JP5091789B2 - Porous body composed of components derived from diatomaceous earth - Google Patents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 17
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
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- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- Drying Of Gases (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明はケイソウ土由来の多孔質体及びその製造方法に関するものである。 The present invention relates to a porous body derived from diatomaceous earth and a method for producing the same.
ケイソウ土は、それ自体多孔質体であり、珪藻が化石化したものである。この性質によって、断熱材や吸着材として汎用されている。
この多孔質の空隙は、０．１ｎｍから１０μｍの範囲に分布しているが、ほとんど平均的に存在し、空隙のサイズによって差はあまりない。
Diatomaceous earth is itself a porous body and is a fossilized diatom. Due to this property, it is widely used as a heat insulating material and an adsorbing material.
The porous voids are distributed in the range of 0.1 nm to 10 μm, but are almost average, and there is not much difference depending on the size of the voids.
更に、各サイズの空隙の容積が非常に小さく、どのサイズにおいても０．０１ｍｌ／ｇ以下である。これでは、特定のサイズのものを除去しようとしてもすぐに空隙が一杯になる。 Furthermore, the void volume of each size is very small, and is 0.01 ml / g or less at any size. This quickly fills the gap even if a specific size is to be removed.
このような一般的なケイソウ土と異なり、北海道稚内層の幌延町の約４５ｋｍ2 にわたり分布しているケイ酸化合物層は、珪藻泥岩 (珪質泥岩）と呼ばれ、細孔容積が大きいのが特徴である。これは、細孔半径が２〜５０ｎｍ付近のものが主であり、特に小さい（２〜５０ｎｍ）細孔で０．０２ｍｌ／ｇ以上の空隙を有している。 Unlike these common diatomaceous earths, the silicic acid compound layer distributed over about 45 km 2 in Horonobe-cho, Hokkaido Wakkanai Formation is called diatom mudstone (siliceous mudstone) and has a large pore volume. It is a feature. This is mainly one having a pore radius of about 2 to 50 nm, particularly a small (2 to 50 nm) pore having a void of 0.02 ml / g or more.
しかし、この珪藻泥岩であっても、細孔半径が１００ｎｍ以上のものは殆ど存在しない。この１００ｎｍ以上の大きな細孔が、菌や微生物、またその他の大きな分子の有機物を捕捉するためには必要なのである。 However, even this diatomaceous mudstone has almost no pore radius of 100 nm or more. These large pores of 100 nm or more are necessary for capturing bacteria, microorganisms, and other large molecular organic substances.
特に、微細な細孔によって化学物質等を除去し、大きな細孔によって微生物等を除去しようとすると、どうしても２種以上の吸着剤が必要になる。 In particular, two or more kinds of adsorbents are inevitably required to remove chemical substances and the like through fine pores and remove microorganisms and the like through large pores.
以上のような現状に鑑み本発明者は鋭意研究の結果、本発明珪藻はこのケイソウ土由来の成分からなる多孔質体を完成したものであり、その特徴とするところは、ケイソウ土から製造される多孔質体であって、該多孔質体の細孔半径は、０．１ｎｍから１０μｍの範囲に分布し、該細孔は、細孔分布曲線において、細孔半径が１〜１０ｎｍの間に０．０２ｍｌ／ｇを超えるピークがあり、同じく細孔半径が１００ｎｍ以上のところにも０．０２ｍｌ／ｇを超えるピークがあるものである点にある。 As a result of earnest research, the present inventor has completed the porous body composed of components derived from this diatomaceous earth as a result of intensive studies, and the feature thereof is that it is produced from diatomaceous earth. The porous body has a pore radius distributed in the range of 0.1 nm to 10 μm, and the pore is between 1 to 10 nm in the pore distribution curve. There is a peak exceeding 0.02 ml / g, and there is also a peak exceeding 0.02 ml / g when the pore radius is 100 nm or more.
ここで、ケイソウ土由来とは、原料がケイソウ土であるということであり、どのようなケイソウ土でもよい。ここでいうケイソウ土とは、珪藻という植物性プランクトンの化石であり、その生成場所によって種々の物性のものがある。 Here, diatomaceous earth origin means that the raw material is diatomaceous earth, and any diatomaceous earth may be used. Diatomaceous earth here is a fossil of phytoplankton called diatom, and there are various physical properties depending on the place where it is produced.
本発明はこのケイソウ土から製造する多孔質体であり、細孔は、０．１ｎｍから１０μｍの範囲に分布している。 The present invention is a porous body produced from this diatomaceous earth, and the pores are distributed in the range of 0.1 nm to 10 μm.
本発明の特徴は、細孔サイズによって空隙量が異なる点である。まず、細孔半径が１〜１０ｎｍの非常に小さい細孔が、０．０２ｍ１／ｇ以上存在する。通常のケイソウ土では、細孔のサイズにかかわらず、０．００５ｍ１／ｇ以下であり、この数値も非常に特異である。
しかし、細孔半径が１〜１０ｎｍのものがすべて０．０２ｍ１／ｇ以上の容積を有しているとい意味ではなく、細孔分布曲線（横軸が細孔半径、縦軸が単位重量あたりの細孔容積）において、細孔半径が１〜１０ｎｍの間に０．０２ｍ１／ｇを越えるピークがあるという意味である。
A feature of the present invention is that the amount of voids varies depending on the pore size. First, there are 0.02 ml / g or more of very small pores having a pore radius of 1 to 10 nm. Ordinary diatomaceous earth is 0.005 ml / g or less regardless of the pore size, and this value is also very unique.
However, not all pore radii with a diameter of 1 to 10 nm have a volume of 0.02 ml / g or more, but a pore distribution curve (the horizontal axis is the pore radius and the vertical axis is the unit weight per unit weight). This means that there is a peak exceeding 0.02 ml / g when the pore radius is 1 to 10 nm.
更に、本発明多孔質体は、半径が１００ｎｍ以上の細孔も同様に０．０２ｍ１／ｇ以上存在する。
細孔半径が１〜１０ｎｍの非常に小さい細孔が、０．０２ｍ１／ｇ以上存在するものはほとんどないが、前記した通り幌延のものはこれに近い値を有していることが知られている。しかし、この半径が１００ｎｍ以上の細孔が０．０２ｍ１／ｇ以上存在するものはまったくない。
これも上記同様、細孔半径が１００ｎｍ以上のところに０．０２ｍ１／ｇを越えるピークがあるという意味である。
Furthermore, the porous body of the present invention has 0.02 m1 / g or more of pores having a radius of 100 nm or more.
There are very few very small pores having a pore radius of 1 to 10 nm, but 0.02 ml / g or more exist, but Horonobe's is known to have a value close to this as described above. Yes. However, none of the pores having a radius of 100 nm or more exist at least 0.02 m1 / g.
This also means that there is a peak exceeding 0.02 m1 / g where the pore radius is 100 nm or more, as described above.
このような特殊な細孔分布を持つものは本発明で初めて製造されたものであり、天然には存在しない。天然物では、細孔半径ばらつきは正規分布するため、２ヶ所に大きなピークが存在する等ということはない。また、このような分布を持つように製造するということも従来考えられたことはない。即ち、１つのもののサイズを変えことは想起しても、その多量に存在する細孔の分布を変えるということは想起しないということである。 Those having such a special pore distribution are produced for the first time in the present invention and do not exist in nature. In natural products, pore radius variation is normally distributed, so there are no large peaks at two locations. In addition, it has never been considered to manufacture such a distribution. That is, changing the size of one thing reminds us not to change the distribution of pores present in large quantities.
また、本発明ではすべてのサイズで細孔容積が大きいのではなく、細孔半径が１ｎｍ以下、１０ｎｍ〜１００ｎｍのものは０．００５ｍｌ／ｇ〜０．０２ｍｌ／ｇの間であることが望ましい。更に、２０μｍ以上のものは０．０１ｍｌ／ｇ以下であることが望ましい。 In the present invention, not all pore sizes have a large pore volume, but those having a pore radius of 1 nm or less and 10 nm to 100 nm are preferably between 0.005 ml / g and 0.02 ml / g. Furthermore, it is desirable that the thing of 20 micrometers or more is 0.01 ml / g or less.
次に本発明多孔質体の製造方法について説明する。本発明は上記の構造であればよく、その製造方法は限定しないが、特に以下に説明する方法が好適であった。 Next, the manufacturing method of this invention porous body is demonstrated. The present invention may be any of the structures described above, and the manufacturing method thereof is not limited, but the method described below is particularly suitable.
原料としては、嵩比重が１．２５〜２．３５、細孔の９０％以上が半径数ｎｍ〜１００ｎｍの範囲にあり、かつ０．０２ｍ１／ｇ以上の最大細孔容積を有するもので、ＳｉＯ2 含有率が８０％以上のケイソウ土を用いる。このようなものの例としては、前記した稚内層の幌延町の珪藻泥岩がある。 The raw material has a bulk specific gravity of 1.25 to 2.35, 90% or more of the pores are in the range of a few nm to 100 nm in radius, and has a maximum pore volume of 0.02 m1 / g or more. Use diatomaceous earth with a content of 80% or more. An example of such is the diatomaceous mudstone of Horonobe-cho, Wakkanai Formation.
これを粉末にして用いるのであるが粉末のサイズは特に限定はしない。１０μｍ〜１ｍｍ程度が好適である。 Although this is used as a powder, the size of the powder is not particularly limited. About 10 μm to 1 mm is preferable.
この粉体を５ｋＮ以上の力で打錠する。打錠の方法は特別なものでなく通常の方法でよい。装置も通常の打錠装置でよい。５ｋＮという力は実験で求めたもので、理論から出したものではない。これ以下の力では、大きなサイズの細孔が所定量できなかったのである。
打錠には、直接打錠法と乾式造粒法があり、大量に処理するには後者が適している。前者は１００Ｎ以上の硬度までの調製が可能である。後者は５０Ｎ程度までの硬度が限界であり、ローラーコンパクターや多角ロールプレスを使用する。いずれも打錠圧は５ｋＮ以上であり、通常、５〜１２ｋＮで製造することができる。乾式造粒法の場合のロール圧縮圧は４〜１０ＭＰａが標準である。細孔半径領域を数十μｍ以上に広げるには、いずれの設備あるいは方法を用いても可能であるが、硬度で２０Ｎ以上とすることが望ましい。しかし、安価な機能性素材として提供するには天然ケイ酸質鉱物を原料に、５ｋＮ以上で打錠することにより数百ｎｍの細孔半径の細孔を付加することができる。５ｋＮ以下の場合には、付加した細孔半径の殆どが１００ｎｍ以下となる。打錠圧力の上限については、特に限定はないが、１５ｋＮ以上では硬度が１００Ｎ以上となる。細孔半径だけではなく、種々の用途に応じた硬度を選択することが必要である。
This powder is compressed with a force of 5 kN or more. The tableting method is not special and may be a normal method. The device may also be a normal tableting device. The force of 5 kN was obtained experimentally, not from theory. With a force less than this, a predetermined amount of large-sized pores could not be formed.
For tableting, there are a direct tableting method and a dry granulation method, and the latter is suitable for mass processing. The former can be prepared to a hardness of 100 N or more. The latter has a limit of hardness up to about 50 N, and uses a roller compactor and a polygonal roll press. In any case, the tableting pressure is 5 kN or more, and it can be usually produced at 5 to 12 kN. The roll compression pressure in the case of the dry granulation method is typically 4 to 10 MPa. In order to expand the pore radius region to several tens of μm or more, any equipment or method can be used, but the hardness is preferably 20 N or more. However, in order to provide it as an inexpensive functional material, pores having a pore radius of several hundred nm can be added by tableting with natural siliceous mineral at 5 kN or more. In the case of 5 kN or less, most of the added pore radius is 100 nm or less. The upper limit of the tableting pressure is not particularly limited, but at 15 kN or more, the hardness is 100 N or more. It is necessary to select not only the pore radius but also the hardness according to various applications.
本発明の新規多孔質体は、天然物起源であることから、共存微生物を滅菌するため、１００℃以上４００℃以下の温度で加熱処理を行ってもよい。効率的には１２０℃で２０分間直接加熱することで共存微生物の生菌は除去できるが、胞子などの休眠細胞を死滅させるためには４００℃で３０分程度の加熱処理を行なう方がより好適である。 Since the novel porous body of the present invention originates from natural products, it may be subjected to heat treatment at a temperature of 100 ° C. or higher and 400 ° C. or lower in order to sterilize the coexisting microorganisms. Although it is possible to remove viable bacteria of coexisting microorganisms by heating directly at 120 ° C. for 20 minutes efficiently, it is more preferable to heat at 400 ° C. for about 30 minutes in order to kill dormant cells such as spores. It is.
本発明多孔質体は、多孔質であること、２箇所に大きなピークを有する細孔分布を有していること等を使用して種々の用途に使用できる。勿論、このような特徴を利用しない用途であっても問題はない。即ち、本発明多孔質体は、用途は限定しないということである。 The porous body of the present invention can be used for various applications by being porous and having a pore distribution having large peaks at two locations. Of course, there is no problem even if the application does not use such features. That is, the use of the porous body of the present invention is not limited.
種々の用途の中でも特に有効なものについて以下に説明する。
まず、本発明多孔質体は、付加した細孔を利用した分子ふるいとして使用できる。分子ふるい作用は、表面荷電に依存せず有機物やミクロンサイズの生菌状態の細菌類や放線菌・糸状菌の胞子などが捕捉できる。
Of the various uses, those that are particularly effective will be described below.
First, the porous body of the present invention can be used as a molecular sieve using added pores. The molecular sieving action does not depend on the surface charge and can capture organic matter, micron-sized live bacteria, actinomycetes, filamentous fungi spores, and the like.
農業分野において、最も大きな問題は肥料、堆肥の多量施用と温暖化により土壌表面に肥料成分などが蓄積していることである。施設栽培においては、塩類濃度障害として知られている。この障害と線虫害や土壌伝染性病害との関連も示唆されている。本発明者らは、全国各地の濃度障害圃場の土壌を入手し、塩類濃度を電気伝導度（ＥＣ）で測定し、土壌に対して５重量％以下の本発明多孔質体を添加し、ＥＣを測定した。結果、同一圃場土壌において、ＥＣが０．８〜２．５までの範囲において処理前の固有ＥＣとＥＣ除去率とに明瞭な負の二次相関が認められた。実圃場における添加量は、圃場のＥＣに依存するが、作土層土壌との混合が均一に行われることが必要である。そのため土壌改良資材として１００ａに対して３０ｋｇ〜６０ｋｇ以上の添加が必要である。本発明に類する資材としてゼオライトが施用されているが、ゼオライトと比較して適用ＥＣ濃度範囲が広く、添加量を軽減でき、かつ、収穫量へのマイナス効果が認められない点等で優れている。 In agriculture, the biggest problem is the accumulation of fertilizer components on the soil surface due to large amounts of fertilizer and compost and global warming. In institutional cultivation, it is known as a salt concentration disorder. It has also been suggested that this disorder is related to nematode damage and soil-borne diseases. The present inventors obtain soils in concentration-impaired fields throughout the country, measure the salt concentration by electrical conductivity (EC), add 5% by weight or less of the porous body of the present invention to the soil, Was measured. As a result, in the same field soil, a clear negative secondary correlation was recognized between the intrinsic EC before treatment and the EC removal rate in the EC range of 0.8 to 2.5. The amount of addition in the actual field depends on the EC of the field, but it is necessary that the mixing with the soil in the soil is uniformly performed. Therefore, it is necessary to add 30 kg to 60 kg or more with respect to 100a as a soil improvement material. Zeolite is applied as a material similar to the present invention, but it is excellent in that the applicable EC concentration range is wide compared to zeolite, the amount added can be reduced, and no negative effect on the yield is observed. .
化成肥料原料の高騰により化学肥料の使用量が見直されようとしているが、土壌特性や灌水などによる流亡を計算し、多量の肥料が施肥されているのが現状である。省力化から、元肥として一度に多量施肥する農家も増えてきており、環境への肥料成分の流出には歯止めはかかっていない。肥料メーカーは、有機合成化合物によるコーティング技術を用いて除放性肥料などの開発を行っている。土壌中に存在しない有機合成化合物が肥料成分とともに施肥されることへの問題点は指摘されていないが、本来は避けるべきことあり、将来においては農薬以上の危険性も懸念される。 The amount of chemical fertilizer used is being revised due to soaring chemical fertilizer raw materials, but the current situation is that a large amount of fertilizer is applied by calculating the runoff due to soil characteristics and irrigation. Due to labor savings, an increasing number of farmers apply large amounts of fertilizer at once as the original fertilizer, and there is no stoppage on the outflow of fertilizer components to the environment. Fertilizer manufacturers are developing controlled-release fertilizers using coating technology with organic synthetic compounds. No problem has been pointed out that organic synthetic compounds that are not present in the soil are fertilized together with fertilizer components, but there are concerns that should be avoided in the future, and there are concerns over the dangers beyond agricultural chemicals in the future.
有機合成化合物によるコーティング技術を用いることなく、本発明の多孔質体の細孔内に水溶性肥料成分を捕捉し、分子ふるい効果により保持時間をもたせることで、除放性肥料として使用できる。肥料原体に対して、本発明の多孔質体を混合した。肥料原体が固体の場合、本発明の多孔質体を５重量％以上を混合することが必要である。混合量は肥料成分と溶出パターンに依存するため任意に調節することが可能である。５重量％以下の場合、混合が不均一となり除放性肥料としての特性を出すことが難しい。肥料原体が液体で固体肥料とする場合、本発明の多孔質体に対して、肥料原体を６０重量％以下を捕捉させる。好ましくは、２０重量％前後を捕捉させることにより、特に除放性肥料としての特性が強く発現する。６０重量％以上の場合、スラリー状となり、速効性肥料成分部分が大きくなる。これら技術は、肥料使用量を軽減することだけでなく、周辺環境への肥料成分の流出を軽減する。固体肥料中の水溶性成分である硝酸イオン、アンモニウムイオン、窒素化合物を初期の土壌水分が高い状態において、溶出した水溶性肥料成分を選択的に本発明の多孔質体細孔内に捕捉する。このことにより、肥料成分の流亡を防ぐことができる。栽培経過においては、灌水や根から代謝する根酸あるいは無機塩などを含む水溶液により、細孔から土壌中に脱離して除放性肥料として作用する。 Without using a coating technique with an organic synthetic compound, the water-soluble fertilizer component is captured in the pores of the porous body of the present invention, and the retention time is given by the molecular sieving effect, so that it can be used as a controlled release fertilizer. The porous body of the present invention was mixed with the fertilizer base. When the fertilizer raw material is solid, it is necessary to mix 5% by weight or more of the porous body of the present invention. The amount of mixing depends on the fertilizer component and elution pattern, and can be adjusted arbitrarily. When the amount is 5% by weight or less, mixing becomes uneven and it is difficult to obtain characteristics as a controlled release fertilizer. When the fertilizer base is liquid and solid fertilizer, 60% by weight or less of the fertilizer base is captured with respect to the porous body of the present invention. Preferably, by capturing around 20% by weight, particularly the characteristics as a controlled release fertilizer are strongly developed. In the case of 60% by weight or more, it becomes a slurry, and the fast-acting fertilizer component portion becomes large. These techniques not only reduce fertilizer usage, but also reduce the outflow of fertilizer components to the surrounding environment. The water-soluble fertilizer components that have been eluted with nitrate ions, ammonium ions, and nitrogen compounds, which are water-soluble components in the solid fertilizer, are selectively captured in the pores of the porous body of the present invention. This can prevent the fertilizer component from flowing away. In the course of cultivation, it is detached from the pores into the soil and acts as a release fertilizer by irrigation and an aqueous solution containing root acid or inorganic salt metabolized from the roots.
土壌だけでなく用水も同様にＥＣが問題であり、さらに、用水の場合には腐性微生物の増殖が収穫農産物の洗浄後の腐敗、生花の水挿しによる保存時の腐敗、作物育苗における水挿しによる発根過程での軟化腐敗の原因とされている。この対策として、殺菌剤（農薬）の使用が行なわれてきた。しかし、作物残留性の問題から、持続性の高い薬剤が使用されなくなってきたため、その対策が必要となってきた。用水の腐敗原因は、用水中に共存する微生物の栄養源となる炭素源、窒素源、リン酸源だけでなく植物体の切り口からの代謝物を栄養物として腐性微生物が摂取して、増殖することにより生じる。これらの微生物の栄養源となる成分あるいは微生物のいずれかを用水から除けば腐敗を防ぐことが可能となる。 EC is also a problem in water as well as soil, and in the case of water, the growth of rot microorganisms is caused by rot after washing of harvested agricultural products, rot during storage by inserting fresh flowers, and watering in crop seedlings. It is considered to be the cause of softening rot in the rooting process. As a countermeasure, a bactericide (agricultural chemical) has been used. However, because persistent crops are no longer used due to the problem of crop persistence, countermeasures have become necessary. The cause of spoilage of irrigation water is not only carbon sources, nitrogen sources, and phosphate sources, but also metabolites from the cut end of the plant as nutrients for microorganisms that coexist in the irrigation water. It is caused by doing. It is possible to prevent spoilage by removing any of these microorganisms as nutrient sources or microorganisms from the water.
用水用等には、前記した通り加熱処理を行なうのがよい。
加熱処理した本発明の多孔質体を用水中に添加あるいは、本発明の多孔質体を充填した層を通過させることにより、用水中の栄養分だけでなく、植物体が代謝・排出した栄養分も含め、陽イオンだけでなく、分子ふるい作用により陰イオン、有機物にさらに微生物も捕捉することにより、本発明の多孔質体表面で藻類を含む微生物を増殖させることにより、水中での汚染微生物の増殖を阻止できる。阻止期間は、添加量、栄養分量に依存するが藻類の表面増殖を指標として、本発明の多孔質体の追加あるいは交換を行うことが必要である。露地栽培、施設栽培を問わず低温日照不足や施設栽培においては、夜間の低温過湿において病害の発生が顕著となってきている。作物の生育が遅滞する状況における低温過湿が発病を助長している。このため、予防的に農薬の散布が行われているが、植物体の生育が停滞しているなかでの農薬散布は薬害を伴う場合が多く、予防的効果を発現させることが最近の気温変化に対応できていないのが実情である。
For irrigation and the like, it is preferable to perform the heat treatment as described above.
By adding the heat-treated porous body of the present invention to the working water or passing it through the layer filled with the porous body of the present invention, not only the nutrients in the working water but also the nutrients metabolized and excreted by the plant body are included. In addition to capturing not only cations but also anions and organic substances by molecular sieving action, microorganisms containing algae are grown on the surface of the porous body of the present invention, thereby increasing the growth of contaminating microorganisms in water. I can stop. Although the inhibition period depends on the amount of addition and the amount of nutrients, it is necessary to add or replace the porous material of the present invention using the surface growth of algae as an index. In low temperature sunshine shortage and facility cultivation regardless of open field cultivation or institutional cultivation, the occurrence of diseases has become remarkable due to low temperature overhumidity at night. Low temperature overhumidity in the situation where the growth of crops is delayed is conducive to the disease. For this reason, spraying of agricultural chemicals is carried out prophylactically, but spraying of agricultural chemicals while plant growth is stagnant is often accompanied by phytotoxicity. The fact is that it is not possible to cope with.
本発明者らは、作物の生理学的な検討と施設栽培における圃場内での湿度変化を主に調査検討を行った結果、圃場内の湿度を圃場内温度が低下する前に除去することにより、作物の生育においては地上部の生育が回復し、そのことにより地上部病害においても軽減できることを見出し、圃場内湿度を効果的に除去する方法を開発した。本発明の加熱処理多孔質体の中から、粒子径が０．１ｍｍ以下の粒子を集じんした。粒子径が０．１ｍｍよりも大となると噴霧が困難となるだけでなく、降下速度が速くなり、作物の葉の間や果実周辺まで拡散することなく降下する。但し、０．０１ｍｍ以下の場合には、拡散には優れているが、降下速度が低下するため、圃場内湿度を低下させる効果としては低下する。０．０５ｍｍ〜０．１ｍｍの範囲の粒子径が望ましい。施設栽培圃場において、この粒子を気相中へ上向流に乗せて、噴霧することにより、湿度の高い上部からの雰囲気湿度を急激に低下させ、圃場全体の天井部から自然対流により、ゆっくりと拡散しながら降下を開始する。このことにより、果実や葉表面の余剰水分とともに栄養分も捕捉する。吸湿、吸水時に栄養分や微生物の胞子なども付着させて降下する。結果、湿度の低下だけでなく圃場雰囲気内の有機物、微生物（胞子）量も低下させる。湿度の低下により、低温であっても植物体へのストレスが軽減される。また、果実表面や葉先での露結を防止する。 As a result of mainly investigating the humidity change in the field in the physiological examination of the crop and the cultivation in the facility, the present inventors have removed the humidity in the field before the temperature in the field decreases, In the growth of crops, we found that the growth of the above-ground part was recovered, and that it was possible to reduce even the above-ground disease, and developed a method for effectively removing the humidity in the field. From the heat-treated porous body of the present invention, particles having a particle diameter of 0.1 mm or less were collected. When the particle diameter is larger than 0.1 mm, not only spraying becomes difficult, but also the descending speed becomes fast, and it descends without spreading between the leaves of the crops and around the fruits. However, in the case of 0.01 mm or less, although it is excellent in diffusion, since the descending speed is reduced, the effect of reducing the humidity in the field is reduced. A particle size in the range of 0.05 mm to 0.1 mm is desirable. In a facility-cultivated field, this particle is put in an upward flow into the gas phase and sprayed to rapidly reduce the atmospheric humidity from the upper part of the humidity, and slowly from the ceiling of the entire field by natural convection. Start descent while spreading. This captures nutrients as well as excess water on the fruit and leaf surfaces. At the time of moisture absorption and water absorption, nutrients and microbial spores also adhere and fall. As a result, not only the humidity is reduced, but also the amount of organic matter and microorganisms (spores) in the field atmosphere is reduced. The decrease in humidity reduces the stress on the plant even at low temperatures. It also prevents condensation on the fruit surface and leaf tips.
本発明の多孔質体には以下のような大きな効果がある。
（１） 本発明多孔体は、天然ケイ酸化合物であるため、陽イオンだけでなく、陰イオンや有機物、さらにはミクロンサイズの微生物に対しても作用するため、分子ふるい機能を有する。
（２） 本発明多孔質体を空気中で滞留時間を長く、かつ、植物体間を浮遊させることにより付着微生物や有機物の不活性化ができる。
（３） 植物体の生育には影響を与えない創傷作用により、植物体表面の余剰水分、有機物、微生物を吸着することもできる。
（４） 本発明の多孔質体を濃度障害圃場土壌に対して、一定量を添加混合することにより、栽培可能範囲のＥＣ（電気伝導度：ｍＳ／ｃｍ）濃度まで低下させる土壌改良資材として効果がある。
（５） これにより、肥料製造、堆肥製造に使用することにより肥料成分の流亡を軽減できる（肥料原体および堆肥原料を本発明の多孔質体を混合）。
（６） 固体肥料原体に本発明多孔質体を１０重量％以上を混合することにより除放性固体肥料の製造ができる。
（７） 本発明多孔質体を１００℃以上４００℃以下の温度で加熱処理することにより、各種有機物および微生物を保持できる水保存材が得られる。この素材を生花および農作物の挿し木時の用水に添加することにより、一定期間、用水の腐敗を防止する。
（８） 本発明多孔質体を前述の方法で加熱処理し、粒子径が０．１ｍｍ以下を集じんし、これを気相中に噴霧することにより、施設圃場内の湿度を急激に低下させることだできる。農業現場において、湿度除去材としての実用性が認められた。
The porous body of the present invention has the following great effects.
(1) Since the porous body of the present invention is a natural silicate compound, it acts not only on cations but also on anions, organic substances, and even micron-sized microorganisms, and thus has a molecular sieving function.
(2) The porous body of the present invention has a long residence time in air and can inactivate adhering microorganisms and organic substances by floating between plants.
(3) Surplus moisture, organic matter, and microorganisms on the surface of the plant body can be adsorbed by a wound action that does not affect the growth of the plant body.
(4) The porous material of the present invention is effective as a soil improvement material that reduces the EC (electric conductivity: mS / cm) concentration within the cultivatable range by adding and mixing a certain amount of the porous material of the present invention to the soil with a concentration disorder. There is.
(5) Thereby, the runoff of the fertilizer component can be reduced by using it for fertilizer manufacture and compost manufacture (the fertilizer raw material and compost raw material are mixed with the porous body of the present invention).
(6) A controlled-release solid fertilizer can be produced by mixing 10% by weight or more of the porous body of the present invention with a solid fertilizer base.
(7) By heat-treating the porous body of the present invention at a temperature of 100 ° C. or higher and 400 ° C. or lower, a water storage material capable of holding various organic substances and microorganisms can be obtained. By adding this material to the water used when cutting fresh flowers and crops, the water is prevented from decaying for a certain period of time.
(8) The porous body of the present invention is heat-treated by the above-mentioned method, and the particle diameter is collected to 0.1 mm or less and sprayed into the gas phase to rapidly reduce the humidity in the facility field. I can do it. Practicality as a moisture removal material was recognized in the agricultural field.
本発明を以下に示す実施例に基づきより詳細に説明する。
実施例１
幌延地区の珪藻泥岩（珪質泥岩）を原料に用いた。打錠機を用いて、直接打錠法により半連続的に処理を行った。打錠圧力は１０ｋＮで行った。打錠処理後、粉砕し、原料との細孔分布の比較を行った。原料に対する比較対照として、市販秋田層ケイソウ土（対照１）、市販ゼオライト（対照２）を用い細孔分布を測定した。これらの結果をまとめて図１に示した。
The present invention will be described in more detail based on the following examples.
Example 1
Diatomite (siliceous mudstone) from the Horonobe area was used as a raw material. Semi-continuous processing was performed by a direct tableting method using a tableting machine. The tableting pressure was 10 kN. After tableting, the mixture was pulverized and the pore distribution compared with the raw material was compared. As a comparative control for the raw materials, the pore distribution was measured using commercially available Akita-layer diatomaceous earth (Control 1) and commercially available zeolite (Control 2). These results are summarized in FIG.
原料比較において、幌延地区の珪藻泥岩は市販のケイソウ土、ゼオライトと比較して細孔半径は類似するが細孔容積量で大きく異なる（ピークの高さが高い）。加圧処理したものと原料を比較すると細孔半径が小さい領域で両者はほぼ一致するが、打錠加処理には空隙量の多い細孔の半径が大きくなっているのがはっきりと分かる。 In the raw material comparison, diatomaceous mudstone in Horonobe district has a similar pore radius compared to commercially available diatomaceous earth and zeolite, but greatly differs in pore volume (high peak height). Comparing the pressure-treated material with the raw material, the two are almost the same in the region where the pore radius is small, but it can be clearly seen that the radius of the pore having a large amount of voids is increased in the tableting treatment.
実施例２（塩類濃度除去）
千葉県のトマト栽培農家の圃場土壌を用いて、塩類濃度をＥＣメーターで測定した。塩類濃度の異なる土壌に対して、２０重量％の本発明多孔質体を混合し所定の方法でＥＣを測定した。結果を図２に示した。混合して直ちに加水した方法での測定において、明瞭な二次相関で高ＥＣにおいても塩類除去能を示した。
Example 2 (Removal of salt concentration)
The salt concentration was measured with an EC meter using the field soil of a tomato farmer in Chiba Prefecture. 20% by weight of the porous body of the present invention was mixed with soil having different salt concentrations, and EC was measured by a predetermined method. The results are shown in FIG. In the measurement by the method of adding water immediately after mixing, the salt removal ability was shown even at high EC with a clear secondary correlation.
実施例３（肥料成分の肥効期間）
有機入り複合肥料（窒素：６％、リン酸：８％、カリ：６％）、複合液肥（窒素：６％、リン酸：８％、カリ：４％）を用い、本発明多孔質体を有機入り複合肥料に対して１０重量％を添加、混合した。比較例として、市販ゼオライトを同様に１０重量％を添加、混合した。複合液肥を本発明多孔質体に対して４０重量％を添加、混合して一昼夜静置してから使用した。比較例として、市販ゼオライトに対しても同様に４０重量％を添加、混合して一昼夜静置してから使用した。２０Ｌ容積のプランターを使用して、イチゴ苗（とよのか）３株／プランターを各３連で栽培した。施肥設計は慣行の１／２の窒素量とした。赤玉土細粒にピートモスを４：１で混合した用土１５ｋｇに対して、窒素３ｇとなるように肥料を加えた。対照として、無添加の肥料を用いた。複合液肥は、用土に対して必要な水に希釈して調整を行った。９０日間、施設内で栽培を行い、収量および根量を比較することにした。結果を第１表に示した。長期間にわたり肥料効果が認められた。
Using the organic fertilizer (nitrogen: 6%, phosphoric acid: 8%, potash: 6%) and compound liquid fertilizer (nitrogen: 6%, phosphoric acid: 8%, potash: 4%) 10 wt% was added to and mixed with the organic fertilizer. As a comparative example, 10% by weight of commercially available zeolite was similarly added and mixed. The composite liquid fertilizer was used after adding 40% by weight to the porous body of the present invention, mixing and allowing to stand overnight. As a comparative example, 40% by weight was similarly added to a commercial zeolite, mixed and allowed to stand for a whole day and night. Using a planter with a capacity of 20 L, 3 strains of strawberry seedlings (Toyooka) / planter were cultivated in triplicate. The fertilization design was set to 1/2 the conventional amount of nitrogen. Fertilizer was added to 3 g of nitrogen with respect to 15 kg of soil in which peat moss was mixed 4: 1 with red jade soil fine grains. As a control, additive-free fertilizer was used. The complex liquid fertilizer was adjusted by diluting it with the necessary water for the soil. It was decided to cultivate in the facility for 90 days and compare the yield and root mass. The results are shown in Table 1. Fertilizer effect was observed for a long time.
実施例４（水保存剤）
本発明の多孔質体を１９０℃で３０分加熱処理を行った。この処理物を用いて、キクの生花１００株の保存用水に１ｇ／Ｌ添加した。対照は添加せずそのまま用水に挿した。挿し木後の保存性を比較した。結果を表２に示した。対照と比較して腐敗率が非常に少ないことが分かった。
The porous body of the present invention was heat-treated at 190 ° C. for 30 minutes. Using this treated product, 1 g / L was added to storage water for 100 chrysanthemum flowers. The control was not added and was inserted into the water as it was. The preservability after cutting was compared. The results are shown in Table 2. It was found that the decay rate was very low compared to the control.
また、トルコキキョウの腋芽、トマトの腋芽、キュウリの剪定葉を同熱処理物１ｇ／Ｌ添加した用水中で各５０株の発根処理を行った。対照は添加せずそのまま用水に挿した。発根率を比較した 。結果を表３に示した。本発明多孔質体を用いたものでは非常に高い発根率を示した。
実施例５（除湿材）
宮崎県内のキュウリ（品種：エクセレント）施設栽培圃場（２０ａと２６ａの同型施設）において、 粉体散布機を用いて圃場内湿度が高くなる一月から二月において、圃場を閉める前に本発明多孔質体を２００℃で４０分処理を行い０．１ｍｍパスの粒子を集塵して使用した。調製した本発明化合物を１００ｇ／１０ａを１回／７日を行い、圃場内の湿度の変化を無散布の同型ハウスと比較した。湿度は散布前と翌朝の密閉状態での湿度を測定した。結果を表４に示した。比較例と比べて１０％程度湿度が低下した。
In the cucumber (variety: Excellent) facility cultivation field in Miyazaki Prefecture (the same type facility of 20a and 26a), the present invention is used before closing the field in January to February when the field humidity becomes high using a powder spreader. The material was treated at 200 ° C. for 40 minutes to collect 0.1 mm pass particles for use. 100 g / 10a of the prepared compound of the present invention was performed once every 7 days, and the humidity change in the field was compared with a non-spray type house. Humidity was measured in a sealed state before spraying and in the next morning. The results are shown in Table 4. The humidity decreased by about 10% compared to the comparative example.
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