JP2006055160A - Rare earth chelate compound-added agricultural bed soil and method for producing the same - Google Patents

Rare earth chelate compound-added agricultural bed soil and method for producing the same Download PDF

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JP2006055160A
JP2006055160A JP2005159783A JP2005159783A JP2006055160A JP 2006055160 A JP2006055160 A JP 2006055160A JP 2005159783 A JP2005159783 A JP 2005159783A JP 2005159783 A JP2005159783 A JP 2005159783A JP 2006055160 A JP2006055160 A JP 2006055160A
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rare earth
chelate compound
floor soil
earth chelate
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Byun Yupu Chan
ユプ チャン、ビュン
Je-Sun Kim
キム、ジェ−スン
Je-Yon Choo
チョー、ジェ−ヨン
Sun Gon Wi
ゴン ウィ、スン
Jin-Hon Kim
キム、ジン−ホン
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Korea Atomic Energy Research Institute KAERI
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/10—Growth substrates; Culture media; Apparatus or methods therefor based on or containing inorganic material
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/30—Growth substrates; Culture media; Apparatus or methods therefor based on or containing synthetic organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds

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  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Cultivation Of Plants (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide rare earth compound-added agricultural bed soil of functional and environmentally-friendly type, and to provide a method for producing the same. <P>SOLUTION: This agricultural bed soil is obtained by mixing a rare earth chelate compound with ordinary bed soil in a sole or mixed form, wherein the rare earth chelate compound is obtained by forming chelate bonding of one or more organic acid salts selected from various kinds of organic acid salts to one or more substances selected from rare earth elements. The rare earth chelate-added agricultural bed soil accelerates growth of a crop, decreases a nitrate-nitrogen content in the crop, decreases an amount of a residual agrochemical therein, further decreases accumulation of the rare earth element in the soil by increasing an absorption and translocation ratio of the rare earth element into a plant body, and furthermore accelerates growth of a plant. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、希土キレート化合物を添加した機能性環境親和型の農業用床土及びその製造方法に関するものである。より詳細には、作物の育苗で最も基本になる床土を製造するに当たり、各種有機酸塩から選択された一つ以上の有機酸塩に希土類から選択された一つ以上の物質をキレート結合させて得た希土キレート化合物を、単独または混合形態で通常の床土に混合して得られる農業用床土及びその製造方法に関するものである。   The present invention relates to a functional environmentally friendly agricultural floor soil to which a rare earth chelate compound is added and a method for producing the same. More specifically, in the production of bed soil, which is the most basic for raising seedlings of crops, one or more substances selected from rare earths are chelated to one or more organic acid salts selected from various organic acid salts. It is related with the agricultural floor soil obtained by mixing the rare earth chelate compound obtained by mixing with normal floor soil individually or in the mixed form, and its manufacturing method.

農業技術の発達によって農作物の周年栽培が可能になるに伴って相対的に床土の使用量も増加している。栽培方法及び育苗移植方法が普及し始めた初期には、生産量を高めることに目的をおいていたが、現在の栄農方法は商業農に発達することにより、床土の重要性が再認識されるようになり、育苗方法も改善されてきた。育苗は、大部分人為的な環境下の狭い空間で密植状態で行われるので、作物個体間で必然的に水分・光・養分の競合が起きる。したがって、作物の地下部を構成する床土が優良であるかどうかが育苗の成敗を決定する。このような床土の基本条件は下記のように整理できる。   With the development of agricultural technology, the use of floor soil has increased relatively as the annual cultivation of crops becomes possible. In the early days when cultivation methods and seedling transplanting methods began to spread, the goal was to increase production, but the current Sakae method developed into commercial agriculture, reaffirming the importance of floor soil. As a result, seedling raising methods have been improved. Since seedlings are mostly densely planted in a narrow space under an artificial environment, competition between water, light and nutrients inevitably occurs among crop individuals. Therefore, the success or failure of raising seedlings is determined by whether or not the floor soil constituting the underground part of the crop is excellent. The basic conditions for such floor soil can be summarized as follows.

第一に、病虫害がない土壌でなければならない。
第二に、排水性・通気性・保水性等の物理性が良くなければならない。
第三に、化学性が良いもので、酸度・塩濃度・無機養分等の変化が少ないものでなくてはならない。
第四に、調製が容易で再現性があるものが求められる。 First, it must be soil free from pests.
Second, physical properties such as drainage, breathability, and water retention must be good.
Thirdly, it must have good chemical properties and little change in acidity, salt concentration, inorganic nutrients, etc.
Fourth, what is easy to prepare and reproducible is required.

このように、作物の生産性向上のための農業用床土に対して絶え間ない研究開発が行なわれている。例を挙げると、「育苗用床土材料としてモミガラの加工方法及びそれを利用して製造した混合床土」という名称で「膨軟化モミガラの粒子を所定の大きさ以下になるように調節する工程と、粒子を調節した膨軟化モミガラに尿素200mg/Ｌ乃至600mg/Ｌと砕き促進剤のコオラン（商標）、そして所定量の水分を200mL/L乃至400mL/Lを投入して砕く工程とを経て製造される床土材料と、前記の砕いたモミガラに適正副材料を適正比率で混合して製造される混合床土」が開示されている（特許文献１参照）。しかし、該発明は、通常のモミガラを特定な大きさにして農業用床土の一構成要素として使用する方法を提供したにすぎない。   In this way, continuous research and development has been conducted on agricultural soil for improving crop productivity. For example, the process of adjusting the particles of swollen-softening rice bran to a predetermined size or less under the name of “processing method of rice straw as a seedling material for raising seedlings and mixed bed soil produced using the same” And the step of crushing by adding 200 mg / L to 600 mg / L of urea, Koolane (trademark) as a crushing accelerator, and 200 mL / L to 400 mL / L of a predetermined amount of water to a softened rice cracker with controlled particles. "A mixed floor soil manufactured by mixing an appropriate sub-material in an appropriate ratio with the above-ground ground material to be manufactured" (see Patent Document 1). However, the invention only provided a method of using a normal rice bran to a specific size and as a component of agricultural floor soil.

一方、「微細銀粒子またはコロイダルシルバーをゼオライトに吸着させた殺菌及び生育促進植物用床土」という名称で「ナノ(Nano)粒子の銀を精製水に均一に分散させた銀溶液または電気分解で作られたコロイダルシルバー(粒径1-4ナノメータ)をゼオライトに吸着させた作物栽培用床土」を開示している（特許文献２参照）。該発明は、銀が持っている殺菌力とゼオライトが持っている生育促進機能とを利用して、病害と栄養欠乏に露出しやすい作物の若い苗を育てる専用人工土壌を提供するもので、残留毒性や薬害がまったくない状態で、様々な菌株に使用することにより、親環境的に作物を栽培できる作用効果があるだけである。   On the other hand, under the name of “floor soil for sterilization and growth promoting plants in which fine silver particles or colloidal silver is adsorbed on zeolite”, a silver solution in which nano particles of silver are uniformly dispersed in purified water or electrolysis is used. “Crop cultivation floor soil in which produced colloidal silver (particle size: 1-4 nanometer) is adsorbed on zeolite” is disclosed (see Patent Document 2). The present invention provides a dedicated artificial soil for growing young seedlings of crops that are easily exposed to diseases and nutritional deficiencies by utilizing the bactericidal power of silver and the growth promoting function of zeolite. By using it for various strains in the state of no toxicity and no phytotoxicity, it only has the effect of cultivating crops environmentally.

一方、希土(rare earth, RE)というのは、漢字の示す通り地球上に希少に存在する珍しくて貴重な土壌という意味である。元素周期律表の原子番号５７のランタン(La)からルテチウム(Lu)まで１５種の元素をひとまとめにしてランタノイドと呼び、原子番号２１のスカンジウム(Sc)と３９のイットリウム(Y)を加えた合計１７個の元素をまとめて希土類(rare earth elements, REE)と呼ぶ。   On the other hand, rare earth (RE) means rare and precious soil that exists rarely on the earth as indicated by kanji. The 15 elements from the lanthanum (La) of atomic number 57 to lutetium (Lu) in the periodic table are collectively called lanthanoids, and the sum of scandium (Sc) of atomic number 21 and yttrium (Y) of 39 The 17 elements are collectively called rare earth elements (REE).

このような特徴を有する希土類は、最近、機能性材料として応用範囲が拡大され、超伝導半導体、高密度記憶素子、レーザー、特殊合金剤、精油触媒剤、特殊ガラス、新セラミック、永久磁石、ＴＶブラウン管、蛍光ランプ等の新素材先端製品の生産に利用されないところがないくらいの物質であり、中国が希土類の世界最大資源国として独歩の位置にある輸出国であり、日本はその世界最大の消費国である。韓国は年間約1,250万ドル(1997年)相当の希土類金属を輸入して利用している。このような希土類金属の工業的利用とは異なり、農業での利用は活発ではない方であったが、最近、中国を中心に農業分野の応用研究が活発になされている。希土類金属は植物の青色光吸収率を高め、光合成作用を促進して、澱粉類分解酵素の活力を高め、種子発芽を促進させる一方、保湿機能が強力で農作物が干ばつに耐える能力が増加されると報告されている。特に、植物体の各種酵素及び生理活性物質、ホルモン等が活性促進され、量的、質的生長促進を通じた生産量増加と品質向上、耐病性及び耐環境性増進、農薬残留量及び硝酸塩の降下効果が顕著なことが明らかにされた。   Rare earths with these characteristics have recently been expanded as functional materials, such as superconducting semiconductors, high-density memory elements, lasers, special alloying agents, essential oil catalyst agents, special glasses, new ceramics, permanent magnets, TVs. It is a substance that has never been used for the production of cutting-edge products such as cathode ray tubes and fluorescent lamps. China is an exporter that has a position as the world's largest source of rare earths. Japan is the world's largest consumer. It is. South Korea imports and uses rare earth metals worth approximately $ 12.5 million (1997) annually. Unlike such industrial use of rare earth metals, the use in agriculture was less active, but recently, applied research in the agricultural field has been actively conducted mainly in China. Rare earth metals increase the blue light absorption rate of plants, promote photosynthetic action, increase the activity of starch degrading enzymes, promote seed germination, while increasing moisturizing function and the ability of crops to withstand drought It is reported. In particular, the activity of various plant enzymes, bioactive substances, hormones, etc. is promoted, increasing production and quality through promotion of quantitative and qualitative growth, disease resistance and environmental resistance, pesticide residue and nitrate drop It was revealed that the effect was remarkable.

硝酸塩の場合、ヒトがこれを多量に摂取すると胃で亜硝酸塩に還元された後、血液中のヘモグロビンと結合してメトヘモグロビン(methemoglobin)を形成するため、血液の酸素運搬能力が低下し、特に乳児の場合には、青色症(blue baby syndrome)を起こし、唾液に存在するエス．エピデルミデス(S. epidermides) 等の各種細菌によって、亜硝酸塩に還元された後、食品中に含まれているアミン類と反応してN-ニトロサミン(nitrosamine)が生成され得る。このN-ニトロサミンは、強力な発癌性がある物質として報告されている。合わせて、硝酸塩の過多摂取は甲状腺肥大の原因になる。ヒトの硝酸塩摂取量の85％以上が野菜を通じて、残りは飲み水等を通して摂取されていることが知られていて、各国別の野菜を通じた硝酸塩摂取量は、ドイツの場合72.4％、米国75.0％、日本89.9％であることが報告されている。韓国人は野菜の摂取量が日本より多く、野菜を通じた硝酸塩の摂取量もさらに多いと推定されていて、韓国人の一日の硝酸塩摂取量はFAO/WHOの一日摂取許容量(ADI, Acceptable Daily Intake)219mgを1.8?3.4倍も超過しているという報告がある。   In the case of nitrate, when it is consumed in large quantities by humans, it is reduced to nitrite in the stomach and then combined with hemoglobin in the blood to form methemoglobin. In the case of infants, S. is present in saliva causing blue baby syndrome. After being reduced to nitrite by various bacteria such as S. epidermides, N-nitrosamine can be produced by reacting with amines contained in food. This N-nitrosamine has been reported as a potent carcinogenic substance. In addition, excessive nitrate intake causes thyroid hypertrophy. It is known that over 85% of human nitrate intake is taken through vegetables and the rest is taken through drinking water, etc. The nitrate intake through vegetables by country is 72.4% in Germany and 75.0% in the US Japan is reported to be 89.9%. Koreans are estimated to have higher intakes of vegetables than in Japan and even higher intakes of nitrates through vegetables.The daily intake of nitrates by Koreans is the FAO / WHO daily intake allowance (ADI Acceptable Daily Intake) is reported to exceed 219mg by 1.8 to 3.4 times.

最近になって、環境農業と安全農産物に対する国民的な関心が高まり2000年以後、韓国内でも希土類を利用した環境営農資材の供給が一部なされている。これらは主に、ちしゃのような作物の水耕栽培に微量に利用され、最近では一般露地土壌にも相当量処理されている。この過程で幾つかの深刻な副次的影響(side effect)の発生があり得ると予想される。即ち、現在一部で利用されている希土類営農資材は、不溶性の酸化物形態である希土鉱物を一部水溶性を持った塩化物(chloride form)または窒酸化物(nitrate form)に合成して利用しているが、これらは土壌生態系内に好ましくない影響を与え得る。例えば、Cl-は土壌溶液中で塩類集積と共に植物の養分吸収を阻害し得、NO3 -もまたCl-と類似な土壌内での行動を見せるだけではなく、それ自体が硝酸塩の母胎になり得るため、可能なかぎりこれら使用を少なくすることが好ましいと報告されている。 Recently, public interest in environmental agriculture and safe agricultural products has increased, and since 2000, the supply of environmental farming materials using rare earths has been partially made in Korea. These are mainly used in a small amount for hydroponics of crops such as chisha, and recently, a considerable amount is also treated on general open soil. It is expected that some serious side effects may occur during this process. In other words, rare earth farming materials that are currently used in part synthesize rare earth minerals, which are insoluble oxide forms, into partially water-soluble chloride or nitrate forms. However, these can adversely affect the soil ecosystem. For example, Cl − can inhibit plant nutrient absorption along with salt accumulation in soil solution, and NO 3 − not only shows similar behavior in soil as Cl − , but also becomes a mother of nitrate. It is reported that it is preferable to reduce these uses as much as possible.

また、従来の農業用床土は、膨脹性粘土鉱物(ゼオライト、パーライト)、ピート、有機窒肥料等を単純に混合して、幼苗期に植物体を機械的に支持する役割に限定した側面が強く、作物生育に対する機能的役割において不備な点があった。   In addition, conventional agricultural floor soil has an aspect that is limited to the role of mechanically supporting plants during the seedling stage by simply mixing inflatable clay minerals (zeolite, pearlite), peat, organic nitrogen fertilizer, etc. Strong and deficient in the functional role for crop growth.

したがって、本発明者らは、前記したような床土の基本的な機能を有しながら、作物生育に優れ、農薬残留量を減少させられる床土を提供するために鋭意研究した結果、希土類を特定形態にして床土に混合することにより、その目的を達成して本発明を完成した。即ち、本発明者らは、前記の問題を解決するためCl-やNO3 -による土壌生態系の副作用を減らして、植物体への吸収が有利な特定有機酸塩を利用して希土類元素をキレーションさせて得られる希土キレート化合物を混合した農業用床土を提供することにより、幼苗期植物体の旺盛な養分吸収過程で希土元素が植物体内へ吸収移動され、既存の塩化物及び硝酸塩形態の希土粉末及び液肥より植物体内への吸収移行量が多く、希土元素の土壌蓄積を減少させることにより土壌生態系の安定性問題を解消し、合わせて植物体内で硝酸態窒素の形成に大きく寄与することになる硝酸還元酵素(nitrate reductase enzyme)に影響を与え、体内硝酸態窒素の蓄積を低減させ作物の生育促進及び農薬残留量の減少効果を確認することにより本発明を完成した。
大韓民国特許出願公開第２００１−１７７４６号 大韓民国特許出願公開第２００４−５０２５８号 Therefore, the present inventors have conducted intensive research to provide a bed soil that has the basic functions of a bed soil as described above, has excellent crop growth, and can reduce the residual amount of agricultural chemicals. By mixing with floor soil in a specific form, the object was achieved and the present invention was completed. That is, the present inventors have, Cl order to solve the above problems - or NO 3 - by reducing the by side effects of soil ecosystem, the absorption by utilizing the advantageous specific organic acid salts rare earth element to a plant By providing agricultural soil with mixed rare earth chelate compounds obtained by chelation, rare earth elements are absorbed and transferred into the plant during the vigorous nutrient absorption process of the seedling plant, and existing chlorides and nitrates The amount of absorption and transfer into the plant body is higher than that of the rare earth powder and liquid fertilizer, which reduces the soil accumulation of rare earth elements and eliminates the stability problem of the soil ecosystem, together with the formation of nitrate nitrogen in the plant body The present invention was completed by confirming the effects of nitrate reductase enzyme, which contributes greatly to the growth of the plant, reducing the accumulation of nitrate nitrogen in the body, promoting the growth of crops, and reducing the residual amount of agricultural chemicals. .
Korean Patent Application Publication No. 2001-17746 Republic of Korea Patent Application Publication No. 2004-50258

本発明の目的は、前記のような従来の農業用床土及び希土類元素の農家使用過程で発生し得る様々な問題点である、露地土壌内への希土類元素の蓄積、希土類元素の植物体への低い吸収移行率、現在利用されている希土類元素の液肥及び粉末から出るCl-及びNO3 -との副作用の解消と合わせて、作物の生育促進、作物の硝酸態窒素吸収抑制及び作物中農薬残留量の減少効果がある、農業用床土及びその製造方法を提供することである。 The object of the present invention is the accumulation of rare earth elements in the open soil, the rare earth element plant, which are various problems that can occur in the conventional agricultural floor soil and rare earth element farm use processes as described above. low absorption migration rates of, leaving the liquid fertilizer and powders of rare earth elements that are currently utilized Cl - and NO 3 - in conjunction with elimination of side effects and, growth promotion of crops, crop nitrate nitrogen absorption suppressing and crops in agricultural chemicals An object of the present invention is to provide agricultural floor soil and a method for producing the same, which has an effect of reducing residual amount.

前記目的を達成するために、本発明は、各種有機酸塩から選択された一つ以上の有機酸塩に希土類から選択された一つ以上の物質をキレート結合させて得た希土キレート化合物を、単独または混合形態で通常の床土に混合して得られる農業用床土を提供する。   To achieve the above object, the present invention provides a rare earth chelate compound obtained by chelating one or more substances selected from rare earths to one or more organic acid salts selected from various organic acid salts. Agricultural floor soil obtained by mixing with ordinary floor soil alone or in a mixed form is provided.

また、本発明は、EDTA(ethylene diamine tetra acetate)塩、クエン酸塩、酒石酸塩等のような有機酸塩から一つを選択して、それを水溶液にする工程と、前記水溶液に希土類から選択された一物質を一定当量で加えてキレート結合を形成させる工程と、前記反応液で希土キレート化合物結晶を析出させ、それをろ過して結晶を得る工程と、前記得られた希土キレート化合物を一定比率で床土に混合する工程とからなる農業用床土の製造方法を提供する。   The present invention also includes a step of selecting one from an organic acid salt such as EDTA (ethylene diamine tetra acetate) salt, citrate, tartrate, and the like, and selecting the aqueous solution from a rare earth. A step of forming a chelate bond by adding a certain amount of the obtained substance, a step of precipitating a rare earth chelate compound crystal in the reaction solution and filtering it to obtain a crystal, and the obtained rare earth chelate compound The present invention provides a method for producing agricultural floor soil comprising the step of mixing the soil with the floor soil at a constant ratio.

以下、本発明をより詳細に説明する。
本発明の農業用床土は、土壌、腐葉土及び有機質肥料が共に混合された通常の床土材料に、各種有機酸塩から選択された一つ以上の有機酸塩に希土類から選択された一つ以上の物質をキレート結合させて得た希土キレート化合物を、単独または混合形態で混合して得ることができる。 Hereinafter, the present invention will be described in more detail.
The agricultural floor soil of the present invention is a normal floor soil material in which soil, humus and organic fertilizer are mixed together, and one or more organic acid salts selected from various organic acid salts are selected from rare earths. The rare earth chelate compound obtained by chelating the above substances can be obtained alone or mixed in a mixed form.

前記有機酸塩は、EDTA(ethylene diamine tetra acetate)塩、クエン酸塩、酒石酸塩から選択することが好ましい。   The organic acid salt is preferably selected from EDTA (ethylene diamine tetra acetate) salt, citrate salt, and tartrate salt.

前記通常の床土材料に希土キレート化合物を添加する比率は、0.05乃至100mg/kgとすることが好ましい。   The ratio of adding the rare earth chelate compound to the normal floor soil material is preferably 0.05 to 100 mg / kg.

添加比率が、0.05mg/kg以下になると希土元素がほとんど植物体内に吸収移行されず、希土キレート化合物添加による作用効果がほとんど現われず、添加比率を100mg/kg以上にすると希土元素が植物体へ吸収移行されて残った希土元素が土壌に蓄積されるだけでなく、追加添加による付加的な効果を示すものではないため、好ましくない。   When the addition ratio is 0.05 mg / kg or less, rare earth elements are hardly absorbed and transferred into the plant body, and the effect of adding rare earth chelate compounds hardly appears, and when the addition ratio is 100 mg / kg or more, rare earth elements are not absorbed. The rare earth element remaining after being absorbed and transferred to the plant body is not only accumulated in the soil, but also does not show an additional effect due to the addition, which is not preferable.

前記希土類元素は、元素周期律表の原子番号５７のランタン(La)から原子番号７１のルテチウム(Lu)までの１５種の元素と原子番号２１のスカンジウム(Sc)と原子番号３９のイットリウム(Y)の中から選択された一つ以上のものであることが好ましい。   The rare earth elements include 15 elements from lanthanum (La) with atomic number 57 to lutetium (Lu) with atomic number 71, scandium (Sc) with atomic number 21 and yttrium (Y) with atomic number 39 in the periodic table. 1) or more selected from the group consisting of

前記本発明の農業用床土は、土壌、腐葉土及び有機質肥料が混合された通常の床土材料に、前記希土キレート化合物を一定量付加して３乃至４回程度混合して２乃至４週間腐熟させることが好ましい。   Agricultural floor soil of the present invention is prepared by adding a certain amount of the rare earth chelate compound to ordinary floor soil material mixed with soil, humus and organic fertilizer, and mixing it 3 to 4 times for 2 to 4 weeks. It is preferable to ripen.

前記通常の床土土壌の材料としては、磨砂土、パーライト(Perlite)、バーミキュライト(Vermiculite)、ゼオライト(Zeolite)等を使用でき、これら土壌は床土製造時に使用される植物支持体の役割をする。   As the material of the normal floor soil, sandy soil, perlite, vermiculite, zeolite (Zeolite), etc. can be used, and these soils serve as plant supports used in the production of floor soil. .

また、通常の床土の一構成分である腐葉土材料は、韓国内外で床土製造に使用されるすべての植物副産物を含み、有機質肥料としては市販の副産物肥料を使用できる。   Further, the humus material, which is a component of ordinary floor soil, includes all plant by-products used for floor soil production in Korea and abroad, and commercially available by-product fertilizers can be used as organic fertilizers.

また、本発明による床土は育苗過程を経た作物、即ち、果菜類と葉菜類の生育に好ましく使用でき、このように育苗過程に本発明による床土を利用する場合、収穫した作物の食品の安定性確保と作物数量増大の効果を得られる。   In addition, the bed soil according to the present invention can be preferably used for the growth of crops that have undergone a seedling process, that is, fruit vegetables and leafy vegetables. Thus, when the bed soil according to the present invention is used for the seedling process, the food stability of the harvested crops can be stabilized. The effect of ensuring sex and increasing crop quantity can be obtained.

前記本発明による農業用床土は、
各種有機酸塩から選択された有機酸塩を精製水に溶解して水溶液として含む工程と、
前記水溶液に希土類から選択された一物質を一定当量で加えてキレート結合を形成させる工程と、
前記反応液で希土キレート化合物結晶を析出させ、それをろ過して結晶を得る工程と、
前記得られた希土キレート化合物を一定比率で通常の床土に混合する工程とにより製造される。 The agricultural soil according to the present invention is:
A step of dissolving an organic acid salt selected from various organic acid salts in purified water and containing it as an aqueous solution;
Adding a substance selected from rare earths to the aqueous solution at a constant equivalent to form a chelate bond;
Precipitating rare earth chelate compound crystals in the reaction solution and filtering them to obtain crystals;
The obtained rare earth chelate compound is mixed with a normal floor soil at a constant ratio.

前記有機酸塩は、EDTA(ethylene diamine tetra acetate)塩、クエン酸塩、酒石酸塩から選択することが好ましい。   The organic acid salt is preferably selected from EDTA (ethylene diamine tetra acetate) salt, citrate salt, and tartrate salt.

前記EDTA、クエン酸または酒石酸の水溶液に添加する希土元素は、EDTA、クエン酸または酒石酸：希土元素が１：１の当量比で添加することが好ましい。   The rare earth element added to the aqueous solution of EDTA, citric acid or tartaric acid is preferably added at an equivalent ratio of 1: 1 of EDTA, citric acid or tartaric acid: rare earth element.

上述したように前記通常の床土材料に希土キレート化合物を添加する比率は、0.05乃至100mg/kgにすることが好ましい。添加比率が0.05mg/kg以下であると希土キレート化合物添加による作用効果がなく、添加比率を100mg/kg以上にしても追加添加による付加的な効果を示すものではないため、好ましくない。   As described above, the ratio of adding the rare earth chelate compound to the normal floor soil material is preferably 0.05 to 100 mg / kg. If the addition ratio is 0.05 mg / kg or less, there is no action and effect due to the addition of the rare earth chelate compound, and even if the addition ratio is 100 mg / kg or more, the additional effect due to the addition is not preferable.

前記希土類元素は、元素周期律表の原子番号５７のランタン(La)から原子番号７１のルテチウム(Lu)までの１５種の元素と原子番号２１のスカンジウム(Sc)と原子番号３９のイットリウム(Y)の中から選択された一つ以上のものであることが好ましい。   The rare earth elements include 15 elements from lanthanum (La) with atomic number 57 to lutetium (Lu) with atomic number 71, scandium (Sc) with atomic number 21 and yttrium (Y) with atomic number 39 in the periodic table. 1) or more selected from the group consisting of

前記土壌、腐葉土及び有機質肥料が混合された通常の床土材料に希土キレート化合物の付加工程により得られる希土キレート化合物を含有した床土は、通常２乃至４週間腐熟させた後、使用することが好ましい。   The floor soil containing the rare earth chelate compound obtained by adding the rare earth chelate compound to the normal floor soil material mixed with the soil, humus and organic fertilizer is usually used after saturating for 2 to 4 weeks. It is preferable.

前記のように構成された本発明は、希土鉱物の使用において従来と同じ塩化物または窒化物の形態を利用しないで、EDTA塩、クエン酸塩、酒石酸塩のような有機酸塩を利用して希土類元素の化学的な合成を行なって得られる希土キレート化合物を使用することにより、従来の問題点であるCl-やNO3 -による土壌生態系の副作用を減らし、植物体への吸収が有利なEDTA塩、クエン酸塩、酒石酸塩のような有機酸塩のキレート化合物を使用するため、希土元素の植物体への転移率を大きく向上させられる。したがって、幼苗期植物体の旺盛な養分吸収過程で希土元素が植物体内に吸収移動される。既存の塩化物及び硝酸塩形態の希土粉末及び液肥よりも、本発明によるEDTA及び有機酸を利用したキレート形態の方が植物体内への吸収移行量が非常に多く、希土元素の土壌蓄積を減少させるので土壌生態系の安定性問題を解消できる。合わせて、植物体内で硝酸態窒素の形成に大きく寄与することになる硝酸還元酵素(nitrate reductase enzyme)に影響を与え、体内硝酸態窒素の蓄積を低減させて作物の生育促進及び農薬残留量を減少させる効果を示す。 The present invention configured as described above uses organic acid salts such as EDTA salt, citrate salt, and tartrate salt without using the same chloride or nitride form as before in the use of rare earth minerals. Te by using chemical synthesis and conducted rare earth chelate compounds obtained rare earth element, a conventional problem Cl - or NO 3 - reduce the side effects of soil ecosystems, the absorption of the plant Use of organic acid chelate compounds such as advantageous EDTA salts, citrates, and tartrates greatly improves the rate of transfer of rare earth elements to plants. Therefore, the rare earth elements are absorbed and transferred into the plant body in the vigorous nutrient absorption process of the seedling plant. Compared to existing rare earth powder and liquid fertilizer in the form of chloride and nitrate, the chelate form using the EDTA and organic acid according to the present invention has a much larger amount of absorption and transfer to the plant body, and the soil accumulation of rare earth elements is increased. This reduces the stability problem of the soil ecosystem. At the same time, it affects nitrate reductase enzyme, which greatly contributes to the formation of nitrate nitrogen in the plant body, reduces the accumulation of nitrate nitrogen in the body, and promotes the growth of crops and the residual amount of pesticides. Demonstrate the effect.

このように、本発明による農業用床土は、希土キレート化合物が作物における農薬残留量減少効果、植物体中硝酸態窒素の蓄積減少効果、希土元素の植物体への吸収移行率増加、希土元素の土壌蓄積減少及び植物生育促進効果をもたらす。   Thus, in the agricultural soil according to the present invention, the rare earth chelate compound reduces the residual amount of agricultural chemicals in crops, reduces the accumulation of nitrate nitrogen in the plant, increases the absorption transfer rate of rare earth elements to the plant, Reduces soil accumulation of rare earth elements and promotes plant growth.

以下、本発明を実施例によりさらに詳細に説明するが、本発明の範囲がこれらの実施例によって限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the scope of the present invention is not limited by these Examples.

実施例1：希土キレート化合物の製造
EDTA塩37.2gを精製水に溶解して水溶液にし、そこにランタン43.3gを加えてpH 6.5に調製し、その水溶液を撹拌してキレート結合を形成させる。 Example 1: Production of rare earth chelate compound
37.2 g of EDTA salt is dissolved in purified water to form an aqueous solution, and 43.3 g of lanthanum is added thereto to adjust the pH to 6.5, and the aqueous solution is stirred to form a chelate bond.

前記反応液から希土キレート化合物結晶を析出させ、それをろ過して希土キレート化合物を得た。   A rare earth chelate compound crystal was precipitated from the reaction solution and filtered to obtain a rare earth chelate compound.

本発明の希土キレート化合物は、基本的に希土化合物の濃度を100mmole水準で、キレート化合物の濃度を100mmoleにして１：１当量的に反応させる。   The rare earth chelate compound of the present invention is basically reacted at a 1: 1 equivalent with the rare earth compound concentration at the 100 mmole level and the chelate compound concentration at 100 mmole.

実施例２〜１５：希土キレート化合物の製造
前記実施例1のEDTAの代りに次の表１に示すようにクエン酸または酒石酸を使用して希土元素を表１に示したように使用し、それ以外は実施例1と同様にして各実施例２〜１５による希土キレート化合物を得た。 Examples 2 to 15: Production of rare earth chelate compound In place of the EDTA of Example 1, the rare earth elements were used as shown in Table 1 using citric acid or tartaric acid as shown in Table 1 below. Otherwise, the rare earth chelate compounds according to Examples 2 to 15 were obtained in the same manner as in Example 1.

実施例１６〜３０：希土キレート化合物含有床土の製造
土壌、腐葉土及び有機質肥料等、床土原料の炭素と窒素の含量及び重金属汚染物質の含量を分析して、床土原料としての適合性可否を判定した後、これら床土原料の配合比率を磨砂土50重量％、腐葉土30重量％、有機質肥料20重量％に調節して均一に粉砕し、3〜4回良く混合して3週間腐熟させた。このように腐熟させた床土に前記実施例１乃至１５により製造した希土キレート化合物を各々10mg/kgの比率で付加して再び3回よく混合して、実施例１６乃至３０の本発明による機能性環境親和型の農業用床土を製造した。 Examples 16-30: Manufacture of rare earth chelate compound-containing floor soil Analyzing the contents of carbon, nitrogen and heavy metal pollutants in the soil, humus and organic fertilizer, etc., and suitability as a floor soil material After judging whether or not it is possible, adjust the blending ratio of these floor soil materials to 50% by weight sand, 30% by weight humus, and 20% by weight organic fertilizer, grind them uniformly, mix well 3-4 times and ripen for 3 weeks I let you. According to the present invention of Examples 16 to 30, the rare earth chelate compounds prepared in Examples 1 to 15 were added to the floor soil thus ripened in a ratio of 10 mg / kg and mixed well three times. A functional environmentally friendly agricultural floor soil was produced.

実施例３１〜４５：希土キレート化合物の付加比率を30mg/kgにする以外は前記実施例１６乃至３０と同様にして、本実施例３１乃至４５の農業用床土を各々製造した。 Examples 31 to 45: Agricultural floor soils of Examples 31 to 45 were produced in the same manner as in Examples 16 to 30 except that the addition ratio of the rare earth chelate compound was changed to 30 mg / kg.

実施例４６〜６０：希土キレート化合物の付加比率を50mg/kgにする以外は前記実施例１６乃至３０と同様にして、本実施例４６乃至６０の農業用床土を各々製造した。 Examples 46 to 60: Agricultural floor soils of Examples 46 to 60 were produced in the same manner as in Examples 16 to 30 except that the addition ratio of the rare earth chelate compound was 50 mg / kg.

実施例６１〜７５：希土キレート化合物の付加比率を100mg/kgにする以外は前記実施例１６乃至３０と同様にして、本実施例６１乃至７５の農業用床土を各々製造した。 Examples 61 to 75: Agricultural floor soils of Examples 61 to 75 were produced in the same manner as in Examples 16 to 30 except that the addition ratio of the rare earth chelate compound was 100 mg / kg.

実験例１：作物生育状態測定
前記実施例４６により製造した農業用床土をプラスチック育苗ポットに入れ白菜種子を播種して白菜幼苗を得た。播種後３０日目に白菜幼苗を本圃に移植して、通常の床土で白菜幼苗を得たものと作物生育過程を比較した。本発明の希土キレート化合物で処理した実施例４６による床土と一般床土とを対象に白菜生育過程を調査した結果、本発明による床土で処理した実験区で白菜生育がはるかに良好だった(図２参考;左側が実施例４６による床土で栽培した白菜)。 Experimental Example 1: Crop Growth State Measurement The agricultural floor soil produced in Example 46 was placed in a plastic nursery pot and seeded with Chinese cabbage seeds to obtain Chinese cabbage seedlings. On the 30th day after sowing, Chinese cabbage seedlings were transplanted into the main field, and the growth process of the Chinese cabbage seedlings obtained from the normal floor soil was compared with that obtained. As a result of investigating the growth process of Chinese cabbage on the floor soil of Example 46 treated with the rare earth chelate compound of the present invention and the general floor soil, the growth of Chinese cabbage was much better in the experimental section treated with the floor soil of the present invention. (Refer to FIG. 2; left side is Chinese cabbage cultivated on floor soil according to Example 46).

実験例２：硝酸態窒素の含量測定
前記実施例１６、３１、４６及び６１により製造した農業用床土と通常の床土をプラスチック育苗ポットに入れ、白菜種子を播種して白菜幼苗を得た。播種後３０日目に各白菜幼苗を本圃に移植して生育させた後、白菜中硝酸態窒素の含量を調査し、その結果を図３に示した。図３から分かるように、本発明による床土で処理した白菜が対照群のものに比べて白菜中硝酸態窒素の含量が約４乃至１５％程度低減したことが確認できる。 Experimental Example 2: Content measurement of nitrate nitrogen Agricultural floor soil produced according to Examples 16, 31, 46 and 61 and ordinary floor soil were placed in a plastic seedling pot, and Chinese cabbage seeds were sown to obtain Chinese cabbage seedlings. . On the 30th day after sowing, each Chinese cabbage seedling was transplanted and grown in this field, and then the content of nitrate nitrogen in the Chinese cabbage was investigated, and the results are shown in FIG. As can be seen from FIG. 3, it can be confirmed that the content of nitrate nitrogen in the Chinese cabbage is about 4 to 15% lower than that of the control group.

実験例３：残留農薬含量測定
前記実施例１６、３１、４６及び６１により製造した農業用床土と通常の床土をプラスチック育苗ポットに入れ、白菜種子を播種して白菜幼苗を得た。播種後３０日目に各白菜幼苗を本圃に移植して生育させた。生育過程中にマンコジ（農薬名）水和剤を散布した。収穫後、白菜中残留農薬の含量を調査し、その結果を図４に示した。図４から分かるように、本発明による床土で処理した白菜が対照群のものに比べて白菜中農薬(マンコジ水和剤)の含量が４乃至２０％程度低減されたことが確認できる。 Experimental Example 3 Measurement of Residual Pesticide Content The agricultural floor soil produced in Examples 16, 31, 46 and 61 and ordinary floor soil were placed in a plastic nursery pot, and Chinese cabbage seeds were sown to obtain Chinese cabbage seedlings. On the 30th day after sowing, each Chinese cabbage seedling was transplanted and grown in this field. During the growth process, Mankoji (agrochemical name) wettable powder was sprayed. After harvesting, the content of pesticide residue in Chinese cabbage was investigated, and the results are shown in FIG. As can be seen from FIG. 4, it can be confirmed that the content of the pesticide in the Chinese cabbage (mangoji wettable powder) in the Chinese cabbage treated with the floor soil according to the present invention was reduced by about 4 to 20% compared to the control group.

前記のように構成された本発明の希土キレート化合物を添加した農業用床土は、作物の生育を促進させ、作物中硝酸態窒素の含量低減と農薬残留量を低減させるだけでなく、希土元素の植物体への吸収移行率を増加させて希土元素の土壌蓄積減少及び植物生育を促進させる。したがって、育苗過程を経る作物に本発明による希土キレート化合物が添加された床土を利用する場合、食品の安定性確保と作物数量増大の効果を得ることができる。   Agricultural floor soil to which the rare earth chelate compound of the present invention configured as described above is added not only promotes the growth of crops, reduces the content of nitrate nitrogen in crops and reduces the residual amount of agricultural chemicals, but also rares. Increase the rate of absorption and transfer of soil elements to plants to promote the reduction of soil accumulation and plant growth of rare earth elements. Therefore, when using the bed soil in which the rare earth chelate compound according to the present invention is added to the crop that has undergone the seedling raising process, the effects of ensuring the stability of food and increasing the number of crops can be obtained.

本発明の方法で製造した希土キレート化合物を添加した機能性環境親和型の農業用床土の写真である。It is a photograph of the functional environmentally friendly agricultural floor soil to which the rare earth chelate compound produced by the method of the present invention is added. 本発明の方法で製造した希土キレート化合物を添加した機能性環境親和型の農業用床土と一般床土で栽培した白菜の３０日目の生育段階を比較した写真で、左側が本発明による床土で栽培したものである。A photograph comparing the growth stage of a Chinese cabbage grown on a functional environmentally friendly agricultural floor soil added with a rare earth chelate compound produced by the method of the present invention and a general floor soil on the 30th day, and the left side is according to the present invention. It is cultivated in floor soil. 本発明の方法で製造した希土キレート化合物を各々の濃度別に添加した機能性環境親和型の農業用床土と一般床土で栽培した白菜中の硝酸態窒素の低減率を示したグラフである。It is the graph which showed the reduction rate of the nitrate nitrogen in the Chinese cabbage cultivated by the functional environmental affinity type agricultural floor soil which added the rare earth chelate compound manufactured by the method of the present invention for each concentration, and general floor soil. . 本発明の方法で製造した希土キレート化合物を各々の濃度別に添加した機能性環境親和型の農業用床土と一般床土で栽培した白菜中農薬(マンコジ水和剤)の低減率を示したグラフである。It showed the reduction rate of pesticides in Chinese cabbage (mangoji wettable powder) cultivated in functional and environmentally friendly agricultural floor soil and general floor soil added with rare earth chelate compound manufactured by the method of the present invention for each concentration It is a graph.

Claims (12)

有機酸塩に希土類から選択された一つ以上の物質をキレート結合させて得た希土キレート化合物を単独または混合形態で通常の床土に混合して得ることを特徴とする、希土キレート化合物が添加された農業用床土。   A rare earth chelate compound obtained by mixing a rare earth chelate compound obtained by chelating one or more substances selected from rare earths with an organic acid salt alone or mixed with ordinary floor soil Agricultural floor soil with added. 前記有機酸塩が、EDTA(ethylene diamine tetra acetate)、クエン酸、酒石酸から選択された一つ以上のものであることを特徴とする、請求項１に記載の希土キレート化合物が添加された農業用床土。   The agriculture to which the rare earth chelate compound according to claim 1 is added, wherein the organic acid salt is at least one selected from EDTA (ethylene diamine tetra acetate), citric acid, and tartaric acid. Floor soil. 前記希土キレート化合物の添加比率が、0.05乃至100mg/kgであることを特徴とする、請求項１に記載の希土キレート化合物が添加された農業用床土。   The agricultural floor soil to which the rare earth chelate compound is added according to claim 1, wherein the addition ratio of the rare earth chelate compound is 0.05 to 100 mg / kg. 前記希土キレート化合物の添加比率が、10乃至100mg/kgであることを特徴とする、請求項３に記載の希土キレート化合物が添加された農業用床土。   The agricultural floor soil added with the rare earth chelate compound according to claim 3, wherein the addition ratio of the rare earth chelate compound is 10 to 100 mg / kg. 前記希土類元素が、元素周期律表の原子番号５７のランタン(La)から原子番号７１のルテチウム(Lu)までの１５種の元素と、原子番号２１のスカンジウム(Sc)と原子番号３９のイットリウム(Y)の中から選択された一つ以上のものであることを特徴とする、請求項１に記載の希土キレート化合物が添加された農業用床土。   The rare earth element includes 15 elements from lanthanum (La) with atomic number 57 to lutetium (Lu) with atomic number 71, scandium (Sc) with atomic number 21 and yttrium with atomic number 39 in the periodic table. The agricultural floor soil to which the rare earth chelate compound according to claim 1 is added, characterized in that it is one or more selected from Y). 前記農業用床土が、隧道用、園芸用または花卉用の一つであることを特徴とする、請求項１に記載の希土キレート化合物が添加された農業用床土。   The agricultural floor soil added with the rare earth chelate compound according to claim 1, wherein the agricultural floor soil is one for swaying, horticultural or flowering. 有機酸塩から一つを選択してそれを精製水に溶解して水溶液として含む工程と、
前記水溶液に希土類から選択された一物質を一定当量で加えてキレート結合を形成させる工程と、
前記反応液で希土キレート化合物結晶を析出させ、それをろ過して結晶を得る工程と、
前記得られた希土キレート化合物を一定比率で通常の床土に混合する工程とからなることを特徴とする、希土キレート化合物が添加された農業用床土の製造方法。 Selecting one of the organic acid salts and dissolving it in purified water to contain it as an aqueous solution;
Adding a substance selected from rare earths to the aqueous solution at a constant equivalent to form a chelate bond;
Precipitating rare earth chelate compound crystals in the reaction solution and filtering them to obtain crystals;
A method for producing an agricultural floor soil to which a rare earth chelate compound is added, comprising the step of mixing the obtained rare earth chelate compound with a normal floor soil at a constant ratio. 前記有機酸塩が、EDTA、クエン酸、酒石酸から選択された一つ以上のものであることを特徴とする、請求項７に記載の希土キレート化合物が添加された農業用床土の製造方法。   The method for producing an agricultural floor soil to which a rare earth chelate compound is added according to claim 7, wherein the organic acid salt is at least one selected from EDTA, citric acid, and tartaric acid. . 前記希土キレート化合物の添加比率が、0.05乃至100mg/kgであることを特徴とする、請求項７に記載の希土キレート化合物が添加された農業用床土の製造方法。   The method for producing agricultural floor soil to which the rare earth chelate compound is added according to claim 7, wherein the addition ratio of the rare earth chelate compound is 0.05 to 100 mg / kg. 前記希土キレート化合物の添加比率が、10乃至100mg/kgであることを特徴とする、請求項９に記載の希土キレート化合物が添加された農業用床土の製造方法。   The method for producing agricultural floor soil to which the rare earth chelate compound is added according to claim 9, wherein the addition ratio of the rare earth chelate compound is 10 to 100 mg / kg. 前記有機酸塩の水溶液に添加する希土元素は、有機酸塩：希土元素が１：１の当量比になるように添加することを特徴とする、請求項７に記載の希土キレート化合物が添加された農業用床土の製造方法。   The rare earth chelate compound according to claim 7, wherein the rare earth element added to the organic acid salt aqueous solution is added so that the equivalent ratio of organic acid salt: rare earth element is 1: 1. Of agricultural floor soil to which is added. 前記希土類元素が、元素周期律表の原子番号５７のランタン(La)から原子番号７１のルテチウム(Lu)までの１５種の元素と原子番号２１のスカンジウム(Sc)と原子番号３９のイットリウム(Y)の中から選択された一つ以上のものであることを特徴とする、請求項７に記載の希土キレート化合物が添加された農業用床土の製造方法。   The rare earth elements include 15 elements from lanthanum (La) of atomic number 57 to lutetium (Lu) of atomic number 71, scandium (Sc) of atomic number 21 and yttrium (Y) of atomic number 39 in the periodic table. The method for producing an agricultural floor soil to which the rare earth chelate compound according to claim 7 is added, wherein at least one selected from the group consisting of
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KR102119741B1 (en) * 2019-08-19 2020-06-08 주식회사 정인바이오 Functional fertilizer composition including natural mineral for pesticide residue removal and gas injury treatment and the method of manufacturing therof
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KR101042531B1 (en) 2008-08-01 2011-06-17 백도현 Preparing method of compressed bed soil for raising seeding using chelated thereof
KR101039746B1 (en) * 2008-08-26 2011-06-08 한국원자력연구원 Antifungal composition, agricultural chemical formulation and agricultural liquid fertilizer containing rare earth element or its chelate complex
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JP2008043221A (en) * 2006-08-11 2008-02-28 Taisei Corp Greening base material, greening structure and greening method
KR102119741B1 (en) * 2019-08-19 2020-06-08 주식회사 정인바이오 Functional fertilizer composition including natural mineral for pesticide residue removal and gas injury treatment and the method of manufacturing therof
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