JP5912887B2 - Method for producing silicate fertilizer - Google Patents
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Description
本発明は、ケイ酸肥料の製造方法に関する。 The present invention relates to a method for producing a silicate fertilizer.
イネや麦などのイネ科植物はケイ酸吸収性を有すること、及び、イネ科植物の育苗時にケイ酸を施用することは生育向上や病害発生の抑制に有効であることが、知られている。
ケイ酸を供給するための材料としてはスラグ、ケイ酸カルシウム水和物、及びシリカゲル等が挙げられる。これらはケイ酸質肥料として用いられている。中でも、スラグ、及びケイ酸カルシウム水和物は比較的安価であることから、ケイ酸質肥料として広く施用されている。
例えば、特許文献１には、水熱合成して得られるケイ酸カルシウム水和結晶を含有するケイ酸質材を、石膏をバインダーとして粒状にしてなるケイ酸質肥料造粒品が記載されている。
ここで、ケイ酸質肥料は、肥料等試験法において、塩酸又はアルカリで抽出される形態のケイ酸の量（可溶性ケイ酸量）で評価されており、規格上、可溶性ケイ酸量が１５質量％以上のものである。
しかし、実際にイネ科植物に肥料を施用する際には、弱酸性〜中性の湛水条件で施用されることから、塩酸等で抽出されるケイ酸の量（可溶性ケイ酸量）ではなく、水で抽出される形態のケイ酸の量が多い肥料が求められている。
It is known that gramineous plants such as rice and wheat have silicic acid absorptivity, and that silicic acid application at the time of seedling of gramineous plants is effective in improving growth and suppressing disease occurrence. .
Examples of the material for supplying silicic acid include slag, calcium silicate hydrate, and silica gel. These are used as siliceous fertilizers. Especially, since slag and calcium silicate hydrate are comparatively cheap, they are widely applied as siliceous fertilizers.
For example, Patent Literature 1 describes a siliceous fertilizer granulated product obtained by granulating a siliceous material containing calcium silicate hydrate crystals obtained by hydrothermal synthesis using gypsum as a binder. .
Here, the siliceous fertilizer is evaluated by the amount of silicic acid in the form extracted with hydrochloric acid or alkali (soluble silicic acid amount) in the test method for fertilizers and the like, and the soluble silicic acid amount is 15 mass on the standard. % Or more.
However, when fertilizer is actually applied to gramineous plants, since it is applied under mildly acidic to neutral flooding conditions, it is not the amount of silicic acid extracted with hydrochloric acid or the like (the amount of soluble silicic acid) There is a need for fertilizers that are high in the amount of silicic acid that is extracted with water.
本発明の目的は、水で抽出される形態のケイ酸の量（以下、「水溶性ケイ酸量」ともいう。）が多いケイ酸肥料の製造方法を提供することにある。 An object of the present invention is to provide a method for producing a silicate fertilizer having a large amount of silicic acid extracted with water (hereinafter also referred to as “water-soluble silicic acid amount”).
本発明者らは、上記課題を解決するために鋭意検討した結果、非晶質シリカゲル様化合物、ケイ酸カルシウム水和物、及び、結晶性シリカの含有率が特定の数値範囲であり、かつ、水溶性ケイ酸量が特定の数値範囲であるケイ酸肥料を製造するための方法であって、ケイ酸カルシウム水和物であるトバモライトを含むオートクレーブ養生軽量気泡コンクリートを、水を供給することなく、４０〜９５％の相対湿度かつ炭酸ガス雰囲気下で放置して、ケイ酸肥料を得るケイ酸肥料の製造方法によれば、前記の目的を達成することができることを見出し、本発明を完成した。
すなわち、本発明は、以下の［１］〜［２］を提供するものである。
［１］ 非晶質シリカゲル様化合物の含有率が３０〜８０質量％であり、ケイ酸カルシウム水和物の含有率が５０質量％以下（ただし、０質量％は含まない。）であり、結晶性シリカの含有率が２０質量％以下であり、かつ、水溶性ケイ酸量が０．５〜１．８質量％であるケイ酸肥料を製造するための方法であって、ケイ酸カルシウム水和物であるトバモライトを含むオートクレーブ養生軽量気泡コンクリートを、水を供給することなく、４０〜９５％の相対湿度かつ炭酸ガス雰囲気下で放置して、上記ケイ酸肥料を得ることを特徴とするケイ酸肥料の製造方法。
［２］ 上記炭酸ガス雰囲気が、炭酸ガスを２体積％以上の含有率で含むものである、前記［１］に記載のケイ酸肥料の製造方法。
As a result of intensive studies to solve the above problems, the present inventors have found that the content of amorphous silica gel-like compound , calcium silicate hydrate, and crystalline silica is in a specific numerical range, and A method for producing a silicic acid fertilizer having an amount of water-soluble silicic acid in a specific numerical range, wherein autoclaved lightweight lightweight concrete containing tobermorite is a calcium silicate hydrate, without supplying water, According to the method for producing a silicate fertilizer obtained by leaving it in a relative humidity of 40 to 95% and a carbon dioxide atmosphere to obtain a silicate fertilizer , the inventors have found that the above-mentioned object can be achieved and completed the present invention.
That is, the present invention provides the following [1] to [ 2 ].
[ 1 ] The content of the amorphous silica gel-like compound is 30 to 80% by mass, the content of calcium silicate hydrate is 50% by mass or less (however, 0% by mass is not included), and crystals A method for producing a silicic acid fertilizer having a silica content of 20% by mass or less and a water-soluble silicic acid content of 0.5 to 1.8% by mass , comprising calcium silicate hydration the autoclave curing lightweight concrete comprising at which tobermorite ones, without supplying water, allowed to stand under a relative humidity and carbon dioxide gas atmosphere of 40% to 95%, silicic acid, characterized in that obtaining the silicate fertilizers Fertilizer manufacturing method.
[2] The method for producing a silicate fertilizer according to [ 1 ], wherein the carbon dioxide atmosphere includes carbon dioxide at a content of 2% by volume or more.
本発明のケイ酸肥料の製造方法によって得られたケイ酸肥料は、水溶性ケイ酸量が多いため、弱酸性〜中性の湛水条件で施用した際に、より多くのケイ酸が作物（例えば、イネ科植物）に吸収されて、作物の成長量が増加する。また、病害の発生を抑制することができる。
また、本発明のケイ酸肥料の製造方法によると、水溶性ケイ酸量が多いケイ酸肥料を簡易に、かつ、経済的に製造することができる。
Since the silicic acid fertilizer obtained by the method for producing a silicic acid fertilizer of the present invention has a large amount of water-soluble silicic acid, when applied under mildly acidic to neutral flooding conditions, more silicic acid is produced in crops ( For example, it is absorbed by gramineous plants) to increase crop growth. Moreover, the occurrence of disease can be suppressed.
Moreover, according to the manufacturing method of the silicate fertilizer of this invention, the silicate fertilizer with much water-soluble silicic acid amount can be manufactured simply and economically.
以下、本発明について詳細に説明する。
本発明のケイ酸肥料の製造方法によって得られたケイ酸肥料（以下、「本発明のケイ酸肥料」ともいう。）は、非晶質シリカゲル様化合物を３０〜８０質量％の含有率で含む。
本明細書中、ケイ酸肥料とは、水で抽出可能なケイ酸を含む肥料をいう。
また、非晶質シリカゲル様化合物とは、ケイ酸カルシウム水和物を炭酸ガスに接触させて、ケイ酸カルシウム水和物を炭酸化させることで生成する、非晶質シリカを含む物質である。非晶質シリカを含むことは、例えば、ＦＴ−ＩＲスペクトルにおける１０８０ｃｍ−１での吸収によって確認することができる。該物質はカルシウム（Ｃａ）、ケイ素（Ｓｉ）、酸素（Ｏ）、炭素（Ｃ）及び水素（Ｈ）を含み、さらに、アルミニウム（Ａｌ）等を含んでいてもよい。
ケイ酸肥料中の上記非晶質シリカゲル様化合物の含有率は、ケイ酸肥料に含まれるトバモライト、炭酸カルシウム、結晶性シリカ、及び、その他の成分（ただし、非晶質シリカゲル様化合物を除く。）の各含有率を、ＸＲＤ（Ｘ線回折）、ＸＲＦ（蛍光Ｘ線分析）、及び、ＩＣＰ発光分光分析等を用いて測定し、ケイ酸肥料の合計（１００質量％）から、上記非晶質シリカゲル様化合物以外の含有率を差し引くことで算出することができる。
なお、「その他の成分」の含有率は、ＸＲＤ、ＸＲＦによって算出することができる。
上記非晶質シリカゲル様化合物は、水溶性ケイ酸量が多いため、弱酸性〜中性の湛水条件で施用した際に、水に溶出するケイ酸の量が多い。
本発明のケイ酸肥料の非晶質シリカゲル様化合物の含有率は、製造の容易性や水溶性ケイ酸量を多くする観点から、３０〜８０質量％である。該含有率が１質量％未満の場合、水溶性ケイ酸量が少なくなり、施肥効果が小さくなる。該含有率が９０質量％を超えると、ケイ酸肥料の製造が困難となる。
本発明のケイ酸肥料には、上記非晶質シリカゲル様化合物の他に、炭酸カルシウム、ケイ酸カルシウム水和物（例えば、トバモライト）、及び結晶性シリカ等を含んでもよい。
本発明のケイ酸肥料の成分組成は、非晶質シリカゲル様化合物の含有率が３０〜８０質量％であり、ケイ酸カルシウム水和物の含有率が５０質量％以下（ただし、０質量％は含まない。）であり、かつ、結晶性シリカの含有率が２０質量％以下であるものが挙げられる。
Hereinafter, the present invention will be described in detail.
The silicate fertilizer obtained by the method for producing a silicate fertilizer of the present invention (hereinafter also referred to as “the silicate fertilizer of the present invention”) contains an amorphous silica gel-like compound at a content of 30 to 80 % by mass. .
In this specification, a silicic acid fertilizer means the fertilizer containing the silicic acid extractable with water.
The amorphous silica gel-like compound is a substance containing amorphous silica that is produced by bringing calcium silicate hydrate into contact with carbon dioxide gas to carbonate the calcium silicate hydrate. Inclusion of amorphous silica can be confirmed, for example, by absorption at 1080 cm −1 in the FT-IR spectrum. The substance contains calcium (Ca), silicon (Si), oxygen (O), carbon (C) and hydrogen (H), and may further contain aluminum (Al) or the like.
The content of the amorphous silica gel-like compound in the silicate fertilizer is the tobermorite, calcium carbonate, crystalline silica, and other components contained in the silicate fertilizer (excluding the amorphous silica gel-like compound). Is measured using XRD (X-ray diffraction), XRF (fluorescence X-ray analysis), ICP emission spectroscopic analysis, and the like, and the above amorphous (100% by mass) of the above-mentioned amorphous It can be calculated by subtracting the content other than the silica gel-like compound.
The content of “other components” can be calculated by XRD and XRF.
Since the amorphous silica gel-like compound has a large amount of water-soluble silicic acid, the amount of silicic acid eluted in water is large when applied under weakly acidic to neutral flooding conditions.
The content of the amorphous silica gel-like compound in the silicate fertilizer of the present invention is 30 to 80 % by mass from the viewpoint of ease of production and increasing the amount of water-soluble silicic acid. When the content is less than 1% by mass, the amount of water-soluble silicic acid is reduced and the fertilization effect is reduced. When this content rate exceeds 90 mass%, manufacture of a silicate fertilizer will become difficult.
The silicate fertilizer of the present invention may contain calcium carbonate, calcium silicate hydrate (for example, tobermorite), crystalline silica and the like in addition to the above amorphous silica gel-like compound.
The component composition of the silicate fertilizer of the present invention is that the content of amorphous silica gel-like compound is 30 to 80% by mass , and the content of calcium silicate hydrate is 50% by mass or less (however, 0% by mass is And the content of crystalline silica is 20% by mass or less.
本発明のケイ酸肥料はケイ酸カルシウム水和物であるトバモライトを含むオートクレーブ養生軽量気泡コンクリートを、水を供給することなく、４０〜９５％の相対湿度かつ炭酸ガス雰囲気下で放置することで得ることができる。
ケイ酸カルシウム水和物に炭酸ガスを接触させることで、ケイ酸カルシウム水和物が炭酸化されて、非晶質シリカゲル様水和物が生成される。なお、炭酸化に伴って、不可避的に炭酸カルシウムが生成されるが、イネ科植物等の生育上特に問題は生じない。
上記ケイ酸カルシウム水和物としては、例えば、トバモライト、ゾノトライト、ジャイロライト、フォシャジャイト、ヒレブランタイト等が挙げられる。また、ケイ酸カルシウム水和物は純粋な物ではなく、ＣＳＨゲルや未反応のケイ酸質原料が含まれていてもよい。
中でも、入手の容易性、及び経済性の観点から、トバモライトを用いる。トバモライトは、入手の容易性の観点から、主成分としてトバモライトを含むオートクレーブ養生軽量気泡コンクリート（ＡＬＣ）を用いる。
オートクレーブ養生軽量気泡コンクリートとは、ケイ酸質原料と石灰質原料を主原料とし、これに発泡剤を加えて予備養生させた後、オートクレーブ中で水熱合成して得られる多孔質ケイ酸カルシウム水和物を主成分とする軽量気泡コンクリートである。該コンクリートは、建材や断熱材として大量に製造されており、容易に入手することができて経済的である。また、廃棄物利用の観点から、オートクレーブ養生軽量気泡コンクリートの製造工程において生じる不良品や、建設現場で発生する端材を利用してもよい。
上記ケイ酸カルシウム水和物は炭酸ガスとの反応性を向上させる観点から、予めボールミル等の粉砕機を用いて粉砕して、粉粒状にしたものを用いることが好ましい。ケイ酸カルシウム水和物の粒度（粒径）は、好ましくは２ｍｍ以下、より好ましくは１ｍｍ以下、特に好ましくは０．５ｍｍ以下である。なお、粒度とは、最大寸法（例えば、断面が楕円の場合、長径寸法）をいう。
上記炭酸ガス雰囲気における炭酸ガス濃度は、処理時間の短縮化、及び、炭酸ガス雰囲気の形成の容易性の観点から、好ましくは２〜１００体積％、より好ましくは４〜４０体積％、特に好ましくは５〜３０体積％である。該濃度が２体積％未満であると、非晶質シリカゲル様化合物が生成するのに多大な時間を要するので好ましくない。
処理を行う際の温度は、処理時間の短縮化の観点から、好ましくは１０〜１００℃、より好ましくは１３〜４５℃、特に好ましくは１５〜３０℃である。該温度が１０℃未満であると、非晶質シリカゲル様化合物を生成するのに多大な時間を要するので好ましくない。該温度が１００℃を超えると、熱エネルギーのコストが増大するので好ましくない。
また、処理を行う際の相対湿度は、処理時間の短縮化、及び、目的とする相対湿度の調整の容易性の観点から、４０〜９５％、特に好ましくは５０〜８０％である。該湿度が２％未満であると、非晶質シリカゲル様化合物を生成するのに多大に時間を要するので好ましくない。
処理を行う時間は、好ましくは１日以上、より好ましくは５日以上、特に好ましくは２０日以上である。１日未満であると、得られるケイ酸肥料中の非晶質シリカゲル様化合物の含有率が少なくなる場合がある。
The silicate fertilizer of the present invention is obtained by leaving autoclaved lightweight lightweight concrete containing tobermorite, a calcium silicate hydrate , in a relative humidity of 40 to 95% and a carbon dioxide atmosphere without supplying water. be able to.
By contacting carbon dioxide with the calcium silicate hydrate, the calcium silicate hydrate is carbonated to produce an amorphous silica gel-like hydrate. In addition, although calcium carbonate is inevitably produced | generated with carbonation, a problem does not arise in particular on the growth of gramineous plants etc.
Examples of the calcium silicate hydrate include tobermorite, zonotrite, gyrolite, foshygite, and lebrantite . In addition, calcium silicate hydrate is not pure and may contain CSH gel or unreacted siliceous raw material.
Among these, tobermorite is used from the viewpoint of availability and economy . Tobermorite, from the viewpoint of easy availability, use autoclave curing lightweight concrete (ALC) containing tobermorite as a main component.
Autoclaved lightweight lightweight concrete is a porous calcium silicate hydrate obtained by hydrothermal synthesis in an autoclave after pre-curing by adding a foaming agent to a siliceous raw material and calcareous raw material. It is a lightweight cellular concrete mainly composed of materials. The concrete is manufactured in large quantities as a building material or a heat insulating material, and can be easily obtained and is economical. In addition, from the viewpoint of waste utilization, defective products generated in the manufacturing process of autoclaved lightweight lightweight concrete or scraps generated at a construction site may be used.
From the viewpoint of improving the reactivity with carbon dioxide gas, it is preferable to use the calcium silicate hydrate that has been pulverized in advance using a pulverizer such as a ball mill. The particle size (particle size) of calcium silicate hydrate is preferably 2 mm or less, more preferably 1 mm or less, and particularly preferably 0.5 mm or less. In addition, a particle size means the largest dimension (For example, when a cross section is an ellipse, it is a major axis dimension).
The carbon dioxide gas concentration in the carbon dioxide atmosphere is preferably 2 to 100% by volume, more preferably 4 to 40% by volume, and particularly preferably from the viewpoints of shortening the processing time and ease of forming the carbon dioxide gas atmosphere. 5 to 30% by volume. If the concentration is less than 2% by volume, it takes a long time to produce an amorphous silica gel-like compound, which is not preferable.
The temperature for performing the treatment is preferably 10 to 100 ° C, more preferably 13 to 45 ° C, and particularly preferably 15 to 30 ° C, from the viewpoint of shortening the treatment time. If the temperature is less than 10 ° C., it takes a long time to produce an amorphous silica gel-like compound, which is not preferable. If the temperature exceeds 100 ° C., the cost of thermal energy increases, which is not preferable.
Moreover, the relative humidity at the time of processing is 40 to 95% , particularly preferably 50 to 80%, from the viewpoint of shortening the processing time and ease of adjusting the target relative humidity. If the humidity is less than 2%, it takes a long time to produce an amorphous silica gel-like compound, which is not preferable.
The time for performing the treatment is preferably 1 day or more, more preferably 5 days or more, and particularly preferably 20 days or more. If it is less than 1 day, the content of the amorphous silica gel-like compound in the resulting silicic acid fertilizer may be reduced.
本発明のケイ酸肥料は、通常のケイ酸質肥料（例えば、シリカゲル肥料）とは異なり、水溶性ケイ酸量が多い。
本発明のケイ酸肥料の水溶性ケイ酸量は、作物の成長への好ましい影響、及び、目的とする水溶性ケイ酸量を得ることの容易性の観点から、０．５〜１．８質量％、特に好ましくは０．６〜１．８質量％である。
本発明のケイ酸肥料を、水田等の弱酸性〜中性の湛水条件において施用した場合、より多くのケイ酸が水中に溶出し、作物（例えば、イネ科植物）のケイ酸の吸収量が多くなるため、作物の成長量を増加させることができる。また、病害発生の抑制が期待できる。
Unlike a normal siliceous fertilizer (for example, silica gel fertilizer), the silicic acid fertilizer of the present invention has a large amount of water-soluble silicic acid.
The water-soluble silicic acid amount of the silicate fertilizer of the present invention is 0.5 to 1.8 mass from the viewpoint of favorable influence on the growth of crops and the ease of obtaining the target water-soluble silicic acid amount. % , Particularly preferably 0.6 to 1.8% by mass.
When the silicic acid fertilizer of the present invention is applied under mildly acidic to neutral flooding conditions such as paddy fields, more silicic acid is eluted in the water, and the amount of silicic acid absorbed by the crop (eg, Gramineae) Therefore, the amount of crop growth can be increased. Moreover, suppression of disease occurrence can be expected.
以下、実施例によって本発明を説明する。
１．使用原料
以下に示す原料を使用した。
（１）ＡＬＣ（Ｎｏ．１）：エーアンドエーマテリアル社製の軽量気泡コンクリートの端材
（２）ＡＬＣ（Ｎｏ．２）：エーアンドエーマテリアル社製の軽量気泡コンクリートの端材
（３）シリカゲル肥料：富士シリシア社製の「イネルギー」
（４）培土：福田石材社製の福田培土
（５）水稲：コシヒカリ
（６）水：イオン交換水
Hereinafter, the present invention will be described by way of examples.
1. Raw materials used The raw materials shown below were used.
(1) ALC (No. 1): Milled material of lightweight cellular concrete manufactured by A & A Materials (2) ALC (No. 2): Milled material of lightweight cellular concrete manufactured by A & A Materials (3) Silica gel fertilizer: Fuji Silysia “Energy”
(4) Culture soil: Fukuda culture soil made by Fukuda Stone Company (5) Rice: Koshihikari (6) Water: Ion exchange water
使用原料の化学組成を、走査型蛍光Ｘ線分析装置（リガク社製、商品名「ＺＳＸ１００ｅ」）を用いて分析を行った。結果を表１に示す。 The chemical composition of the raw materials used was analyzed using a scanning X-ray fluorescence analyzer (trade name “ZSX100e” manufactured by Rigaku Corporation). The results are shown in Table 1.
［実施例１］
ＡＬＣ（Ｎｏ．１）の端材を、粉砕機を用いて、１ｍｍ以下の粒度になるまで粉砕した。得られた粉末状のＡＬＣを中性化促進槽に入れて、炭酸ガス濃度５体積％、窒素（Ｎ２）濃度８０体積％、酸素（Ｏ２）濃度１５体積％、温度２０℃、相対湿度６５％の条件下で７日間静置して、ケイ酸肥料Ａを得た。
得られたケイ酸肥料Ａを、ＸＲＤ（Ｘ線回折）、ＦＴ−ＩＲ（フーリエ変換赤外分光法）を用いて定性分析を行った後、各種鉱物について定量分析を行った。
また、ケイ酸肥料Ａを、フーリエ変換型赤外線分光装置（日本分光社製、ＦＴ−ＩＲ−６１００）を用いて分析を行ったところ、ＦＴ−ＩＲスペクトルにおいて１０８０ｃｍ−１に吸収が認められ、非晶質のＳｉＯ２が含まれていることが判明した。
トバモライトの含有率は、「肥料等試験法（２０１１）可溶性ケイ酸定量」に基づいて溶解した試料の溶液を、ＩＣＰ発光分光分析を用いて測定した。
炭酸カルシウムの含有率は、差動型示差熱天秤（ブルカーエイエックスエス社製、ＴＧ−ＤＴＡ２０２０ＳＡ）を用いて測定した。
結晶性シリカの含有率は、「肥料等試験法（２０１１）可溶性ケイ酸定量」に基づいて溶解した試料の残渣を、ＸＲＤを用いて測定した。
その他の成分の含有率は、走査型蛍光Ｘ線分析装置（リガク社製、ＺＳＸ１００ｅ）を用いて測定した。
非晶質シリカゲル様化合物の含有率は、全体の量（１００質量％）から、トバモライト、炭酸カルシウム、結晶性シリカ、及び、その他の成分の和（％）を差し引くことによって算出した。ケイ酸肥料Ａの鉱物組成を表２に示す。
また、ケイ酸肥料Ａの水溶性ケイ酸量を、「肥料分析法（１９９２）水溶性ケイ酸定量」に基づいて測定した。結果を表３に示す。
[Example 1]
The end material of ALC (No. 1) was pulverized to a particle size of 1 mm or less using a pulverizer. The obtained powdered ALC was put into a neutralization promoting tank, carbon dioxide gas concentration 5% by volume, nitrogen (N 2 ) concentration 80% by volume, oxygen (O 2 ) concentration 15% by volume, temperature 20 ° C., relative humidity. The silicate fertilizer A was obtained by leaving still for 7 days under the condition of 65%.
The obtained silicate fertilizer A was subjected to qualitative analysis using XRD (X-ray diffraction) and FT-IR (Fourier transform infrared spectroscopy), and then quantitative analysis was performed on various minerals.
Further, when the silicate fertilizer A was analyzed using a Fourier transform infrared spectrometer (manufactured by JASCO Corporation, FT-IR-6100), absorption was observed at 1080 cm −1 in the FT-IR spectrum, and non- It was found that crystalline SiO 2 was contained.
The content of tobermorite was measured using ICP emission spectroscopic analysis for a sample solution dissolved based on “Fertilizer test method (2011) Soluble silicate determination”.
The content rate of calcium carbonate was measured using a differential type differential thermal balance (manufactured by Bruker AXS, TG-DTA2020SA).
The content of the crystalline silica was measured using XRD for the residue of the sample dissolved based on “Fertilizer etc. Test Method (2011) Soluble Silicic Acid Determination”.
The content of other components was measured using a scanning X-ray fluorescence analyzer (manufactured by Rigaku Corporation, ZSX100e).
The content of the amorphous silica gel-like compound was calculated by subtracting the sum (%) of tobermorite, calcium carbonate, crystalline silica, and other components from the total amount (100% by mass). The mineral composition of silicate fertilizer A is shown in Table 2.
Further, the amount of water-soluble silicic acid of silicate fertilizer A was measured based on “Fertilizer analysis method (1992) Determination of water-soluble silicic acid”. The results are shown in Table 3.
［実施例２］
７日間の静置に代えて、２８日間静置する以外は、実施例１と同様にして、ケイ酸肥料Ｂを得た。得られたケイ酸肥料Ｂについて、実施例１と同様にして分析を行った。結果を表２及び３に示す。
また、ケイ酸肥料Ｂを、フーリエ変換型赤外線分光装置（日本分光社製、ＦＴ−ＩＲ−６１００）を用いて分析を行ったところ、ＦＴ−ＩＲスペクトルにおいて１０８０ｃｍ−１に吸収が認められ、非晶質のＳｉＯ２が含まれていることが判明した。
［実施例３］
ＡＬＣ（Ｎｏ．１）の代わりに、ＡＬＣ（Ｎｏ．２）を用いる以外は、実施例１と同様にして、ケイ酸肥料Ｃを得た。得られたケイ酸肥料Ｃについて、実施例１と同様にして分析を行った。結果を表２及び３に示す。
また、ケイ酸肥料Ｃを、フーリエ変換型赤外線分光装置（日本分光社製、ＦＴ−ＩＲ−６１００）を用いて分析を行ったところ、ＦＴ−ＩＲスペクトルにおいて１０８０ｃｍ−１に吸収が認められ、非晶質のＳｉＯ２が含まれていることが判明した。
［実施例４］
ＡＬＣ（Ｎｏ．１）の代わりに、ＡＬＣ（Ｎｏ．２）を用いる以外は、実施例２と同様にして、ケイ酸肥料Ｄを得た。得られたケイ酸肥料Ｄについて、実施例１と同様にして分析を行った。結果を表２及び３に示す。
また、ケイ酸肥料Ｄを、フーリエ変換型赤外線分光装置（日本分光社製、ＦＴ−ＩＲ−６１００）を用いて分析を行ったところ、ＦＴ−ＩＲスペクトルにおいて１０８０ｃｍ−１に吸収が認められ、非晶質のＳｉＯ２が含まれていることが判明した。
［比較例１〜３］
ＡＬＣ（Ｎｏ．１）、ＡＬＣ（Ｎｏ．２）、及びシリカゲル肥料を、各々比較例１〜３とした。各原料の鉱物組成及び水溶性ケイ酸量を実施例１と同様にして分析を行った。結果を表２及び表３に示す。
[Example 2]
Silicate fertilizer B was obtained in the same manner as in Example 1 except that it was allowed to stand for 28 days instead of 7 days. The obtained silicate fertilizer B was analyzed in the same manner as in Example 1. The results are shown in Tables 2 and 3.
Further, when the silicate fertilizer B was analyzed using a Fourier transform infrared spectrometer (manufactured by JASCO Corporation, FT-IR-6100), absorption was observed at 1080 cm −1 in the FT-IR spectrum, and non- It was found that crystalline SiO 2 was contained.
[Example 3]
Silicate fertilizer C was obtained in the same manner as in Example 1 except that ALC (No. 2) was used instead of ALC (No. 1). The obtained silicate fertilizer C was analyzed in the same manner as in Example 1. The results are shown in Tables 2 and 3.
Further, when the silicate fertilizer C was analyzed using a Fourier transform infrared spectrometer (manufactured by JASCO Corporation, FT-IR-6100), absorption was observed at 1080 cm −1 in the FT-IR spectrum, and non- It was found that crystalline SiO 2 was contained.
[Example 4]
Silicate fertilizer D was obtained in the same manner as in Example 2 except that ALC (No. 2) was used instead of ALC (No. 1). The obtained silicate fertilizer D was analyzed in the same manner as in Example 1. The results are shown in Tables 2 and 3.
Further, when the silicate fertilizer D was analyzed using a Fourier transform infrared spectrometer (manufactured by JASCO Corporation, FT-IR-6100), absorption was recognized at 1080 cm −1 in the FT-IR spectrum, and non- It was found that crystalline SiO 2 was contained.
[Comparative Examples 1-3]
ALC (No. 1), ALC (No. 2), and silica gel fertilizer were used as Comparative Examples 1 to 3, respectively. The mineral composition of each raw material and the amount of water-soluble silicic acid were analyzed in the same manner as in Example 1. The results are shown in Tables 2 and 3.
［実施例５〜１０、比較例４〜７］
水稲育苗用培土（福田石材社製、福田培土）３０００ｇに各肥料を表４に記載された施用量で加えて混合し、苗床とした。該苗床にコシヒカリを播き、イオン交換水を加えて充分に灌水させて育苗試験を行った。３０日後に、地上部分の苗を刈り取り、乾燥器に入れて、８０℃の条件下で恒量になるまで乾燥させた。その後、乾燥させた苗の質量（地上部乾物質量）を測定した。
乾燥させた苗１．０ｇを採取して、無水炭酸ナトリウム１０ｇと混合した。混合物を白金るつぼに入れて、９００℃に加熱してアルカリ溶融を行った。放冷後、固塊を熱蒸留水で溶解し、０．５Ｎ塩酸２００ｍｌとなるように塩酸と蒸留水を加えて希釈した。溶液中のケイ素濃度をＩＣＰ発光分析法で測定し、苗１本あたりのケイ酸（ＳｉＯ２）量に換算して地上部ケイ酸質量を測定した。結果を表４に示す。
[Examples 5 to 10, Comparative Examples 4 to 7]
Each fertilizer was added to 3000 g of paddy rice seedling cultivation soil (Fukuda Stone Co., Ltd., Fukuda cultivation soil) at the application rate shown in Table 4 and mixed to prepare a nursery. Koshihikari was sown on the seed bed, and ion-exchanged water was added to allow sufficient irrigation to conduct a seedling raising test. After 30 days, the seedlings on the ground were cut and placed in a dryer, and dried at 80 ° C. until a constant weight was reached. Thereafter, the mass of the dried seedling (the amount of dry matter on the ground) was measured.
1.0 g of dried seedlings was collected and mixed with 10 g of anhydrous sodium carbonate. The mixture was placed in a platinum crucible and heated to 900 ° C. for alkali melting. After allowing to cool, the solid mass was dissolved with hot distilled water, and diluted with hydrochloric acid and distilled water to 200 ml of 0.5N hydrochloric acid. The silicon concentration in the solution was measured by ICP emission spectrometry, and converted to the amount of silicic acid (SiO 2 ) per seedling, and the above-ground silicic acid mass was measured. The results are shown in Table 4.
表２に示されるように、ケイ酸カルシウム水和物を炭酸ガス雰囲気下に放置することで、非晶質シリカゲル様化合物を含むケイ酸肥料を製造することができる。また、該肥料は、表３、４で示されるように、水溶性ケイ酸量が増加しており、該肥料をイネ科植物に施用すれば、吸収されるケイ酸量が増えて、イネ科植物の成長量が増大することがわかる。 As shown in Table 2, a silicate fertilizer containing an amorphous silica gel-like compound can be produced by leaving calcium silicate hydrate in a carbon dioxide atmosphere. In addition, as shown in Tables 3 and 4, the fertilizer has an increased amount of water-soluble silicic acid. When the fertilizer is applied to a gramineous plant, the amount of silicic acid absorbed increases, It can be seen that the amount of plant growth increases.
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