JP3995776B2

JP3995776B2 - Alkali extraction humic acid material

Info

Publication number: JP3995776B2
Application number: JP32770897A
Authority: JP
Inventors: 博青木; 政信村上
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 1997-11-28
Filing date: 1997-11-28
Publication date: 2007-10-24
Anticipated expiration: 2017-11-28
Also published as: JPH11157976A

Description

【０００１】
【産業上の利用分野】
本発明は肥料の効果発現促進に優れるアルカリ抽出腐植酸を多く含有し、かつ、ハンドリングが良好な粉状の腐植酸質資材に関する。
【０００２】
【従来の技術】
今日、農業生産にとって土壌健全化の必要性は広く認識されている。腐植酸はフミン酸とも呼ばれ、土壌有機物の中核をなす物であり、作物の成長促進、根の活性化のほか、土壌自体の物理性改善、肥沃化、微生物の増殖、多様化など、土壌の総合的な健全化に大きな働きをしている。このため従来より普通肥料として腐植酸アンモニア肥料、腐植酸加里肥料、腐植酸苦土肥料、腐植酸りん肥等があり、又、土壌改良資材として各種の腐植酸質資材が供給されている。これらの普通肥料、土壌改良資材で使用されている腐植酸は、通常、石炭又は亜炭を硝酸又は硝酸及び硫酸で分解して生成しているのでニトロフミン酸とも呼ばれている（特開昭６２−１００４９５号公報等参照）。しかしながら、このような酸分解物では本来腐植酸が内包する有用物質である糖やアミノ酸類が少なからず分解されてしまうという欠点がある。
【０００３】
これらの有用物質を活用すべく、石炭、リグニン含有層からアルカリ抽出した腐植酸もあるが、吸湿性が高いため溶液状又はスラリー状でしか供給出来ず、輸送や使用時において、取り扱い性が不便という問題がある。また、アルカリ抽出液に無機酸を加えpH３以下として沈殿物を生成させ、これを濾別乾燥して固体を得ることも出来る（特開平４−３６３３８７号公報参照）が、この方法では前述のように、作物にとって有用な糖やアミノ酸が分解されてしまう欠点がある。
【０００４】
【発明が解決しようとする課題】
本発明は、上記従来の課題を解決するものであり、その目的とするところは糖やアミノ酸の有用物資が分解されず粉状で取り扱い性に優れた有効成分量の高いアルカリ抽出腐植酸質資材を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明の目的はアルカリ抽出された腐植酸液またはアルカリ抽出された腐植酸液を肥料成分に含む複合肥料液と多孔質担体、特に含水二酸化珪素とを含有する事によって達成される。
【０００６】
【発明の実施の形態】
以下本発明を詳細に説明する。
本発明において用いる腐植酸は通常の石炭や、亜炭、泥炭、褐炭などの低品位炭を水酸化ナトリウム、水酸化カリウム、消石灰、アンモニア等のアルカリ水溶液で抽出した物を使用する。このアルカリ抽出液を有用物質が酸分解されない程度に、さらにpH7〜12程度に硫酸、硝酸、塩酸、燐酸で調整することは差し支えない。また、窒素、燐酸、カリなどが配合された液状複合肥料に本アルカリ抽出液が混入された形態でも良い。液状複合肥料へのアルカリ抽出液の混入比率は特に制限はないが、通常、0.1%から50%、さらに好ましくは0.1%から10%の範囲で選ばれる。液状複合肥料中の窒素、燐酸、カリの比率については対象となる作物に応じて適宜決められるが、最低限、アルカリ抽出液が混入されたあとの液状複合肥料中の窒素、燐酸又はカリのいずれか２以上について、それぞれの最も大きい主成分の合計量が8%以上であることが好ましい。
【０００７】
多孔質担体としては粉状の含水二酸化珪素、さらにはシリカゲル、ホワイトカーボン等の含水無晶形二酸化珪素が望ましい。含水無晶形二酸化珪素は天然の物でも珪酸ナトリウムと硫酸を反応させた合成物でも良い。この含水無晶形二酸化珪素はその比表面積が５０ｍ²／ｇ以上、さらに好ましくは７０ｍ²／ｇであることが望ましい。また、その表面に１個／ｎｍ²以上のシラノール基を含有する物が良い。
【０００８】
アルカリ抽出腐植酸液またはアルカリ抽出腐植酸液を含む複合肥料液と含水無晶形二酸化珪素との混合は任意の方法で行われ、特に制限はないが、ホイール型やブレード型、ロール型などの混練機を用いると便利である。混合比率は目的とする有効成分量で異なってくるが、担体１００重量部に対して、腐植酸または肥料液の比率が最低、１０重量部が好ましく、特に１００重量部以上が良い。また、腐植酸または肥料液の上限は無いが、４００重量部までは混合でき、場合によっては、１０００重量部、又は、２０００重量部まで可能である。ただし、アルカリ抽出腐植酸液を含む複合肥料液と含水無晶形二酸化珪素を混合する場合、混合品の窒素、水溶性燐酸又は水溶性カリのいずれか２以上の主成分の合計量が5%以上となるような混合比率が望まれる。
【０００９】
混合品は有効成分量を高めたり、更に取り扱い性を向上させるため、乾燥し水分を調整することは可能であるが、本発明によれば、乾燥しなくても充分な有効成分量と良好な取り扱い性を有する粉状体が得やすい。万一、混合品がべたついて乾燥する場合、乾燥方法は特に限定されないが、腐植酸、糖、アミノ酸などの有用物質が変成するような高温度、具体的には120℃以上は避けた方が良い。
【００１０】
【実施例】
以下、実施例、比較例により、本発明をさらに詳細に説明するが、本発明はその要旨を越えない限り、これらに限定されるものではない。なお、以下において「部」は「重量部」を表し、「％」は「重量％」を表す。
実施例１
Leonardite（石炭、リグニン含有層）からアルカリ抽出された腐植酸を含有する液体肥料（JH Biotech社商品名Humax Ferax-S 窒素5%、水溶性燐酸10%、水溶性カリ5%、アルカリ抽出腐植酸1.4% pH10.0）とホワイトカーボン（シオノギ製薬社製「カープレックス22S」比表面積165m²/g 平均粒径5.5μm シラノール基８個／ｎｍ ²）を１：４、１：１、２：１の重量比でそれぞれダルトン社製万能ミキサーで５分間混合し、混合後の性状及びpH（g/100cc）を測定した。尚、pH（g/100cc）とは、１ｇの固体を１００ccの水に溶解、懸濁させて測定したときのpHである。
【００１１】
【表１】

さらにそれぞれの混合品100gを採り、75℃の乾燥器内で静置乾燥させ、水分を５％未満にした。その後、室内に放置し性状を観察した。
【００１２】
【表２】

比較例１
Leonardite（石炭、リグニン含有層）からアルカリ抽出された腐植酸を含有する液体肥料（JH Biotech社製商品名「Humax Ferax-S」窒素5%、水溶性燐酸10%、水溶性カリ5%、アルカリ抽出腐植酸1.4% pH10.0）とゼオライト（平均粒径 1.09mm）を１：２、１：１の重量比でそれぞれダルトン社製万能ミキサーで５分間混合し、混合後の性状及びpH（g/100cc）を測定した。
【００１３】
【表３】

さらに１：２の混合品100gを採り、75℃の乾燥器内で静置乾燥させ、水分を５％未満にした。その後、室内に放置し性状を観察した。
【００１４】
【表４】

混合乾燥時間性状腐植酸液100部セ゛オライト 200部１時間吸湿なし
比較例２
Leonardite（石炭、リグニン含有層）からアルカリ抽出された腐植酸を含有する液体肥料（JH Biotech社製商品名「Humax Ferax-S」窒素5%、水溶性燐酸10%、水溶性カリ5%、アルカリ抽出腐植酸1.4% pH10.0）とベントナイト（笠岡産平均粒径 0.08mm）を１：３、１：２、１：１の重量比でそれぞれダルトン社製万能ミキサーで５分間混合し、混合後の性状及びpH（g/100cc）を測定した。
【００１５】
【表５】

さらに１：３の混合品100gを採り、75℃の乾燥器内で静置乾燥させ、水分を５％未満にした。その後、室内に放置し性状を観察した。
【００１６】
【表６】

比較例３
Leonardite（石炭、リグニン含有層）からアルカリ抽出された腐植酸を含有する液体肥料（JH Biotech社製商品名「Humax Ferax-S」窒素5%、水溶性燐酸10%、水溶性カリ5%、アルカリ抽出腐植酸1.4% pH10.0）とバーミキュライトを１：２、１：１の重量比でそれぞれダルトン社製万能ミキサーで５分間混合し、混合後の性状及びpH（g/100cc）を測定した。
【００１７】
【表７】

さらに１：２の混合品100gを採り、75℃の乾燥器内で静置乾燥させ、水分を５％未満にした。その後、室内に放置し性状を観察した
【００１８】
【表８】

比較例４
アルカリ抽出された腐植酸を含有する液体肥料（JH Biotech社製、商品名「Humax」 pH10.0）100gを採り、75℃の乾燥器内で静置乾燥したところ２４時間後でもスラリー状であり粉状品は得られなかった。
【００１９】
【発明の効果】
本発明によれば糖やアミノ酸の有用物資が分解されず粉状で取り扱い性に優れた有効成分量の高いアルカリ抽出腐植酸質資材を提供することができる。[0001]
[Industrial application fields]
The present invention relates to a powdery humic acid material that contains a large amount of alkali-extracted humic acid that is excellent in promoting the effect of fertilizer and that has good handling.
[0002]
[Prior art]
Today, the need for soil consolidation for agricultural production is widely recognized. Humic acid, also known as humic acid, is the core of soil organic matter. In addition to promoting the growth of crops and activating the roots, the soil itself is improved in physical properties, fertilization, microbial growth, and diversification. It plays a major role in the overall health of the company. For this reason, conventionally, there are humic acid ammonia fertilizer, humic acid potassium fertilizer, humic acid bitter fertilizer, humic acid phosphorus fertilizer and the like as ordinary fertilizers, and various humic acid materials are supplied as soil improvement materials. The humic acid used in these ordinary fertilizers and soil improvement materials is usually produced by decomposing coal or lignite with nitric acid or nitric acid and sulfuric acid, so it is also called nitrohumic acid (Japanese Patent Laid-Open No. Sho 62-62). No. 1000049 publication). However, such an acid degradation product has a disadvantage that sugars and amino acids, which are inherently useful substances contained in humic acid, are decomposed to some extent.
[0003]
In order to make use of these useful substances, some humic acids are extracted from coal and lignin-containing layers by alkali. However, because of their high hygroscopicity, they can only be supplied in solution or slurry form, which is inconvenient to handle during transportation and use. There is a problem. Further, an inorganic acid can be added to the alkaline extract to produce a precipitate with a pH of 3 or less, and this can be filtered and dried to obtain a solid (see JP-A-4-363387). In addition, sugars and amino acids useful for crops are degraded.
[0004]
[Problems to be solved by the invention]
The present invention solves the above-mentioned conventional problems, and the object of the present invention is to provide an alkali-extracted humic acid material having a high amount of active ingredients excellent in handleability without being decomposed in useful materials such as sugars and amino acids. The purpose is to provide.
[0005]
[Means for Solving the Problems]
The object of the present invention is achieved by containing an alkali-extracted humic acid solution or a composite fertilizer solution containing an alkali-extracted humic acid solution as a fertilizer component and a porous carrier, particularly hydrous silicon dioxide.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The humic acid used in the present invention is obtained by extracting ordinary coal or low-grade coal such as lignite, peat and lignite with an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, slaked lime and ammonia. The alkaline extract may be adjusted with sulfuric acid, nitric acid, hydrochloric acid, or phosphoric acid to a pH of 7 to 12 so that useful substances are not decomposed by acid. Further, the alkaline extract may be mixed with a liquid composite fertilizer containing nitrogen, phosphoric acid, potash and the like. The mixing ratio of the alkaline extract to the liquid composite fertilizer is not particularly limited, but is usually selected in the range of 0.1% to 50%, more preferably 0.1% to 10%. The ratio of nitrogen, phosphoric acid, and potash in the liquid compound fertilizer is appropriately determined according to the target crop, but at the minimum, any of nitrogen, phosphoric acid, or potash in the liquid compound fertilizer after the alkaline extract is mixed. Or more, it is preferable that the total amount of each largest main component is 8% or more.
[0007]
As the porous carrier , hydrated silicon dioxide in powder form, and hydrated amorphous silicon dioxide such as silica gel and white carbon are desirable. The hydrous amorphous silicon dioxide may be a natural product or a synthetic product obtained by reacting sodium silicate and sulfuric acid. The water-containing amorphous silicon dioxide has a specific surface area of 50 m ² / g or more, more preferably 70 m ² / g. Moreover, the thing containing the silanol group of 1 piece / nm < ² > or more on the surface is good.
[0008]
The mixing of the alkali-extracted humic acid solution or the compound fertilizer solution containing the alkali-extracted humic acid solution and the hydrated amorphous silicon dioxide is carried out by any method, and although there is no particular limitation, kneading of wheel type, blade type, roll type, etc. It is convenient to use a machine. The mixing ratio varies depending on the target amount of the active ingredient, but the ratio of humic acid or fertilizer liquid is preferably at least 10 parts by weight, particularly 100 parts by weight or more, with respect to 100 parts by weight of the carrier. Moreover, although there is no upper limit of humic acid or a fertilizer liquid, it can mix up to 400 weight part and can be up to 1000 weight part or 2000 weight part depending on the case. However, when mixing compound fertilizer solution containing alkali extracted humic acid solution and hydrous amorphous silicon dioxide, the total amount of two or more main components of nitrogen, water-soluble phosphoric acid or water-soluble potassium in the mixture is 5% or more. A mixing ratio such that
[0009]
In order to increase the amount of the active ingredient in the mixed product or to further improve the handleability, it is possible to adjust the moisture by drying, but according to the present invention, the amount of the active ingredient is sufficient and good even without drying. It is easy to obtain a powdery material having handleability. In the unlikely event that the mixture is sticky and dry, the drying method is not particularly limited, but it should be avoided to avoid high temperatures such as humic acid, sugar, and amino acids, specifically 120 ° C or higher. good.
[0010]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these, unless the summary is exceeded. In the following, “part” represents “part by weight”, and “%” represents “% by weight”.
Example 1
Liquid fertilizer containing humic acid alkali-extracted from Leonardite (coal, lignin-containing layer) (JH Biotech brand name Humax Ferax-S nitrogen 5%, water-soluble phosphoric acid 10%, water-soluble potassium 5%, alkali-extracted humic acid 1.4% pH 10.0) and white carbon (“Carplex 22S” manufactured by Shionogi Pharmaceutical Co., Ltd., specific surface area 165 m ² / g, average particle size 5.5 μm, 8 silanol groups / nm ² ) 1: 4, 1: 1, 2: 1 Were mixed with a universal mixer manufactured by Dalton for 5 minutes, and the properties and pH (g / 100 cc) after mixing were measured. The pH (g / 100 cc) is a pH measured when 1 g of solid is dissolved and suspended in 100 cc of water.
[0011]
[Table 1]

Further take mixed product 100g each, left to stand dried in a 75 ° C. oven and the moisture to less than 5%. Then, it was left in the room and the properties were observed.
[0012]
[Table 2]

Comparative Example 1
Liquid fertilizer containing humic acid extracted from alkali from Leonardite (coal, lignin-containing layer) (trade name “Humax Ferax-S” manufactured by JH Biotech) Nitrogen 5%, water-soluble phosphoric acid 10%, water-soluble potassium 5%, alkali Extracted humic acid 1.4% pH 10.0) and zeolite (average particle size 1.09mm) were mixed at a weight ratio of 1: 2, 1: 1 for 5 minutes using a Dalton universal mixer, respectively. Properties after mixing and pH (g / 100cc) was measured.
[0013]
[Table 3]

Further 1: taking a mixed product 100g of 2, left to stand dried in a 75 ° C. oven and the moisture to less than 5%. Then, it was left in the room and the properties were observed.
[0014]
[Table 4]

Mixing Drying time Properties Humic acid solution 100 parts Geolite 200 parts 1 hour No moisture absorption
Comparative Example 2
Liquid fertilizer containing humic acid extracted from Leonardite (coal, lignin-containing layer) (JH Biotech's product name “Humax Ferax-S” Nitrogen 5%, water-soluble phosphoric acid 10%, water-soluble potassium 5%, alkali Extracted humic acid 1.4% pH 10.0) and bentonite (Kasaoka average particle size 0.08mm) were mixed at a weight ratio of 1: 3, 1: 2, and 1: 1 for 5 minutes using Dalton's universal mixer. The properties and pH (g / 100 cc) were measured.
[0015]
[Table 5]

Further 1: taking a mixed product 100g of 3, left to stand dried in a 75 ° C. oven and the moisture to less than 5%. Then, it was left in the room and the properties were observed.
[0016]
[Table 6]

Comparative Example 3
Liquid fertilizer containing humic acid extracted from alkali from Leonardite (coal, lignin-containing layer) (trade name “Humax Ferax-S” manufactured by JH Biotech) Nitrogen 5%, water-soluble phosphoric acid 10%, water-soluble potassium 5%, alkali Extracted humic acid 1.4% pH 10.0) and vermiculite were mixed at a weight ratio of 1: 2, 1: 1 with a universal mixer manufactured by Dalton for 5 minutes, respectively, and the properties and pH (g / 100 cc) after mixing were measured.
[0017]
[Table 7]

Further 1: taking a mixed product 100g of 2, left to stand dried in a 75 ° C. oven and the moisture to less than 5%. After that, we left it indoors and observed the properties.
[Table 8]

Comparative Example 4
100 g of liquid fertilizer containing humic acid extracted with alkali (JH Biotech, trade name “Humax” pH10.0) was taken and left standing in a dryer at 75 ° C., and it was still slurry after 24 hours. A powdery product was not obtained.
[0019]
【The invention's effect】
According to the present invention, it is possible to provide an alkali-extracted humic acid material having a high amount of active ingredient that is in a powder form and has excellent handleability without being decomposed in useful materials such as sugars and amino acids.

Claims

A powdery alkali-extracted humic acid material comprising an alkali-extracted humic acid solution or a composite fertilizer solution containing an alkali-extracted humic acid solution and a porous carrier , wherein the porous carrier is hydrous silicon dioxide An alkali-extracted humic acid material characterized by that .

Humic acid electrolyte material according to claim 1 having a specific surface area of the hydrated silicon dioxide, characterized in that at 50 m ² / g or more.

Humic acid electrolyte material according to claim 1 or 2, characterized in that it has a silanol group on the surface of the hydrated silicon dioxide 1 / nm ² or more.