WO2007013218A1 - Agent d'apport de fer, agent d'apport de fer pour les plantes contenant ledit agent d'apport de fer et procede de production dudit agent d'apport de fer - Google Patents

Agent d'apport de fer, agent d'apport de fer pour les plantes contenant ledit agent d'apport de fer et procede de production dudit agent d'apport de fer Download PDF

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Publication number
WO2007013218A1
WO2007013218A1 PCT/JP2006/310701 JP2006310701W WO2007013218A1 WO 2007013218 A1 WO2007013218 A1 WO 2007013218A1 JP 2006310701 W JP2006310701 W JP 2006310701W WO 2007013218 A1 WO2007013218 A1 WO 2007013218A1
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Prior art keywords
iron
supply agent
ions
iron supply
aqueous solution
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PCT/JP2006/310701
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English (en)
Japanese (ja)
Inventor
Satoshi Mori
Hirohiko Sasamoto
Masaharu Yasui
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Aichi Steel Corporation
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Application filed by Aichi Steel Corporation filed Critical Aichi Steel Corporation
Priority to JP2007528360A priority Critical patent/JP4096207B2/ja
Publication of WO2007013218A1 publication Critical patent/WO2007013218A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements

Definitions

  • Iron supply agent plant iron supply agent containing the same, and method for producing the same
  • 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.
  • 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 ⁇ 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).
  • EDTA ethylenediamine tetraacetic acid
  • Patent Document 1 Japanese Patent Laid-Open No. 8-277183
  • 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.
  • the water-soluble inorganic iron salt is easily oxidized to Fe 3+ which does not easily maintain the Fe 2+ state.
  • 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.
  • EDTA is essentially trivalent iron that is used as the EDTA iron complex.
  • 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.
  • 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.
  • the present inventors paid attention to an organic acid having a chelating power against iron and examined the organic acid iron.
  • ferrous citrate obtained by boiling metal iron, which is also known in the past
  • aqueous citrate solution Fe (OH)
  • 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.
  • compounds with strong ion binding properties such as iron citrate ammonium have been difficult to obtain the effect of suppressing Fe 2+ ion oxidation.
  • the present invention is as follows.
  • 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).
  • the 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%.
  • 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 ”).
  • 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.
  • 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.
  • 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 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”).
  • the matrix comprising the biodegradable extender contains the citrate and the FeO;
  • iron supplier of the third invention 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”).
  • 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.
  • 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.
  • 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
  • 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").
  • the matrix comprising the biodegradable extender contains the citrate and the FeO;
  • 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.
  • 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.
  • 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.
  • the iron content can be supplied with a particularly high probability.
  • 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.
  • the resulting high Fe 2+ ion concentration 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.
  • a biodegradable binder 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.
  • the Fe 2+ supply amount can be easily kept within an appropriate range, and is excellent in versatility.
  • the iron supply agent 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.
  • 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.
  • the use of organic acids (especially cuenic acid) is safe for use with no environmental impact.
  • a germination promoting effect and a growth promoting effect are obtained.
  • the iron content can be supplied with a particularly high probability.
  • 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.
  • 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.
  • a biodegradable binder 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.
  • the Fe 2+ supply amount can be easily kept within an appropriate range, and is excellent in versatility.
  • the iron supply agent 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.
  • 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.
  • the use of organic acids (especially cuenic acid) is safe for use with no environmental impact.
  • a germination promoting effect and a growth promoting effect are obtained.
  • the iron content can be supplied with a particularly high probability.
  • 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.
  • 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.
  • a biodegradable binder 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.
  • the Fe 2+ supply amount can be easily kept within an appropriate range, and is excellent in versatility.
  • the iron supply agent 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.
  • 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.
  • 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.
  • 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.
  • FIG. 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 ().
  • 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.
  • the “organic acid” is an acid having a carboxyl group and a Z or hydroxyl group.
  • 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.
  • an aqueous solution containing an organic acid and FeO citrate, acetic acid and tartaric acid are preferred because the Fe 2+ ion concentration is high relative to the organic acid concentration.
  • citrate, acetic acid and tartaric acid are preferred because the Fe 2+ ion concentration is high relative to the organic acid concentration.
  • the concentration of Fe 2+ ions with respect to the concentration of the organic acid is particularly high, so quenate is most preferred.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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! / ⁇ Organic acid and completely dissolved ⁇ FeO are contained, they are separated by a method such as filtration. The process to perform can be provided.
  • the iron supply agent of the first invention may contain a pyroligneous acid solution for anti-mold.
  • 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.
  • ultraviolet irradiation can be performed in advance for the same purpose.
  • the ultraviolet irradiation conditions are not particularly limited, it is preferable to use ultraviolet rays having a wavelength of 200 to 380 nm.
  • 72 10 4 ⁇ 3 for irradiation It is preferable to irradiate 111 2 or more.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the pressure when the pressure is reduced when removing water, 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.
  • the iron supply agent of the second invention can usually be dissolved almost entirely in water at a temperature of 15 ° C or higher.
  • 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
  • the properties of the aqueous solution in which this iron supply agent is dissolved will be described later.
  • 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.
  • 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.
  • This iron supply agent can be obtained, for example, by mixing organic acid powder and FeO powder.
  • 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.
  • 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.
  • 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.
  • 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.
  • each ion concentration is a value measured by a measuring method of an example described later.
  • the iron supply agent of the first invention 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.
  • 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.
  • the content of each complex with respect to the total iron supply agent is not particularly limited!
  • 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 ⁇ 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.
  • 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.
  • 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 /
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the plant iron supplier of the present invention may contain 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.
  • Biodegradable plastic 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
  • 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.
  • 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.
  • 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.
  • 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.
  • the biodegradable extender can be applied as it is.
  • 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.
  • 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.
  • various modification treatments include alkali extraction treatment, neutralization treatment (such as phosphoric acid neutralization treatment, and maternal lime neutralization treatment).
  • peat examples 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the effect of FeO of Sani ⁇ system according to the click E phosphate also together be obtained, prolonged connexion from stable Fe 2 + ions Can be supplied.
  • 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.
  • the method for producing the plant iron supply agent is not particularly limited.
  • 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.
  • 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.
  • 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! /.
  • 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.
  • 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.
  • any water can be used as described above.
  • the amount of the organic acid powder, FeO powder, and water charged in the "mixture” is not particularly limited.
  • 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.
  • the above mixture may or may not contain other components in addition to the organic acid powder, FeO powder and water.
  • other components 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.
  • 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.
  • 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.
  • the production method of the present invention can include a step of removing a water-insoluble component after the dissolving step.
  • 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 ⁇ m or less) as the filtration filter.
  • 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 ⁇ 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.
  • a purification step 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 / ⁇ ⁇ .
  • 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.
  • dust from which the chlorine content has been removed by washing with water (partially or entirely) is preferred.
  • 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).
  • 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.
  • 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).
  • the "reducing agent” is a component that reduces an iron compound that has been oxidized to a valence of 2 or more.
  • metallic iron, a mixture thereof, carbon, a mixture thereof, or the like can be used.
  • 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 ⁇ m 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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).
  • a granulated product containing metallic iron 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).
  • this granulated product 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.
  • 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.
  • 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.
  • 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.
  • Forged shot dust collection powder with a particle size of 100 m 82%, iron powder 10% with an average particle size of 75 ⁇ m, 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.
  • a vacuum heating tank roll hearth furnace
  • 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.
  • 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.
  • Fe 2+ ion concentration is 389mgZ l
  • Fe 3+ ion concentration is 1 86MgZ liter
  • 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.
  • 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.
  • 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).
  • EIMS electrospray ionization mass spectrometry
  • Micromass type “Q-TOF” was used for the measurement device, and electrospray ionization (ESI) was used for the ionization method.
  • the ion mode was positive ion mode
  • the capillary voltage was 3000V
  • the cone voltage was 20V
  • the solvent removal temperature was 120 ° C.
  • the resulting chart is shown in FIG.
  • the peak is considered to be derived from citrate.
  • the compound constituting the peak of mass 439 contains Fe.
  • 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.
  • 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.
  • 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.
  • 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 is 0.5 mgZ liter, of which the Fe 2+ ion concentration is 0.3 mgZ liter.
  • 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.
  • test soil 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.
  • 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.
  • Fig. 5 shows an explanatory diagram based on an image obtained by digitally photographing this cultivation area on April 13.
  • Fig. 6 shows an explanatory diagram using images obtained by digitally photographing this cultivation area on April 20.
  • Fig. 7 shows an explanatory diagram based on an image obtained by digitally photographing this cultivation area on April 13.
  • Fig. 8 shows an explanatory diagram based on images obtained by digitally photographing this cultivation area on April 20.
  • FIG. 9 shows an explanatory diagram based on an image obtained by digitally photographing this cultivation area on April 13.
  • Fig. 10 shows an explanatory diagram based on an image obtained by digitally photographing this cultivation area on April 16.
  • 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)
  • Fig. 12 shows an explanatory diagram based on the image obtained by digitally photographing this cultivation area on April 13.
  • Fig. 13 shows an explanatory diagram based on the image obtained by digitally photographing this cultivation area on April 13.
  • FIG. 14 shows an explanatory diagram based on images obtained by digitally photographing this cultivation area on April 16.
  • 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 )
  • citrate anhydride purity 99.8% or more
  • peat-treated soil improver made by Nippon Fertilizer Co., Ltd., trade name “Kumiai Hyhumin Special A )
  • a plant iron supplier (Experimental Example 10) was obtained.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Cultivation Of Plants (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

L'objectif de l'invention est de créer un agent d'apport de fer et un agent d'apport de fer pour les plantes capable de fournir une solution aqueuse avec une concentration élevée en ions Fe2+ et des caractéristiques réduites d'oxydation des ions Fe2+. A cet effet, l'agent d'apport de fer selon l'invention comprend une solution aqueuse dans laquelle un acide organique contenant un groupe carboxyle et/ou un groupe hydroxyle (plus particulièrement de l'acide citrique) et du FeO sont dissous. Dans une variante, l'agent d'apport de fer peut être préparé par élimination de l'eau d'une solution aqueuse dans laquelle un acide organique contenant un groupe carboxyle et/ou un groupe hydroxyle (plus particulièrement de l'acide citrique) et du FeO sont dissous. L'agent d'apport de fer peut être préparé selon un procédé comprenant une étape de dissolution au cours de laquelle un mélange de poudre d'acide organique (plus particulièrement de la poudre d'acide citrique ), de la poudre de FeO et de l'eau est chauffé pour former une solution aqueuse dans laquelle l'acide organique et le FeO sont dissous. La poudre de FeO utilisée est obtenue de préférence par chauffage sous vide de granulés produits par granulation d'une poussière et/ou de granulés contenant du fer, eux-mêmes produits par granulation d'une poussière contenant du fer avec un agent réducteur, puis refroidissement rapide des granulés obtenus sous pression réduite.
PCT/JP2006/310701 2005-07-29 2006-05-29 Agent d'apport de fer, agent d'apport de fer pour les plantes contenant ledit agent d'apport de fer et procede de production dudit agent d'apport de fer WO2007013218A1 (fr)

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PCT/JP2006/310702 WO2007013219A1 (fr) 2005-07-29 2006-05-29 Agent d'apport de fer pour les plantes pour utilisation sur un sol alcalin et procédé de production dudit agent d'apport de fer

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009150927A1 (fr) * 2008-06-09 2009-12-17 Sugimoto Mikio Procédé de production d’un composé chélaté métallique à l’état liquide et composé chélaté métallique
JP2010517379A (ja) * 2007-01-17 2010-05-20 クゥアルコム・インコーポレイテッド 地域モビリティエージェントとして機能する基地局の構成
JP2010228951A (ja) * 2009-03-26 2010-10-14 Aichi Steel Works Ltd 植物用鉄供給剤及びその製造方法
JP2011050934A (ja) * 2009-09-04 2011-03-17 Nihon Technical Development Center Co Ltd 水質浄化及び水産資源育成用の固形物
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JP2010517379A (ja) * 2007-01-17 2010-05-20 クゥアルコム・インコーポレイテッド 地域モビリティエージェントとして機能する基地局の構成
WO2009150927A1 (fr) * 2008-06-09 2009-12-17 Sugimoto Mikio Procédé de production d’un composé chélaté métallique à l’état liquide et composé chélaté métallique
US20110065945A1 (en) * 2008-06-09 2011-03-17 Mikio Sugimoto Method for producing liquid metal chelate compound and metal chelate compound
JP2010228951A (ja) * 2009-03-26 2010-10-14 Aichi Steel Works Ltd 植物用鉄供給剤及びその製造方法
JP2011050934A (ja) * 2009-09-04 2011-03-17 Nihon Technical Development Center Co Ltd 水質浄化及び水産資源育成用の固形物
EP3912967A4 (fr) * 2019-05-08 2022-08-24 Fertinagro Biotech, S.L. Additif potentialisateur de l'efficacité du purin de porc comme fertilisant

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