WO2011099185A1

WO2011099185A1 - Iron ion supply material, method for manufacturing iron ion supply material, and method for supplying iron ion

Info

Publication number: WO2011099185A1
Application number: PCT/JP2010/062974
Authority: WO
Inventors: 林明夫; 宇田川悦郎; 金子諒子; 小林延朗; 鷹野明; 光藤浩之; 吉澤千秋; 長谷川治
Original assignee: Ｊｆｅミネラル株式会社
Priority date: 2010-02-15
Filing date: 2010-07-26
Publication date: 2011-08-18
Also published as: JP2011160764A; KR20120120321A; KR101496531B1; JP4729120B1

Abstract

Provided is an iron ion supply material which can supply dissolved iron, which is easily absorbed by plants, to water and/or soil over a long period of time. The aforementioned material comprises A) a substance containing an iron oxide and/or metallic iron (includes cases in which substances contain only iron oxide and/or metallic iron), and B) one or more organic acids selected from among gluconic acid and glutamic acid. The material can generate an organic acid iron by bonding iron which is eluted from an iron source to an organic acid, and can stably supply the organic acid iron to water and/or soil over a long period of time.

Description

Iron ion supply material, manufacturing method thereof, and iron ion supply method

The present invention provides an iron ion supply material for supplying iron in a form that can be easily ingested by plants (for example, seaweed and seaweed in water and various agricultural crops in land) in water and land. The present invention relates to a manufacturing method thereof, and an iron ion supply method using the iron ion supply material.

Regardless of plants in water, land plants (for example, seaweed and seaweed in water, various agricultural crops in land), iron is an essential element for growth. This causes problems such as leaf abnormalities. Iron is thought to be taken up by plants as divalent iron ions.
In recent years, the growth of seaweeds and seaweeds in coastal sea areas has declined and has been regarded as a problem. This problem is also thought to be due to the lack of soluble iron that can be used by seaweeds and seaweeds.
In coastal waters, the iron concentration itself is high, but in seawater, iron is easily oxidized to become trivalent iron and insolubilized, so it is thought that seaweed and seaweed cannot be ingested.

As a method for solving such problems and supplying iron in water in a form that can be easily ingested by seaweeds and seaweeds, for example, Patent Document 1 discloses agricultural, forestry and fisheries containing organic acid iron (iron fulvic acid). A method is shown in which a concrete porous artificial reef including waste and humus soil is installed in water and organic acid iron is supplied from the artificial reef into the water. In Patent Documents 2 and 3, a mixture of steel slag, woody humus, and marine waste is filled into a water-permeable bag, and this is placed in water. A method for supplying iron fulvic acid combined with fulvic acid contained in woody humic plants into water is shown.

On the other hand, terrestrial plants such as agricultural crops also need to receive a sufficient amount of iron for stable growth. In particular, alkaline soil is an environment in which iron ions are difficult to elute and iron deficiency is likely to occur.

JP 2001-61368 A JP 2005-34140 A JP 2006-345738 A

The techniques of Patent Documents 1 to 3 require materials such as humus and marine waste, but it is difficult to stably obtain a large amount of these materials, and therefore, general-purpose use is difficult. It is also difficult to apply to wide water areas such as lakes and marine areas. In addition, these methods bring terrestrial microorganisms into the water area at a high concentration, which is not preferable from the viewpoint of the influence on the ecosystem.

Therefore, the object of the present invention is to provide a stable supply of soluble iron (iron ions) that can be easily ingested by plants regardless of whether it is water or land, and the same effect can be obtained especially in an alkaline environment. It is to provide an iron ion supply material that can be used.
In addition, another object of the present invention is to provide a general-purpose use by using a material that can be obtained in a large amount and at a low cost as an iron source, and an iron ion supply material that can be applied to a wide area of water and land. Is to provide.
Furthermore, another object of the present invention is to provide a method for producing an iron ion supply material capable of stably producing such an iron ion supply material and an iron ion supply method using the iron ion supply material. It is in.

The present inventors use one or more organic acids selected from gluconic acid and glutamic acid, and a material in which the organic acid coexists with an iron source (iron oxide and / or metallic iron-containing substance) is used in water or soil. It was found that the function of supplying organic acid iron stably over a long period of time was particularly high, and that such a function could be exhibited even in an alkaline environment.
In addition, by using gluconic acid and glutamic acid in combination, especially when using slag as an iron source or when using an iron ion supply material in an alkaline (high pH) environment such as alkaline soil, From this stage, it was found that iron chelate can be produced continuously for a long period of time and iron ions can be supplied to water and soil.
It was also found that by incorporating powdered gluconic acid (organic acid powder, organic acid salt, etc.), the elution of gluconic acid was moderately suppressed, and the elution sustainability comparable to the above was obtained.

The present invention has been made on the basis of such findings and has the following gist.
[1] Iron oxide and / or metal iron-containing substance (A) (including a substance consisting only of iron oxide and / or metal iron) and one or more organic substances selected from gluconic acid and glutamic acid An iron ion supply material comprising an acid (B).
[2] The iron ion supply material of [1] above, wherein the iron oxide and / or metal iron-containing substance (A) is steel slag, non-ferrous smelting slag, refuse molten slag, dust, scale, iron powder, iron oxide powder An iron ion supply material comprising at least one selected from iron, iron sand and iron ore.

[3] The iron ion supply material according to [1] or [2], wherein at least a part of the iron oxide and / or metal iron-containing substance (A) is steel slag.
[4] In the iron ion supply material of any one of [1] to [3], the organic acid (B) source is at least one selected from organic acid powders, organic acid salts, and organic acid-containing substances. An iron ion supply material characterized by being.
[5] The iron ion supply material according to any one of [1] to [4], wherein the organic acid (B) contains gluconic acid and glutamic acid.

[6] An organic acid formed by combining an iron content derived from iron oxide and / or metal iron-containing substance (A) and an organic acid (B) in the iron ion supply material of any one of [1] to [5] An iron ion supply material characterized by containing iron.
[7] In the iron ion supply material according to any one of [1] to [6] above, a powdery mixed raw material containing iron oxide and / or metal iron-containing substance (A) and organic acid (B) is formed. An iron ion supply material, which is a molded product obtained by the above or a crushed body thereof.
[8] The iron ion supply material according to [7], wherein the molded product is a briquette obtained by compacting a powdery mixed raw material.
[9] The iron ion supply material according to [7], wherein the molded product is a hydrated solidified product obtained by hydrating and hardening a powdery mixed raw material containing a binder.

[10] In the iron ion supply material of [9] above, the hydrated solidified body contains iron oxide and / or metal iron-containing substance (A) mainly composed of powdered steelmaking slag, and as a main binder. An iron ion supply material, which is a hydrated solidified product obtained by hydrating and hardening a mixed raw material to which fine powder of blast furnace slag is added.
[11] The iron ion supply material according to the above [7], wherein the molded product is a carbonate solidified product obtained by carbonizing a powdery mixed raw material.
[12] In the iron ion supply material according to any one of [1] to [6], a powdery mixed raw material containing iron oxide and / or metal iron-containing substance (A) and organic acid (B) is granulated. An iron ion supply material, characterized in that it is a granulated product obtained as described above.
[13] In the iron ion supply material according to any one of [7] to [12] above, at least a part of the organic acid (B) contained in the molded product or granulated product is contained in gluconic acid powder and gluconate. An iron ion supply material characterized by being at least one selected from the group consisting of:

[14] An iron ion supply material comprising a solvent containing an organic acid iron produced by combining one or more organic acids selected from gluconic acid and glutamic acid and iron.
[15] The iron ion supply material according to the above [14], wherein the organic acid iron in the solvent is the following (a) and / or (b).
(A) Organic acid iron extracted into the solvent from the iron ion supply material of any one of [1] to [13] (b) A substance containing iron oxide and / or metal iron (provided that iron oxide is added) And / or one or more organic acids selected from gluconic acid and glutamic acid, and the iron and organic substances eluted from the iron oxide and / or metallic iron-containing material. Organic acid iron produced by combining acids

[16] A substance containing iron oxide and / or metal iron (including a substance composed only of iron oxide and / or metal iron) and one or more organic acids selected from gluconic acid and glutamic acid A method for producing an iron ion supply material, comprising forming a powdery mixed raw material into a molded product.
[17] An iron ion supply material characterized in that, in the production method of [16], a powdery mixed raw material is compacted, and the granular iron contained in the raw material is solidified as a main binder component to form a briquette. Production method.
[18] The iron ion supply characterized in that in the production method of [16], the powdery mixed raw material is hydrated and hardened by a hydration reaction of a binder contained in the raw material to obtain a hydrated solidified product. Material manufacturing method.

[19] The iron ion supply material according to [16], wherein the powdery mixed raw material is solidified by a carbonation reaction of uncarbonated Ca contained in the raw material to obtain a carbonized solid body. Manufacturing method.
[20] An iron oxide and / or metal iron-containing substance (including a substance composed only of iron oxide and / or metal iron) and one or more organic acids selected from gluconic acid and glutamic acid A method for producing an iron ion supply material, wherein a granulated mixed raw material is granulated into a granulated product.
[21] An iron ion supply method, characterized in that the iron ion supply material of any one of [1] to [15] is dispersed or installed in water or embedded in the bottom of water.
[22] An iron ion supply method, characterized in that the iron ion supply material according to any one of [1] to [15] is sprayed on soil.

In the iron ion supply material of the present invention, the iron content eluted from the iron source and one or more organic acids selected from gluconic acid and glutamic acid are combined to produce organic acid iron. Dissolvable iron (iron ions) that can be easily ingested by plants can be stably supplied over a long period of time, and the same effect can be obtained particularly in an alkaline environment.
In addition, by using slag such as steel slag, which is a material that can be obtained in large quantities and at low cost, the iron source can be used universally and can be applied to a wide area such as water and land. Can be a feed material.

In addition, when gluconic acid and glutamic acid are used in combination as organic acids, especially when slag is used as an iron source or when an iron ion supply material is used in an alkaline (high pH) environment such as alkaline soil, It is possible to generate iron chelate continuously for a long period from the initial stage of installation and supply iron ions to water and soil.
Moreover, by mix | blending powdery gluconic acid (an organic acid powder, organic acid salt, etc.), the elution property of gluconic acid is moderately suppressed, and the elution sustainability equivalent to the above is obtained.
Moreover, according to the manufacturing method of the iron ion supply material of this invention, the iron ion supply material which has the above outstanding performances can be manufactured stably.
In addition, according to the iron ion supply method of the present invention, soluble iron (iron ions) that can be easily ingested by plants can be stably supplied over a long period of time using an iron ion supply material having excellent performance as described above. can do.

Graph showing the relationship between pH and iron ion concentration of a solution in which organic acid (gluconic acid, glutamic acid) and metallic iron powder are added to artificial seawater

The iron ion supply material of the present invention is a material containing iron oxide and / or metallic iron-containing substance (A) and one or more organic acids (B) selected from gluconic acid and glutamic acid. This iron ion supply material is formed by combining an iron component eluted from an iron source and / or metallic iron-containing substance (A) with at least one organic acid selected from gluconic acid and glutamic acid. It is possible to stably supply soluble iron (iron ions) that can be easily ingested by plants regardless of water or land, and can obtain the same effect even in an alkaline environment. .

The iron oxide and / or metal iron-containing substance (A) as the iron source (hereinafter simply referred to as “iron source (A)” for convenience of explanation) may be any material that contains iron oxide and / or metal iron. Further, it may be a substance composed only of iron oxide and / or metallic iron.
Examples of the iron source (A) include steel slag, non-ferrous smelted slag, refuse molten slag, dust, scale, iron powder, iron oxide powder, iron sand, iron ore, and the like. Can do.
Steel slag (slag generated in the steel manufacturing process) includes blast furnace slag, steelmaking slag, ore reduction slag, and the like. Blast furnace slag includes blast furnace slow cooling slag and blast furnace granulated slag. Steelmaking slag includes steelmaking slag generated in hot metal pretreatment, converter blowing, casting, and other processes (for example, decarburization slag, hot metal dephosphorization slag, hot metal desulfurization slag, hot metal desulfurization slag, ingot slag, etc. ), And electric furnace slag.

Non-ferrous smelting slag includes copper smelting slag and various alloyed iron slags. Examples of the garbage melting slag include garbage incineration ash melting slag, garbage direct melting slag, and the like. These slags include a slowly cooled crystalline one and a rapidly cooled glass cullet-like one. Typical examples of the dust include dust generated in the steel manufacturing process (for example, converter dust, blast furnace dust, etc.). As a scale, the scale (for example, mill scale etc.) which generate | occur | produces in a steel manufacturing process is mentioned as a typical thing.

As the iron source (A), the one containing iron oxide as a solid solution, such as slag, is preferable to pure iron oxide because it has high reactivity with organic acids and high iron ion elution ability.
Table 1 shows the results of examining the elution properties of iron ions in water for samples obtained by mixing various iron sources and gluconic acid. This test was conducted under the following conditions.
(1) Various iron sources were put in a plastic bag with a chuck, 0.075 mass% of gluconic acid of the iron source amount was added and mixed, and then allowed to stand overnight to prepare a sample.
(2) After putting 10 g of a sample into a 250 mL plastic bottle and injecting 200 mL of artificial seawater, continuous shaking was performed at 200 rpm for 24 hours with a shaking device.
(3) The contents of the plastic bottle after shaking were filtered with a 0.45 μm filter, and the Fe concentration of the liquid after filtration was measured. The analysis of the Fe concentration in the liquid was performed using ICP-AES (inductively coupled plasma emission spectrometer).

As shown in Table 1, the amount of iron ions eluted from the iron oxide reagent is small. On the other hand, non-ferrous slag such as copper smelting slag and refuse melting slag has a large amount of iron ion elution, but lacks long-term elution sustainability due to its high elution ability. In contrast, steel slag (steel-making slag in Table 1) has a moderate elution capacity of iron ions (elution capacity higher than that of the reagent iron oxide and lower than that of non-ferrous slag), and thus elution over a long period of time. It also has sustainability. In addition, steel slag has an advantage of being inexpensive and available in large quantities.
Moreover, although metallic iron and iron oxide other than the reagent have higher elution ability of iron ions than steel slag, it can be said that it has moderate elution ability compared to the iron oxide and non-ferrous slag of the reagent. However, since these metallic iron and iron oxide have considerably higher elution ability of iron ions than steel slag, long-term elution persistence is inferior to steel slag. Furthermore, it is more expensive than steel slag and is difficult to obtain in large quantities.

In view of the above, as the iron source (A), steel slag, non-ferrous smelting slag, and municipal waste molten slag are particularly preferable, and an iron source (A) mainly composed of one or more of these or more than one of these. ) (Including the case where the iron source (A) is composed only of slag such as steel slag. The same applies hereinafter). Among steel slags, steel slag is particularly preferable from the viewpoints of having a moderate elution ability as described above, having a long-term elution sustainability, stable components, and the like. Therefore, the iron source (A) containing steel slag or mainly composed of steel slag (including the case where the iron source (A) is composed only of steel slag, the same applies hereinafter) is preferable. Incidentally, slag because low pH is desirable, the CaO contained in slag may be used one obtained by carbonation to CaCO _3.
Among steel slags, steelmaking slag containing a large amount of iron is preferable from the viewpoint of iron content.

As the organic acid (B), at least one selected from gluconic acid and glutamic acid is used. Among them, gluconic acid is a strong acid and has high solubility in water. It has the feature that it can be maintained. That is, gluconic acid can elute iron ions as complex ions and maintain the same ions even under high pH. On the other hand, since glutamic acid has a low solubility in water, iron ions can be gradually and continuously eluted to ensure long-term elution durability.

FIG. 1 shows the results of examining the relationship between the pH and Fe concentration of a solution obtained by adding an organic acid (gluconic acid, glutamic acid) and metallic iron powder to artificial seawater. This test was conducted under the following conditions.
(1) An organic acid was added to 200 mL of artificial seawater at pH 8 so that the pH would be about 6-7.
(2) 0.1 g of metallic iron powder was added to the artificial seawater to which the organic acid was added, and the mixture was shaken continuously at 200 rpm for 2 hours with a shaking device.
(3) The sample after shaking was processed with a centrifugal separator at 4000 rpm for 15 minutes, and the supernatant liquid filtered through a 0.45 μm filter was used as sample A liquid.
(4) 1M sodium hydroxide was gradually added to the sample A solution to raise the pH by 1 to 2 from the initial pH. After this pH adjustment, the mixture was allowed to stand for 2 hours, and then treated with a centrifugal separator at 4000 rpm for 15 minutes. The supernatant was filtered with a 0.45 μm filter, and the Fe concentration of the filtrate was measured. The analysis of the Fe concentration in the liquid was performed using ICP-AES (inductively coupled plasma emission spectrometer).
(5) The operation (4) was repeated several times until the pH reached 10 to 11, and the Fe concentration at each pH was analyzed.

As shown in FIG. 1, when glutamic acid is used, the Fe concentration becomes considerably low when the pH is about pH 8, which is the pH of seawater. On the other hand, when gluconic acid is used, the Fe concentration is maintained at a high level even at pH 8-11.
Glutamic acid and gluconic acid have the above-mentioned characteristics regarding the elution of iron ions, and it is preferable to use glutamic acid and gluconic acid in combination (combined addition) in the sense that each characteristic is utilized. However, (i) when slag (especially steel slag) is used as the iron source (A), (ii) when the iron ion supply material is used in an alkaline (high pH) environment such as alkaline soil, glutamic acid and gluconic acid Is particularly preferable.

In the case of (i) above, the following effects can be expected by the combined use of glutamic acid and gluconic acid. Generally, slag such as steel slag (especially steelmaking slag) contains free CaO, so at the initial stage when the iron ion supply material is installed in water or soil, the vicinity of the surface of the material has a high pH, Gluconic acid, which is a strong acid with high solubility, makes the vicinity of the surface of the material acidic, thereby facilitating iron elution and iron chelation. Such production of iron chelate by gluconic acid is stably maintained up to about pH 12. On the other hand, since glutamic acid has low solubility, it is not consumed immediately even when touched with water, and iron ions (iron chelate) are gradually and continuously eluted. The production of iron chelate by such glutamic acid is stably maintained up to about pH 8.5 (natural seawater has a pH of about 8.2). By the above, iron chelate can be produced | generated continuously for a long period from the initial stage of material installation, and iron ion can be supplied to water or soil.

In the case of (ii) above, when the iron ion supply material is installed in an alkaline environment (such as alkaline soil), gluconic acid, which is a highly soluble strong acid, acidifies the vicinity of the surface of the material and elution of iron occurs. It tends to occur and chelate iron. On the other hand, since glutamic acid has low solubility, it is not consumed immediately even when it is in contact with water, and iron chelate (iron ions) is gradually and continuously eluted. As described above, iron chelate can be generated continuously for a long period from the initial stage of material installation, and iron ions can be supplied to soil or the like.

The organic acid (B) source may be an organic acid powder, an organic acid salt (powder), an organic acid-containing substance (including an organic acid-containing solution) or the like, and one or more of these may be used as the iron source (A). Can be mixed. Examples of the organic acid salt include sodium gluconate, calcium gluconate, magnesium gluconate and the like regarding gluconic acid, and one or more of these can be used. As mentioned earlier, gluconic acid has a high solubility in water, and the elution period (elution persistence) tends to be shorter than that of glutamic acid. However, gluconate (powder) and gluconic acid powder as an iron source ( The elution of gluconic acid is moderately suppressed by mix | blending with A) and setting it as an iron ion supply material. For this reason, the elution persistence equivalent to the case where gluconic acid and glutamic acid as described above are used together (combined addition) is obtained. Such elution persistence of gluconic acid is particularly obtained when the iron ion supply material is a molded product or granulated product (particularly in the case of briquettes) such as briquettes, hydrated solidified bodies, carbonated solidified bodies, etc. Cheap. Therefore, it is preferable that at least a part of the organic acid (B) contained in the molded product or the granulated product is one or more selected from gluconic acid powder and gluconate.

The content of gluconic acid or glutamic acid in the material is not particularly specified. However, in order to produce a preferable amount of iron chelate, in each case where gluconic acid and glutamic acid are added alone, or both are added together, gluconic acid is 0% relative to the amount of iron source (A). 0.025 mass% or more, and glutamic acid is preferably contained in an amount of 0.1 mass% or more. Moreover, since an effect will be saturated even if it contains an organic acid excessively, it is preferable to make 5 mass% into an upper limit, respectively, with respect to the amount of iron sources (A), both gluconic acid and glutamic acid.
On the other hand, when the iron ion supply material is a briquette as will be described later, when each of gluconic acid and glutamic acid is added alone, or both of them are added together, the amount of iron source (A), Gluconic acid is preferably contained in an amount of 0.25 mass% or more, preferably 0.50 mass% or more, and glutamic acid is contained in an amount of 0.75 mass% or more, preferably 1.50 mass% or more.

As will be described later, when the iron ion supply material is a hydrated solid (artificial stone), (i) as the amount of organic acid added increases, the pH decreases and the strength of the hydrated solid decreases. Since there is a tendency, it is preferable to balance the elution of iron ions and ensuring the strength of the hydrated solidified body. (Ii) The iron ion supply material composed of the hydrated solidified body (artificial stone material) In many cases, it is used as a base, and in such a usage form, it is only necessary to supply iron in the vicinity of the surface layer of the hydrated solidified body, so that it is not necessary to add so much organic acid. Therefore, from these viewpoints, the lower limit of the content of gluconic acid relative to the amount of iron source (A) is 0 in both cases of adding gluconic acid and glutamic acid alone or adding both of them together. .025 mass% It is preferable that the lower limit of the content of glutamic acid and 0.6 mass%.
In addition, when the iron ion supply material is a carbonated solid as described later, since the point (ii) is the same as the hydrated solid, from this viewpoint, when adding gluconic acid and glutamic acid alone, In both cases where both are added in combination, the lower limit of the gluconic acid content relative to the amount of iron source (A) is preferably 0.025 mass%, and the lower limit of the glutamic acid content is preferably 0.6 mass%.

In addition, the iron ion supply material preferably has the following characteristics (a) or (b), and particularly preferably has both characteristics (a) and (b). Therefore, it is preferable to select the type and blending ratio of the iron source (A) and the organic acid (B) so that such characteristics can be obtained.
(A) Seawater and iron ion feed material are mixed at a mass ratio of 10: 1, continuously shaken with a shaking device at 200 rpm for 24 hours, and the liquid after shaking is filtered with a 0.45 μm filter, after filtration The Fe concentration of the liquid is 100 ppb or more.
(B) For the same iron ion supply material, the following test (i) is repeated every day (every 24 hours) by changing the seawater, and the measured Fe concentration is 10 ppb or more for 10 consecutive days. To continue.
Test (I): Seawater and iron ion supply material were made to have a mass ratio of 10: 1, and the iron ion supply material was immersed in seawater and stirred slowly, then allowed to stand for 24 hours, and the liquid was filtered with a 0.45 μm filter. Filter, and measure the Fe concentration of the liquid after filtration.

However, when the iron ion supply material is a hydrated solidified body (artificial stone), the characteristics (a) and (b) to be satisfied from the viewpoints of (i) and (ii) described above are as follows: It is preferable that it is such. Therefore, the types and blending ratios of the iron source (A) and organic acid (B) are selected so that the following characteristics (a) or (b), preferably both characteristics (a) and (b), can be obtained. It is preferable to do. The same applies from the viewpoint of (ii) described above when the iron ion supply material is a solidified carbonate.
(A) Seawater and iron ion feed material are mixed at a mass ratio of 10: 1, continuously shaken with a shaking device at 200 rpm for 24 hours, and the liquid after shaking is filtered with a 0.45 μm filter, after filtration The Fe concentration in the solution is 20 ppb or more.
(B) For the same iron ion supply material, the following test (I) is repeated every day (every 24 hours) by changing the seawater, and the day when the measured Fe concentration is 5 ppb or more is 28 consecutive days. To continue.
Test (I): Seawater and iron ion supply material were made to have a mass ratio of 10: 1, and the iron ion supply material was immersed in seawater and stirred slowly, then allowed to stand for 24 hours, and the liquid was filtered with a 0.45 μm filter. Filter, and measure the Fe concentration of the liquid after filtration.

The iron ion supply material of the present invention may contain components other than the iron source (A) and the organic acid (B). For example, binders, binders, fly ash, alkaline stimulants (slaked lime, cement, etc.) added to form briquettes and hydrated solids described later, and chemical admixtures such as lignin sulfonic acid and naphthalene. Examples thereof include, but are not limited to, water-reducing agents such as sulfonic acid and polymer admixtures such as polyacrylic acid. Moreover, you may contain organic acids other than gluconic acid and glutamic acid.

There is no special restriction | limiting in the form of the iron ion supply material of this invention, For example, it is good as arbitrary forms, such as a granular material, a granulated material, a molded object, its crushed body. Therefore, for example, a powdery iron source (A) such as slag impregnated with an organic acid-containing liquid and then dried may be used. It is preferable that In addition, when obtaining a granulated material and a molded object, although the granular mixed raw material containing an iron source (A) and an organic acid (B) is granulated or shape | molded, the particle size of a granular mixed raw material is usually For example, in the case of briquette or carbonate solidified body, it is preferably 5 mm or less, and in the case of hydrated solid body, it is preferably about 25 mm or less.
The form of the iron ion supply material of the present invention is, for example, in the case of expecting a slow effect when installed in a water area, in the sense of reducing the specific surface area, such as granular or briquette, hydrated solidified body, carbonated solidified body or the like It is preferable to use a massive molded product or a crushed body thereof.

The briquette is a powdery mixed raw material containing an iron source (A) and an organic acid (B) (usually a mixture of an iron source (A) such as slag and an organic acid (B)) to an appropriate size. Obtained by molding (usually compaction molding). When forming a briquette, it is preferable to use granular iron (metallic iron) in the mixed raw material and oxidize and heat the granular iron during compacting to use as a main binder. As the granular iron, either or both of the granular iron contained in the iron source (A) itself and the granular iron mixed in the mixed raw material may be used.
Further, since slag such as steel slag generally contains a considerable amount of granular iron, the iron source (A) mainly composed of slag such as steel slag (the iron source (A) consists only of slag such as steel slag). In the case of using the same, the briquette having a predetermined strength can be obtained without using a special binder by using the granular iron contained in the slag. In general, slag such as steel slag contains components that cause a hydration reaction (CaO, SiO _2, etc.), and the strength of the components increases with time after the molding due to the action of these components.

The briquette is mainly composed of a component that causes a hydration reaction (for example, a component containing CaO and SiO ₂ , and optionally including one or more of Al ₂ O ₃ , MgO, etc.) It may be solidified by reaction. In particular, since slag such as steel slag generally contains a considerable amount of CaO and SiO ₂ , when using an iron source (A) mainly composed of slag such as steel slag, CaO contained in the slag, by using the hydration curing reaction of SiO _2, without the addition of special binders, it is possible to obtain briquettes with a predetermined strength.

When using iron source (A) mainly composed of slag such as steel slag and manufacturing briquettes without adding a special binder, powdery mixed raw material (iron source (A) and organic containing water appropriately) The powdered and mixed raw material containing acid (B) is compacted (compressed) with a briquette molding machine, and the molded product is appropriately cured as necessary to be solidified to a predetermined strength.
In addition, when adding a special binder, a powdered mixed raw material (a powdered mixed raw material containing an iron source (A) and an organic acid (B)) blended with a binder is compacted (compressed) with a briquetting machine. The molded product thus obtained is appropriately cured and solidified to a predetermined strength. The binder to be blended, the above-mentioned granulated metallic iron (metallic iron) and produce a hydration reaction components (CaO, SiO _2, etc.) in addition to, for example, phosphoric acid, clays, bentonite, polyvinyl alcohol, carboxymethyl cellulose, polyacrylic acid One or more of molasses, lignin, magnesium sulfate, starch and the like can be used.

The hydrated solidified product is obtained by solidifying a powdery mixed raw material containing an iron source (A) and an organic acid (B) by a hydration hardening reaction of a binder (component that causes a hydration reaction) contained in the raw material. Obtained. In general, the binder includes CaO and SiO ₂ , and optionally further includes one or more of Al ₂ O ₃ and MgO. The binder may use components contained in the iron source (A) or may be added to the mixed raw material. As the binder to be added, one or more of cement, blast furnace slag fine powder, fly ash, slaked lime, and the like can be used.
If necessary, the mixed raw material of the hydrated solid body may further contain one or more kinds selected from powdered granulated blast furnace granulated slag, an alkali stimulant, an admixture and the like as described later.
Hydrated solidified material is obtained by kneading a mixed raw material containing a binder with water, pouring the kneaded product into a mold or casting it in a yard, curing it, curing it for a certain period, and then crushing it into a lump as necessary To make a product.

Further, as the hydrated solidified body, it is particularly preferable to use an iron source (A) mainly composed of granular steelmaking slag and to use blast furnace slag fine powder as a main binder. In this case, the granular steelmaking slag becomes the main aggregate of the hydrated solidified body. Such a hydrated solidified body (hereinafter referred to as “slag hydrated solidified body”) has a high strength that is not inferior to that of concrete, which is the same hydrated solidified body. The pH is low (generally about “1” lower than concrete), and steelmaking slag contains not only iron but also Si (silicic acid) and P (phosphoric acid), so Si and P are highly soluble. These are also nutrients for aquatic plants.

If necessary, the mixed raw material of the slag hydrated solid can further contain one or more selected from powdered blast furnace granulated slag, fly ash, alkali stimulant, admixture and the like.
The granulated blast furnace granulated slag is blended as a part of the iron source (A) and the aggregate, but has weak hydraulic properties. The material is solidified by alkali stimulation and contributes to strength.
The fly ash has a feature that the content of SiO ₂ is large and the shape is close to a sphere compared with other materials of the slag hydrated solidified body. This fly ash acts as a pozzolanic substance, helps to improve the strength at long-term ages, reduces the alkalinity of the slag hydrated solid body as a whole, and the amount of alkaline substance eluted when the hydrated solidified body is immersed in water It also works to reduce

As the alkali stimulating material, for example, Ca-based materials such as slaked lime and cement can be used. The ground granulated blast furnace slag has latent hydraulic properties, and curing is accelerated by alkali stimulation. For this reason, high intensity | strength can be obtained more stably by adding an alkali stimulating material.
As the admixture (AE agent, water reducing agent, AE water reducing agent, high-performance AE water reducing agent, etc.), an admixture for concrete is effective for adjusting the mixing water and the air amount.

In order to obtain a slag hydrated solid body having an appropriate quality (particularly high strength), the raw material content excluding the organic acid (B) is preferably as follows. First, regarding the basic components, it is preferable that the steelmaking slag as the iron source (A) is 60 to 85 mass% and the fine powder of the blast furnace slag as the binder is 5 to 15 mass%. Moreover, when adding 1 or more types, such as granulated blast furnace slag, fly ash, an alkali stimulant, and an admixture, with respect to steelmaking slag and blast furnace slag fine powder, these total amounts may be 10 mass% or less. preferable.
The slag hydrated solidified material is kneaded with the above-mentioned mixed raw material, poured into a mold or yard-dried, cured, cured for a certain period, and then lumped as necessary. It is made into a product by crushing.
The hydrated solid body needs to have an appropriate strength, and preferably has a strength of at least 10 N / mm ² at 28 days of age.

The carbonated solidified product is obtained by solidifying a powdery mixed raw material containing an iron source (A) and an organic acid (B) with calcium carbonate produced by a carbonation reaction of uncarbonated Ca contained in the raw material as a main binder. Can be obtained. In general, a carbonation reaction is caused by bringing uncarbonated Ca contained in a mixed raw material into contact with carbon dioxide gas through water, and the mixed raw material is consolidated using calcium carbonate generated by this carbonation reaction as a main binder, A blocked carbonated solid is obtained. Uncarbonated Ca may use the component contained in an iron source (A), and may add it to a mixed raw material.
Generally, steel slag contains a considerable amount of uncarbonated Ca (CaO and / or Ca (OH) ₂ ). Therefore, if steel slag is used as the iron source (A), the uncarbonated Ca is carbonated. It can be used for conversion.

As a specific manufacturing method, (1) a method in which a mixed raw material is filled into a mold and carbon dioxide gas (usually carbon dioxide-containing gas; the same applies hereinafter) is blown into the raw material packed layer to solidify the raw material packed layer. (2) There is a method of pre-molding the mixed raw material by compression molding or the like, placing the preform in a carbon dioxide atmosphere, and infiltrating the carbon dioxide gas into the inside, thereby solidifying the preform. In general, the water content of the mixed raw material is suitably about 1 to 10 mass%. Further, the CO ₂ concentration of the carbon dioxide-containing gas is not particularly limited, but it is preferable to set the CO ₂ concentration to 3% or more for efficient treatment.

Moreover, when using an iron ion supply material on land (for example, using it as a fertilizer material), for example, it is preferable to form a granule, a pellet or the like in order to facilitate application. . In this case, as the iron source (A), it is preferable to use the following steelmaking slag (however, the following (4) is a processed product of steelmaking slag) serving as a fertilizer raw material.
(1) Hot metal desiliconized slag containing 10% by mass or more of soluble silicic acid, preferably 20% by mass or more, more preferably 30% by mass or more (silica fertilizer raw material)
(2) Hot metal dephosphorization slag having a phosphoric acid concentration of 7 mass% or more, preferably 10 mass% or more (raw material for phosphate fertilizer)
(3) Hot metal dephosphorization slag containing 10% by mass or more of soluble silicic acid and 2% by mass or more of soluble phosphoric acid (raw material for silicic acid phosphoric acid fertilizer)
(4) Hot metal desiliconized slag (for ku-soluble potash fertilizers) fused with a potash raw material (for example, one or more of potash-containing minerals such as potash salt, potash bicarbonate, potash sulfate, and potash feldspar) material)

For example, the above steelmaking slag (fertilizer raw material) is used as the iron source (A), and the mixed raw material containing the iron source (A) and the organic acid (B) is molded or granulated to form granules or pellets. The molded product or granulated product. At that time, a binder is added to the mixed raw material as necessary. As the binder, for example, one or more of phosphoric acid, clay, bentonite, polyvinyl alcohol, carboxymethyl cellulose, polyacrylic acid, molasses, lignin, magnesium sulfate, starch and the like can be used.
For the granulated material, for example, an appropriate amount of water is added, and a mixed raw material to which a binder is added as necessary is obtained by using a granulator such as a rotating dish granulator or a rotating cylindrical granulator, for example, an average. It can be obtained by granulating to a particle size of about 0.5 to 6 mm and drying the granulated product.
Prior art fertilizers using steelmaking slag could hardly be expected to elute iron as an active ingredient, but the iron ion supply material (fertilizing material) of the present invention is in addition to active ingredients such as phosphoric acid and silicic acid. Since iron is also eluted, it can exhibit excellent performance as a fertilizer material.

In the present invention, a solvent containing organic acid iron produced by combining one or more organic acids selected from gluconic acid and glutamic acid with iron may be used as a liquid iron ion supply material. In this case, the organic acid iron in the solvent comprises the following (a) and / or (b).
(A) Organic acid iron (b) extracted from a solid iron ion supply material (an iron ion supply material containing an iron source (A) and an organic acid (B)) in a solvent such as water or an aqueous solution (b) ) Put iron source (A) and organic acid (B) (one or more selected from organic acid powder, organic acid salt, organic acid-containing substance) into a solvent such as water or aqueous solution. An organic acid iron produced by combining an iron acid eluted from an iron source (A) with an organic acid For example, a solid iron ion supply material or an iron source (A) and an organic acid (B) can be added to seawater, tap water, etc. It is immersed in a solvent and stirred, and the supernatant liquid can be collected to obtain a liquid iron ion supply material.

In the iron ion supply method using the iron ion supply material described above, in the case of a water area, the iron ion supply material is sprayed or installed (including the case where it is submerged in the bottom of the water) or buried in the bottom of the water. In this case, the iron ion supply material is sprayed on the soil. Further, the iron ion supply material composed of the above-described solvent is also sprayed on water or soil.
Moreover, when installing an iron ion supply material in a water area, for example, (ii) About granular or lump-shaped molded articles, such as a briquette, a hydrated solidified body, and a carbonate solidified body, it sinks in a use sea area as it is, (ii) Water permeability It is possible to adopt a form such as (iii) placing in a rigid container having an opening or a hole, or (iii) suspending in water in a water-permeable bag (net). In general, the input amount of the iron ion supply material is preferably set so as to increase the Fe concentration in the input water region by at least about 2 to 3 ppb.

[Example 1]
As the iron source (A), hot metal dephosphorization slag (particle size 5 mm or less) and metallic iron powder (granular iron recovered from steel slag) are used, and hot metal dephosphorization slag and / or metal iron powder and gluconic acid and / or 20 g of mixed raw material mixed with glutamic acid was pressed on one side with a load of 2 t and compacted to form a briquette having a diameter of 20 mm and a height of 20 mm. Gluconic acid was added to the iron source (A) as an aqueous solution and glutamic acid as a powder. In addition, the briquette which does not mix | blend gluconic acid and glutamic acid was created as a comparative example.
About the above briquette, Fe elution amount in water and Fe elution persistence were measured and evaluated by the following methods. The results are shown in Table 2 together with the mixing ratio of the iron source (A) and the organic acid (B).

(1) Fe elution amount Briquette (20 g) was immersed in 200 mL of artificial seawater, and was continuously shaken at 200 rpm for 24 hours with a shaking device. The liquid after continuous shaking was filtered with a 0.45 μm filter, and the Fe concentration of the liquid after filtration was measured. The analysis of the Fe concentration in the liquid was performed using ICP-AES (inductively coupled plasma emission spectrometer).
(2) Fe elution persistence For the same briquette, the following test (a) is repeated every day (every 24 hours) by replacing artificial seawater, and the number of days in which the measured Fe concentration is 10 ppb or more (continuous days) ). The analysis of the Fe concentration in the liquid was performed using ICP-AES (inductively coupled plasma emission spectrometer).
Test (a): Place 200 mL of artificial seawater in a beaker with a briquette (20 g) suspended in the air, slowly stir with a stirrer and let stand for 24 hours, and then filter the solution with a 0.45 μm filter. The Fe concentration is measured.

[Example 2]
Hot iron dephosphorized slag (particle size of 2 mm or less) is used as the iron source (A), and gluconic acid and / or glutamic acid is added to the hot metal dephosphorized slag, and blast furnace granulated slag fine powder (binding material), fly ash And water was added to the mixed raw material containing ordinary Portland cement and kneaded. The amount of the raw materials excluding the organic acid, hot metal dephosphorization slag: 2083kg / ^{m 3} - the kneaded product, blast furnace slag: 374kg / ^{m 3} - the kneaded product, fly ash: 61kg / ^{m 3} - the kneaded product, ordinary Portland cement : 88 kg / m ³ -kneaded material, water: 231 kg / m ³ -kneaded material. This kneaded product was filled into a mold (φ100 mm × 200 mm), cured by sealing curing for 7 days, de-framed, and then cured in water at 20 ° C. for 21 days to obtain a hydrated solidified product. Gluconic acid was added to the iron source (A) as an aqueous solution and glutamic acid as a powder. In addition, the hydrated solid body which does not mix | blend gluconic acid and glutamic acid was created as a comparative example.
The obtained hydrated solid body was crushed to a particle size of 5 mm or less, and about 20 g of this crushed material, the amount of Fe elution in water and the elution persistence of Fe were measured and evaluated in the same manner as in Example 1. Further, the strength (σ28) of the hydrated solid body at the age of 28 days was measured. The results are shown in Table 3 together with the compounding ratio of the organic acid (B).

[Example 3]
As iron source (A), hot metal dephosphorization slag (particle size 5 mm or less) and metallic iron powder (granular iron recovered from steel slag) were used, and hot metal dephosphorization slag, metallic iron powder and gluconate (sodium gluconate) 20 g of mixed raw material mixed with powder) was pressed on one side with a load of 2 t and compacted to form a briquette having a diameter of 20 mm × height of 20 mm.
About this briquette, the amount of Fe elution in water and the elution persistence of Fe were measured and evaluated by the same method as in Example 1. The results are shown in Table 4 together with the mixing ratio of the iron source (A) and the organic acid (B).

Claims

Iron oxide and / or metallic iron-containing substance (A) (including a substance composed only of iron oxide and / or metallic iron) and one or more organic acids selected from gluconic acid and glutamic acid (B ) Containing iron ions.
The iron oxide and / or metal iron-containing substance (A) is at least one selected from steel slag, non-ferrous smelting slag, dust melting slag, dust, scale, iron powder, iron oxide powder, sand iron, iron ore The iron ion supply material according to claim 1, wherein the iron ion supply material is provided.
The iron ion supply material according to claim 1 or 2, wherein at least a part of the iron oxide and / or metal iron-containing substance (A) is steelmaking slag.
4. The iron ion supply material according to claim 1, wherein the organic acid (B) source is at least one selected from organic acid powders, organic acid salts, and organic acid-containing substances. .
The iron ion supply material according to any one of claims 1 to 4, which contains gluconic acid and glutamic acid as the organic acid (B).
The iron according to any one of claims 1 to 5, which contains an organic acid iron produced by combining an iron component derived from iron oxide and / or a metallic iron-containing substance (A) and an organic acid (B). Ion supply material.
A molded product obtained by molding a powdery mixed raw material containing iron oxide and / or metallic iron-containing substance (A) and organic acid (B), or a crushed body thereof. The iron ion supply material in any one of 6.
The iron ion supply material according to claim 7, wherein the molded product is a briquette obtained by compacting a powdery mixed raw material.
The iron ion supply material according to claim 7, wherein the molded product is a hydrated solidified product obtained by hydrating and curing a powdery mixed raw material containing a binder.
Hydrated and solidified hydrated and hardened mixed raw material containing iron oxide and / or metallic iron-containing substance (A) mainly composed of granular steelmaking slag and blast furnace slag fine powder added as the main binder The iron ion supply material according to claim 9, which is a hydrated solidified product.
The iron ion supply material according to claim 7, wherein the molded product is a carbonate solidified product obtained by carbonizing a powdery mixed raw material.
7. A granulated product obtained by granulating a powdery mixed raw material containing iron oxide and / or metallic iron-containing substance (A) and organic acid (B). Iron ion supply material in any one.
13. The organic acid (B) contained in the molded product or granulated product is at least one selected from gluconic acid powder and gluconate salt. The iron ion supply material described in 1.
An iron ion supply material comprising a solvent containing organic acid iron produced by combining one or more organic acids selected from gluconic acid and glutamic acid and iron.
The iron ion supply material according to claim 14, wherein the organic acid iron in the solvent is the following (a) and / or (b).
(A) Organic acid iron extracted in the solvent from the iron ion supply material according to any one of claims 1 to 13 (b) In the solvent, an iron oxide and / or metal iron-containing substance (provided that iron oxide and And / or one or more organic acids selected from gluconic acid and glutamic acid, and the iron and organic acids eluted from the iron oxide and / or metallic iron-containing material. Organic acid iron formed by combining
A granular material containing an iron oxide and / or metallic iron-containing substance (including a substance consisting only of iron oxide and / or metallic iron) and one or more organic acids selected from gluconic acid and glutamic acid A method for producing an iron ion supply material, wherein a mixed raw material is formed into a molded product.
The method for producing an iron ion supply material according to claim 16, wherein the powdery mixed raw material is compacted, and the granular iron contained in the raw material is solidified as a main binder component to form a briquette.
The method for producing an iron ion supply material according to claim 16, wherein the powdery mixed raw material is hydrated and hardened by a hydration reaction of a binder contained in the raw material to obtain a hydrated solidified product.
The method for producing an iron ion supply material according to claim 16, wherein the powdery mixed raw material is solidified by a carbonation reaction of uncarbonated Ca contained in the raw material to obtain a carbonized solid.
A granular material containing an iron oxide and / or metallic iron-containing substance (including a substance consisting only of iron oxide and / or metallic iron) and one or more organic acids selected from gluconic acid and glutamic acid A method for producing an iron ion supply material, wherein the mixed raw material is granulated into a granulated product.
An iron ion supply method, characterized in that the iron ion supply material according to any one of claims 1 to 15 is dispersed or installed in water or buried in the bottom of water.
An iron ion supply method, wherein the iron ion supply material according to any one of claims 1 to 15 is sprayed on soil.