JP5869233B2 - Method for producing humic acid-containing activator - Google Patents
Method for producing humic acid-containing activator Download PDFInfo
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- JP5869233B2 JP5869233B2 JP2011104761A JP2011104761A JP5869233B2 JP 5869233 B2 JP5869233 B2 JP 5869233B2 JP 2011104761 A JP2011104761 A JP 2011104761A JP 2011104761 A JP2011104761 A JP 2011104761A JP 5869233 B2 JP5869233 B2 JP 5869233B2
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims description 31
- 239000004021 humic acid Substances 0.000 title claims description 31
- 239000012190 activator Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims 4
- 239000002689 soil Substances 0.000 claims description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 18
- 239000011707 mineral Substances 0.000 claims description 18
- 229910052604 silicate mineral Inorganic materials 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004927 clay Substances 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 244000005700 microbiome Species 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052610 inosilicate Inorganic materials 0.000 claims description 6
- 229910052640 jadeite Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003905 agrochemical Substances 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229950011008 tetrachloroethylene Drugs 0.000 description 4
- 241000251468 Actinopterygii Species 0.000 description 3
- 241000723353 Chrysanthemum Species 0.000 description 3
- 235000007516 Chrysanthemum Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910052695 Americium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910052781 Neptunium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 239000005602 Propyzamide Substances 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- LXQXZNRPTYVCNG-UHFFFAOYSA-N americium atom Chemical compound [Am] LXQXZNRPTYVCNG-UHFFFAOYSA-N 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 229910052612 amphibole Inorganic materials 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- LFNLGNPSGWYGGD-UHFFFAOYSA-N neptunium atom Chemical compound [Np] LFNLGNPSGWYGGD-UHFFFAOYSA-N 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- PHNUZKMIPFFYSO-UHFFFAOYSA-N propyzamide Chemical compound C#CC(C)(C)NC(=O)C1=CC(Cl)=CC(Cl)=C1 PHNUZKMIPFFYSO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052645 tectosilicate Inorganic materials 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は、植物育成に適した土壌改良、水産及び畜産の分野等における飼育環境の改善及びこれらの分野における有害物質の無害化、除去に好適な活性剤に関する。 The present invention relates to an active agent suitable for soil improvement suitable for plant growth, improvement of the breeding environment in the fields of fisheries and livestock, and the detoxification and removal of harmful substances in these fields.
これまでに重金属汚染土壌を安定化処理するための汚染土壌処理剤が提案されている（特許文献１）。
しかし、同公報に開示する汚染土壌処理剤はフミン酸（腐植酸）化合物等の粉末キレート剤と酸化マグネシウム粉末を混合することで擬集コロイドを形成させるものであるために、還元作用や分解作用等の効果が期待されるものではなく、重金属の不溶化作用があっても、残留農薬の分解や土質の改善効果が不充分であった。
また、原材料が高価であった。
So far, a contaminated soil treatment agent for stabilizing heavy metal-contaminated soil has been proposed (Patent Document 1).
However, the contaminated soil treatment agent disclosed in the publication is a mixture of powder chelating agent such as humic acid (humic acid) compound and magnesium oxide powder to form a pseudo-colloidal colloid. However, even if heavy metals were insolubilized, the effects of decomposition of residual agricultural chemicals and improvement of soil quality were insufficient.
Moreover, the raw material was expensive.
特許文献２には、金属イオン、電磁波及び遠赤外線を放射する多孔質の活性体を用いた浄水方法を開示するが、その効果が出現するには長期間有するものであった。 Patent Document 2 discloses a water purification method using a porous active material that emits metal ions, electromagnetic waves, and far infrared rays.
本発明は、土壌中の重金属及び残留農薬等の無害化のみならず、植物の育成に適した土質改善に効果的で、さらには水産、畜産の分野にて飼育に適した水質の改善にも効果的な活性剤の提供を目的とする。 The present invention is effective not only for detoxifying heavy metals and residual agricultural chemicals in soil, but also for improving soil quality suitable for plant growth, and also for improving water quality suitable for breeding in the fields of fisheries and livestock. The object is to provide an effective activator.
本発明に係る活性剤は、ケイ酸塩鉱物を粉砕して得られた粉末と、フミン酸からなる液状の腐植酸とを混練及び乾燥して得られ、土壌又は水中の重金属類及び化学物質を吸着し、土壌中又は水中の微生物を活性化させることを特徴とする。 The activator according to the present invention is obtained by kneading and drying a powder obtained by pulverizing a silicate mineral and a liquid humic acid composed of humic acid, to remove heavy metals and chemical substances in soil or water. It is characterized by adsorbing and activating microorganisms in soil or water.
ここで、腐植酸はフミン酸とも称される。
動植物の遺体等が土に埋もれ、土壌中の微生物の働きによって複雑に分解・重合を繰り返して生成した腐植質のうち、アルカリに溶け、酸に溶けない物質を腐植酸と総称し、特定の構造を持った単一物質ではなく、複雑な構造を持った複数の化合物の混合物であり、不定形の高分子物質である。
なお、アルカリに可溶、酸に可溶なものをフルボ酸という。
腐植酸は、弱電解質としての特性を有し、コロイド性、界面活性、キレート性、良分散性等を有していることは、これまでに知られているところである。
しかし、本発明者らの研究によれば、腐植酸のみでは重金属の還元作用や残留農薬等の有害有機化学物質の分解作用が不充分であった。
そこで本発明者らは、吸着作用、還元作用及び触媒作用等の多能な機能を有するケイ酸塩鉱物の粉末と混合することで本発明に至った。
Here, humic acid is also referred to as humic acid.
Of the humic substances produced by the repeated decomposition and polymerization of microorganisms in the soil by the action of microorganisms in the soil, the bodies of animals and plants etc. are collectively called humic acid, which is soluble in alkali and insoluble in acid. It is not a single substance with a complex but a mixture of a plurality of compounds having a complex structure, and is an amorphous polymer substance.
A substance soluble in alkali and soluble in acid is called fulvic acid.
Humic acid has been known to date as a weak electrolyte and has colloidal properties, surface activity, chelating properties, good dispersibility, and the like.
However, according to the study by the present inventors, humic acid alone was insufficient in reducing heavy metals and decomposing harmful organic chemicals such as residual agricultural chemicals.
Therefore, the present inventors have reached the present invention by mixing with silicate mineral powder having multiple functions such as adsorption, reduction and catalysis.
腐植酸は一般的に液体のものが入手しやすい。
その場合に、ケイ酸塩鉱物を３００〜３６０メッシュ程度の粉末に粉砕し、パウダー状にしたものに液状の腐植酸を加えて混練し乾燥させると、その後の取扱いが容易になる。
また、ケイ酸塩鉱物を粉末に粉砕したままでは魚類等の飼育水等の水処理に用いた場合に水に、にごりが生じる場合がある。
そこで活性剤の用途によっては、ケイ酸塩鉱物の粉末を所定の大きさ、例えば、直径１ｍｍ〜３０ｍｍの略球状、あるいは、直径１０ｍｍ〜２０ｍｍの略球状に８００℃〜１０００℃条件下で焼成したものに液状の腐植酸を含浸させ、その後に乾燥させて活性剤としてもよい。
ここで粉末状ケイ酸塩鉱物の焼成条件が８００℃未満では焼成が不充分で１０００℃を超えると、ケイ酸塩がガラス化し多孔性が失われるからである。
Humic acid is generally easily available in liquid form.
In that case, if the silicate mineral is pulverized into a powder of about 300 to 360 mesh, and the powdered product is added with liquid humic acid and kneaded and dried, the subsequent handling becomes easy.
In addition, when the silicate mineral is pulverized into a powder, the water may be contaminated when used for water treatment such as breeding water for fish.
Therefore, depending on the use of the activator, the silicate mineral powder is calcined at a predetermined size, for example, approximately spherical with a diameter of 1 mm to 30 mm, or approximately spherical with a diameter of 10 mm to 20 mm, at 800 ° C. to 1000 ° C. The product may be impregnated with liquid humic acid and then dried to form an active agent.
This is because if the firing condition of the powdered silicate mineral is less than 800 ° C., the firing is insufficient, and if it exceeds 1000 ° C., the silicate is vitrified and the porosity is lost.
ケイ酸塩鉱物は、鉱物学的にケイ素原子に配位子が付いたアニオン構造の相違により分類されている。
（１）単鎖状、２本鎖状のアニオン構造を有するものはイノケイ酸塩鉱物に分類され、ヒスイ輝石、角閃石類等が含まれる。
（２）層状のアニオン構造を有するものはフィロケイ酸鉱物に分類され、ろう石、白土、カオリナイト等が含まれる。
（３）四面体の単体、２量体のアニオン構造を主に有するものはネソケイ酸塩鉱物、ソロケイ酸塩鉱物に分類され、ケイ素原子の一部がアルミニウム原子等他の原子に置換された３次元構造を有するものはテクトケイ酸塩鉱物に分類される。
この（３）の分類に属する鉱物は火山岩の一種である流紋岩や深成岩の一種である花崗岩に多く含まれている。
Silicate minerals are classified by mineralogical differences in anionic structures with ligands attached to silicon atoms.
(1) Those having a single-chain or double-chain anion structure are classified as inosilicate minerals, and include jadeite and amphibole.
(2) Those having a layered anionic structure are classified as phyllosilicate minerals, and include, for example, wax stone, clay, kaolinite and the like.
(3) Tetrahedral simple substance and dimer having mainly anionic structure are classified into nesosilicate mineral and solosilicate mineral, and some of silicon atoms are replaced with other atoms such as aluminum atoms. Those having a dimensional structure are classified as tectosilicate minerals.
Minerals belonging to this category (3) are abundant in granite, a kind of volcanic rock and rhyolite and a kind of plutonic rock.
新潟県糸魚川市姫川流域には、ヒスイ輝石、酸性白土等、活性に優れた多くの鉱物が産出され、本発明者らの研究ではイノケイ酸塩鉱物には遷移元素が多く含まれることから触媒活性に優れ、フィロケイ酸塩鉱物には還元活性に優れていることが明らかになった。 Many active minerals such as jadeite and acid clay are produced in the Himekawa basin in Itoigawa City, Niigata Prefecture. In our research, inosilicate minerals contain a large amount of transition elements, so catalytic activity is high. It was revealed that the phyllosilicate mineral is excellent in reducing activity.
そこで、それぞれの特有の性質を組み合せるのがよく、前記ケイ酸塩鉱物の粉末は、イノケイ酸塩鉱物４〜２０質量％、フィロケイ酸塩鉱物１６〜４０質量％及び残部がその他のケイ酸塩鉱物からなる混合粉末であるのが好ましい。
また、腐植酸の効果をより発揮し、微生物の活動を活発にさせるには多孔性に優れた流紋岩を用いるのが好ましく、前記イノケイ酸塩鉱物はヒスイ輝石であり、前記フィロケイ酸塩鉱物はろう石、白土及びカオリナイトのうちいずれか１種以上であり、前記その他のケイ酸塩鉱物は流紋岩であるのがさらに好ましい。
Therefore, it is preferable to combine the respective unique properties, and the silicate mineral powder is composed of 4 to 20% by mass of inosilicate mineral, 16 to 40% by mass of phyllosilicate mineral, and the rest being other silicates. A mixed powder made of mineral is preferred.
Moreover, it is preferable to use rhyolite having excellent porosity in order to exert the effect of humic acid more and activate the activity of microorganisms. The inosilicate mineral is jadeite and the phyllosilicate mineral. More preferably, it is at least one of agarite, clay, and kaolinite, and the other silicate mineral is rhyolite.
この場合にも、各種用途に応用するのに取扱いやすい観点からは、ケイ酸塩鉱物の混合粉末に対してさらに粘土２０〜４０質量％を加え、焼成した多孔質セラミックスに腐植酸が含有されているものであってもよい。
この場合に粘土は焼成時のバインダーとして作用し、所定の大きさの球径に製造しやすくなる。
腐植酸は焼成後に含浸させ、乾燥するとよい。
In this case as well, from the viewpoint of easy handling for application to various uses, 20-40% by mass of clay is further added to the mixed powder of silicate mineral, and the fired porous ceramic contains humic acid. It may be.
In this case, the clay acts as a binder at the time of firing, and can be easily manufactured to a spherical diameter of a predetermined size.
Humic acid is preferably impregnated after baking and dried.
本発明に係る活性剤は、重金属類や残留農薬等の有害化合物を吸着し、還元作用及び触媒作用に優れるケイ酸塩鉱物の粉末あるいは、これを焼成した粒状のセラミックスとキレート活性、界面活性、微生物育生効果等に優れる腐植酸とを結合させたことにより、次のような活性を有する。
まず第１に、土壌中に加えた場合に重金属類を取り込み無害化し、残留農薬を分解無害化する。
第２に、土壌中の微生物の活動を活性化し、土質の改善が促進される。
第３に、魚類等を飼育する水槽に投入すると有害物が水中から取り除かれ微生物の活性により水質が浄化する。
The activator according to the present invention adsorbs toxic compounds such as heavy metals and residual agricultural chemicals, and is excellent in reducing action and catalytic action. By combining with humic acid having excellent microbial growth effect, etc., it has the following activities.
First of all, when added to soil, heavy metals are taken in and detoxified, and residual agricultural chemicals are decomposed and detoxified.
Secondly, the activity of microorganisms in the soil is activated and the improvement of soil quality is promoted.
Third, when it is put into a fish tank where fish and the like are bred, harmful substances are removed from the water and the water quality is purified by the activity of microorganisms.
本発明に係る活性剤の効果を確認すべく、比較実験を実施したので以下説明する。
＜試験品＞の調整
各ケイ酸塩鉱物を３００〜３６０メッシュ程度の粉末にし、粉砕したものを所定の割合に混合し、これに腐植酸１〜５％を加えた後に乾燥し、試験項目として六価クロム、トリクロロエチレン、テトラクロロエチレン、プロピザミド（除草剤）を添加した。
Ａ：田んぼの土のみに試験係る標準物質を混合したもの。
Ｂ：質量比で流紋岩：ヒスイ輝石：白土を１０：５：１０の割合で混合した粉末に腐植酸を含浸乾燥したもの。
Ｃ：質量比で流紋岩：ヒスイ輝石：白土を２０：１：４の割合で混合した粉末に腐植酸を含浸乾燥させたもの。
上記のとおり調整し、約２４時間放置後に環境庁告示第４６号（平成３年８月２３日）に準拠し、試験品Ａ，Ｂ，Ｃと重量体積比１０％の溶媒（ｐＨ５．８〜６．３）と混合し、６時間連続振とうする。
静置後、遠心分離した上澄み液を濾過し、分析した。
その結果を図１の表に示す。
表中、初期濃度は標準物質を水のみで６時間振とうし、分析した値である。
また、表中吸着率は初期濃度１００％に対する比率である。
この結果、Ａの田んぼの土のみの場合でも六価クロム：４３％，プロピザミド（除草剤）：５０％吸着が認められた。
また、トリクロロエチエレン，テトラクロロエチレンは田んぼの土だけでは殆ど吸着されなかった。
これに対して、試験品Ｂ（実施例１）では六価クロム：８３％，トリクロロエチレン：２７％，テトラクロロエチレン：５６％，プロピザミド：８３％までそれぞれ吸着率が上昇した。
また、試験品Ｃ（実施例２）で上記吸着率は六価クロム：８０％，トリクロロエチレン：１５％，テトラクロロエチレン：４３％，プロピザミド：８３％といずれもＡの土のみよりも高い吸着率を示した。
なお、六価クロムは無害とされる三価クロムに還元されて吸着されていることも明らかになった。
よって、本発明に係る活性剤は重金属類、化学物質、農薬等の吸着に優れていることが明らかになった。
A comparative experiment was conducted to confirm the effect of the activator according to the present invention, which will be described below.
Preparation of <test product> Each silicate mineral is made into a powder of about 300 to 360 mesh, and the pulverized material is mixed in a predetermined ratio, and 1 to 5% of humic acid is added thereto, followed by drying. Hexavalent chromium, trichlorethylene, tetrachloroethylene, and propizzamide (herbicide) were added.
A: A mixture of standard substances for testing only in paddy soil.
B: A powder obtained by mixing rhyolite: jadeite: white clay in a ratio of 10: 5: 10 and impregnating and drying with humic acid.
C: A powder obtained by mixing rhyolite: jadeite: white clay in a ratio of 20: 1: 4 by impregnation and drying with humic acid.
In accordance with Environment Agency Notification No. 46 (August 23, 1991) after being adjusted as described above and allowed to stand for about 24 hours, the test products A, B, C and a 10% by weight solvent (pH 5.8 to 6.3) and shake continuously for 6 hours.
After standing, the centrifuged supernatant was filtered and analyzed.
The results are shown in the table of FIG.
In the table, the initial concentration is a value obtained by shaking the standard substance with water alone for 6 hours.
The adsorption rate in the table is a ratio to the initial concentration of 100%.
As a result, adsorption of hexavalent chromium: 43% and propizzamide (herbicide): 50% was recognized even in the case of the rice field A alone.
Trichloroethylene and tetrachloroethylene were hardly adsorbed only in the paddy soil.
In contrast, in the test product B (Example 1), the adsorption rate increased to hexavalent chromium: 83%, trichlorethylene: 27%, tetrachloroethylene: 56%, and propizzamide: 83%.
Further, in the test product C (Example 2), the above adsorption rates are hexavalent chromium: 80%, trichloroethylene: 15%, tetrachloroethylene: 43%, propyzamide: 83%, and all show higher adsorption rates than the soil of only A. It was.
It was also found that hexavalent chromium was reduced and adsorbed to harmless trivalent chromium.
Therefore, it became clear that the activator according to the present invention is excellent in adsorption of heavy metals, chemical substances, agricultural chemicals and the like.
次に、上記試験品Ｂ，Ｃに用いたケイ酸塩鉱物の粉末を８００〜１０００℃にて焼成し、約直径１０〜２０ｍｍのセラミックスボールを製造し、このセラミックスボールを腐植酸水溶液に浸漬後、取り出して自然乾燥させた。
このようにして得られた活性剤が菊芋の育生にどのような効果があるか確認した。
５月１１日に種付けし、図２に示した支柱の左側手前の部分はそのままにし、反対の右側奥は根元に上記セラミックスボールを数粒ずつ撒いた。
図２の写真は約５ヶ月経過した１０月の状態を示す。
左側手前の部分の菊芋の背丈は約９０〜１００ｃｍであったのに対して、本発明に係る活性剤を撒いた部分は２ｍ以上の背丈になっていた。
従って、本発明に係る活性剤は植物の育生促進効果を有することが明らかになった。
Next, the silicate mineral powder used in the test products B and C is fired at 800 to 1000 ° C. to produce a ceramic ball having a diameter of about 10 to 20 mm, and the ceramic ball is immersed in a humic acid aqueous solution. , Taken out and air dried.
The effect of the active agent thus obtained on the growth of chrysanthemum was confirmed.
The seeds were seeded on May 11, the left front portion of the column shown in FIG. 2 was left as it was, and the ceramic ball was seeded several times at the base of the opposite right back.
The photograph in FIG. 2 shows the state in October after about 5 months.
The height of chrysanthemum on the left front side was about 90 to 100 cm, whereas the portion coated with the activator according to the present invention had a height of 2 m or more.
Therefore, it became clear that the active agent which concerns on this invention has the growth promotion effect of a plant.
腐植酸は、複雑な構造を持った複数の化合物の混合物であり、高いキレート性を有する。
本発明者らが凍結乾燥したフミン酸試料について、赤外吸収スペクトル及びＮＭＲスペクトル解析をした結果、分子量が約１０万以下のものは、芳香族系のＣＯＯＨ基及びＯＨ基が支配的な官能基であったが、分子量がそれ以上のものは脂肪族系のＣＯＯＨ基及びＯＨ基が支配的な官能基であったことから、卓越した錯形成能力を有する。
よって、イオン強度、酸化還元環境により価数が変化するアクチニド元素、例えばウラン、プルトニウム、トリウムやアメリシウム、ネプツニウム等の放射性元素（放射性核種）を錯体として取り込むことができる。
よって、本発明に係る多孔質セラミックスに腐植酸を固定化した活性剤を用いれば、汚染土壌、汚染水等に含有する放射性核種を選択的に吸着回収することも可能である。
Humic acid is a mixture of a plurality of compounds having a complex structure and has a high chelating property.
As a result of infrared absorption spectrum and NMR spectrum analysis of the humic acid sample freeze-dried by the present inventors, those having a molecular weight of about 100,000 or less are functional groups in which aromatic COOH groups and OH groups are dominant. However, those having a molecular weight higher than that have an excellent complex-forming ability because aliphatic COOH groups and OH groups were dominant functional groups.
Therefore, radioactive elements (radionuclides) such as uranium, plutonium, thorium, americium, and neptunium, whose valence changes depending on ionic strength and redox environment, can be incorporated as a complex.
Therefore, if an activator in which humic acid is immobilized on the porous ceramic according to the present invention is used, it is possible to selectively adsorb and recover radionuclides contained in contaminated soil, contaminated water, and the like.
Claims (3)
前記ケイ酸塩鉱物の粉末は、イノケイ酸塩鉱物４〜２０質量％、フィロケイ酸塩鉱物１６〜４０質量％及び残部がその他のケイ酸塩鉱物からなる混合粉末であることを特徴とする腐植酸含有活性剤の製造方法。 It is obtained by kneading and drying powder obtained by grinding silicate mineral and liquid humic acid made of humic acid, adsorbing heavy metals and chemicals in soil or water, and in soil or water Activates microorganisms,
Powder of the silicate minerals, inosilicate minerals 4-20 wt%, humic acid, which is a mixed powder phyllosilicate mineral 16-40% by weight and the balance being other silicate minerals A method for producing a contained active agent .
前記フィロケイ酸塩鉱物はろう石、白土及びカオリナイトのうちいずれか１種以上であり、
前記その他のケイ酸塩鉱物は流紋岩であることを特徴とする請求項１記載の腐植酸含有活性剤の製造方法。 The inosilicate mineral is jadeite,
The phyllosilicate mineral is any one or more of wax, clay and kaolinite,
The method for producing a humic acid-containing activator according to claim 1, wherein the other silicate mineral is rhyolite.
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