WO2007013218A1 - Iron-supplying agent, iron supplying agent for plant comprising the same, and process for production of the same - Google Patents

Abstract

[PROBLEMS] To provide an iron-supplying agent and an iron-supplying agent for plant which can provide an aqueous solution having a high Fe2+ ion concentration and reduced in the oxidation of Fe2+ ions. [MEANS FOR SOLVING PROBLEMS] The iron-supplying agent comprises an aqueous solution which has dissolved therein an organic acid having a carboxyl group and/or a hydroxyl group (particularly citric acid) and FeO. Alternatively, the iron-supplying agent may be prepared by removing water from an aqueous solution which has dissolved therein an organic acid having a carboxyl group and/or a hydroxyl group (particularly citric acid) and FeO. The iron-supplying agent can be prepared by a process comprising the dissolution step in which a mixture of an organic acid powder (particularly a citric acid powder), an FeO powder and water is heated to give an aqueous solution having the organic acid and FeO dissolved therein. The FeO powder used is preferably produced by heating under vacuum granules which are produced by granulating an iron-containing dust and/or granules which are produced by granulating an iron-containing dust together with a reducing agent and then quickly cooling the resulting granules under reduced pressure.

Description

 Specification

 Iron supply agent, plant iron supply agent containing the same, and method for producing the same

[0001] The present invention relates to an iron supply agent, an iron supply agent for plants containing the same, and a method for producing the same. More particularly, the present invention relates to an iron supply agent having a high Fe ²⁺ ion concentration in an aqueous solution state, in which oxidation of Fe ²⁺ ions is suppressed, a plant iron supply agent containing the same, and a method for producing the same.

 Background art

[0002] Iron is a trace essential element for plants, and deficiency is known to cause peculiar symptoms such as yellowing of leaves and impaired synthesis of proteins. Iron is taken up in an ionized state. However, among Fe ions, Fe ³⁺ ions are known to be difficult to obtain a satisfactory effect on plants even if they are supplied. For this reason, some efforts have been made to supply iron as Fe ²⁺ ions. However, Fe ²⁺ ions of iron powder as a composition for supplying the iron for this plant that it is desired to be stably supplied for a long time an easy tool Fe ²⁺ ions become Sani匕Well F e ³⁺ In addition, the use of iron furnaces, converter furnaces, and iron hydroxide has been proposed (see, for example, Patent Document 1). Further, a method using a water-soluble inorganic iron salt such as iron sulfate and iron nitrate, and a method using an EDTA iron complex with ethylenediamine tetraacetic acid (hereinafter simply referred to as “EDTA”) are known.

Patent Document 1: Japanese Patent Laid-Open No. 8-277183

 Disclosure of the invention

 Problems to be solved by the invention

[0004] However, the iron content eluted from the iron-containing composition described in Patent Document 1 is mostly Fe ^3+, and it is considered difficult for plants to take up. In addition, the water-soluble inorganic iron salt is easily oxidized to Fe ³⁺ which does not easily maintain the Fe ²⁺ state. In addition, there is a problem of causing accumulation of salts as in the past. In other words, water-soluble inorganic metal salts have been used for a long time as various fertilizers, and the strong acid anions that make up these water-soluble metal salts are used in other soils. It has become a problem to combine with these elements to form a water-insoluble salt and accumulate it in the soil. A water-soluble inorganic iron salt cannot solve this problem. Furthermore, it is essentially trivalent iron that is used as the EDTA iron complex. In addition, EDTA is a strong chelating agent, and there are concerns about fixing heavy metals in soil and causing soil contamination, and dissolving in groundwater to cause water contamination.

[0005] The present invention is intended to solve the aforementioned conventional problems, has a high Fe ²⁺ I O emissions concentration in aqueous solution, the iron supply agent oxidation is suppressed in Fe ²⁺ ions, this It aims at providing the iron supply agent for plants to contain, and its manufacturing method.

 Means for solving the problem

[0006] The present inventors paid attention to an organic acid having a chelating power against iron and examined the organic acid iron. As a result, for example, ferrous citrate obtained by boiling metal iron, which is also known in the past, and aqueous citrate solution, Fe (OH)

Of the ferric citrate obtained by reacting 3 with an aqueous solution of citrate, ferrous citrate (Fe ²⁺ ) is poor in water solubility and does not supply enough Fe ²⁺ , 2 iron (Fe ³⁺⁾ is water-soluble can be sufficiently obtained does not contain 1Z4 degree to force Fe ²⁺ ions of the total Fe I on, it was not divided Fe ²⁺ ion amount is insufficient. In addition, compounds with strong ion binding properties such as iron citrate ammonium have been difficult to obtain the effect of suppressing Fe ²⁺ ion oxidation.

In contrast, solids and pastes obtained by boiling citrate powder, FeO powder and water, and solids obtained by drying the aqueous solution obtained by refining these, It was found that when it was dissolved in water, the concentration of Fe ²⁺ ions was specifically high, and that Fe ²⁺ ions were not easily oxidized. The present invention has been completed based on this finding.

[0007] The present invention is as follows.

 (1) An iron supply agent comprising an aqueous solution obtained by dissolving an organic acid having a carboxyl group and a Z or hydroxyl group and FeO (hereinafter referred to as `` iron supply agent of the first invention '') Called).

(2) When Fe ²⁺ ions and Fe ³⁺ ions are contained, and the total of the Fe ²⁺ ions and the Fe ³⁺ ions is 100% by mass, the Fe ²⁺ ions are 50 to 90%. The iron supply agent according to the above (1), which is mass%. (3) The iron supply agent according to (1), wherein the Fe ²⁺ ion concentration force observed in the aqueous solution after standing for 168 hours is 75% or more of the Fe ²⁺ ion concentration observed immediately after the start of measurement.

 (4) The iron supply agent according to (1) above, which contains at least citrate as the organic acid.

(5) and dimeric complexes Kuen acid and / or Kuen acid ion was two coordinated to one Fe ²⁺ ion, Kuen acid and Z or Kuen acid ion for one Fe ²⁺ ions The iron supplier according to (4) above, comprising three coordinated trimer complexes.

 (6) The iron supply agent for plants comprising the iron supply agent according to any one of the above (1) to (5) (hereinafter referred to as “the iron supply for plants of the first invention”) Agent ”).

 (7) The iron supplier for plants according to (6) above, which contains a biodegradable binder.

 (8) The iron supply agent for plants according to (6) above, which contains a biodegradable extender.

 (9) The plant iron supply agent according to (6) above, which contains 5% by mass or more of the iron supply agent when the total amount of the iron supply agent for plants is 100% by mass.

 (10) An iron supplier obtained by removing water from an aqueous solution obtained by dissolving an organic acid having a carboxyl group and a Z or hydroxyl group, and FeO (hereinafter referred to as `` the second invention ''). Iron supply ").

(11) an aqueous solution obtained by dissolving this iron supplying agent contains a Fe ²⁺ ions and Fe ³⁺ ions, when the total of the Fe ²⁺ ions and the Fe ³⁺ ions is 100 mass% And the Fe ²⁺ ion is 50 to 90% by mass.

(12) The aqueous solution obtained by dissolving the iron supply agent has an Fe ²⁺ ion concentration force observed in the aqueous solution after standing for 168 hours, and is 75% or more of the Fe ²⁺ ion concentration observed immediately after the dissolution. The iron supply agent according to (10) above.

 (13) The iron supply agent according to the above (10), which contains at least citrate as the organic acid.

(14) an aqueous solution obtained by dissolving this iron supply agent, a dimeric complex Kuen acid and Z or Kuen acid ion was two coordinated to one Fe ²⁺ ions, one Fe ²⁺ ions The iron supplier according to the above (13), comprising: a quaternary acid and a trimeric complex in which Z or three citrate ions are coordinated.

(15) The iron supply agent according to any one of (10) and (14) above is contained. The plant iron supply agent (hereinafter referred to as “the plant iron supply agent of the second invention”).

 (16) The iron supplier for plants according to (15) above, which contains a biodegradable binder.

 (17) The iron supply agent for plants according to the above (15), which contains a biodegradable extender.

 (18) The plant iron supply agent according to (15) above, which contains 5% by mass or more of the iron supply agent when the total amount of the iron supply agent for plants is 100% by mass.

 (19) containing cenoic acid as the organic acid,

 Containing peat as the biodegradable extender,

 The matrix comprising the biodegradable extender contains the citrate and the FeO;

 The plant iron supply agent according to the above (17), which is used in alkaline soil.

 (20) An iron supplier comprising an organic acid having a carboxyl group and a Z or hydroxyl group and FeO (hereinafter referred to as “iron supplier of the third invention”).

(21) an aqueous solution obtained by dissolving this iron supplying agent contains a Fe ²⁺ ions and Fe ³⁺ ions, when the total of the Fe ²⁺ ions and the Fe ³⁺ ions is 100 mass% And the Fe ²⁺ ion is 50 to 90% by mass.

(22) The aqueous solution obtained by dissolving the iron supply agent has an Fe ²⁺ ion concentration force observed in the aqueous solution after standing for 168 hours, and is 75% or more of the Fe ²⁺ ion concentration observed immediately after the dissolution. The iron supply agent according to (20) above.

 (23) The iron supply agent according to (20) above, which contains at least citrate as the organic acid.

Aqueous solution (24) was dissolved the iron supplying agent comprising the one and the dimeric complexes Kuen acid and Z or Kuen acid ion was two coordinated against Fe ²⁺ ions, one Fe ²⁺ ions The iron supplier according to the above (23), which contains a ternary complex in which three citrates and Z or three citrate ions are coordinated.

 (25) A plant iron supply agent characterized by containing the iron supply agent according to any one of the above (20) to (24) (hereinafter referred to as “the plant iron of the first invention”). "Supplier").

 (26) The iron supplier for plants according to the above (25), which contains a biodegradable binder.

(27) The iron supplier for plants according to (25) above, which contains a biodegradable extender. (28) The plant iron supply agent according to (25), which contains 5% by mass or more of the iron supply agent, when the total amount of the iron supply agent for plants is 100% by mass.

 (29) containing cenoic acid as the organic acid,

 Containing peat as the biodegradable extender,

 The matrix comprising the biodegradable extender contains the citrate and the FeO;

 The plant iron supply agent according to (27), which is used in alkaline soil.

 (30) A dissolution step of heating an organic acid powder having a carboxyl group and Z or hydroxyl group, FeO powder, and water to obtain an aqueous solution obtained by dissolving the organic acid and FeO is provided. The manufacturing method of the iron supply agent characterized by the above-mentioned.

 (31) The method for producing an iron supply agent according to (30), further comprising a drying step for removing water.

 (32) The method for producing an iron supply agent according to (30), wherein the organic acid contains at least citrate.

 (33) The FeO powder is prepared by vacuum heating a granulated product obtained by granulating iron-containing dust and a granulated product obtained by granulating Z or iron-containing dust and a reducing agent. The method for producing an iron supply agent according to the above (30), which is FeO powder obtained by vacuum quenching.

The invention's effect

According to the iron supply agent of the first invention, a high Fe ²⁺ ion concentration can be obtained. That is, for example, a high Fe ²⁺ ion concentration can be obtained even in soil, and iron can be supplied with high probability. In addition, the resulting Fe ²⁺ ions are effectively suppressed in acidity, so that iron can be supplied with a high probability. In addition, the use of organic acids (especially cuenic acid) is safe for use with less environmental impact. Furthermore, when used on plants, a germination promoting effect and a growth promoting effect are obtained.

In the case of a predetermined Fe ²⁺ ion ratio, the iron content can be supplied with a particularly high probability. When the Fe ²⁺ ion concentration after standing for a predetermined time is 75% or more immediately after the start of measurement, the Fe ²⁺ ion has particularly high acidity and can stably supply Fe ²⁺ ions for a long time.

When at least citrate is contained as an organic acid, the above effects can be obtained particularly greatly. Togashi.

When a dimer complex and a trimer complex are contained, a high Fe ²⁺ ion concentration can be obtained, and a particularly high antioxidant property is exhibited.

[0009] According to the plant for iron supply agent in the first invention, the resulting high Fe ²⁺ ion concentration. That is, for example, even when water is dissolved in soil, a high Fe ²⁺ ion concentration can be obtained, and iron can be supplied with high probability. Furthermore, since the Fe ²⁺ ions obtained are effectively suppressed in acidity, iron can be supplied with a high probability. In addition, the use of organic acids (especially quenoic acid) is safe for use with less environmental impact. Furthermore, germination promotion effect and growth promotion effect can be obtained.

In the case of containing a biodegradable binder, it can be an iron supply agent for plants having sustained release that stably and gradually supplies Fe ²⁺ over a long period of time. Furthermore, it can be made into the solid substance which contains other components other than an iron supply agent simultaneously.

In the case of containing a biodegradable extender, the Fe ²⁺ supply amount can be easily kept within an appropriate range, and is excellent in versatility.

When the iron supply agent is contained in an amount of 5% by mass or more, the effect of supplying Fe ²⁺ can be obtained particularly surely.

[0010] According to the iron supply agent of the second invention, an aqueous solution having a high Fe ²⁺ ion concentration can be obtained. That is, for example, even when water is dissolved in soil, a high Fe ²⁺ ion concentration can be obtained, and iron can be supplied with a high probability. Furthermore, since the Fe ²⁺ ions obtained by making the solution water effectively suppress the oxidation, iron can be supplied with a high probability. In addition, the use of organic acids (especially cuenic acid) is safe for use with no environmental impact. In addition, when used on plants, a germination promoting effect and a growth promoting effect are obtained.

In the case of a predetermined Fe ²⁺ ion ratio, the iron content can be supplied with a particularly high probability. When the Fe ²⁺ ion concentration after standing for a predetermined time is 75% or more immediately after dissolution, the Fe ²⁺ ion has particularly high acidity and can stably supply Fe ²⁺ ions for a long period of time.

 When at least citrate is contained as the organic acid, the above effects can be obtained particularly greatly.

When containing dimeric and trimeric complexes, high Fe ²⁺ ion concentrations are obtained, and Particularly high!

[0011] According to the plant iron supplier of the second invention, a high Fe ²⁺ ion concentration can be obtained. That is, for example, even when water is dissolved in soil, a high Fe ²⁺ ion concentration can be obtained, and iron can be supplied with high probability. Furthermore, since the Fe ²⁺ ions obtained are effectively suppressed in acidity, iron can be supplied with a high probability. In addition, the use of organic acids (especially quenoic acid) is safe for use with less environmental impact. Furthermore, germination promotion effect and growth promotion effect can be obtained.

In the case of containing a biodegradable binder, it can be an iron supply agent for plants having sustained release that stably and gradually supplies Fe ²⁺ over a long period of time. Furthermore, it can be made into the solid substance which contains other components other than an iron supply agent simultaneously.

In the case of containing a biodegradable extender, the Fe ²⁺ supply amount can be easily kept within an appropriate range, and is excellent in versatility.

When the iron supply agent is contained in an amount of 5% by mass or more, the effect of supplying Fe ²⁺ can be obtained particularly surely.

When containing citrate, peat as a biodegradable extender, and containing citrate and FeO in a matrix made of biodegradable extender and used in alkaline soil, Fe ²⁺ is Fe ^{3 +} is Sani spoon is it is suppressed to be the supply of iron with high probability even in alkaline soils.

[0012] According to the iron supply agent of the third invention, an aqueous solution having a high Fe ²⁺ ion concentration can be obtained. That is, for example, even when water is dissolved in soil, a high Fe ²⁺ ion concentration can be obtained, and iron can be supplied with a high probability. Furthermore, since the Fe ²⁺ ions obtained by making the solution water effectively suppress the oxidation, iron can be supplied with a high probability. In addition, the use of organic acids (especially cuenic acid) is safe for use with no environmental impact. In addition, when used on plants, a germination promoting effect and a growth promoting effect are obtained.

In the case of a predetermined Fe ²⁺ ion ratio, the iron content can be supplied with a particularly high probability. When the Fe ²⁺ ion concentration after standing for a predetermined time is 75% or more immediately after dissolution, the Fe ²⁺ ion has particularly high acidity and can stably supply Fe ²⁺ ions for a long period of time.

When at least citrate is contained as an organic acid, the above effects can be obtained particularly greatly. Togashi.

When a dimer complex and a trimer complex are contained, a high Fe ²⁺ ion concentration can be obtained, and a particularly high antioxidant property is exhibited.

[0013] According to the plant iron supplier of the third invention, a high Fe ²⁺ ion concentration can be obtained. That is, for example, even when water is dissolved in soil, a high Fe ²⁺ ion concentration can be obtained, and iron can be supplied with high probability. Furthermore, since the Fe ²⁺ ions obtained are effectively suppressed in acidity, iron can be supplied with a high probability. In addition, the use of organic acids (especially quenoic acid) is safe for use with less environmental impact. Furthermore, germination promotion effect and growth promotion effect can be obtained.

In the case of containing a biodegradable binder, it can be an iron supply agent for plants having sustained release that stably and gradually supplies Fe ²⁺ over a long period of time. Furthermore, it can be made into the solid substance which contains other components other than an iron supply agent simultaneously.

In the case of containing a biodegradable extender, the Fe ²⁺ supply amount can be easily kept within an appropriate range, and is excellent in versatility.

When the iron supply agent is contained in an amount of 5% by mass or more, the effect of supplying Fe ²⁺ can be obtained particularly surely.

When containing citrate, peat as a biodegradable extender, and containing citrate and FeO in a matrix made of biodegradable extender and used in alkaline soil, Fe ²⁺ is Fe ^{3 +} is Sani spoon is it is suppressed to be the supply of iron with high probability even in alkaline soils.

[0014] According to the production method of the present invention, it is possible to stably and reliably obtain an iron supply agent having an aqueous solution force obtained by dissolving the organic acid of the present invention and FeO.

 In the case of providing a drying step for removing water from the aqueous solution, the iron supplier obtained by removing the water from the aqueous solution obtained by dissolving the organic acid of the present invention and FeO is stably and reliably provided. Can be obtained.

 When the FeO powder is an FeO powder obtained by vacuum-cooling a granulated product and then vacuum-quenching, the anti-acidic property is particularly high and the iron supply agent can be obtained reliably and stably.

Brief Description of Drawings FIG. 1 is a graph showing the correlation between the elapsed time in which an aqueous solution in which the iron supply agent of the product of the present invention (Experimental Examples 1 to 14) is dissolved is left and the Fe ²⁺ ion concentration.

FIG. 2 is a graph showing the correlation between elapsed time and Fe ²⁺ ion concentration when an oxidation acceleration test is performed on an aqueous solution in which the iron supplier of the product of the present invention (Experimental Examples 5 and 6) is dissolved. .

 [Fig. 3] A chart by mass spectrometry, in which the upper part is an aqueous solution in which the iron supplier of the product of the present invention (Experimental Example 7) is dissolved, the middle part is iron (III) citrate, and the lower part is anhydrous citrate. It is.

 4 is a chart obtained by further colliding Ar gas with a peak of mass 439 in the iron supply agent chart of the product of the present invention (Experimental Example 7) in the upper part of FIG.

 FIG. 5 is an explanatory diagram of Hayasaki Cosmos watered with the product of the present invention (Experimental Example 8).

 FIG. 6 is an explanatory diagram of Hayasaki Cosmos watered with the product of the present invention (Experimental Example 8).

 FIG. 7 is an explanatory diagram of Hayasaki Cosmos watered with a reference product (Reference Example 1).

 FIG. 8 is an explanatory diagram of Hayasaki Cosmos watered with a reference product (Reference Example 1).

 FIG. 9 is an explanatory diagram of banana peppers irrigated with the product of the present invention (Experimental Example 8).

 FIG. 10 is an explanatory diagram of banana peppers irrigated with a reference product (Reference Example 1).

 FIG. 11 is an explanatory view of a spray chrysanthemum irrigated with the product of the present invention (Experimental Example 8).

 FIG. 12 is an explanatory diagram of a spray chrysanthemum irrigated with a reference product (Reference Example 1).

 FIG. 13 is an explanatory diagram of an all-day bloom pine needle button irrigated with a product of the present invention (Experimental Example 8).

 FIG. 14 is an explanatory diagram of an all-day bloom pine needle button irrigated with a reference product (Reference Example 1).

 [Fig. 15] Rice seedlings grown in the seedling culture medium containing the iron supply agent for plants of the product of the present invention (Experimental Examples 9 and 10) and those that do not contain this! /, Grown in the seedling culture medium (Reference Example 2) It is explanatory drawing which compared the mode of breeding with the rice seedling.

 [Fig.16] Rice seedlings grown in the seedling culture medium containing the iron supply agent for plants of the product of the present invention (Experimental examples 9-1 and 9-2), and the seedlings without this! / It is explanatory drawing which compared the mode of breeding with the rice seedling grown in 2).

 [Fig.17] Rice seedlings grown in the seedling culture medium containing the iron supply agent for plants of the product of the present invention (Experimental examples 10-1 and 10-2), and the seedlings without this! /, Seedling culture medium (Reference Example 2) It is explanatory drawing which compared the mode of breeding with the rice seedling grown by ().

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

 [1] Iron supply agent

 The iron supplier of the first invention is characterized in that it comprises an aqueous solution obtained by dissolving an organic acid having a carboxyl group and / or a hydroxyl group and FeO.

 The iron supply agent of the second invention is characterized by removing water from an aqueous solution obtained by dissolving an organic acid having a carboxyl group and / or a hydroxyl group and FeO. That is, the other iron supply agent can be obtained by removing water from the iron supply agent.

 The iron supply agent according to the third invention is characterized by containing an organic acid having a carboxyl group and / or a hydroxyl group and FeO.

[0017] (1) Iron supply agent of the first invention

The “organic acid” is an acid having a carboxyl group and a Z or hydroxyl group. As the organic acid, examples of the organic acid having a carboxyl group include citrate (including citrate anhydride), acetic acid, tartaric acid and oxalic acid. Examples of the organic acid having a hydroxyl group include ascorbic acid. Examples of the organic acid having both a carboxyl group and a hydroxyl group include citrate and tartaric acid. These may be used alone or in combination of two or more. Of these, citrate, acetic acid, tartaric acid and oxalic acid are preferred because of their excellent stability. Furthermore, when an aqueous solution containing an organic acid and FeO is prepared, citrate, acetic acid and tartaric acid are preferred because the Fe ²⁺ ion concentration is high relative to the organic acid concentration. Among these, when an aqueous solution containing no irritating odor or containing an organic acid and FeO is prepared, the concentration of Fe ²⁺ ions with respect to the concentration of the organic acid is particularly high, so quenate is most preferred.

[0018] The "aqueous solution" is an aqueous solution obtained by dissolving an organic acid and FeO. That is, it is an aqueous solution not containing undissolved organic acid and FeO. However, it may be a supernatant in a solid-liquid coexisting solution containing V, an organic acid and / or FeO that is not dissolved.

Further, the dissolved state of the organic acid and FeO in the aqueous solution is not particularly limited. That is, for example, this aqueous solution can contain an organic acid iron complex and an organic acid ion. Among these, it is particularly preferable that an organic acid iron complex is contained, and further, as described above. When an acid is contained, a taenoic acid complex is preferably contained. This iron citrate complex is preferably a multimeric complex in which citrate and Z or a plurality of citrate ions are coordinated to one Fe ²⁺ ion, particularly a dimer complex (one Fe ² ion). It is preferable that a cation and / or a complex in which two citrate ions are coordinated with respect to the ⁺ ion, and further a dimer complex and a trimer complex (one Fe ²⁺ ion In contrast, it is more preferable to contain both citrate and a complex in which three citrate ions are coordinated.

 [0019] The amount of the organic acid and FeO dissolved in the aqueous solution is not particularly limited, but usually the organic acid (particularly quenic acid) per 100 ml of water is 0.05 g or more (preferably 0.5 g to the temperature of the aqueous solution). The solubility limit of organic acid in degrees). On the other hand, FeO per 100 ml of water is 10 to 25 parts by mass (particularly 20 to 25 parts by mass) when the content of the organic acid is 100 parts by mass.

 [0020] The water constituting the aqueous solution is not particularly limited, and various types of water can be used. Water that is usually used, such as tap water, industrial water, agricultural water, and ground water, which may be highly purified water such as pure water and ion exchange water, may be used.

 [0021] A method for obtaining this aqueous solution is not particularly limited, but it can be obtained by a production method described later. That is, (1) it can be obtained by heating a mixture containing organic acid powder, FeO powder and water. In addition, (2) it can also be obtained by adding FeO powder to an organic acid aqueous solution in which the entire amount has been dissolved in advance and heating it with heat. Alternatively, (3) organic acid powder and FeO powder may be further added to an organic acid aqueous solution in which a predetermined amount is dissolved and heated. Furthermore, (4) it can be obtained by mixing organic acid powder, FeO and water without heating. Furthermore, (5) In addition to the above (1) to (4), when it is not completely dissolved! / ヽ Organic acid and completely dissolved ヽ FeO are contained, they are separated by a method such as filtration. The process to perform can be provided.

[0022] The iron supply agent of the first invention may contain a pyroligneous acid solution for anti-mold. When the wood vinegar solution is contained, the content of the wood vinegar solution is preferably 10% by mass or less (usually 1% by mass or more) of the whole iron supply agent. Furthermore, ultraviolet irradiation can be performed in advance for the same purpose. Although the ultraviolet irradiation conditions are not particularly limited, it is preferable to use ultraviolet rays having a wavelength of 200 to 380 nm. In addition, 72 10 ⁴ ^ 3 for irradiation. It is preferable to irradiate 111 ² or more. Furthermore, when storing, it is preferable to store at a low temperature. The temperature is not particularly limited, but 15 ° C or less is preferred! The properties of the iron supply agent of the first invention will be described later.

[0023] (2) Iron supply agent of the second invention

 On the other hand, the iron supply agent of the second invention is obtained by removing the aqueous solution water. The above “removal” means an operation of removing a part or all of water from the aqueous solution, but usually the water content is 90% by mass or less based on the whole iron supply agent of the first invention. In particular, the solid content is 10% by mass or less (preferably 5% by mass or less), and the pasty product is 60 to 90% by mass (preferably 65 to 85% by mass). The iron supply agent of the second invention may be a solid product obtained by removing substantially all of the water from the aqueous solution, or may be a paste product obtained by removing a part of the water from the aqueous solution. Of these, solids are preferred.

Further, the removal method is not particularly limited, and means such as reduced pressure heating drying, normal pressure heating drying, non-heating reduced pressure drying, and freeze drying can be used. Of these, reduced pressure hot air drying is preferred. This is because Fe ²⁺ can be prevented from being oxidized in the process of removing this water. In addition to drying under reduced pressure, drying under low oxygen may be used.

[0024] When heating is performed when water is removed, the heating temperature of the aqueous solution is not particularly limited, but is preferably maintained at 150 ° C or lower. This is because the Fe ³⁺ ion concentration tends to increase above 150 ° C. The temperature of the aqueous solution by heating is more preferably 140 ° C. or less, particularly preferably 135 ° C. or less, and particularly preferably 130 ° C. or less. On the other hand, the lower limit temperature is not particularly limited and may be any temperature that causes transpiration of water under the pressure environment when water is removed. For example, 60 ° C or higher is preferable, and 80 ° C or higher is preferable. More preferred is 100 ° C or more, more preferred is 115 ° C or more, and particularly preferred is 120 ° C or more. These upper limit temperature and lower limit temperature at the time of heating can be combined. That is, for example, 60 to 150 ° C is preferable, and 100 to 140 ° C is more preferable, and 110 to 130 ° C is more preferable. Other combinations may be used.

[0025] Further, when the pressure is reduced when removing water, the pressure is not particularly limited, but is preferably 0.1 to 50 kPa force S, more preferably 0.1 to 20 kPa force S, and further preferably 3 to 15 kPa force. 4 to 10 kPa is particularly preferred.

[0026] The iron supply agent of the second invention can usually be dissolved almost entirely in water at a temperature of 15 ° C or higher. For example, for 100 ml of pure water at a temperature of 25 ° C, 0.1 lg or more (or 0.1-12 0 g, in particular 0.1 to 50 g, in particular 0.1 to 15 g) can be dissolved. The properties of the aqueous solution in which this iron supply agent is dissolved will be described later.

[0027] (3) Iron supply agent of the third invention

 The iron supply agent of the third invention contains an organic acid having a carboxyl group and / or a hydroxyl group and FeO. That is, for example, an iron supply agent containing organic acid powder and FeO powder. As a result of this iron supply agent, the iron supply agent (aqueous solution) of the first invention is obtained as a result of rainfall, irrigation, moisture in the soil, and the like. That is, the organic acid iron aqueous solution (particularly iron citrate aqueous solution) is formed. As a result, the effect of the iron supplier of the first invention can be obtained as it is. This iron supply agent can be obtained, for example, by mixing organic acid powder and FeO powder.

 In addition, this iron supply agent may contain water. That is, an iron supplier obtained by mixing an organic acid aqueous solution and FeO powder, an iron supplier obtained by mixing an organic acid aqueous solution (for example, a saturated aqueous solution), organic acid powder and FeO powder, and the like are included.

 Moreover, this iron supply agent can reduce the elution rate of an organic acid using the biodegradable binder etc. which are mentioned later. Thereby, it is possible to provide a release property.

 Each of the above-mentioned organic acids, FeO, water, etc. can be applied as they are.

[0028] (4) Items common to the iron supply agents of the first invention, the second invention and the third invention

The aqueous solution containing the iron supplier of the first invention, the aqueous solution of the iron supplier of the second invention, and the aqueous solution of the iron supplier of the third invention contain Fe ²⁺ ions and Fe ³⁺ ions, respectively. , when the sum of the Fe ²⁺ ions and Fe ³⁺ ions is 100 mass _^0/0, Fe ²⁺ ions 50 to 90 wt% (further 60-90% by weight, in particular 70 to 90% by weight) It can be. That, Fe ³⁺ I ON as possible out to 10 to 50 mass _^0/0 (further 10 to 40 mass _^0/0, especially 10 to 30 mass _^0/0). That is, an aqueous solution containing Fe ²⁺ at a high concentration can be obtained. However, each ion concentration is a value measured by a measuring method of an example described later.

[0029] In particular, when cenoic acid is used as the organic acid, the iron supply agent of the first invention, the aqueous solution in which the iron supply agent of the second invention is made water-soluble, and the iron supply agent of the third invention are made water-soluble. In aqueous solution, a dimer in which two citrate ions and / or two citrate ions are coordinated to one Fe ²⁺ ion And a trimer complex in which three citrate and Z or three citrate ions are coordinated to one Fe ²⁺ ion. The content of each complex is not particularly limited. In addition, the content of each complex with respect to the total iron supply agent is not particularly limited!

[0030] In addition, the aqueous solution in which the iron supply agent of the first invention, the iron supply agent in the second invention are dissolved in water, and the aqueous solution in which the iron supply agent of the third invention is dissolved in water are recognized when left standing for 168 hours. The Fe ²⁺ ion concentration obtained can be 75% or more of the Fe ²⁺ ion concentration (mg Z liters) observed immediately after dissolution (immediately after measurement in the iron supplier of the first invention). That is, it is possible to hold the long-term stability to Fe ²⁺ ions, can be supplied to excellence in Fe ²⁺ ions Kosani匕性to be oxidized is suppressed to Fe ^3+. However, the above-mentioned neglect shall be in a dark place at a temperature of 25 ° C where there is virtually no ultraviolet light. Each ion concentration is a value measured by a measuring method of an example described later.

[0031] Furthermore, the iron supply agent of the first invention, the aqueous solution in which the iron supply agent of the second invention is dissolved in water, and the aqueous solution in which the iron supply agent of the third invention is dissolved in water are ultraviolet rays (especially wavelengths of 200 to 380 nm). Irradiation can improve the Fe ²⁺ ion concentration. In particular, an aqueous solution with an Fe ²⁺ ion concentration of 80% or less of the total Fe ion concentration (mgZ liter) (especially 70% or less, usually 50% or more) is irradiated with ultraviolet rays with a wavelength of 253 nm at 72 X 10 ⁴ ws / When irradiated with cm ² , the Fe ²⁺ ion concentration (mgZ liter) can be improved to 85% or more (further 90% or more, particularly 95% or more, usually 99.9% or less). This ion concentration is measured by the measurement method of the examples described later.

[0032] The iron supply agent of the first invention, the iron supply agent of the second invention and the iron supply agent of the third invention can be used as an iron supply agent for plants, which will be described later, and an iron supply agent for livestock (chicken, pig, Cattle, etc.) and iron supply agents for seafood (cultured fish, cultured shellfish, etc.). In addition, it can be used in various fields that require the supply of various Fe ²⁺ ions. When used as an iron supplier for various uses other than those for plants, for example, the iron supplier of the second invention may contain a biodegradable binder as in the iron supplier for plants described later. It can contain biodegradable extenders and can contain other components.

 [0033] [2] Iron supply agent for plants

The iron supply agent for plants of the first invention is characterized by containing the iron supply agent of the first invention. The iron supply agent for plants of the second invention is characterized by containing the iron supply agent of the second invention. The iron supply agent for plants of the 3rd invention contains the iron supply agent of 3rd invention, It is characterized by the above-mentioned. These plant iron supply agents of the present invention may be used alone or in combination of two or more.

 [0034] The iron supply agent of the first invention, the iron supply agent of the second invention or the iron supply agent of the third invention contained in each plant iron supply agent (hereinafter also simply referred to as "iron supply agent") The content is not particularly limited! However, when the total amount of the iron supply agent for plants is 100% by mass, it is contained in an amount of 5% by mass or more in terms of the iron supply agent of the second invention (in terms of complete dry mass). It is preferable. If it is this range, the effect which contains an iron supply agent can fully be acquired. The content is preferably 95% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less. For plants, iron is a trace essential element, so it is not necessary to give it too much.

 [0035] Furthermore, the plant iron supplier of the present invention may contain a biodegradable binder.

By containing a biodegradable binder, the iron supply is gradually released as this binder is decomposed to produce Fe ²⁺ . Therefore, Fe ²⁺ ions can be supplied stably over a long period of time. That is, sustained release can be imparted to the plant iron supplier.

 As the biodegradable binder, a biodegradable plastic can be used. Biodegradable plastics include polyalkylene succinate-based resins (polybutylene succinate resin, polyethylene succinate resin, etc.), polylactic acid-based resin, urea resin, poly-plastic filler-based resin, Examples thereof include cellulose-based resin, starch-based resin, and polybulal alcohol-based resin. These may be used alone or in combination of two or more.

 The content of the biodegradable binder is not particularly limited, but is 10% by mass or less (more preferably 2-7% by mass, usually 1% by mass or more) when the total amount of iron supply for plants is 100% by mass. It is preferable that

[0036] The plant iron supply agent of the present invention may contain a biodegradable extender. The biodegradable extender is a component other than the above-mentioned noinda having biodegradability. Examples of the biodegradable extender include peat, straw, shochu, sake lees, citrate lees, rice husks, snow flowers, cocoons, humus, chicken manure, compost, cow manure, bone meal, and clay. Only one of these may be used 2 More than one species may be used in combination. The biodegradable extender may or may not have a predetermined function for plants. Examples of the component having a predetermined function include components that serve as nutrients for plants.

 The content of the biodegradable extender is not particularly limited, but can be 50 to 94% by mass (preferably 70 to 94% by mass) when the total amount of iron supply for plants is 100% by mass. Within this range, even when a small amount of iron supply agent is mixed with a large amount of soil, an appropriate amount can be mixed.

 [0037] The plant iron supply agent of the present invention may contain other components in addition to the iron supply agent, the biodegradable binder and the biodegradable extender. Other ingredients include lipoic acid, oryza oil, various vitamins, Mn, Zn, Cu, Cr, Si, Mg, Ca, Co, Mo, Ni, B, etc. (for example, metallic state, metallic acid Compounds such as S and C1, and the like. These may be used alone or in combination of two or more. The other components are preferably 10 parts by mass or less when the total of the iron supplier, the biodegradable binder, and the biodegradable extender contained in the plant iron supplier is 100 parts by mass.

 [0038] The method of using the plant iron supplier of the present invention is not particularly limited. For example, if it is in liquid form, spray (sprinkle soil, root of the target plant, foliar spray, etc.) or immerse (use as a culture solution for hydroponics. Soak the root of the target plant, etc.) ), And mixing with soil. If it is solid, use it for mixing with soil (powder, lump), spraying on soil (powder), filling in soil (powder, lump), etc. A method is mentioned.

 [0039] In particular, among the plant iron supply agents of the present invention, (1) the plant iron supply agent containing the iron supply agent of the first invention, or (2) the iron supply agent of the second invention. A plant iron supply agent that contains citrate as an organic acid, a biodegradable extender is included, and the matrix composed of the biodegradable extender contains chenate and FeO. The plant iron supplier can be suitably used in alkaline soil.

As the biodegradable extender used in this case, the biodegradable extender can be applied as it is. Among these biodegradable extenders, peat, straw, shochu, sake lees and taenoic acid lees Peat is particularly preferred. These biodegradable extenders may be used alone or in combination of two or more.

 [0040] Among the iron supply agents for plants containing the citrate and the biodegradable extender, those containing peat as the biodegradable extender are particularly preferable.

 The peat may be a mixture of these peats that may be used as collected or subjected to various modification treatments. Examples of the various modification treatments include alkali extraction treatment, neutralization treatment (such as phosphoric acid neutralization treatment, and maternal lime neutralization treatment).

 Examples of the peat include grassy peat (mainly organic components derived from various types of peat, moss and moss) and woody peat. Further, peats obtained by modifying these can be mentioned. These may be used alone or in combination of two or more.

[0041] The peat has a water repellent effect. For this reason, for example, when a plant iron supply agent is used in alkaline soil, a high ambient force pH and an aqueous solution or the like can be prevented from entering the plant iron supply agent. Therefore, the pH is kept low, the decrease in solubility of FeO is suppressed, and the oxidation of Fe ²⁺ ions is further suppressed. Therefore, it is possible to supply Fe ^{2+ ions} stably over a long period of time. That is, excellent sustained release can be imparted by this plant iron supply agent.

[0042] Further, in the case of a 100 wt% Kuen acid, FeO and the sum of the peat, Kuen acid is contained 5-15 wt _^0/0, FeO is that is contained 5 to 10 weight _^0/0 preferable. The citrate content is more preferably 7 to 13% by mass, and the FeO content is more preferably 7 to 8% by mass. Thus, reduction in the solubility of FeO is sufficiently suppressed, and the oxidation of Fe ²⁺ ions is more sufficiently suppressed, prolonged connexion can be stably supplied to Fe ²⁺ ions.

[0043] Further, it is preferable that the matrix composed of the biodegradable extender has a granular strength in which citrate and FeO are contained. The shape of the particles constituting the granule is not particularly limited, and may be any of a sphere, an ellipsoid, a hemisphere, a cube, a cuboid, a cylinder, a plecket, and the like. Further, the granular body may be a dense body or a porous body. In addition, the particle size (diameter in the case of a sphere, shortest dimension in the case of other shapes) is preferably 50 mm or less (more preferably 10 mm or less, further preferably 6 mm or less, usually 0.5 mm or more). [0044] By suppressing the contact of citrate and FeO with the external environment by the water-repellent biodegradable extender as described above, for example, when this plant iron supplier is used in alkaline soil, Increase in pH inside the body is suppressed. This suppresses the decrease in FeO solubility. Furthermore, since the oxidation of Kuen acid by oxygen in the air is suppressed, the effect of FeO of Sani匕抑system according to the click E phosphate also together be obtained, prolonged connexion from stable Fe ² + ions Can be supplied.

 [0045] In addition, the alkaline soil refers to 10 g of air-dried soil, added with 25 ml of distilled water and shaken for 1 hour, and when the pH of the resulting suspension is measured, the pH exceeds 7. It means soil. Therefore, the alkaline soil includes an alkaline soil obtained by alkalinizing an original alkaline soil and a non-alkaline soil (fertilization, desertification, etc.). Examples of the basic alkaline soil include soils containing various calcareous components such as shell fossil soils, calcareous soils, and sandy soils. These may be used alone or in combination of two or more. Furthermore, a mixed soil of a soil containing these various calcareous components and a non-alkaline soil, which is an alkaline soil as a whole is included.

 [0046] The method for producing the plant iron supply agent is not particularly limited. For example, the plant iron supply agent of the second invention is obtained by mixing and granulating the iron supply agent of the second invention and peat. Can be obtained. The iron supply agent for plants of the third invention can be obtained by mixing and granulating the iron supply agent of the third invention (that is, for example, taenoic acid powder and FeO powder) and peat.

 The mixing method is not particularly limited, and the mixing may be performed by an extruder or the like using a dry blend using a mortar mixer, an omni mixer, or the like. Furthermore, the granulation method is not particularly limited, but it is usually granulated by an extrusion method. Further, it is preferable that mixing and granulation are continuously performed by extrusion molding because the process can be simplified. The temperature for dry blending and extrusion molding is not particularly limited, and it may be room temperature (for example, 15 to 35 ° C) or may be heated to about 40 to 90 ° C if necessary! /.

 For this citrate powder and FeO powder, the respective descriptions in the following [4] Method for producing iron supply can be applied as they are.

 [0047] [3] Method for producing iron supply agent

The production method of the present invention is not particularly limited as described above, and various methods can be used. However, for example, it is possible to provide a dissolution step of heating a mixture containing organic acid powder, FeO powder, and water to obtain an aqueous solution obtained by dissolving the organic acid and FeO.

 [0048] The "organic acid powder" is a powder containing the organic acid as a main component (usually a purity of 99% or more), and the particle shape and the like are not particularly limited as long as the purity and powder form.

 The “FeO powder” is a powder containing FeO as a main component. The amount of FeO contained in this FeO powder is not particularly limited, but usually FeO is 50% by mass or more (preferably 65% by mass or 100% by mass) with respect to the entire FeO powder. . This FeO powder can be any type of FeO powder. FeO powder described later (granulated product obtained by granulating iron-containing dust, and Z or iron-containing dust and reducing agent). Granulated products obtained by granulation, FeO powder obtained by vacuum heating and vacuum quenching), and various commercially available FeO powders can be used. Among these, FeO powder obtained by heating the above granulated product in a vacuum and then quenching in a vacuum is preferred.

 As the “water”, any water can be used as described above.

 [0049] The amount of the organic acid powder, FeO powder, and water charged in the "mixture" is not particularly limited. For example, when using citrate, the citrate powder (assuming a purity of 100%): Fe 2 O The mass ratio of powder (assuming purity 100%): water (assuming purity 100%) is preferably 60-90: 7-28: 3-20. 65-85: 10-24: It is more preferable to use at a ratio of 5 to 17.5. It is particularly preferable to use at a ratio of 68 to 72:10 to 22:10 to 15.

 [0050] The above mixture may or may not contain other components in addition to the organic acid powder, FeO powder and water. When other components are contained, they may be contained in a state dissolved in water or in a state not dissolved in water. Examples of other components include methanol and ethanol. By containing these, water can be removed more smoothly even under a reduced pressure environment. These may be used alone or in combination of two or more.

[0051] The heating conditions in the above "heating" are not particularly limited, but the heating temperature is preferably maintained at 150 ° C or lower. This is because the Fe ³⁺ ion concentration tends to increase above 150 ° C. The temperature of the aqueous solution by this heating is more preferably 140 ° C or lower, more preferably 135 ° C or lower, and further preferably 130 ° C or lower. On the other hand, the lower limit temperature is not particularly limited. For example, 40 ° C or higher is preferable, and 50 ° C or higher is more preferable. 60 ° C or higher is particularly preferable. The upper limit temperature and the lower limit temperature at the time of heating can be combined. That is, for example, 40 to 150 ° C is preferred, 50 to 140 ° C is more preferred, and 60 to 130 ° C is more preferred. Combinations other than these may be used. The pressure conditions for heating are not particularly limited.

By this heating, more citrate is dissolved in water, and the amount of FeO dissolved is increased accordingly, and the concentration of the target Fe ²⁺ ion or Fe ²⁺ ion complex is considered to increase.

 [0052] The production method of the present invention can include a step of removing a water-insoluble component after the dissolving step. Examples of the water-insoluble component include organic acid powder that cannot be dissolved and FeO powder that cannot be dissolved. The removal method is not particularly limited, but can usually be performed by filtration. That is, a filtration step can be provided. The filtration conditions at this time are not particularly limited. For example, it is preferable to use a membrane filter having a pore size of 10 m or less (more preferably 5 m or less, more preferably 3 μm or less) as the filtration filter.

[0053] In addition, when obtaining the iron supply agent of the second invention, it is possible to further include a drying step for removing the aqueous solution, hydraulic water, after the dissolving step. The drying conditions in this drying step are not particularly limited, and natural drying may be performed, but it is preferable to use the above-described removal method and drying conditions. That is, it is preferable to remove water by heating under reduced pressure. Moisture is water soluble by reducing gradually and Kosani匕性excellent Fe ²⁺ ion component (Fe 2 ⁺ complex and the like) is concentrated by heating, and that the iron supply agent of the second invention is obtained Conceivable.

 [0054] Furthermore, when obtaining the iron supply agent of the second invention, a purification step can be further provided. The purification process is a process for purifying water-soluble components. That is, for example, an iron supply agent obtained by removing water from the aqueous solution is brought into contact with water to dissolve the dissolvable part, and then the water-insoluble component is removed and extracted in the same manner as above. And a re-drying step for removing water from the extraction aqueous solution obtained in this extraction step.

 [0055] The FeO powder used in the production method of the present invention is a granulated product obtained by granulating iron-containing dust, and is formed by granulating Z or iron-containing dust and a reducing agent. Preferably, the granulated product is FeO powder obtained by vacuum heating and vacuum quenching.

This FeO powder (FeO powder obtained using the above granulated product and Z or granulated product) is Fe Besides O, it is usually CaAl O, FeAl O, CaFe Si O, CaSi O and MgFe O.

 This is because 2 4 2 4 2 2 6 2 5 2 4 of at least one double acid compound is contained. These double oxides may contain only one kind or two or more kinds. The content of the composite oxide is preferably 0.5 to 10% by mass when the entire FeO powder is 100% by mass. Within this range, it is possible to obtain an iron supplier that is particularly excellent in acid resistance.

 Further, the shape of the particles constituting the FeO powder is not particularly limited, but is a FeO powder having a particle size of 5000 m or less and mixed with various particle sizes, and further includes porous particles. It may be.

[0056] The "dust containing iron" (hereinafter, simply referred to as "dust") is one containing iron (such as dust collection powder). This iron includes iron oxide, other iron compounds and metallic iron. These may contain only 1 type, or 2 or more types. The amount of iron contained in the dust is not particularly limited, but usually 30% by mass or more (more preferably 35 to 90% by mass, still more preferably 40 to 80% in terms of metallic iron when the total dust is 100% by mass. Mass%). The dust may contain other components in addition to iron. Other components include Zn, Ni, Cu and Mn. These may be simple metals or compounds such as oxides. Furthermore, these may contain only 1 type, and may contain 2 or more types.

 The shape of the dust is not particularly limited, and may be a small piece or a mixture of powder and small pieces, but is usually a powder. The average particle size of the powder is not particularly limited, but is preferably 3 to 10 / ζ πι.

[0057] This dust includes forged shot dust collected in the forging process (powder collected in the process of driving the forging shot ball into the iron-based member to be processed) and various dusts generated in the steel making process. {Powder collected in the process of melting iron-based materials in various furnaces to produce iron-based products for the purpose of smoke prevention (electric furnace dust, blast furnace dust, converter dust, cupola dust, etc.)} Can be mentioned. These may be used alone or in combination of two or more. In particular, dust from which the chlorine content has been removed by washing with water (partially or entirely) is preferred. In particular, the chlorine content in the dust is preferably 0.5% by mass or less (more preferably 0.4% by mass or less, and still more preferably 0.3% by mass or less). [0058] The above "granulated product" contains dust or dust and a reducing agent. This granulated product is subsequently reduced or oxidized from Fe 2 O, Fe 2 O and Fe (single) to FeO during vacuum heating.

 2 3 3 4

 It is.

 The shape of the particles constituting the granulated product is not particularly limited, and may be any of a sphere, an ellipsoid, a hemisphere, a cube, a cuboid, a cylinder, a plecket, and the like. Further, the granulated product may be a dense body or a porous body. Further, the particle size (diameter in the case of a sphere, shortest dimension in the case of other shapes) is preferably 25 mm or less (more preferably 15 mm or less, further preferably 10 mm or less, usually 3 mm or more).

[0059] The "reducing agent" is a component that reduces an iron compound that has been oxidized to a valence of 2 or more. As the reducing agent, metallic iron, a mixture thereof, carbon, a mixture thereof, or the like can be used. In particular, reducing agents used for iron cutting scraps, iron polishing scraps, iron powder, pig iron and steel, various waste materials (tire scraps, wood waste materials, etc.) and the like are preferable. These may be used alone or in combination of two or more.

 The shape of the reducing agent is not particularly limited, but it is preferable that the contact area with the dust is large, so that powder, granules, small pieces, etc. are particularly preferable. Furthermore, the average particle size is preferably 200 m or less (preferably 180 μm or less).

 The content of the reducing agent in the granulated product is not particularly limited, but when the dust is 100 parts by mass, it is 100 parts by mass or less (more preferably 90 parts by mass or less, more preferably 80 parts by mass or less, usually 30 parts by mass). Part or more) is preferred.

[0060] The granulated product usually contains noinda. The type of binder is not limited, but alumina cement is preferred. The blending amount is preferably 3 to 20 parts by mass (more preferably 3 to 15 parts by mass, further preferably 3 to 12 parts by mass) when the total amount of dust or dust and reducing agent is 100 parts by mass. . In this range, granulation can be performed smoothly and embrittlement of the granulated product can be suppressed.

[0061] By performing the "vacuum heating", the FeO concentration in the FeO powder can be increased. The degree of vacuum during this vacuum heating is not particularly limited, but is preferably 0.1 to 13.3 kPa (more preferably 2.6 to 13.3 kPa, particularly preferably 4.0 to 6.7 kPa). In this range, it is possible to effectively suppress residual metallic iron and oxidation of FeO to Fe 2 O and the like. In this vacuum atmosphere Even under an inert gas that reproduces the partial pressure of oxygen, it is possible to obtain FeO powder by heating in the same way instead of this vacuum heating.

[0062] The heating temperature (measured value obtained by measuring the granulated product itself) during vacuum heating is preferably 600 to 1100 ° C (more preferably 800 to 950 ° C). However, when the granulated product contains a reducing agent, it is preferably 800 ° C or higher. In this range, FeO powder with a particularly high FeO content can be obtained, and dust can be prevented from melting during the heating process.

 The heating time is not particularly limited, but is preferably 30 minutes or longer (more preferably 30 minutes or longer and within 6 hours).

 When zinc oxide or the like is contained in the dust, it is reduced to metal zinc, which can be recovered by evaporation under a vacuum of 600 ° C or higher and about 1.56 kPa. This can further improve the purity of FeO.

 [0063] The granulated product is usually heated using a heat treatment furnace. The heat treatment furnace is not particularly limited as long as it includes at least a heater and can uniformly heat the granulated product to be charged. Examples of the heat treatment furnace include a roller hearth furnace and a rotary kiln. The granulated product is powdered by, for example, a stirring means equipped with a stirring blade while moving in the heat treatment furnace. This heat treatment furnace may be equipped with a recovery device for recovering metallic zinc and the like produced by the reduction. The amount of granulated product input to the heat treatment furnace is not particularly limited. Usually, it is preferable that the input amount is 100 mm or less, particularly 80 mm or less, and further 30 mm or less.

 [0064] By the above "vacuum quenching", the high-temperature FeO powder produced by vacuum heating can be cooled without being oxidized. The degree of vacuum during this vacuum quenching is not particularly limited, but is preferably 13.3 kPa or less (more preferably 6.7 kPa or less, usually 5.3 kPa or more). The temperature drop rate is not particularly limited, but it is preferably 5 to 150 ° CZ. In this vacuum quenching, it is preferable to cool to 300 ° C or lower (more preferably 200 ° C or lower, particularly preferably 150 ° C or lower).

[0065] In particular, for the purpose of obtaining FeO powder having a higher FeO content, it is preferable to use a granulated product containing metallic iron. The content of metallic iron is 5% by mass or more (more preferably 5 to 85% by mass, even more preferably, when the total amount of iron contained in the granulated product is 100% by mass Is preferably 8 to 50% by mass). When this granulated product is used, for example, an FeO powder having a FeO content of 80 mass% or more (more preferably 85 mass% or more, particularly 90 mass% or more) based on the total iron content can be obtained.

[0066] Dust constituting the granulated product containing metallic iron as described above {the following (3) and (4)} and a combination of a dust and a reducing agent {the following (1), (2) and (5 )} Includes (1) a mixture of electric furnace dust and metallic iron (iron powder, etc.), (2) a mixture of blast furnace dust and metallic iron (iron powder, etc.), (3) converter dust only, (4 ) Forged shot dust collection powder only, (5) A mixture of forged shot dust collection powder and metallic iron (iron powder, etc.). These may be used alone or in combination of two or more.

 Example

 Hereinafter, the present invention will be specifically described with reference to examples.

 [l] Manufacture of FeO powder

 (1) FeO powder using electric furnace dust

Fe (35.8 mass%), Zn (22.7 mass%), C (5.95 mass%), Ca (2.92 mass%), Mn (2.89 mass%), C1 (2.89 mass%) and Si (2. 16% by mass) or the like is contained, the electric arc furnace dust having an average particle diameter of 10 mu m (steelmaking dust) 47.6 mass _^0/0, the average particle size is 75 mu m iron It was granulated into a cylindrical shape having a diameter of 8 mm and a length of about 20 mm using 47.6 mass% of powder and 4.8 mass% of alumina cement. The obtained granulated product was heated in a vacuum heating tank (roller hearth furnace) at 800 ° C. for 30 minutes, then at 850 ° C. for 30 minutes, and then at 900 ° C. for 1 hour. Next, vacuum quenching is performed in a vacuum quenching bath to 400 ° C at a rate of temperature drop of 20 ° CZ, and the atmosphere in the vacuum cooling bath is replaced with nitrogen, followed by cooling to 200 ° C at a rate of temperature drop of 13 ° CZ, Thereafter, the temperature was lowered to room temperature to obtain FeO powder.

 The FeO contained in this FeO powder was quantified by a calibration curve prepared in advance by X-ray diffraction using a mixed powder obtained by mixing a reagent FeO powder and a silicon powder at a predetermined ratio. Was 65% by mass.

[0068] (2) FeO powder using forged shot dust collection powder (used in [4] and [8] below)

Fe (80.0 mass%), Zn (0.02 mass%), Ca (0.01 mass%), Mn (0.06 mass%), Si (0.06 mass%), etc. Forged shot dust collection powder with a particle size of 100 m 82%, iron powder 10% with an average particle size of 75 μm, alumina cement 5%, bentonite 3% It was granulated into a cylindrical shape having a diameter of 8 mm and a length of about 20 mm. The obtained granulated product was heated in a vacuum heating tank (roller hearth furnace) at 800 ° C. for 30 minutes, then at 850 ° C. for 30 minutes, and then at 900 ° C. for 1 hour.

 Next, vacuum quenching is performed in a vacuum quenching bath to 400 ° C at a rate of temperature drop of 20 ° CZ, and the atmosphere in the vacuum cooling bath is replaced with nitrogen, followed by cooling to 200 ° C at a rate of temperature drop of 13 ° CZ, Thereafter, the temperature was lowered to room temperature to obtain an FeO powder that was an aggregate force of spherical particles having a diameter of 1.8 mm.

 The FeO contained in this FeO powder was quantified by a calibration curve prepared in advance by X-ray diffraction using a mixed powder obtained by mixing a reagent FeO powder and a silicon powder at a predetermined ratio. Was 90% by mass.

 [0069] [2] Manufacture of iron supply agents

 (1) Use citrate as organic acid

 Chenic acid (purity 99% or more) 15.4 kg and 5.6 kg of water were mixed in a pressure vessel, and the temperature in the liquid was gradually raised to 80 ° C. When the temperature reached 80 ° C, 3.3 kg of the FeO powder obtained in [1] (1) above was added. Thereafter, the liquid temperature was raised to 130 ° C over 4 hours. When the liquid temperature reached 130 ° C, the inside of the container was depressurized to about 8 kPa, and this state was maintained for 100 minutes. As a result, 17 kg of massive iron supply agent was obtained. Thereafter, the massive iron supply agent was pulverized by a pulverizer into powder.

 [0070] (2) Use acetic acid as organic acid

 12 kg of acetic acid (purity 99% or more) and 5.6 kg of water were mixed in a pressure vessel, and the liquid temperature was gradually raised to 80 ° C. When the temperature reached 80 ° C, 7.3 kg of the FeO powder obtained in [1] (1) above was added. Thereafter, the liquid temperature was raised to 130 ° C over 4 hours. When the liquid temperature reached 130 ° C, the inside of the container was depressurized to about 8 kPa, and this state was maintained for 100 minutes. As a result, 17.5 kg of massive iron supplier was obtained. Thereafter, the massive iron supply agent was pulverized by a pulverizer into powder.

 [0071] (3) Using tartaric acid as the organic acid

15 kg of tartaric acid (purity 99% or more) and 5.6 kg of water were mixed in a pressure vessel, and the liquid temperature was gradually raised to 80 ° C. And when the temperature reaches 80 ° C, it is obtained by [1] (1) above. 7.3 kg of the FeO powder was added. Thereafter, the liquid temperature was raised to 130 ° C over 4 hours. When the liquid temperature reached 130 ° C, the inside of the container was depressurized to about 8 kPa, and this state was maintained for 100 minutes. As a result, 20 kg of massive iron supply agent was obtained. Thereafter, the massive iron supply agent was pulverized with a pulverizer into powder.

 [0072] (4) Using oxalic acid as the organic acid

 18 kg of oxalic acid (purity 99% or more) and 5.6 kg of water were mixed in a pressure vessel, and the liquid temperature was gradually raised to 80 ° C. When the temperature reached 80 ° C, 7.3 kg of the FeO powder obtained in [1] (1) above was added. Thereafter, the liquid temperature was raised to 130 ° C over 4 hours. When the liquid temperature reached 130 ° C, the inside of the container was depressurized to about 8 kPa, and this state was maintained for 100 minutes. As a result, 21 kg of massive iron supply agent was obtained. Thereafter, the massive iron supply agent was pulverized with a pulverizer into powder.

[0073] [ ³ ] Measurement of Fe ²⁺ ion concentration

(l) Fe ²⁺ ion concentration

The iron supply obtained in [2] (1) above was stirred and mixed in ion-exchanged water at a temperature of 20 ° C to a concentration of 10 gZ liter (1.0% by mass) (approximately 5 minutes) Stirring). Then, filter using a membrane filter (pore size 1 m), and then immediately attach the water quality measurement pack to the UV'visible light spectrophotometer (manufactured by Shimadzu Corporation, model “UV1240”). The Fe ²⁺ ions and the total amount of Fe ions contained in the obtained aqueous solution were measured (the total Fe ion amount force was converted to the Fe ³⁺ ion amount by subtracting the Fe ²⁺ ion amount). Further, the Fe ²⁺ ion concentration was measured by a phenantorin phosphorus absorptiometry based on JIS K0102. In this measurement, the work was always carried out in a room where direct sunlight was not inserted.

[0074] The results of this measurement, Fe ²⁺ ion concentration is 389mgZ l, Fe ³⁺ ion concentration is 1 86MgZ liter, and a total of 100 mass _^0/0 of the Fe ²⁺ ions and Fe ³⁺ ions Fe ²⁺ ions was 68 mass _^0/0 when. In other words, the obtained aqueous solution contains Fe ³⁺ ions → Fe ²⁺ ions ^2.1 times as much as Fe ³⁺ ions, and an aqueous solution having a high Fe ²⁺ ion concentration is obtained.

[0075] (2) Fe ²⁺ ion concentration at each concentration of each iron supply agent

In the same manner as (1) above, four types of iron provided with different organic acids obtained in [2] (1) to (4) above. The feeds were prepared to the concentrations shown in Table 1 and the Fe ²⁺ ion concentration in each aqueous solution was measured. The results are shown in Table 1.

[0076] [Table 1] Table 1

[0077] From the results in Table 1, it can be seen that oxalic acid shows almost no change in Fe ²⁺ ion concentration up to low concentration strength and high concentration. It can also be seen that acetic acid has a high concentration of Fe ²⁺ ions but a low concentration of Fe ²⁺ ions compared to other organic acids. In addition, kenic acid and tartaric acid do not have the above-mentioned problems, but kenic acid is more inferior to tartaric acid. , Cal Fe ²⁺ ion concentration per mass of iron supplying agent at any concentration that is high partial. That is, it can be seen that Fe ²⁺ ions can be supplied most efficiently.

 [0078] [4] Evaluation of antioxidant properties

 (1) Anti-acidity by leaving indoors

[2] Using the three types of iron supply agents with different organic acids obtained in (1) to (3) above, the concentration of each iron supply agent is the value shown in Table 2 in the same manner as in [3] above. Experimental Examples 11 1 to 3-4 prepared in this way were prepared iron supply aqueous solutions. Measure the Fe ²⁺ ion concentration in the same manner as in [3] above for the aqueous solutions of each of these experimental examples, then leave it in the room and measure the Fe ²⁺ ion concentration in the same manner at each time shown in Table 2. did. The results are also shown in Table 2. Also, in Table 2, experimental examples 11 to 14 using citrate are graphed and shown in FIG.

[0079] Further, 2.5 g of ascorbic acid was dissolved in 500 ml of distilled water to prepare an ascorbic acid aqueous solution. Then, 1. Og of the FeO powder obtained in [1] (2) above was added to this aqueous solution, stirred for 30 minutes, and then filtered to remove impurities. Then, 20 ml each was taken from the filtered aqueous solution and put into two containers, and the aqueous solution in one container was adjusted to pH 6.0 with sodium hydroxide aqueous solution (Example 6-2). did. The pH of the other aqueous ascorbate aqueous solution (Experimental Example 6-1) that had not been adjusted for pH was 3.4. These two Asukorubin iron solution (Experimental Examples 6-1 and 6-2) was similarly measured F e ²⁺ ion concentration also, together appended below the Fe ²⁺ ion concentration of pH measurement (Table 2 Did). The results are also shown in Table 2.

[0080] From the results in Table 2, when the organic acids are quenoic acid, tartaric acid, acetic acid and ascorbic acid, the fluctuations from the initial concentration related to the concentration of the iron supply agent are all small and suppressed. It can be seen that it has excellent acid resistance. That is, for example, as shown in FIG. 1, in Experimental Example 1 1 is over 82.3% of the initial value, in Experimental Example 1 2 is over 81.9% of the initial value, and in Experimental Example 1 3 is the initial value. 88.7% or more for the value, and 87.3% or more for the initial value in Experimental Example 14; in both cases, an ion concentration of 80% or more with respect to the initial Fe ²⁺ concentration over a long period of time. Is retained. Therefore, it can be seen that it has excellent acid resistance. It can also be seen that in the iron supply agents using ascorbic acid in Experimental Examples 6-1 and 6-2, the pH fluctuation is also suppressed to a small extent. [0081] [Table 2]

 Table 2

 [0082] (2) Antioxidant property by accelerated oxidation test

[2] Experimental example 4 obtained in the same manner as in the above [3] using two types of iron supply agents having different organic acids obtained in (1) to (2) {Iron supply concentration 10 gZ liter (0 1 mass%)} and Experimental Example 5 {Iron-supplier concentration 5gZ liter (0.5 mass%)} Test was carried out. That is, 0.6 liters of air was sent into each aqueous solution (200 milliliters) of Experimental Examples 5 and 6 using an air pump for publishing at a time shown in Table 3 in the same manner as in [3] above. ^{The 2+} ion concentration was measured. The results are also shown in Table 3. In addition, Table 3 is graphically shown in Fig. 2.

[0083] [Table 3] Table 3

[0084] From Table 3 and FIG. 2, when the organic acid is citrate, the concentration fluctuation is suppressed to be small even in the oxidation acceleration test, and it has excellent acid resistance. I understand. In particular, in Experiment Example 4 with a concentration of 1.0% by mass, it can be seen that the Fe ²⁺ concentration of 77% is maintained even after 288 hours (12 days later) from the initial value.

 [0085] [5] Evaluation by ultraviolet irradiation

Using the iron supplier obtained in [2] (1) above, an aqueous solution of Experimental Example 6 {iron supplier concentration 6 gZ liter (0.6 mass%)} was obtained in the same manner as [3] above. The Fe ion concentration immediately after preparation of the aqueous solution obtained in Experimental Example 6 was 824 mgZ liters in total Fe ion concentration, of which Fe ²⁺ ion concentration was 534 mgZ liters.

Thereafter, 90 liters of the aqueous solution of Experimental Example 6 was irradiated with ultraviolet rays (wavelength 253 nm) of 72 Χ 10 ⁴ / ζ ^ 3 Ζη ² for 18 hours. The Fe ion concentration immediately after irradiation of the aqueous solution of Experimental Example 6 obtained by ultraviolet irradiation was 824 mgZ liters of total Fe ion concentration, of which Fe ²⁺ ion concentration was 8 lOmgZ liters. After that, when the aqueous solution after UV irradiation in Experimental Example 6 was stored in a dark place, it was recovered to the Fe ²⁺ ion concentration just after the preparation after 21 days. [0086] From this result, it can be seen that the reaction in which Fe ³⁺ ions are converted to Fe ²⁺ ions is proceeding without being oxidized by ultraviolet irradiation. Therefore, it can be seen that, unlike a conventional Fe ²⁺ ion solution containing an inorganic compound as a main component, it has excellent storage stability without the problem of oxidative degradation due to sunlight or ultraviolet rays.

 [0087] [6] Evaluation by mass spectrometry

Using the iron supplier obtained in [2] (1) above, an aqueous solution of Experimental Example 7 {Iron supplier concentration 10 gZ liter (1.0 mass%)} was obtained in the same manner as [3] above. The Fe ion concentration immediately after the preparation of the obtained aqueous solution of Experimental Example 7 was 86 mgZ liters in total Fe ion concentration, of which the Fe ²⁺ ion concentration was 330 mgZ liters.

 Thereafter, the aqueous solution of Experimental Example 7 was diluted 10-fold with methanol. The substances contained in this diluted solution were subjected to mass spectrometry using electrospray ionization mass spectrometry (ESIMS). Micromass type “Q-TOF” was used for the measurement device, and electrospray ionization (ESI) was used for the ionization method. Furthermore, the ion mode was positive ion mode, the capillary voltage was 3000V, the cone voltage was 20V, and the solvent removal temperature was 120 ° C. The resulting chart is shown in FIG.

 Furthermore, when mass analysis was performed on the peak of mass 439 in the obtained chart by collision with Ar gas (Collisiion Energy: 120 eV), a peak was generated at mass 55.9. As a result, it was found that Fe contained in the compound constituting the peak of mass 439. The resulting chart is shown in FIG.

 In addition, as a result of the comparative test, iron (III) citrate (Wako Pure Chemicals, FeC H 2 O, all Fe

6 5 7 Measures a similar solution of citrate anhydride (manufactured by Wako Pure Chemicals, CHO) with a chart obtained by measuring a similar solution with an on-concentration of 584 mgZ liter and Fe ²⁺ ion concentration of 142 mgZ liter.

 6 8 7

 The chart obtained in this way is shown in FIG.

[0089] From the results of FIGS. 3 and 4, from the chart with citrate anhydride, mass 215 ([CHO + Na] ⁺ ) and mass 407 ([2 (CHO) + Na] + )of

 6 8 7 6 8 7

 The peak is considered to be derived from citrate.

In addition, as a result of reanalysis of mass 439, it can be seen that the compound constituting the peak of mass 439 contains Fe. By subtracting the mass corresponding to Fe, Thus, the peak at mass 439 is thought to be due to a dimer complex in which two citrate and Z or two citrate ions are coordinated with Fe ions. Similarly, the peak at mass 631 is thought to be due to a trimeric complex in which three citrate and Z or three citrate ions are coordinated to Fe ions, and the peak at mass 823 is relative to Fe ions. It is thought to be due to a tetrameric complex coordinated with quaternary acid and Z or citrate ion force S4.

[0090] Furthermore, when compared with an aqueous solution in which iron (III) citrate is dissolved (total Fe ion concentration 584 mgZ liter, Fe ²⁺ ion concentration 142 mgZ liter), the peaks of mass 439 and mass 631 are small, and the relative content Is expected to be small.

Summing up these results, the iron supplier of the present invention contains more dimer complexes and trimer complexes than the iron (III) citrate aqueous solution. cause of Fe ²⁺ ions, and has a high antioxidant, yet is stable to ultraviolet light, is considered to be a factor in increasing the Fe ²⁺ ions is observed rather.

[0091] [7] Evaluation of plant iron supply (liquid)

 (1) Preparation of iron supply solution for plants (used as irrigation solution)

In the same manner as in [3] above, an aqueous solution containing an iron supply agent at a concentration of 10 gZ liter (1.0 mass%) was obtained. This aqueous solution was diluted 1000 times with water to obtain an irrigation solution (plant iron supply solution, one experimental example 8 of the present invention). The total Fe ion concentration in the obtained irrigation solution (Experimental Example 8) is 0.5 mgZ liter, of which the Fe ²⁺ ion concentration is 0.3 mgZ liter.

For comparison, a commercially available aqueous solution containing Fe ²⁺ ions (produced by Menedal Co., Ltd., product name “Plant Vigor Elementary Menedale”, aqueous solution containing ferrous sulfate) was diluted 100-fold to a irrigation solution (reference example). 1) was obtained. The total Fe ion concentration in the obtained irrigation solution is 0.4 mgZ liter, of which the Fe ²⁺ ion concentration is 0.4 mgZ liter.

[0092] (2) Preparation of experimental cultivation area

 As a test soil, a commercially available seedling culture soil was spread in a plastic container measuring 30 cm long × 28 cm wide × 4 cm deep to a depth of 4 cm to form an experimental cultivation zone.

[0093] (3) Sowing, irrigation, growth

On April 1st each of the above experimental cultivation areas, 30g each of 4 kinds of seeds of early blooming cosmos, banana peppers, spray chrysanthemum and all-day blooming pine needle buttons were equally distributed. Then, each irrigation solution was irrigated so that 1 liter of water was evenly applied at the diio opening. After that, each irrigation solution (Experimental Example 8 and Reference Example 1) should be applied equally to each experimental cultivation area at 10:00 a.m. twice at 8 am and 5 pm daily. Continued irrigation.

[0094] (4) Results

 (i 1) Hayasaki Cosmos (using the irrigation solution of Experimental Example 8)

 Germination was confirmed on April 6. Fig. 5 shows an explanatory diagram based on an image obtained by digitally photographing this cultivation area on April 13. In addition, Fig. 6 shows an explanatory diagram using images obtained by digitally photographing this cultivation area on April 20.

 (i 2) Hayasaki Cosmos (using the irrigation solution of Reference Example 1)

 Germination was confirmed on April 8. Fig. 7 shows an explanatory diagram based on an image obtained by digitally photographing this cultivation area on April 13. In addition, Fig. 8 shows an explanatory diagram based on images obtained by digitally photographing this cultivation area on April 20.

 From the above results, germination is fast in the cultivation section using Experimental Example 8. Furthermore, when compared with Fig. 5 and Fig. 7, in the cultivation plot using Reference Example 1, the true leaves began to appear, whereas in the cultivation plot using Experimental Example 8, the true leaves began to grow greatly. It can be seen that the subsequent growth is fast.

 [0095] (ii 1) Banana pepper (using the irrigation solution of Experimental Example 8)

 Germination was confirmed on April 6. Fig. 9 shows an explanatory diagram based on an image obtained by digitally photographing this cultivation area on April 13.

 (ii 2) Banana bell pepper (using the irrigation solution of Reference Example 1)

 Germination was confirmed on April 8. Fig. 10 shows an explanatory diagram based on an image obtained by digitally photographing this cultivation area on April 16.

 From the above results, it can be seen that germination is fast in the cultivation area using Experimental Example 8. The subsequent growth was faster when Experimental Example 8 was used.

[Iii] (iii 1) Spray chrysanthemum (using the irrigation solution of Experimental Example 8)

Germination was confirmed on April 13. Fig. 11 shows an explanatory diagram based on images obtained by digitally photographing this cultivation area on April 13. (iii 2) Spray chrysanthemum (using the irrigation solution of Reference Example 1)

 Germination was confirmed on April 16. Fig. 12 shows an explanatory diagram based on the image obtained by digitally photographing this cultivation area on April 13.

 From the above results, it can be seen that germination is fast in the cultivation area using Experimental Example 8. The subsequent growth was faster when Experimental Example 8 was used.

[0097] (iv- 1) All-day Sakimatsuba button (using the irrigation solution of Experimental Example 8)

 Germination was confirmed on April 13. Fig. 13 shows an explanatory diagram based on the image obtained by digitally photographing this cultivation area on April 13.

 (iv-2) All-day Sakimatsuba button (uses the irrigation solution of Reference Example 1)

 Germination was confirmed on April 16. Fig. 14 shows an explanatory diagram based on images obtained by digitally photographing this cultivation area on April 16.

 From the above results, it can be seen that germination is fast in the cultivation area using Experimental Example 8. There were also many germinations.

[0098] [8] Evaluation of plant iron supplier used for rice seedlings

 (1) Iron supply agent for plants (Aqueous solution in dry product, Experiment 9)

 800 g of succinic anhydride (purity 99.8%) and 2 liters of water were placed in a stainless steel beaker and stirred at room temperature (20 ° C) to dissolve the succinic anhydride in water. Thereafter, lOOg of the FeO powder obtained in [1] (2) above was added, and stirring was continued for another 30 minutes. Next, the filtrate obtained by filtering this liquid (using filter paper) was dried for 72 hours in a dryer adjusted to 90 ° C. to make a paste, and further cooled to room temperature to make a lump. . The obtained lump was pulverized in a mortar and then passed through a sieve having an opening of 1. Omm to obtain an iron supply agent for plants (Experimental Example 9) having a particle size of 1. Omm or less.

[0099] (2) Production of plant iron supply agent (containing peat, Experimental Example 10)

 FeO powder obtained in [1] and (2) above, citrate anhydride (purity 99.8% or more), and peat-treated soil improver (made by Nippon Fertilizer Co., Ltd., trade name “Kumiai Hyhumin Special A )) Is mixed at a ratio of 7.5% by mass: 10.0% by mass: 82.5% by mass and then granulated into a cylindrical shape having a diameter of 3 mm and a length of about 6 mm to contain peat. A plant iron supplier (Experimental Example 10) was obtained.

[0100] (3) Rice seedlings Rice (variety: Nihonbare) seeds were allowed to germinate for 2 days in a petri dish with tissue paper and moistened at room temperature. Thereafter, the following seedling culture soil was introduced into each cultivation pot, and 20 seeded rice plants were sown directly (seeding on January 15). At the time of sowing, rice seeds were embedded at a surface strength of about 0.5 cm. Each pot for cultivation was placed in a human meteorological device, and rice was grown until March 10 under the following seedling conditions, and the effect of the iron supply agent for plants was evaluated.

[0101] (4) Used seedling culture soil

 Reference Example 2: Shell fossil soil (containing approximately 70% by weight of CaCO, the same shall apply hereinafter)

 Three

 Fertilizer (Chisso Asahi Fertilizer Co., Ltd., trade name “Long Total 70”, the same shall apply hereinafter) The soil containing lg was used as the seedling culture soil.

 Experimental Example 91: soil containing 300 mL of the above shell fossil soil and the above fertilizer lg and the plant iron supplier 0. lg of Experimental Example 9 was used as a seedling culture soil.

 Experimental Example 9 2; Soil containing 300 mL of the above-mentioned shell fossil soil and the above fertilizer lg and 1.0 g of the plant iron supply agent of Experimental Example 9 was used as the seedling culture soil.

 Experimental Example 10-1: A soil obtained by mixing 300 mL of the above-mentioned shell fossil soil with the above fertilizer lg and 1.0 g of the iron supply agent for plants of Experimental Example 10 was used as a seedling culture soil.

 Experimental Example 10-2: Soil in which 300 mL of the above-mentioned shell fossil soil was mixed with the above fertilizer lg and 2.0 g of the plant iron supply agent of Experimental Example 10 was used as a seedling culture soil.

[0102] (5) Seedling conditions

 Using an artificial meteorograph (manufactured by Nippon Medical Instrument Co., Ltd., model “LH-100SJ”), sunshine is adjusted to 14 hours (illuminance is 1500 lux, temperature is 25 ° C) and night is adjusted to 10 hours (temperature is 20 ° C) In addition, 50 ml of distilled water was initially added to each pot, and irrigation was carried out so that the mass of each pot was maintained at 400 g every day throughout the seedling period. In addition, each pot was randomly repositioned every day throughout the growing period so that the lighting (sunshine) was evenly illuminated.

[0103] On March 10 when the seedlings were finished, 20 plant heights were measured for each pot, and the average value was calculated. Further, the SPAD value (green density, which is an index of the amount of chlorophyll) was measured using a chlorophyll meter (model “SPAD-502” manufactured by Minolta Co., Ltd.). Then from each pot The seedlings were taken out, sifted through the root soil, and digitally photographed (an illustration of the resulting image is shown in Figure 15). After that, it was dried for 7 days, and then almost all of the root soil was screened out. Then, the above-ground dry weight and root dry weight (total of dry weight and dredged weight) were measured. The results are shown in Table 4.

 Regarding the plant height and SPAD value of seedlings, the average value and standard deviation of 20 seedlings in each pot are described.

[0104] [Table 4]

 Table 4

 [0105] (6) Evaluation results

 Based on the results in Table 4 and Figures 15-17, the seedlings from Reference Example 2 with fertilizer but not fertilizer for plants were 15.9 cm in plant height, 13.0 cm in SPAD, and dry on the ground. The weight was 0.38 g and the root dry matter weight was 0.3 lg.

 On the other hand, in Experimental Example 9-1, which was given the plant iron supply agent in Experimental Example 9 of 0.lg, the plant iron supply agent was used even in alkaline soil, although the amount was small. The effect of blending was confirmed. In other words, the plant height and SPAD value is 1.5 times, the above-ground dry weight is 2.6 times, and the root dry weight is 1.7 times that of Reference Example 2, which is superior to Reference Example 2. I can speak of something.

Furthermore, in Experiment Example 9-2, in which the amount of the iron supply agent for plants was increased to 10 times the amount of Experiment Example 91, the effect of increasing the amount was recognized. In other words, plant height is 1.1 times smaller than Example 9-1, but SPAD value is 1.4 times, aboveground dry weight is 1.4 times, and root dry weight is 2.4. It was twice. In Example 92, there is a possibility that the iron supply threshold is large, where the standard deviation of plant height and SPAD value is large. For this reason, it may be better to add more plant iron supply agents.

[0106] In addition, in Experimental Example 10-1 to which the plant iron supply agent of Experimental Example 10 of Og was given, the effect of adding the plant iron supply agent in alkaline soil was also observed. That is, plant height is 1.7 times, SPAD value is 2.1 times, aboveground dry weight is 2.9 times, and root dry weight is 2.8 times that of Reference Example 2. It turns out that it is superior.

 In addition, in Experimental Example 10-2, the amount of the plant iron supply agent was increased to twice that of Experimental Example 10-1, and the plant height and SPAD values were 1.1 times that of Experimental Example 10-1. The above-ground dry weight was 0.65 times and the root dry weight was 0.77 times. Thus, it is difficult to recognize a clear difference between Experimental Example 10-1 and Experimental Example 10-2. This is because a delayed action effect due to containing a biodegradable bulking agent appears. Conceivable. That is, it can be seen that the iron supply agent for plant of Experimental Example 9 has an immediate effect, whereas the iron supply agent for plant of Experimental Example 10 has a delayed effect. Therefore, it is considered that the difference will be recognized by raising seedlings for a longer period.

 Industrial applicability

[0107] The iron supply agent of the present invention is widely used in the field of agriculture, forestry and fisheries. That is, for example, it is widely used for the production of agricultural products, the production of horticultural plants, the production and maintenance of parks and golf courses, the maintenance of forests, the breeding of livestock, and the cultivation of seafood. The plant iron supply aqueous solution and the plant iron supply agent of the present invention are widely used in the field of agriculture and forestry. That is, for example, it is widely used for production of agricultural products, hydroponics, production of horticultural plants, production and maintenance of parks and golf courses, forest maintenance, and the like. In particular, it is useful as a plant growth promoter in the production field of various agricultural products. It can also be used to solve food problems caused by plant growth in barren lands around the world and to improve the global environment by promoting absorption of carbon dioxide.

Claims

 The scope of the claims

 [I] An iron supplier comprising an aqueous solution obtained by dissolving an organic acid having a carboxyl group and Z or hydroxyl group, and FeO.

[2] When Fe ²⁺ ions and Fe ³⁺ ions are contained and the total of the Fe ²⁺ ions and the Fe ³⁺ ions is 100 mass%, the Fe ²⁺ ions are 50 to 90%. The iron supply agent according to claim 1, wherein the iron supply agent is in mass%.

[3] The iron supply agent according to claim 1, wherein the Fe ²⁺ ion concentration observed in the aqueous solution after standing for 168 hours is 75% or more of the Fe ²⁺ ion concentration observed immediately after the start of measurement.

[4] The iron supply agent according to claim 1, containing at least citrate as the organic acid.

[5] and dimeric complexes Kuen acid and Z or Kuen acid ion was two coordinated to one Fe ²⁺ ion, Kuen acid and Z or Kuen acid ion for one Fe ²⁺ ions The iron supply agent according to claim 4, comprising a trimeric complex coordinated in three.

[6] A plant iron supplier comprising the iron supplier according to any one of claims 1 to 5.

 [7] The iron supplier for plants according to claim 6, which contains a biodegradable binder.

 [8] The plant iron supply agent according to [6] containing a biodegradable extender.

 [9] The iron supplier for plants according to claim 6, which contains 5% by mass or more of the iron supplier when the total iron supplier for plants is 100% by mass.

[10] An iron supplier obtained by removing water from an aqueous solution obtained by dissolving an organic acid having a carboxyl group and a Z or hydroxyl group and FeO.

[II] an aqueous solution obtained by dissolving this iron supply agent, when containing the Fe ²⁺ ions and Fe ³⁺ ions, and the sum of the said Fe ² + ions and the Fe ³⁺ ions is 100 mass% The iron supplier according to claim 10, wherein the Fe ²⁺ ion is 50 to 90% by mass.

[12] The aqueous solution obtained by dissolving the iron supply agent has a Fe ²⁺ ion concentration force observed in the aqueous solution after standing for 168 hours, and is 75% or more of the Fe ²⁺ ion concentration observed immediately after the dissolution. The iron supply agent according to claim 10.

13. The iron supply agent according to claim 10, containing at least citrate as the organic acid.

[14] The aqueous solution in which the iron supply agent is dissolved contains citrate and Z for one Fe ²⁺ ion. Or a dimer complex in which two citrate ions are coordinated, and a trimer complex in which three citrate and Z or three citrate ions are coordinated to one Fe ²⁺ ion. The iron supply agent according to 13.

 [15] A plant iron supplier comprising the iron supplier according to any one of claims 10 to 14.

 16. The plant iron supply agent according to claim 15, containing a biodegradable binder.

 17. The plant iron supply agent according to claim 15, comprising a biodegradable extender.

 18. The plant iron supply agent according to claim 15, which contains 5% by mass or more of the iron supply agent when the total iron supply agent for plants is 100% by mass.

[19] containing cenoic acid as the organic acid,

 Containing peat as the biodegradable extender,

 The matrix comprising the biodegradable extender contains the citrate and the FeO;

 The plant iron supplier according to claim 17, which is used in alkaline soil.

[20] An iron supplier comprising an organic acid having a carboxyl group and a Z or hydroxyl group and FeO.

[21] The aqueous solution obtained by dissolving the iron supplier contains Fe ²⁺ ions and Fe ³⁺ ions, and the Fe ²

When the total of + ions and Fe ³⁺ ions is 100 mass%, the Fe ²⁺ ions are 50 to 9

The iron supply agent according to claim 20, which is 0% by mass.

Aqueous solution [22] is dissolved in the iron supplying agent comprising is a 168-hour standing was immediately Fe ²⁺ ion concentration force lysis observed in aqueous solution accepted is Fe ²⁺ ion concentration of 75% or more after The iron supply agent according to claim 20.

23. The iron supply agent according to claim 20, containing at least citrate as the organic acid.

[24] an aqueous solution obtained by dissolving this iron supply agent, a dimeric complex Kuen acid and Z or Kuen acid ion was two coordinated to one Fe ²⁺ ions, one Fe ²⁺ ions 24. The iron supplier according to claim 23, comprising: a trimeric complex in which three citrate and Z or three citrate ions are coordinated.

[25] The iron supply agent according to any one of claims 20 to 24 is contained. Iron supply agent for plants.

 [26] The iron supplier for plants according to claim 25, comprising a biodegradable binder.

 27. The plant iron supply agent according to claim 25, comprising a biodegradable extender.

 28. The plant iron supply agent according to claim 25, which contains 5% by mass or more of the iron supply agent when the total amount of the iron supply agent for plants is 100% by mass.

[29] containing cenoic acid as the organic acid,

 Containing peat as the biodegradable extender,

 The matrix comprising the biodegradable extender contains the citrate and the FeO;

 The plant iron supplier according to claim 27, which is used in alkaline soil.

[30] A dissolution step is provided in which an organic acid powder having a carboxyl group and Z or hydroxyl group, an FeO powder, and water are heated to obtain an aqueous solution obtained by dissolving the organic acid and FeO. The manufacturing method of the iron supply agent characterized by the above-mentioned.

31. The method for producing an iron supply agent according to claim 30, further comprising a drying step for removing the aqueous solution water.

 32. The method for producing an iron supply agent according to claim 30, wherein the organic acid contains at least citrate.

 [33] The FeO powder is prepared by vacuum-heating a granulated product obtained by granulating iron-containing dust and a granulated product obtained by granulating Z or iron-containing dust and a reducing agent. 31. The method for producing an iron supply agent according to claim 30, which is FeO powder obtained by vacuum quenching.