but the range of selection of the raw material type is widened and the cost can be reduced. The content of the alumina component is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, most preferably 3.0% by mass or less, and 2.2% by mass. It is even more preferred that:
Here, the problem of containing the alumina component in an amount of 1.2% by mass or more, that is, the problem of inhibiting the supply of SiO ₂ is that the range of the molar ratio [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] is 2 The problem is solved by dividing into two cases and setting a specific particle size range for each case. Further, the present embodiment can solve the problem that the presence of the alumina component lowers the dissolution rate of silicic acid, and that the content of other components substantially decreases as the content increases.

In the first amorphous composition, the molar ratio of the total of CaO and MgO to the total of SiO ₂ and P ₂ O ₅ [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] in terms of mol. Is 1.20 to 1.35, and the particle diameter is 0.5 mm or less, thereby eliminating the problem of containing the alumina component at 1.2% by mass or more. When the particle size is 0.5 mm or less, the molar ratio is 1.20 to 1.35, so that the abundance of Ca ions and Mg ions decreases, and the pH increases in a fine environment near the surface of the material particles. Is considered to be reduced, and the effect of suppressing the elution by the Al compound is presumed to be reduced. As a result, the above problem is considered to be eliminated. The particle size is preferably at least 0.01 mm.

In the second amorphous composition, the molar ratio of the total of CaO and MgO to the total of SiO ₂ and P ₂ O ₅ [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ ) in terms of moles] )] Is 1.35 to 1.45 and the particle size is 0.15 mm to 0.5 mm, so that the particle size in the fine environment near the material particle surface is smaller than when the particle size is 0.15 mm or less. It is presumed that the increase in pH is suppressed, and the effect of suppressing the elution by the Al compound is reduced, and as a result, the above problem is considered to be eliminated. Preferably, the molar ratio is greater than 1.35.

  The particle diameters of the first amorphous composition and the second amorphous composition are, for example, a crushed molten granulated material precursor whose particle size is not adjusted is crushed by a crusher, and the crushed material is sieved with various sieves. By doing so, it can be adjusted to a desired range.

The crushed molten product according to the present embodiment including the first amorphous composition or the second amorphous composition will be described in more detail below.
As described above, the crushed molten material according to the present embodiment contains MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components. The total content of these in the crushed melt is preferably 87% by mass or more, and more preferably 90% by mass or more.

  Many of the conventionally known silicate-eluting substances contain potassium as a main component, for example, potassium silicate fertilizer, whereas the molten granulated product according to the present embodiment contains this as a main component. Absent. As a result, disadvantages such as an increase in product price, erosion of the furnace material of the manufacturing equipment, and difficulty in operation are easily eliminated.

It is preferable that the amorphous composition and the crushed molten material according to the present embodiment are amorphous in order to enhance the dissolution property of silicic acid. The extent of the amorphous, according to the experimental investigation results of the present ^{inventors, NMR-29} Si chemical shift value (hereinafter, simply referred to as NMR-Si) for, which half value width has a more spread 10ppm Is enough. The method for measuring NMR-Si is described in JP-A-2000-34185.

The SiO ₂ content according to the present embodiment is preferably 30% by mass or more, and more preferably 32 to 45% by mass. When the content is 30% by mass or more, a sufficient amount of eluted silicic acid can be secured, and the value as siliceous material or fertilizer can be increased.

  MgO according to the present embodiment has the effect of lowering the melting temperature and the effect of increasing the dissolution rate of silicic acid, and is also effective as a fertilizer component. The MgO content is preferably 1 to 20% by mass, more preferably 7 to 18% by mass. When the content is 1 to 20% by mass, the above-described effects are easily obtained, and no antagonism is caused in the absorbability of the fertilizer component of the applied plant.

The P ₂ O ₅ content according to the present embodiment is preferably 1 to 12% by mass, and more preferably 4 to 10% by mass. When the content is 1 to 12% by mass, the dissolution rate of silicic acid can be increased, and the application of P ₂ O ₅ can be further maintained without the need for mixed application of phosphorus fertilizer.

  The CaO content according to the present embodiment is preferably from 5 to 35% by mass, and more preferably from 8 to 35% by mass. When the content is 5 to 35% by mass, good fertilizing effect is easily obtained.

  In the present embodiment, in addition to the above-mentioned components constituting the main components, boron and manganese which are effective as trace components may be contained. The presence of boron or manganese has the effect of lowering the melting temperature and increasing the fluidity of the granulated melt in the production method described below, and also promotes the amorphous composition to be obtained and the granulated melt. It also has the effect of promoting the dissolution of silicic acid. Further, iron oxide, aluminum oxide, and the like which are inevitably mixed may be included.

Regarding the amorphous composition of the present embodiment, the method for obtaining a crushed molten product, first, as raw materials, phosphate rock, silica stone, magnesite ore, limestone, ferronickel slag, ferromanganese slag, various blast furnace slag, various steelmaking slag Ordinary raw materials containing P ₂ O ₅ , CaO, MgO, or SiO ₂ such as slag, slag, and fly ash can be used. However, serpentine is not used. Alternatively serpentinite, MgO and SiO ₂ source preferably includes a ferronickel slag.
In addition, various blast furnace slags and various steelmaking slags (silical) have a high alumina content, but can be used as raw materials for the amorphous composition and the crushed molten material of the present embodiment.

Here, ferronickel slag refers to slag (mine slag) that is by-produced when smelting and collecting ferronickel from nickel ore or the like. As the ferronickel slag, for example, a ferronickel slag fine aggregate (range of particle size = less than 5 mm) conforming to JIS A5011-2 “Slag aggregate for concrete part 2: ferronickel slag fine aggregate” is classified or / And those prepared by pulverizing to have a particle size of 0.1 mm to 1.0 mm.
Ferronickel slag is expected to have a smaller loss on ignition than natural raw materials. Therefore, it is easy to calculate the balance of the amount, and the components of the product are stable. As a result, it is possible to contribute to improvement in productivity. Also, in particular, by using ferronickel slag instead of serpentine, it becomes easy to obtain an amorphous composition or a crushed molten material that can be reduced in cost and is effective as a fertilizer.

In consideration of the amount of volatile components and the like, the raw material as described above is adjusted so that the product has a desired composition, that is, in the case of the first molten granulated product, the alumina component is set to 1.2% by mass or more, It is blended so that the ratio [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] becomes 1.20 to 1.35. In the case of the second granulated melt, the alumina component is set to 1.2% by mass or more, and the molar ratio [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] is set to 1.35 to 1.45. To mix.
Assuming formulation as described above, the MgO 1 to 20 wt%, a SiO ₂ 30 to 50 _wt%, P 2 _{O 5} to 12 wt%, the CaO content to be 5 to 35 wt% It is preferable to design the composition.

  After blending, the blend is melted at a high temperature. As a furnace (melting furnace) used for melting, an electric furnace such as an external heating electric furnace, an arc furnace, a high-frequency heating furnace, or a variety of combustion gas furnaces such as a flat furnace can be used. The melting temperature is preferably 1350 ° C. or higher, depending on the composition. It is preferable to melt at a temperature about 150 ° C. or more higher than the temperature at which the raw material having the target composition is completely melted, since a sufficient cooling rate can be obtained from the melting temperature to a temperature at which crystallization does not proceed. As the melting furnace, an electric furnace and a flat furnace are selected as described later, since the melt can be rapidly cooled and an amorphous inorganic composition can be easily obtained. The melting temperature is preferably 3000 ° C. or lower, more preferably 2000 ° C. or lower.

  The quenching of the melt is indispensable in order to attain the amorphization of the obtained composition and the crushed melt and to enhance the dissolution of silicic acid. In the case of crystalline, it is generally known that the composition is strongly bonded and the components are not eluted, and when used for fertilizer utilizing the eluted components, it is necessary to be amorphous . The quenching is generally performed by applying a method of spraying water having a mass of 20 to 40 times the mass of the melt extracted from the furnace, or a method of immersing the melt in a large amount of water. As a cooling method for obtaining the amorphous composition of the present invention, the time required from the melting temperature to 100 ° C. is preferably 20 seconds or less, preferably 10 seconds or less, and particularly, the raw material is completely melted. Since it is preferable to keep the temperature between 200 ° C. above and below the temperature within 5 seconds, a method of cooling by applying a jet water flow is preferable. Further, the cooling method using the jet water stream has an effect that a sandy substance can be directly obtained from the melt, and the pulverization as a subsequent step can be omitted.

  Thereafter, in the case where the first amorphous composition is used, classification is performed by the above-described sieving so that the particle size becomes 0.5 mm or less. When the second amorphous composition is used, classification is performed so that the particle size becomes 0.15 mm to 0.5 mm. It is preferable to use a sieve described in JIS Z8801.

  The amorphous composition or the crushed melt obtained in this manner can be used as it is as a fertilizer or a soil modifier, but can also be used as a granular material described below for various uses.

The amorphous composition or the crushed molten material of the present embodiment preferably has a silica content elution rate of 75% or more in a 4% by mass citrate buffer (the initial value of pH is 5.5), More preferably, it is at least 80%.
Here, the above-mentioned elution rate is the amount of silicic acid (soluble silicic acid) eluted in the citrate buffer expressed as a percentage with respect to the total amount of SiO ₂ in the crushed molten material.

In view of the above, the amorphous composition according to another aspect of the present invention includes, as a chemical component, MgO, SiO ₂ , CaO, and P ₂ O _5, and an amorphous component containing an alumina component of 1.2% by mass or more. And a molar ratio [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] of the total of CaO and MgO to the total of SiO ₂ and P ₂ O ₅ in terms of moles is 1.20. When the particle diameter of the amorphous composition is adjusted to 0.5 mm or less, the amorphous composition has an elution rate of silicic acid of 75% or more, or as a chemical component. comprises MgO and SiO ₂ and CaO and _P 2 _{O 5,} a amorphous composition containing more than 1.2 mass% of alumina component, when the molar basis, of SiO ₂ and _P 2 _{O 5} The molar ratio of the sum of CaO and MgO to the sum [ When (CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] is 1.35 to 1.45, and the particle diameter of the amorphous composition is adjusted to 0.15 mm to 0.5 mm, the dissolution rate of silicic acid is Is preferably 75% or more.

The first amorphous composition, the second amorphous composition, or the crushed melt can be used alone, but may be a crushed-melt-containing composition containing at least one of these. . In this case, the content of the first amorphous composition and / or the second amorphous composition, or the content of the crushed molten material is not limited as long as these effects are sufficiently exhibited. , 15% by mass or more, more preferably 30% by mass or more. For example, in the case of a composition containing a crushed molten material containing the first amorphous composition, in addition to the first crushed molten material, a crushed molten material containing an alumina component of 1.2% by mass or more, The ratio [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] is not in the range of 1.20 to 1.35, or the crushed molten material whose particle size exceeds 0.5 mm, or the composition or particle size It may also contain other different crushed molten water.

[2. Granular material]
The amorphous composition, the crushed molten substance, or the composition containing the crushed molten substance according to the present invention may be formed into a granular material with a binder. By making it granular, it can be supplied in a form that is easy to handle during fertilization.

  In the case of granulation, the granulation method is not limited, and examples thereof include a tumbling granulation method, an extrusion granulation method, a compression granulation method, and a stirring granulation method. The particle size at the time of granulation can also be appropriately selected, but can be preferably selected from a range of about 1 to 5 mm.

  When a binder is used during granulation, the type of the binder is not particularly limited, and various binders can be used. For example, various starches, starches, gums such as xanthan gum, molasses, waste yeast liquid, alcohol fermentation waste liquid concentrate, stephen wastewater concentrate, polyvinyl alcohol (PVA), polyvinyl pyrrolidone, lignin sulfonate, Carboxymethyl cellulose (CMC) and the like can be mentioned. Furthermore, various granulation auxiliaries can be contained, and there is no particular limitation, and various types can be used. For example, various clay minerals such as diatomaceous earth, bentonite, montmorillonite, hectorite, saponite, stevensite, beidellite, swellable mica, vermiculite, zeolite, gypsum, gypsum hemihydrate, and anhydrous gypsum can be exemplified.

The amount of the amorphous composition, the crushed melt or the crushed melt-containing composition according to the present invention in the granular material is preferably about 85 to 97% by mass from the viewpoint of ensuring its effectiveness.
The total amount of MgO, SiO ₂ , P ₂ O ₅ , CaO, and Al ₂ O ₃ is preferably at least 80% by mass, more preferably at least 90% by mass in the crushed molten material.

[3. fertilizer]
Embodiments according to the fertilizer of the present invention include an amorphous composition, a crushed molten substance, a composition containing a crushed molten substance, or the above-mentioned granular material. If necessary, the fertilizer may be mixed with other fertilizers such as nitrogen and potash to obtain a composite fertilizer having a desired composition.

  The fertilizer of the present invention can be used according to the same method of use as known or commercially available fertilizers. For example, it may be directly applied to the soil where plants are grown. In addition, it can be used in any form of base fertilizer (base manure) or topdressing.

  Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited thereto.

The raw materials used in the examples and comparative examples are as follows.
・ Phosphite ore and peridotite (Toho Olivin Kogyo Co., Ltd.)
・ Magnesite ore (Magball, Fuji Mineral Materials Co., Ltd.)
・ Hard lime (made by Ueda Lime Manufacturing Co., Ltd.)
・ Ferronickel slag (Eggplant sand, Nippon Yakin Kogyo Co., Ltd.)
・ Stone (Chubu Mining Co., Ltd.)
・ Blast furnace slag (Keikaru) (Nippon Steel Corporation)
In the crushed melts of the present example and the comparative example, the term “amorphous” means that the half width of NMR-Si has a spread of 10 ppm or more. In the table, the term “amorphous” means that the half width of NMR-Si has a spread of 10 ppm or more. The term "crystalline" means that the half width of NMR-Si is less than 10 ppm.

[Examples 1 and 2 and Comparative Examples 1 and 2]
Phosphorite, peridotite, magnesite ore, hard calcined lime, ferronickel slag, and so on, as chemical components, MgO, SiO ₂ , P ₂ O ₅ , CaO, and Al ₂ O _{3 at the} ratios shown in Table 1 below. And quartzite were mixed, put in a platinum crucible, placed in an electric furnace, and heated and melted at 1500 ° C. The melt taken out of the electric furnace was quickly poured into water to obtain an unadjusted size of the granulated melt.
The molar ratio [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] was determined from the content ratio.

The granulated molten water whose particle size had not been adjusted was pulverized with a top grinder. The pulverized product is put into a sieve having an opening of 212 μm, and the sieve frame is manually beaten at a rate of 120 times per minute while tilting the sieve at 20 °. During this time, the sieve is leveled four times a minute. , And rotated 90 °, and smashed the sieve frame 1-2 times. When fine powder was attached to the back surface of the sieve net, it was gently removed from the back surface of the sieve with an appropriate brush, and the fine powder was placed under the sieve.
These operations were repeated, passed through a sieve, and the samples passed through the sieve were combined and mixed to produce a crushed molten product. The sieve was hand-sieved in accordance with the official method, and the second sieve (opening) was 150 μm.
The sieve described in JIS Z8801 was used.

[Comparative Example 3]
Phosphorite, peridotite, magnesite ore, hard calcined lime, ferronickel slag, and so on, as chemical components, MgO, SiO ₂ , P ₂ O ₅ , CaO, and Al ₂ O _{3 at the} ratios shown in Table 1 below. And quartzite were mixed, put in a platinum crucible, placed in an electric furnace, heated at 1500 ° C., and then cooled to room temperature at a cooling rate of about 2 ° C./min without quenching as in Example 1. Thus, a sample was prepared.

[Example 4]
Phosphorite, hard-burned lime, magnesite ore, siliceous and quartzite were mixed so that MgO, SiO ₂ , P ₂ O ₅ , CaO, and Al ₂ O ₃ as chemical components had the ratios shown in Table 1 below. Except for the above, a granulated melt was produced in the same manner as in Example 1.

Example 8
Phosphorite, hard-burned lime, magnesite ore, siliceous and silica were mixed so that the chemical components were MgO, SiO ₂ , P ₂ O ₅ , CaO, and Al ₂ O _{3 in the} proportions shown in Table 2 below. Except for the above, a granulated melt was produced in the same manner as in Example 1.

[Reference Example 4]
Phosphorite, serpentine, hard-burned lime, magnesite ore and silica are mixed so that MgO, SiO ₂ , P ₂ O ₅ , CaO, and Al ₂ O ₃ as chemical components have the ratios shown in Table 1 below. Except that, a granulated melt was produced in the same manner as in Example 1.

[Example 3]
A crushed molten product was produced in the same manner as in Example 1 except that the particle size was changed from 0.212 mm to 0.300 mm by changing the sieve mesh.

〔Measuring method〕
(Measurement of chemical components)
Fertilizer analysis method (Ministry of Agriculture, Forestry and Fisheries, National Institute for Agricultural and Environmental Technology)-1992 version-was analyzed by the method of total analysis of each component. Each component, MgO conversion value, SiO ₂ conversion _value, P 2 _{O 5} converted value, CaO conversion value, was measured as calculated _{as Al} 2 _{O 3} value.
(Measurement of dissolution rate)
The amount of silicic acid eluted in a 4% sodium citrate buffer solution (initial pH value: 5.5) was measured for the granulated melt prepared in Examples and Comparative Examples, and the elution rate of silicic acid was measured. Table 1 shows the results.
In addition, the specific measuring method of the elution rate was as follows.
A solution obtained by adding a 2N aqueous sodium hydroxide solution to a citric acid aqueous solution was added to a beaker, and 1 g of the molten granulated product was added to 150 ml of a 4% by mass sodium citrate buffer adjusted to pH 5.5. Rocked for one hour. After the filtrate obtained by filtering this solution through filter paper was diluted with pure water, the amount of SiO ₂ (the amount of eluted silicic acid) contained in the filtrate was measured by ICP (inductively coupled plasma emission spectroscopy). The elution rate was determined from the obtained amount of eluted silicic acid and the amount of SiO ₂ in the crushed molten product.

[Examples 5 to 7 and Comparative Example 5]
Phosphorite, peridotite, magnesite ore, hard calcined lime, ferronickel slag, and so on so that MgO, SiO ₂ , P ₂ O ₅ , CaO, and Al ₂ O ₃ as chemical components have the ratios shown in Table 2 below. The silica stone was mixed, placed in a platinum crucible, placed in an electric furnace, and heated and melted at 1500 ° C. The melt taken out of the electric furnace was quickly poured into water to obtain an unadjusted size of the granulated melt.
The molar ratio [(CaO + MgO) / (SiO ₂ + P ₂ O ₅ )] was determined from the content ratio.

The granulated molten water whose particle size had not been adjusted was pulverized with a top grinder. The crushed product is put into a sieve having an opening of 500 μm, and the sieve frame is manually beaten at a rate of 120 times a minute while the sieve is inclined at 20 °. During this time, the sieve is leveled four times a minute. , And rotated 90 °, and smashed the sieve frame 1-2 times. When fine powder was attached to the back surface of the sieve net, it was gently removed from the back surface of the sieve with an appropriate brush, and the fine powder was placed under the sieve.
These operations were repeated, passed through a sieve, and the samples passed through the sieve were combined and mixed to produce a crushed molten product. The sieve was hand-sieved in accordance with the official method, and the second sieve (opening) was 150 μm.

[Comparative Example 6]
A crushed molten product was produced in the same manner as in Example 5, except that the particle size was changed to 0.106 mm or less by changing the sieve size.

[Comparative Example 7]
A crushed molten product was produced in the same manner as in Example 4, except that the particle size was changed from 0.600 mm to 3.35 mm by changing the sieve mesh.

(Measurement of dissolution rate)
The dissolution rate was determined in the same manner as in Example 1 for the crushed melts of Examples 5 to 8 and Comparative Examples 5 to 7. The results are shown in Table 2 below.

As shown in Tables 1 and 2, the dissolution rate was high and good results were obtained in all Examples. In addition, although the elution rate is as good as that of the granulated smelt using serpentine, in this example, ferronickel slag and keikaru are used instead of serpentine, so that the case of using serpentine The cost is equal to or less than that, and safety can be secured.
Advantageous Effects of Invention According to the present invention, it is possible to provide a crushed molten product that does not use serpentine, can reduce costs, and is effective as a fertilizer. In addition, even if a large amount of the alumina component is contained, it is possible to provide a crushed molten product in which the elution of SiO ₂ is favorable.

  The crushed molten product of the present invention is useful as a crop in which silicic acid in soil works usefully, particularly as a soil-making material or fertilizer for rice action.

Claims (9)

An amorphous composition containing MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components, and containing an alumina component in an amount of 1.2% by mass or more,
In when the molar basis, the total molar ratio of said CaO and MgO to the total of the SiO ₂ and _{P 2 O 5 [(CaO +} MgO) / (SiO 2 + P 2 O 5)] is 1.20 to 1.35 Yes,
An amorphous composition having a particle size of 0.5 mm or less. An amorphous composition containing MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components, and containing an alumina component in an amount of 1.2% by mass or more,
In when the molar basis, the total molar ratio of said CaO and MgO to the total of the SiO ₂ and _{P 2 O 5 [(CaO +} MgO) / (SiO 2 + P 2 O 5)] is 1.35 to 1.45 Yes,
An amorphous composition having a particle size of 0.15 mm to 0.5 mm. The amorphous composition according to claim 1, wherein the MgO and SiO ₂ sources include ferronickel slag.   The amorphous composition according to any one of claims 1 to 3, wherein a dissolution rate of silicic acid is 75% or more.   A granulated melt containing the amorphous composition according to claim 1.   A composition comprising the crushed molten product according to claim 5.   A fertilizer comprising the crushed molten substance according to claim 5 or the crushed molten substance-containing composition according to claim 6. An amorphous composition containing MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components, and containing an alumina component in an amount of 1.2% by mass or more,
In when the molar basis, the total molar ratio of said CaO and MgO to the total of the SiO ₂ and _{P 2 O 5 [(CaO +} MgO) / (SiO 2 + P 2 O 5)] is 1.20 to 1.35 An amorphous composition wherein the dissolution rate of silicic acid is 75% or more when the particle diameter of a certain amorphous composition is adjusted to 0.5 mm or less. An amorphous composition containing MgO, SiO ₂ , CaO, and P ₂ O ₅ as chemical components, and containing an alumina component in an amount of 1.2% by mass or more,
In when the molar basis, the total molar ratio of said CaO and MgO to the total of the SiO ₂ and _{P 2 O 5 [(CaO +} MgO) / (SiO 2 + P 2 O 5)] is 1.35 to 1.45 An amorphous composition wherein the dissolution rate of silicic acid is 75% or more when the particle diameter of a certain amorphous composition is adjusted to 0.15 mm to 0.5 mm.