JP6653858B2 - Method for extracting fulvic acid and humic acid, and method for fractionating humic substances - Google Patents
Method for extracting fulvic acid and humic acid, and method for fractionating humic substances Download PDFInfo
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- 239000002509 fulvic acid Substances 0.000 title claims description 104
- 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 title claims description 103
- 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 title claims description 103
- 229940095100 fulvic acid Drugs 0.000 title claims description 103
- 239000004021 humic acid Substances 0.000 title claims description 99
- 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 98
- 239000000126 substance Substances 0.000 title claims description 56
- 238000000034 method Methods 0.000 title claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 106
- 239000000243 solution Substances 0.000 claims description 38
- 238000000605 extraction Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 19
- 238000010306 acid treatment Methods 0.000 claims description 17
- 230000001954 sterilising effect Effects 0.000 claims description 17
- 238000004659 sterilization and disinfection Methods 0.000 claims description 15
- 239000011343 solid material Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002663 humin Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000005194 fractionation Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 81
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 33
- 239000007864 aqueous solution Substances 0.000 description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003864 humus Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 239000002689 soil Substances 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000002361 compost Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- -1 etc.) Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000061 acid fraction Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 235000013402 health food Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 244000000000 soil microbiome Species 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 238000000177 wavelength dispersive X-ray spectroscopy Methods 0.000 description 1
Landscapes
- Fertilizers (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Compounds Of Unknown Constitution (AREA)
Description
本発明は、腐植物質に含まれるフルボ酸およびフミン酸を抽出するための方法、およびその方法を利用した腐植物質の分画方法に関する。 The present invention relates to a method for extracting fulvic acid and humic acid contained in humic substances, and a method for fractionating humic substances using the method.
植物体や動物の糞尿等の有機物を原料として製造された腐植堆肥は、戦後の化学肥料、農薬の多用によって衰弱化した土壌の回復に高い効果を発揮するとともに、植物の育成に欠かせない物質であることが知られている。このため、農業上の窒素、リン酸、カリ等の主要な栄養素に代わって盛んに利用されるようになり、その製造量も急激に増えつつある。 Humus compost made from organic matter, such as plant and animal manure, is highly effective in restoring soil that has been weakened by extensive use of post-war chemical fertilizers and pesticides, and is an essential material for plant growth. It is known that For this reason, it has been actively used in place of major nutrients such as nitrogen, phosphoric acid, and potash in agriculture, and the production amount thereof is also rapidly increasing.
腐植堆肥中に含有される“腐植物質”は、重合度が高く、微生物がこれ以上分解することができない、炭素を骨格とした複合体、より具体的にはリグニンやタンニンが生分解された末に生成されるフェリハイドライト複合体である。近年の研究成果により、腐植物質は水質の浄化、土壌改善、殺菌作用、接触分解作用等の様々な有益な効果を有していることが明らかになりつつある。 The "humic substances" contained in humus compost have a high degree of polymerization and cannot be further decomposed by microorganisms. Carbon-based complexes, more specifically, lignin and tannin are biodegraded It is a ferrihydrite complex produced in. Recent research results have revealed that humic substances have various beneficial effects such as water purification, soil improvement, bactericidal action, and catalytic decomposition action.
腐植物質には、アルカリおよび酸の両方に可溶な成分であるフルボ酸、アルカリには可溶だが酸には不溶な成分であるフミン酸（腐植酸ともいう）、およびアルカリにも酸にも不溶な成分であるヒューミンで構成されている。このうち特にフルボ酸は、植物性プランクトンを含む植物の高い生育促進効果を有することが明らかになっており、近年、人体に対する生理活性効果も期待され、土壌成分から抽出されるフルボ酸のみならず、人為的に量産された植物由来物の生分解残渣から単離抽出されたフルボ酸が健康食品として摂取されている。また、フミン酸も農工業における有用な物資として知られている。 Humic substances include fulvic acid, a component soluble in both alkali and acid, humic acid (also known as humic acid), a component soluble in alkali but insoluble in acid, and both alkali and acid. It is composed of humin, an insoluble component. Among them, fulvic acid has been particularly shown to have a high growth promoting effect on plants including phytoplankton, and in recent years, a physiologically active effect on the human body is also expected, and in addition to fulvic acid extracted from soil components, In addition, fulvic acid isolated and extracted from biodegradation residues of artificially mass-produced plant-derived products is consumed as health food. Humic acid is also known as a useful material in agriculture and industry.
腐植物質からフルボ酸およびフミン酸を抽出する際には、従来、水酸化ナトリウム等の化学薬品が溶解したアルカリ性水溶液が用いられていた。例えば、国際腐植物質学会（ＩＨＳＳ：International Humic Substances Society）が提唱する標準的な手法（ＩＨＳＳ法、http://www.humicsubstances.org/soilhafa.html）では、所定の濃度の水酸化ナトリウム水溶液および水酸化カリウム水溶液を用いることが規定されている。また、特許文献１（特開２０１５−１４７７０２号公報）には、そこに記載されている発明において用いられる腐植酸水溶液を調製する際に、腐植物質水溶液にアルカリ性物質を添加して、腐植物質水溶液のｐＨを９．５以上に調整することが記載されており、そのためのアルカリ性物質として水酸化ナトリウムおよび水酸化カリウムが例示されている。 In extracting fulvic acid and humic acid from humic substances, an alkaline aqueous solution in which a chemical such as sodium hydroxide is dissolved has conventionally been used. For example, in a standard method (IHSS method, http://www.humicsubstances.org/soilhafa.html) proposed by the International Humic Substances Society (IHSS), a predetermined concentration of sodium hydroxide aqueous solution and It is specified that an aqueous solution of potassium hydroxide be used. Further, Patent Literature 1 (Japanese Patent Application Laid-Open No. 2015-147702) discloses that when preparing an aqueous humic acid solution used in the invention described therein, an alkaline substance is added to the aqueous humic substance solution, Is described as adjusting the pH to 9.5 or more, and sodium hydroxide and potassium hydroxide are exemplified as alkaline substances therefor.
上述したような従来のフルボ酸およびフミン酸の抽出方法に用いられる水酸化ナトリウムや水酸化カリウムは強塩基であり、それらの水夜液が人体に触れると火傷や失明のリスクがある。そのような危険性を避けるため取扱いには極めて高い注意を要し、例えばオイルパン、安全防護具といった装備や環境整備が必要となり、生産コスト（設備コスト、管理コスト、ランニングコスト等）がかかる。 Sodium hydroxide and potassium hydroxide used in the conventional methods for extracting fulvic acid and humic acid as described above are strong bases, and there is a risk of burns and blindness when their aqueous solution contacts the human body. In order to avoid such danger, handling requires extremely high care. For example, equipment such as an oil pan and safety protective equipment and environmental maintenance are required, and production costs (equipment costs, management costs, running costs, etc.) are required.
また、水酸化ナトリウム等の化学薬品の水溶液を用いる場合は、フルボ酸およびフミン酸の品質確保の観点から、水溶液のｐＨを一定の値に調整しなければならないが、製造の都度そのような水溶液を調製する工程が必要となる。所定の量の腐植物質からより多くのフルボ酸およびフミン酸を抽出しようとする場合、より多くの水酸化ナトリウム等の化学薬品を水に溶解して、アルカリ性のより強い水溶液を調製する必要があるため、生産コストの上昇につながる。 When using an aqueous solution of a chemical such as sodium hydroxide, the pH of the aqueous solution must be adjusted to a constant value from the viewpoint of ensuring the quality of fulvic acid and humic acid. Is required. When trying to extract more fulvic and humic acids from a given amount of humic substances, it is necessary to dissolve more chemicals such as sodium hydroxide in water to prepare a more alkaline aqueous solution This leads to an increase in production costs.
さらに、これらのアルカリ性水溶液で抽出処理を行った後、酸を用いて中和処理を行う必要があるが、それにより副産物として塩類が生成してしまう。例えば、水酸化ナトリウム（NaOH）を用いた抽出処理の後、塩酸（HCl）を用いて中和処理を行えば、塩化ナトリウム（NaCl）が生成し、水酸化カリウム（KOH）を用いた抽出処理の後、硫酸（H2SO4）で中和処理を行えば、硫酸カリウム（K2SO4）が生成する。フルボ酸およびフミン酸は、農業分野やパーソナルケアの分野で使用することが想定されているため、上記のようにして生成した塩類が混入していると、植物や人体に対して悪影響を与えるおそれがある。また、塩酸を使用した場合プラント等が腐蝕し錆等の発生につながる。品質管理の問題やプラントの耐久年数にもかかわるため、これらの問題を解決することも可能となる。 Furthermore, after performing the extraction treatment with these alkaline aqueous solutions, it is necessary to carry out a neutralization treatment using an acid, which results in the formation of salts as a by-product. For example, if an extraction treatment using sodium hydroxide (NaOH) is performed and then a neutralization treatment is performed using hydrochloric acid (HCl), sodium chloride (NaCl) is generated, and the extraction treatment using potassium hydroxide (KOH) is performed. Thereafter, if a neutralization treatment is performed with sulfuric acid (H 2 SO 4 ), potassium sulfate (K 2 SO 4 ) is generated. Fulvic acid and humic acid are supposed to be used in the fields of agriculture and personal care, so if the salts generated as described above are mixed, they may have an adverse effect on plants and the human body There is. Further, when hydrochloric acid is used, the plant and the like are corroded, which leads to generation of rust and the like. These problems can be solved because they are related to quality control problems and the life of the plant.
加えて、水酸化ナトリウム水溶液等を用いた場合には、フルボ酸およびフミン酸以外の成分、例えば腐植堆肥等に含まれているリグニンやセルロールなども溶出しやすい。そのような成分は植生などに影響を与えることがあり、結果的にフルボ酸およびフミン酸本来の機能が発揮されなくなるおそれがある。
本発明は、従来よりも高品質なフルボ酸およびフミン酸の抽出物が得られ、かつ安全に、低コストで実施することができる手段を提供することを課題とする。
In addition, when an aqueous solution of sodium hydroxide or the like is used, components other than fulvic acid and humic acid, for example, lignin and cellulose contained in humus compost and the like are also easily eluted. Such components may affect vegetation and the like, and as a result, the essential functions of fulvic acid and humic acid may not be exhibited.
An object of the present invention is to provide a means capable of obtaining a higher quality extract of fulvic acid and humic acid than before and providing a safe and low-cost extract.
本発明者らは、水酸化ナトリウム等の化学薬品を溶解した水溶液ではなくアルカリ性電解水を用いることにより、副生する塩類の生成量を抑制し、従来と同等以上の高い効率で、腐植物質からフルボ酸およびフミン酸を簡便かつ安全に抽出することができることを見出した。 The present inventors have found that by using alkaline electrolyzed water instead of an aqueous solution in which chemicals such as sodium hydroxide are dissolved, the amount of salts produced as by-products can be suppressed, and a high efficiency equal to or higher than that of conventional products, It has been found that fulvic acid and humic acid can be easily and safely extracted.
すなわち、本発明は一つの側面において、アルカリ性電解水に腐植物質を含有する固形原料を浸漬することにより、その腐植物質のうちフルボ酸およびフミン酸をアルカリ性電解水中に抽出し、ヒューミンと分離することを特徴とする、フルボ酸およびフミン酸の抽出方法を提供する。前記アルカリ性電解水は４０〜７０℃であることが好ましいがそれ以上の温度でもそれ以下の温度でも抽出は可能である。前記アルカリ性電解水のｐＨ（２５℃）は１１．０〜１３．０であることが好ましい。 That is, in one aspect of the present invention, by immersing a solid material containing humic substances in alkaline electrolyzed water, fulvic acid and humic acid among the humic substances are extracted into the alkaline electrolyzed water and separated from humin. And a method for extracting fulvic acid and humic acid. The alkaline electrolyzed water is preferably at 40 to 70 ° C., but extraction can be performed at a higher temperature or a lower temperature. The pH (25 ° C.) of the alkaline electrolyzed water is preferably 11.0 to 13.0.
本発明はもう一つの側面において、上記のような抽出方法を用いた処理により、フルボ酸およびフミン酸が抽出されたアルカリ性電解水処理液を調製し、その処理液とヒューミンを含有する残渣とを分離する工程（アルカリ性電解水処理工程）を含むことを特徴とする、腐植物質の分画方法を提供する。この分画方法はさらに、アルカリ性電解水処理液を加熱殺菌する工程（加熱殺菌工程）、および／または、アルカリ性電解水処理液に酸を添加する処理により、フルボ酸を含有する酸処理液と、フミン酸を含有する沈殿物とを分離する工程（酸処理工程）を含むことができる。 In another aspect, the present invention provides an alkaline electrolyzed water treatment liquid from which fulvic acid and humic acid have been extracted by treatment using the above-described extraction method, and treating the treatment liquid and a residue containing humin. A method for fractionating humic substances, comprising a step of separating (alkaline electrolytic water treatment step). The fractionation method further comprises a step of heat-sterilizing the alkaline electrolyzed water treatment liquid (heat sterilization step), and / or an acid treatment liquid containing fulvic acid by a treatment of adding an acid to the alkaline electrolyzed water treatment liquid, A step of separating from a precipitate containing humic acid (acid treatment step) can be included.
本発明で用いるアルカリ性電解水は、水酸化ナトリウム等の強塩基の水溶液のような人体に対する危険性がなく、作業上の安全性の確保が容易である。また、アルカリ性水溶液を用いた抽出処理の効率を高めたければ、よりアルカリ性の強いアルカリ性水溶液を用いればよく、好ましくは加熱すればよいが、水酸化ナトリウム等の化学薬品の使用量を増やす場合に比べてコストの上昇は抑えられる。さらに、フルボ酸およびフミン酸の抽出処理の際に、副生する塩類の量が抑制され、あわせて腐植物質の固形原料からのリグニンやセルロースの溶出も抑制されるので、純度の高いフルボ酸およびフミン酸を製造することができる。このような本発明により得られるフルボ酸およびフミン酸を使用することにより、障害発生のリスクを低減しつつ、それらが有する機能性を向上させることが可能となる。 The alkaline electrolyzed water used in the present invention has no danger to the human body as in the case of an aqueous solution of a strong base such as sodium hydroxide or the like, and it is easy to secure work safety. In addition, if it is desired to increase the efficiency of the extraction treatment using an alkaline aqueous solution, a more alkaline aqueous solution may be used, and preferably heating may be performed, but compared with a case where the amount of use of a chemical such as sodium hydroxide is increased. The rise in costs can be suppressed. Furthermore, during the extraction treatment of fulvic acid and humic acid, the amount of by-produced salts is suppressed, and the elution of lignin and cellulose from the solid raw material of humic substances is also suppressed. Humic acid can be produced. By using such fulvic acid and humic acid obtained by the present invention, it is possible to improve the functionality of the fulvic acid and the humic acid while reducing the risk of occurrence of a failure.
−フルボ酸およびフミン酸の抽出方法−
本発明によるフルボ酸およびフミン酸の抽出方法は、アルカリ性電解水に腐植物質を含有する固形原料を浸漬することにより、その腐植物質のうちフルボ酸およびフミン酸をアルカリ性電解水中に抽出し、ヒューミンと分離する、という方法である。この抽出方法を用いた処理は、図１中に「アルカリ性電解水処理」として示されている。
-Extraction method of fulvic acid and humic acid-
The method for extracting fulvic acid and humic acid according to the present invention comprises immersing a solid material containing humic substances in alkaline electrolytic water to extract fulvic acid and humic acid from the humic substances into alkaline electrolytic water, It is a method of separating. The treatment using this extraction method is shown as “alkaline electrolyzed water treatment” in FIG.
・腐植物質
腐植物質は、生物（主に植物）の死後、その生物体を構成していたリグニン、多糖類、タンパク質、脂質、核酸等の有機物が、化学的および微生物学的な作用を受けることにより生成する、化学構造が特定されない高分子化合物などの有機物の総称である。このような腐植物質は一般的に、アルカリおよび酸に対する溶解性に基づいて、フルボ酸（アルカリ可溶・酸可溶成分）、フミン酸（アルカリ可溶・酸不可溶成分、腐植酸ともいう）およびヒューミン（アルカリ不可溶、酸不可溶成分）の３成分に分類される。これらの各成分も、多様な有機物の混合物となっている。腐植物質が生成した環境により、腐植物質の組成、すなわち上記３成分の含有量や、各成分に該当する有機物の種類および含有量は変動する。
-Humic substances Humic substances are substances in which organic matter, such as lignin, polysaccharides, proteins, lipids, and nucleic acids, that constitutes the organism after the death of the organism (mainly plants) undergoes chemical and microbiological effects. Is a generic term for organic substances such as polymer compounds whose chemical structure is not specified. Such humic substances are generally based on solubility in alkali and acid, such as fulvic acid (alkali-soluble / acid-soluble component), humic acid (alkali-soluble / acid-insoluble component, also called humic acid). And humin (alkaline insoluble and acid insoluble components). Each of these components is also a mixture of various organic substances. The composition of the humic substance, that is, the content of the above three components, and the type and content of the organic substance corresponding to each component vary depending on the environment in which the humic substance is generated.
フルボ酸、フミン酸およびヒューミンはそれぞれ、国際腐植物質学会（ＩＨＳＳ：International Humic Substances Society）が提唱する標準的な手法（ＩＨＳＳ法、http://www.humicsubstances.org/soilhafa.htmlおよび図２参照）により、土壌（腐植土、湖底堆積物、泥炭等）、堆肥（人工腐植）、天然水（湖沼水、河川水、地下水等）などの腐植物質を含有する原料から、分離精製することができる物質とされている。本発明におけるフルボ酸およびフミン酸は、ＩＨＳＳ法において「１Ｍ ＮａＯＨでｐＨ７に中和」および「０．１Ｍ ＮａＯＨで４時間振盪」を用いるとされている処理を、アルカリ性電解水を用いて行うことにより得られる物質である。 Each of fulvic acid, humic acid and humin is a standard method (IHSS method, http://www.humicsubstances.org/soilhafa.html and FIG. 2) proposed by the International Humic Substances Society (IHSS). ), It can be separated and purified from raw materials containing humic substances such as soil (humus, lake bottom sediment, peat, etc.), compost (artificial humus), natural water (lake water, river water, groundwater, etc.). It is a substance. The fulvic acid and humic acid in the present invention may be treated with alkaline electrolyzed water in the IHSS method, assuming that "neutralize to pH 7 with 1 M NaOH" and "shake with 0.1 M NaOH for 4 hours" are used. Is a substance obtained by
本発明では、上記の腐植物質を含有する原料のうち、土壌、堆肥等の固形状の原料（本明細書において「腐植物質固形原料」という。）を用い、それをアルカリ性電解水に浸漬してフルボ酸およびフミン酸を抽出する。 In the present invention, among the raw materials containing humic substances described above, solid raw materials such as soil and compost (hereinafter referred to as “humic solid solid raw materials”) are used and immersed in alkaline electrolytic water. Extract fulvic acid and humic acid.
・アルカリ性電解水
アルカリ性電解水は、当業者にとって周知のように、隔膜を挟んで配置された陰極および陽極を備える電解槽内で水を電気分解したときに陰極側で生成する、水酸化物イオン（ＯＨ-）を含む水である。電気分解のために電解補助剤（例えばＮａＣｌ）を用いたときには、その電解補助剤から生成する陽イオン（例えばＮａ+）もアルカリ性電解水に含まれる。
Alkaline electrolyzed water Alkaline electrolyzed water, as is well known to those skilled in the art, is a hydroxide ion generated on the cathode side when water is electrolyzed in an electrolytic cell having a cathode and an anode arranged with a diaphragm interposed therebetween. (OH − ) -containing water. When an electrolysis aid (eg, NaCl) is used for electrolysis, cations (eg, Na + ) generated from the electrolysis aid are also included in the alkaline electrolyzed water.
アルカリ性電解水と一般的なアルカリ性水溶液（例えばＮａＯＨ水溶液、ＫＯＨ水溶液）を比較すると、ｐＨが同じであるとしても溶存酸素量（ＤＯ）および酸化還元電位（ＯＲＰ）が異なるため、両者は物質として区別しうる。すなわち、アルカリ性電解水は、電気分解の際に陰極において水（Ｈ2Ｏ）から水素ガス（Ｈ2）および水酸化物イオン（ＯＨ-）が生じ、水中の溶存酸素はその水素ガスと反応して減少するため、ＤＯおよびＯＲＰはアルカリ性水溶液よりも低くなる。 When alkaline electrolyzed water is compared with a general alkaline aqueous solution (for example, NaOH aqueous solution, KOH aqueous solution), even if the pH is the same, the dissolved oxygen amount (DO) and the oxidation-reduction potential (ORP) are different. Can. In other words, alkaline electrolyzed water generates hydrogen gas (H 2 ) and hydroxide ions (OH − ) from water (H 2 O) at the cathode during electrolysis, and dissolved oxygen in the water reacts with the hydrogen gas. DO and ORP are lower than the alkaline aqueous solution.
本発明では、ｐＨ９〜１０程度の弱アルカリ性電解水（飲用アルカリ性電解水、いわゆる「アルカリイオン水」）を用いることもできるし、ｐＨが１０以上の強アルカリ性電解水を用いることもできる。アルカリ性電解水のｐＨは、１０．０〜１３．０が好ましく、１１．０〜１３．０がより好ましく、１２．０〜１３．０が特に好ましい。アルカリ性電解水のｐＨの値は、本発明を実施する温度環境下（通常は室温、例えば２０〜２５℃）における測定値、または他の温度での測定値に基づくその温度環境下での換算値とする。強アルカリ性を長期間保持した電解水は、例えば、特開平８−２４８６５号公報に記載された技術に基づいて製造することができる。 In the present invention, weakly alkaline electrolyzed water having a pH of about 9 to 10 (drinkable alkaline electrolyzed water, so-called “alkaline ionized water”) can be used, or strongly alkaline electrolyzed water having a pH of 10 or more can be used. The pH of the alkaline electrolyzed water is preferably 10.0 to 13.0, more preferably 11.0 to 13.0, and particularly preferably 12.0 to 13.0. The pH value of the alkaline electrolyzed water is a measured value under a temperature environment in which the present invention is performed (usually room temperature, for example, 20 to 25 ° C.), or a converted value under the temperature environment based on a measured value at another temperature. And Electrolyzed water that maintains strong alkalinity for a long period of time can be produced, for example, based on the technique described in JP-A-8-24865.
なお、アルカリ性電解水を用いて抽出処理を行っている最中、時間の経過と共にｐＨが低下する（アルカリ性側から中性側に変化する）が、所望の濃度の抽出液が得られる限り特に問題はない。フルボ酸およびフミン酸の抽出処理により得られるアルカリ性電解水処理液を、フルボ酸およびフミン酸を分画することなく、つまり酸処理することなく、フルボ酸およびフミン酸の混合物としてそのまま用いるような場合には、上記のようにｐＨが中性に近づくことにより、土壌等への影響を小さなものとすることができる。 During the extraction process using the alkaline electrolyzed water, the pH decreases with the passage of time (changes from the alkaline side to the neutral side), but as long as an extract having a desired concentration can be obtained, there is no particular problem. There is no. When the alkaline electrolyzed water treatment solution obtained by the extraction treatment of fulvic acid and humic acid is used as it is as a mixture of fulvic acid and humic acid without fractionating fulvic acid and humic acid, that is, without acid treatment In this case, the influence on soil and the like can be reduced by bringing the pH closer to neutral as described above.
・抽出条件
アルカリ性電解水に浸漬する前に、腐植物質固形原料はあらかじめ十分に乾燥させておくことが好ましい。また、腐植物質固形原料は通常、根などを取り除き、篩にかけたものを用いる。
-Extraction conditions Before immersion in alkaline electrolyzed water, the humic solid material is preferably sufficiently dried in advance. Further, as the humic solid raw material, one obtained by removing roots and the like and sieving is usually used.
腐植物質固形原料を浸漬するアルカリ性電解水は、４０〜７０℃に加熱することが好ましい。このような加熱されたアルカリ性電解水中を用いれば、腐植物質固形原料からのフルボ酸およびフミン酸の抽出効率（抽出速度および最終的な抽出液の濃度）を向上させることができる。 The alkaline electrolyzed water into which the humic solid material is immersed is preferably heated to 40 to 70 ° C. Use of such heated alkaline electrolyzed water can improve the extraction efficiency (extraction rate and final extract concentration) of fulvic acid and humic acid from humic solid materials.
アルカリ性電解水への腐植物質固形原料の浸漬時間は、所望の濃度の抽出液が得られるよう適宜調節する。通常は１２時間以上であるが、原料の状態によって調整する。特に時間の上限はない。 The immersion time of the humic solid material in the alkaline electrolyzed water is appropriately adjusted so as to obtain an extract having a desired concentration. Usually, it is 12 hours or more, but it is adjusted according to the state of the raw material. There is no particular upper limit for time.
−分画方法−
本発明による腐植物質の分画方法は、少なくとも、上述したような本発明の抽出方法を用いた処理により、フルボ酸およびフミン酸が抽出されたアルカリ性電解水処理液を調製し、その処理液とヒューミンを含有する不溶残渣とを分離する工程（アルカリ性電解水処理工程）を含む。本発明による腐植物質の分画方法は、必要に応じて、アルカリ性電解水処理工程の後に、後処理工程として、アルカリ性電解水処理液を加熱殺菌する工程（加熱殺菌工程）を含んでいてもよく、さらに、アルカリ性電解水処理工程または加熱殺菌工程の後に、アルカリ性電解水処理液に酸を添加する処理により、フルボ酸を含有する酸処理液と、フミン酸を含有する沈殿物とを分離する工程（酸処理工程）を含んでいてもよい。すなわち、製造目的に応じて、フルボ酸およびフミン酸を分離する必要がなくそれらの混合液を得られればよい場合は、上記の酸処理工程は不要であるし、その混合液からさらにフルボ酸およびフミン酸それぞれの粗製物または精製物を得たい場合は、上記の酸処理工程を実施すればよい。
-Fractionation method-
The method for fractionating humic substances according to the present invention comprises, at least, a treatment using the extraction method of the present invention as described above to prepare an alkaline electrolyzed water treatment solution from which fulvic acid and humic acid have been extracted. A step of separating from the insoluble residue containing humin (alkaline electrolyzed water treatment step) is included. The method for fractionating humic substances according to the present invention may optionally include, after the alkaline electrolyzed water treatment step, a step of heat sterilizing the alkaline electrolyzed water treatment liquid (heat sterilization step) as a post-treatment step. Further, after the alkaline electrolyzed water treatment step or the heat sterilization step, a process of adding an acid to the alkaline electrolyzed water treatment liquid, thereby separating an acid treatment liquid containing fulvic acid and a precipitate containing humic acid. (Acid treatment step). That is, if it is sufficient to obtain a mixed solution of fulvic acid and humic acid without the need to separate the fulvic acid and humic acid depending on the production purpose, the above-mentioned acid treatment step is unnecessary, and further from the mixed solution, fulvic acid and humic acid If it is desired to obtain a crude or purified humic acid, the above-mentioned acid treatment step may be performed.
このような本発明の腐植物質の分画方法は基本的にＩＨＳＳ法（図２参照）に準じており、ＩＨＳＳ法においてアルカリ性水溶液（水酸化ナトリウム水溶液または水酸化カリウム水溶液）を用いて行われている処理を、アルカリ性電解水を用いて行う処理に置き換えることによって実施することができる。すなわち、本発明では少なくとも、ＩＨＳＳ法において「０．１Ｍ ＮａＯＨ」を用いて行われるとされている、「残さ土壌」（腐植物質固形原料に相当）からフルボ酸およびフミン酸を抽出する処理を、「アルカリ性電解水」を用いて行うようにすればよい。 Such a method for fractionating humic substances of the present invention basically conforms to the IHSS method (see FIG. 2), and is performed using an alkaline aqueous solution (aqueous sodium hydroxide solution or aqueous potassium hydroxide solution) in the IHSS method. Can be implemented by replacing the existing process with a process using alkaline electrolyzed water. That is, in the present invention, at least the process of extracting fulvic acid and humic acid from “residual soil” (corresponding to humic solid material), which is said to be performed using “0.1 M NaOH” in the IHSS method, What is necessary is just to carry out using "alkaline electrolyzed water".
なお、ＩＨＳＳ法は学術的な目的で、各種の試料に含まれる腐植物質を共通の指標の元で比較検討するために作られた方法である。本発明の腐植物質の分画方法は、目的とする製品の品質を考慮したときに、ＩＨＳＳ法で行われている工程の一部が不要であれば、それを省略することもできる。例えば、ＩＨＳＳ法では、本発明のアルカリ性電解水処理工程に相当する１ＭのＮａＯＨ水溶液を用いた工程の前に、まず腐植物質固形原料（風乾土）を１ＭのＨＣｌ水溶液で処理する工程が行われ、そこで得られた第１の上澄み液と、当該ＨＣｌ処理の残渣土壌に対して行われた１ＭのＮａＯＨ水溶液での処理により得られた第２の上澄み液を、フルボ酸の精製のために用いる（図１参照）が、本発明では、アルカリ性電解水処理工程および酸処理工程により十分な濃度のフルボ酸画分が得られるようであれば、ＩＨＳＳ法で最初に行われていた１ＭのＨＣｌ水溶液で処理する工程を省略することができる。 Note that the IHSS method is a method created for academic purposes to compare and examine humic substances contained in various samples under a common index. In the method for fractionating humic substances of the present invention, if a part of the steps performed by the IHSS method is unnecessary when the quality of the target product is taken into consideration, it can be omitted. For example, in the IHSS method, before the step using an aqueous 1 M NaOH solution corresponding to the alkaline electrolyzed water treatment step of the present invention, a step of first treating a humic solid material (air-dry soil) with an aqueous 1 M HCl solution is performed. The first supernatant obtained therefrom and the second supernatant obtained by treating the residual soil of the HCl treatment with a 1 M aqueous NaOH solution are used for purification of fulvic acid. However, in the present invention, if a fulvic acid fraction having a sufficient concentration can be obtained by the alkaline electrolyzed water treatment step and the acid treatment step, a 1M HCl aqueous solution which has been first performed by the IHSS method is used. Can be omitted.
（１）アルカリ性電解水処理工程
アルカリ性電解水処理工程は具体的には、例えば図２に示すように、（１ａ）アルカリ性電解水に腐植物質含有固形原料を浸漬することにより、その腐植物質のうちフルボ酸およびフミン酸をアルカリ性電解水中に抽出する工程（アルカリ性電解水浸漬工程）、および（１ｂ）当該工程により得られる、フルボ酸およびフミン酸が溶解しているアルカリ性電解水処理液（フルボ酸・フミン酸画分）と、アルカリ性電解水に溶解しなかった残渣（ヒューミン画分）とを分離する工程（不溶残渣分離工程）によって実施することができる。換言すれば、アルカリ性電解水処理工程を含む本発明の腐植物質の分画方法は、フルボ酸・フミン酸画分、ヒューミン画分それぞれの製造方法といえる。アルカリ性電解水処理工程に含まれる各工程は、従来の腐植物質の分画方法と同様の、一般的な器具ないし装置を用いて行うことができる。
(1) Alkaline electrolyzed water treatment step Specifically, the alkaline electrolyzed water treatment step is, for example, as shown in FIG. A step of extracting fulvic acid and humic acid into alkaline electrolytic water (alkaline electrolytic water immersion step); (Humic acid fraction) and a residue (humin fraction) not dissolved in the alkaline electrolyzed water (insoluble residue separation step). In other words, the method for fractionating humic substances of the present invention including the alkaline electrolytic water treatment step can be said to be a method for producing each of the fulvic acid / humic acid fraction and the humin fraction. Each of the steps included in the alkaline electrolyzed water treatment step can be performed using a common instrument or device similar to the conventional method for fractionating humic substances.
アルカリ性電解水浸漬工程は、例えば、容器内に腐植物質固形原料を充填しておき、そこにアルカリ性電解水を投入し、撹拌、混合するようにすればよい。このような手順は、アルカリ性電解水に腐植物質固形原料を投入するよりも、浸漬直後のアルカリ性電解水のｐＨの変動を抑制することができるため好ましい。アルカリ性電解水のｐＨおよび量（腐植物質固形原料との混合割合）や処理時間などの条件は、前述したような本発明の「フルボ酸およびフミン酸の抽出方法」の条件を考慮しながら、適宜調節することができる。例えば、アルカリ性電解水の投入量は、腐植物質固形原料に対して約１０倍量が好ましい。 In the alkaline electrolytic water immersion step, for example, a container is filled with a humic solid material, and alkaline electrolytic water is charged therein, followed by stirring and mixing. Such a procedure is preferable because the fluctuation of the pH of the alkaline electrolyzed water immediately after immersion can be suppressed as compared with the case where the humic solid material is added to the alkaline electrolyzed water. Conditions such as the pH and amount of alkaline electrolyzed water (mixing ratio with the humic substance solid raw material) and the treatment time are appropriately determined in consideration of the above-mentioned “Method for extracting fulvic acid and humic acid” of the present invention. Can be adjusted. For example, the input amount of the alkaline electrolyzed water is preferably about 10 times the amount of the humic solid material.
不溶残渣分離工程は、例えば、遠心分離および／または濾過を行うことにより、フルボ酸・フミン酸画分としてアルカリ性電解水処理液を回収すればよい。必要であれば、例えば遠心分離によってフルボ酸およびフミン酸を含有する上澄みを回収した後、その上澄みを所望の孔径および材質のフィルターで濾過することにより、分子量がより小さいフルボ酸と、分子量がより大きいフミン酸を分画して、それぞれフルボ酸画分の溶液およびフミン酸画分の溶液として回収することも可能である。 In the insoluble residue separation step, for example, centrifugation and / or filtration may be performed to collect the alkaline electrolyzed water treatment liquid as a fulvic acid / humic acid fraction. If necessary, a supernatant containing fulvic acid and humic acid is recovered by, for example, centrifugation, and then the supernatant is filtered through a filter having a desired pore size and material. It is also possible to fractionate the large humic acid and recover it as a solution of the fulvic acid fraction and a solution of the humic acid fraction, respectively.
（２）加熱殺菌工程
次の酸処理工程を行わず、アルカリ性電解水処理液を製品とする場合、または次の酸処理工程を行うまで一定期間保管する場合などには、アルカリ性電解水処理液の後処理工程として、加熱殺菌（レトルト殺菌）工程を行うことが好ましい。
(2) Heat sterilization step In the case where an alkaline electrolyzed water treatment liquid is used as a product without performing the next acid treatment step, or when the alkaline electrolyzed water treatment liquid is stored for a certain period of time until the next acid treatment step is performed, for example, As a post-treatment step, a heat sterilization (retort sterilization) step is preferably performed.
加熱殺菌工程の条件は適宜調節することができるが、土壌菌などが含まれることを前提とすると、アルカリ電解水を封入後、芯温が１１０℃以上となるよう１５分から２０分加熱し、レトルト殺菌することが望ましい。このような一般的な条件下では、アルカリ性電解水処理液に含まれるフルボ酸およびフミン酸の含有量に実質的な影響は無い。 The conditions of the heat sterilization step can be adjusted as appropriate. However, assuming that soil bacteria and the like are contained, after filling the alkaline electrolyzed water, the mixture is heated for 15 to 20 minutes so that the core temperature becomes 110 ° C. or higher, and the retort is heated. It is desirable to sterilize. Under such general conditions, there is substantially no effect on the contents of fulvic acid and humic acid contained in the alkaline electrolyzed water treatment solution.
（３）酸処理工程
酸処理工程は具体的には、例えば図２に示すように、（３ａ）アルカリ性電解水処理液（フルボ酸・フミン酸画分）に酸性の水溶液を添加する工程（酸添加工程）、および（３ｂ）当該工程により得られる、フルボ酸が溶解している酸処理液（フルボ酸画分）と、酸に不溶であるために生じた沈殿物（フミン酸画分）とを分離する工程（沈殿分離工程）によって実施することができる。換言すれば、酸処理工程を含む本発明の腐植物質の分画方法は、フルボ酸画分、フミン酸画分それぞれの製造方法といえる。酸処理工程に含まれる各工程も、従来の腐植物質の分画方法と同様の、一般的な器具ないし装置を用いて行うことができる。
(3) Acid Treatment Step Specifically, the acid treatment step is, for example, as shown in FIG. 2, a step of adding an acidic aqueous solution to the (3a) alkaline electrolyzed water treatment solution (fulvic acid / humic acid fraction) (acid Addition step), and (3b) an acid-treated solution (fulvic acid fraction) in which fulvic acid is dissolved, which is obtained in the step, and a precipitate (humic acid fraction) generated due to insolubility in acid. (Separation separation step). In other words, the method for fractionating humic substances of the present invention including the acid treatment step can be said to be a method for producing each of the fulvic acid fraction and the humic acid fraction. Each of the steps included in the acid treatment step can also be performed using a common instrument or device similar to the conventional method for fractionating humic substances.
酸添加工程は、例えば、容器内にアルカリ性電解水処理液を入れておき、そこに酸性の水溶液を投入し、撹拌、混合するようにすればよい。添加する酸は、塩酸等の無機酸であってもよいし、クエン酸等の有機酸であってもよい。添加する酸の濃度および量（酸添加後のｐＨ）や処理時間などの条件は、従来の分画方法に準じて、適宜調節することができる。 In the acid addition step, for example, an alkaline electrolyzed water treatment liquid may be placed in a container, an acidic aqueous solution may be charged therein, and the mixture may be stirred and mixed. The acid to be added may be an inorganic acid such as hydrochloric acid or an organic acid such as citric acid. Conditions such as the concentration and amount of the acid to be added (pH after addition of the acid) and the treatment time can be appropriately adjusted according to the conventional fractionation method.
沈殿分離工程は、例えば、遠心分離を行うことにより、酸処理液を上澄みとして回収することができる。必要であればさらに、その上澄みを所望の孔径のフィルターで濾過し、その濾液をフルボ酸画分としてもよい。 In the precipitation separation step, for example, the acid-treated solution can be collected as a supernatant by centrifugation. If necessary, the supernatant may be further filtered through a filter having a desired pore size, and the filtrate may be used as a fulvic acid fraction.
アルカリ性電解水処理工程によって得られる処理液の、フルボ酸およびフミン酸の濃度は、腐植物質固形原料の性状、アルカリ性電解水のｐＨおよび使用量（腐植物質固形原料との混合割合）、抽出温度（加熱の有無）、抽出時間、その他の抽出条件によって変動し、一概に決められるものではない。一例として、抽出温度が４０〜７０℃（加熱あり）の場合、常温（加熱なし）の場合と比較して、フルボ酸の抽出量は１．２〜１．５倍程度、フミン酸の抽出量は２〜３倍程度に向上する傾向にある。 The concentration of fulvic acid and humic acid in the treatment liquid obtained in the alkaline electrolyzed water treatment step is determined by the properties of the humic solid material, the pH and amount of the alkaline electrolyzed water (mixing ratio with the humic solid material), and the extraction temperature ( It varies depending on the presence or absence of heating), the extraction time, and other extraction conditions, and cannot be unconditionally determined. As an example, when the extraction temperature is 40 to 70 ° C. (with heating), the extraction amount of fulvic acid is about 1.2 to 1.5 times that of normal temperature (without heating), and the extraction amount of humic acid. Tends to improve about two to three times.
・その他の工程
必要であれば、酸処理工程後に、フルボ酸およびフミン酸それぞれの純度を高めるための精製工程や、乾燥粉末化工程を、ＩＨＳＳ法に準じて行ってもよい。フルボ酸の精製工程は、ＸＡＤ−８カラムまたはそれと同等の性能を有するＸＤＡ−８カラムを吸着樹脂として用いることにより、また適切な陽イオン交換樹脂を用いることにより、行うことができる。所望に応じてヒューミンについても、純度を高めるための精製工程や、乾燥粉末化工程を行ってもよい。また、酸処理工程後に得られるフルボ酸画分は水溶液の状態であるが、必要に応じて、減圧処理やドライ乾燥等により濃縮してもよい。
-Other Steps If necessary, after the acid treatment step, a purification step for increasing the purity of each of fulvic acid and humic acid and a dry powdering step may be performed according to the IHSS method. The purification step of fulvic acid can be performed by using an XAD-8 column or an XDA-8 column having the same performance as the adsorption resin, and by using an appropriate cation exchange resin. If desired, humin may be subjected to a purification step for increasing the purity or a dry powdering step. The fulvic acid fraction obtained after the acid treatment step is in the form of an aqueous solution, but may be concentrated by a reduced pressure treatment, dry drying, or the like, if necessary.
以上の、本発明に係るフルボ酸およびフミン酸の抽出方法、ならびに腐植物質の分画方法には、本発明の作用効果を阻害しない範囲で、これらの技術分野に属するないし関連する、公知の技術的事項を適宜組み合わせて実施することが可能である。 The above-described methods for extracting fulvic acid and humic acid and the method for fractionating humic substances according to the present invention belong to or are related to these technical fields as long as the effects of the present invention are not inhibited. It is possible to implement by appropriately combining the objectives.
［実施例１］
容器に腐植２００ｇを充填し、そこに常温のｐＨ１２．１のアルカリ性電解水１Ｌを投入し、よく撹拌してから、常温のまま２４時間放置した。その後、不織布フィルターパックにより不溶残渣を除去し、アルカリ性電解水処理液（フルボ酸・フミン酸画分）を回収した。回収したアルカリ性電解水処理液を実施例１の試料とした。なお、実施例１において、腐植投入から５時間経過後のアルカリ性電解水処理液のｐＨは９．０であった。
[Example 1]
The container was filled with 200 g of humus, 1 L of alkaline electrolyzed water having a pH of 12.1 at room temperature was added thereto, stirred well, and allowed to stand at room temperature for 24 hours. Thereafter, insoluble residues were removed with a nonwoven filter pack, and an alkaline electrolyzed water treatment solution (fulvic acid / humic acid fraction) was recovered. The collected alkaline electrolyzed water treatment liquid was used as a sample of Example 1. In Example 1, the pH of the alkaline electrolyzed water treatment solution 5 hours after the humus was introduced was 9.0.
［実施例２］
実施例１と同様にしてアルカリ性電解水処理液を回収した後、その処理液を１２０℃で６０分、加熱殺菌処理した。加熱殺菌処理したアルカリ性電解水処理液を実施例２の試料とした。
[Example 2]
After recovering the alkaline electrolyzed water treatment liquid in the same manner as in Example 1, the treatment liquid was subjected to heat sterilization treatment at 120 ° C. for 60 minutes. The alkaline electrolyzed water treatment liquid subjected to the heat sterilization treatment was used as a sample of Example 2.
［実施例３］
容器に腐植１００ｇを充填し、そこに７０℃に加熱したｐＨ１２のアルカリ性電解水１Ｌを投入し、よく撹拌してから、７０℃に保ったまま８時間保温し、その後１６時間放置した。その後、不織布フィルターパックにより不溶残渣を除去し、アルカリ性電解水処理液を回収した。回収したアルカリ性電解水処理液を実施例３の試料とした。
[Example 3]
A container was filled with 100 g of humus, 1 L of alkaline electrolyzed water having a pH of 12 heated to 70 ° C. was added thereto, and the mixture was stirred well, then kept at 70 ° C. for 8 hours, and then allowed to stand for 16 hours. Thereafter, insoluble residues were removed with a nonwoven filter pack, and an alkaline electrolyzed water treatment solution was recovered. The recovered alkaline electrolyzed water treatment liquid was used as a sample of Example 3.
［実施例４］
実施例３と同様にしてアルカリ性電解水処理液を回収した後、その処理液を１２０℃で６０分、加熱殺菌処理した。加熱殺菌処理したアルカリ性電解水処理液を実施例４の試料とした。
[Example 4]
After collecting the alkaline electrolyzed water treatment liquid in the same manner as in Example 3, the treatment liquid was subjected to heat sterilization treatment at 120 ° C. for 60 minutes. The alkaline electrolyzed water treatment liquid subjected to the heat sterilization treatment was used as a sample of Example 4.
＜フルボ酸およびフミン酸の含有量の測定＞
実施例１〜４の試料（フルボ酸・フミン酸画分）について、そこに含まれるフルボ酸およびフミン酸それぞれの含有量を測定した。測定は、国際腐植物質学会のＩＨＳＳ法（図２参照）に準じて行った。ただし、フッ酸（ＨＦ）処理は行わなかった。また、フルボ酸用吸着樹脂として、XAD-8の代わりにSupelite DAX-8（Sigma-Aldrich製）を用い、陽イオン交換樹脂として、アンバーライトIR120BNa（オルガノ株式会社製）を用いた。
<Measurement of fulvic acid and humic acid content>
For the samples of Examples 1 to 4 (fulvic acid / humic acid fraction), the contents of fulvic acid and humic acid contained therein were measured. The measurement was performed according to the IHSS method of the International Humic Society (see FIG. 2). However, hydrofluoric acid (HF) treatment was not performed. Further, Supelite DAX-8 (manufactured by Sigma-Aldrich) was used instead of XAD-8 as an adsorption resin for fulvic acid, and Amberlite IR120BNa (manufactured by Organo Corporation) was used as a cation exchange resin.
実施例１〜４の結果を表１に示す。アルカリ性電解水処理工程において加熱を行った実施例３および４は、加熱を行わなかった実施例１および２よりも、処理液中の含有量が増加しており、加熱がフルボ酸およびフミン酸の抽出効率を向上させることが示された。また、アルカリ性電解水処理工程後に、処理液の加熱殺菌工程を行った実施例１および３の含有量と、加熱殺菌工程を行わなかった実施例２および４の含有量はほとんど変わらず、加熱殺菌工程がフルボ酸およびフミン酸の処理液中の含有量に実質的に影響を与えるものではないことも示された。 Table 1 shows the results of Examples 1 to 4. In Examples 3 and 4 in which heating was performed in the alkaline electrolyzed water treatment step, the content in the treatment solution was increased as compared with Examples 1 and 2 in which heating was not performed, and heating was performed using fulvic acid and humic acid. It has been shown to improve extraction efficiency. After the alkaline electrolyzed water treatment step, the contents of Examples 1 and 3 in which the heat sterilization step of the treatment liquid was performed and the contents of Examples 2 and 4 in which the heat sterilization step was not performed hardly changed. It was also shown that the process did not substantially affect the content of fulvic acid and humic acid in the processing solution.
［実施例５］
フルボ酸およびフミン酸を抽出する固形原料を、腐食からおが粉はい菌床（固形分中のフルボ酸４．３ｗ／ｗ％、フミン酸６．５ｗ／ｗ％。以下同様）に変更した以外は実施例１と同様にして、フルボ酸・フミン酸抽出処理を行い、抽出液を得た。
[Example 5]
Except that the solid raw material for extracting fulvic acid and humic acid was changed from corrosion to sawdust germ bed (4.3% w / w% fulvic acid in solid content, 6.5% w / w% humic acid; the same applies hereinafter). In the same manner as in Example 1, fulvic acid / humic acid extraction treatment was performed to obtain an extract.
［実施例６］
フルボ酸およびフミン酸を抽出する固形原料を、腐食からおが粉はい菌床に変更した以外は実施例３と同様にして、フルボ酸・フミン酸抽出処理を行い、抽出液を得た。
[Example 6]
A fulvic acid / humic acid extraction treatment was performed in the same manner as in Example 3 except that the solid raw material for extracting fulvic acid and humic acid was changed from corrosive to a sawdust germ bed to obtain an extract.
［比較例１］
フルボ酸およびフミン酸を抽出する固形原料を、腐食からおが粉はい菌床に変更し、抽出に用いる溶媒をアルカリ性電解水（ｐＨ１２）からＫＯＨ水溶液（ｐＨ１２）に変更した以外は実施例１と同様にして、フルボ酸・フミン酸抽出処理を行い、抽出液を得た。
[Comparative Example 1]
Example 1 was repeated except that the solid raw material for extracting fulvic acid and humic acid was changed from corrosion to a sawdust bed, and the solvent used for extraction was changed from alkaline electrolyzed water (pH 12) to KOH aqueous solution (pH 12). Similarly, fulvic acid / humic acid extraction treatment was performed to obtain an extract.
実施例５および６ならびに比較例１の結果を表２に示す。フルボ酸およびフミン酸の抽出にＫＯＨ水溶液を用いる比較例１と比較して、アルカリ性電解水を用いる実施例５および６は、処理液中の成分の濃度、特にフミン酸の濃度が増加しており、抽出時に加熱する実施例６は加熱を行わない実施例５よりもさらに成分の濃度が向上することが示された。 Table 2 shows the results of Examples 5 and 6 and Comparative Example 1. As compared with Comparative Example 1 using an aqueous KOH solution for extraction of fulvic acid and humic acid, Examples 5 and 6 using alkaline electrolyzed water have increased concentrations of components in the treatment liquid, particularly the concentration of humic acid. It was shown that Example 6 in which heating was performed at the time of extraction further improved the concentration of the components as compared with Example 5 in which heating was not performed.
［実施例７］
実施例１と同様の方法で回収したアルカリ性電解水処理液（フルボ酸・フミン酸画分）７５０ｍＬ（７２０〜７７０ｍＬの範囲で調節できる）を撹拌しながら、ｐＨ１の濃塩酸（ＨＣｌ）１５ｍＬ（１２〜１８ｍＬの範囲で調節できる）を加えた。１２時間静置した後、遠心分離により、上澄みのフルボ酸を含有する塩酸処理液（フルボ酸画分）を回収し、フミン酸を含有する沈殿物（フミン酸画分）と分離した。
[Example 7]
While stirring 750 mL of an alkaline electrolyzed water treatment solution (fulvic acid / humic acid fraction) recovered in the same manner as in Example 1 (adjustable in the range of 720 to 770 mL), 15 mL of concentrated hydrochloric acid (HCl) at pH 1 (12 mL). (Adjustable in the range of １８18 mL). After standing for 12 hours, the supernatant was treated with fulvic acid-containing hydrochloric acid-treated solution (fulvic acid fraction) by centrifugation, and separated from a humic acid-containing precipitate (humic acid fraction).
この塩酸処理液（フルボ酸画分）を実施例５の試料とし、ナトリウム（Ｎａ）、カリウム（Ｋ）、塩素（Ｃｌ）および硫黄（Ｓ）それぞれの含有量を、蛍光Ｘ線分析装置（ＷＤＸＲＦ：株式会社リガク製「ＺＳＸ１０１ｅ」）を使用し、ＪＩＳ Ｋ ０１１９（蛍光Ｘ線分析通則）に準じて測定した。測定には点滴法（ＪＩＳ Ｋ ０１１９ ６．２（Ｃ））を用い、検量線法により定量した。 This hydrochloric acid-treated solution (fulvic acid fraction) was used as a sample of Example 5, and the contents of sodium (Na), potassium (K), chlorine (Cl) and sulfur (S) were measured by a fluorescent X-ray analyzer (WDXRF). : "ZSX101e" manufactured by Rigaku Corporation) and measured according to JIS K 0119 (general rules for fluorescent X-ray analysis). The measurement was carried out using a drip method (JIS K 0119 6.2 (C)) and quantified by a calibration curve method.
［実施例８］
実施例１と同様の方法で回収したアルカリ性電解水処理液（フルボ酸・フミン酸画分）７５０ｍＬ（７２０〜７７０ｍＬの範囲で調節できる）を撹拌しながら、ｐＨ１の濃硫酸（Ｈ2ＳＯ4）１５ｍＬ（１２〜１８ｍＬの範囲で調節できる）を加えた。１２時間静置した後、遠心分離により、上澄みのフルボ酸を含有する硫酸処理液（フルボ酸画分）を回収し、フミン酸を含有する沈殿物（フミン酸画分）と分離した。この硫酸処理液（フルボ酸画分）を実施例６の試料とし、ナトリウム（Ｎａ）、カリウム（Ｋ）、塩素（Ｃｌ）および硫黄（Ｓ）それぞれの含有量を、実施例７と同様にして測定した。
Example 8
Concentrated sulfuric acid (H 2 SO 4 ) at pH 1 was stirred while 750 mL of an alkaline electrolyzed water treatment solution (fulvic acid / humic acid fraction) collected in the same manner as in Example 1 was stirred (adjustable in a range of 720 to 770 mL). 15 mL (adjustable in the range of 12-18 mL) was added. After allowing to stand for 12 hours, the supernatant was subjected to centrifugation to collect the supernatant of the sulfuric acid-treated solution containing fulvic acid (fulvic acid fraction), and separated from the precipitate containing humic acid (humic acid fraction). This sulfuric acid-treated solution (fulvic acid fraction) was used as a sample of Example 6, and the contents of sodium (Na), potassium (K), chlorine (Cl) and sulfur (S) were adjusted in the same manner as in Example 7. It was measured.
［比較例２］
容器内で、常温の水１Ｌに水酸化ナトリウム（ＮａＯＨ）５〜６ｇを溶解して、ｐＨ１２．５の水酸化ナトリウム水溶液を調製した。その溶液に腐植２００ｇを投入し、よく撹拌してから、常温のまま２４時間放置した。その後、不織布フィルターパックにより不溶残渣を除去し、水酸化ナトリウム水溶液処理液（フルボ酸・フミン酸画分）を回収した。回収した水酸化ナトリウム水溶液処理液を試料とした。なお、腐植投入から５時間経過後の水酸化ナトリウム水溶液処理液のｐＨは１２．５のままであった。
[Comparative Example 2]
In a container, 5 to 6 g of sodium hydroxide (NaOH) was dissolved in 1 L of water at normal temperature to prepare an aqueous solution of sodium hydroxide having a pH of 12.5. 200 g of humus was added to the solution, stirred well, and then left at room temperature for 24 hours. Thereafter, insoluble residues were removed with a nonwoven filter pack, and a sodium hydroxide aqueous solution treatment solution (fulvic acid / humic acid fraction) was recovered. The collected sodium hydroxide aqueous solution was used as a sample. The pH of the aqueous sodium hydroxide solution after 5 hours from the introduction of the humus remained at 12.5.
上記の水酸化ナトリウム水溶液処理液（フルボ酸・フミン酸画分）７５０ｍＬ（７２０〜７７０ｍＬの範囲で調節できる）を撹拌しながら、ｐＨ１の濃塩酸（ＨＣｌ）１５ｍＬ（１２〜１８ｍＬの範囲で調節できる）を加えた。１２時間静置した後、遠心分離により、上澄みのフルボ酸を含有する塩酸処理液（フルボ酸画分）を回収し、フミン酸を含有する沈殿物（フミン酸画分）と分離した。この塩酸処理液（フルボ酸画分）を比較例３の試料とし、ナトリウム（Ｎａ）、カリウム（Ｋ）、塩素（Ｃｌ）および硫黄（Ｓ）それぞれの含有量を、実施例７と同様にして測定した。 While stirring 750 mL (adjustable in the range of 720 to 770 mL) of the above sodium hydroxide aqueous solution (fluvic acid / humic acid fraction), 15 mL of concentrated hydrochloric acid (HCl) at pH 1 (adjustable in the range of 12 to 18 mL). ) Was added. After standing for 12 hours, the supernatant was treated with fulvic acid-containing hydrochloric acid-treated solution (fulvic acid fraction) by centrifugation, and separated from a humic acid-containing precipitate (humic acid fraction). This hydrochloric acid-treated solution (fulvic acid fraction) was used as a sample of Comparative Example 3, and the contents of sodium (Na), potassium (K), chlorine (Cl) and sulfur (S) were adjusted in the same manner as in Example 7. It was measured.
［比較例３］
容器内で、常温の水１Ｌに水酸化カリウム（ＫＯＨ）５〜６ｇを溶解して、ｐＨ１２．５の水酸化カリウム水溶液を調製した。その溶液に腐植２００ｇを投入し、よく撹拌してから、常温のまま２４時間放置した。その後、不織布フィルターパックにより不溶残渣を除去し、水酸化カリウム水溶液処理液（フルボ酸・フミン酸画分）を回収した。回収した水酸化カリウム水溶液処理液を比較例２の試料とした。なお、比較例２において、腐植投入から５時間経過後の水酸化カリウム水溶液処理液のｐＨは１２．５のままであった。
[Comparative Example 3]
In a container, 5 to 6 g of potassium hydroxide (KOH) was dissolved in 1 L of water at room temperature to prepare a potassium hydroxide aqueous solution having a pH of 12.5. 200 g of humus was added to the solution, stirred well, and then left at room temperature for 24 hours. Thereafter, insoluble residues were removed with a nonwoven filter pack, and a potassium hydroxide aqueous solution (fluvic acid / humic acid fraction) was recovered. The recovered potassium hydroxide aqueous solution was used as a sample of Comparative Example 2. In Comparative Example 2, the pH of the aqueous potassium hydroxide solution after 5 hours from the introduction of the humus remained at 12.5.
上記のアルカリ性電解水処理液（フルボ酸・フミン酸画分）７５０ｍＬ（７２０〜７７０ｍＬの範囲で調節できる）を撹拌しながら、ｐＨ１の濃硫酸（Ｈ2ＳＯ4）１５ｍＬ（１２〜１８ｍＬの範囲で調節できる）を加えた。１２時間静置した後、遠心分離により、上澄みのフルボ酸を含有する硫酸処理液（フルボ酸画分）を回収し、フミン酸を含有する沈殿物（フミン酸画分）と分離した。この硫酸処理液（フルボ酸画分）を比較例４の試料とし、ナトリウム（Ｎａ）、カリウム（Ｋ）、塩素（Ｃｌ）および硫黄（Ｓ）それぞれの含有量を、実施例７と同様にして測定した。 While stirring 750 mL (adjustable in the range of 720 to 770 mL) of the above alkaline electrolyzed water treatment solution (fulvic acid / humic acid fraction), 15 mL of concentrated sulfuric acid (H 2 SO 4 ) at pH 1 (in the range of 12 to 18 mL). Can be adjusted). After allowing to stand for 12 hours, the supernatant was subjected to centrifugation to collect the supernatant of the sulfuric acid-treated solution containing fulvic acid (fulvic acid fraction), and separated from the precipitate containing humic acid (humic acid fraction). This sulfuric acid-treated solution (fulvic acid fraction) was used as a sample of Comparative Example 4, and the contents of sodium (Na), potassium (K), chlorine (Cl) and sulfur (S) were determined in the same manner as in Example 7. It was measured.
実施例７〜８および比較例２〜３の結果を表３に示す。対照として、実施例１と同様の方法で回収したアルカリ性電解水処理液そのもの（フルボ酸分画処理を行っていないもの）についての各成分の含有量の測定結果も表３にあわせて示す。アルカリ性電解水を用いて調製されたフルボ酸・フミン酸画分から得られる実施例７の試料（フルボ酸画分）は、水酸化ナトリウム水溶液を用いて調製されたフルボ酸・フミン酸画分から得られる比較例２の試料（フルボ酸画分）よりもナトリウム（Ｎａ）の含有量が少ないため、それぞれの試料の調製のために用いた塩酸に由来する塩素（Ｃｌ）との反応による塩化ナトリウム（ＮａＣｌ）の生成量も少なくなることが分かる。同様に、アルカリ性電解水を用いて調製されたフルボ酸・フミン酸画分から得られる実施例８の試料（フルボ酸画分）は、水酸化カリウム水溶液を用いて調製されたフルボ酸・フミン酸画分から得られる比較例３の試料（フルボ酸画分）よりもカリウム（Ｋ）の含有量が少ないため、それぞれの試料の調製のために用いた硫酸に由来する硫化物イオン（ＳＯ4 2-）との反応による硫酸カリウム（Ｋ2ＳＯ4）の生成量も少なくなることが分かる。 Table 3 shows the results of Examples 7 and 8 and Comparative Examples 2 and 3. As a control, Table 3 also shows the measurement results of the content of each component in the alkaline electrolyzed water treatment liquid itself (the one not subjected to the fulvic acid fractionation treatment) recovered in the same manner as in Example 1. The sample of Example 7 (fluvic acid fraction) obtained from the fulvic acid / humic acid fraction prepared using alkaline electrolyzed water is obtained from the fulvic acid / humic acid fraction prepared using an aqueous sodium hydroxide solution. Since the content of sodium (Na) is lower than that of the sample of Comparative Example 2 (fulvic acid fraction), sodium chloride (NaCl) by reaction with chlorine (Cl) derived from hydrochloric acid used for preparing each sample was used. ) Is also reduced. Similarly, the sample of Example 8 (fulvic acid fraction) obtained from the fulvic acid / humic acid fraction prepared using alkaline electrolyzed water is the fulvic acid / humic acid fraction prepared using an aqueous potassium hydroxide solution. Since the content of potassium (K) is lower than that of the sample of Comparative Example 3 (fulvic acid fraction) obtained from the sample, the sulfide ion (SO 4 2- ) derived from sulfuric acid used for the preparation of each sample It can be seen that the amount of potassium sulfate (K 2 SO 4 ) produced by the reaction with the compound also decreases.
なお、実施例７および８の試料にもナトリウム（Ｎａ）が少量含まれているのは、アルカリ性電解水の製造の際に電解補助剤として用いたＮａＣｌが残存しているためである。また、実施例７および比較例２の試料にもカリウム（Ｋ）が少量含まれているのは、腐植物質の固形原料として用いた腐植から溶出するためである。 The samples of Examples 7 and 8 also contain a small amount of sodium (Na) because NaCl used as an electrolysis auxiliary in the production of alkaline electrolyzed water remains. Further, the reason why the samples of Example 7 and Comparative Example 2 also contain a small amount of potassium (K) is that they are eluted from the humus used as a solid raw material for humic substances.
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