JP7466119B1 - Iron supplement for plant and animal growth - Google Patents

Iron supplement for plant and animal growth Download PDF

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JP7466119B1
JP7466119B1 JP2024502439A JP2024502439A JP7466119B1 JP 7466119 B1 JP7466119 B1 JP 7466119B1 JP 2024502439 A JP2024502439 A JP 2024502439A JP 2024502439 A JP2024502439 A JP 2024502439A JP 7466119 B1 JP7466119 B1 JP 7466119B1
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梅夫 祖父江
大介 笹本
博彦 笹本
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ソブエクレー株式会社
株式会社ReMA
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Abstract

【課題】溶出する二価鉄イオン(Fe2+)が動植物への摂取率が悪い三価鉄イオン(Fe3+)へ遷移するのを低減して二価鉄イオン(Fe2+)濃度を維持可能な生育用鉄分補給剤を提供する。塩基類の蓄積により土壌や水域が重金属により汚染され易くなるのを防止可能な生育用鉄分補給剤を提供する。水に対する溶解度が高く,かつ二価鉄イオン(Fe2+)濃度を維持可能な生育用鉄分補給剤を提供する。土壌や水域を改質する際に投入量を低減して改質コストが低コスト化可能な生育用鉄分補給剤を提供する。【解決手段】酸化鉄(FeO)及び少なくとも酸化カルシウム(CaO),酸化マグネシウム(MgO),二酸化ケイ素(SiO2)のいずれかを含有し,非晶質及びアルカリ性で,粒状化及び断片化のいずれかの形態からなるスラグを動植物の生育に不可欠な鉄分の補給剤とする。【選択図】図1[Problem] To provide an iron supplement for growth that can maintain the concentration of divalent iron ions (Fe2+) by reducing the transition of eluted divalent iron ions (Fe2+) to trivalent iron ions (Fe3+), which have a low uptake rate for animals and plants. To provide an iron supplement for growth that can prevent soil and water bodies from becoming easily polluted by heavy metals due to the accumulation of bases. To provide an iron supplement for growth that has high solubility in water and can maintain the concentration of divalent iron ions (Fe2+). To provide an iron supplement for growth that can reduce the amount of iron added when reforming soil or water bodies, thereby reducing reforming costs. [Solution] A slag that contains iron oxide (FeO) and at least one of calcium oxide (CaO), magnesium oxide (MgO), and silicon dioxide (SiO2), is amorphous and alkaline, and is in either a granulated or fragmented form, and is used as an iron supplement that is essential for the growth of animals and plants. [Selected Figure] Figure 1

Description

本発明は,海水(水域)中において生息するワカメや昆布等の藻類や土壌に植生される野菜や果樹等,並びに家畜(牛,馬,豚,鳥等),魚介類(魚,貝類)等の動物(人間を除く)等の動植物に対し,その生育に不可欠な微量必須元素である鉄分を効率的かつ低コストで供給することが可能な動植物生育用鉄分補給剤に関する。
なお,本発明において「動植物生育用鉄分補給剤」を単に「生育用鉄分補給剤」と称する。
The present invention relates to an iron supplement for the growth of animals and plants that can efficiently and at low cost supply iron, an essential trace element for the growth of animals and plants, such as seaweed, kelp, and other algae that live in seawater (water areas), vegetables and fruit trees that grow in soil, and animals (excluding humans) including livestock (cows, horses, pigs, birds, etc.), seafood (fish, shellfish), and other animals.
In the present invention, the "iron supplement for animal and plant growth" is simply referred to as the "iron supplement for growth."

鉄分は,上記した各種動植物の生育に必要不可欠な微量必須元素で,例えば陸上植物や藻類にあっては,鉄分の欠乏により光合成不良や花芽の形成不良等の各種の生育不良が発生することが知られている。 Iron is a trace essential element that is essential for the growth of the various plants and animals mentioned above. For example, in terrestrial plants and algae, iron deficiency is known to cause various growth defects such as poor photosynthesis and poor flower bud formation.

植物の内,特に水域に生育する藻類に関しては,近年,沿岸部水域においては鉄不足による藻類の成長や繁殖が減少して石灰藻で覆われる,いわゆる磯焼けやプランクトンの死滅による赤潮等の発生が進行している。その結果,これらの藻類を餌とするウニ,カキ,アワビ,魚等の魚介類の水産資源(動物資源)の減少が顕著になっている。In recent years, the growth and reproduction of algae in coastal waters has decreased due to iron deficiency, causing the waters to become covered with calcareous algae, resulting in the occurrence of so-called coastal barrenness, and red tides caused by the death of plankton. As a result, there has been a noticeable decrease in marine resources (animal resources) of seafood such as sea urchins, oysters, abalone, and fish, which feed on these algae.

従前であれば,森林の腐植土壌中で生成する水溶性フルボ酸鉄(フルボ酸と二価鉄Fe2+がキレート化した化合物)が河川を介して沿岸水域に流入することにより上記磯焼けの発生やプランクトンの死滅による赤潮の発生を抑制していたが,近年においては,森林の荒廃などによりフルボ酸鉄の溶出量が減少して上記磯焼けや赤潮の発生が増大している。 In the past, water-soluble iron fulvic acid (a compound formed by the chelation of fulvic acid and divalent iron (Fe2 + )) produced in forest humus soil flowed into coastal waters via rivers, suppressing the occurrence of the above-mentioned coastal barrenness and red tides caused by the death of plankton. However, in recent years, the amount of iron fulvic acid eluted has decreased due to the degradation of forests, leading to an increase in the occurrence of the above-mentioned coastal barrenness and red tides.

また,陸上植物においても同様で,鉄分の不足により芽や根の成長不良,光合成不良,チッソ同化を行うアミノ酸やたんぱく質の合成不良,花芽の形成不良等が発生し,収穫量の減少を招いている。The same is true for terrestrial plants, where a lack of iron causes poor growth of shoots and roots, poor photosynthesis, poor synthesis of amino acids and proteins that assimilate nitrogen, and poor flower bud formation, resulting in reduced yields.

このような問題に対し、例えば特許文献1に示す肥料用含鉄組成物は,組成物中の全鉄分が3~50wt%であり、かつこの鉄分のうちの25wt%以上が水酸化第一鉄(Fe(OH)2 )、水酸化第二鉄(Fe(OH)3 )および鉄の複塩のなかから選ばれるいずれか1種以上から構成される結晶水を含む鉄化合物から構成され,植物への鉄分の吸収効率に優れているとしている。 To address these problems, for example, the iron-containing composition for fertilizer shown in Patent Document 1 has a total iron content of 3 to 50 wt% in the composition, and at least 25 wt% of this iron content is composed of iron compounds containing water of crystallization composed of one or more types selected from ferrous hydroxide (Fe(OH) 2 ), ferric hydroxide (Fe(OH) 3 ), and double salts of iron, and is said to have excellent iron absorption efficiency in plants.

また,特許文献2に示す水域環境保全材料は,腐植酸供給物質を発酵させて腐植酸を生成させた腐植酸供給物質に鉄鋼スラグの一種である製鋼スラグの鉄含有物質を混合して製造され,該水域環境保全材料を混入又は付着させたコンクリート等の担持体を水域に投入し,水域環境保全材料から溶出する鉄分を水域に供給して海洋植物の鉄分不足を解消しようとしている。 Furthermore, the aquatic environment conservation material shown in Patent Document 2 is produced by mixing a humic acid supplying substance, which has been fermented to produce humic acid, with iron-containing steelmaking slag, a type of steel slag. A support such as concrete mixed with or attached to the aquatic environment conservation material is then dropped into a water body, and the iron leached from the aquatic environment conservation material is supplied to the water body, thereby resolving the iron deficiency in marine plants.

特許文献1及び2に示す物質を動植物生育用の生育用鉄分補給剤として使用する場合には,水に対し,動植物への摂取率が高い二価鉄イオン(Fe2+)の溶解割合が高く,かつ溶出する二価鉄イオン(Fe2+)が酸化して三価鉄イオン(Fe3+)へ遷移する割合が低いことが要求される。 When the substances shown in Patent Documents 1 and 2 are used as iron supplements for the growth of animals and plants, it is required that the proportion of divalent iron ions (Fe2 + ), which have a high uptake rate by animals and plants, that dissolves in water is high, and that the proportion of the dissolved divalent iron ions (Fe2 + ) that are oxidized and converted to trivalent iron ions (Fe3 + ) is low.

しかし,特許文献1の肥料用含鉄組成物にあっては,溶出する鉄分の大部分が三価鉄イオン(Fe3+)で,二価鉄イオン(Fe2+)の割合が低く,また,含有される鉄分が水溶性無機鉄塩のため,二価鉄イオン(Fe2+)の状態を維持することが困難で,酸化により三価鉄イオン(Fe3+)へ遷移し易く,動植物生育用の生育用鉄分の補給剤として有効でなかった。 However, in the iron-containing composition for fertilizer described in Patent Document 1, the majority of the eluted iron is trivalent iron ion (Fe3 + ), with a low proportion of divalent iron ion (Fe2 + ).In addition, since the iron contained is a water-soluble inorganic iron salt, it is difficult to maintain the state of divalent iron ion (Fe2 + ) and it is prone to transition to trivalent iron ion (Fe3 + ) through oxidation, making it ineffective as an iron supplement for the growth of animals and plants.

更に,特許文献1の肥料用含鉄組成物にあっては,塩基類の蓄積により土壌中や水域中の重金属を固定して土壌や水域の汚染を引き起こしたり,土壌にあっては地下水に溶出して水汚染を引き起こす要因になり易く,肥料用含鉄組成物として有効でなかった。また,十分な二価鉄イオン(Fe2+)を溶出させるには,投入量を多くする必要があり,その結果として改質コストが増大する問題を生じさせている。 Furthermore, the iron-containing composition for fertilizer in Patent Document 1 was not effective as an iron-containing composition for fertilizer because it was prone to cause soil or water pollution by fixing heavy metals in the soil or water due to accumulation of bases, or to cause water pollution by eluting into groundwater in the soil. Also, in order to elute a sufficient amount of divalent iron ions (Fe 2+ ), a large input amount was required, which resulted in a problem of increased reforming costs.

一方,特許文献2の水域環境保全材料にあっては,溶出する二価鉄イオン(Fe2+)は,海洋植物による摂取効率が高いが,溶出した二価鉄イオン(Fe2+)は水中の酸素によって酸化されて摂取効率が悪い三価鉄イオン(Fe3+)に遷移して粒状鉄(Fe(OH))になって沈澱し易くなるため,海洋植物に効率的に摂取させることが困難であった。 On the other hand, in the aquatic environment conservation material of Patent Document 2, the dissolved divalent iron ion (Fe2 + ) is highly efficiently taken up by marine plants, but the dissolved divalent iron ion (Fe2 + ) is oxidized by oxygen in the water and changes to trivalent iron ion (Fe3 + ), which is less efficiently taken up, and becomes granular iron ( Fe2 (OH) 3 ), which is prone to settling, making it difficult to allow marine plants to efficiently take it up.

また,製鋼スラグは,酸化第一鉄の他に少なくとも1種類の複合酸化物(CaAl2O3, FeAL2O4, MgAlO, CaFeSiO, MgFeSiO6, CaSiO, MgSiO, FeAlO4, CaFe2O4, CaFeO2, MgFeO2)を含有しているため,水に溶けた際には,水域のpHを8以上(海水のpHは,平均で8.1)にアルカリ化することができ,これにより製鋼スラグから溶出する二価鉄イオン(Fe2+)が酸化して三価鉄イオン(Fe3+)へ遷移するのを低減するのに有効である。 In addition, steelmaking slag contains at least one type of complex oxide ( CaAl2O3 , FeAL2O4 , MgAl2O4, CaFeSiO6 , MgFeSiO6 , CaSiO5 , MgSi2O3 , FeAlO4 , CaFe2O4 , CaFeO2 , MgFeO2 ) in addition to ferrous oxide, so when it dissolves in water, it can alkalize the water to a pH of 8 or higher (the average pH of seawater is 8.1), which is effective in preventing the oxidation of divalent iron ions (Fe2 + ) that dissolve from steelmaking slag and their transition to trivalent iron ions (Fe3 + ).

しかし,製鋼スラグ中の酸化鉄(FeO)は,それ自体が結晶質であるため,水に対する溶解度が低い特性がある。このため,水域において十分な二価鉄イオン(Fe2+)を溶出させるには,投入量を多くする必要があり,その結果として水域改質コストが増大する問題を生じさせている。 However, the iron oxide (FeO) in steelmaking slag is itself crystalline and has low solubility in water, so a large amount of slag needs to be added to dissolve sufficient ferrous ions (Fe2 + ) in the water, which results in an increase in the cost of water treatment.

特開平8-277183号公報Japanese Patent Application Laid-Open No. 8-277183 日本国特許6604017号公報Japanese Patent No. 6604017

特許文献1にあっては,溶出する二価鉄イオン(Fe2+)の状態を維持することが困難で,酸化により動植物への摂取率が悪い三価鉄イオン(Fe3+)へ遷移し易い点にある。 In Patent Document 1, it is difficult to maintain the state of the eluted divalent iron ions (Fe 2+ ), which are prone to transition due to oxidation to trivalent iron ions (Fe 3+ ), which have a low uptake rate in animals and plants.

また,含有された塩基類の蓄積により土壌中や水域中の重金属を固定して土壌や水域の汚染を引き起こしたり,土壌にあっては地下水に溶出して水汚染を引き起こす要因になり易い点にある。 In addition, the accumulation of the contained bases can fix heavy metals in the soil or water, causing soil or water pollution, or in the case of soil, they can easily leach into groundwater and cause water pollution.

更に,十分な二価鉄イオン(Fe2+)を溶出させるには,投入量を多くする必要があり,土壌や水域の改質コストが増大する点にある。 Furthermore, in order to elute a sufficient amount of divalent iron ions (Fe 2+ ), a large amount must be input, which increases the cost of improving the soil or water area.

特許文献2にあっては,溶出する二価鉄イオン(Fe2+)が水中の酸素によって酸化されて三価鉄イオン(Fe3+)に遷移して粒状鉄(Fe(OH))になって沈澱し,海洋植物に効率的に摂取させることが困難になる点にある。 In Patent Document 2, the eluted divalent iron ions (Fe 2+ ) are oxidized by oxygen in the water, transforming into trivalent iron ions (Fe 3+ ), which then become granular iron (Fe 2 (OH) 3 ) and precipitate, making it difficult for marine plants to efficiently ingest the iron.

また,製鋼スラグは,含有された酸化鉄(FeO)が結晶質であるため,水に対する溶解度が低く,十分な二価鉄イオン(Fe2+)を溶出させるには,投入量を多くする必要があり,改質コストが増大する点にある。 In addition, since the iron oxide (FeO) contained in steelmaking slag is crystalline, it has low solubility in water, and in order to dissolve sufficient divalent iron ions (Fe2 + ), a large amount must be added, which increases the cost of reforming.

本発明は,酸化鉄(FeO):20~50%,酸化カルシウム(CaO):20~40%,酸化マグネシウム(MgO):3~10%,二酸化ケイ素(SiO 2 ):10~20%を主要組成とし,最大で10mmに粒状化及び断片化のいずれかの形態に生成された非晶質の電気炉酸化スラグであって,上記電気炉酸化スラグは,上記主要組成が水溶した際にpH8以上のアルカリ性で,かつ三価鉄イオン(Fe 3+ )に対して二価鉄イオン(Fe 2+ )を高い割合で溶出可能で,上記電気炉酸化スラグを動植物の鉄分補給剤として使用することを最も主要な特徴とする。 The present invention provides amorphous electric furnace oxidized slag, which has a main composition of 20-50% iron oxide (FeO), 20-40% calcium oxide (CaO), 3-10% magnesium oxide (MgO), and 10-20% silicon dioxide (SiO2 ) , and is produced in either a granulated or fragmented form up to 10 mm in size, and its most primary feature is that when the main composition of the electric furnace oxidized slag is dissolved in water, it has an alkaline pH of 8 or higher and is capable of eluting a high ratio of divalent iron ions (Fe2+) relative to trivalent iron ions (Fe3 + ) , and the electric furnace oxidized slag can be used as an iron supplement for animals and plants.

本発明は,溶出する二価鉄イオン(Fe2+)が三価鉄イオン(Fe3+)へ遷移するのを低減して二価鉄イオン(Fe2+)濃度を維持可能な生育用鉄分補給剤を提供する。 The present invention provides an iron supplement for plant growth that can maintain the concentration of divalent iron ions (Fe 2+ ) by reducing the transition of eluted divalent iron ions (Fe 2+ ) to trivalent iron ions (Fe 3+ ).

塩基類の蓄積により土壌や水域が重金属により汚染されるのを防止可能な生育用鉄分補給剤を提供する。 We provide an iron supplement for growth that can prevent soil and water from being polluted by heavy metals due to the accumulation of bases.

水に対する溶解度が高く,かつ二価鉄イオン(Fe2+)濃度を維持可能な生育用鉄分補給剤を提供する。 Provided is an iron supplement for plant growth that has high solubility in water and is capable of maintaining the concentration of divalent iron ions (Fe 2+ ).

土壌や水域を改質する際に投入量を低減して改質コストを低コスト化可能な生育用鉄分補給剤を提供する。 We provide an iron supplement for plant growth that can reduce the amount of input when amending soil or water, thereby reducing the cost of amending the soil or water.

本発明に係る生育用鉄分補給剤の製造工程を模式的に示す説明図である。FIG. 2 is an explanatory diagram showing a schematic diagram of a manufacturing process of the iron supplement for growth according to the present invention. 本発明に係る生育用鉄分補給剤の適用した事例1を示す説明図である。FIG. 1 is an explanatory diagram showing Example 1 in which the iron supplement for growth according to the present invention is applied. 本発明に係る生育用鉄分補給剤の適用した事例2を示す説明図である。FIG. 2 is an explanatory diagram showing Example 2 in which the iron supplement for growth according to the present invention is applied. 本発明に係る生育用鉄分補給剤の適用した事例3を示す説明図である。FIG. 3 is an explanatory diagram showing Example 3 in which the iron supplement for growth according to the present invention is applied. 本発明に係る生育用鉄分補給剤の適用した事例4を示す説明図である。FIG. 4 is an explanatory diagram showing Example 4 in which the iron supplement for growth according to the present invention is applied.

酸化鉄(FeO):20~50%,酸化カルシウム(CaO):20~40%,酸化マグネシウム(MgO):3~10%,二酸化ケイ素(SiO 2 ):10~20%を主要組成とし,最大で10mmに粒状化及び断片化のいずれかの形態に生成された非晶質の電気炉酸化スラグは,上記主要組成が水溶した際にpH8以上のアルカリ性で,かつ三価鉄イオン(Fe 3+ )に対して二価鉄イオン(Fe 2+ )を高い割合で溶出可能で,上記電気炉酸化スラグを動植物の鉄分補給剤として使用することを最良の形態とする。 Amorphous electric furnace oxidized slag, which has a main composition of 20-50% iron oxide (FeO), 20-40% calcium oxide (CaO), 3-10% magnesium oxide (MgO), and 10-20% silicon dioxide (SiO2 ) , and is produced in either a granulated or fragmented form up to 10 mm in size, has an alkaline pH of 8 or higher when the above main compositions are dissolved in water, and is capable of eluting a high ratio of divalent iron ions (Fe2+) relative to trivalent iron ions (Fe3+), and the best form of this electric furnace oxidized slag is to use it as an iron supplement for animals and plants.

以下,本発明を実施例に従って詳細に説明する。
[生育用鉄分補給剤]
本発明の生育用鉄分補給剤は,酸化鉄(FeO),他に酸化カルシウム(生石灰,CaO),酸化マグネシウム(MgO),二酸化ケイ素(シリカ,SiO2)等を含有する,多くが非晶質の電気炉酸化スラグで,各組成物は,酸化鉄(FeO):20~50%,酸化カルシウム(CaO):20~40%,酸化マグネシウム(MgO):3~10%,二酸化ケイ素(シリカ,SiO2):10~20%の範囲内で含有される。本発明においての好適例としては,FeO:29%,CaO:23%,MgO:5%,SiO2:18%からなる。
The present invention will now be described in detail with reference to examples.
[Iron supplement for plant growth]
The iron supplement for plant growth of the present invention is mostly amorphous electric furnace oxide slag containing iron oxide (FeO), calcium oxide (quicklime, CaO), magnesium oxide (MgO), silicon dioxide (silica, SiO2 ), etc., with each composition containing 20-50% iron oxide (FeO), 20-40% calcium oxide (CaO), 3-10% magnesium oxide (MgO), and 10-20% silicon dioxide (silica, SiO2 ). A preferred example in the present invention is composed of 29% FeO, 23% CaO, 5% MgO, and 18 % SiO2.

上記組成の電気炉酸化スラグは,多くが非晶質(アモルファス)で,結晶性FeOと比べて水に対する溶解率が高く,水溶した際に放出される鉄イオンとしては,三価鉄イオン(Fe3+)に比べて二酸化鉄イオン(Fe2+)の割合が高い特徴を備えている。 Electric arc furnace oxidizing slag with the above composition is mostly amorphous and has a higher solubility in water than crystalline FeO. When dissolved in water, the iron ions released contain a higher proportion of iron dioxide ions (Fe 2+ ) than do iron(III) ions (Fe 3+ ).

また,上記組成の電気炉酸化スラグ中の酸化鉄(FeO)は,水溶した際においては,含有される酸化カルシウム(CaO),酸化マグネシウム(MgO),二酸化ケイ素(SiO2)によりpH:8以上のアルカリ性で,二酸化鉄イオン(Fe2+)が三価鉄イオン(Fe3+)へ遷移するのを低減する特徴を備えている。 In addition, the iron oxide (FeO) in the electric furnace oxidizing slag with the above composition has the characteristic that, when dissolved in water, it has an alkaline pH of 8 or higher due to the calcium oxide (CaO), magnesium oxide (MgO), and silicon dioxide ( SiO2 ) contained in it, which reduces the transition of iron dioxide ions (Fe2 + ) to iron trivalent ions (Fe3 + ).

上記組成の電気炉酸化スラグは,酸化スラグ風砕装置1により粒状に生成されて生育用鉄分補給剤として製造される。スラグ風砕装置1により生成される生育用鉄分補給剤の大きさは,後述するキャリアガスの圧力や吹き飛ばし状態に依存して一様ではなく,大きさ(粒径)に関しては,特に限定されないが,好適例として最大で10mm程度の粒径とすることが望ましい。また,上記好適例以上の粒径で生成された場合にあっては,破砕装置により破砕して粒径を調整すればよい。 The electric furnace oxidized slag having the above composition is produced as an iron supplement for growth by forming granules in the oxidized slag air crusher 1. The size of the iron supplement for growth produced by the slag air crusher 1 is not uniform, depending on the pressure of the carrier gas and the blowing state described later, and there is no particular limit to the size (particle size), but it is preferable to have a particle size of about 10 mm as a preferred example. If the granules are produced with a particle size larger than the preferred example, the particle size can be adjusted by crushing them with a crushing device.

なお,上記説明においては,生育用鉄分補給剤の大きさに付いて最大で10mm程度が望ましいとしたが,生育用鉄分補給剤の大きさは,使用用途に応じて適宜決定される。すなわち,生育用鉄分補給剤の大きさが大きい場合には,水への溶解率が悪くなって短期間に動植物へ摂取させ難くなるが,長期間にわたって低濃度の二酸化鉄イオン(Fe2+)を安定的に補給する用途に適している。反対に生育用鉄分補給剤の大きさが小さい場合には,水への溶解率が高くなって短期間に高濃度の二酸化鉄イオン(Fe2+)を補給することができる。したがって,二酸化鉄イオン(Fe2+)が補給される土壌や水域の状態(鉄分濃度)に応じて上記範囲内で適宜決定すればよい。 In the above description, it is desirable that the size of the iron supplement for growth is about 10 mm at most, but the size of the iron supplement for growth is appropriately determined depending on the intended use. That is, if the size of the iron supplement for growth is large, the solubility in water is poor and it is difficult for animals and plants to ingest it in a short period of time, but it is suitable for the purpose of stably supplying low concentrations of iron dioxide ions (Fe 2+ ) over a long period of time. On the other hand, if the size of the iron supplement for growth is small, the solubility in water is high and it is possible to supply high concentrations of iron dioxide ions (Fe 2+ ) in a short period of time. Therefore, the size may be appropriately determined within the above range depending on the state (iron concentration) of the soil or water area to which the iron dioxide ions (Fe 2+ ) are to be supplied.

生育用鉄分補給剤は,その粒径を細かくすることにより水に対する溶解率を高めることが可能で,これに伴って水に溶けだす二価鉄イオン(Fe2+)の濃度を高めることができることが知られている。このため,酸化スラグ風砕装置1により所定の粒径に生成されて生育用鉄分補給剤にあっては,更に破砕装置により粒径を,例えば0.007mm程度に微粉砕してもよい。 It is known that the iron supplement for plant growth can be made more soluble in water by reducing the particle size, and the concentration of divalent iron ions (Fe2 + ) dissolved in water can be increased accordingly. Therefore, the iron supplement for plant growth produced to a specified particle size by the oxidized slag air crusher 1 may be further pulverized to a particle size of, for example, about 0.007 mm by a crusher.

Figure 0007466119000002
Figure 0007466119000002

表1は,結晶性及び粒径が異なる生育用鉄分補給剤中の酸化鉄(FeO)をクエン酸水(2%)に添加して1時間,攪拌して溶解した際に,鉄(Fe)の量を100とした場合における水への溶解率を示す。 Table 1 shows the solubility of iron oxide (FeO) in iron growth supplements with different crystallinity and particle size in water when the iron oxide (FeO) was added to citric acid water (2%) and stirred for 1 hour to dissolve, with the amount of iron (Fe) set at 100.

粒径が同じ結晶性及び非結晶性の酸化鉄(FeO)にあっては,非晶質酸化鉄は,結晶質酸化鉄と比較し,水への溶解率が20倍であることを示している。また,粒径が0.007mmの非晶質酸化鉄にあっては,粒径が最大で10mmの非晶質酸化鉄と比べて水への溶解率が5倍であることを示している。この事実から,粒径が0.007mmの生育用鉄分補給剤にあっては,粒径が最大で10mmの生育用鉄分補給剤に対し,消費量を1/5にすることができ,改質コストの低減を可能にしている。 When comparing crystalline and amorphous iron oxide (FeO) with the same particle size, the amorphous iron oxide has a 20 times higher solubility in water than the crystalline iron oxide. Additionally, the amorphous iron oxide with a particle size of 0.007 mm has a 5 times higher solubility in water than the amorphous iron oxide with a maximum particle size of 10 mm. Based on this fact, the iron supplement for growth with a particle size of 0.007 mm can be consumed in one-fifth the amount of iron supplement for growth with a particle size of up to 10 mm, making it possible to reduce the cost of amendment.

但し,生育用鉄分補給剤の粒径を細かくすることにより水への溶解率が高くなるが,水に対して短時間(短期間)に溶解するため,適用土壌及び水域を長期にわたって改質する必要がある場合には,適用土壌及び水域に対する投入量を多くする必要があり,改質コストが増大する恐れがある。このため,生育用鉄分補給剤の粒径は,適用土壌及び水域の鉄分の不足状況や改質の進展状況等に応じて決定する必要がある。 However, although the solubility in water increases when the particle size of the iron supplement for plant growth is made finer, it dissolves in water in a short time (short period), so if the applicable soil and water area need to be amended over a long period of time, it is necessary to increase the amount of the supplement added to the applicable soil and water area, which may increase the amendment costs. For this reason, the particle size of the iron supplement for plant growth needs to be determined according to the iron deficiency status of the applicable soil and water area and the progress of amendment, etc.

[生育用鉄分補給剤の製造方法]
上記組成の生育用鉄分補給剤は,図1に示す酸化スラグ風砕装置1により製造される。
[Method of manufacturing iron supplement for growth]
The iron supplement for growth having the above composition is produced by an oxidized slag air-milling apparatus 1 shown in FIG.

図1に示すスラグ鍋3内には,酸化鉄(FeO)を多く含む溶融状態の電気炉酸化スラグが溜められる。 Molten electric furnace oxidizing slag containing a large amount of iron oxide (FeO) is stored in the slag ladle 3 shown in FIG.

電気炉から排出される電気炉酸化スラグは,溶解中に吹き込まれる酸素により発生する酸化鉄(FeO)の他に酸化マグネシウム(MgO),二酸化ケイ素(SiO2),精錬のために加えられる酸化カルシウム(CaO)等を含んでいる。 The electric furnace oxidized slag discharged from the electric furnace contains iron oxide (FeO), which is produced by the oxygen blown in during melting, as well as magnesium oxide (MgO), silicon dioxide (SiO 2 ), and calcium oxide (CaO), which is added for refining purposes.

スラグ鍋3の近傍には,吹付ノズル5が配置され,該吹付ノズル3は,上記スラグ鍋3から流下する溶融状態の電気炉酸化スラグにキャリアガスを吹き付けて溶融状態の電気炉酸化スラグを吹き飛ばして粒状化させる。 A spray nozzle 5 is disposed near the slag ladle 3, and the spray nozzle 3 sprays a carrier gas onto the molten electric furnace oxidizing slag flowing down from the slag ladle 3, thereby blowing off the molten electric furnace oxidizing slag and granulating it.

キャリアガスとしては,その種類に制限はなく,例えば空気(圧縮空気),窒素,酸素等のいずれであってもよい。また,キャリアガスは,要求される生育用鉄分補給剤の粒径に対応する圧力で噴射されるように調整制御される。There is no limit to the type of carrier gas, and it may be, for example, air (compressed air), nitrogen, oxygen, etc. The carrier gas is adjusted and controlled so that it is sprayed at a pressure that corresponds to the particle size of the required iron growth supplement.

すなわち,比較的大径の生育用鉄分補給剤を生成する場合には,キャリアガスの圧力を,電気炉酸化スラグを吹き飛ばし可能な範囲で比較的低圧に,反対に比較的小径の生育用鉄分補給剤を生成する場合には,キャリアガスの圧力を高圧にそれぞれ設定し,キャリアガスの圧力により生育用鉄分供給剤の粒径を調整可能にする。 In other words, when producing a relatively large-diameter iron supply agent for growth, the pressure of the carrier gas is set to a relatively low pressure within a range that allows the electric furnace oxide slag to be blown away, and conversely, when producing a relatively small-diameter iron supply agent for growth, the pressure of the carrier gas is set to a high pressure, making it possible to adjust the particle size of the iron supply agent for growth by the pressure of the carrier gas.

また,キャリアガスには,本発明に係る生育用鉄分補給剤を混合し,電気炉酸化スラグを吹き飛ばす際に流下する溶融状態の電気炉酸化スラグに生育用鉄分補給剤を衝突させ,その衝突エネルギーにより吹き飛ばされる電気炉酸化スラグを微細化することができる。 In addition, the carrier gas can be mixed with the iron supply for growth according to the present invention, and the iron supply for growth can be collided with the molten electric furnace oxidized slag flowing down when the electric furnace oxidized slag is blown away, and the electric furnace oxidized slag blown away can be finely divided by the collision energy.

上記キャリアガスにより溶融状態の電気炉酸化スラグが吹き飛ばされる領域には,遮蔽体7が設けられ,該遮蔽体7内の上部には,複数(多数)の噴射急冷部材9が電気炉酸化スラグの吹き飛ばし領域に亘るように設けられている。 A shield 7 is provided in the area where the molten electric furnace oxidizing slag is blown away by the carrier gas, and a plurality (a large number) of jet quenching members 9 are provided in the upper part of the shield 7 so as to cover the area where the electric furnace oxidizing slag is blown away.

各噴射急冷部材9は,遮蔽体7内において吹き飛ばされる溶融状態の電気炉酸化スラグに対して水又はミスト(望ましくは冷却水又は冷却ミスト)を噴射して急冷し,粒状の生育用鉄分補給剤に生成する。 Each jet quenching member 9 jets water or mist (preferably cooling water or cooling mist) onto the molten electric furnace oxidizing slag being blown away within the shield 7, quenching it and generating granular iron supplements for growth.

溶融状態の電気炉酸化スラグは,噴射急冷部材9から噴射される水により急冷されることにより適宜の大きさ(粒径),好適例としては最大10mm程度の大きさで粒状化され,かつその多くが非晶質状態で固化され,その自重によりストックヤード11に落下集積される。 The molten electric furnace oxidizing slag is quenched by the water jetted from the jet quenching element 9, and granulated to an appropriate size (grain size), preferably a maximum size of about 10 mm. Most of the granules are solidified in an amorphous state, and fall under their own weight into the stockyard 11 and are accumulated.

ストックヤード11に落下集積された電気炉酸化スラグは,異なる粒径で混在した状態で生育用鉄分補給剤として提供してもよいが,所望の粒径ごとのメッシュからなる複数のふるい装置(図示せず)により所定の粒径ごとの生育用鉄分補給剤に選別した形態で提供してもよい。 The electric furnace oxidized slag that has fallen and accumulated in the stockyard 11 may be provided as an iron supplement for growth in a state where it is mixed with different particle sizes, or it may be provided in a form in which it has been sorted into iron supplements for growth of predetermined particle sizes using a multiple sieving device (not shown) consisting of meshes for each desired particle size.

なお,風砕により生成される生育用鉄分補給剤の大きさ(粒径)は,特に限定されず,大小混在した形態で生成される。しかし,粒径が過度に大きい場合には,二価鉄イオン(Fe2+)の溶出効率が悪くなるため,望ましくは最大10mm程度の粒径にする必要がある。このように生成された生育用鉄分補給剤の粒径が過度に大きい場合には,破砕装置により粉砕して上記した最大10mm程度の粒径にすればよい。 The size (particle size) of the iron supplement for growth produced by air crushing is not particularly limited, and it is produced in a form of a mixture of large and small particles. However, if the particle size is too large, the efficiency of elution of divalent iron ions (Fe 2+ ) decreases, so it is preferable to make the particle size about 10 mm at maximum. If the particle size of the iron supplement for growth produced in this way is too large, it may be crushed by a crushing device to the above-mentioned maximum particle size of about 10 mm.

また,上記した粒径に生成された生育用鉄分補給剤を破砕装置により,更にミクロン単位,ナノ単位まで微粒子化して水に対する溶解率を高め,溶出する二価鉄イオン(Fe2+)の濃度を高めてもよい。破砕装置としては,上記のように急冷され,粒径が異なる電気炉酸化スラグをジョークラッシャー,回転衝撃破砕機等の従来公知の破砕装置により粒径が,例えば0.007mmになるまで破砕し,微粒子状の生育用鉄分補給剤として提供してもよい。 In addition, the iron supplement for growth produced to the above particle size may be further atomized to the micron or nano unit size by a crushing device to increase the solubility in water and increase the concentration of ferrous ions (Fe2 + ) that are dissolved. As for the crushing device, the electric furnace oxidized slag that has been quenched as described above and has different particle sizes may be crushed to a particle size of, for example, 0.007 mm by a conventionally known crushing device such as a jaw crusher or a rotary impact crusher, and the crushed slag may be provided as a particulate iron supplement for growth.

[事例1]
図2に示す生育用鉄分補給剤は,電気炉酸化スラグで,酸化鉄(FeO):29%,酸化カルシウム(CaO):23%,酸化マグネシウム(MgO):5%,二酸化ケイ素(SiO):18%で,粒径は,0.5~2mmからなる。
[Case 1]
The iron supplement for growth shown in Figure 2 is electric furnace oxidized slag, consisting of 29% iron oxide (FeO), 23% calcium oxide (CaO), 5% magnesium oxide (MgO), and 18% silicon dioxide (SiO 2 ), with particle sizes of 0.5 to 2 mm.

本発明に係る生育用鉄分補給剤が混合されていない土壌の「対照区」に対し,「本発明品」においては,生育用鉄分補給剤を土壌1リットルに対して5gを混合し,10リットルのプランターに6株の「モロヘイヤ」を30日間,栽培した際の生育状態を示す。 In contrast to the "control group" of soil that did not contain the iron growth supplement of the present invention, the "product of the present invention" was mixed with 5g of iron growth supplement per 1 liter of soil, and the growth conditions of six "molokheiya" plants were grown in a 10-liter planter for 30 days.

本発明に係る生育用鉄分補給剤が混合された土壌での栽培例にあっては,「対照区」に対し,いずれの項目において高い指数を示し,高濃度の二価鉄イオン(Fe2+)が長期にわたって補給されたと考察される。 In the cultivation example in soil mixed with the iron growth supplement of the present invention, higher indexes were shown in all items compared to the ``control area,'' and it is considered that high concentrations of divalent iron ions (Fe2 + ) were supplied over the long term.

[事例2]
図3においては,事例1と同様の生育用鉄分補給剤を,土壌1リットルに対して5gを混合し,8号鉢に3株の「赤キャベツ」を19日間,栽培した際の生育状態を示す。
[Case 2]
FIG. 3 shows the growth state of three "red cabbage" plants grown in No. 8 pots for 19 days after mixing 5 g of the same iron supplement for growth as in Example 1 with 1 liter of soil.

本発明に係る生育用鉄分補給剤が混合された土壌での栽培例にあっては,「対照区」に対し,いずれの項目において高い指数を示し,高濃度の二価鉄イオン(Fe2+)が長期にわたって補給されたと考察される。
[事例3]
図4においては,事例1と同様の生育用鉄分補給剤を,土壌1リットルに対して5gを混合し,10リットルのプランターに6株の「イタリアンパセリ」を22日間,栽培した際の生育状態を示す。
In the cultivation example in soil mixed with the iron growth supplement of the present invention, higher indexes were shown in all items compared to the ``control area,'' and it is considered that high concentrations of divalent iron ions (Fe2 + ) were supplied over the long term.
[Case 3]
FIG. 4 shows the growth state of six "Italian parsley" plants grown in a 10-liter planter for 22 days after mixing 5 g of the same iron growth supplement as in Example 1 with 1 liter of soil.

本発明に係る生育用鉄分補給剤が混合された土壌での栽培例にあっては,「対照区」に対し,いずれの項目において高い指数を示し,高濃度の二価鉄イオン(Fe2+)が長期にわたって補給されたと考察される。 In the cultivation example in soil mixed with the iron growth supplement of the present invention, higher indexes were shown in all items compared to the ``control area,'' and it is considered that high concentrations of divalent iron ions (Fe2 + ) were supplied over the long term.

[事例4]
図5に示す生育用鉄分補給剤は,事例1-3で使用した生育用鉄分補給剤と同様の組成で,粒径が0.007mmの生育用鉄分補給剤を土壌1リットルに対して1g及び粒径が0.5~2mmの生育用鉄分補給剤を土壌1リットルに対して5gを土壌にそれぞれ混合し,10リットルのプランターに5株の「コマツナ」を18日間,栽培した際の生育状態を示す。
[Case 4]
The iron supplement for growth shown in Figure 5 has the same composition as the iron supplement for growth used in Case 1-3, and 1 g of iron supplement for growth with a particle size of 0.007 mm and 5 g of iron supplement for growth with a particle size of 0.5 to 2 mm were mixed into the soil at a rate of 1 liter of soil, and the growth condition of five "Komatsuna" plants grown in a 10-liter planter for 18 days is shown.

本発明に係る生育用鉄分補給剤が混合された各土壌での栽培例にあっては,「対照区」に対し,いずれの項目において高い指数を示し,高濃度の二価鉄イオン(Fe2+)が長期にわたって補給されたと考察される。 In the cultivation examples in each soil mixed with the iron growth supplement of the present invention, higher indexes were shown in all items compared to the ``control area,'' and it is considered that high concentrations of divalent iron ions (Fe2 + ) were supplied over the long term.

[考察]
上記事例1-4から本発明に係る生育用鉄分補給剤は,水に対する溶解率が高く,少なくとも植物に対して摂取効率が高い二酸化鉄イオン(Fe2+)を補給することができた。
[Discussion]
From the above Examples 1-4, it was found that the iron supplement for plant growth according to the present invention had a high solubility in water and was able to supply iron dioxide ions (Fe 2+ ) that had a high uptake efficiency at least for plants.

また,生育用鉄分補給剤がアルカリ性であるため,水に溶解した二酸化鉄イオン(Fe2+)が三価鉄イオン(Fe3+)へ遷移するのを抑制し,二酸化鉄イオン(Fe2+)を長期にわたって安定的に補給することができた。 In addition, because the iron supplement for plant growth is alkaline, it suppresses the transition of iron dioxide ions (Fe 2+ ) dissolved in water to trivalent iron ions (Fe 3+ ), making it possible to stably replenish iron dioxide ions (Fe 2+ ) over the long term.

上記説明は,陸上植物に付いて説明したが,藻類等の海洋植物に対しては,本発明に係る生育用鉄分補給剤を,例えば藻礁ブロックに取付けたり,ロープ等に取付けられる袋(不織布)に収容したりして水域に溶出可能にすることにより実施可能である。 The above explanation has been given with regard to terrestrial plants, but for marine plants such as algae, the iron growth supplement of the present invention can be applied by attaching it to, for example, an algal reef block or by storing it in a bag (non-woven fabric) that can be attached to a rope or the like, allowing it to dissolve into the water.

上記説明は,スラグ鍋から流下する溶融状態の電気炉酸化スラグをキャリアガスにより吹き飛ばしながら噴射急冷部材から噴射する水又はミストにより急冷して多くが非晶質で粒状化した電気炉酸化スラグを生成したが,スラグ鍋に溜められて溶融状態の電気炉酸化スラグを,必要により内蔵された水管や冷媒管により冷却された冷却台や冷却ロール(圧延ロール)上に流下させて平板状又はブロック状にしながら噴射急冷部材から水又はミストを噴射して急冷した電気炉酸化スラグとしてもよい。 In the above explanation, the molten electric furnace oxidized slag flowing down from the slag ladle is blown away by a carrier gas while being quenched by water or mist sprayed from a jet quenching member to produce electric furnace oxidized slag that is mostly amorphous and granulated. However, the molten electric furnace oxidized slag stored in the slag ladle may also be allowed to flow down onto a cooling table or cooling roll (rolling roll) cooled by an incorporated water pipe or refrigerant pipe as necessary, forming it into a plate or block shape, and then quenched by spraying water or mist from a jet quenching member to produce electric furnace oxidized slag.

この場合にあっては,電気炉酸化スラグは,急冷により多くが非晶化されるが粒状化することができない。このため,平板状又はブロック状に生成された酸化スラグにあっては,上記した破砕装置により所望の大きさ(最大10mm)になるように破砕して断片化された生育用鉄分補給剤に生成すればよい。 In this case, the electric furnace oxidized slag is largely decrystallized by rapid cooling, but cannot be granulated. Therefore, in the case of oxidized slag produced in a plate or block shape, it is sufficient to produce fragmented iron supplements for growth by crushing them to the desired size (maximum 10 mm) using the above-mentioned crushing device.

上記説明は,酸化スラグ風砕装置1により電気炉酸化スラグを吹き飛ばしながら急冷して最大10mm程度の大きさに粒状化して生育用鉄分補給剤を生成するものとしたが,酸化スラグ風砕装置により風砕及び急冷し,望ましくは最大10mm程度の大きさに直接,生成する製造態様としたが,これよりも大きさで電気炉酸化スラグを生成した後に破砕装置により上記大きさに生成する迂回的製造態様であってもよい。 In the above explanation, electric furnace oxidized slag is blown away and rapidly cooled by the oxidized slag air crushing device 1, and granulated to a maximum size of about 10 mm to produce an iron supplement for growth. Although the production method is such that the oxidized slag is air-crushed and rapidly cooled by the oxidized slag air crushing device to directly produce granules preferably in a maximum size of about 10 mm, a roundabout production method in which electric furnace oxidized slag is produced at a larger size and then granulated to the above-mentioned size by a crushing device may also be used.

Claims (6)

酸化鉄(FeO):20~50%,酸化カルシウム(CaO):20~40%,酸化マグネシウム(MgO):3~10%,二酸化ケイ素(SiO 2 ):10~20%を主要組成とし,最大で10mmに粒状化及び断片化のいずれかの形態に生成された非晶質の電気炉酸化スラグであって,
上記電気炉酸化スラグは,上記主要組成が水溶した際にpH8以上のアルカリ性で,かつ三価鉄イオン(Fe 3+ )に対して二価鉄イオン(Fe 2+ )を高い割合で溶出可能で,
上記電気炉酸化スラグを動植物の鉄分補給剤として使用することを特徴とする動植物生育用鉄分補給剤。
Amorphous electric furnace oxidized slag having a main composition of iron oxide (FeO): 20-50%, calcium oxide (CaO): 20-40%, magnesium oxide (MgO): 3-10%, silicon dioxide (SiO2 ) : 10-20%, and produced in either a granulated or fragmented form up to a maximum size of 10 mm;
The electric furnace oxidizing slag has an alkaline pH of 8 or more when the main components are dissolved in water, and is capable of dissolving a high ratio of divalent iron ions (Fe 2+ ) to trivalent iron ions (Fe 3+ ),
An iron supplement for the growth of animals and plants, characterized in that the electric furnace oxidized slag is used as an iron supplement for animals and plants.
請求項1において,
溶融状態の電気炉酸化スラグをキャリアガスにより吹き飛ばして粒状化しながら噴射急冷部材から噴射される冷却水により急冷した動植物生育用鉄分補給剤。
In claim 1,
This iron supplement for plant and animal growth is made by blowing away molten electric furnace oxide slag with a carrier gas, granulating it, and then quenching it with cooling water sprayed from a spray quenching member .
請求項2において,
生成される動植物生育用鉄分補給剤の大きさに対応してキャリアガス圧力を可変可能にした動植物生育用鉄分補給剤。
In claim 2,
An iron supplement for plant and animal growth, in which the carrier gas pressure can be varied in accordance with the size of the iron supplement for plant and animal growth produced .
請求項1において,
溶融状態の電気炉酸化スラグを平板状及びブロック状のいずれの形態で急冷した後に断片化した動植物生育用鉄分補給剤。
In claim 1,
An iron supplement for plant and animal growth , made by rapidly cooling molten electric furnace oxidized slag in either a plate or block form and then fragmenting it .
請求項2において,
粒状化及び断片化された電気炉酸化スラグは,所定の大きさに破砕された動植物生育用鉄分補給剤。
In claim 2,
Granulated and fragmented electric furnace oxidized slag is crushed to a specified size to provide an iron supplement for plant and animal growth.
請求項4において,
粒状化及び断片化された電気炉酸化スラグは,所定の大きさに破砕された動植物生育用鉄分補給剤。
In claim 4,
Granulated and fragmented electric furnace oxidized slag is crushed to a specified size to provide an iron supplement for plant and animal growth.
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